Water-repellent and oil-repellent composition

Abstract

Provided is a novel water-repellant and oil-repellant composition for nonwoven fabric, comprising: (1) a hydrocarbon-containing polymer which has a repeating unit derived from a monomer (a) that includes a hydrocarbon group having 6-40 carbon atoms; and (2) a water-soluble polymer.

Description

Water and oil repellent composition

[0001] The present disclosure relates to a water and oil repellent composition for non-woven fabrics.

[0002] In Patent Document 1, it is disclosed that an oil-resistant composition containing (1) a polysaccharide and (2) an oil-resistant polymer can impart oil resistance to paper. In Patent Document 1, there is no mention of substrates other than paper, nor is there any mention of imparting water and oil repellency.

[0003] Japanese Patent Application Laid-Open No. 2022-65650

[0004] An object of the present disclosure is to provide a novel water and oil repellent composition for non-woven fabrics.

[0005] The present disclosure includes the following aspects: [Item 1] A water and oil repellent composition for non-woven fabrics, comprising (1) a hydrocarbon-containing polymer having a repeating unit derived from a monomer (a) having a hydrocarbon group with 6 to 40 carbon atoms, and (2) a water-soluble polymer. [Item 2] The water and oil repellent composition for non-woven fabrics according to Item 1, wherein the amount of the hydrocarbon-containing polymer (1) is 10% by weight or more and 50% by weight or less based on the total amount of the hydrocarbon-containing polymer (1) and the water-soluble polymer (2). [Item 3] The water and oil repellent composition according to Item 1 or 2, wherein the water-soluble polymer (2) is at least one selected from the group consisting of polysaccharides and polyvinyl alcohol. [Item 4] The water and oil repellent composition according to any one of Items 1 to 3, further comprising a penetrant and an antistatic agent. [Item 5] The water and oil repellent composition according to any one of Items 1 to 4, wherein the monomer (a) has a hydrocarbon group with 12 to 30 carbon atoms. [Item 6] The monomer (a) has the formula: CH2=C(-X ａ )-C(=O)-Y ａ (R ａ ) ｋ [In the formula, R ａ are each independently a hydrocarbon group with 6 to 40 carbon atoms, X ａ is a hydrogen atom, a monovalent organic group or a halogen atom, and Y ａ is a divalent to tetravalent hydrocarbon group with 1 carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２A water-repellent and oil-repellent composition according to any one of claims 1 to 5, represented by: [Claim 7] The monomer (a) comprises monomer (a2), wherein the monomer (a2) is a group consisting of at least one selected from - or -NH- (excluding hydrocarbon groups), and k is 1 to 3. ａ２ )-C(=O)-Y ａ２１ -Z(-Y ａ２２ -R ａ２ ) ｎ [In the formula, R ａ２ Each of these is independently a hydrocarbon group having 6 to 40 carbon atoms, X ａ２ Y is a hydrogen atom, a monovalent organic group, or a halogen atom. ａ２１ is -O- or -NH-, Y ａ２２ These are independently -O-, -C(=O)-, and -S(=O). ２ -, -NH- or -CH ２ A water-repellent and oil-repellent composition according to any one of claims 1 to 6, represented by: - ​​a group consisting of at least one selected from, where Z is a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2. [Claim 8] The hydrocarbon-containing polymer (1) comprises repeating units derived from a hydrophilic group-containing monomer (b), wherein the monomer (b) is of the formula: CH ２ = CX ｂ C(=O)-Y ｂ - (R ｂ O) ｎ -A ｂ [In the formula, X ｂ is a hydrogen atom or a methyl group, Y ｂ is -O- or -NH-, and R ｂ Each of these is an alkylene group having 2 to 6 carbon atoms, and A ｂ This is a hydrogen atom, an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, or CH ２ = CX ｂA water-repellent and oil-repellent composition according to any one of claims 1 to 7, wherein the oxyalkylene (meth)acrylate is represented by C(=O)-, and n is an integer from 1 to 90. [Clause 9] A water-repellent and oil-repellent composition according to any one of claims 1 to 8, wherein the hydrocarbon-containing polymer (1) comprises (c) an ionic group-containing monomer, and the monomer (c) comprises an olefinic carbon-carbon double bond and an anionic group or a cationic group. [Clause 10] The monomer (a) is monomer (a2), and the monomer (a2) is represented by the formula: CH2=C(-X ａ２ )-C(=O)-Y ａ２１ -Z(-Y ａ２２ -R ａ２ ) ｎ [In the formula, R ａ２ Each of these is independently a hydrocarbon group having 6 to 40 carbon atoms, X ａ２ Y is a hydrogen atom, a monovalent organic group, or a halogen atom. ａ２１ is -O- or -NH-, Y ａ２２ These are independently -O-, -C(=O)-, and -S(=O). ２ -, -NH- or -CH ２ - is a group composed of at least one selected from, where Z is a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2. ] is represented as, where the monomer (b) is monomer (b1), and the monomer (b1) is CH ２ = CX ｂ C(=O)-O-(R ｂ O) ｎ -A ｂｉ [In the formula, X ｂ Each is independently a hydrogen atom or a methyl group, R ｂ Each of these is an alkylene group having 2 to 6 carbon atoms, and A ｂｉEach is independently a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, and n is an integer from 1 to 90. The water-soluble polymer (2) is at least one selected from the group consisting of starch and polyvinyl alcohol, and the water-repellent and oil-repellent composition comprises a penetrating agent and an antistatic agent, the water-repellent composition according to any one of claims 1 to 9. [Claim 11] A method for producing a water-repellent and oil-repellent composition for nonwoven fabrics, comprising (1) a hydrocarbon-containing polymer having repeating units derived from a monomer (a) having hydrocarbon groups having 6 to 40 carbon atoms, and (2) a water-soluble polymer, the method comprising the steps of polymerizing the monomer (a) in the presence of an organic solvent to obtain a polymer liquid containing the hydrocarbon-containing polymer (1), and volatilizing the organic solvent from the polymer liquid and adding water. [Claim 12] A nonwoven fabric product treated with the water-repellent and oil-repellent agent according to any one of claims 1 to 10. [Item 13] A method for producing a nonwoven fabric product, comprising the step of treating a nonwoven fabric substrate with a water-repellent and oil-repellent composition described in any one of items 1 to 10.

[0006] By using this disclosure, it is possible to effectively impart water-repellent and oil-repellent properties to a nonwoven fabric substrate.

[0007] <Water- and oil-repellent agent> The water- and oil-repellent agent in this disclosure comprises a hydrocarbon-containing polymer (1) and a water-soluble polymer (2). The water- and oil-repellent agent may also contain other components.

[0008] The water-repellent and oil-repellent agent in this disclosure does not necessarily have to contain any one selected from the group consisting of compounds having 8 or more carbon atoms in a fluoroalkyl group, compounds having 8 or more carbon atoms in a perfluoroalkyl group, compounds having 4 or more carbon atoms in a fluoroalkyl group, compounds having 4 or more carbon atoms in a perfluoroalkyl group, compounds having a perfluoroalkyl group, compounds having a fluoroalkyl group, and compounds having a fluorine atom. The water-repellent and oil-repellent agent in this disclosure can impart water-repellent and oil-repellent properties to a substrate even without containing these fluorine compounds.

[0009] [(1) Hydrocarbon-containing polymer] Hydrocarbon-containing polymer (1) is a polymer obtained by polymerizing vinyl monomers and exhibits liquid repellency. Here, the vinyl monomer may be any compound having a polymerizable carbon-carbon double bond (ethylenically unsaturated double bond) (>C=C<), and may be a monomer containing a vinyl group, vinylene group, vinylidene group, acryloyl group, methacryloyl group, or derivative groups thereof. Typically, hydrocarbon-containing polymer (1) is an acrylic polymer having repeating units derived from (meth)acrylic monomers.

[0010] The hydrocarbon-containing polymer (1) has a monovalent hydrocarbon group having 6 to 40 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group is branched or linear, and is more preferably linear. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group (alkyl group). The number of carbon atoms in the hydrocarbon group may be 6 or more, 7 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 10 or more, 12 or more, or 16 or more, and may also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, 25 or less, or 20 or less.

[0011] The HD (n-hexadecane) contact angle of the hydrocarbon-containing polymer (1) may be 10° or more, 15° or more, 25° or more, 35° or more, 55° or more, 55° or more, or 65° or more, preferably 30° or more, and may also be 100° or less, 90° or less, or 75° or less. By having an HD contact angle of the hydrocarbon-containing polymer (1) above the lower limit, good liquid repellency (especially oil repellency and oil resistance) can be imparted to the substrate. The HD contact angle is the static contact angle of the hydrocarbon-containing polymer (1) with respect to the spin-coated film, as shown in the examples, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle 1 second after dropping.

[0012] The water contact angle of the hydrocarbon-containing polymer (1) may be 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, or 100° or more, and may also be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. By having a water contact angle of the hydrocarbon-containing polymer (1) above the lower limit, good liquid repellency (especially water repellency and water resistance) can be imparted to the substrate. The water contact angle is the static contact angle of the hydrocarbon-containing polymer (1) with respect to the spin-coated film, as shown in the examples, and is obtained by dropping 2 μL of water onto the spin-coated film and measuring the contact angle 1 second after the drop.

[0013] The hydrocarbon-containing polymer (1) is preferably a compound having carbon of bio-based origin. The degree of bio-basedness is measured in accordance with ASTM D6866. The degree of bio-basedness may be 20% or more, preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, most preferably 80% or more or 90% or more, for example 100%. A high degree of bio-basedness means that the amount of fossil resource-based materials represented by petroleum etc. is small, and from this viewpoint, a higher degree of bio-basedness of the hydrocarbon-containing polymer (1) is preferable.

[0014] The hydrocarbon-containing polymer (1) in this disclosure does not necessarily have to contain any of the group selected from the group consisting of fluoroalkyl groups having 8 or more carbon atoms, perfluoroalkyl groups having 8 or more carbon atoms, fluoroalkyl groups having 4 or more carbon atoms, perfluoroalkyl groups having 4 or more carbon atoms, perfluoroalkyl groups, fluoroalkyl groups, and fluorine atoms. Even if the hydrocarbon-containing polymer (1) does not contain these fluorine-containing groups, it can still impart oil resistance to the substrate.

[0015] The weight-average molecular weight of the hydrocarbon-containing polymer (1) may be 3,000 or more, 5,000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, 500,000 or more, 750,000 or more, 1,000,000 or more, 1,500,000 or more, 2,000,000 or more, and may also be 1,000,000 or less, 7,500,000 or less, 5,000,000 or less, 3,000,000 or less, 2,000,000 or less, 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, or 5,000 or less, and one of them is between 100,000 and 2,000,000. Here, the weight-average molecular weight is the polystyrene-equivalent molecular weight determined by GPC measurement.

[0016] The melting point or glass transition point (e.g., melting point) of the hydrocarbon-containing polymer (1) may be 0°C or higher, 10°C or higher, 20°C or higher, 30°C or higher, 35°C or higher, 40°C or higher, 45°C or higher, 50°C or higher, or 55°C or higher, and may also be 200°C or lower, 150°C or lower, 100°C or lower, 80°C or lower, 60°C or lower, or 70°C or lower.

[0017] The hydrocarbon-containing polymer (1) has repeating units derived from a monomer (a) having a hydrocarbon group with 6 to 40 carbon atoms. In addition to the repeating units derived from monomer (a), the hydrocarbon-containing polymer (1) may have (b) a monomer having a hydrophilic group, (c) an ionic group-containing monomer, and / or (d) repeating units derived from other monomers. In particular, it is preferable that the hydrocarbon-containing polymer (1) has repeating units formed from (b) a monomer having a hydrophilic group. Furthermore, it is preferable that the hydrocarbon-containing polymer (1) has repeating units formed from (c) an ionic group-containing monomer, in addition to monomers (a) and (b). In addition to monomers (a), (b), and (c), the hydrocarbon-containing polymer (1) may have (d) repeating units formed from other monomers.

[0018] [(a) Hydrocarbon group-containing monomer] The hydrocarbon-containing polymer (1) has repeating units derived from monomer (a) having a hydrocarbon group with 6 to 40 carbon atoms. Monomer (a) may be a monomer.

[0019] The hydrocarbon group of monomer (a) may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be branched or linear, and is more preferably linear. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group (alkyl group). The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 10 or more, 12 or more, 14 or more, or 16 or more, and may also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, 25 or less, or 20 or less.

[0020] Monomer (a) may contain an amide group, a urea group, or a urethane group. The hydrocarbon monomer may be a combination of a hydrocarbon monomer having an amide group, a urea group, or a urethane group and a hydrocarbon monomer not having an amide group, a urea group, or a urethane group. The effects of this disclosure can be favorably achieved by including such groups in monomer (a).

[0021] A monomer (a) having a hydrocarbon group with 6 to 40 carbon atoms is given by the formula: CH2=C(-X ａ )-C(=O)-Y ａ (R ａ ) ｋ [In the formula, R ａ Each of these is independently a hydrocarbon group having 6 to 40 carbon atoms, X ａ Y is a hydrogen atom, a monovalent organic group, or a halogen atom. ａ This refers to divalent to tetravalent hydrocarbon groups with one carbon atom (especially -CH ２ -, -CH=), -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２It is preferably a monomer represented by ], which is a group consisting of at least one selected from - or -NH- (excluding hydrocarbon groups), and k is 1 to 3.

[0022] X ａ This may be a hydrogen atom, a methyl group, a halogen other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. ａ Examples include hydrogen atoms, methyl groups, chlorine atoms, bromine atoms, iodine atoms, and cyano groups. ａ It is preferable that the element is a hydrogen atom, a methyl group, or a chlorine atom. ａ It is particularly preferable that it be a hydrogen atom.

[0023] Y ａ It is a divalent to tetravalent group. ａ It is preferable that the group is divalent. ａ This is a hydrocarbon group having 1 carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ Preferably, the group is composed of at least one selected from - or -NH- (excluding hydrocarbon groups). An example of a C1 hydrocarbon group is -CH ２ -, -CH(-) ２ or -C(-) ３ These are some examples.

[0024] Y ａ -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'- , -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'- [Wherein, Y' is a direct bond, -O-, -NH- or -S(=O) ２ - and R' is - (CH ２ ) m - (m is an integer between 1 and 5) or -C ６ H ４ - (phenylene group). ] This may be the case.

[0025] Y ａSpecific examples include -O-, -NH-, -O-C(=O)-, -C(=O)-NH-, -NH-C(=O)-, -O-C(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C ６ H ４ -, -O-(CH ２ ) m -O-, -NH-(CH ２ ) m -NH-, -O-(CH ２ ) m -NH-, -NH-(CH ２ ) m -O-, -O-(CH ２ ) m -O-C(=O)-, -O-(CH ２ ) m -C(=O)-O-, -NH-(CH ２ ) m -O-C(=O)-, -NH-(CH ２ ) m -C(=O)-O-, -O-(CH ２ ) m -O-C(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-O-, -O-(CH ２ ) m -C(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-, -O-(CH ２ ) m -NH-C(=O)-NH-, -O-(CH ２ ) m -O-C ６ H ４ -, -O-(CH ２ ) m -NH-S(=O) ２ -, -O-(CH ２ ) m -S(=O) ２ -NH-, -NH-(CH ２ ) m -O-C(=O)-NH-, -NH-(CH ２ ) m -NH-C(=O)-O-, -NH-(CH ２ ) m -C(=O)-NH-, -NH-(CH２ ) m -NH-C(=O)-, -NH-(CH ２ ) m -NH-C(=O)-NH-, -NH-(CH ２ ) m -O-C ６ H ４ -, -NH-(CH ２ ) m -NH-C ６ H ４ -, -NH-(CH ２ ) m -NH-S(=O) ２ -, or -NH-(CH ２ ) m -S(=O) ２ -NH- [wherein m is 1 to 5, especially 2 or 4].

[0026] Y ａ is -O-, -NH-, -O-(CH ２ ) m -O-C(=O)-, -O-(CH ２ ) m -NH-C(=O)-, -O-(CH ２ ) m -OC(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-O-, -O-(CH ２ ) m -NH-C(=O)-NH-, -O-(CH ２ ) m -NH-S(=O) ２ -, -O-(CH ２ ) m -S(=O) ２ -NH-, -NH-(CH ２ ) m -NH-S(=O) ２ -, or -NH-(CH ２ ) m -S(=O) ２ -NH- [wherein m is an integer from 1 to 5, particularly 2 or 4.] is preferable. Y ａ is -O- or -O-(CH ２ ) m -NH-C(=O)-, especially -O-(CH ２ )m It is more preferable that it be -NH-C(=O)-.

[0027] R ａ The hydrocarbon group is preferably a linear or branched hydrocarbon group. The hydrocarbon group may be a linear hydrocarbon group in particular. The hydrocarbon group is preferably an aliphatic hydrocarbon group, especially a saturated aliphatic hydrocarbon group, and especially an alkyl group. The number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example 16 to 26 or 15 to 26, and especially 18 to 22 or 17 to 22.

[0028] An example of monomer (a) is given by equation (a1): CH2 = C(-X ａ１ ) - C (= O) - Y ａ１ -R ａ１ [In the formula, R ａ１ X is a hydrocarbon group having 6 to 40 carbon atoms. ａ１ Y is a hydrogen atom, a monovalent organic group, or a halogen atom. ａ１ is -O- or -NH-. The monomer is represented by (a2): CH2=C(-X ａ２ )-C(=O)-Y ａ２１ -Z(-Y ａ２２ -R ａ２ ) ｎ [In the formula, R ａ２ Each of these is independently a hydrocarbon group having 6 to 40 carbon atoms, X ａ２ Y is a hydrogen atom, a monovalent organic group, or a halogen atom. ａ２１ is -O- or -NH-, Y ａ２２ These are independent of each other, and can be directly bonded, or -O-, -C(=O)-, -S(=O) ２ -, -NH- or -CH ２ A monomer represented by ], where Z is a directly bonded or divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2.

[0029] ((a1) monomer) The monomer (a1) is given by the formula: CH2 = C(-X ａ１ )-C(=O)-Y ａ１ -R ａ１ [In the formula, R ａ１X is a hydrocarbon group having 6 to 40 carbon atoms. ａ１ Y is a hydrogen atom, a monovalent organic group, or a halogen atom. ａ１ It is a compound represented by -O- or -NH-.

[0030] The monomer (a1) is Y ａ１ A long-chain acrylate ester monomer in which is -O-, or Y ａ１ It is a long-chain acrylamide monomer with -NH-. ａ１ This is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and especially an alkyl group. ａ１ In this, the number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example 16 to 26, and particularly preferably 18 to 22. ａ１ This may be a hydrogen atom, a methyl group, a halogen other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. A hydrogen atom, a methyl group, or a chlorine atom is preferred.

[0031] Preferred examples of long-chain acrylate ester monomers are lauryl (meth)acrylate, stearyl (meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, eicosyl α-chloroacrylate, and behenyl α-chloroacrylate. Preferred examples of long-chain acrylamide monomers are stearyl (meth)acrylamide, eicosyl (meth)acrylamide, and behenyl (meth)acrylamide.

[0032] ((a2) monomer) Monomer (a2) is a different monomer from monomer (a1). Monomer (a2) is -O-, -C(=O)-, -S(=O) ２ -, -NH- or -CH ２ It is a (meth)acrylate or (meth)acrylamide having a group composed of at least one selected from the following. The monomer (a2) is given by the formula: CH2=C(-X ａ２ )-C(=O)-Y ａ２１ -Z(-Y ａ２２ -R ａ２ ) ｎ [In the formula, R ａ２Each of these is independently a hydrocarbon group having 6 to 40 carbon atoms, X ａ２ Y is a hydrogen atom, a monovalent organic group, or a halogen atom. ａ２１ is -O- or -NH-, Y ａ２２ These are independent of each other, and can be directly bonded, or -O-, -C(=O)-, -S(=O) ２ -, -NH- or -CH ２ A compound represented by ] is a group composed of at least one selected from the following, where Z is a directly bonded, or divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2. ａ２２ And / or Z does not have to be directly joined. Y ａ２２ And Z does not necessarily have to be in a direct bond at the same time.

[0033] R ａ２ This is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and especially an alkyl group. ａ２ In this, the number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example 16 to 26 or 15 to 26, and particularly preferably 18 to 22 or 17 to 22.

[0034] X ａ２ This may be a hydrogen atom, a methyl group, a halogen other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. A hydrogen atom, a methyl group, or a chlorine atom is preferred.

[0035] Y ａ２２ -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'-, -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'- [where Y' is independent, directly combined, -O-, -NH-, or -S(=O)] ２ - and R' is - (CH ２ ) ｍ - (where m is an integer from 1 to 5), a linear hydrocarbon group having unsaturated bonds with 1 to 5 carbon atoms, a branched hydrocarbon group having 1 to 5 carbon atoms, or - (CH ２ )ｌ -C ６ H ４ -(CH ２ ) ｌ - (where l is an independent integer from 0 to 5, and -C) ６ H ４ (- is a phenylene group). ] This may be the case.

[0036] Y ａ２２ Specific examples include direct bond, -O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O) ２ -, -S (=O) ２ -NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -OC ６ H ４ -, -NH-C ６ H ４ -, -O-(CH ２ ) m -O-, -NH-(CH ２ ) m -NH-, -O-(CH ２ ) m -NH-, -NH-(CH ２ ) m -O-, -O-(CH ２ ) m -O-C(=O)-, -O-(CH ２ ) m -C(=O)-O-, -NH-(CH ２ ) m -OC(=O)-, -NH-(CH ２ ) m -C(=O)-O-, -O-(CH ２ ) m -OC(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-O-, -O-(CH ２ ) m -C(=O)-NH-, -O-(CH ２ ) m -NH-C(=O)-, -O-(CH ２ ) m -NH-C(=O)-NH-, -O-(CH ２ ) m -O-C６ H ４ -, -NH-(CH ２ ) m -OC(=O)-NH-, -NH-(CH ２ ) m -NH-C(=O)-O-, -NH-(CH ２ ) m -C(=O)-NH-, -NH-(CH ２ ) m -NH-C(=O)-, -NH-(CH ２ ) m -NH-C(=O)-NH-, -NH-(CH ２ ) m -O-C ６ H ４ -, -NH-(CH ２ ) m -NH-C ６ H ４ - [In the formula, m is an integer between 1 and 5.]

[0037] Y ａ２２ is -O-, -NH-, -O-C(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O) ２ -, -S (=O) ２ -NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -OC ６ H ４ - is preferable. Y ａ２２ It is even more preferable that -NH-C(=O)-, -C(=O)-NH-, -O-C(=O)-NH-, -NH-C(=O)-O-, or -NH-C(=O)-NH-. ａ２２ The bond does not have to be direct.

[0038] Z is a directly bonded, or divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and may have a linear or branched structure. The number of carbon atoms in Z is preferably 2 to 4, particularly 2. Specific examples of Z include directly bonded, -CH ２ -ien-CH ２ CH ２ -ien-CH ２ CH ２ CH ２ -ien-CH ２CH ２ CH ２ CH ２ -ien-CH ２ CH ２ CH ２ CH ２ CH ２ -ien-CH ２ CH(-) ２ ien-CH ２ (CH-)CH ２ -ien-CH ２ CH ２ CH = ien - CH ２ CH ２ CH ２ CH ２ CH(-) ２ ien-CH ２ CH ２ (CH-)CH ２ -ien-CH ２ CH ２ CH ２ CH(-) ２ Therefore, Z does not have to be a direct bond.

[0039] The monomer (a2) is CH2=C(-X ａ２ )-C(=O)-O-(CH ２ ) m -NH-C(=O)-R ａ２ ,CH ２ = C(-X) ａ２ )-C(=O)-O-(CH ２ ) ｍ -OC(=O)-NH-R ａ２ ,CH ２ = C(-X) ａ２ )-C(=O)-O-(CH ２ ) ｍ -NH-C(=O)-OR ａ２ ,CH ２ = C(-X) ａ２ )-C(=O)-O-(CH ２ ) ｍ -NH-C(=O)-NH-R ａ２ It is preferable that R ａ２ and X ａ２ This is equivalent to the above. ]. The monomer (a2) is CH2=C(-X ａ２ )-C(=O)-O-(CH ２ ) m-NH-C(=O)-R ａ２ It is particularly preferable that this be the case.

[0040] Monomer (a2) can be produced by reacting a hydroxyalkyl (meth)acrylate or hydroxyalkyl (meth)acrylamide with a long-chain alkyl isocyanate. Examples of long-chain alkyl isocyanates include lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, and behenyl isocyanate. Alternatively, monomer (a2) can also be produced by reacting a (meth)acrylate having an isocyanate group in its side chain, such as 2-methacryloyloxyethyl methacrylate, with a long-chain alkylamine or long-chain alkyl alcohol. Examples of long-chain alkylamines include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, and behenylamine. Examples of long-chain alkyl alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.

[0041] Preferred examples of monomer (a) are as follows: stearyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, behenyl α-chloroacrylate; stearyl (meth)acrylamide, behenyl (meth)acrylamide;

[0042]

[0043]

[0044]

[0045]

[0046]

[0047] [In the above formula, n is a number from 6 to 40, and m is a number from 1 to 5.] The compound in the above chemical formula is an acrylic compound in which the α-position is a hydrogen atom, but specific examples may be a methacle compound in which the α-position is a methyl group and an α-chloroacrylic compound in which the α-position is a chlorine atom.

[0048] The monomer (a2) is given by formula: R ａ２２ -C(=O)-NH-R ａ２３ -O-R ａ２１ [In the formula, R ａ２１ R is an organic residue having an ethylenically unsaturated polymerizable group. ａ２２ R is a hydrocarbon group having 6 to 40 carbon atoms. ａ２３ It is preferably an amide group-containing monomer represented by ], which is a hydrocarbon group having 1 to 5 carbon atoms.

[0049] R ａ２１ This is an organic residue having an ethylenically unsaturated polymerizable group, and is not particularly limited as long as it has a double bond between carbon atoms. Specifically, -C(=O)CR ａ２１１ =CH ２ ----CHR ａ２１１ =CH ２ ien-CH ２ CHR ａ２１１ =CH ２ Examples include organic residues having ethylenically unsaturated polymerizable groups, such as R ａ２１１ Examples include a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Also, R ａ２１ In addition to ethylenically unsaturated polymerizable groups, it may have various organic groups, such as chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, and polysiloxane groups, and these organic groups may be substituted with various substituents. ａ２１ -C(=O)CR ａ２１１ =CH ２ It is preferable that this be the case.

[0050] R ａ２２ This is a hydrocarbon group having 6 to 40 carbon atoms, preferably an alkyl group, and includes chain hydrocarbon groups, cyclic hydrocarbon groups, etc. Among these, a chain hydrocarbon group is preferred, and a linear saturated hydrocarbon group is particularly preferred. ａ２２The number of carbon atoms is 6 to 40, preferably 11 to 27, and particularly preferably 15 to 23.

[0051] R ａ２３ This is a hydrocarbon group having 1 to 5 carbon atoms, preferably an alkyl group. The hydrocarbon group having 1 to 5 carbon atoms may be linear or branched, and may have unsaturated bonds, but linear is preferred. ａ２３ The number of carbon atoms is preferably 2 to 4, and particularly preferably 2. ａ２３ It is preferable that it is an alkylene group.

[0052] A monomer containing an amide group is R ａ２２ Those that have only one type (for example, R ａ２２ (only compounds with 17 carbon atoms), or R ａ２２ Those that are combinations of multiple things (for example, R ａ２２ A compound with 17 carbon atoms and R ａ２２ It may be a mixture of a compound having 15 carbon atoms.

[0053] An example of an amide group-containing monomer is alkyl (meth)acrylate carboxylic acid amide. Specific examples of amide group-containing monomers include palmitic acid amide ethyl (meth)acrylate, stearic acid amide ethyl (meth)acrylate, behenic acid amide ethyl (meth)acrylate, myristate acid amide ethyl (meth)acrylate, lauric acid amide ethyl (meth)acrylate, isostearate ethyl amide (meth)acrylate, oleic acid ethyl amide (meth)acrylate, tert-butylcyclohexylcaproic acid amide ethyl (meth)acrylate, adamantane carboxylic acid ethyl amide (meth)acrylate, naphthalene carboxylic acid amide ethyl (meth)acrylate, anthracene carboxylic acid amide ethyl (meth)acrylate, palmitic acid amide propyl (meth)acrylate, stearate amide propyl (meth)acrylate, palmitic acid amide ethyl vinyl ether, stearate amide ethyl vinyl ether, palmitic acid amide ethyl allyl ether, stearate amide ethyl allyl ether, or mixtures thereof.

[0054] The amide group-containing monomer is preferably stearamide ethyl (meth)acrylate. The amide group-containing monomer may be a mixture containing stearamide ethyl (meth)acrylate. In a mixture containing stearamide ethyl (meth)acrylate, the amount of stearamide ethyl (meth)acrylate may be, for example, 40% or more by weight, 50% or more by weight, 60% or more by weight, or 70% or more by weight, or 90% or less by weight, 80% or less by weight, or 70% or less by weight, based on the total weight of the amide group-containing monomer. The remaining monomer may be, for example, palmitic acid amide ethyl (meth)acrylate.

[0055] Of monomer (a), the amount of monomer (a2) may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, or 80% by weight or more, and is preferably 30% by weight or more.

[0056] [(b) Hydrophilic group-containing monomer] The hydrocarbon-containing polymer (1) may contain a hydrophilic group-containing monomer (b). Monomer (b) is a monomer other than monomer (a) that has a hydrophilic group. The hydrophilic group is preferably an oxyalkylene group (the alkylene group has 2 to 6 carbon atoms), and more preferably an oxyethylene group. In particular, monomer (b) is preferably an oxyalkylene (meth)acrylate, for example, polyalkylene (or monoalkylene) glycol mono(meth)acrylate and / or polyalkylene (or monoalkylene) glycol di(meth)acrylate, or polyalkylene (or monoalkylene) glycol mono(meth)acrylamide.

[0057] Monomer (b) is given by formula: CH ２ = CX ｂ C(=O)-Y ｂ - (R ｂ O) ｎ -A ｂ [In the formula, X ｂ is a hydrogen atom or a methyl group, Y ｂ is -O- or -NH-, and R ｂEach of these is an alkylene group having 2 to 6 carbon atoms, and A ｂ This is a hydrogen atom, an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, or CH ２ = CX ｂ It is preferable that the oxyalkylene (meth)acrylate is represented by [C(=O)-, where n is an integer from 1 to 90].

[0058] An example of monomer (b) is given by formula: CH ２ = CX ｂ C(=O)-O-(R ｂ O) ｎ -A ｂｉ (b1) CH ２ = CX ｂ C(=O)-O-(R ｂ O) ｎ -C(=O)CX ｂ =CH ２ (b2), or CH ２ = CX ｂ C(=O)-NH-(R ｂ O) ｎ -A ｂｉ (b3) [In the formula, X ｂ Each is independently a hydrogen atom or a methyl group, R ｂ Each of these is an alkylene group having 2 to 6 carbon atoms, and A ｂｉ Each is independently a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, and n is an integer from 1 to 90. Preferably, these are represented by [ ] (each being monomer (b1), monomer (b2), or monomer (b3)).

[0059] n may be, for example, 1 to 50, especially 1 to 30, particularly 1 to 15, or 2 to 15. Alternatively, n may be, for example, 1. ｂ This may be a linear or branched alkylene group, for example, formula -(CH ２ ) ｘ - or - (CH ２ ) ｘ１ - (CH(CH ３ )) ｘ２-[In the formula, x1 and x2 are between 0 and 6, for example, 2 and 5, and the sum of x1 and x2 is between 1 and 6. -(CH ２ ) ｘ１ - and - (CH (CH ３ )) ｘ２ The order of the hyphens is not limited to the given formula and may be random. The base may be represented by ]. - (R ｂ O) n -In this case, R may be of two or more types (for example, 2 to 4 types, especially 2 types), -(R ｂ O) n - is, for example, - (R １ O) ｎ１ - and - (R ２ O) ｎ２ - [wherein, R １ and R ２ The combination may be: 1, n1 and n2 are mutually distinct alkylene groups having 2 to 6 carbon atoms, n1 and n2 are numbers of 1 or more, and the sum of n1 and n2 is 2 to 90.

[0060] R in equations (b1), (b2), and (b3) ｂ R is particularly preferably an ethylene group, a propylene group, or a butylene group, and especially preferably a butylene group. ｂ R may be a combination of two or more alkylene groups. In that case, it is preferable that at least one of R is an ethylene group, a propylene group, or a butylene group. ｂ Examples of combinations include ethylene group / propylene group combinations, ethylene group / butylene group combinations, and propylene group / butylene group combinations. Monomer (b) may be a mixture of two or more types. In that case, at least one of monomer (b) is R in formula (b1), (b2), or (b3). ｂ It is preferable that the group is an ethylene group, a propylene group, or a butylene group. Furthermore, when using polyalkylene glycol di(meth)acrylate represented by formula (b2), it is not preferable to use it alone as monomer (b), but rather to use it in combination with monomer (b1). In that case as well, it is preferable that the compound represented by formula (b2) be kept to less than 30% by weight of monomer (b) used.

[0061] Specific examples of the monomer (b) can be exemplified by, for example, the following, but are not limited thereto. CH2=CHCOO-CH2CH2O-H CH2=CHCOO-CH2CH2CH2O-H CH2=CHCOO-CH2CH(CH3)O-H CH2=CHCOO-CH(CH3)CH2O-H CH2=CHCOO-CH2CH2CH2CH2O-H CH2=CHCOO-CH2CH2CH(CH3)O-H CH2=CHCOO-CH2CH(CH3)CH2O-H CH2=CHCOO-CH(CH3)CH2CH2O-H CH2=CHCOO-CH2CH(CH2CH3)O-H CH2=CHCOO-CH2C(CH3)2O-H CH2=CHCOO-CH(CH2CH3)CH2O-H CH2=CHCOO-C(CH3)2CH2O-H CH2=CHCOO-CH(CH3)CH(CH3)O-H CH2=CHCOO-C(CH3)(CH2CH3)O-H CH2=CHCOO-(CH2CH2O)2-H CH2=CHCOO-(CH2CH2O)4-H CH2=CHCOO-(CH2CH2O)5-H CH2=CHCOO-(CH2CH2O)6-H CH2=CHCOO-(CH2CH2O)5-CH3 CH2=CHCOO-(CH2CH2O)9-CH3 CH2=CHCOO-(CH2CH2O) 23 -CH3 CH2=CHCOO-(CH2CH2O) 90 -CH3

[0062] CH2=CHCOO-(CH2CH(CH3)O)9-H CH2=CHCOO-(CH2CH(CH3)O)9-CH3 CH2=CHCOO-(CH2CH(CH3)O) 12 -CH3 CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=CHCOO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9 CH2=CHCOO-(CH2CH2O) 23 -OOC(CH3)C=CH2 CH2=CHCOO-(CH2CH2O) 20 -(CH2CH(CH3)O)5-CH2-CH=CH2

[0063] CH2=CHCOO-(CH2CH2O)9-H CH2=C(CH3)COO-CH2CH2O-H CH2=C(CH3)COO-CH2CH2CH2O-H CH2=C(CH3)COO-CH2CH(CH3)O-H CH2=C(CH3)COO-CH(CH3)CH2O-H CH2=C(CH3)COO-CH2CH2CH2CH2O-H CH2=C(CH3)COO-CH2CH2CH(CH3)O-H CH2=C(CH3)COO-CH2CH(CH3)CH2O-H CH2=C(CH3)COO-CH(CH3)CH2CH2O-H CH2=C(CH3)COO-CH2CH(CH2CH3)O-H CH2=C(CH3)COO-CH2C(CH3)2O-H CH2=C(CH3)COO-CH(CH2CH3)CH2O-H CH2=C(CH3)COO-C(CH3)2CH2O-H CH2=C(CH3)COO-CH(CH3)CH(CH3)O-H CH2=C(CH3)COO-C(CH3)(CH2CH3)O-H CH2=C(CH3)COO-(CH2CH2O)2-H CH2=C(CH3)COO-(CH2CH2O)4-H CH2=C(CH3)COO-(CH2CH2O)5-H CH2=C(CH3)COO-(CH2CH2O)6-H CH2=C(CH3)COO-(CH2CH2O)9-H CH2=C(CH3)COO-(CH2CH2O)5-CH3 CH2=C(CH3)COO-(CH2CH2O)9-CH3 CH2=C(CH3)COO-(CH2CH2O) 23 -CH3 CH2=C(CH3)COO-(CH2CH2O) 90 -CH3 CH2=C(CH3)COO-(CH2CH(CH3)O)9-H

[0064] CH2=C(CH3)COO-(CH2CH(CH3)O)9-CH3 CH2=C(CH3)COO-(CH2CH(CH3)O) 12-CH3 CH2=C(CH3)COO-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=C(CH3)COO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=C(CH3)COO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9 CH2=C(CH3)COO-(CH2CH2O) 23 -OOC(CH3)C=CH2 CH2=C(CH3)COO-(CH2CH2O) 20 -(CH2CH(CH3)O)5-CH2-CH=CH2

[0065] CH2=CH-C(=O)-NH-CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH(CH3)OH CH2=CH-C(=O)-NH-CH(CH3)CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH2CH(CH3)OH CH2=CH-C(=O)-NH-CH2CH(CH3)CH2O-H CH2=CH-C(=O)-NH-CH(CH3)CH2CH2O-H CH2=CH-C(=O)-NH-CH2CH(CH2CH3)OH CH2=CH-C(=O)-NH-CH2C(CH3)2O-H CH2=CH-C(=O)-NH-CH(CH2CH3)CH2O-H CH2=CH-C(=O)-NH-C(CH3)2CH2O-H CH2=CH-C(=O)-NH-CH(CH3)CH(CH3)OH CH2=CH-C(=O)-NH-C(CH3)(CH2CH3)OH CH2=CH-C(=O)-NH-(CH2CH2O)2-H CH2=CH-C(=O)-NH-(CH2CH2O)4-H CH2=CH-C(=O)-NH-(CH2CH2O)5-H CH2=CH-C(=O)-NH-(CH2CH2O)6-H CH2=CH-C(=O)-NH-(CH2CH2O)9-H CH2=CH-C(=O)-NH-(CH2CH2O)5-CH3 CH2=CH-C(=O)-NH-(CH2CH2O)9-CH3 CH2=CH-C(=O)-NH-(CH2CH2O) 23-CH3 CH2=CH-C(=O)-NH-(CH2CH2O) 90 -CH3

[0066] CH2=CH-C(=O)-NH-(CH2CH(CH3)O)9-H CH2=CH-C(=O)-NH-(CH2CH(CH3)O)9-CH3 CH2=CH-C(=O)-NH-(CH2CH(CH3)O) 12 -CH3 CH2=CH-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=CH-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=CH-C(=O)-NH-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0067] CH2=C(CH3)-C(=O)-NH-CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)OH CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH2CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH2CH(CH3)OH CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-CH2CH(CH2CH3)OH CH2=C(CH3)-C(=O)-NH-CH2C(CH3)2O-H CH2=C(CH3)-C(=O)-NH-CH(CH2CH3)CH2O-H CH2=C(CH3)-C(=O)-NH-C(CH3)2CH2O-H CH2=C(CH3)-C(=O)-NH-CH(CH3)CH(CH3)OH CH2=C(CH3)-C(=O)-NH-C(CH3)(CH2CH3)OH CH2=C(CH3)-C(=O)-NH-C(CH3)(CH2CH3)OH CH2=C(CH3)-C(=O)-NH-(CH2CH2O)2-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)4-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)6-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 23 -CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 90 -CH3

[0068] CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O)9-H CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O)9-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O) 12-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=C(CH3)-C(=O)-NH-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0069] The monomer (b) is X ２ It is preferable that the monomer (b) is a hydrogen atom and is an acrylate or acrylamide. Monomer (b) is particularly preferably hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or hydroxyethyl acrylamide.

[0070] [(c) Ionic group-containing monomer] The hydrocarbon-containing polymer (1) may contain an ionic group-containing monomer (c). Monomer (c) is a monomer other than monomer (a) and monomer (b). Monomer (c) is preferably a monomer containing an olefinic carbon-carbon double bond and an ionic group (particularly an acrylic monomer). The ionic group is an anionic group and / or a cationic group.

[0071] Monomers having anionic groups include monomers having a carboxyl group, a sulfonic acid group, or a phosphate group. Specific examples of monomers having anionic groups include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, (meth)acrylate phosphoric acid, vinylbenzenesulfonic acid, acrylamide tert-butylsulfonic acid, or salts thereof.

[0072] Examples of salts of anionic groups include alkali metal salts, alkaline earth metal salts, or ammonium salts, such as methylammonium salt, ethanolammonium salt, and triethanolammonium salt.

[0073] In monomers having cationic groups, examples of cationic groups are amino groups, preferably tertiary amino groups and quaternary amino groups. In tertiary amino groups, the two groups bonded to the nitrogen atom are the same or different, and are an aliphatic group having 1 to 5 carbon atoms (especially alkyl groups), an aromatic group having 6 to 20 carbon atoms (aryl groups), or an aromatic aliphatic group having 7 to 25 carbon atoms (especially aralkyl groups, such as benzyl groups (C)). ６ H ５ -CH ２ It is preferable that the quaternary amino group is a C1-C5 aliphatic group (especially alkyl group), a C6-C20 aromatic group (aryl group), or a C7-C25 aromatic aliphatic group (especially aralkyl group, for example benzyl group (C)). ６ H ５ -CH ２ It is preferable that the tertiary amino group and quaternary amino group have a carbon-carbon double bond remaining to the nitrogen atom. The cationic group may be in the form of a salt.

[0074] The cationic group, which is a salt, is a salt with an acid (organic or inorganic acid). Organic acids, such as carboxylic acids having 1 to 20 carbon atoms (especially monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid), are preferred. Dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate and their salts are preferred.

[0075] Specific examples of monomers having cationic groups are as follows: CH2=CHCOO-CH2CH2-N(CH3)2 and its salts (e.g., acetate) CH2=CHCOO-CH2CH2-N(CH2CH3)2 and its salts (e.g., acetate) CH2=C(CH3)COO-CH2CH2-N(CH3)2 and its salts (e.g., acetate) CH2=C(CH3)COO-CH2CH2-N(CH2CH3)2 and its salts (e.g., acetate) CH2=CHC(O)N(H)-CH2CH2CH2-N(CH3)2 and its salts (e.g., acetate) CH2=CHCOO-CH2CH2-N(-CH3)(-CH2-C6H5) and its salts (e.g., acetate) CH2=C(CH3)COO-CH2CH2-N(-CH2CH3)(-CH2-C6H5) and its salts (e.g., acetate) CH2=CHCOO-CH2CH2-N + (CH3)3Cl - CH2=CHCOO-CH2CH2-N + (-CH3)2(-CH2-C6H5)Cl - CH2=C(CH3)COO-CH2CH2-N + (CH3)3Cl - CH2=CHCOO-CH2CH(OH)CH2-N + (CH3)3Cl - CH2=C(CH3)COO-CH2CH(OH)CH2-N + (CH3)3Cl - CH2=C(CH3)COO-CH2CH(OH)CH2-N + (-CH2CH3)2(-CH2-C6H5)Cl - CH2=C(CH3)COO-CH2CH2-N + (CH3)3Br - CH2=C(CH3)COO-CH2CH2-N + (CH3)3I - CH2=C(CH3)COO-CH2CH2-N + (CH3)3O - SO3CH3 CH2=C(CH3)COO-CH2CH2-N + (CH3)(-CH2-C6H5)2Br -

[0076] The ionic group-containing monomer (c) is preferably methacrylic acid, acrylic acid, or dimethylaminoethyl methacrylate, and more preferably methacrylic acid or dimethylaminoethyl methacrylate.

[0077] [(d) Other monomers] The hydrocarbon-containing polymer (1) may have repeating units derived from monomers other than monomers (a) to (c). Examples of other monomers include halogenated olefin monomers and crosslinkable monomers.

[0078] (Halogenated Olefin Monomer) The hydrocarbon-containing polymer (1) may have repeating units derived from halogenated olefin monomers. Preferably, the halogenated olefin monomer does not have fluorine atoms. Preferably, the halogenated olefin monomer is an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms, or iodine atoms. Preferably, the halogenated olefin monomer is a chlorinated olefin having 2 to 20 carbon atoms, and more preferably, an olefin having 2 to 5 carbon atoms having 1 to 5 chlorine atoms. Preferred specific examples of halogenated olefin monomers are halogenated vinyl, for example, vinyl chloride, vinyl bromide, vinyl iodide, and halogenated vinylide, for example, vinylidene chloride, vinylidene bromide, and vinylidene iodide. Vinyl chloride is preferred because it has high water repellency (especially water repellency durability). The presence of repeating units derived from halogenated olefin monomers increases the wash durability provided by the hydrocarbon-containing polymer (1).

[0079] (Crossable Monomer) The hydrocarbon-containing polymer (1) has a crosslinkable monomer having at least two reactive groups and / or ethylenically unsaturated double bonds (preferably (meth)acrylate groups), and the crosslinkable monomer (d) may be a monomer that does not contain fluorine atoms. It may be a compound that does not contain fluorine atoms. The crosslinkable monomer (d) may be a compound having at least two ethylenically unsaturated double bonds (preferably (meth)acrylate groups), or a compound having at least one ethylenically unsaturated double bond and at least one reactive group. Examples of reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups, etc.

[0080] The crosslinkable monomer may be a mono(meth)acrylate, di(meth)acrylate, or mono(meth)acrylamide having a reactive group. Alternatively, the crosslinkable monomer may be a di(meth)acrylate.

[0081] One example of a crosslinkable monomer is a vinyl monomer having a hydroxyl group. Examples of crosslinkable monomers include, but are not limited to, diacetone (meth)acrylamide, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.

[0082] (Cyclic hydrocarbon group-containing monomer) The hydrocarbon-containing polymer (1) may have a cyclic hydrocarbon group-containing monomer. The cyclic hydrocarbon group-containing monomer is a monomer having a cyclic hydrocarbon group, and may be a monomer having one ethylenically unsaturated double bond and a cyclic hydrocarbon group.

[0083] The monomer containing the cyclic hydrocarbon group preferably has a (meth)acrylic group as the ethylenically unsaturated double bond, for example, it may have a (meth)acrylate group or a (meth)acrylamide group as the ethylenically unsaturated double bond.

[0084] The cyclic hydrocarbon group may be alicyclic or aromatic, and is preferably alicyclic. The cyclic hydrocarbon group may be saturated or unsaturated, and is preferably saturated. The cyclic hydrocarbon group may be monocyclic, polycyclic, or crosslinked, and is preferably crosslinked. The cyclic hydrocarbon group may have a chain-like group (for example, a linear or branched hydrocarbon group).

[0085] The number of carbon atoms in the cyclic hydrocarbon group may be 4 or more, 6 or more, or 8 or more, and may be 30 or less, 26 or less, 22 or less, 18 or less, or 14 or less.

[0086] Specific examples of cyclic hydrocarbon groups include cyclohexyl group, t-butylcyclohexyl group, adamantyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, bornyl group, isobornyl group, norbornyl group, dicyclopentanyl group, dicyclopentenyl group, benzyl group, phenyl group, naphthyl group, 2-t-butylphenyl group, residues obtained by removing one or more hydrogen atoms from these groups (e.g., cyclohexylene group, adamantylene group, phenylene group, naphthylene group, etc.), and substituted groups thereof.

[0087] Specific examples of monomers containing cyclic hydrocarbon groups include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, compounds in which these acrylates are substituted with acrylamide, styrene, α-methylstyrene, p-methylstyrene, etc. These may be used alone or in combination of two or more.

[0088] Other monomers (d) are not limited to these examples and include acrylonitrile, organosiloxane-containing (meth)acrylates, short-chain alkyl (meth)acrylates, vinyl acetate, vinyl alkyl ethers, etc. Other monomers (d) may be used alone or in combination of two or more.

[0089] [Composition of Polymer (1)] The combinations of monomers that constitute the repeating units of the hydrocarbon-containing polymer (1) are, for example, as follows: Monomer (a) Monomer (a) + monomer (b) Monomer (a) + monomer (c) Monomer (a) + monomer (b) + monomer (c) Monomer (a) + monomer (b) + monomer (d) Monomer (a) + monomer (c) + monomer (d) Monomer (a) + monomer (b) + monomer (c) + monomer (d) Preferably, the combination of monomers that constitute the repeating units of the polymer is "monomer (a) + monomer (b) + monomer (c)".

[0090] The amount of repeating units (repeating unit (a)) formed from monomer (a) may be 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, relative to the hydrocarbon-containing polymer (1) (or relative to the total of repeating unit (a) and repeating unit (b)), for example, 75% by weight or more, and may also be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, or 45% by weight or less.

[0091] The amount of repeating units (repeating unit (b)) formed from monomer (b) may be 3% by weight or more, 5% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, or 25% by weight or more with respect to the hydrocarbon-containing polymer (1) (or the total of repeating unit (a) and repeating unit (b)), for example, 5% by weight or more, and may also be 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, or 5% by weight or less.

[0092] The amount of repeating units (repeating unit (c)) formed from monomer (c) may be 3% by weight or more, 5% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, or 25% by weight or more, relative to the hydrocarbon-containing polymer (1) (or relative to the total of repeating units (a) and repeating units (b)), and may also be 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, or 5% by weight or less.

[0093] The amount of repeating units (repeating unit (d)) formed from monomer (d) may be 3% by weight or more, 5% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, or 25% by weight or more, relative to the hydrocarbon-containing polymer (1) (or relative to the total of repeating units (a) and repeating units (b)), and may also be 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, or 5% by weight or less.

[0094] [Polymerization Method] The hydrocarbon-containing polymer (1) can be produced by known polymerization methods, and the conditions for the polymerization reaction can be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization.

[0095] In solution polymerization, a method is employed in which monomers are dissolved in an organic solvent in the presence of a polymerization initiator, followed by nitrogen purging, and then heating and stirring at a temperature of 30 to 120°C for 1 to 10 hours. Examples of polymerization initiators include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, per 100 parts by weight of monomer.

[0096] Organic solvents are inert to monomers and dissolve them, and may include esters (e.g., esters with 2 to 40 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones with 2 to 40 carbon atoms, specifically methyl ethyl ketone, diisobutyl ketone, and methyl isobutyl ketone), and alcohols (e.g., alcohols with 1 to 40 carbon atoms, specifically ethanol, butanol, and isopropyl alcohol). Specific examples of organic solvents include acetone, chloroform, HCHC225, isopropyl alcohol, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, and trichlorotrifluoroethane. The organic solvent is used in an amount of 10 to 3000 parts by weight, for example, 50 to 2000 parts by weight, per 100 parts by weight of the total monomers.

[0097] Water-soluble organic solvents may be used as organic solvents. For example, water-soluble organic solvents such as ketones (e.g., acetone, methyl ethyl ketone, etc.) or alcohols (e.g., propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, etc.) may be used.

[0098] In emulsion polymerization, a method is employed in which monomers are emulsified in water in the presence of a polymerization initiator and an emulsifier, and then polymerized by stirring at a temperature of 50 to 80°C for 1 to 20 hours after nitrogen purging. The polymerization initiators used are water-soluble ones such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, sodium peroxide, potassium persulfate, and ammonium persulfate, or oil-soluble ones such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, per 100 parts by weight of monomer.

[0099] To obtain a polymer aqueous dispersion with excellent stability during storage, it is desirable to polymerize the monomers by micronizing them in water using an emulsifying device that can impart strong crushing energy, such as a high-pressure homogenizer or an ultrasonic homogenizer. Various emulsifiers, including anionic, cationic, and nonionic types, can be used as emulsifiers, and are used in an amount ranging from 0.5 to 20 parts by weight per 100 parts by weight of monomer. It is preferable to use anionic and / or nonionic and / or cationic emulsifiers. If the monomers are not completely miscible, it is preferable to add a compatibilizer that allows them to be sufficiently miscible, such as a water-soluble organic solvent or a low molecular weight monomer. Adding a compatibilizer can improve emulsification and copolymerization properties.

[0100] As the water-soluble organic solvent, the organic solvents mentioned above may be used. For example, acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, etc., may be used in a range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of water. In addition, as low molecular weight monomers, methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., may be used in a range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of the total amount of monomers.

[0101] In polymerization, a chain transfer agent may be used. The molecular weight of the polymer can be changed depending on the amount of chain transfer agent used. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (especially alkyl mercaptans (e.g., with 1 to 40 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium bisulfite. The amount of chain transfer agent used may be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, per 100 parts by weight of the total amount of monomer.

[0102] [Amount of hydrocarbon group-containing polymer (1)] The amount of hydrocarbon group-containing polymer (1) in the water-repellent and oil-repellent agent may be 0.01% by weight or more, 0.03% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, or 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 3% by weight or less.

[0103] The amount of hydrocarbon group-containing polymer (1) may be 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, or 40% by weight or more, with a preference of 10% by weight or more, and may also be 200 parts by weight or less, 150 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, or 15 parts by weight or less, with a preference of 50 parts by weight or less.

[0104] [(2) Water-soluble polymers] The water- and oil-repellent agent in this disclosure comprises a water-soluble polymer (2).

[0105] The water solubility of the water-soluble polymer (2) at 25°C may be 0.1 g / l or more, 0.5 g / l or more, 1 g / l or more, 3 g / l or more, 5 g / l or more, 10 g / l or more, 20 g / l or more, or 30 g / l or more, and preferably 3 g / l or more.

[0106] The weight-average molecular weight of the water-soluble polymer (2) may be 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and may also be 1000000 or less, 750000 or less, 500000 or less, 3000000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, 5000 or less, or 3000 or less.

[0107] The viscosity of the water-soluble polymer (2), when diluted by 4% by weight, at 20°C, may be 300 mPa·s or more, 500 mPa·s or more, 1000 mPa·s or more, 1500 mPa·s or more, 2000 mPa·s or more, 2500 mPa·s or more, or 3000 mPa·s or more, and may also be 10000 mPa·s or less, 9000 mPa·s or less, 8000 mPa·s or less, 7000 mPa·s or less, 6000 mPa·s or less, 5000 mPa·s or less, 4000 mPa·s or less, 3000 mPa·s or less, 2000 mPa·s or less, or 1000 mPa·s or less. Viscosity was measured using a Type B viscometer (BL type, manufactured by Tokyo Keiki Co., Ltd.) under a predetermined temperature and atmosphere by preparing an aqueous dispersion of a water-soluble polymer (2) at a predetermined weight percent concentration.

[0108] The water-soluble polymer (2) may be hydrophobically modified. The hydrophobically modified water-soluble polymer (2) may mean a compound modified with, for example, one or more, two or more, three or more, five or more, ten or more, thirty or more, or fifty or more hydrophobic functional groups (e.g., hydrocarbon groups having 6 or more, 10 or more, 12 or more, 15 or more, or 18 or more carbon atoms).

[0109] Examples of water-soluble polymers (2) include polysaccharides, synthetic polyols, polyamines, polycarboxylic acids, polyamides, polyethers, etc., and are preferably polysaccharides or synthetic polyols.

[0110] The water-soluble polymer (2) is preferably a polyol, and may be a polysaccharide or a synthetic polyol. The number of hydroxyl groups in the polyol may be 10 or more, 15 or more, 30 or more, 50 or more, or 100 or more, and may also be 3000 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less.

[0111] Polysaccharides may be acidic polysaccharides, neutral sugars, and / or basic sugars, but are preferably neutral. Acidic polysaccharides are generally polysaccharides having a carboxyl group (-COOH), etc. Specific examples of acidic polysaccharides are carrageenan, pectin, gum arabic, xanthan gum, gellan gum, agar, and tragacanth gum. Neutral polysaccharides are polysaccharides that are electrically neutral. Specific examples of neutral polysaccharides are tamarind seed gum, guar gum, locust bean gum, starch, and pullulan. Basic polysaccharides are polysaccharides having an amino group (-NH2), etc. Specific examples of basic polysaccharides are chitosan. Specific examples of polysaccharides include starch, xanthan gum, karaya gum, gellan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, and pullulan.

[0112] As the polysaccharide, starch is preferred. The starch may be unmodified starch or modified starch. The starch may be modified starch that has undergone at least one modification, such as esterification modification, hydrophobization modification, etherification modification, oxidation modification, alkali modification, enzyme modification, and bleach modification. Examples of modified starches include acetylated adipic acid crosslinked starch, acetylated oxidized starch, acetylated phosphate crosslinked starch, alkenyl succinate esterified starch, acetate starch, oxidized starch, hydroxyalkylated starch (alkyl group having 2 to 40 or 2 to 10 carbon atoms, particularly 2 or 3 carbon atoms), hydroxyalkylated phosphate crosslinked starch (alkyl group having 2 to 40 or 2 to 10 carbon atoms, particularly 2 or 3 carbon atoms), phosphate crosslinked starch, phosphorylated starch, phosphate monoesterified phosphate crosslinked starch, acid-modified starch, alkali-treated starch, enzyme-treated starch, bleach-treated starch, and cationized starch (quaternary ammonium starch). Dextrin, which is starch that has been reduced in molecular weight by chemical or enzymatic methods, can also be mentioned. The starch may be pregelatinized starch. Pregelatinized starch is starch in which the hydrogen bonds between sugar chains have been broken, leaving the sugar chains free.

[0113] Synthetic polyols are synthetic polyols having a plurality of hydroxyl groups (for example, 10 or more, 50 or more, 100 or more, or 500 or more) in their molecule. Preferably, examples include polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer, hydroxybutyl (meth)acrylate polymer, polyvinyl alcohol (saponification degree of 80% or more, 90% or more, or 95% or more, etc.), and polyvinyl alcohol may be particularly preferred.

[0114] Specific examples of water-soluble polymers (2) include polysaccharides such as starch, pullulan, amylose, cellulose, cellulose derivatives, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa-carrageenan, iota-carrageenan, isomaltodextrin, gellan gum, and tamarind seed gum; synthetic polyols such as polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer, hydroxybutyl (meth)acrylate polymer, and polyvinyl alcohol; and polyethyl Examples include polyamines such as lenimine, polyvinylamine, and polyallylamine; polyamides such as polyvinylpyrrolidone, polyacrylamide, poly(N,N-dimethylacrylamide), poly(N-vinylacetamide), poly-N-isopropylacrylamide, polyoxazolines (e.g., poly(2-methyl-2-oxazoline), poly(2-ethyl-2-oxazoline), poly(2-propyl-2-oxazoline)), and polyamideimides; and polyethers such as polyethylene glycol, polypropylene glycol, and polyvinyl methyl ether.

[0115] [Amount of water-soluble polymer (2)] The amount of water-soluble polymer (2) may be 30 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, 750 parts by weight or more, 1000 parts by weight or more, 1500 parts by weight or more, or 2000 parts by weight or more, per 100 parts by weight of hydrocarbon-containing polymer (1), preferably 100 parts by weight or more, and may also be 5000 parts by weight or less, 4500 parts by weight or less, 4000 parts by weight or less, 3500 parts by weight or less, 3000 parts by weight or less, 2500 parts by weight or less, 2000 parts by weight or less, 1500 parts by weight or less, 1000 parts by weight or less, 750 parts by weight or less, 500 parts by weight or less, 300 parts by weight or less, or 100 parts by weight or less, preferably 900 parts by weight or less.

[0116] [Penetrating Agent] The water-repellent and oil-repellent agent may contain a penetrating agent. A penetrating agent is an additive that improves the penetration of the water-repellent and oil-repellent agent composition into a nonwoven fabric substrate. Examples of penetrating agents in this disclosure include compounds having ether groups, ester groups, or hydroxyl groups in their molecules, such as alkyl monools (e.g., C3-30, C5-C10 alkyl monools, particularly C6 monools which are preferred for their balance of penetration and odor), alkylene glycols (e.g., C3-30, C5-C10, particularly 1,2-alkylene glycols), their monoalkyl ethers and monoalkyl esters, and surfactants (particularly nonionic surfactants (acetylene group-containing nonionic surfactants) or anionic surfactants). Specific examples of surfactants are provided in the section [Surfactants] below. Examples of specific products include Dispanol (registered trademark) and Alkanol 6112 (manufactured by DU PONT) series from NOF Corporation. The penetrating agent may be aromatic or aliphatic, preferably aliphatic, and may not have heteroatoms other than oxygen. The number of carbon atoms in the penetrating agent may be 3 or more, 5 or more, 8 or more, 10 or more, 15 or more, or 20 or more, and may also be 60 or more, 50 or more, 40 or less, 30 or less, or 20 or less. Using the penetrating agent in combination with an antistatic agent is preferable from the viewpoint of achieving the effects of the present invention well.

[0117] [Amount of Penetrant] The amount of penetrant may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, or 500 parts by weight or more, preferably 30 parts by weight or more, and may also be 1000 parts by weight or less, 800 parts by weight or less, 600 parts by weight or less, 400 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, preferably 500 parts by weight or less.

[0118] [Antistatic Agents] Water-repellent and oil-repellent agents may contain antistatic agents. An antistatic agent is an additive that prevents the generation of static electricity in a product. Antistatic agents in this disclosure include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, and primary, secondary, and tertiary amino groups; sulfonates, sulfate esters, phosphonates, and phosphate esters (phosphate ester compounds (for example, butyl phosphate metal salts such as LUROL ASY (manufactured by Goulston) and ZELEC) Examples include anionic antistatic agents having anionic functional groups such as TY (manufactured by Stepan, etc.); amphoteric antistatic agents such as alkyl betaine and its derivatives, imidazoline and its derivatives, alanine and its derivatives; and nonionic antistatic agents such as amino alcohol and its derivatives, glycerin and its derivatives, polyethylene glycol and its derivatives. Surfactants may also be used as antistatic agents, and specific examples thereof are provided below under [Surfactants]. The antistatic agent is preferably cationic, anionic, or amphoteric (for example, anionic), and may be an ionic conductive polymer obtained by polymerizing or copolymerizing monomers having cationic, anionic, or amphoteric ionic conductive groups. These may be used alone or in combination of two or more. Using the antistatic agent in combination with a penetrating agent is preferable from the viewpoint of achieving the effects of the present invention well.

[0119] [Amount of Antistatic Agent] The amount of antistatic agent may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 300 parts by weight or more, or 500 parts by weight or more, preferably 10 parts by weight or more, and may also be 1000 parts by weight or less, 800 parts by weight or less, 600 parts by weight or less, 400 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, preferably 100 parts by weight or less.

[0120] [Liquid Medium] The water- and oil-repellent agent may contain a liquid medium. The liquid medium is water, an organic solvent, or a mixture of water and an organic solvent. Preferably, it is a mixture of water and an organic solvent. By including an organic solvent, good water repellency, slip resistance, and storage stability can be achieved.

[0121] Examples of organic solvents include esters (e.g., esters having 2 to 40 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes having 5 to 10 carbon atoms, specifically naphtha and kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain compounds having at least one hydroxyl group (e.g., polyhydric alcohols such as alcohols and glycol-based solvents, ether forms of polyhydric alcohols (e.g., monoether forms)). These may be used individually or in combination of two or more.

[0122] [Amount of liquid medium] The amount of liquid medium may be 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, or 97% by weight or more relative to the water-repellent and oil-repellent agent, or it may be 99.9% by weight or less, 99% by weight or less, 95% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, or 50% by weight or less.

[0123] The amount of organic solvent may be 0.5% or more by weight, 1% or more by weight, 2% or more by weight, 3% or more by weight, 5% or more by weight, 7.5% or more by weight, 10% or more by weight, 12.5% ​​or more by weight, 15% or more by weight, or 20% or more by weight relative to the water-repellent and oil-repellent agent, or it may be 75% or less by weight, 50% or less by weight, 40% or less by weight, 30% or less by weight, 25% or less by weight, 20% or less by weight, 15% or less by weight, 10% or less by weight, or 5% or less by weight.

[0124] The amount of organic solvent may be 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, or 40% by weight or more relative to the liquid medium, and may also be 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, 12.5% ​​by weight or less, 7.5% by weight or less, or 5.0% by weight or less.

[0125] The amount of organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more per 100 parts by weight of hydrocarbon-containing polymer (1), and may also be 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less.

[0126] The amount of organic solvent may be 0.5 parts by weight or more, 1 part by weight or more, 1.5 parts by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, or 40 parts by weight or more, per 100 parts by weight of water, or 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 25 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0127] [Silicone] The water- and oil-repellent agent in this disclosure may contain silicone in addition to the hydrocarbon-containing polymer (1). By including silicone, it is possible to obtain a good combination of water repellency, slip resistance, and storage stability.

[0128] Silicone is formulated with the formula: (R 53 )3Si-O-[-Si(R 51 )2-O-] a -[-Si(R 51 ) ２ -O-] ｂ -Si(R 53 )3 (S1) [wherein, R ５１ Each of these independently represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, or an alkoxy group having 1 to 40 carbon atoms, R ５３Each of these independently represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a saturated hydrocarbon group having 1 to 40 carbon atoms, where a represents an integer of 0 or more, b represents an integer of 1 or more, and (a + b) is between 5 and 200. The polymer may be represented by [ ].

[0129] R ５１ and R ５３ In this, the alkyl group having 1 to 40 carbon atoms and the aryl group having 6 to 40 carbon atoms may be unsubstituted or substituted. ５１ and R ５３ Specific examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group; cyclopentyl group, cyclohexyl group, cycloheptyl group; phenyl group, tolyl group, naphthyl group, or groups in which some or all of the hydrogen atoms bonded to these groups are substituted with halogen atoms, amino groups, cyano groups, etc. ５１ and R ５３ It is preferable that it be a methyl group or an ethyl group. ５１ and R ５３ In this context, the alkoxy group having 1 to 40 carbon atoms may be linear or branched. Examples of alkoxy groups having 1 to 40 carbon atoms include the methoxy group, ethoxy group, propoxy group, and butoxy group.

[0130] The silicone may have at least one long-chain hydrocarbon group. For example, R in formula (S1) ５１ At least one of R ５３ At least one of the following, or R ５１ and R ５３ At least one of each of them may be a long-chain hydrocarbon group, ５１At least one of the groups (for example, one) may be a long-chain hydrocarbon group. Here, the long-chain hydrocarbon group may be a saturated hydrocarbon group with 6 or more, 10 or more, 15 or more, or 20 or more atoms, preferably 10 or more or 23 or more atoms. Here, the hydrocarbon group may be linear or branched, and is preferably an alkyl group. Specific examples of hydrocarbon groups are hexyl group (6 carbon atoms), octyl group (8 carbon atoms), lauryl group (12 carbon atoms), myristyl group (14 carbon atoms), stearyl group (18 carbon atoms), behenyl group (22 carbon atoms), tricosyl group (23 carbon atoms), lignoceryl group (tetracosyl group, 24 carbon atoms), cellotyl group (hexacosyl group, 26 carbon atoms), montyl group (octacosyl group, 28 carbon atoms), merisyl group (triacontane group, 30 carbon atoms), and dotriacontane group (32 carbon atoms).

[0131] In terms of being easy to manufacture industrially and readily available, the long-chain hydrocarbon group R ５１ and R ５３ Other than R ５１ and R ５３ It is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

[0132] a is a non-negative integer. In terms of ease of industrial manufacture and availability, a may be 40 or less, 30 or less, or 20 or less, and is preferably 30 or less.

[0133] The sum of a and b is between 5 and 200. Preferably, the sum of a and b is between 10 and 100, and more preferably between 40 and 60, in terms of ease of industrial manufacture, availability, and handling. a may be between 0 and 150, for example, 1 and 100. The lower limit of b may be 1, 2, or 3, and the upper limit of b may be 150, 10, or 5.

[0134] If a or b is 2 or more, there are multiple instances of R. ５１ and R ５２ Each of these may be the same or different.

[0135] R ５１ and R ５３ Base (for example, when represented by the following formula (S2) R ５１and R ５２ Base and R ５３ It is preferable that 50 mol% or more of the total number of groups are methyl groups.

[0136] The order of existence of the repeating units enclosed by a or b is not limited to the order shown in the chemical formula, but is arbitrary. That is, the silicone may be a random polymer or a block polymer.

[0137] For example, silicone is given by formula: (R 53 )3Si-O-[-Si(R 51 )2-O-] a -[-Si(R 51 )(R 52 )-O-] ｂ -Si(R 53 )3 (S2) [wherein, R ５１ Each of these independently represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a long-chain hydrocarbon group. ５２ Each of these independently represents a long-chain hydrocarbon group, R ５３ Each of these independently represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a long-chain hydrocarbon group, where a represents an integer of 0 or more, b represents an integer of 1 or more, and (a + b) is between 5 and 200. The polymer may be represented by [ ]. In formula (S2), R ５１ and R ５３ It may have an alkyl group having 3 to 40 carbon atoms or an unsaturated hydrocarbon group having 6 to 40 carbon atoms (for example, a hydrocarbon group having an aromatic ring), but it is preferable that it does not have these groups.

[0138] Examples of silicones are as follows: [In the formula, a represents an integer from 0 to 150, b represents an integer from 1 to 150, (a + b) is from 5 to 200, and n is an integer from 1 to 36 (preferably n is a long-chain hydrocarbon group).]

[0139] Silicones can be synthesized by conventionally known methods. For example, a silicone can be obtained by hydrosilylation of an α-olefin with a silicone having an SiH group.

[0140] Examples of silicones having SiH groups include methyl hydrogen silicone with a degree of polymerization of 10 to 200, or copolymers of dimethylsiloxane and methyl hydrogen siloxane. Among these, methyl hydrogen silicone is preferred because it is easy to manufacture industrially and readily available. Hydrogen silicone (e.g., methyl hydrogen silicone) is a type of polydiorganosiloxane in which part of the side chain is replaced with hydrogen, and the hydrogen atoms are directly bonded to silicon atoms. When using hydrogen silicone, a catalyst may be used to improve reactivity. For example, zinc, tin, manganese, cobalt, iron, and amine-based catalysts can be used. Organic acid metal salts are preferred as catalysts, and fatty acids are preferred as organic acids. From a safety standpoint, zinc stearate can be used. It is preferable to use the catalyst at a concentration of 10 to 40% relative to the methyl hydrogen silicone, as this makes it easier to exhibit its effect. Two or more types of amino-modified, epoxy-modified, carboxy-modified, and methyl hydrogen silicones may be mixed. All of them are silicones having reactive groups and preferably have film-forming properties. Film-forming properties refer to the ability of a silicone to form a solid film, rather than an oily or gel-like film, after being applied to the fiber surface in an emulsion state.

[0141] α-olefins are compounds from which long-chain hydrocarbon groups are derived in silicones. Specific examples of α-olefins include 1-tricosene, 1-tetracosene, 1-hexacosene, 1-octacosene, 1-triaconthene, and 1-dotriaconthene. The hydrosilylation reaction may be carried out by reacting the α-olefin with the silicone having the SiH group in a stepwise or one-time manner, in the presence of a catalyst as needed.

[0142] The usage amounts of the silicone having an SiH group and the α-olefin used in the hydrosilylation reaction can be appropriately selected according to, for example, the SiH group equivalent of the silicone having an SiH group, the number average molecular weight, etc.

[0143] Examples of the catalyst used in the hydrosilylation reaction include compounds such as platinum and palladium, and among them, platinum compounds are preferred. Examples of the platinum compound include platinum(IV) chloride.

[0144] The reaction conditions of the hydrosilylation reaction are not particularly limited and can be adjusted as appropriate. The reaction temperature is, for example, 10 to 200°C, preferably 50 to 150°C. The reaction time can be, for example, 3 to 12 hours when the reaction temperature is 50 to 150°C. The hydrosilylation reaction is preferably carried out under an inert gas atmosphere. Examples of the inert gas include nitrogen, argon, etc. The reaction proceeds even without a solvent, but a solvent may be used. Examples of the solvent include dioxane, methyl isobutyl ketone, toluene, xylene, butyl acetate, etc.

[0145] [Reactive silicone] The silicone may contain a reactive silicone. Examples of the reactive silicone include polysiloxanes having reactive groups in the side chain, one terminal, both terminals, or the side chain and both terminals. From the viewpoint of excellent anti-slip properties and excellent water repellency at the same time, it may be a polysiloxane having reactive groups in the side chain and / or both terminals. The reactive silicone is not particularly limited as long as it has a reactive group in the molecule. For example, amino-modified silicone, epoxy-modified silicone, carboxy-modified silicone, hydrogen-modified silicone, etc. may be mentioned. The reactive silicone may be one in which one or more substituents in the above formula (S1) or formula (S2) are replaced with reactive groups.

[0146] Examples of amino-modified silicones include those having a structure in which an amino group is bonded to an organic group directly attached to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. Alkylene groups with two or more carbon atoms are preferred. Divalent aromatic groups with six or more carbon atoms are preferred. The amino group may be a primary amino group, a secondary amino group, or a tertiary amino group. Examples of organic groups to which an amino group is bonded include: 2-aminoethyl group, N-methyl-2-aminoethyl group, N,N-dimethyl-2-aminoethyl group, N-ethyl-2-aminoethyl group, N,N-diethyl-2-aminoethyl group, N,N-methylethyl-2-aminoethyl group, 3-aminopropyl group, N-methyl-3-aminopropyl group, N,N-dimethyl-3-aminopropyl group, N-ethyl-3-anopropyl group, N,N-diethyl-3-aminopropyl group, and N,N-methylethyl-3-aminopropyl group. These functional groups may be located on the side chains or at the terminal ends of the polysiloxane.

[0147] Examples of epoxy-modified silicones include those having a structure in which an epoxy group is bonded to an organic group directly attached to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. Typically, the bond with the organic group is in the form of a glycidyl ether. Examples of such functional groups include 3-glycidoxypropyl group and 2-glycidoxyethyl group. These functional groups may be located on the side chains or at the terminals of the polysiloxane.

[0148] Examples of carboxylated silicones include those having a structure in which a carboxyl group is bonded to an organic group directly connected to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. Alkylene groups with two or more carbon atoms are preferred. Divalent aromatic groups with six or more carbon atoms are preferred. Examples of such functional groups include 3-carboxypropyl and 2-carboxyethyl groups. These functional groups may be located on the side chains or at the terminals of the polysiloxane.

[0149] [Amount of silicone] The amount of silicone may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, based on 100 parts by weight of the hydrocarbon-containing polymer (1), and may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0150] [Wax] The water and oil repellent agent in the present disclosure preferably contains wax separately from the hydrocarbon-containing polymer (1). By containing wax, it can have good water repellency, anti-slip property, and storage stability. The water and oil repellent agent in the present disclosure may contain both silicone and wax, or may contain only one of silicone and wax.

[0151] Examples of the wax include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (such as polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, animal and vegetable wax, and mineral wax. Hydrocarbon wax, particularly paraffin wax, is preferred. Specific examples of the compounds constituting the wax include normal alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane), normal alkenes (e.g., 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene, 1-hentriacontene, 1-dotriacontene, 1-tritriacontene, 1-tetratriacontene, 1-pentatriacontene, 1-hexatriacontene). The carbon number of the compounds constituting the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be 200 to 2000, for example, 250 to 1500, 300 to 1000. These may be used alone or in combination of two or more.

[0152] The melting point of the wax may be 50°C or higher, 55°C or higher, 60°C or higher, 65°C or higher, or 70°C or higher, preferably 55°C or higher, more preferably 60°C or higher, and may also be 120°C or lower, 100°C or lower, 80°C or lower, 75°C or lower, 70°C or lower, or 65°C or lower. The melting point of the wax is measured in accordance with JIS K 2235-1991.

[0153] [Amount of wax] The amount of wax may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more per 100 parts by weight of hydrocarbon-containing polymer (1), or it may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0154] [Organic Acids] Water-repellent and oil-repellent agents may contain organic acids. Known organic acids can be used. Preferred organic acids include carboxylic acids, sulfonic acids, sulfinic acids, etc., with carboxylic acids being particularly preferred. Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., with formic acid or acetic acid being particularly preferred. In this disclosure, one organic acid may be used, or two or more may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0155] [Amount of Organic Acid] The amount of organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more per 100 parts by weight of hydrocarbon-containing polymer (1), or it may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of organic acid may be adjusted so that the pH of the water-repellent and oil-repellent agent is 3 to 10, for example 5 to 9, and particularly 6 to 8. The water-repellent and oil-repellent agent may be acidic (pH 7 or less, for example 6 or less).

[0156] [Surfactants] Water-repellent and oil-repellent agents preferably contain surfactants. In water-repellent and oil-repellent agents, the surfactant may include a nonionic surfactant. By including a surfactant, good water repellency, slip resistance, and storage stability can be achieved. Furthermore, the surfactant may include one or more surfactants selected from cationic surfactants, anionic surfactants, and amphoteric surfactants. It is preferable to use a combination of a nonionic surfactant and a cationic surfactant. Note that the surfactant may be separate from other additives such as the antistatic agents and penetrating agents mentioned above.

[0157] [Nonionic surfactants] Examples of nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides.

[0158] Examples of ethers are compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0159] Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are 1-6 valent (especially 2-5 valent) alcohols with 1-50 carbon atoms (especially 10-30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2-50 carbon atoms, especially 5-30 carbon atoms.

[0160] Examples of ester ethers are compounds obtained by adding an alkylene oxide (especially ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are 1-6 valent (especially 2-5 valent) alcohols with 1-50 carbon atoms (especially 3-30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2-50 carbon atoms, especially 5-30 carbon atoms.

[0161] Examples of alkanolamides are formed from fatty acids and alkanolamines. Alkanolamides may be monoalkanolamides or dialkanolaminos. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. Alkanolamines may be alkanols having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0162] The polyhydric alcohol may be a divalent to pentavalent alcohol with 10 to 30 carbon atoms. The amine oxide may be an oxide of an amine (secondary amine or preferably tertiary amine) (for example, with 5 to 50 carbon atoms).

[0163] The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group of the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic surfactant is generally preferably 2 to 100. The nonionic surfactant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides, and is preferably a nonionic surfactant having an oxyalkylene group.

[0164] Nonionic surfactants may be alkylene oxide adducts of linear and / or branched aliphatic (saturated and / or unsaturated) groups, polyalkylene glycol esters of linear and / or branched fatty acids (saturated and / or unsaturated), polyoxyethylene (POE) / polyoxypropylene (POP) copolymers (random copolymers or block copolymers), alkylene oxide adducts of acetylene glycol, etc. Among these, those in which the alkylene oxide adduct portion and the polyalkylene glycol portion are structured as polyoxyethylene (POE), polyoxypropylene (POP), or POE / POP copolymers (which may be random copolymers or block copolymers) are preferred. Furthermore, nonionic surfactants are preferably structured without aromatic groups due to environmental concerns (biodegradability, endocrine disruptors, etc.).

[0165] Nonionic surfactants are defined by formula: R 1 O-(CH ２ CH ２ O) p -(R 2 O) q -R 3 [In the formula, R 1R is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group or acyl group having 2 to 22 carbon atoms. 2 Each of them is independently identical or distinct, an alkylene group having 3 or more carbon atoms (for example, 3 to 10), R 3 The compound may be represented by [ ], where is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, and q is 0 or a number of 1 or more.

[0166] R 1 The carbon atoms have 8 to 20 carbon atoms, and are more preferably 10 to 18 carbon atoms. 1 Preferred specific examples include the lauryl group, tridecyl group, and oleyl group. 2 Examples include propylene groups and butylene groups. In nonionic surfactants, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R 2 O) q - may form a polyoxyalkylene chain. The nonionic surfactant may be a polyoxyethylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) in the center. Examples of hydrophobic oxyalkylene chains include oxypropylene chains, oxybutylene chains, and styrene chains, but oxypropylene chains are preferred among them.

[0167] Specific examples of nonionic surfactants include ethylene oxide, hexylphenol, isooctatylphenol, hexadecanol, oleic acid, and alkanes (C). １２ -C １６ ) Thiol, sorbitan monofatty acid (C ７ -C １９ ) or alkyl (C １２ -C １８ This includes condensation products with amines, etc.

[0168] The proportion of polyoxyethylene blocks can be 5 to 80% by weight, for example 30 to 75% by weight, and particularly 40 to 70% by weight, relative to the molecular weight of the nonionic surfactant (copolymer). The average molecular weight of the nonionic surfactant is generally 300 to 5,000, for example 500 to 3,000. The nonionic surfactant may be a mixture of compounds with an HLB (hydrophilic-hydrophobic balance) of less than 15 (particularly 5 or less) and compounds with an HLB of 15 or more. An example of a compound with an HLB of less than 15 is sorbitan fatty acid ester. An example of a compound with an HLB of 15 or more is polyoxyethylene alkyl ether. The weight ratio of compounds with an HLB of less than 15 to compounds with an HLB of 15 or more may be 90:10 to 20:80, for example 85:15 to 55:45. The nonionic surfactant may be a single type or a mixture of two or more types.

[0169] [Cationic surfactants] Cationic surfactants are preferably compounds that do not have an amide group.

[0170] Cationic surfactants may be amine salts, quaternary ammonium salts, or oxyethylene-added ammonium salts. Specific examples of cationic surfactants are not limited to alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt-type surfactants such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, benzethonium chloride, and other quaternary ammonium salt-type surfactants.

[0171] A preferred example of a cationic surfactant is R 21 -N + (-R 22 )(-R 23 )(-R 24 ) X - [In the formula, R 21 , R 22 , R 23 and R 24 This is a compound of ] where is a hydrocarbon group having 1 to 40 carbon atoms, and X is an anionic group.21 , R 22 , R 23 and -R 24 Specific examples of X are alkyl groups (e.g., methyl group, butyl group, stearyl group, palmityl group). Specific examples of X are halogens (e.g., chlorine) and acids (e.g., hydrochloric acid, acetic acid). The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (alkyl group with 4 to 40 carbon atoms).

[0172] The cationic surfactant is preferably an ammonium salt. The cationic surfactant has the formula: R 1 p - N + R 2 q X － [In the formula, R 1 is C12 or higher (for example, C １２ ~C ５０ ) linear and / or branched aliphatic (saturated and / or unsaturated) groups, R 2 R may be an ammonium salt represented by ] where is an H or C1-C4 alkyl group, a benzyl group, a polyoxyethylene group (number of oxyethylene groups e.g. 1 (particularly 2, especially 3) to 50) (CH3, C2H5 are particularly preferred), X is a halogen atom (e.g.), a C1-C4 fatty acid base, p is 1 or 2, q is 2 or 3, and p+q=4. １ The number of carbon atoms may be 12 to 50, for example, 12 to 30.

[0173] Specific examples of cationic surfactants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, and N-[2-(diethylamino)ethyl]oleamide hydrochloride.

[0174] Examples of anionic surfactants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfone fatty acid salts, N-acyl amino acid type surfactants, phosphate mono or diester type surfactants, and sulfosuccinate esters.

[0175] Examples of amphoteric surfactants include alanines, imidazolinium betaines, amide betaines, and betaine acetate. Specifically, these include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylaminoacetic acid betaine, and fatty acid amidopropyl dimethylaminoacetic acid betaine.

[0176] The surfactant may consist of one or more nonionic surfactants, cationic surfactants, and amphoteric surfactants.

[0177] [Amount of surfactant] The amount of surfactant may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more per 100 parts by weight of hydrocarbon-containing polymer (1), or it may be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0178] [Curing agent] The water-repellent and oil-repellent agent may contain a curing agent (active hydrogen reactive compound or active hydrogen-containing compound). After polymerization to obtain a hydrocarbon-containing polymer (1), the curing agent may be added to the water-repellent and oil-repellent agent.

[0179] The curing agent (crosslinking agent) in the water and oil repellent can cure the hydrocarbon-containing polymer (1). The curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with the active hydrogen or active hydrogen-reactive group of the hydrocarbon-containing polymer (1). Examples of the active hydrogen-reactive compound are polyisocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of the active hydrogen-containing compound are hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, melamine compounds, and urea-based compounds.

[0180] The curing agent may be a polyisocyanate compound. The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound acts as a crosslinking agent. Examples of the polyisocyanate compound include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates.

[0181] Examples of the aliphatic polyisocyanate are trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanates such as 2,6-diisocyanatomethyl caproate, and lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane and other aliphatic triisocyanates. These may be used alone or in combination of two or more.

[0182] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 1,3,5-triisocyanatocyclohexane, 4,4'methylenebis(cyclohexyl isocyanate), and 1,3-bis(isocyanatomethyl)cyclohexane. These may be used individually or in combination of two or more.

[0183] Examples of aromatic aliphatic polyisocyanates include aromatic aliphatic diisocyanates and aromatic aliphatic triisocyanates. Specific examples of aromatic aliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or mixtures thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used individually or in combination of two or more.

[0184] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylenediisocyanate, p-phenylenediisocyanate, 4,4'-diphenyldiisocyanate, 1,5-naphthalenediisocyanate, 2,4'- or 4,4'-diphenylmethanediisocyanate or mixtures thereof, 2,4- or 2,6-tolylenediisocyanate or mixtures thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate, etc. These may be used individually or in combination of two or more.

[0185] Examples of polyisocyanate derivatives include various derivatives of the polyisocyanate compounds described above, such as dimers, trimers, biuretes, allophanates, carbodiimides, uretodiones, uretoimines, isocyanurates, and iminooxadiazinediones. These may be used individually or in combination of two or more.

[0186] These polyisocyanates can be used individually or in combination of two or more. It is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound in which the isocyanate group of a polyisocyanate compound is blocked with a blocking agent. The use of a blocked polyisocyanate compound is preferable because it is relatively stable in aqueous solutions and can be used in the same aqueous solutions as water-repellent and oil-repellent agents.

[0187] Blocking agents sequester free isocyanate groups. Blocked polyisocyanate compounds can be easily reacted with hydroxyl groups by heating them to, for example, 100°C or higher, for example, 130°C or higher, which regenerates the isocyanate groups. Examples of blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, oxime compounds, and pyrazole compounds. Polyisocyanate compounds can be used alone or in combination of two or more.

[0188] Epoxy compounds are compounds that contain an epoxy group. Examples of epoxy compounds include epoxy compounds containing a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether. Chloromethyl group-containing compounds are compounds that contain a chloromethyl group. Examples of chloromethyl group-containing compounds include chloromethyl polystyrene. Carboxyl group-containing compounds are compounds that contain a carboxyl group. Examples of carboxyl group-containing compounds include (poly)acrylic acid and (poly)methacrylic acid.

[0189] Specific examples of ketone group-containing compounds include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of hydrazide compounds include hydrazine, carbohydrazide, and adipic acid hydrazide. Specific examples of melamine compounds include melamine resin and methyl etherified melamine resin. Specific examples of urea-based compounds include dimethylol dihydroxyethylene urea (DMDHEU) and dimethyl dihydroxyethylene urea. Catalysts such as organic acids, metal chlorides, and metal nitrates may also be included.

[0190] [Amount of curing agent] The amount of curing agent may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more per 100 parts by weight of hydrocarbon-containing polymer (1), and may also be 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of curing agent is preferably 0.1 parts by weight or more and 20 parts by weight or less, more preferably 0.1 parts by weight or more and 10 parts by weight or less per 100 parts by weight of hydrocarbon-containing polymer (1).

[0191] [Other Components] The water-repellent and oil-repellent agent may contain other components besides those listed above. Other components may be added after the hydrocarbon-containing polymer (1) has been manufactured. Examples of other components include water-repellent and / or oil-repellent agents, anti-slip agents, antistatic agents, preservatives, antibacterial agents, deodorants, penetrating agents, etc. These may be used alone or in combination of two or more. In addition to the above components, other components such as texture adjusters, softeners, antibacterial agents, flame retardants, wrinkle inhibitors, crosslinking agents, film-forming aids, compatibilizers, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, defoaming agents, shrinkage inhibitors, wrinkle inhibitors, shape-retaining agents, drape-retaining agents, ironing-improving agents, polymer dispersants, scum dispersants, fluorescent whitening agents, dye fixatives, antifoaming agents, etc., may be used alone or in combination of two or more.

[0192] [Preservatives] Preservatives can be used primarily to enhance preservative and bactericidal properties and maintain preservation during long-term storage. Examples of preservatives include isothiazolone-type organic sulfur compounds, benzisothiazolone-type organic sulfur compounds, benzoic acids, and 2-bromo-2-nitro-1,3-propanediol. The preservative content is preferably 0.0001 to 1% by weight relative to the total weight of the water-repellent and oil-repellent agent. If the preservative content is above the lower limit of the above range, the effect of adding the preservative is sufficiently obtained, and if it is below the upper limit, the storage stability of the water-repellent and oil-repellent agent is good.

[0193] [Antibacterial agents] Antibacterial agents are components that suppress the growth of bacteria on fibers and also suppress the generation of unpleasant odors derived from microbial decomposition products. Examples of antibacterial agents include cationic disinfectants such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide)zinc, polyhexamethylene biguanidine hydrochloride, 8-oxyquinoline, and polylysine.

[0194] [Deodorizers] Examples of deodorizers include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, and aminocarboxylic acid metal complexes (such as the zinc complex of trisodium methylglycinediacetate described in International Publication No. 2012 / 090580).

[0195] [Anti-slip agent] This is an ingredient that has the effect of suppressing slippage of fibers and shifting of seams during sewing and wearing. Examples of anti-slip agents include polysiloxane compounds, colloidal silicas, silicone resin derivatives, colloidal organosilicones, and amino-modified silicones.

[0196] [Fabric softener] Fabric softener is an ingredient that gives fabrics a soft and smooth texture. Examples of fabric softener ingredients include cationic surfactants such as quaternary ammonium salts and amine salts, anionic surfactants such as soap, sulfated oils, higher alcohol sulfate esters and sulfonates, nonionic surfactants such as polyhydric alcohols and polyethylene glycols, amphoteric surfactants such as betaine and amino acid types, and siloxane resins.

[0197] [Amount of other components] The amount of other components may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, per 100 parts by weight of hydrocarbon-containing polymer (1), or 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0198] <Manufacturing of Water- and Oil-Repellent Agents> The manufacturing method of the water- and oil-repellent agent of this disclosure is not limited to the above, but may include the steps of polymerizing the monomer (a) in the presence of an organic solvent to obtain a polymer solution containing the hydrocarbon-containing polymer (1), and volatilizing the organic solvent from the polymer solution and adding water. The water- and oil-repellent agent obtained by this manufacturing method may have good performance.

[0199] The volatile organic solvent may be any organic solvent described in the [polymerization method] above, and may be a highly volatile organic solvent with a boiling point lower than that of water. In particular, the step of obtaining the polymer may be solution polymerization, and may be solution polymerization in which water is not used as the solvent. The amount of organic solvent used may be 30% by weight or more, 50% by weight or more, 75% by weight or more, 90% by weight or more, or 95% by weight or more in the polymerization solvent.

[0200] The volatilization of the organic solvent may be carried out until the remaining amount of the organic solvent is 10% by weight or less, 5% by weight or less, 3% by weight or less, 1% by weight or less, or 0.1% by weight or less.

[0201] After evaporation, it may be added to water, and other additives may also be added.

[0202] To ensure high water repellency, it is preferable to subject the water-repellent and oil-repellent agent to ultrasound (ultrasonic treatment). It is preferable to perform the ultrasonic treatment immediately before applying it to the object to be treated. For example, the water-repellent and oil-repellent agent should be applied to the object 1 minute to 1 hour after the ultrasonic treatment. Ultrasonic treatment can be performed by applying ultrasound to the water-repellent and oil-repellent agent. There are no particular restrictions on the ultrasonic generator, but an output of 500W or more, for example 500 to 2000W, is preferable for efficient mixing. The ultrasonic treatment time may be 0.5 to 60 minutes. For example, a uniform water-repellent and oil-repellent agent can be obtained by treating it for 10 minutes with a 500W ultrasonic generator.

[0203] To obtain a polymer aqueous dispersion with excellent stability during storage, it is desirable to polymerize the monomers by micronizing them in water using an emulsifying device that can impart strong crushing energy, such as a high-pressure homogenizer or an ultrasonic homogenizer. Various emulsifiers, including anionic, cationic, and nonionic types, can be used as emulsifiers, and are used in an amount ranging from 0.5 to 20 parts by weight per 100 parts by weight of monomer. It is preferable to use anionic and / or nonionic and / or cationic emulsifiers. If the monomers are not completely miscible, it is preferable to add a compatibilizer that allows them to be sufficiently miscible, such as a water-soluble organic solvent or a low molecular weight monomer. Adding a compatibilizer can improve emulsification and copolymerization properties.

[0204] The water-repellent and oil-repellent agent may be in the form of a solution, emulsion (especially an aqueous dispersion), or aerosol.

[0205] <Uses of Water- and Oil-Repellent Agents> Examples of uses of water- and oil-repellent agents in this disclosure include external treatment agents (surface treatment agents) or internal treatment agents, repellents (water-repellent agents, oil-repellent agents or water- and oil-repellent agents, etc., especially water-repellent agents), antifouling agents, dirt-removing agents, release agents, mold release agents (external mold release agents or internal mold release agents), etc.

[0206] <Method for manufacturing nonwoven fabric products> The method for manufacturing nonwoven fabric products in this disclosure includes a step of treating a nonwoven fabric substrate with a water-repellent and oil-repellent agent.

[0207] [Processing Method] The water- and oil-repellent agent of this disclosure can be applied to a nonwoven fabric substrate as a treatment agent (especially a surface treatment agent) by conventionally known methods. The water- and oil-repellent agent of this disclosure may be diluted by dispersing it in an organic solvent or water as necessary, and then applied to the surface of the substrate by known methods such as immersion coating, spray coating, foam coating, etc., and dried. After drying, a nonwoven fabric product with the solid components of the water- and oil-repellent agent attached is obtained. If necessary, it may also be applied together with a suitable crosslinking agent and cured. Furthermore, the water- and oil-repellent agent of this disclosure can be used in combination with various additives such as water-repellent and / or oil-repellent agents, anti-slip agents, antistatic agents, texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, anti-wrinkle agents, drying rate modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, ultraviolet absorbers, antioxidants, pH adjusters, insecticides, and defoaming agents. Examples of various additives may be the same as those described in the "other components" section of the water-repellent and oil-repellent agent mentioned above. The concentration of the hydrocarbon-containing polymer (1) in the treatment agent that comes into contact with the substrate may be changed as appropriate depending on the application, but may be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0208] [Nonwoven Fabric Base Material] Various examples of nonwoven fabric base materials can be given, but these include natural animal and plant fibers such as cotton, linen, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; inorganic fibers such as glass fibers, carbon fibers, and asbestos fibers; or mixed fibers thereof. The nonwoven fabric base material may be a nonwoven fabric, a fabric base material in the form of clothing, or a fabric base material such as a carpet, or it may be a fiber, yarn, or intermediate product in a state before it is made into a fabric (for example, sliver or roving yarn).

[0209] Examples of natural fibers include cellulose fibers such as cotton, flax, and pulp, as well as chitin, chitosan, wool, and silk. Specific examples of wood pulp include mechanical pulps such as groundwood pulp (GP), pressed groundwood pulp (PGW), and thermomechanical pulp (TMP); chemical pulps such as high-yield unbleached softwood kraft pulp (HNKP; N material), bleached softwood kraft pulp (NBKP; N material, NB material), unbleached hardwood kraft pulp (LUKP; L material), and bleached hardwood kraft pulp (LBKP, L material); recycled paper pulp such as deinking pulp (DIP) and waste pulp (WP), and semi-chemical pulp (CP). Note that nonwoven fabric products are not paper products and do not need to contain pulp as a raw material.

[0210] Examples of synthetic fibers include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and copolymerized polyester; polyolefins such as linear low-density polyethylene, low-density polyethylene, high-density polyethylene, and polypropylene; polyamides such as nylon 6, nylon 66, nylon 610, and nylon 46; acrylic fibers such as polyacrylonitrile; polyvinyl alcohol, polyurethane, and polyvinyl chloride. Examples of semi-synthetic fibers include acetate and triacetate. Examples of regenerated fibers include rayon, cupro, polynosic rayon, lyocell, and Tencel. Examples of inorganic fibers include glass fiber and carbon fiber.

[0211] "Treatment" refers to applying a water-repellent and oil-repellent agent to a substrate by immersion, spraying, coating, etc. Through treatment, the polymer, which is the active ingredient of the water-repellent and oil-repellent agent, penetrates into the interior of the substrate and / or adheres to the surface of the substrate.

[0212] The water- and oil-repellent agent can be applied to a nonwoven fabric substrate (e.g., cloth) by any known method for treating the nonwoven fabric substrate with a liquid. The nonwoven fabric substrate may be immersed in the water- and oil-repellent agent, or the solution may be applied to or sprayed onto the nonwoven fabric substrate. The treated substrate is preferably dried and cured by heating to exhibit water- and oil-repellent properties. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. Good performance can also be obtained with low-temperature heating (e.g., 100°C to 140°C) in this disclosure. The heating time may be 5 seconds to 60 minutes in this disclosure, for example, 30 seconds to 3 minutes.

[0213] Alternatively, the water-repellent and oil-repellent agent may be applied to the nonwoven fabric substrate by a cleaning method, for example, by washing or dry cleaning.

[0214] [Pretreatment of nonwoven fabric substrate] The nonwoven fabric substrate may be pretreated before being treated with the water-repellent and oil-repellent agent of this disclosure. Pretreatment of the nonwoven fabric substrate can impart excellent durability to the nonwoven fabric product after treatment with the water-repellent and oil-repellent agent.

[0215] Examples of pretreatments for nonwoven fabric substrates include cationization by reaction with reactive quaternary ammonium salts, anionization by sulfonation, carboxylation, phosphorylation, etc., acetylation, benzoylation, carboxymethylation, grafting, tannic acid treatment, and polymer coating after anionization.

[0216] The method for pre-treating the nonwoven fabric substrate is not limited, but it can be pre-treated by conventionally known methods. The pre-treatment solution may be diluted by dispersing it in an organic solvent or water as needed, and then applied to the surface of the nonwoven fabric substrate by known methods such as immersion coating, spray coating, or foam coating, followed by drying. The pH and temperature of the pre-treatment solution may be adjusted according to the desired degree of treatment.

[0217] The pretreatment method for nonwoven fabric substrates involves adding -SO to the fibers. ３ M １ (In the formula, M １ (represents a monovalent cation) a monovalent group represented by -COOM２ (In the formula, M ２ A monovalent group represented by (where represents a monovalent cation), and -O-P(O)(OX １ ) (OX ２ ) (wherein, X １ and X ２ The process may include a step of conferring at least one functional group (hereinafter sometimes referred to as a "specific functional group") selected from the group consisting of monovalent groups (each representing a hydrogen atom or an alkyl group having 1 to 22 carbon atoms).

[0218] M １ Examples include H, K, Na, or ammonium ions which may have substituents. ２ Examples include H, K, Na, or ammonium ions which may have substituents. １ or X ２ If it is an alkyl group, it is preferably an alkyl group having 1 to 22 carbon atoms, and more preferably an alkyl group having 4 to 12 carbon atoms.

[0219] Fibers containing the above-mentioned specific functional groups (hereinafter sometimes referred to as "functional group-containing fibers") can be prepared, for example, by the following methods: (i) A compound having the above-mentioned specific functional group is attached to a fiber material. Note that the attachment of the compound may be such that a portion of the compound and a portion of the fiber are chemically bonded, to the extent that a sufficient amount of the above-mentioned specific functional group remains. (ii) Fibers are prepared in which the above-mentioned specific functional group is directly introduced into the material constituting the fiber.

[0220] (i) For example, a functional group-containing fiber can be obtained by a functional group introduction step in which the fiber material is treated with a pretreatment solution containing one or more compounds having the above-mentioned specific functional group.

[0221] There are no particular restrictions on the material of the fiber material, and examples include natural fibers such as cotton, linen, silk, and wool; semi-synthetic fibers such as rayon and acetate; synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene; and composite fibers and blended fibers thereof. The fiber material may take any form, such as fibers (tow, sliver, etc.), yarn, knitted fabrics (including interwoven fabrics), woven fabrics (including interwoven fabrics), nonwoven fabrics, and paper.

[0222] In this embodiment, from the viewpoint of obtaining good water repellency in the resulting nonwoven fabric product, it is preferable to use fiber materials containing polyamide and polyester as materials, and in particular, it is preferable to use nylon such as nylon 6, nylon 6,6, polyester such as polyethylene terephthalate (PET), polytrimethyl terephthalate, polylactic acid, and mixed fibers containing these.

[0223] Above - SO ３ M １ As a compound having this property, phenolic polymers can be used. Examples of such phenolic polymers include those containing at least one compound represented by the following general formula.

[0224] [In the formula, X ２ Ha-SO ３ M ３ (In the formula, M ３ (where represents a monovalent cation) or a group represented by the following general formula, where n is an integer between 20 and 3000.

[0225] [In the formula, M ４ This represents a monovalent cation.

[0226] The above M ３ Examples include H, K, Na, or ammonium ions which may have substituents.

[0227] The above M ４ Examples include H, K, Na, or ammonium ions which may have substituents.

[0228] The compound represented by the above general formula may, for example, be a formalin condensate of phenolsulfonic acid or a formalin condensate of sulfonated bisphenol S.

[0229] Above - COOM ２ Examples of compounds having this property include polycarboxylic acid polymers.

[0230] As polycarboxylic acid polymers, for example, polymers synthesized by conventionally known radical polymerization methods using acrylic acid, methacrylic acid, maleic acid, etc. as monomers, or commercially available polymers can be used.

[0231] One method for producing polycarboxylic acid polymers is to add a radical polymerization initiator to an aqueous solution of the monomer and / or its salt, and heat the reaction at 30 to 150°C for 2 to 5 hours. At this time, alcohols such as methanol, ethanol, isopropyl alcohol, or aqueous solvents such as acetone may be added to the aqueous solution of the monomer and / or its salt. Examples of radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, redox polymerization initiators formed by combinations of persulfates and sodium bisulfite, hydrogen peroxide, and water-soluble azo polymerization initiators. These radical polymerization initiators may be used alone or in combination of two or more. Furthermore, during radical polymerization, a chain transfer agent (e.g., octyl thioglycolate) may be added to adjust the degree of polymerization.

[0232] In radical polymerization, copolymerizable monomers can be used in addition to the monomers mentioned above. Examples of copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, as well as acrylamide, acrylates, and methacrylates. Acrylates and methacrylates are preferably those having a hydrocarbon group with 1 to 3 carbon atoms, which may have substituents such as hydroxyl groups. Examples of such acrylates or methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, and propyl methacrylate. These copolymerizable monomers may be used individually or in combination of two or more.

[0233] The carboxyl groups in the polycarboxylic acid polymer may be free or neutralized by alkali metals or amine compounds. Examples of alkali metals include sodium, potassium, and lithium, while examples of amine compounds include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0234] The weight-average molecular weight of the polycarboxylic acid polymer is preferably 1,000 to 20,000, and more preferably 3,000 to 15,000, from the viewpoint of obtaining good water repellency in the resulting nonwoven fabric product.

[0235] For polycarboxylic acid polymers, commercially available products such as "NeoCrystal 770" (manufactured by Nikka Chemical Co., Ltd., product name) and "Cellopol PC-300" (manufactured by Sanyo Chemical Industries, Ltd., product name) can be used.

[0236] The above -O-P(O)(OX １ ) (OX ２ Examples of compounds having the following are phosphate ester compounds represented by the following general formula. [In the formula, X １ or X ２ This is synonymous with the above, X ３ This represents an alkyl group having 1 to 22 carbon atoms.

[0237] As the phosphate ester compound mentioned above, phosphate monoesters, diesters, and triesters in which the alkyl ester portion has an alkyl group having 1 to 22 carbon atoms, as well as mixtures thereof, can be used.

[0238] From the viewpoint of obtaining a nonwoven fabric product with good water repellency, it is preferable to use lauryl phosphate ester or decyl phosphate ester.

[0239] For the phosphate ester compound, commercially available products such as "Phosphanol ML-200" (manufactured by Toho Chemical Industry Co., Ltd., trade name) can be used.

[0240] The pretreatment solution containing one or more compounds having the above-mentioned specific functional groups can, for example, be an aqueous solution of the compounds described above. The pretreatment solution may also contain acids, alkalis, surfactants, chelating agents, etc.

[0241] Methods for treating fibrous materials with the above-mentioned pretreatment solution include, for example, padding, immersion, spraying, and coating. For padding, for example, methods using padding equipment described on pages 396-397 of the Dictionary of Textile Dyeing and Processing (published in 1963 by Nikkan Kogyo Shimbun) and pages 256-260 of Color Dyeing Chemistry III (published in 1975 by Jikkyo Shuppan Co., Ltd.) can be used. For coating, for example, methods using coating machines described on pages 473-477 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Senshi-sha) can be used. For immersion, for example, methods using batch-type dyeing machines described on pages 196-247 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Senshi-sha) can be used, and liquid flow dyeing machines, air flow dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, cheese dyeing machines, etc. can be used. Examples of spray treatments include air sprays that atomize the treatment solution using compressed air, and air sprays that use a hydraulic atomization system. The concentration of the treatment solution and the treatment conditions such as heat treatment after application can be adjusted as appropriate, taking into consideration the purpose, performance, and other conditions. If the pretreatment solution contains water, it is preferable to dry it to remove the water after it has been applied to the fiber material. There are no particular restrictions on the drying method, and either a dry heat method or a wet heat method may be used. There are no particular restrictions on the drying temperature, but for example, drying at room temperature to 200°C for 10 seconds to several days is sufficient. If necessary, after drying, heat treatment may be performed at a temperature of 100 to 180°C for about 10 seconds to 5 minutes.

[0242] Furthermore, if the fiber material is to be dyed, the pretreatment with the pretreatment solution may be performed before dyeing or in the same bath as the dyeing. However, if reducing soaping is performed, there is a risk that the compounds having the specific functional groups adsorbed during the process (for example, phenolic polymer compounds, etc.) may be removed. Therefore, it is preferable to perform the pretreatment after reducing soaping following dyeing.

[0243] The treatment temperature during the immersion process can be 60 to 130°C. The treatment time can be 5 to 60 minutes.

[0244] In the functional group introduction step using the pretreatment solution, it is preferable to treat the material in such an amount that the amount of compound having the specified functional group attached is 1.0 to 7.0 parts by weight per 100 parts by weight of the fiber material. Within this range, a high level of both durable water repellency and texture can be achieved.

[0245] The pretreatment solution is preferably adjusted to a pH of 3 to 5. pH adjustment can be done using pH adjusting agents such as acetic acid or malic acid.

[0246] In the pretreatment solution, salt can also be used in combination to effectively adsorb the compound having the above-mentioned specific functional group onto the fiber material through a salting-out effect. Examples of salts that can be used include sodium chloride, sodium carbonate, ammonium sulfate, and sodium sulfate.

[0247] In the functional group introduction step using a pretreatment solution, it is preferable to remove any compounds having the specified functional groups that have been excessively treated. One method of removal is washing with water. By performing sufficient removal, it is possible to suppress the inhibition of the development of water repellency in the subsequent water-repellent treatment, and in addition, the texture of the resulting nonwoven fabric product will be improved. Furthermore, it is preferable to thoroughly dry the resulting functional group-containing fibers before contacting them with a hydrocarbon-based water repellent.

[0248] (ii) Examples of fibers in which the above-mentioned specific functional groups are directly introduced into the material constituting the fiber include cationic dyeable polyester (CD-PET).

[0249] From the viewpoint of obtaining good water repellency in the resulting textile product, the functional group-containing fibers preferably have a surface zeta potential of -100 to -0.1 mV, and more preferably -50 to -1 mV. The surface zeta potential of the fibers can be measured, for example, using the zeta potential and particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0250] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims.

[0251] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0252] <Synthesis Example 1> A 500 ml reactor equipped with an HBA stirrer, thermometer, reflux condenser, dropping funnel, nitrogen inlet, and heating device was prepared, and 100 parts of the solvent methyl ethyl ketone (MEK) were added. Subsequently, a monomer consisting of 78 parts of stirred stearamide ethyl acrylate (C18AmEA, melting point 70°C), 16 parts of hydroxybutyl acrylate (HBA, Tg: -40°C), and 6 parts of dimethylaminoethyl methacrylate (DM) (total monomer 100 parts), and 1.2 parts of the initiator perbutyl PV (PV) were added in this order, and copolymerization was carried out by mixing and stirring this mixture under a nitrogen atmosphere at 65-80°C for 12 hours. The solid content of the obtained copolymer-containing solution was 50% by weight. As a post-treatment, 142 g of 0.4% aqueous acetic acid solution was added to 50 g of the obtained copolymer solution and dispersed. MEK was then removed by distillation under reduced pressure while heating using an evaporator to obtain a milky white copolymer dispersion (volatile organic solvent content of 1% by weight or less). Deionized water was then added to obtain an aqueous dispersion with a solid content of 15% by mass. The melting point of this copolymer was 66°C. The molecular weight of the obtained copolymer was analyzed by gel permeation chromatography, and the mass-average molecular weight in terms of polystyrene was 900,000. Table 1 shows information on the polymer composition, etc.

[0253] <Synthesis Example 2> The same procedure as in Synthesis Example 1 was used, except that 75 parts of stearate acrylate (StA, melting point 30°C) and 19 parts of HBA were used instead of stearate amidoethyl acrylate, to obtain a milky white copolymer aqueous dispersion (volatile organic solvent content 1% by weight or less). Deionized water was added to obtain an aqueous dispersion with a solid content of 15%. The melting point of this copolymer was 46°C. Table 1 shows information on the polymer composition, etc.

[0254] <Synthesis Example 3> [Synthesis of Isocyanurate Derivatives] In a reactor equipped with a thermometer, stirrer, nitrogen inlet tube, and condenser, under a nitrogen atmosphere, 500 parts by mass of 1,6-hexamethylene diisocyanate (HDI, manufactured by Mitsui Chemicals, trade name: Takenate 700), 0.25 parts by mass of 2,6-di(tert-butyl)-4-methylphenol (also known as dibutylhydroxytoluene, BHT, hindered phenol antioxidant), and 0.25 parts by mass of tetraphenyl dipropylene glycol diphosphite (organic phosphite ester, co-catalyst) were mixed. Then, 10.7 parts by mass of 1,3-butanediol was added to this mixture, and nitrogen was introduced into the liquid phase for 1 hour. After that, the mixture was heated to 80°C and reacted for 3 hours, then cooled to 60°C. Subsequently, 0.2 parts by mass of trimethyl-N-2-hydroxypropylammonium 2-ethylhexanoate was added as an isocyanurate catalyst, and the reaction was allowed to proceed for 1.5 hours. Then, 0.04 parts by mass of o-toluenesulfonamide was added per 100 parts by mass of HDI. After that, the reaction mixture was passed through a thin-film distillation apparatus (temperature 150°C, vacuum 93.3 Pa) and distilled until the amount of remaining HDI monomer was 0.5% or less, to obtain an aliphatic polyisocyanate derivative (isocyanurate derivative of hexamethylene diisocyanate). The obtained isocyanate derivative had an isocyanate group content of 20.9% and an average number of isocyanate functional groups of 3.0.

[0255] [Production of hydrocarbon-based polyurethane] In a reactor equipped with a stirrer, thermometer, cooler, and nitrogen gas inlet tube, 100.20 g of the isocyanurate derivative obtained above, 67.60 g of Calcol 8098 (stearyl alcohol, manufactured by Kao Corporation) and 22.30 g of oleic alcohol were mixed and reacted at 110°C under a nitrogen atmosphere for 4 hours until the concentration of isocyanate groups reached 3.67%. Next, the reaction solution was cooled to 80°C, and 9.90 g of N-methyldiethanolamine was added as a cationic active hydrogen compound and reacted at 80°C for 1 hour. Next, 50.00 g of methyl ethyl ketone was added as a solvent and reacted at 80°C until the disappearance of isocyanate groups could be confirmed by infrared absorption spectroscopy. Next, 57.69 g of methyl ethyl ketone was added to the reaction solution, the temperature was raised to 80°C, and the mixture was stirred until the reaction solution was completely dissolved, and then cooled to 75°C. Subsequently, 18.96 g of acetic acid was added as an acid compound to neutralize the mixture. Next, while maintaining the reaction solution at 75°C, 800.0 g of deionized water heated to 70°C was gradually added to emulsify (internal emulsification). Then, the solvent was removed using an evaporator under reduced pressure at a water bath temperature of 60°C until the solid content concentration reached 20% by weight or more. Finally, an aqueous dispersion containing polyurethane was obtained by adjusting the solid content concentration, excluding the acid compound (acetic acid), with deionized water to 20% by weight.

[0256] <Synthesis Example 4> 116 g of sorbitan tristearate and 150 g of 4-methyl-2-pentanone (MIBK) were charged into a 500 mL four-necked flask equipped with a stirring rod, thermometer, and reflux tube. Next, to remove excess water vapor from the mixture, the mixture was stirred while maintaining its temperature at 70°C, refluxed for 1 hour, and then allowed to cool to 50°C. Then, while maintaining stirring, 30 g of desmodulo N-100 (a biuret derivative of hexamethylene diisocyanate, Covestro) was added dropwise using a dropper funnel. After the addition was complete, one drop of dibutyltin dilaurate was added as a catalyst, and the mixture was reacted at 80°C for 1 hour. Next, 25 g of sorbitan monostearate was added, and the mixture was reacted at 80°C for a further 4 hours. Next, after cooling to 60°C, the reaction mixture was collected and slowly mixed with water at 60°C containing an arbitrary amount of cationic emulsifier and polyoxyethylene alkyl ether. The mixture was stirred using a homomixer at 6000 rpm for 1 minute, and then emulsified and dispersed using ultrasound for 15 minutes. After that, the solvent (MIBK) was removed by vacuum, and then pure water was added to adjust the concentration to obtain an aqueous dispersion containing polyurethane with a solid content of 20%.

[0257] <Synthesis Example 5> 150 g of methyl ethyl ketone (MEK) and 51 g of stearyl alcohol were charged into a 500 mL four-necked flask equipped with a stirring rod, thermometer, and reflux tube. Next, to remove excess water vapor from the mixture, the mixture was stirred while maintaining its temperature at 70°C, refluxed for 1 hour, and then allowed to cool to 50°C. Then, 30 g of Desmodulo N3200A (a biuret derivative of hexamethylene diisocyanate, manufactured by Covestro) was added to the mixture, and the reaction was carried out at 80°C for 4 hours. After cooling to 60°C, the reaction mixture was collected, and the reaction mixture was slowly mixed with 60°C water containing an arbitrary amount of polyoxyethylene alkyl ether. This mixture was stirred in a homomixer at 6000 rpm for 1 minute, and then emulsified and dispersed using ultrasound for 15 minutes. Next, the solvent (MEK) was removed by a reduced pressure operation, and then pure water was added to adjust the concentration, obtaining an aqueous dispersion containing polyurethane with a solid content of 20%.

[0258] <Synthesis Example 6> In a 1000 mL flask, 190.6 g of trimethylolpropane, 808.2 g of stearic acid, and 1.2 g of p-toluenesulfonic acid were placed, and a dehydration reaction was carried out at 140-210°C for 3 hours under a nitrogen stream to obtain the product. The acid value and hydroxyl value of the obtained product were measured, and the acid value was 1.8 mg KOH / g and the hydroxyl value was 89 mg KOH / g. In a separate container, 715.5 g of the above product, 180.2 g of hexamethylene diisocyanate, and 1.3 g of bismuth-based catalyst (Nitto Kasei Co., Ltd., Neostan U-600) were placed, and the reaction was carried out at 80°C for 5 hours. The reaction was carried out until the NCO% reached 5.0. After the reaction, the temperature was lowered to 40°C, and then 103.0 g of 3,5-dimethylpyrazole was added, and the reaction was carried out at 40°C for 1 hour to obtain the isocyanate derivative. In addition, in the isocyanate derivative, two hydroxyl groups in trimethylolpropane form an ester group with stearic acid, and one hydroxyl group forms a urethane bond with hexamethylene diisocyanate, which has one end protected by 3,5-dimethylpyrazole.

[0259] In a 500 mL stainless steel container, 40 g of the isocyanate derivative obtained above, 50 g of methyl ethyl ketone, 10 g of polyglycerin fatty acid ester, and 5 g of cationic emulsifier were placed and heated to 50°C to dissolve. Then, 295 g of hot water at 80°C was added, and the mixture was emulsified for 20 minutes using an ultrasonic emulsifier while maintaining the temperature at 80°C. After cooling, a 10% dispersion of the isocyanate derivative was obtained.

[0260] <Examples 1-22 / Comparative Examples 1-11> Treatment solutions (1000 g) were prepared as shown in Table 3-1 or 3-2 below. The fabric (fiber base material) to be treated in this test was polypropylene nonwoven fabric (45 g / m²). ２ ) was used. One sheet of polypropylene nonwoven fabric (45 g / m²) was used. ２ A piece of fabric (510 mm x 205 mm) was immersed in this treatment solution (WPU 130%), passed through mangle rolls, and dried in a pin tenter at 130°C for 30 seconds to obtain a test cloth (treated cloth). The obtained test cloth was evaluated using the test method described below.

[0261] <Example 23> A treatment solution was prepared by mixing 6 g of n-hexanol, 13 g of PVA with a degree of saponification of 98% and a viscosity of 6000 mPa·s (4% dilution, 20°C), and 981 g of pure water. The nonwoven fabric was immersed in the solution using the same treatment method as described above and dried in a pin tenter at 130°C for 30 seconds. Subsequently, the fabric was further immersed and dried in a treatment solution prepared by mixing 6 g of n-hexanol, 2 g of the anionic antistatic agent LUROL ASY, and 53 g of the 15% dispersion of the polymer obtained in Synthesis Example 1 to obtain a test cloth, which was evaluated in the same manner as in the other examples. The hydrocarbon-containing polymer (1) ÷ (hydrocarbon-containing polymer (1) + water-soluble polymer (2)) (weight %) was 23.5%.

[0262] [Alcohol-Repellent IPA] (Specifically, the alcohol-repellent properties were evaluated according to the following procedure in accordance with AATCC Test Method 193-2007.) The treated cloth was stored in a constant temperature and humidity chamber at 21°C and 50% humidity for at least 4 hours. The test solution (isopropyl alcohol (IPA), water, and mixtures thereof, shown in Table 2) was also stored at 21°C. The test was conducted in a constant temperature and humidity chamber at 21°C and 50% humidity. Five 50 μL drops of the test solution were gently placed onto the test cloth using a micropipette. After 30 seconds, if four or five drops remained on the test cloth, the test solution was deemed acceptable. Alcohol repellency is evaluated using a 12-grade system ranging from Fail, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10, based on the highest isopropyl alcohol (IPA) content (by weight) of the passing test solution. A higher grade indicates better alcohol repellency.

[0263]

[0264] [Alcohol-repellent EtOH] The evaluation was performed using the same method as described for [Alcohol-repellent IPA], except that IPA was replaced with EtOH (ethanol).

[0265] [Water Pressure Resistance] A water pressure resistance test was conducted in accordance with AATCC Test Method 193. Specifically, under conditions of a water temperature of 21°C and a pressure increase rate of 60 mbar / min (water temperature 21°C), the water pressure resistance was defined as the pressure at which three water droplets passed through a 20 cm x 20 cm test cloth, or the pressure at which the evaluation sample broke.

[0266] [Antistatic properties] In accordance with WSP40.1, a load voltage (100V) was applied to the evaluation sample, and the surface electrical resistance (GΩ) was measured after 30 seconds. The surface electrical resistance is preferably 400 or less, more preferably 300 or less, more preferably 200 GΩ or less, more preferably 100 GΩ or less, and particularly preferably 80 GΩ or less.

Claims

1. A water-repellent and oil-repellent composition for nonwoven fabrics comprising (1) a hydrocarbon-containing polymer having repeating units derived from a monomer (a) having a hydrocarbon group with 6 to 40 carbon atoms, and (2) a water-soluble polymer.

2. The water- and oil-repellent composition for nonwoven fabrics according to claim 1, wherein the amount of the hydrocarbon-containing polymer (1) is 10% by weight or more and 50% by weight or less of the total amount of the hydrocarbon-containing polymer (1) and the water-soluble polymer (2).

3. The water-soluble polymer (2) is at least one selected from the group consisting of polysaccharides and polyvinyl alcohol, according to claim 1 or 2.

4. A water-repellent and oil-repellent composition according to any one of claims 1 to 3, comprising a penetrating agent and an antistatic agent.

5. The water-repellent and oil-repellent composition according to any one of claims 1 to 4, wherein the monomer (a) has a hydrocarbon group having 12 or more carbon atoms and 30 or fewer carbon atoms.

6. The monomer (a) has the formula: CH2=C(−X ａ )−C(=O)−Y ａ (R ａ ) ｋ [In the formula, R ａ is, independently of each other, a hydrocarbon group having 6 to 40 carbon atoms, X ａ is a hydrogen atom, a monovalent organic group or a halogen atom, Y ａ is a divalent to tetravalent hydrocarbon group having 1 carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ - or -NH- and is a group composed of at least one or more selected therefrom (excluding hydrocarbon groups), and k is 1 to 3.], The water- and oil-repellent composition according to any one of claims 1 to 5.

7. The monomer (a) contains monomer (a2), and monomer (a2) is given by the formula: CH2 = C(-X ａ２ )-C(=O)-Y ａ２１ -Z(-Y ａ２２ -R ａ２ ) ｎ [In the formula, R ａ２ Each of these is independently a hydrocarbon group having 6 to 40 carbon atoms, X ａ２ is a hydrogen atom, a monovalent organic group, or a halogen atom, Y ａ２１ is -O- or -NH-, Y ａ２２ These are independently -O-, -C(=O)-, and -S(=O). ２ -, -NH- or -CH ２ A water-repellent and oil-repellent composition according to any one of claims 1 to 6, which is represented by: - ​​a group consisting of at least one selected from, where Z is a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2.

8. The hydrocarbon-containing polymer (1) comprises repeating units derived from a hydrophilic group-containing monomer (b), wherein the monomer (b) is of the formula: CH ２ = CX ｂ C(=O)-Y ｂ - (R ｂ O) ｎ -A ｂ [In the formula, X ｂ is a hydrogen atom or a methyl group, Y ｂ is -O- or -NH-, and R ｂ Each of these is an alkylene group having 2 to 6 carbon atoms, and A ｂ This is a hydrogen atom, an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, or CH ２ = CX ｂ A water-repellent and oil-repellent composition according to any one of claims 1 to 7, wherein the oxyalkylene (meth)acrylate is represented by C(=O)-, and n is an integer from 1 to 90.

9. The water-repellent and oil-repellent composition according to any one of claims 1 to 8, wherein the hydrocarbon-containing polymer (1) comprises (c) an ionic group-containing monomer, and the monomer (c) comprises an olefinic carbon-carbon double bond and an anionic group or a cationic group.

10. The monomer (a) is monomer (a2), and the monomer (a2) is given by the formula: CH2 = C(-X ａ２ )-C(=O)-Y ａ２１ -Z(-Y ａ２２ -R ａ２ ) ｎ [In the formula, R ａ２ Each of these is independently a hydrocarbon group having 6 to 40 carbon atoms, X ａ２ is a hydrogen atom, a monovalent organic group, or a halogen atom, Y ａ２１ is -O- or -NH-, Y ａ２２ These are independently -O-, -C(=O)-, and -S(=O). ２ -, -NH- or -CH ２ - is a group composed of at least one selected from, where Z is a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2. ] is represented as, where the monomer (b) is monomer (b1), and the monomer (b1) is CH ２ = CX ｂ C(=O)-O-(R ｂ O) ｎ -A ｂｉ [In the formula, X ｂ Each is independently a hydrogen atom or a methyl group, R ｂ Each of these is an alkylene group having 2 to 6 carbon atoms, and A ｂｉ Each is independently a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, and n is an integer from 1 to 90. The water-soluble polymer (2) is at least one selected from the group consisting of starch and polyvinyl alcohol, and the water-repellent and oil-repellent composition comprises a penetrating agent and an antistatic agent, according to any one of claims 1 to 9.

11. A method for producing a water-repellent and oil-repellent composition for nonwoven fabrics, comprising: (1) a hydrocarbon-containing polymer having repeating units derived from a monomer (a) having 6 to 40 hydrocarbon groups, and (2) a water-soluble polymer, wherein the production method comprises the steps of: polymerizing the monomer (a) in the presence of an organic solvent to obtain a polymer solution containing the hydrocarbon-containing polymer (1); and volatilizing the organic solvent from the polymer solution and adding water.

12. A nonwoven fabric product treated with a water-repellent and oil-repellent agent according to any one of claims 1 to 10.

13. A method for producing a nonwoven fabric product, comprising the step of treating a nonwoven fabric substrate with a water-repellent and oil-repellent composition according to any one of claims 1 to 10.

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