Oil resistant agent

Abstract

Provided is a novel oil-resistant agent having excellent oil resistance, the oil-resistant agent containing: (1) a hydrocarbon-containing polymer having a repeating unit derived from a monomer (a) having a hydrocarbon group having 6-40 carbon atoms; (2) a water-soluble polymer; and (3) a polycarboxylic acid.

Description

Technical Field

[0001] The present invention relates to an oil-proofing agent, in particular to an oil-proofing agent suitable for treating fibers and paper. Background Art

[0002] In recent years, the development of non-fluorine-based treatment agents that can impart liquid repellency and liquid resistance to various substrates has been progressing.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 2003-206409 Summary of the Invention

[0006] Problems to be solved by the invention

[0007] Patent Document 1 discloses a composition for forming a coating having excellent water resistance and other properties on a substrate surface, characterized in that the composition contains a polymer having hydroxyl groups and / or amino groups and a polybasic acid as essential components (excluding a combination of glycerolated chitosan and 1,2,3,4-butanetetracarboxylic acid).

[0008] Patent Document 1 does not describe the use of a long-chain hydrocarbon group having 6 or more carbon atoms, nor does it describe oil resistance.

[0009] The present invention provides a new oil-proofing agent having excellent oil resistance.

[0010] Technical means to solve problems

[0011] Preferred embodiments of the present invention are as follows.

[0012] [Item 1] An oil-resistant agent comprising:

[0013] (1) a hydrocarbon-containing polymer having repeating units derived from a monomer (a), wherein the monomer (a) has a hydrocarbon group having 6 to 40 carbon atoms;

[0014] (2) water-soluble polymers; and

[0015] (3) Polycarboxylic acids.

[0016] [Item 2] The oil-resistant agent according to Item 1, wherein the water-soluble polymer (2) is a polyol.

[0017] [Item 3] The oil-resistant agent according to Item 1 or 2, wherein the water-soluble polymer (2) is at least one selected from polysaccharides and polyvinyl alcohol.

[0018] [Item 4] The oil resistant agent according to any one of Items 1 to 3, wherein the molecular weight of the polycarboxylic acid is 1000 or less.

[0019] [Item 5] The oil resistant agent according to any one of Items 1 to 4, wherein the polycarboxylic acid is a hydroxypolycarboxylic acid.

[0020] [Item 6] The oil-resistant agent according to any one of Items 1 to 5, wherein the polycarboxylic acid is at least one selected from citric acid, malic acid, tartaric acid, and hydroxymalonic acid.

[0021] [Item 7] The oil resistant agent according to any one of Items 1 to 6, wherein the monomer (a) has a hydrocarbon group having 12 to 30 carbon atoms.

[0022] [Item 8] The oil resistant agent according to any one of Items 1 to 7, wherein

[0023] The above monomer (a) is represented by the formula: CH2=C(-X a )-C(=O)-Y a (R a ) k express.

[0024] [Where R a are each independently a hydrocarbon group having 6 to 40 carbon atoms,

[0025] X a is a hydrogen atom, a monovalent organic group or a halogen atom,

[0026] Y a A group consisting of at least one selected from a divalent to tetravalent hydrocarbon group having 1 carbon atom (particularly -CH2-, -CH=), -C6H4-, -O-, -C(=O)-, -S(=O)2-, or -NH- (excluding a hydrocarbon group),

[0027] k is 1 to 3.]

[0028] [Item 9] The oil resistant agent according to any one of Items 1 to 8, wherein

[0029] The above monomer (a) includes monomer (a2),

[0030] The above monomer (a2) is represented by the formula: CH2=C(-X a2 )-C(=O)-Y a21 -Z(-Y a22 -R a2 ) n express.

[0031] [Where R a2 are each independently a hydrocarbon group having 6 to 40 carbon atoms,

[0032] X a2 is a hydrogen atom, a monovalent organic group or a halogen atom,

[0033] Y a21 is -O- or -NH-,

[0034] Y a22 are each independently a group consisting of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, or -CH2-,

[0035] Z is a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms,

[0036] n is 1 or 2.]

[0037] [Item 10] The oil resistant agent according to any one of Items 1 to 9, wherein

[0038] The hydrocarbon-containing polymer (1) comprises repeating units derived from (b) a monomer containing a hydrophilic group,

[0039] The above monomer (b) is of the formula: CH2=CX b C(=O)-Y b -(R b O) n -A b The oxyalkylene (meth)acrylate shown.

[0040] [Where,

[0041] X b is a hydrogen atom or a methyl group,

[0042] Y b is -O- or -NH-,

[0043] R b is an alkylene group having 2 to 6 carbon atoms,

[0044] A b A hydrogen atom, an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, or CH2=CX b C(=O)-,

[0045] n is an integer from 1 to 90.]

[0046] [Item 11] The oil resistant agent according to any one of Items 1 to 10, wherein

[0047] The hydrocarbon-containing polymer (1) contains (c) a monomer containing an ion-donating group,

[0048] The monomer (c) contains an ethylenic carbon-carbon double bond and an anion-providing group or a cationic-providing group.

[0049] [Item 12] A product treated with the oil-proofing agent according to any one of Items 1 to 11.

[0050] [Item 13] The product according to Item 12, which is a fiber product or a paper product.

[0051] [Item 14] The product according to Item 12 or 13, which is oil-resistant paper or water-resistant paper.

[0052] [Item 15] The product according to any one of Items 12 to 14, which is a food packaging material or a food container.

[0053] Effects of the Invention

[0054] The oil-proofing agent of the present invention has excellent oil resistance. The oil-proofing agent of the present invention has good oil resistance. The oil-proofing agent of the present invention can improve oil stains from creases. DETAILED DESCRIPTION

[0055] Definition of terms

[0056] As used herein, an "n-valent group" refers to a group having n valent bonds, i.e., a group that forms n bonds. Furthermore, an "n-valent organic group" refers to an n-valent group containing carbon. Such organic groups are not particularly limited and may be hydrocarbon groups or derivatives thereof. Hydrocarbon derivatives refer to groups having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, etc., at the end of the hydrocarbon group or in its molecular chain.

[0057] When used in this specification, "hydrocarbon group" is a group containing carbon and hydrogen, and is a group obtained by removing hydrogen atoms from hydrocarbon. Such a hydrocarbon group is not particularly limited, and examples thereof include C 1－20 Hydrocarbon groups, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The aforementioned "aliphatic hydrocarbon groups" may be linear, branched, or cyclic, and may be saturated or unsaturated. Furthermore, the hydrocarbon group may contain one or more ring structures. Where expressly stated, the hydrocarbon group may be substituted with one or more substituents.

[0058] In this specification, regardless of whether "independently at each occurrence", "independently of each other", "independently of each other" or equivalent expressions are explicitly stated, unless otherwise specified, when a term (symbol) that appears multiple times in a chemical structure is defined, the definition applies independently at each occurrence.

[0059] It should be understood that the chemical structures described in this specification do not include chemical structures that are considered chemically impossible or extremely unstable by those skilled in the art.

[0060] Oil-resistant agent

[0061] The oil-proofing agent of the present invention imparts oil resistance to substrates (e.g., fiber substrates, paper substrates). The oil-proofing agent can function as at least one agent selected from a water-repellent, an oil-repellent, and a water-proofing agent. By using the oil-proofing agent of the present invention, oil resistance can be imparted without excessively increasing the air permeability of the treated paper. Therefore, it is useful in applications requiring air permeability, such as food wrapping paper for fried chicken or French fries, and plastic wrap.

[0062] The oil-proofing agent of the present invention contains (1) a hydrocarbon-containing polymer, (2) a water-soluble polymer, and (3) a polycarboxylic acid.

[0063] The oil-resistant agent of the present invention may not contain any compound selected from the group consisting of a compound having a fluoroalkyl group with 8 or more carbon atoms, a compound having a perfluoroalkyl group with 8 or more carbon atoms, a compound having a fluoroalkyl group with 4 or more carbon atoms, a compound having a perfluoroalkyl group with 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The oil-resistant agent of the present invention can impart oil resistance to a substrate even without containing these fluorine compounds.

[0064] [(1) Hydrocarbon-containing polymers]

[0065] The hydrocarbon-containing polymer (1) has a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, in particular a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be branched or linear, 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 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.

[0066] The HD (n-hexadecane) contact angle of the hydrocarbon-containing polymer (1) can 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 can be 100° or less, 90° or less, or 75° or less. By having an HD contact angle above the above lower limit, the hydrocarbon-containing polymer (1) can be well endowed with liquid repellency (especially oil repellency and oil resistance) on the substrate. As shown in the examples, the HD contact angle is a static contact angle of a spin-coated film of the hydrocarbon-containing polymer (1), and refers to the value obtained by dropping 2 μL of HD on the spin-coated film and measuring the contact angle 1 second after the drop.

[0067] The water contact angle of the hydrocarbon-containing polymer (1) can 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 can be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. When the hydrocarbon-containing polymer (1) has a water contact angle above the above lower limit, liquid repellency (particularly water repellency and water resistance) can be imparted to the substrate well. As shown in the examples, the water contact angle is a static contact angle of a spin-coated film of the hydrocarbon-containing polymer (1), and refers to the value obtained by dropping 2 μL of water on the spin-coated film and measuring the contact angle 1 second after the drop.

[0068] The hydrocarbon-containing polymer (1) is preferably a compound containing carbon of bio-based origin. The bio-based content is measured according to ASTM D6866. The bio-based content may be 20% or more, preferably 30% or more, more preferably 50% or more, further preferably 60% or more, even more preferably 70% or more, most preferably 80% or more or 90% or more, for example 100%. A high bio-based content means that the amount of fossil resource-based materials such as petroleum used is small. From this perspective, the higher the bio-based content of the hydrocarbon-containing polymer (1), the better.

[0069] The hydrocarbon-containing polymer (1) of the present invention may not have any group selected from the group consisting of a fluoroalkyl group having 8 or more carbon atoms, a perfluoroalkyl group having 8 or more carbon atoms, a fluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group, a fluoroalkyl group, and a fluorine atom. Even if the hydrocarbon-containing polymer (1) does not contain these fluorine-containing groups, it can still impart oil resistance to the substrate.

[0070] 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, or 500,000 or more, and may be 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.

[0071] The melting point or glass transition temperature (e.g., melting point) of the hydrocarbon-containing polymer (1) may be 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 be 200°C or lower, 150°C or lower, 100°C or lower, 80°C or lower, or 70°C or lower.

[0072] The hydrocarbon-containing polymer (1) has repeating units derived from a monomer (a) having a hydrocarbon group having 6 or more and 40 or less carbon atoms. In addition to the repeating units derived from the monomer (a), the hydrocarbon-containing polymer may also have repeating units derived from (b) a monomer having a hydrophilic group, (c) a monomer having an ion-donating group, and / or (d) other monomers. It is particularly preferred that the hydrocarbon-containing polymer (1) has repeating units formed from (b) a monomer having a hydrophilic group. It is further preferred that the hydrocarbon-containing polymer (1) has repeating units formed from (c) a monomer having an ion-donating group, in addition to repeating units formed from the monomers (a) and (b). The hydrocarbon-containing polymer (1) may also have repeating units formed from (d) other monomers, in addition to repeating units formed from the monomers (a), (b), and (c).

[0073] [(a) Hydrocarbon group-containing monomer]

[0074] The hydrocarbon-containing polymer (1) has a repeating unit derived from a monomer (a) having a hydrocarbon group having a carbon number of 6 to 40. The monomer (a) may be a monomer.

[0075] The hydrocarbon group possessed by monomer (a) can be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and the aliphatic hydrocarbon group is particularly preferably a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group is branched or straight-chain, more preferably straight-chain. The hydrocarbon group can be saturated or unsaturated. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group (alkyl group). The number of carbon atoms of the hydrocarbon group can 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 can 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.

[0076] Monomer (a) may contain an amide group, a urea group, or a carbamate group. The hydrocarbon monomer may be a combination of a hydrocarbon monomer having an amide group, a urea group, or a carbamate group and a hydrocarbon monomer not having an amide group, a urea group, or a carbamate group. By having monomer (a) contain such a group, the effects of the present invention can be well achieved.

[0077] The monomer (a) having a hydrocarbon group with 6 to 40 carbon atoms is preferably of the formula: CH2=C(-X a )-C(=O)-Y a (R a ) k The monomers shown.

[0078] [Where R a are each independently a hydrocarbon group having 6 to 40 carbon atoms,

[0079] Xa is a hydrogen atom, a monovalent organic group or a halogen atom,

[0080] Y a A group consisting of at least one selected from a divalent to tetravalent hydrocarbon group having 1 carbon atom (particularly -CH2-, -CH=), -C6H4-, -O-, -C(=O)-, -S(=O)2-, or -NH- (excluding a hydrocarbon group),

[0081] k is 1 to 3.]

[0082] X a X 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 of X include hydrogen, methyl, chlorine, bromine, iodine, and cyano. a Preferably, it is a hydrogen atom, a methyl group, or a chlorine atom. a A hydrogen atom is particularly preferred.

[0083] Y a Y is a divalent to tetravalent group. a A divalent group is preferred.

[0084] Y a Preferably, the group is composed of at least one selected from a hydrocarbon group having 1 carbon atom, -C6H4-, -O-, -C(=O)-, -S(=O)2-, or -NH- (excluding hydrocarbon groups). Examples of hydrocarbon groups having 1 carbon atom include -CH2-, -CH= having a branched structure, or -C≡ having a branched structure.

[0085] Y a It may be -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 -(CH2)] m -(m is an integer from 1 to 5) or -C6H4-(phenylene)].

[0086] Y a Specific 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-C6H4-, -O-(CH2) m-O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -O-C(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -O-C(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -O-C(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -O-C6H4-, -O-(CH2) m -NH-S(=O)2-, -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -O-C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2)[[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​-NH-C(=O)-NH-, -O-(CH2) m -NH-S(=O)2-, -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -NH-S(=O)2- or -NH-(CH2) m -S(=O)2-NH- [wherein, m is an integer of 1 to 5, particularly 2 or 4] Y a More preferably, it is -O- or -O-(CH2) m -NH-C(=O)-, especially -O-(CH2) m -NH-C(=O)-.

[0088] R a A linear or branched hydrocarbon group is preferred. The hydrocarbon group may particularly be a linear hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and especially an alkyl group. The hydrocarbon group preferably has 12 to 30 carbon atoms, for example, 16 to 26 or 15 to 26, particularly 18 to 22 or 17 to 22.

[0089] Examples of monomer (a) include:

[0090] Formula (a1): CH2=C(-X a1 )-C(=O)-Y a1 -R a1 [Where R a1 is a hydrocarbon group having 6 to 40 carbon atoms, X a1 is a hydrogen atom, a monovalent organic group or a halogen atom, Y a1 is a monomer represented by -O- or -NH-]; and

[0091] Formula (a2): CH2=C(-X a2 )-C(=O)-Y a21 -Z(-Y a22 -R a2 ) n [Where R a2 are each 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 Each independently represents a direct bond or a group consisting of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH- or -CH2-, Z represents a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n represents 1 or 2] a monomer.

[0092] ((a1) monomer)

[0093] Monomer (a1) is of the formula: CH2=C(-X a1 )-C(=O)-Y a1 -R a1 The compound shown.

[0094] [Where R a1 is a hydrocarbon group having 6 to 40 carbon atoms,

[0095] X a1 is a hydrogen atom, a monovalent organic group or a halogen atom,

[0096] Y a1 is -O- or -NH-.]

[0097] Monomer (a1) is Y a1 Long-chain acrylate monomers containing -O-, or Y a1 It is a long-chain acrylamide monomer with -NH-.

[0098] R a1 Preferably, it is an aliphatic hydrocarbon group, in particular a saturated aliphatic hydrocarbon group, and especially an alkyl group. a1 In the hydrocarbon group, the number of carbon atoms is preferably 12 to 30, for example 16 to 26, particularly 18 to 22.

[0099] X a1 It 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, and is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0100] Preferred specific examples of the long-chain acrylate monomer include lauryl (meth)acrylate, stearyl (meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, eicosyl α-chloroacrylate, and behenyl α-chloroacrylate.

[0101] Preferred specific examples of the long-chain acrylamide monomer include stearyl (meth)acrylamide, eicosyl (meth)acrylamide, and behenyl (meth)acrylamide.

[0102] ((a2) monomer)

[0103] Monomer (a2) is a monomer different from monomer (a1). Monomer (a2) is a (meth)acrylate or (meth)acrylamide having a group consisting of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, or -CH2-.

[0104] Monomer (a2) may be of the formula: CH2=C(-X a2 )-C(=O)-Y a21 -Z(-Y a22-R a2 ) n The compound shown.

[0105] [Where R a2 are each independently a hydrocarbon group having 6 to 40 carbon atoms,

[0106] X a2 is a hydrogen atom, a monovalent organic group or a halogen atom,

[0107] Y a21 is -O- or -NH-,

[0108] Y a22 are each independently a direct bond, or a group consisting of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, or -CH2-,

[0109] Z is a direct bond, or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms,

[0110] n is 1 or 2.]

[0111] Y a22 and / or Z may not be a direct bond. a22 and Z are not directly bonded.

[0112] R a2 Preferably, it is an aliphatic hydrocarbon group, in particular a saturated aliphatic hydrocarbon group, and especially an alkyl group. a2 The number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example 16 to 26 or 15 to 26, particularly 18 to 22 or 17 to 22.

[0113] X a2 It 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, and is preferably a hydrogen atom, a methyl group, or a chlorine atom.

[0114] Y a22 Can be -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'-.

[0115] [wherein, Y' is independently a direct bond, -O-, -NH- or -S(=O)2-,

[0116] R' is -(CH2) m-(m is an integer of 1 to 5), a linear hydrocarbon group having an unsaturated bond and having 1 to 5 carbon atoms, a hydrocarbon group having a branched structure and having 1 to 5 carbon atoms, or -(CH2) l -C6H4-(CH2) l -(l is each independently an integer of 0 to 5, -C6H4- is a phenylene group)]

[0117] Y a22 Specific examples include direct bonding, -O-, -NH-, -O-C(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O)2-, -S(=O)2-NH-, -O-C(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-, -NH-C6H4-, -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -O-C(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -O-C(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -O-C(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -O-C6H4-, -NH-(CH2) m -O-C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4-, -NH-(CH2) m -NH-C6H4-.

[0118] [Wherein, m is an integer from 1 to 5.]

[0119] Y a22 Preferred are -O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O)2-, -S(=O)2-NH-, -O-C(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-. Y a22 More preferably, it is -NH-C(=O)-, -C(=O)-NH-, -O-C(=O)-NH-, -NH-C(=O)-O-, or -NH-C(=O)-NH-. a22 It may not be a direct bond.

[0120] Z is a direct bond, or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and may have a straight chain structure or a branched structure. The number of carbon atoms in Z is preferably 2 to 4, particularly 2. Specific examples of Z include a direct bond, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH= with a branched structure, -CH2(CH-)CH2- with a branched structure, -CH2CH2CH= with a branched structure, -CH2CH2CH2CH2CH= with a branched structure, -CH2CH2(CH-)CH2-, and -CH2CH2CH2CH= with a branched structure. Z may not be a direct bond.

[0121] Monomer (a2) is preferably CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-R a2 、CH2=C(-X a2 )-C(=O)-O-(CH2) m -O-C(=O)-NH-R a2 、CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-O-R a2 、CH2=C(-X a2 )-C(=O)-O-(CH2) m -NH-C(=O)-NH-R a2 [where R a2 and X a2 Same meaning as above].

[0122] Monomer (a2) is particularly preferably CH2=C(-Xa2 )-C(=O)-O-(CH2) m -NH-C(=O)-R a2 .

[0123] Monomer (a2) can be produced by reacting a hydroxyalkyl (meth)acrylate or a 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.

[0124] 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 a 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.

[0125] Preferred examples of monomer (a) are as follows:

[0126] Stearyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, behenyl α-chloroacrylate;

[0127] Stearyl (meth)acrylamide, behenyl (meth)acrylamide;

[0128]

[0129]

[0130] [In the above formula, n is a number from 6 to 40, and m is a number from 1 to 5.]

[0131] The compound of the above chemical formula is an acrylic acid compound in which the α-position is a hydrogen atom. Specific examples thereof include a methacrylic acid compound in which the α-position is a methyl group and an α-chloroacrylic acid compound in which the α-position is a chlorine atom.

[0132] Monomer (a2) is preferably of the formula: R a22 -C(=O)-NH-R a23 -O-R a21 The amide-containing monomers shown.

[0133] [Where R a21 is an organic residue having an ethylenically unsaturated polymerizable group,

[0134] R a22 is a hydrocarbon group having 6 to 40 carbon atoms,

[0135] Ra23 It is a hydrocarbon group having 1 to 5 carbon atoms.]

[0136] R a21 It 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 elements. Specific examples include -C(=O)CR a211 =CH2, -CHR a211 =CH2, -CH2CHR a211 =CH2 or other organic residues having an ethylenically unsaturated polymerizable group, R a211 Examples include hydrogen atoms and alkyl groups having 1 to 4 carbon atoms. a21 In addition to the ethylenically unsaturated polymerizable group, it may also have various organic groups, for example, chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, polysiloxane groups and the like, and these organic groups may be substituted with various substituents. a21 Preferably -C(=O)CR a211 =CH2.

[0137] R a22 It is a hydrocarbon group with 6 to 40 carbon atoms, preferably an alkyl group, and examples thereof include chain hydrocarbon groups and cyclic hydrocarbon groups. Among them, chain hydrocarbon groups are preferred, and linear saturated hydrocarbon groups are particularly preferred. a22 The number of carbon atoms is 6 or more and 40 or less, preferably 11 to 27, and particularly preferably 15 to 23.

[0138] R a23 It 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 an unsaturated bond, but is preferably linear. a23 The number of carbon atoms in R is preferably 2 to 4, particularly preferably 2. a23 An alkylene group is preferred.

[0139] The monomer containing an amide group can be R a22 One type of monomer (e.g., only R a22 The compound having 17 carbon atoms), or R a22 For a variety of combinations (such as R a22 The compound with 17 carbon atoms and R a22 a mixture of compounds having 15 carbon atoms).

[0140] Examples of the amide group-containing monomer include carboxylic acid amide alkyl (meth)acrylate.

[0141] Specific examples of the amide group-containing monomer include palmitamideethyl (meth)acrylate, stearamideethyl (meth)acrylate, behenamideethyl (meth)acrylate, myristamideethyl (meth)acrylate, lauramideethyl (meth)acrylate, isostearic acid acetamide (meth)acrylate, oleic acid acetamide (meth)acrylate, tert-butylcyclohexylhexanamideethyl (meth)acrylate, adamantanecarboxylic acid acetamide (meth)acrylate, naphthamideethyl (meth)acrylate, anthracenecarboxamideethyl (meth)acrylate, palmitamidepropyl (meth)acrylate, stearamidepropyl (meth)acrylate, myristamideethyl vinyl ether, stearamideethyl vinyl ether, palmitamideethyl allyl ether, stearamideethyl allyl ether, or mixtures thereof.

[0142] The amide-containing monomer is preferably stearamidoethyl (meth)acrylate. The amide-containing monomer may be a mixture containing stearamidoethyl (meth)acrylate. In the mixture containing stearamidoethyl (meth)acrylate, the amount of stearamidoethyl (meth)acrylate relative to the weight of all amide-containing monomers may be, for example, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and may be less than 90% by weight, less than 80% by weight, or less than 70% by weight. The remaining monomers may be, for example, palmitamide ethyl (meth)acrylate.

[0143] In monomer (a), the amount of monomer (a2) can 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.

[0144] [(b) Monomer containing a hydrophilic group]

[0145] The hydrocarbon-containing polymer (1) may contain a monomer (b) containing a hydrophilic group. Monomer (b) is a monomer other than monomer (a) and is a monomer having a hydrophilic group. The hydrophilic group is preferably an oxyalkylene group (the alkylene group has 2 to 6 carbon atoms), particularly an oxyethylene group. Monomer (b) is particularly preferably an oxyalkylene (meth)acrylate, such as a polyalkylene (or monoalkylene) glycol mono(meth)acrylate and / or a polyalkylene (or monoalkylene) glycol di(meth)acrylate, or a polyalkylene (or monoalkylene) glycol mono(meth)acrylamide.

[0146] Monomer (b) is preferably of the formula: CH2=CX b C(=O)-Y b -(R b O) n -A bThe oxyalkylene (meth)acrylate shown.

[0147] [Where, X b is a hydrogen atom or a methyl group,

[0148] Y b is -O- or -NH-,

[0149] R b are each independently an alkylene group having 2 to 6 carbon atoms,

[0150] A b A hydrogen atom, an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, or CH2=CX b C(=O)-,

[0151] n is an integer from 1 to 90.]

[0152] An example of monomer (b) is preferably the formula: CH2=CX b C(=O)-O-(R b O) n -A bi (b1) and CH2=CX b C(=O)-O-(R b O) n -C(=O)CX b =CH2(b2), CH2=CX b C(=O)-NH-(R b O) n -A bi The compound shown in (b3).

[0153] [Where, X b are each independently a hydrogen atom or a methyl group,

[0154] A bi are each independently a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms,

[0155] R b are each independently an alkylene group having 2 to 6 carbon atoms,

[0156] n is an integer from 1 to 90.]

[0157] n is, for example, 1 to 50, particularly 1 to 30, and especially 1 to 15 or 2 to 15. Alternatively, n may be 1, for example.

[0158] R b It can be a straight chain or branched alkylene group, for example, it can be of the formula -(CH2) x - or -(CH2) x1 -(CH(CH3)) x2-[wherein, x1 and x2 are 0 to 6, for example, 2 to 5, and the total of x1 and x2 is 1 to 6, -(CH2) x1 - and -(CH(CH3)) x2 - is not limited to the described formula and may be random] shown in the group.

[0159] In - (R b O) n -, R may be 2 or more (for example, 2 to 4, especially 2), -(R b O) n - For example, it can be -(R 1 O) n1 - and - (R 2 O) n2 -[Where R 1 and R 2 Each of the alkylene groups is different from the other, and each of the alkylene groups has 2 to 6 carbon atoms, wherein n1 and n2 are 1 or more, and the total of n1 and n2 is 2 to 90.

[0160] R in formulas (b1), (b2) and (b3) b Particularly preferred are ethylene, propylene or butylene, especially butylene. b It can be a combination of two or more alkylene groups. In this case, it is preferred that at least one R is an ethylene group, a propylene group, or a butylene group. b The combination of ethylene and propylene, ethylene and butylene, and propylene and butylene can be listed. Monomer (b) can be a mixture of two or more. In this case, it is preferred that at least one monomer (b) is R in formula (b1), (b2) or (b3). b A monomer that is an ethylene, propylene, or butylene group. Furthermore, when using a polyalkylene glycol di(meth)acrylate represented by formula (b2), it is preferably not used alone as monomer (b) but is preferably used in combination with monomer (b1). In this case, the compound represented by formula (b2) preferably accounts for less than 30% by weight of the monomer (b) used.

[0161] Specific examples of the monomer (b) include the following, but are not limited to these.

[0162] CH2=CHCOO-CH2CH2O-H

[0163] CH2=CHCOO-CH2CH2CH2O-H

[0164] CH2=CHCOO-CH2CH(CH3)OH

[0165] <h2 style=";text-align:left;direction:ltr">CH2=CHCOO-CH(CH3)CH2O-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0166] <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-CH2CH2CH2CH2O-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0167] <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-CH2CH2CH(CH3)OH<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0168] <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-CH2CH(CH3)CH2O-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0169] <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-CH(CH3)CH2CH2O-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0170] <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-CH2CH(CH2CH3)OH<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0171] <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-CH2C(CH3)2O-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0172] <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-CH(CH2CH3)CH2O-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0173] <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-C(CH3)2CH2O-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0174] <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-CH(CH3)CH(CH3)OH<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0175] <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-C(CH3)(CH2CH3)OH<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0176] <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)2-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0177] <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)4-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0178] <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)5-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0179] <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)6-H<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0180] <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)5-CH3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0181] <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)9-CH3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0182] <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)<h2 style=";text-align:left;direction:ltr"> 23 <h2 style=";text-align:left;direction:ltr"> -CH3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0183] <h2 style=";text-align:left;direction:ltr"> CH2=CHCOO-(CH2CH2O)<h2 style=";text-align:left;direction:ltr"> 90 <h2 style=";text-align:left;direction:ltr"> -CH3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0184] CH2=CHCOO-(CH2CH(CH3)O)9-H

[0185] CH2=CHCOO-(CH2CH(CH3)O)9-CH3

[0186] CH2=CHCOO-(CH2CH(CH3)O) 12 -CH3

[0187] CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)2-H

[0188] CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3

[0189] CH2=CHCOO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0190] CH2=CHCOO-(CH2CH2O) 23 -OOC(CH3)C=CH2

[0191] CH2=CHCOO-(CH2CH2O) 20 -(CH2CH(CH3)O)5-CH2-CH=CH2

[0192] CH2=CHCOO-(CH2CH2O)9-H

[0193] CH2=C(CH3)COO-CH2CH2O-H

[0194] CH2=C(CH3)COO-CH2CH2CH2O-H

[0195] CH2=C(CH3)COO-CH2CH(CH3)O-H

[0196] CH2=C(CH3)COO-CH(CH3)CH2O-H

[0197] CH2=C(CH3)COO-CH2CH2CH2CH2O-H

[0198] CH2=C(CH3)COO-CH2CH2CH(CH3)O-H

[0199] CH2=C(CH3)COO-CH2CH(CH3)CH2O-H

[0200] CH2=C(CH3)COO-CH(CH3)CH2CH2O-H

[0201] CH2=C(CH3)COO-CH2CH(CH2CH3)O-H

[0202] CH2=C(CH3)COO-CH2C(CH3)2O-H

[0203] CH2=C(CH3)COO-CH(CH2CH3)CH2O-H

[0204] CH2=C(CH3)COO-C(CH3)2CH2O-H

[0205] CH2=C(CH3)COO-CH(CH3)CH(CH3)O-H

[0206] CH2=C(CH3)COO-C(CH3)(CH2CH3)O-H

[0207] CH2=C(CH3)COO-(CH2CH2O)2-H

[0208] CH2=C(CH3)COO-(CH2CH2O)4-H

[0209] CH2=C(CH3)COO-(CH2CH2O)5-H

[0210] CH2=C(CH3)COO-(CH2CH2O)6-H

[0211] CH2=C(CH3)COO-(CH2CH2O)9-H

[0212] CH2=C(CH3)COO-(CH2CH2O)5-CH3

[0213] CH2=C(CH3)COO-(CH2CH2O)9-CH3

[0214] CH2=C(CH3)COO-(CH2CH2O) 23 -CH3

[0215] CH2=C(CH3)COO-(CH2CH2O) 90 -CH3

[0216] CH2=C(CH3)COO-(CH2CH(CH3)O)9-H

[0217] CH2=C(CH3)COO-(CH2CH(CH3)O)9-CH3

[0218] CH2=C(CH3)COO-(CH2CH(CH3)O) 12 -CH3

[0219] CH2=C(CH3)COO-(CH2CH2O)5-(CH2CH(CH3)O)2-H

[0220] CH2=C(CH3)COO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3

[0221] CH2=C(CH3)COO-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0222] CH2=C(CH3)COO-(CH2CH2O) 23 -OOC(CH3)C=CH2

[0223] CH2=C(CH3)COO-(CH2CH2O) 20 -(CH2CH(CH3)O)5-CH2-CH=CH2

[0224] CH2=CH-C(=O)-NH-CH2CH2O-H

[0225] CH2=CH-C(=O)-NH-CH2CH2CH2O-H

[0226] CH2=CH-C(=O)-NH-CH2CH(CH3)OH

[0227] CH2=CH-C(=O)-NH-CH(CH3)CH2O-H

[0228] CH2=CH-C(=O)-NH-CH2CH2CH2CH2O-H

[0229] CH2=CH-C(=O)-NH-CH2CH2CH(CH3)OH

[0230] CH2=CH-C(=O)-NH-CH2CH(CH3)CH2O-H

[0231] CH2=CH-C(=O)-NH-CH(CH3)CH2CH2O-H

[0232] CH2=CH-C(=O)-NH-CH2CH(CH2CH3)OH

[0233] CH2=CH-C(=O)-NH-CH2C(CH3)2O-H

[0234] CH2=CH-C(=O)-NH-CH(CH2CH3)CH2O-H

[0235] CH2=CH-C(=O)-NH-C(CH3)2CH2O-H

[0236] CH2=CH-C(=O)-NH-CH(CH3)CH(CH3)OH

[0237] CH2=CH-C(=O)-NH-C(CH3)(CH2CH3)OH

[0238] CH2=CH-C(=O)-NH-(CH2CH2O)2-H

[0239] CH2=CH-C(=O)-NH-(CH2CH2O)4-H

[0240] CH2=CH-C(=O)-NH-(CH2CH2O)5-H

[0241] CH2=CH-C(=O)-NH-(CH2CH2O)6-H

[0242] CH2=CH-C(=O)-NH-(CH2CH2O)9-H

[0243] CH2=CH-C(=O)-NH-(CH2CH2O)5-CH3

[0244] CH2=CH-C(=O)-NH-(CH2CH2O)9-CH3

[0245] CH2=CH-C(=O)-NH-(CH2CH2O) 23 -CH3

[0246] CH2=CH-C(=O)-NH-(CH2CH2O) 90 -CH3

[0247] CH2=CH-C(=O)-NH-(CH2CH(CH3)O)9-H

[0248] CH2=CH-C(=O)-NH-(CH2CH(CH3)O)9-CH3

[0249] CH2=CH-C(=O)-NH-(CH2CH(CH3)O) 12 -CH3

[0250] CH2=CH-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)2-H

[0251] CH2=CH-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3

[0252] CH2=CH-C(=O)-NH-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0253] CH2=C(CH3)-C(=O)-NH-CH2CH2O-H

[0254] CH2=C(CH3)-C(=O)-NH-CH2CH2CH2O-H

[0255] CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)OH

[0256] CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2O-H

[0257] CH2=C(CH3)-C(=O)-NH-CH2CH2CH2CH2O-H

[0258] CH2=C(CH3)-C(=O)-NH-CH2CH2CH(CH3)OH

[0259] CH2=C(CH3)-C(=O)-NH-CH2CH(CH3)CH2O-H

[0260] CH2=C(CH3)-C(=O)-NH-CH(CH3)CH2CH2O-H

[0261] CH2=C(CH3)-C(=O)-NH-CH2CH(CH2CH3)OH

[0262] CH2=C(CH3)-C(=O)-NH-CH2C(CH3)2O-H

[0263] CH2=C(CH3)-C(=O)-NH-CH(CH2CH3)CH2O-H

[0264] CH2=C(CH3)-C(=O)-NH-C(CH3)2CH2O-H

[0265] CH2=C(CH3)-C(=O)-NH-CH(CH3)CH(CH3)OH

[0266] CH2=C(CH3)-C(=O)-NH-C(CH3)(CH2CH3)OH

[0267] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)2-H

[0268] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)4-H

[0269] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-H

[0270] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)6-H

[0271] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-H

[0272] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-CH3

[0273] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)9-CH3

[0274] CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 23 -CH3

[0275] CH2=C(CH3)-C(=O)-NH-(CH2CH2O) 90 -CH3

[0276] CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O)9-H

[0277] CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O)9-CH3

[0278] CH2=C(CH3)-C(=O)-NH-(CH2CH(CH3)O) 12 -CH3

[0279] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)2-H

[0280] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3

[0281] CH2=C(CH3)-C(=O)-NH-(CH2CH2O)8-(CH2CH(CH3)O)6-CH2CH(C2H5)C4H9

[0282] As monomer (b), X 2 The monomer (b) is particularly preferably hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate or hydroxyethyl acrylamide.

[0283] [(c) Monomer containing an ion-donating group]

[0284] The hydrocarbon-containing polymer (1) may contain a monomer (c) containing an ion-providing group. 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 ion-providing group (particularly an acrylic monomer). The ion-providing group is an anion-providing group and / or a cation-providing group.

[0285] As the monomer with an anion providing group, a monomer with a carboxyl group, a sulfonic acid group or a phosphoric acid group can be enumerated. Specific examples of the monomer with an anion providing group include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinylsulfonic acid, (meth) allylsulfonic acid, styrenesulfonic acid, phosphoric acid (meth) acrylate, vinylbenzenesulfonic acid, acrylamide tert-butylsulfonic acid, or their salts.

[0286] Examples of the salt of the anion-donating group include alkali metal salts, alkaline earth metal salts, and ammonium salts, such as methylammonium salts, ethanolammonium salts, and triethanolammonium salts.

[0287] In monomers having cation-providing groups, examples of cation-providing groups include amino groups, preferably tertiary amino groups and quaternary amino groups. In tertiary amino groups, the two groups to which the nitrogen atom is bonded may be the same or different, and are preferably aliphatic groups having 1 to 5 carbon atoms (especially alkyl groups), aromatic groups having 6 to 20 carbon atoms (aryl groups), or aromatic aliphatic groups having 7 to 25 carbon atoms (especially aralkyl groups, such as benzyl (C6H5-CH2-)). In quaternary amino groups, the three groups to which the nitrogen atom is bonded may be the same or different, and are preferably aliphatic groups having 1 to 5 carbon atoms (especially alkyl groups), aromatic groups having 6 to 20 carbon atoms (aryl groups), or aromatic aliphatic groups having 7 to 25 carbon atoms (especially aralkyl groups, such as benzyl (C6H5-CH2-)). In tertiary amino groups and quaternary amino groups, the remaining group to which the nitrogen atom is bonded may have a carbon-carbon double bond. The cation-providing group may be in the form of a salt.

[0288] The cation-donating group serving as the salt is a salt with an acid (organic or inorganic). Preferred are organic acids, such as carboxylic acids having 1 to 20 carbon atoms (particularly monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid). Preferred are dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and salts thereof.

[0289] Specific examples of the monomer having a cation-providing group are as follows.

[0290] CH2=CHCOO-CH2CH2-N(CH3)2 and its salts (e.g. acetate)

[0291] CH2=CHCOO-CH2CH2-N(CH2CH3)2 and its salts (e.g. acetate)

[0292] CH2=C(CH3)COO-CH2CH2-N(CH3)2 and its salts (e.g. acetate)

[0293] CH2=C(CH3)COO-CH2CH2-N(CH2CH3)2 and its salts (e.g. acetate)

[0294] CH2=CHC(O)N(H)-CH2CH2CH2-N(CH3)2 and its salts (e.g. acetate)

[0295] CH2=CHCOO-CH2CH2-N(-CH3)(-CH2-C6H5) and its salts (e.g. acetate)

[0296] CH2=C(CH3)COO-CH2CH2-N(-CH2CH3)(-CH2-C6H5) and its salts (e.g. acetate)

[0297] CH2=CHCOO-CH2CH2-N + (CH3)3Cl -

[0298] CH2=CHCOO-CH2CH2-N + (-CH3)2(-CH2-C6H5)Cl -

[0299] CH2=C(CH3)COO-CH2CH2-N + (CH3)3Cl -

[0300] CH2=CHCOO-CH2CH(OH)CH2-N + (CH3)3Cl -

[0301] CH2=C(CH3)COO-CH2CH(OH)CH2-N + (CH3)3Cl -

[0302] CH2=C(CH3)COO-CH2CH(OH)CH2-N + (-CH2CH3)2(-CH2-C6H5)Cl -

[0303] CH2=C(CH3)COO-CH2CH2-N + (CH3)3Br -

[0304] CH2=C(CH3)COO-CH2CH2-N + (CH3)3I -

[0305] CH2=C(CH3)COO-CH2CH2-N + (CH3)3O - SO3CH3

[0306] CH2=C(CH3)COO-CH2CH2-N + (CH3)(-CH2-C6H5)2Br -

[0307] As the ion-donating group-containing monomer (c), methacrylic acid, acrylic acid, or dimethylaminoethyl methacrylate is preferred, and methacrylic acid or dimethylaminoethyl methacrylate is more preferred.

[0308] [(d) Other monomers]

[0309] The hydrocarbon-containing polymer (1) may have repeating units derived from monomers other than the monomers (a) to (c). Examples of other monomers include halogenated olefin monomers and crosslinking monomers.

[0310] (Halogenated olefin monomer)

[0311] The hydrocarbon-containing polymer (1) may have repeating units derived from a halogenated olefin monomer. The halogenated olefin monomer preferably does not have a fluorine atom. The halogenated olefin monomer is preferably an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms, or iodine atoms. The halogenated olefin monomer is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms and having 1 to 5 chlorine atoms. Preferred specific examples of the halogenated olefin monomer include: vinyl halides, such as vinyl chloride, vinyl bromide, and vinyl iodide; and vinylidene halides, such as vinylidene chloride, vinylidene bromide, and vinylidene iodide. Vinyl chloride is preferred because it improves water repellency (particularly water repellency durability). The presence of repeating units derived from a halogenated olefin monomer improves the washing durability provided by the hydrocarbon-containing polymer (1).

[0312] (cross-linking monomer)

[0313] In the hydrocarbon-containing polymer (1), the crosslinking monomer has at least two reactive groups and / or ethylenically unsaturated double bonds (preferably (meth)acrylate groups), and the crosslinking monomer (d) may be a monomer containing no fluorine atoms or a compound containing no fluorine atoms. The crosslinking 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 the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, and a carboxyl group.

[0314] The crosslinking monomer may be a mono(meth)acrylate, a di(meth)acrylate, or a mono(meth)acrylamide having a reactive group. Alternatively, the crosslinking monomer may be a di(meth)acrylate.

[0315] An example of a crosslinking monomer is a vinyl monomer having a hydroxyl group. Examples of the crosslinking monomer 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.

[0316] (Cyclic hydrocarbon group-containing monomer)

[0317] The hydrocarbon-containing polymer (1) may contain 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.

[0318] The cyclic hydrocarbon group-containing monomer preferably has a (meth)acrylic group as an ethylenically unsaturated double bond, and may have, for example, a (meth)acrylate group or a (meth)acrylamide group as an ethylenically unsaturated double bond.

[0319] The cyclic hydrocarbon group may be alicyclic or aromatic, preferably alicyclic. The cyclic hydrocarbon group may be saturated or unsaturated, preferably saturated. The cyclic hydrocarbon group may be a monocyclic group, a polycyclic group, or a bridged ring group, preferably a bridged ring group. The cyclic hydrocarbon group may have a chain group (e.g., a straight-chain or branched hydrocarbon group).

[0320] 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.

[0321] Specific examples of cyclic hydrocarbon groups include cyclohexyl, tert-butylcyclohexyl, adamantyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, bornyl, isobornyl, norbornyl, dicyclopentyl, dicyclopentenyl, benzyl, phenyl, naphthyl, 2-tert-butylphenyl, residues obtained by removing one or more hydrogen atoms from these groups (for example, cyclohexylene, adamantylene, phenylene, naphthylene, etc.), and groups which are substitutes thereof.

[0322] Specific examples of the cyclic hydrocarbon group-containing monomer include cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, compounds obtained by replacing these acrylates with acrylamide, styrene, α-methylstyrene, p-methylstyrene, etc. These monomers can be used alone or in combination of two or more.

[0323] Other monomers (d) include, but are not limited to, acrylonitrile, organosiloxane-containing (meth)acrylates, short-chain alkyl (meth)acrylates, vinyl acetate, and vinyl alkyl ethers. Other monomers (d) may be used alone or in combination of two or more.

[0324] [Composition of polymer (1)]

[0325] The combination of monomers constituting the repeating unit of the hydrocarbon-containing polymer (1) is, for example, as follows.

[0326] Monomer (a)

[0327] Monomer (a) + monomer (b)

[0328] Monomer (a) + monomer (c)

[0329] Monomer (a) + monomer (b) + monomer (c)

[0330] Monomer (a) + monomer (b) + monomer (d)

[0331] Monomer (a) + monomer (c) + monomer (d)

[0332] Monomer (a) + monomer (b) + monomer (c) + monomer (d)

[0333] The combination of monomers constituting the repeating unit of the polymer is preferably "monomer (a) + monomer (b) + monomer (c)".

[0334] The amount of the repeating units formed from monomer (a) (repeating units (a)) relative to the hydrocarbon-containing polymer (or relative to the total of the repeating units (a) and the repeating units (b)) may be 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and may 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.

[0335] The amount of the repeating units formed from monomer (b) (repeating units (b)) relative to the hydrocarbon-containing polymer (or relative to the total of the repeating units (a) and the repeating units (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, and may 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.

[0336] The amount of the repeating units formed from the monomer (c) (repeating units (c)) relative to the hydrocarbon-containing polymer (or relative to the total of the repeating units (a) and the repeating units (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, and may 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.

[0337] The amount of the repeating units formed from monomer (d) (repeating units (d)) relative to the hydrocarbon-containing polymer (or relative to the total of the repeating units (a) and the repeating units (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, and may 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.

[0338] [Polymerization method]

[0339] The hydrocarbon-containing polymer (1) can be produced by a known polymerization method, and the polymerization reaction conditions can be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization.

[0340] In solution polymerization, a method can be employed in which the monomers are dissolved in an organic solvent in the presence of a polymerization initiator, the solvent is nitrogen purged, and then heated and stirred at 30 to 120° C. for 1 to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The amount of the polymerization initiator used is 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, per 100 parts by weight of the monomers.

[0341] The organic solvent is a substance that is inactive toward the monomers but can dissolve them, and may be, for example, an ester (e.g., an ester having 2 to 40 carbon atoms, specifically ethyl acetate and butyl acetate), a ketone (e.g., a ketone having 2 to 40 carbon atoms, specifically methyl ethyl ketone, diisobutyl ketone, and methyl isobutyl ketone), or an alcohol (e.g., an alcohol having 1 to 40 carbon atoms, specifically ethanol, butanol, and isopropanol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropanol, 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 amount of the organic solvent used is in the range of 10 to 3000 parts by weight, for example, 50 to 2000 parts by weight, based on 100 parts by weight of the total monomers.

[0342] In emulsion polymerization, the monomers are emulsified in water in the presence of a polymerization initiator and an emulsifier, nitrogen exchange is performed, and then polymerization is carried out by stirring at 50-80°C for 1-20 hours. Examples of polymerization initiators include water-soluble substances 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; and oil-soluble substances such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The amount of polymerization initiator used is 0.01-10 parts by weight per 100 parts by weight of the monomers.

[0343] In order to obtain a polymer aqueous dispersion with excellent shelf stability, it is preferred to use an emulsifying device that can provide strong crushing energy, such as a high-pressure homogenizer or an ultrasonic homogenizer, to micronize the monomers in water and polymerize them. In addition, various anionic, cationic, or nonionic emulsifiers can be used as emulsifiers, and the amount used is in the range of 0.5 to 20 parts by weight relative to 100 parts by weight of the monomers. Anionic and / or nonionic and / or cationic emulsifiers are preferably used. In the case where the monomers are not completely compatible, it is preferred to add a compatibilizer that fully compatibilizes these monomers, such as a water-soluble organic solvent or a low molecular weight monomer. By adding a compatibilizer, the emulsification and copolymerization properties can be improved.

[0344] As the water-soluble organic solvent, the above-mentioned organic solvents can be used. Examples include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, and ethanol. The amount used is 1 to 50 parts by weight, for example, 10 to 40 parts by weight, relative to 100 parts by weight of water. Furthermore, as low-molecular-weight monomers, methyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate can be used. The amount used is 1 to 50 parts by weight, for example, 10 to 40 parts by weight, relative to 100 parts by weight of the total monomer amount.

[0345] A chain transfer agent may be used during polymerization to adjust the molecular weight of the polymer depending on the amount of chain transfer agent used. Examples of chain transfer agents include thiol group-containing compounds (particularly alkyl mercaptans (e.g., those having 1 to 40 carbon atoms)) such as lauryl mercaptan, thioglycol, and thioglycerol, and inorganic salts such as sodium hypophosphite and sodium bisulfite. The amount of chain transfer agent used is in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, based on 100 parts by weight of the total monomer amount.

[0346] [Amount of hydrocarbon group-containing polymer]

[0347] In the oil-resistant agent, the amount of the hydrocarbon group-containing polymer 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, or 30% by weight or more, and may be 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. The hydrocarbon group-containing polymer itself may be used as the oil-resistant agent.

[0348] 〔(2) Water-soluble polymer〕

[0349] The oil-proofing agent of the present invention contains a water-soluble polymer (2).

[0350] The weight average molecular weight of the water-soluble polymer (2) may be 1,000 or more, 3,000 or more, 5,000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 3,000,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 5,000 or less, or 3,000 or less.

[0351] The water-soluble polymer (2) may be hydrophobically modified. The hydrophobically modified water-soluble polymer (2) may refer to a compound in which 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 six or more, ten or more, twelve or more, fifteen or more, or eighteen or more carbon atoms) are modified.

[0352] The water-soluble polymer (2) may be a polycarboxylic acid. The water-soluble polymer (2) may also have other acidic functional groups.

[0353] Examples of the water-soluble polymer (2) include polysaccharides, synthetic polyols, polyamines, polyamides, polyethers, and the like. Preferred examples include polysaccharides and synthetic polyols.

[0354] The water-soluble polymer (2) is preferably a polyol, particularly 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 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.

[0355] The polysaccharide may be an acidic polysaccharide, a neutral polysaccharide and / or an alkaline polysaccharide, preferably a neutral polysaccharide.

[0356] Acidic polysaccharides are generally polysaccharides having carboxyl groups (-COOH) and the like. Specific examples of acidic polysaccharides include carrageenan, pectin, gum arabic, xanthan gum, gellan gum, agar, and tragacanth gum. Neutral polysaccharides are electrically neutral polysaccharides. Specific examples of neutral polysaccharides include tamarind gum, guar gum, locust bean gum, starch, and pullulan. Alkaline polysaccharides are polysaccharides having amino groups (-NH2) and the like. A specific example of alkaline polysaccharides includes chitosan. Specific examples of polysaccharides include starch, xanthan gum, karaya gum, Brunei gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, and pullulan.

[0357] As polysaccharides, starch is preferred. Starch may be unmodified starch or modified starch. Starch may be modified starch that has been subjected to at least one of esterification modification, hydrophobization modification, etherification modification, oxidation modification, alkali modification, enzyme modification, and bleaching modification. Examples of modified starch include acylated adipic acid cross-linked starch, acylated oxidized starch, acylated phosphate cross-linked starch, alkenyl succinate-esterified starch, acetic starch, oxidized starch, hydroxyalkylated starch (the number of carbon atoms in the alkyl group is 2 to 40 or 2 to 10, particularly 2 or 3), hydroxyalkylated phosphate cross-linked starch (the number of carbon atoms in the alkyl group is 2 to 40 or 2 to 10, particularly 2 or 3), phosphate cross-linked starch, phosphated starch, monophosphate cross-linked starch, acid-modified starch, alkali-treated starch, enzyme-treated starch, bleached starch, and cationic starch (quaternized starch). Dextrins obtained by chemically or enzymatically reducing starch molecular weight may also be mentioned. Starch may be alpha-starch. Alpha-starch refers to starch in which the hydrogen bonds between sugar chains in the starch are broken and the sugar chains are free.

[0358] Synthetic polyols are synthetic polyols having multiple (e.g., 10 or more, 50 or more, 100 or more, or 500 or more) hydroxyl groups in the molecule, preferably polyglycerol, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer, hydroxybutyl (meth)acrylate polymer, polyvinyl alcohol, etc., and particularly polyvinyl alcohol can be used.

[0359] Specific examples of the water-soluble polymer (2) include: polysaccharides such as starch, pullulan, amylose, cellulose, cellulose derivatives, carrageenan, guar gum, chitin, chitosan, locust bean gum, κ-carrageenan, ι-carrageenan, isomalt dextrin, gellan gum, tamarind gum, etc.; synthetic polymers such as polyglycerol, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer, hydroxybutyl (meth)acrylate polymer, polyvinyl alcohol, etc. Polyols; polyamines such as polyethyleneimine, polyethyleneamine, and polyallylamine; polyamides such as polyvinylpyrrolidone, polyacrylamide, poly(N,N-dimethylacrylamide), poly(N-vinylacetamide), poly-N-propyleneacrylamide, polyoxazolines (e.g., poly(2-methyl-2-oxazoline), poly(2-ethyl-2-oxazoline), poly(2-propyl-2-oxazoline)), and polyamideimide; polyethers such as polyethylene glycol, polypropylene glycol, and polyvinyl methyl ether; and the like.

[0360] [quantity]

[0361] The amount of the water-soluble polymer (2) relative to 100 parts by weight of the hydrocarbon-containing polymer (1) 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, and may 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, or 300 parts by weight or less.

[0362] [(3) Polycarboxylic acid]

[0363] The oil-proofing agent of the present invention contains a polycarboxylic acid (3). The polycarboxylic acid (3) contains two or more carboxylic acids in the molecule. The oil-proofing agent of the present invention contains a polycarboxylic acid (3), which improves oil resistance and reduces oil stains from creases. Furthermore, blistering during the treatment of the oil-proofing agent can be suppressed.

[0364] The weight average molecular weight of the polycarboxylic acid (3) may be 100 or more, 150 or more, 200 or more, or 250 or more, and may be 1,000,000 or less, 750,000 or less, 500,000 or less, 3,000,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 5,000 or less, 3,000 or less, 2,000 or less, 1,000 or less, 750 or less, 500 or less, or 300 or less. The polycarboxylic acid is preferably a low molecular weight (e.g., a molecular weight of 1,000 or less).

[0365] The polycarboxylic acid (3) may be a natural product, a synthetic product or a partially synthetic product.

[0366] Examples of the polycarboxylic acid include aromatic polycarboxylic acids, aliphatic polycarboxylic acids, hydroxy polycarboxylic acids, and high molecular weight polycarboxylic acids. Preferred examples include hydroxy polycarboxylic acids.

[0367] Specific examples of polycarboxylic acids (3) include aromatic polycarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, trimesic acid, and pyromellitic acid; aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, oxalic acid, fumaric acid, maleic acid, and tetrahydrophthalic acid; hydroxy polycarboxylic acids having hydroxy groups in the molecule such as citric acid, malic acid, tartaric acid, and hydroxymalonic acid; and polymeric polycarboxylic acids such as poly(meth)acrylic acid, alginic acid, polycarboxylic acid, and hyaluronic acid.

[0368] [quantity]

[0369] The amount of the polycarboxylic acid (3) relative to 100 parts by weight of the hydrocarbon-containing polymer (1) may be 10 parts by weight or more, 30 parts by weight or more, 60 parts by weight or more, 90 parts by weight or more, 120 parts by weight or more, 150 parts by weight or more, 180 parts by weight or more, 200 parts by weight or more, or 250 parts by weight or more, and may be 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, 400 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, or 100 parts by weight or less.

[0370] Dispersant

[0371] The oil-proofing agent of the present invention may or may not contain a dispersant. In particular, when the monomer (c) is present, the water dispersibility of the hydrocarbon-containing polymer (1) is improved, and the amount of the dispersant can be reduced.

[0372] The dispersant may be at least one selected from an organic dispersant and an inorganic dispersant. The dispersant may be non-anionic, and may be at least one selected from a nonionic dispersant, a cationic dispersant, an amphoteric dispersant, and an inorganic dispersant. The oil-resistant agent may not contain an anionic dispersant. The dispersant may contain a dispersant other than a fatty acid ester.

[0373] As the dispersant, an organic dispersant and an inorganic dispersant may be used separately, or a combination of an organic dispersant and an inorganic dispersant may be used.

[0374] As the dispersant, an organic dispersant can be used. Organic dispersants can be divided into nonionic dispersants, anionic dispersants, cationic dispersants, and amphoteric dispersants. Organic dispersants refer to surfactants.

[0375] The dispersant may be a non-fluorine dispersant.

[0376] [Nonionic dispersant]

[0377] The dispersant may contain a nonionic dispersant. The nonionic dispersant may be a nonionic surfactant.

[0378] The nonionic dispersant may be a low molecular weight or a high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2,500 or less, 1,000 or less, 750 or less, or 250 or less.

[0379] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols and amine oxides.

[0380] Examples of ethers include compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0381] Examples of esters include esters of alcohols and fatty acids. Examples of alcohols include monovalent to hexavalent (particularly divalent to pentavalent) alcohols (e.g., aliphatic alcohols) having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms). Examples of fatty acids include saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0382] Examples of ester ethers include compounds formed by adding an alkylene oxide (particularly ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols include monovalent to hexavalent (particularly divalent to pentavalent) alcohols (e.g., aliphatic alcohols) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). Examples of fatty acids include saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0383] Examples of alkanolamides are formed from fatty acids and alkanolamines. Alkanolamides may be monoalkanolamides or dialkanolamides. Examples of fatty acids include 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, and having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0384] The polyol may be a divalent to pentavalent alcohol having 10 to 30 carbon atoms.

[0385] The amine oxide may be an oxide of an amine (for example, having 5 to 50 carbon atoms) (secondary amine or preferably tertiary amine).

[0386] The nonionic dispersant is preferably a nonionic dispersant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms of the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic dispersant is usually preferably 2 to 100.

[0387] The nonionic dispersant is selected from ethers, esters, ester ethers, alkanolamides, polyols and amine oxides, and is preferably a nonionic dispersant having an oxyalkylene group.

[0388] The nonionic dispersant may be an alkylene oxide adduct of a linear and / or branched aliphatic (saturated and / or unsaturated) group, a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of an acetylene glycol, etc. Among these, preferably, the structure of the alkylene oxide adduct portion and the polyalkylene glycol portion is polyoxyethylene (POE), polyoxypropylene (POP), or a POE / POP copolymer (which may be a random copolymer or a block copolymer).

[0389] Furthermore, the nonionic dispersant preferably has a structure without any aromatic group.

[0390] The nonionic dispersant can be of the formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 The compound shown.

[0391] [Where R 1 is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an acyl group,

[0392] Each R 2 are independent, may be the same or different, and are alkylene groups having 3 or more carbon atoms (e.g., 3 to 10),

[0393] R 3 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, and p is a number greater than 2.

[0394] q is a number greater than or equal to 0 or 1.]

[0395] R 1 The number of carbon atoms is preferably 8 to 20, particularly 10 to 18. 1 Preferred specific examples include lauryl, tridecyl, and oleyl.

[0396] R 2 Examples of propylene and butylene are propylene and butylene.

[0397] In the nonionic dispersant, p may be a number greater than 3 (e.g., 5 to 200). q may be a number greater than 2 (e.g., 5 to 200). That is, -(R 2 O) q -Polyoxyalkylene chains can be formed.

[0398] The nonionic dispersant may be a polyoxyethylene alkylene alkyl ether having a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) at the center. Examples of the hydrophobic oxyalkylene chain include oxypropylene chains, oxybutylene chains, and styrene chains, with oxypropylene chains being preferred.

[0399] Specific examples of nonionic dispersants include: ethylene oxide and hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkane (C 12 -C 16 ) thiol, sorbitan monofatty acid (C7-C 19 ) or alkyl (C 12 -C 18) condensation products of amines, sorbitan fatty acid esters, glycerol fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, lecithin derivatives, etc.

[0400] The proportion of the polyoxyethylene block 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 dispersant (copolymer).

[0401] The average molecular weight of the nonionic dispersant is generally 300 to 5,000, for example, 500 to 3,000.

[0402] The nonionic dispersant may be a single species or a mixture of two or more species. The nonionic dispersant may be a mixture of a compound having an HLB (hydrophilicity-hydrophobicity balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or greater.

[0403] [Cationic dispersant]

[0404] The dispersant may contain a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 10000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The cationic dispersant may be a compound without an amide group.

[0405] Cationic dispersants may be low molecular weight or high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2,500 or less, 1,000 or less, 750 or less, or 250 or less.

[0406] Cationic dispersants may be amine salts, quaternary ammonium salts, or ethylene oxide addition type ammonium salts. Specific examples of cationic dispersants, while not particularly limited, include amine salt dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines; and quaternary ammonium salt dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, and benzalkonium chloride.

[0407] Preferred examples of cationic dispersants include R 21 -N + (-R 22 )(-R 23 )(-R 24 )X － The compound shown.

[0408] [Where R 21 、R 22 、R 23 and R 24 is a hydrocarbon group having 1 to 40 carbon atoms,

[0409] X is an anionic group.]

[0410] R 21 、R 22 、R 23 and -R 24 Specific examples of are alkyl groups (eg, methyl, butyl, stearyl, palmityl). Specific examples of X are halogen (eg, chlorine) and acid (eg, hydrochloric acid, acetic acid).

[0411] The cationic dispersant is particularly preferably a monoalkyltrimethylammonium salt (the alkyl group has 4 to 40 carbon atoms).

[0412] The cationic dispersant is preferably an ammonium salt. The cationic dispersant may be of the formula: R 1 p -N + R 2 q X － The ammonium salts shown.

[0413] [Where R 1 C12 or above (e.g. C 12 ~C 50 ) a linear and / or branched aliphatic (saturated and / or unsaturated) group,

[0414] R 2 is H or a C1-4 alkyl group, benzyl, or polyoxyethylene (the number of oxyethylene groups is, for example, 1 (particularly 2, especially 3) to 50) (particularly preferably CH3 or C2H5),

[0415] X is a halogen atom (for example, ), a C1-C4 fatty acid salt group,

[0416] p is 1 or 2, q is 2 or 3, and p+q=4.]

[0417] R 1 The number of carbon atoms in can be 12 to 50, for example, 12 to 30.

[0418] Specific examples of cationic dispersants include: dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydroxypolyoxyethylene)ammonium chloride, benzyldodecyldi(hydroxypolyoxyethylene)ammonium chloride, and N-[2-(diethylamino)ethyl]oleamide hydrochloride.

[0419] [Anionic dispersants]

[0420] The dispersant may contain an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant may not contain an anionic dispersant.

[0421] Anionic dispersants may be low molecular weight or high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2,500 or less, 1,000 or less, 750 or less, or 250 or less.

[0422] Examples of anionic dispersants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-fatty sulfonates, N-acylamino acid type dispersants, phosphoric acid monoester or diester type dispersants and sulfosuccinates.

[0423] [Amphoteric dispersants]

[0424] The dispersant may contain an amphoteric dispersant, which may be an amphoteric surfactant.

[0425] The amphoteric dispersant may be a low molecular weight dispersant or a high molecular weight dispersant. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2,500 or less, 1,000 or less, 750 or less, or 250 or less.

[0426] Examples of the amphoteric dispersant include alanines, imidazolinium betaines, amidobetaines, betaine acetate, and the like. Specific examples include lauryl betaine, stearyl betaine, laurylcarboxymethylhydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, and fatty acid amidopropyldimethylaminoacetic acid betaine.

[0427] [Inorganic dispersants]

[0428] The dispersant may contain an inorganic dispersant.

[0429] The average primary particle size of the inorganic dispersant may be 5 nm or more, 30 nm or more, 100 nm or more, 1 μm or more, 10 μm or more, or 25 μm or more, and may be 100 μm or less, 50 μm or less, 10 μm or less, 1 μm or less, 500 nm or less, or 300 nm or less. The average primary particle size can be measured, for example, by observation using a microscope (a scanning electron microscope or a transmission electron microscope).

[0430] Examples of inorganic dispersants include: polyvalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and hydroxyapatite; carbonates such as calcium carbonate and magnesium carbonate; silicates such as calcium metasilicate; sulfates such as calcium sulfate and barium sulfate; hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

[0431] [quantity]

[0432] The amount of the dispersant relative to 100 parts by weight of the hydrocarbon-containing polymer (1) may be 0.01 parts by weight or more, 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, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less.

[0433] Liquid medium

[0434] The oil-resistant agent of the present invention may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The oil-resistant agent may be a dispersion or a solution. The oil-resistant agent of the present invention may be water-dispersible and may contain at least water. The oil-resistant agent may be combined with a dispersion medium and used as a treatment liquid, for example.

[0435] 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 a compound having at least one hydroxyl group (e.g., polyols such as alcohols and glycol solvents, ethers of polyols (e.g., monoethers), etc.). These may be used alone or in combination of two or more.

[0436] [quantity]

[0437] The amount of the liquid medium relative to 1 part by weight of the hydrocarbon-containing polymer (1) 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, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 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.

[0438] The amount of water relative to 1 part by weight of the hydrocarbon-containing polymer (1) 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, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 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.

[0439] The amount of the organic solvent relative to 1 part by weight of the hydrocarbon-containing polymer (1) 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, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 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.

[0440] Silicone

[0441] The oil-proofing agent of the present invention may contain silicone (polyorganosiloxane). By containing silicone, in addition to good liquid repellency, it is possible to achieve both good feel and durability.

[0442] As the organosilicon, known organosilicon can be used. Examples of organosilicon include polydimethylsiloxane, modified organosilicon (amino-modified, epoxy-modified organosilicon, carboxyl-modified organosilicon, methyl hydrogen organosilicon, etc.). The organosilicon may be a waxy organosilicon wax. These may be used alone or in combination of two or more.

[0443] The weight average molecular weight of the silicone may be 1,000 or more, 10,000 or more, or 50,000 or more, and may be 500,000 or less, 2,500,000 or less, 100,000 or less, or 50,000 or less.

[0444] [quantity]

[0445] The amount of the organosilicon relative to 100 parts by weight of the hydrocarbon-containing polymer (1) 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, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 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.

[0446] 〔wax〕

[0447] The oil-proofing agent of the present invention may contain wax. By containing wax, it is possible to impart good liquid repellency to the substrate.

[0448] As the example of wax, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax, polypropylene wax etc.), oxidized polyolefin wax, organosilicon wax, animal and plant wax and mineral wax etc. can be enumerated.Preferred paraffin wax.The specific example of the compound constituting the wax has normal alkane (for example tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontan, undecane, dotriacontan, tritriacontan, tetratriacontan, pentacontan, hexacosane), normal olefin (for example 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosane, triacontan, undecane, dotriacontan, tritriacontan, tetratriacontan, pentacontan, hexacosane). The number of carbon atoms in the compound 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 or 300 to 1000. These may be used alone or in combination of two or more.

[0449] 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 be 200°C or lower, 150°C or lower, 130°C or lower, 120°C or lower, 110°C or lower, 100°C or lower, 80°C or lower, or 50°C or lower, preferably 120°C or lower. The melting point of the wax is measured in accordance with JIS K 2235-1991.

[0450] [quantity]

[0451] The amount of the wax relative to 100 parts by weight of the hydrocarbon-containing polymer (1) 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, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 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.

[0452] [Organic acid]

[0453] The oil-resistant agent of the present invention may contain an organic acid. As the organic acid, a known organic acid different from the above-mentioned polycarboxylic acid (3) can be used. As the organic acid, carboxylic acid, sulfonic acid, sulfinic acid, etc. are preferably listed, and carboxylic acid is particularly preferred. The carboxylic acid may be a monocarboxylic acid. As the carboxylic acid, formic acid, acetic acid, propionic acid, butyric acid, etc., for example, acetic acid, can be listed. In the present invention, the organic acid may be used alone or in combination of two or more. For example, formic acid and acetic acid can be used in combination. By containing polycarboxylic acid (3) and an organic acid (especially carboxylic acid), foaming during treatment of the oil-resistant agent can be suppressed.

[0454] [quantity]

[0455] The amount of the organic acid relative to 100 parts by weight of the hydrocarbon-containing polymer (1) 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, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 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. The amount of the organic acid and / or polycarboxylic acid may be adjusted so that the pH of the oil-proofing agent (treatment liquid) is 1 to 10, 3 to 10, for example, 5 to 9, and particularly 6 to 8. The oil-proofing agent may be acidic (pH 7 or less, 6.5 or less, 6 or less, 5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, or 2 or less, and may be 0.5 or more, 1 or more, 1.5 or more, or 2.0 or more).

[0456] [Curing agent]

[0457] The oil-proofing agent of the present invention may contain a curing agent (an active hydrogen-reactive compound or an active hydrogen-containing compound).

[0458] The curing agent (crosslinking agent) in the oil-resistant agent can effectively cure the hydrocarbon-containing polymer (1). The curing agent can 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 active hydrogen-reactive compounds include isocyanate compounds, epoxy compounds, chloromethyl-containing compounds, carboxyl-containing compounds, and hydrazide compounds. Examples of active hydrogen-containing compounds include hydroxyl-containing compounds, amino-containing compounds, carboxyl-containing compounds, keto-containing compounds, hydrazide compounds, and melamine compounds.

[0459] The curing agent may contain an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. A polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound acts as a crosslinking agent. Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (e.g., a blocked polyisocyanate compound). The blocked isocyanate compound is a compound in which the isocyanate group of the isocyanate compound is masked by a blocking agent to inhibit the reaction.

[0460] Examples of aliphatic polyisocyanates include 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, 2,6-diisocyanato Aliphatic diisocyanates of methyl hexanoate 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, etc. These can be used alone or in combination of two or more.

[0461] 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), and 1,3,5-triisocyanatocyclohexane. These can be used alone or in combination of two or more.

[0462] 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-phenylenediisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylphenylenediisocyanate) or a mixture thereof, and 1,3,5-triisocyanatomethylbenzene. These can be used alone or in combination of two or more.

[0463] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, triphenylmethane-4,4',4"-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These can be used alone or in combination of two or more.

[0464] Examples of polyisocyanate derivatives include various derivatives of the above-mentioned polyisocyanate compounds, such as dimers, trimers, biuret, allophanate, carbodiimide, uretdione, uretimine, isocyanurate, and iminooxadiazinedione. These can be used alone or in combination of two or more.

[0465] These polyisocyanates may be used alone or in combination of two or more.

[0466] As the polyisocyanate compound, a compound in which the isocyanate groups of the polyisocyanate compound are blocked by a blocking agent, i.e., a blocked polyisocyanate compound (blocked isocyanate) is preferably used. Blocked polyisocyanate compounds are preferably used because they are relatively stable in solution and can be used in the same solution as the oil-resistant agent.

[0467] A blocking agent is a substance that blocks the chains of free isocyanate groups. When the blocked polyisocyanate compound is heated to, for example, 100°C or higher, such as 130°C or higher, the isocyanate groups are regenerated, allowing them to readily react with hydroxyl groups. Examples of blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, and oxime compounds. These polyisocyanate compounds can be used alone or in combination of two or more.

[0468] Epoxy compounds are compounds having an epoxy group. Examples of epoxy compounds include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether, and sorbitol polyglycidyl ether.

[0469] The chloromethyl group-containing compound is a compound having a chloromethyl group. Examples of the chloromethyl group-containing compound include chloromethyl polystyrene and the like.

[0470] The carboxyl group-containing compound is a compound having a carboxyl group. Examples of the carboxyl group-containing compound include (poly)acrylic acid, (poly)methacrylic acid, and the like.

[0471] Specific examples of the ketone group-containing compound include (poly)diacetone acrylamide and diacetone alcohol.

[0472] Specific examples of the hydrazide compound include hydrazine, carbohydrazide, adipic acid hydrazide, and the like.

[0473] Specific examples of the melamine compound include melamine resins and methyl etherified melamine resins.

[0474] [quantity]

[0475] The amount of the curing agent relative to 100 parts by weight of the hydrocarbon-containing polymer (1) 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, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 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.

[0476] [Other ingredients]

[0477] The oil-proofing agent may contain other ingredients in addition to the above-mentioned ingredients. Examples of other ingredients include polysaccharides, paper strengthening agents, coagulants, retention aids, coagulants, binder resins, anti-slip agents, sizing agents, paper strengthening agents, fillers, antistatic agents, preservatives, UV absorbers, antibacterial agents, deodorants, and fragrances. These may be used alone or in combination of two or more.

[0478] In addition to the above-mentioned components, other components may be added, such as water- and / or oil-repellents, water- and / or oil-resistant agents, dispersants, feel modifiers, softeners, flame retardants, paint fixatives, wrinkle-proofing agents, drying speed modifiers, crosslinking agents, film-forming aids, solubilizers, antifreeze agents, viscosity modifiers, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, penetrants, defoamers, shrinkage-proofing agents, anti-wrinkle agents for washing, shape-retaining agents, drape-retaining agents, ironing-enhancing agents, whitening agents, whitening agents, fabric softening clay, anti-migration agents such as polyvinyl pyrrolidone, polymer dispersants, soil release agents, scum dispersants, disodium 4,4-bis(2-sulfonylphenyl)biphenyl (TINOPAL manufactured by Ciba Specialty Chemicals) CBS-X) and other fluorescent brighteners, dye fixing agents, anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine, bleaching agents, fiber surface modifiers such as cellulase, amylase, protease, lipase, cutinase and other enzymes, foam inhibitors, silk protein powder as an additive that can impart the feel and functions of silk such as moisture absorption and release properties, surface-modified products or emulsified dispersions thereof (for example, K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk solution (Ue Mao), SILKGEN G Soluble S (Ichimaru Pharma Co., Ltd.)), anti-fouling agents (for example, nonionic polymer compounds composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (for example, FR627 manufactured by Huying Chemical Industry Co., Ltd.), CLARIANT These may be used alone or in combination of two or more.

[0479] [Paper strength enhancer, coagulant, retention aid or coagulant]

[0480] Examples of paper strengthening agents, coagulants, retention aids, or coagulants include styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichlorides and polyalkylene polyamines, dicyandiamide-aldehyde condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0481] [Sizing agent]

[0482] Examples of sizing agents include cellulose-reactive sizing agents, rosin-based sizing agents such as rosin-based soaps, rosin-based emulsions / dispersions, cellulose-reactive sizing agents, emulsions / dispersions of acid anhydrides such as alkyl and alkenyl succinic anhydrides (ASA), alkenyl and alkyl ketene dimers (AKD) and polymers, and anionic, cationic and amphoteric polymers of ethylenically unsaturated monomers, such as copolymers of styrene and acrylates.

[0483] [Antistatic agent]

[0484] Examples of antistatic agents include: quaternary ammonium salts, pyridinium salts, and cationic antistatic agents having cationic functional groups such as primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfates, phosphonates, and phosphates; amphoteric antistatic agents such as alkyl betaines and their derivatives, imidazolines and their derivatives, and alanine and its derivatives; and nonionic antistatic agents such as amino alcohols and their derivatives, glycerol and its derivatives, and polyethylene glycol and its derivatives. Ion-conductive polymers obtained by polymerizing or copolymerizing these cationic, anionic, and zwitterionic monomers having ion-conductive groups may also be used. These may be used alone or in combination of two or more.

[0485] [preservative]

[0486] Preservatives are primarily used to enhance antiseptic and bactericidal properties and ensure long-term preservation. Examples of preservatives include isothiazolinone-based organic sulfur compounds, benzisothiazolinone-based organic sulfur compounds, benzoic acids, and 2-bromo-2-nitro-1,3-propanediol.

[0487] [Ultraviolet absorber]

[0488] Ultraviolet absorbers are agents that protect against ultraviolet rays. They absorb ultraviolet rays and convert them into infrared or visible light for release. Examples of ultraviolet absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, and 4-tert-butyl-4'-methoxybenzoylmethane.

[0489] [Antibacterial agents]

[0490] Antimicrobial agents are ingredients that inhibit the growth of bacteria on fibers and the generation of odors from microbial degradation products. Examples of antimicrobial agents include cationic fungicides such as quaternary ammonium salts, bis(2-pyridylthio-1-oxide)zinc, polyhexamethylene biguanide hydrochloride, 8-oxoquinoline, and polylysine.

[0491] [Deodorant]

[0492] Examples of deodorants include highly branched cyclodextrin (Cluster Dextrin), methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, and aminocarboxylic acid-based metal complexes (zinc complex of trisodium methylglycine diacetate described in International Publication No. 2012 / 090580).

[0493] [quantity]

[0494] The amount of each or the total amount of other components relative to 100 parts by weight of the hydrocarbon-containing polymer (1) 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, 75 parts by weight or more, or 100 parts by weight or more, and may be 1000 parts by weight or less, 500 parts by weight or less, 300 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.

[0495] <Method for producing treated fiber or paper products>

[0496] The method for producing a product treated with an oil-resistant agent in the present invention includes a step of treating a substrate with the above-mentioned oil-resistant agent.

[0497] "Treatment" refers to applying the oil-resistant agent to the substrate by dipping, spraying, coating, or the like. By treatment, the hydrocarbon-containing polymer (1), which is the active ingredient of the oil-resistant agent, adheres to the interior and / or surface of the substrate. Adhesion can be physical or chemical. For example, the hydrocarbon-containing polymer (1) can be physically modified or chemically modified (reacted) with hydroxyl groups on the substrate (fiber, paper, glass, etc.).

[0498] [Base material]

[0499] The substrate treated with the oil-proofing agent in the present invention is not limited, but is preferably a fiber product or a paper product, particularly a paper product.

[0500] The oil-proofing agent of the present invention can impart liquid repellency to a substrate (e.g., a fiber substrate or a paper substrate), and can function as at least one of a water-repellent agent, an oil-repellent agent, an oil-proofing agent, and a water-proofing agent. The substrate treated with the oil-proofing agent of the present invention is, for example, oil-resistant paper or water-resistant paper.

[0501] Examples of fiber product base materials include natural fibers of plant and animal origin, 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 fiber, carbon fiber, and asbestos fiber; and blends thereof. Fiber products include knitted, woven, and non-woven fabrics, as well as clothing (e.g., water-repellent clothing, such as raincoats) and carpets. However, fibers, yarns, and intermediate fiber products (e.g., slivers or yarns) in their pre-fabricated state may also be processed.

[0502] Examples of substrates for paper products include paper made from bleached or unbleached chemical pulps such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulps such as wood pulp, mechanical pulp or thermomechanical pulp, waste paper pulps such as used newspapers, used magazine paper, waste corrugated paper or deinked waste paper, paper substrates containing multiple materials (e.g., mixed substrates composed of pulp fibers and synthetic fibers), containers made of paper, and molded articles made of paper. Specific examples of paper products include food packaging materials, release paper, peeling paper, food containers, gypsum board base paper, coated base paper, medium-quality paper, ordinary lining and core, neutral pure white roll paper, neutral lining, rust-proof lining and metal-composite paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, neutral information paper, molded paper (molded containers), and the like. Preferred examples include food packaging materials and food containers.

[0503] The substrates treated with the oil-resistant agent of the present invention are not limited to fiber products or paper products. In addition to these, stone, filters (such as electrostatic filters), dust masks, fuel cell components (such as gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, bricks, cement, metals and oxides, kiln-fired products, plastics, coatings and plasters can also be listed.

[0504] When the substrate is glass, the manufactured glass product can be an optical component. The surface (outermost layer) of the glass substrate can be formed with certain layers (or films), such as a hard coating or an anti-reflection layer. The anti-reflection layer can use any of a single-layer anti-reflection layer and a multi-layer anti-reflection layer. Examples of inorganic substances that can be used in the anti-reflection layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, CeO2, MgO, Y2O3, SnO2, MgF2, WO3, etc. These inorganic substances can be used alone, or two or more of them can be used in combination (for example, in the form of a mixture). When a multi-layer anti-reflection layer is made, it is preferred that SiO2 and / or SiO be used in its outermost layer. When the article to be manufactured is an optical glass component for a touch panel, part of the surface of the substrate (glass) can have a transparent electrode, for example, a thin film of indium tin oxide (ITO) or indium zinc oxide is used. In addition, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating layer, a polarizing film, a phase difference film, and a liquid crystal display module, etc., depending on its specific style.

[0505] [Handling method]

[0506] The oil-resistant agent of the present invention can be applied to a substrate as a treatment agent (especially a surface treatment agent) by existing well-known methods. As a treatment method, the oil-resistant agent of the present invention can be dispersed in an organic solvent or water as needed for dilution, and attached to the interior and / or surface of the substrate by known methods such as dipping, spraying, and foaming, and then dried. After drying, a product with a solid component of the oil-resistant agent attached can be obtained. In addition, it can also be applied together with an appropriate cross-linking agent as needed for curing. The oil-resistant agent of the present invention can also be further used in combination with various additives such as water-repellent and / or oil-repellent agents, anti-slip agents, antistatic agents, hand-feel regulators, softeners, antibacterial agents, flame retardants, paint fixatives, anti-wrinkle agents, drying speed regulators, cross-linking agents, film-forming aids, solubilizers, antifreeze agents, viscosity regulators, ultraviolet absorbers, antioxidants, pH regulators, insect repellents, defoamers, etc. As examples of various additives, the same substances as those described in the above description of "other ingredients" can be used. The concentration of the oil repellent in the treatment agent in contact with the substrate can be appropriately changed depending on the intended use, and may be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0507] The oil-proofing agent can be applied to the substrate by any known method for treating the substrate with a liquid. The substrate can be immersed in the oil-proofing agent, or the solution can be attached to or sprayed on the substrate. In order to make the treated substrate exhibit liquid repellency, it is preferably dried and cured by heating. The heating temperature is, for example, 100°C to 200°C, 100°C to 170°C or 100°C to 120°C. In the present invention, good performance can be obtained even with low-temperature heating (for example, 100°C to 140°C). In the present invention, the heating time can be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes. When the fiber product is paper, it can be coated on the paper, or the solution can be attached to or sprayed on the paper, or it can be mixed with the pulp slurry before papermaking for treatment. The treatment can be an external addition treatment or an internal addition treatment. Alternatively, the oil-proofing agent can be applied to the fiber product by a cleaning method, for example, it can be applied by washing or applied to the fiber product by a dry cleaning method.

[0508] [Handling of paper products]

[0509] Examples of the paper substrate include paper, containers made of paper, and molded articles made of paper (for example, pulp molded articles). The hydrocarbon polymer (1) of the present invention can adhere well to the paper substrate.

[0510] Paper can be produced by conventional papermaking methods. An internal addition method, in which an oil-resistant agent is added to the pulp slurry before papermaking, or an external addition method, in which an oil-resistant agent is applied to the paper after papermaking, can be employed. The external addition method is preferred for the treatment method of the present invention.

[0511] The sizing of the external addition treatment method can also be classified according to the coating method as follows.

[0512] One coating method is to pass the paper between two rubber rollers, supply the coating liquid (glue liquid) to the formed nip, form a coating liquid storage part called a glue pool, and pass the paper through the coating liquid storage part to coat the glue liquid on both sides of the paper, which is the so-called glue pool type double roller sizing. Other coating methods include gate roller type and film transfer sizing that use a surface transfer mold to apply the glue liquid. In the glue pool type double roller sizing, the glue liquid easily penetrates into the interior of the paper; in the surface transfer mold, the glue liquid components easily stay on the surface of the paper. Compared with the glue pool type double roller sizing, the surface transfer mold is more likely to have a coating layer stay on the surface of the paper, and the oil-resistant layer formed on the surface is more than that of the glue pool type double roller sizing. In the present invention, even when the former glue pool type double roller sizing is used, it is also possible to impart properties to the paper. The paper treated in this way can exhibit excellent oil resistance and water resistance by simply drying it at room temperature or high temperature, and then optionally performing a heat treatment at a temperature below 300°C, for example below 200°C, especially within the temperature range of 80°C to 180°C, depending on the properties of the paper.

[0513] The present invention can be used in gypsum board base paper, coated base paper, medium-quality paper, ordinary lining and core, neutral pure white roll paper, neutral lining, rust-proof lining, metal composite paper, kraft paper, etc. It can also be used in neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, and neutral information paper.

[0514] As pulp raw materials, any waste paper pulp such as bleached or unbleached chemical pulps such as sulfate pulp or sulfite pulp, bleached or unbleached high-yield pulps such as wood pulp, mechanical pulp, or thermomechanical pulp, or waste paper such as waste newspaper, waste magazine paper, waste corrugated paper, or deinked waste paper can be used. Furthermore, mixtures of the above pulp raw materials with synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin, and polyvinyl alcohol can also be used.

[0515] Adding a sizing agent can improve the water resistance of paper. Examples of sizing agents include cationic sizing agents, anionic sizing agents, and rosin-based sizing agents (e.g., acidic rosin-based sizing agents and neutral rosin-based sizing agents). The amount of sizing agent can be 0.01 to 5% by weight relative to the pulp.

[0516] The paper may be prepared as needed with commonly used additives such as starch, modified starch, carboxymethyl cellulose, polyamide polyamine-epichlorohydrin resin, and the like, as well as paper strength enhancers, coagulants, fixatives, retention aids, dyes, fluorescent dyes, viscosity control agents, and defoamers. Starch and modified starch are preferably used. As needed, an oil-resistant agent may be applied to the paper using a sizing press, gate roller coater, biller blade coater, or calender.

[0517] When added externally, the amount of the hydrocarbon-containing polymer (1) contained in the oil-resistant layer is preferably 0.01 to 2.0 g / m 2 , especially 0.1~1.0g / m 2 The oil-resistant layer is preferably formed of an oil-resistant agent and starch and / or modified starch. The solid content of the oil-resistant agent for paper in the oil-resistant layer is preferably 2 g / m 2 the following.

[0518] When internally added, the oil-proofing agent is preferably mixed with the pulp so that the amount of the oil-proofing agent becomes 0.01 to 50 parts by weight or 0.01 to 30 parts by weight, for example 0.01 to 10 parts by weight, particularly 0.2 to 5.0 parts by weight, based on 100 parts by weight of the pulp forming the paper.

[0519] When adding external sizing, oil resistance can also be imparted to paper by using a so-called sizing tank type double-roll sizing process in which a treatment liquid is retained between the rollers and the base paper is passed through the treatment liquid between the rollers at an arbitrary roller speed and nip pressure.

[0520] In the present invention, as a method for setting a coating layer (oil-resistant layer), a coating machine or impregnation device such as a sizing coater, a film transfer coater, a gate roller coater, a metal rod and metal blade coater, an air knife coater, a roller coater, a rod coater, a blade coater, a gravure coater, etc., various printing machines, etc. can be used, but are not limited to these.

[0521] In the external addition treatment, the paper substrate may contain additives such as sizing agents, paper strengthening agents, coagulants, retention aids, or coagulants. The additives may be nonionic, cationic, anionic, or amphoteric. The ionic charge density of the additives may be -10,000 to 10,000 μeq / g, preferably -4,000 to 8,000 μeq / g, and more preferably -1,000 to 7,000 μeq / g. The amount of additives such as sizing agents, paper strengthening agents, coagulants, retention aids, or coagulants (solid components or active ingredients) relative to the pulp is generally 0.1 to 10% by weight (e.g., 0.2 to 5.0% by weight). In the case of a paper substrate containing a cationic additive (e.g., sizing agents, paper strengthening agents, coagulants, retention aids, or coagulants), the oil-resistant agent may be anionic; in the case of a paper substrate containing anionic additives, the oil-resistant agent may be cationic, but the present invention is not limited to these.

[0522] In the internal addition treatment, it is preferred to make paper from a pulp slurry having a pulp concentration of 0.5 to 5.0 wt% (e.g., 2.5 to 4.0 wt%). Additives (e.g., sizing agents, paper strengthening agents, coagulants, retention aids, or coagulants) and hydrocarbon-containing polymers (1) may be added to the pulp slurry. Since the pulp is generally anionic, it is preferred that at least one of the additive and the hydrocarbon-containing polymer (1) be cationic or amphoteric in order to ensure good fixation of the additive and the hydrocarbon-containing polymer (1) on the paper. It is preferred to use a combination in which the additive is cationic or amphoteric and the hydrocarbon-containing polymer (1) is anionic, a combination in which the additive is anionic and the hydrocarbon-containing polymer (1) is cationic or amphoteric, or a combination in which the additive and the hydrocarbon-containing polymer (1) are cationic or amphoteric. It is more preferred to make paper in a manner such that the ionic charge density of additives such as sizing agents, paper strengthening agents, coagulants, retention aids or coagulants is -1000 to 7000 μeq / g, and it is further preferred to make paper in a manner such that the ionic charge density is 100 to 1000 μeq / g (for example, 330 μeq / g, 420 μeq / g or 680 μeq / g).

[0523] Examples of additives (such as sizing agents, paper strengthening agents, coagulants, retention aids or coagulants) include alkyl ketene dimers, alkenyl succinic anhydrides, styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, condensates of alkylene dichlorides and polyalkylene polyamines, dicyandiamide-aldehyde condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0524] [Pretreatment of fiber products]

[0525] The fiber product may be pretreated before being treated with the oil-proofing agent of the present invention. By pretreating the fiber product, the oil-proofing agent can be used to impart excellent durability to the fiber product after treatment.

[0526] Examples of pretreatment of fiber products include cationization treatment by reaction with reactive quaternary ammonium salts, anionization treatment by sulfonation, carboxylation, phosphorylation, etc., acetylation treatment after anionization treatment, benzoylation treatment, carboxymethylation treatment, grafting treatment, tannic acid treatment, polymer coating treatment, etc.

[0527] The method for pre-treating fiber products is not limited, and conventionally known methods can be used. A pre-treatment solution can be dispersed in an organic solvent or water, diluted as needed, applied to the interior and / or surface of the fiber product by known methods such as dipping, spraying, or foam coating, and then dried. The pH and temperature of the pre-treatment solution can be adjusted to the desired degree of treatment. As an example of a method for pre-treating fiber products, a method for pre-treating fiber products using a hydrocarbon-based water-repellent agent will be described in detail.

[0528] The pre-treatment method of fiber products may include providing the fiber with a 1 (where M 1 represents a monovalent cation), a monovalent group represented by -COOM 2 (where M 2 represents a monovalent cation) and -O-P(O)(OX 1 )(OX 2 )(where X 1 and X 2 A step of each independently representing one or more functional groups (hereinafter sometimes referred to as "specific functional groups") in a monovalent group represented by a hydrogen atom or an alkyl group having 1 to 22 carbon atoms.

[0529] As M1 , H, K, Na or an ammonium ion which may have a substituent. 2 , H, K, Na or an ammonium ion which may have a substituent. 1 or X 2 In the case of an alkyl group, an alkyl group having 1 to 22 carbon atoms is preferred, and an alkyl group having 4 to 12 carbon atoms is more preferred.

[0530] The fiber containing the above-mentioned specific functional group (hereinafter sometimes referred to as "functional group-containing fiber") can be produced, for example, by the following method.

[0531] (i) The compound having the specific functional group is attached to the fiber material, wherein the compound may be attached so that a portion of the compound is chemically bonded to a portion of the fiber within a range where a sufficient amount of the specific functional group remains.

[0532] (ii) Fibers are prepared in which the above-mentioned specific functional groups are directly introduced into the material constituting the fibers.

[0533] In the case of (i), for example, the fiber material is treated with a pretreatment solution containing one or more compounds having the above-mentioned specific functional groups, and a fiber containing a functional group can be obtained through such a functional group introduction step.

[0534] The raw materials of the fiber material are not particularly limited, and examples thereof 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 blends thereof. The fiber material may be in any form, such as fibers (tow, yarn, etc.), silk, braids (including blends), woven fabrics (including blends), and non-woven fabrics.

[0535] In this embodiment, from the viewpoint of good water repellency of the obtained fiber product, it is preferred to use a fiber material containing polyamide and polyester as raw materials, and it is particularly preferred to use nylon such as nylon 6, nylon 6,6, polyethylene terephthalate (PET), polytrimethylene terephthalate, polyester such as polylactic acid, and mixed fibers containing them.

[0536] As a 1 As a compound, a phenolic polymer can be used. As such a phenolic polymer, for example, a substance containing at least one compound represented by the following general formula can be mentioned.

[0537]

[0538] [Where, X 2 Representation - SO3M 3 (where M3 represents a monovalent cation) or a group represented by the following general formula, wherein n is an integer from 20 to 3000.]

[0539]

[0540] [Where M 4 represents a monovalent cation.]

[0541] As the above M 3 , H, K, Na or an ammonium ion which may have a substituent can be mentioned.

[0542] As the above M 4 , H, K, Na or an ammonium ion which may have a substituent can be mentioned.

[0543] The compound represented by the above general formula may be, for example, a formalin condensate of phenolsulfonic acid or a formalin condensate of sulfonated bisphenol S.

[0544] As a company with the above-mentioned 2 The compound includes polycarboxylic acid polymers.

[0545] As the polycarboxylic acid-based polymer, for example, a polymer synthesized by using acrylic acid, methacrylic acid, maleic acid, or the like as a monomer according to a conventionally known radical polymerization method, or a commercially available product can be used.

[0546] As a method for producing a polycarboxylic acid polymer, for example, a method of adding a free radical polymerization initiator to an aqueous solution of the above-mentioned monomers and / or their salts and heating the reaction at 30 to 150° C. for 2 to 5 hours can be cited. At this time, an alcohol such as methanol, ethanol, isopropanol, or an aqueous solvent such as acetone can also be added to the aqueous solution of the above-mentioned monomers and / or their salts. As a free radical polymerization initiator, for example, persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, redox polymerization initiators using a combination of persulfate and sodium bisulfite, hydrogen peroxide, water-soluble azo polymerization initiators, etc. can be cited. These free radical polymerization initiators can be used alone or in combination of two or more. In addition, during free radical polymerization, a chain transfer agent (such as octyl thioglycolate) can be added to adjust the degree of polymerization.

[0547] In addition to the above-mentioned monomers, copolymerizable monomers can also be used during free radical polymerization. Examples of copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate; acrylamide, acrylates, and methacrylates. Acrylates and methacrylates preferably have a hydrocarbon group having 1 to 3 carbon atoms that may have a substituent such as a hydroxyl group. Examples of such acrylates and methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, and propyl methacrylate. These copolymerizable monomers can be used alone or in combination of two or more.

[0548] The carboxyl groups in the polycarboxylic acid polymer may be free or neutralized with an alkali metal or an amine compound. Examples of the alkali metal include sodium, potassium, and lithium; and examples of the amine compound include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0549] The weight average molecular weight of the polycarboxylic acid polymer is preferably 1,000 to 20,000, more preferably 3,000 to 15,000, from the viewpoint of good water repellency of the resulting fiber product.

[0550] As the polycarboxylic acid-based polymer, commercially available products such as “NEOCRYSTAL 770” (trade name, manufactured by Nikka Chemical Co., Ltd.) and “Celopol PC-300” (trade name, manufactured by Sanyo Chemical Industries, Ltd.) can be used.

[0551] As the above-mentioned -O-P(O)(OX 1 )(OX 2 ) compounds, for example, the phosphate compounds represented by the following general formula can be mentioned.

[0552]

[0553] [Where, X 1 or X 2 The meaning is the same as above, X 3 represents an alkyl group having 1 to 22 carbon atoms.]

[0554] As the phosphoric acid ester compound, phosphoric acid monoesters, diesters, triesters, and mixtures thereof in which the alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms can be used.

[0555] From the viewpoint of good water repellency of the obtained fiber product, lauryl phosphate and decyl phosphate are preferably used.

[0556] As the phosphate compound, for example, a commercially available product such as "PHOSPHANOL ML-200" (trade name, manufactured by Toho Chemical Industry Co., Ltd.) can be used.

[0557] The pretreatment solution containing one or more compounds having the above-mentioned specific functional groups may be, for example, an aqueous solution of the above-mentioned compounds. In addition, the pretreatment solution may further contain an acid, an alkali, a surfactant, a chelating agent, and the like.

[0558] As a method for treating the fiber material with the above-mentioned pretreatment liquid, for example, pad dyeing, dipping, spraying, and coating can be cited. As a pad dyeing method, for example, the method using a pad dyeing device described on pages 396-397 of the Fiber Dyeing Processing Dictionary (published by Nikkan Kogyo Shimbun in 1975) or on pages 256-260 of Color Dyeing Chemistry III (published by Jikyo Publishing Co., Ltd. in 1975) can be cited. As a coating method, for example, the method using a coating machine described on pages 473-477 of the Dyeing and Finishing Equipment Overview (published by Textile Company in 1975) can be cited. As an immersion method, for example, the method using a batch dyeing machine described on pages 196-247 of the Dyeing and Finishing Equipment Overview (published by Textile Company in 1975) can be cited. Liquid flow dyeing machines, air flow dyeing machines, drum dyeing machines, hank dyeing machines, washing dyeing machines, and bobbin dyeing machines can also be used. As a spray treatment, for example, a method of spraying the treatment liquid into a mist by using compressed air, or a method of spraying the gas by using a hydraulic atomization method can be cited. The concentration of the treatment liquid at this time and the treatment conditions such as the heat treatment after the treatment can be appropriately adjusted in consideration of various conditions such as its purpose and performance. In addition, when the pre-treatment liquid contains water, it is preferably dried after adhering to the fiber material to remove the water. There is no particular limitation on the drying method, and any method of dry heat method and wet heat method can be used. There is no particular limitation on the drying temperature, and for example, it can be dried at room temperature to 200°C for 10 seconds to several days. If necessary, a heat treatment at a temperature of 100 to 180°C for about 10 seconds to 5 minutes can be performed after drying.

[0559] Among them, when the fiber material is the dyed material, the treatment with the pretreatment liquid can be carried out before dyeing or in the same bath as dyeing. However, when performing reduction soaping, since the adsorbed compounds having the above-mentioned specific functional groups (such as phenolic polymer compounds, etc.) may fall off during the process, it is preferably carried out after the reduction soaping after dyeing.

[0560] The treatment temperature in the immersion treatment can be set to 60 to 130° C. The treatment time can be set to 5 to 60 minutes.

[0561] In the functional group introduction step using a pretreatment solution, the treatment is preferably performed with the compound having the specific functional group attached in an amount of 1.0 to 7.0 parts by weight per 100 parts by weight of the fiber material. Within this range, both durable water repellency and a high level of hand feel can be achieved.

[0562] The pH of the pretreatment liquid is preferably adjusted to 3 to 5. A pH adjuster such as acetic acid or malic acid can be used for pH adjustment.

[0563] In the pretreatment solution, a salt may be used to more effectively adsorb the compound having the specific functional group onto the fiber material through the salting-out effect. Examples of the salt include sodium chloride, sodium carbonate, ammonium sulfate, and sodium sulfate.

[0564] During the functional group introduction step using a pretreatment solution, it is preferred to remove any over-treated compounds containing the aforementioned specific functional groups. Water washing is an example of a suitable removal method. Sufficient removal can prevent any hindrance to the development of water repellency during the subsequent water-repellent treatment, and the resulting fiber product has a favorable feel. Furthermore, the resulting functional group-containing fiber is preferably thoroughly dried before contacting it with the hydrocarbon-based water-repellent agent.

[0565] (ii) Fibers in which the above-mentioned specific functional groups are directly introduced into a material constituting the fiber include, for example, cationic dyeable polyester (CD-PET).

[0566] From the perspective of achieving good water repellency in the resulting fiber product, the surface zeta potential of the functional group-containing fiber is preferably -100 to -0.1 mV, more preferably -50 to -1 mV. The surface zeta potential of the fiber can be measured, for example, using a zeta potential / particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0567] While the embodiments have been described above, it should be understood that various changes in form and detail may be made without departing from the spirit and scope of the claims.

[0568] Example

[0569] The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples. In the following, unless otherwise specified, parts, % or ratios represent parts by weight, % by weight or ratio by weight.

[0570] <Test method>

[0571] The method of the test performed is as follows.

[0572] [Viscosity of treatment fluid]

[0573] The viscosity (cps) was measured by using a rotational viscometer (type B) to read the fluid resistance (viscous resistance) applied to the rotating body based on the rotational torque and the like.

[0574] [KIT trial]

[0575] Oil resistance (KIT method) is measured using TAPPI T-559 cm-02. The KIT test solution is a mixture of castor oil, toluene, and heptane in the ratios shown in the table below. Place one drop of the test solution listed below on paper and observe the oil penetration after 15 seconds. The highest oil resistance score assigned by the KIT test solution showing no penetration is considered the oil resistance. The higher the KIT test solution number, the higher the oil resistance.

[0576] Mixing ratio (vol%)

[0577]

[0578] [Practical oil resistance test 1]

[0579] A small amount of commercially available olive oil was dripped onto the prepared oil-resistant paper and the penetration was observed after 7 minutes. The following evaluation values ​​were set based on the degree of penetration on the back side.

[0580] 5:0-5%

[0581] 4:6-20%

[0582] 3:21-50%

[0583] 2:51-75%

[0584] 1:76-100%

[0585] [Practical oil resistance test 2]

[0586] Oil-resistant paper with a small amount of commercially available olive oil added was placed in a 70°C oven and removed after 7 minutes to observe the penetration. The evaluation value was set in the same manner as in Oil Resistance Test 1.

[0587] [Practical oil resistance test 3]

[0588] Cut oil-resistant paper into 9×9 cm dimensions and gently fold it along a line connecting the center points of two opposite sides. Use a roller covered with a hard rubber layer to reinforce the crease (8 cm diameter, 7 cm width, and covered with a 0.6 cm thick hard rubber layer, weighing 2450 ± 110 g, with a roller speed of 50-60 cm / second during indentation). The paper is made by pressing the first crease along the line connecting the center points of the two opposite sides, and then pressing the second crease along the line connecting the center points of the other two opposite sides on the same side of the paper. Place the test paper on a platen and place a metal cylinder with an inner diameter of 70 mm on the test paper, securing it with a clamp or other fixture as needed. Then, inject approximately 20 g of corn oil into the cylinder. Remove the oil 20 minutes after it comes into contact with the test paper. If the oil continuously penetrates more than 1 mm from the crease of the test paper, it is considered to be an oil stain from the crease. The oil contact area is measured in 1cm square grids, with 52 grids. The lighter the penetration, the fewer grids are measured. The evaluation value is set according to the following standards.

[0589] 5: 0-10 grids

[0590] 4: 11-15 grids

[0591] 3: 16-20 grids

[0592] 2: 21-30 grids

[0593] 1: 31-52 grids

[0594] [Practical oil resistance test 4]

[0595] Evaluation values ​​were set in the same manner as in the practical oil resistance test 1 except that the impregnation state was observed after 20 minutes.

[0596] [Water resistance Cobb test]

[0597] The Cobb value is measured according to JIS P 8140:1998. A paper substrate is placed on a smooth, solid surface. A metal cylinder with an inner diameter of 112.8 mm is fixed to the surface with a clamp. Water is then poured into the cylinder to a depth of 10 mm. The weight of water absorbed within one minute from the moment the paper substrate comes into contact with the water is calculated. The resulting value is converted to a weight per square meter (g / m²). 2 ), and calculate the water resistance Cobb value.

[0598] [Air permeability value]

[0599] The vent hole diameter was 28.6±0.1 mm and was measured according to JIS P8117 (2009).

[0600] <Synthesis example>

[0601] [Synthesis example 1]

[0602] A 500ml reaction vessel equipped with a stirrer, thermometer, reflux cooler, dropping funnel, nitrogen inlet, and heater was prepared. 100 parts of methyl ethyl ketone (MEK) was added. Then, under stirring, monomers consisting of 78 parts of stearamidoethyl acrylate (C18AmEA, melting point: 70°C), 16 parts of hydroxybutyl acrylate (HBA, Tg: -40°C), and 6 parts of dimethylaminoethyl methacrylate (DM) (total monomers: 100 parts) were added, along with 1.2 parts of t-butyl peroxyvalerate (PV) as an initiator. The mixture was mixed and stirred for 12 hours under a nitrogen atmosphere at 65-80°C to perform copolymerization. The resulting copolymer-containing solution had a solids concentration of 50% by weight. Gel permeation chromatography analysis of the resulting copolymer revealed a polystyrene-equivalent mass average molecular weight of 230,000. As a post-treatment, 142 g of a 0.4% aqueous acetic acid solution was added to 50 g of the resulting copolymer solution and dispersed. The mixture was then heated using an evaporator and MEK was distilled off under reduced pressure to obtain a milky white copolymer aqueous dispersion (containing a volatile organic solvent content of 1% by weight or less). Ion-exchanged water was then added to obtain an aqueous dispersion having a solids concentration of 15% by weight. The melting point of this copolymer was 66°C.

[0603] [Synthesis example 2]

[0604] The same method as in Synthesis Example 1 was followed, except that 75 parts of stearyl acrylate (StA, melting point: 30°C) and 19 parts of hydroxybutyl acrylate (HBA, Tg: -40°C) were used in place of stearamidoethyl acrylate (C18AmEA, melting point: 70°C). A milky white aqueous copolymer dispersion (containing a volatile organic solvent content of 1% by weight or less) was obtained. Ion-exchanged water was added to obtain an aqueous dispersion having a solids concentration of 15% by weight. The melting point of this copolymer was 46°C.

[0605] <Examples and Comparative Examples>

[0606] [Example 1]

[0607] As the base paper, a mixed pulp of LBKP (bleached broadleaf kraft pulp) and NBKP (bleached coniferous kraft pulp) with a basis weight of 48 g / m 2 , paper density is 0.8g / cm 3 , air permeability is 230 seconds, Cobb value is 45g / m 2 paper substrate.

[0608] The oil resistance KIT value of this base paper was 0, and the practical oil tests 1, 2, and 3 all showed 1.

[0609] Using the aqueous dispersion of the copolymer obtained in Synthesis Example 1 as an oil-proofing agent, oil-proof paper (processed paper) was obtained according to the following formulation.

[0610] Water, starch and citric acid were added to the aqueous dispersion of the copolymer obtained in Synthesis Example 1 to prepare a treatment liquid in such a manner that the solid content concentrations of the copolymer, starch and citric acid were 1.4 wt%, 14 wt% and 3 wt%, respectively. The pH of the treatment liquid was 2.0. The paper substrate was immersed in the treatment liquid at about 50°C, squeezed with a pressure roller and dried with a drum dryer to obtain oil-resistant paper. Hydroxyethylated modified starch (concentration of 10 wt%, viscosity of about 11 cps at 50°C) was used as the starch. The dry coating amount of the obtained oil-resistant paper was 7.5 g / m 2 Table 1 shows the results of KIT value, practical oil tests 1, 2, 3, and air permeability value.

[0611] [Example 2]

[0612] The same treatment as in Example 1 was carried out except that the treatment liquid used a starch concentration of 12 wt% and a citric acid concentration of 5 wt%. The obtained dry coating amount was 7.6 g / m 2 The pH of the treatment liquid was 1.8. Table 1 shows the results of the KIT value, practical oil tests 1, 2, and 3, and air permeability.

[0613] [Example 3]

[0614] The same treatment as in Example 1 was carried out except that 2% by weight of tartaric acid was used instead of citric acid. The obtained dry coating weight was 7.5 g / m 2 The pH of the treatment liquid was 2.3. Table 1 shows the results of the KIT value, practical oil tests 1, 2, and 3, and air permeability.

[0615] [Example 4]

[0616] The same treatment as in Example 1 was carried out except that 7% by weight of polyvinyl alcohol was used instead of the starch in Example 1. The obtained dry coating amount was 5.4 g / m 2 The pH of the treatment liquid was 2.1. Table 1 shows the results of the KIT value, practical oil tests 1, 2, and 3, and air permeability.

[0617] [Example 5]

[0618] The same treatment as in Example 3 was carried out except that 0.5 wt% of malic acid was used instead of tartaric acid. The obtained dry coating weight was 7.8 g / m 2 The pH of the treatment liquid was 3.1. Table 1 shows the results of the KIT value, practical oil tests 1, 2, and 3, and air permeability.

[0619] [Comparative Example 1]

[0620] The same treatment as in Example 1 was carried out except that the copolymer and citric acid of Example 1 were not used and the amount of starch was 17 wt%. The obtained dry coating weight was 7.7 g / m 2 Table 1 shows the results of KIT value, practical oil tests 1, 2, 3, and air permeability value.

[0621] [Comparative Example 2]

[0622] The same treatment as in Example 1 was carried out except that the copolymer of Example 1 was not used. The obtained dry coating weight was 7.5 g / m 2 Table 1 shows the results of KIT value, practical oil tests 1, 2, 3, and air permeability value.

[0623] [Comparative Example 3]

[0624] The same treatment as in Example 4 was carried out except that the copolymer and citric acid of Example 4 were not used and the polyvinyl alcohol was 10 wt%. The obtained dry coating weight was 5.6 g / m 2 Table 1 shows the results of KIT value, practical oil tests 1, 2, 3, and air permeability value.

[0625] [Comparative Example 4]

[0626] The same treatment as in Example 4 was carried out except that the copolymer of Example 4 was not used. The obtained dry coating weight was 4.5 g / m 2 Table 1 shows the results of KIT value, practical oil tests 1, 2, 3, and air permeability value.

[0627] [Comparative Example 5]

[0628] The same treatment as in Comparative Example 1 was carried out except that 17% by weight of hydrophobized starch was used instead of the starch in Comparative Example 1. The obtained dry coating amount was 8.2 g / m 2 Table 1 shows the results of KIT value, practical oil tests 1, 2, 3, and air permeability value.

[0629] [Comparative Example 6]

[0630] The same treatment as in Comparative Example 5 was carried out except that 3% by weight of citric acid was used in the treatment solution of Comparative Example 5. The obtained dry coating weight was 9.5 g / m 2 Table 1 shows the results of KIT value, practical oil tests 1, 2, 3, and air permeability value.

[0631] [Comparative Example 7]

[0632] The same treatment as in Comparative Example 1 was carried out except that 1.4 wt% of the copolymer was used. The obtained dry coating weight was 8.0 g / m 2The pH of the treatment liquid was 5.1. Table 1 shows the results of the KIT value, practical oil tests 1, 2, and 3, and air permeability.

[0633] [Comparative Example 8]

[0634] The same treatment as in Comparative Example 3 was carried out except that 1.4 wt% of the copolymer was used. The obtained dry coating weight was 7.4 g / m 2 Table 1 shows the results of KIT value, practical oil tests 1, 2, 3, and air permeability value.

[0635] [Example 6]

[0636] The same treatment as in Example 1 was carried out except that the aqueous dispersion of the copolymer obtained in Synthesis Example 2 was used as the oil-proofing agent. The pH of the treatment solution was 2.0. The dry coating weight of the obtained oil-proof paper was 7.7 g / m 2 Table 1 shows the results of KIT value, practical oil tests 1, 2, 3, 4, and air permeability value.

[0637] [Comparative Example 9]

[0638] The same treatment as in Comparative Example 7 was carried out except that 1.4 wt% of the copolymer obtained in Synthesis Example 2 was used. The obtained dry coating weight was 7.4 g / m 2 The pH of the treatment liquid was 5.1. Table 1 shows the results of the KIT value, practical oil tests 1, 2, 3, and 4, and the air permeability value.

[0639] [Table 1]

[0640] KIT value Practical oil test 1 Practical Oil Test 2 Practical Oil Test 3 Practical oil test 4 Air permeability value Comparative Example 1 1 1 1 1 400 Comparative Example 2 1 1 1 1 320 Comparative Example 3 0 1 l 1 930 Comparative Example 4 0 1 1 1 410 Comparative Example 5 3-4 3 1 1 2200 Comparative Example 6 1 1 l 1 2500 Comparative Example 7 5 4-5 1 2 2000 Comparative Example 8 3 2-3 1 1 2270 Example 1 5 5 3-4 5 810 Example 2 5 5 4 5 620 Example 3 6 4-5 4 5 860 Example 4 5 4-5 1-2 3 1130 Example 5 5-6 4-5 4 5 950 Comparative Example 9 5 4-5 1 2 2 1400 Example 6 5 5 1 5 4 1000

Claims

1. An oil resistant agent, characterized in that: contain: (1) a hydrocarbon-containing polymer having repeating units derived from a monomer (a), wherein the monomer (a) has a hydrocarbon group having 6 to 40 carbon atoms; (2) water-soluble polymers; and (3) Polycarboxylic acids.

2. The oil resistant agent according to claim 1, characterized in that The water-soluble polymer (2) is a polyol.

3. The oil resistant agent according to claim 1 or 2, characterized in that The water-soluble polymer (2) is at least one selected from polysaccharides and polyvinyl alcohol.

4. The oil resistant agent according to any one of claims 1 to 3, characterized in that The molecular weight of the polycarboxylic acid is 1000 or less.

5. The oil resistant agent according to any one of claims 1 to 4, characterized in that The polycarboxylic acid is a hydroxy polycarboxylic acid.

6. The oil resistant agent according to any one of claims 1 to 5, characterized in that The polycarboxylic acid is at least one selected from citric acid, malic acid, tartaric acid and hydroxymalonic acid.

7. The oil resistant agent according to any one of claims 1 to 6, characterized in that The monomer (a) has a hydrocarbon group having 12 to 30 carbon atoms.

8. The oil resistant agent according to any one of claims 1 to 7, characterized in that The monomer (a) is represented by the formula: CH2=C(-X a )-C(=O)-Y a (R a ) k express, Where R a are each independently 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 A group consisting of at least one selected from a divalent to tetravalent hydrocarbon group having 1 carbon atom, -C6H4-, -O-, -C(=O)-, -S(=O)2-, or -NH-, excluding a hydrocarbon group, k is 1 to 3.

9. The oil resistant agent according to any one of claims 1 to 8, characterized in that The monomer (a) comprises a monomer (a2), The monomer (a2) is represented by the formula: CH2=C(-X a2 )-C(=O)-Y a21 -Z(-Y a22 -R a2 ) n express, Where R a2 are each 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 are each independently a group consisting of at least one selected from -O-, -C(=O)-, -S(=O)2-, -NH-, or -CH2-, Z is a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, n is 1 or 2.

10. The oil resistant agent according to any one of claims 1 to 9, characterized in that The hydrocarbon-containing polymer (1) comprises repeating units derived from (b) a monomer containing a hydrophilic group, The monomer (b) is of the formula: CH2=CX b C(=O)-Y b -(R b O) n -A b The oxyalkylene (meth)acrylate shown, Where, X b is a hydrogen atom or a methyl group, Y b is -O- or -NH-, R b are each independently an alkylene group having 2 to 6 carbon atoms, A b A hydrogen atom, an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, or CH2=CX b C(=O)-, n is an integer from 1 to 90.

11. The oil resistant agent according to any one of claims 1 to 10, characterized in that The hydrocarbon-containing polymer (1) contains (c) a monomer containing an ion-donating group, The monomer (c) contains an ethylenic carbon-carbon double bond and an anion-providing group or a cationic-providing group.

12. A product treated with the oil-proofing agent according to any one of claims 1 to 11.

13. The article of claim 12, wherein: It is a fiber product or a paper product.

14. The product according to claim 12 or 13, wherein It is oil-resistant paper or water-resistant paper.

15. The product according to any one of claims 12 to 14, characterized in that It is a food packaging material or a food container.

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