Water- and oil-repellent composition, fiber treating agent, fiber treating method, fiber processed product, and coating agent

Abstract

A water- and oil-repellent composition comprises a copolymer (A) not containing a structural unit having a siloxane bond, a copolymer (B) containing a structural unit having a siloxane bond, a polyether-modified polydimethylsiloxane, and an aqueous medium, wherein the copolymer (A) has a structural unit (a1) derived from a compound having an ethylenically unsaturated bond and an ester bond and not having an amide bond, and a structural unit (a2) derived from a compound having an ethylenically unsaturated bond and an amide bond, and the copolymer (B) has a structural unit (b1) derived from a compound having an ethylenically unsaturated bond and an ester bond and not having an amide bond, a structural unit (b2) derived from a compound having an ethylenically unsaturated bond and an amide bond, and a structural unit (b3) derived from polydimethylsiloxane having an ethylenically unsaturated bond.

Description

Technical Field

[0001] The present invention relates to a water- and oil-repellent composition, a fiber treating agent, a fiber treating method, a fiber processed product, and a coating agent.

[0002] This application claims priority based on Japanese Patent Application No. 2020-218523 filed in Japan on December 28, 2020, the contents of which are incorporated herein by reference. Background Art

[0003] Conventionally, as a method for imparting water and oil repellency to substrates such as fibers and paper, water and oil repellent treatment using a water and oil repellent composition is performed. Examples of such compositions include compounds containing a perfluoroalkyl group having 8 or more carbon atoms.

[0004] However, the compound comprising the perfluoroalkyl group of carbon number 8 or more has the possibility of generating perfluorooctanoic acid (perfluoro-octanoic acid (hereinafter, sometimes abbreviated as " PFOA ") by decomposition or metabolism. About perfluorooctanoic acid, the U.S. Environmental Protection Agency requires to reduce the amount of production. Therefore, a water and oil repellent composition with a compound comprising a perfluoroalkyl group having a short carbon chain has been proposed.

[0005] For example, Patent Document 1 describes a water- and oil-repellent composition comprising a pyrazole-blocked hydrophobic polyisocyanate aqueous dispersion containing a pyrazole-blocked hydrophobic polyisocyanate and a nonionic surfactant, and a water- and oil-repellent component having a perfluoroalkyl group having 6 or less carbon atoms.

[0006] Patent Document 2 describes a water- and oil-repellent composition comprising a fluorinated polymer having a structural unit having a polyfluoroalkyl group having 1 to 6 carbon atoms, a fluorinated polymer having a structural unit based on a fluoroolefin, and an aqueous medium.

[0007] Furthermore, in recent years, research has been conducted to reduce the use of compounds containing short-chain perfluoroalkyl groups. Therefore, water- and oil-repellent compositions that do not contain fluorine-based compounds have been proposed.

[0008] For example, in patent document 3, an oil repellent composition comprising an aqueous emulsion comprising a copolymer (A) dispersed in an aqueous medium (B) and a polyether-modified polydimethylsiloxane (C) is described, wherein the copolymer (A) comprises a structural unit based on an ethylenically unsaturated carboxylic acid ester monomer and a structural unit based on an ethylenically unsaturated carboxylic acid monomer.

[0009] Patent Document 4 describes an oil repellent for fiber treatment containing a silicone-acrylic copolymer obtained by polymerizing monomers containing a (meth)acrylate having a quaternary ammonium group, a (meth)acrylic-modified silicone oil at both ends, and a nonionic hydrophobic ethylenically unsaturated monomer.

[0010] Prior art literature

[0011] Patent Literature

[0012] Patent Document 1: Japanese Patent Application Laid-Open No. 2012-031285

[0013] Patent Document 2: International Publication No. 2012 / 020806

[0014] Patent Document 3: International Publication No. 2018 / 163911

[0015] Patent Document 4: Japanese Patent Application Laid-Open No. 2016-102272 Summary of the Invention

[0016] Problems to be solved by the invention

[0017] However, conventional water- and oil-repellent compositions that do not contain a fluorine-based compound may not be able to impart sufficient oil and water repellency to a substrate.

[0018] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a water- and oil-repellent composition capable of imparting high oil- and water-repellency to a substrate.

[0019] Another object of the present invention is to provide a fiber treating agent, a paper treating agent, and a coating agent that can impart high oil repellency and water repellency to a substrate.

[0020] Methods for solving problems

[0021] The present inventor has repeatedly carried out in-depth research in order to solve the above-mentioned problem.Its result is found that, as long as make the water- and oil-repellent agent composition comprising the copolymer with the structural unit derived from the compound with ethylenically unsaturated bond and amido bond and the copolymer with the structural unit derived from the compound with ethylenically unsaturated bond and amido bond and the structural unit derived from the polydimethylsiloxane with ethylenically unsaturated bond, thus thought of the present invention.

[0022] That is, the present invention relates to the following matters.

[0023] A first aspect of the present invention provides the following water and oil repellent composition.

[0024] [1] A water- and oil-repellent composition comprising: a copolymer (A) not containing a structural unit having a siloxane bond; a copolymer (B) containing a structural unit having a siloxane bond; a polyether-modified polydimethylsiloxane (C); and an aqueous medium (D),

[0025] The above copolymer (A) has:

[0026] Structural unit (a1) derived from a compound having an ethylenically unsaturated bond and an ester bond and having no amide bond, and

[0027] a structural unit (a2) derived from a compound having an ethylenically unsaturated bond and an amide bond;

[0028] The above copolymer (B) has:

[0029] A structural unit (b1) derived from a compound having an ethylenically unsaturated bond and an ester bond and having no amide bond;

[0030] a structural unit (b2) derived from a compound having an ethylenically unsaturated bond and an amide bond; and

[0031] The structural unit (b3) is derived from polydimethylsiloxane having an ethylenically unsaturated bond.

[0032] The water- and oil-repellent composition of the first embodiment of the present invention preferably has the features described in [2] to

[12] below. It is also preferred that any combination of two or more of the features described in [2] to

[12] below be used.

[0033] [2] The water and oil repellent composition according to [1], wherein the structural unit (a1) and the structural unit (b1) are structural units derived from either or both of a hydrocarbon having an ethylenically unsaturated bond and an alkyl (meth)acrylate.

[0034] [3] The water- and oil-repellent composition according to [1] or [2], wherein the structural unit (a2) and the structural unit (b2) are structural units derived from (meth)acrylamide.

[0035] [4] The water- and oil-repellent composition according to any one of [1] to [3], wherein the structural unit (b3) is a structural unit derived from a compound represented by the following formula (1).

[0036]

[0037] (In formula (1), R 1 represents a hydrogen atom or a methyl group; R 2 represents a divalent aliphatic group having 1 to 6 carbon atoms which may contain an ether bond; R 3represents an aliphatic group, aromatic group, or hydroxyl group having 1 to 30 carbon atoms; h is any one of 0, 1, and 2. j represents an integer from 0 to 500.

[0038] [5] The water- and oil-repellent composition according to any one of [1] to [4], wherein the mass ratio of the copolymer (A) to the copolymer (B) is 10 / 90 or more and 90 / 10 or less.

[0039] [6] The water- and oil-repellent composition according to any one of [1] to [5], wherein the copolymer (A) contains 0.10% by mass or more and 20% by mass or less of the structural unit (a2).

[0040] [7] The water- and oil-repellent composition according to any one of [1] to [6], wherein the copolymer (B) contains 0.10% by mass or more and 20% by mass or less of the structural unit (b2).

[0041] [8] The water- and oil-repellent composition according to any one of [1] to [7], wherein the copolymer (B) contains 3.0% by mass or more and 50% by mass or less of the structural unit (b3).

[0042] [9] The water- and oil-repellent composition according to any one of [1] to [8], wherein the polyether-modified polydimethylsiloxane (C) has a hydroxyl group at the terminal of the polyether chain.

[0043]

[10] The water- and oil-repellent composition according to any one of [1] to [9], wherein the polyether-modified polydimethylsiloxane (C) is contained in an amount of 0.10 parts by mass to 20 parts by mass based on 100 parts by mass of the total of the copolymer (A) and the copolymer (B).

[0044]

[11] The water- and oil-repellent composition according to any one of [1] to

[10] , further comprising a surfactant (E).

[0045]

[12] The water- and oil-repellent composition according to

[11] , wherein the surfactant (E) is a cationic surfactant.

[0046] A second aspect of the present invention provides the following fiber treating agent.

[0047]

[13] A fiber treating agent comprising the water- and oil-repellent composition according to any one of [1] to

[12] .

[0048] A third aspect of the present invention provides the following fiber processing method.

[0049]

[14] A method for treating fibers, using the fiber treating agent described in

[13] .

[0050] A fourth aspect of the present invention provides the following coating agent.

[0051]

[15] A coating agent comprising the water- and oil-repellent composition according to any one of [1] to

[12] .

[0052] A fifth aspect of the present invention provides the following processed fiber products.

[0053]

[16] A processed fiber product obtained by attaching the solid component contained in the fiber treatment agent of

[13] to fibers.

[0054] Effects of the Invention

[0055] According to the water- and oil-repellent composition of the present invention, high oil- and water-repellency can be imparted to a substrate.

[0056] Furthermore, the fiber treating agent, paper treating agent, and coating agent of the present invention can impart high oil repellency and water repellency to a substrate because they contain the water- and oil-repellent composition of the present invention. DETAILED DESCRIPTION

[0057] Below, water- and oil-repellent composition of the present invention, fiber treatment agent, paper treatment agent and coating agent are described in detail.In addition, the present invention is not limited to the embodiment shown below.The formation of following explanation can suitably change in the scope that does not exceed the scope of the present invention.For example, the present invention is not limited to following example, in the scope that does not exceed the purpose of the present invention, can add, omit, replace, change number, amount, ratio, composition, kind, position, material, formation etc.

[0058] In the following description, the term "monomer" refers to a compound having a radically polymerizable ethylenically unsaturated bond. The term "ethylenically unsaturated bond" refers to a double bond between carbon atoms other than carbon atoms forming an aromatic ring.

[0059] “(Meth)acryloyl” refers to “acryloyl” or “methacryloyl.” “(Meth)acrylate” refers to “acrylate” or “methacrylate.”

[0060] The term "non-volatile component" refers to a component having a boiling point of 130° C. or higher at 1 atmosphere (1013 hPa) among the components contained in the composition or the like.

[0061] The term "active ingredient" refers to the ingredients in a mixture that falls within a certain category, such as a solution, when used as a mixture. For example, the term "active ingredient" in a solution of polyether-modified polydimethylsiloxane in propylene glycol 1-monomethyl ether" refers to all compounds that fall within the category of polyether-modified polydimethylsiloxane contained in the solution.

[0062] The number average molecular weight and the weight average molecular weight are polystyrene-equivalent values ​​measured using gel permeation chromatography (GPC).

[0063] Unless otherwise specified, the term "ethylenically unsaturated bond" refers to an ethylenically unsaturated bond that is free radical polymerizable.

[0064] In a polymer of a compound having an ethylenically unsaturated bond, the chemical structure of a structural unit derived from a compound having an ethylenically unsaturated bond, excluding the ethylenically unsaturated bond, of the compound has the same chemical structure as the structural unit in the polymer, excluding the portion corresponding to the ethylenically unsaturated bond. For example, a structural unit derived from acrylic acid has the structure -CHCH(COOH)- in the polymer.

[0065] In the following description, the compound from which the structural unit of the polymer originates refers to a compound that corresponds to the structural unit and does not necessarily need to be identical to the monomer used in the actual production process of the polymer.

[0066] Unless otherwise specified, when a polymer has an ionic functional group such as a carboxyl group and a structural unit derived from a compound having an ethylenically unsaturated bond, the structural unit is derived from the same compound, regardless of whether a portion of the functional group is ion-exchanged or not. For example, in a polymer, not only the structure represented by -CH2-C(CH3)(COOH)- but also the structural unit represented by -CH2-C(CH3)(COONa)- is a structural unit derived from methacrylic acid.

[0067] If the chemical structure of the monomer used differs from the chemical structure of the resulting polymer, excluding the chain-like portion corresponding to the ethylenically unsaturated bond, by chemically reacting the polymer after polymerization, the structural units of the polymer will be based on the chemical structure after the chemical reaction, etc., after polymerization. For example, if vinyl acetate is polymerized and the resulting polymer is saponified, the chemical structure of the polymer obtained by saponification will be used as the basis. Therefore, the saponified structural units are not structural units derived from vinyl acetate, but rather structural units derived from vinyl alcohol.

[0068] <1. Water- and oil-repellent composition>

[0069] The water- and oil-repellent composition of present embodiment comprises the copolymer (A) that does not comprise the structural unit with siloxane bond (-Si-O-Si-), the copolymer (B), polyether-modified polydimethylsiloxane (C) and aqueous medium (D) that comprise the structural unit with siloxane bond.The water- and oil-repellent composition of present embodiment can further comprise other compositions such as surfactant (E) as required.The water- and oil-repellent composition of present embodiment can not comprise the compound with the perfluoroalkyl more than carbonatoms 8.The water- and oil-repellent composition of present embodiment can not comprise fluorinated compounds.

[0070] In the water- and oil-repellent composition of present embodiment, multipolymer (A) and multipolymer (B) preferably form emulsion (emulsion) in aqueous medium (D).Here, even if multipolymer (A) and multipolymer (B) are solid, if dispersed in aqueous medium (D), then also form emulsion.That is, multipolymer (A) and multipolymer (B) can form liquid particles, also can form solid particles.

[0071] [1-1. Copolymer (A)]

[0072] The copolymer (A) does not contain a structural unit having a siloxane bond. The copolymer (A) comprises a structural unit (a1) derived from a compound having an ethylenically unsaturated bond and an ester bond and not having an amide bond (hereinafter sometimes abbreviated as "structural unit (a1)"), and a structural unit (a2) derived from a compound having an ethylenically unsaturated bond and an amide bond (hereinafter sometimes abbreviated as "structural unit (a2)"). The copolymer (A) preferably consists only of the structural units (a1) and (a2) excluding the terminal structures.

[0073] The copolymer (A) imparts good oil repellency to the substrate to which the water- and oil-repellent composition of the present embodiment is attached.

[0074] [1-1-1. Structural unit (a1)]

[0075] The copolymer (A) having the structural unit (a1) can impart high oil repellency to the substrate and provide a highly stable water and oil repellent composition. The structural unit (a1) may be composed of one structure or two or more structures.

[0076] The type and content of the compound serving as a source of the structural units (a1) can be appropriately determined, for example, to adjust the glass transition temperature Tg of the copolymer (A). Specifically, in order to lower the glass transition temperature of the copolymer (A), the compound serving as a source of the structural units (a1) may be a compound whose homopolymer has a low glass transition temperature. In order to increase the glass transition temperature of the copolymer (A), the compound serving as a source of the structural units (a1) may be a compound whose homopolymer has a high glass transition temperature.

[0077] The structural unit (a1) is preferably a structural unit derived from one or both of a hydrocarbon having an ethylenically unsaturated bond and an alkyl (meth)acrylate, and more preferably a structural unit derived from an alkyl (meth)acrylate.

[0078] In the case where the compound becoming the source of structural unit (a1) is (meth) alkyl acrylate, it is further preferred that the carbon number of the hydrocarbon structure of the part other than (meth) acryloyloxy is more than 1 and less than 8 (meth) alkyl acrylate.Above-mentioned carbon number is preferably more than 2 and less than 7, more preferably more than 3 and less than 6, more preferably more than 4 and less than 5.This is because the adjustment of the feel of the substrate processed by the water- and oil-repellent composition related to the present embodiment becomes easy.

[0079] Examples of the alkyl (meth)acrylate in which the number of carbon atoms of the hydrocarbon structure of the portion excluding the (meth)acryloyloxy group is 1 or more and 8 or less include methyl (meth)acrylate, ethyl (meth)acrylate, allyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dimethylhexyl (meth)acrylate, and octyl (meth)acrylate.

[0080] When the water- and oil-repellent composition of the present embodiment is included in a paper treatment agent used for paper treatment or a fiber treatment agent used for fiber treatment, among the above-mentioned compounds, the compound that serves as the source of the structural unit (a1) is particularly preferably one or more selected from methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0081] The compound becoming the source of structural unit (a1) can include (meth) alkyl acrylate having a chain hydrocarbon structure with carbon number of more than 9 as the hydrocarbon structure of the part except (meth) acryloyloxy. In this case, it is possible to obtain a water and oil repellent composition that maintains oil repellency while providing better water repellency to substrate.

[0082] When the structural unit (a1) is a structural unit derived from a hydrocarbon having an ethylenically unsaturated bond, an aromatic vinyl compound is preferred. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, and p-methylstyrene.

[0083] [1-1-2. Structural unit (a2)]

[0084] The copolymer (A) having the structural unit (a2) provides a water- and oil-repellent composition capable of imparting high oil repellency to a substrate. The structural unit (a2) may be composed of one structure or may contain two or more structures.

[0085] The compound that becomes the source of structural unit (a2) is a compound with an ethylenically unsaturated bond and an amide bond. As the compound that becomes the source of structural unit (a2), for example, acrylamide, methacrylamide, N-vinylacetamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N,N-dimethyl (methyl) acrylamide, N-methyl-N-ethyl (methyl) acrylamide, N,N-diethyl (methyl) acrylamide, etc. can be mentioned. The compound that becomes the source of structural unit (a2) preferably includes any one or both of acrylamide and methacrylamide, more preferably any one or both of acrylamide and methacrylamide. Structural unit (a2) may or may not include an ester bond.

[0086] [1-1-3. Content of Each Structural Unit in Copolymer (A)]

[0087] The content of the structural unit (a1) in the copolymer (A) is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, and particularly preferably 85% by mass or more, because the resulting water and oil repellent composition has good stability.

[0088] In order to easily ensure the content of the structural units (a2), the content of the structural units (a1) in the copolymer (A) is preferably 99% by mass or less, more preferably 98% by mass or less, further preferably 97% by mass or less, and particularly preferably 96% by mass or less. The content of the structural units (a1) in the copolymer (A) can be, for example, 30% by mass to 99% by mass, 40% by mass to 60% by mass, 60% by mass to 70% by mass, 70% by mass to 80% by mass, 88% by mass to 99% by mass, 90% by mass to 98% by mass, 93% by mass to 97% by mass, or 94% by mass to 96% by mass, as needed.

[0089] In the case of the carbon number of the hydrocarbon structure of the part except (meth) acryloyloxy that the compound becoming the source of structural unit (a1) is more than 1 and less than 8 (meth) alkyl acrylate, the containing rate of the structural unit (a1) in copolymer (A) is preferably more than 30 mass %, more preferably more than 50 mass %, further preferably more than 70 mass %.This is because it is easy to adjust the feel of the substrate processed by the water- and oil-repellent agent composition involved in the present embodiment.

[0090] When the compound serving as a source of the structural unit (a1) is an alkyl (meth)acrylate having a hydrocarbon structure having 1 to 8 carbon atoms in the portion excluding the (meth)acryloyloxy group, the content of the structural unit (a1) in the copolymer (A) is preferably 99% by mass or less, more preferably 98% by mass or less, in order to easily secure the content of the structural unit (a2).

[0091] The content of the structural unit (a2) in copolymer (A) is preferably more than 0.10 mass %, more preferably more than 0.50 mass %, further preferably more than 1.0 mass %, particularly preferably more than 1.8 mass %. This is because it becomes a water and oil repellent composition that can give better oil repellency to substrate.

[0092] The containing rate of the structural unit (a2) in copolymer (A) is preferably below 20 mass %, more preferably below 10 mass %, further preferably below 5.0 mass %, particularly preferably below 3.0 mass %.In order to become the water and oil repellent composition of low cost. In addition, owing to being easy to ensure the containing rate of structural unit (a1), therefore being easy to ensure the good water repellency in the substrate processed with water and oil repellent composition. The containing rate of the structural unit (a2) in copolymer (A) can be such as 0.10 mass %~20.0 mass %, 0.30 mass %~15.0 mass %, 0.50 mass %~8.0 mass %, 0.8 mass %~7.0 mass %, 1.0 mass %~6.0 mass %, 1.2 mass %~4.0 mass %, 1.5 mass %~3.5 mass % as needed.

[0093] The copolymer (A) may contain a polymerization initiator used during the polymerization for producing the copolymer (A). Any polymerization initiator may be selected, and examples thereof include hydrogen peroxide, azo compounds, and organic peroxides. The polymerization initiator may be included as a redox initiator in which the above-mentioned polymerization initiator is used in combination with a reducing agent. The polymerization initiator may contain only one type, or may contain two or more types.

[0094] The copolymer (A) may contain a chain transfer agent used in the polymerization for producing the copolymer (A). The chain transfer agent adjusts the molecular weight of the copolymer (A) produced by polymerization. Examples of chain transfer agents include, for example, mercaptans, thioglycolic acid and its esters, β-mercaptopropionic acid and its esters. The chain transfer agent may contain only one type or two or more types. The amount of the polymerization initiator and the chain transfer agent may be arbitrarily selected. For example, the content of these compounds relative to a total of 100 parts by mass of the monomers may be 0.1 to 10.0% by mass, 0.5 to 5.0% by mass, 1.0 to 3.0% by mass, etc., but is not limited to these examples.

[0095] [1-2. Copolymer (B)]

[0096] The copolymer (B) comprises a structural unit (b1) derived from a compound having an ethylenically unsaturated bond and an ester bond and not having an amide bond (hereinafter sometimes abbreviated as “structural unit (b1)”), a structural unit (b2) derived from a compound having an ethylenically unsaturated bond and an amide bond (hereinafter sometimes abbreviated as “structural unit (b2)”), and a structural unit (b3) derived from a polydimethylsiloxane having an ethylenically unsaturated bond (hereinafter sometimes abbreviated as “structural unit (b3)”).

[0097] The structural unit (b1) and the structural unit (b2) in the present embodiment do not include a structural unit having a siloxane bond.

[0098] The copolymer (B) preferably consists of the structural unit (b1), the structural unit (b2), and the structural unit (b3) excluding the terminal structure.

[0099] The copolymer (B) imparts oil repellency to the substrate to which the water- and oil-repellent composition of the present embodiment is attached, and also imparts good water repellency.

[0100] [1-2-1. Structural unit (b1) and structural unit (b2)]

[0101] About the structure, preferred structure and specific example of the essential element becoming structural unit (b1), it is the same as structural unit (a1).In the water- and oil-repellent composition of the present embodiment, the structural unit (a1) that copolymer (A) has and the structural unit (b1) that copolymer (B) has can be the same or different.

[0102] About the structure, preferred structure and specific example of the essentials becoming structural unit (b2), same as structural unit (a2).In the water- and oil-repellent composition of the present embodiment, the structural unit (a2) that copolymer (A) has and the structural unit (b2) that copolymer (B) has can be identical or different.

[0103] [1-2-2. Structural unit (b3)]

[0104] Structural unit (b3) is the structural unit derived from the polydimethylsiloxane with ethylenically unsaturated bond, is the part of the polysiloxane side chain formed in multipolymer (B).Have structural unit (b3) by multipolymer (B), thus become and can give high water repellent water and oil repellent composition to base material.Structural unit (b3) can only be made up of 1 kind of structure, also can comprise 2 or more structures.

[0105] The structural unit (b3) is preferably a structural unit derived from a compound represented by the following formula (1).

[0106]

[0107] (In formula (1), R 1 represents a hydrogen atom or a methyl group; R 2 represents a divalent aliphatic group having 1 to 6 carbon atoms which may contain an ether bond; R 3 represents an aliphatic group, aromatic group, or hydroxyl group having 1 to 30 carbon atoms; h is any one of 0, 1, and 2. j represents an integer from 0 to 500.

[0108] R in formula (1) 1 represents a hydrogen atom or a methyl group.

[0109] R in formula (1) 2 It is a divalent aliphatic group having 1 to 6 carbon atoms which may contain an ether bond. 2 The number of carbon atoms in R is preferably 1 to 4, and may be 1 to 4 or 2 to 3 as needed. This is because the above number of atoms provides a water- and oil-repellent composition that can impart high oil repellency to a substrate. 2 A hydrocarbon chain is more preferred, and a linear hydrocarbon chain is more preferred, because the resulting water and oil repellent composition can impart high water repellency to a substrate.

[0110] R in formula (1) 3 is an aliphatic group, an aromatic group, or a hydroxyl group having 1 to 30 carbon atoms. 3 It is preferably an aliphatic group having 1 to 30 carbon atoms, more preferably an aliphatic group having 2 to 18 carbon atoms, further preferably an aliphatic group having 2 to 10 carbon atoms, and particularly preferably an aliphatic group having 2 to 6 carbon atoms. For example, the number of carbon atoms may be 3 to 5 or 2 to 4. 3 A hydrocarbon chain is more preferred, and a linear hydrocarbon chain is even more preferred, because the resulting water and oil repellent composition can impart high water repellency to a substrate.

[0111] In formula (1), j is an integer of 0 to 500. To achieve a preferred number average molecular weight range for the compound represented by formula (1), j is preferably an integer of 1 to 400, more preferably an integer of 10 to 300. For example, j may be an integer in the range of 1 to 200, 1 to 150, 1 to 80, 1 to 30, 1 to 10, or 1 to 5.

[0112] The compound serving as a source of the structural unit (b3) may be only one kind of the compound represented by formula (1), or may contain two or more kinds.

[0113] The number average molecular weight of the compound shown in formula (1) is preferably more than 300, more preferably more than 1,000, further preferably more than 3,000, and particularly preferably more than 7,000. Because in the substrate treated with the water- and oil-repellent composition, better water repellency can be obtained. The number average molecular weight of the compound shown in formula (1) is preferably less than 40,000, more preferably less than 20,000, and further preferably less than 15,000. Because the copolymerizability of the compound shown in formula (1) during the polymerization for the manufacture of copolymer (B) improves.

[0114] [1-2-3. Content of Each Structural Unit in Copolymer (B)]

[0115] The content of the structural unit (b1) in the copolymer (B) is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, and particularly preferably 70% by mass or more, because the resulting water and oil repellent composition has excellent stability.

[0116] In order to easily ensure the content of the structural units (b2) and (b3), the content of the structural units (b1) in the copolymer (B) is preferably 96% by mass or less, more preferably 93% by mass or less, and even more preferably 90% by mass or less. The content of the structural units (b1) in the copolymer (B) can be, for example, 30% to 96% by mass, 45% to 95% by mass, 55% to 94% by mass, 60% to 85% by mass, or 65% to 80% by mass.

[0117] In the case of the carbon number of the hydrocarbon structure of the part other than (meth) acryloyloxy that the compound becoming the source of structural unit (b1) is more than 1 and less than 8 (meth) alkyl acrylate, the containing rate of the structural unit (b1) in copolymer (B) is preferably more than 30 mass %, more preferably more than 50 mass %, further preferably more than 70 mass %.Because it is easy to adjust the feel of the substrate processed by the water- and oil-repellent agent composition involved in the present embodiment.

[0118] When the compound serving as a source of the structural unit (b1) is an alkyl (meth)acrylate having a hydrocarbon structure having 1 to 8 carbon atoms in the portion excluding the (meth)acryloyloxy group, the content of the structural unit (b1) in the copolymer (B) is preferably 96% by mass or less, more preferably 93% by mass or less, in order to easily ensure the content of the structural units (b2) and (b3).

[0119] The content of the structural unit (b2) in the copolymer (B) is preferably 0.10% by mass or more, more preferably 0.50% by mass or more, further preferably 0.85% by mass or more, and particularly preferably 1.8% by mass or more. This is because it can impart a water and oil repellent composition with better oil repellency to the substrate.

[0120] The containing ratio of the structural unit (b2) in copolymer (B) is preferably below 20 mass %, more preferably below 10 mass %, further preferably below 5.0 mass %, particularly preferably below 3.0 mass %.Because it becomes the water and oil repellent composition of low cost.In addition, owing to being easy to ensure the containing ratio of structural unit (b1) and structural unit (b3), therefore being easy to ensure the good water repellency in the substrate processed with water and oil repellent composition.The containing ratio of the structural unit (b2) in copolymer (B) can be for example 0.10 mass %~20.0 mass %, 0.30 mass %~15.0 mass %, 0.7 mass %~10.0 mass %, 1.0 mass %~8.0 mass %, 1.2 mass %~6.0 mass %, 1.5 mass %~3.0 mass %.

[0121] The content of the structural unit (b3) in the copolymer (B) is preferably 3.0% by mass or more, more preferably 5.0% by mass or more, and even more preferably 7.0% by mass or more, because the resulting water and oil repellent composition can impart better water repellency to a substrate.

[0122] The containing ratio of the structural unit (b3) in copolymer (B) is preferably below 50 mass %, more preferably below 30 mass %, further preferably below 15 mass %.Because it is easy to ensure the containing ratio of structural unit (b1) and structural unit (b2), the feel of the base material processed by water- and oil-repellent agent composition can be well maintained.The containing ratio of the structural unit (b3) in copolymer (B) can be for example 3.0 mass %~50.0 mass %, 4.0 mass %~47.0 mass %, 5.0 mass %~45.0 mass %, 6.0 mass %~43 mass %, 8.0 mass %~40.0 mass %, 10.0 mass %~25.0 mass %, 15.0 mass %~20.0 mass %.

[0123] In the present embodiment, the containing rate of the structural unit (b3) in the total amount of copolymer (A) and copolymer (B) is preferably more than 1.5 mass %, more preferably more than 2.5 mass %, further preferably more than 3.5 mass %.Because it becomes the water- and oil-repellent composition that can give better water repellency to base material.

[0124] The containing ratio of the structural unit (b3) in the total amount of multipolymer (A) and multipolymer (B) is preferably below 30 mass %, more preferably below 15 mass %, further preferably below 7.5 mass %.Because it is easy to ensure the containing ratio of structural unit (a1) (a2) (b1) and (b2), become the water- and oil-repellent agent composition that can give better water repellency and oil repellency to base material.Such as, the containing ratio of the structural unit (b3) in the above-mentioned total amount can be more than 1.5 mass % and below 30 mass %, more than 2.0 mass % and below 25 mass %, more than 3.0 mass % and below 20 mass %, more than 4.0 mass % and below 15 mass %, more than 5.0 mass % and below 10 mass % etc.

[0125] Multipolymer (B) can comprise the polymerization initiator used when being used to manufacture the polymerization of multipolymer (B).As polymerization initiator, can enumerate the polymerization initiator identical with the polymerization initiator that can comprise in multipolymer (A).In the water- and oil-repellent agent composition of present embodiment, when multipolymer (A) and multipolymer (B) comprise polymerization initiator, the polymerization initiator comprised by multipolymer (A), the polymerization initiator comprised by multipolymer (B) can be identical, also can be different.

[0126] Multipolymer (B) can comprise the chain-transfer agent employed when being used to manufacture the polymerization of multipolymer (B).As chain-transfer agent, can enumerate the chain-transfer agent identical with the chain-transfer agent that can comprise in multipolymer (A).In the water- and oil-repellent agent composition of present embodiment, when multipolymer (A) and multipolymer (B) comprise chain-transfer agent, the chain-transfer agent comprised by multipolymer (A), the chain-transfer agent comprised by multipolymer (B) can be identical, also can be different.

[0127] [1-3. Mixing ratio of copolymer (A) and copolymer (B)]

[0128] In the water- and oil-repellent composition that the present embodiment relates to, the value (the quality of the quality / multipolymer (B) of multipolymer (A)) based on the blending ratio of mass of multipolymer (B) is preferably more than 10 / 90, more preferably more than 20 / 80.Because become the water- and oil-repellent composition that can give better oil repellency to base material.In the water- and oil-repellent composition that the present embodiment relates to, the value of the blending ratio based on mass of multipolymer (A) and multipolymer (B) can be more than 30 / 70, can also be more than 40 / 60.

[0129] In the water- and oil-repellent composition that the present embodiment is related to, the value of the mixing ratio based on mass of multipolymer (A) and multipolymer (B) is preferably below 90 / 10, more preferably below 80 / 20, further preferably below 70 / 30, particularly preferably below 60 / 40.Because become the water- and oil-repellent composition that can give better water repellency to base material.

[0130] [1-4. Polyether-modified polydimethylsiloxane (C)]

[0131] The polyether-modified polydimethylsiloxane (C) is a compound in which a portion or all of the hydrogen atoms of the methyl groups of polydimethylsiloxane are replaced with polyether chains. In other words, the polyether-modified polydimethylsiloxane is a graft copolymer having a polysiloxane main chain and polyether side chains.

[0132] The polyether-modified polydimethylsiloxane (C) imparts good water repellency and oil repellency to the substrate to which the water- and oil-repellent composition of the present embodiment is applied.

[0133] As polyether-modified polydimethylsiloxane (C), it is preferred that there is a material of at least any one of an alkoxy group and a hydroxyl group at the end of a polyether chain, more preferably a material having a hydroxyl group at the end of a polyether chain. In the case where polyether-modified polydimethylsiloxane (C) is a material having a hydroxyl group at the end of a polyether chain, it becomes a water- and oil-repellent composition that can impart better oil repellency to substrate. For example, the type and addition number of the polyether chain can be arbitrarily selected. For example, the position and number of the polyether chain combined with the Si of polydimethylsiloxane can be arbitrarily selected. As the example of a polyether chain, -(CH2O) can be enumerated. x (C2H4O) y (C3H6O) z R, etc., but are not limited to this example. x, y, and z are each an integer of 0 or 1 or greater, and not all of them are 0 at the same time. R is preferably any one of an alkyl group having 1 to 10 carbon atoms and a hydrogen atom. x, y, and z are, for example, 0 to 300, 0 to 100, 0 to 50, 0 to 20, or 0 to 10. The number and arrangement of the methyleneoxy group, ethyleneoxy group, and propyleneoxy group of the polyether chain can be arbitrarily selected, and each can be arranged continuously, alternately, or randomly.

[0134] Examples of commercially available compositions containing a polyether-modified polydimethylsiloxane (C) having a hydroxyl group at the end of the polyether chain include BYK SILCLEAN 3720 manufactured by BYK, TEGO (registered trademark) Protect 5100N manufactured by Ebonic Corporation, and KP-109 manufactured by Shin-Etsu Silicone Co., Ltd.

[0135] The weight average molecular weight of the polyether-modified polydimethylsiloxane (C) is preferably 1,000 or more, more preferably 5,000 or more, and even more preferably 7,000 or more, because the resulting water and oil repellent composition can impart better oil repellency to a substrate.

[0136] The weight average molecular weight of the polyether-modified polydimethylsiloxane (C) is preferably 50,000 or less, more preferably 30,000 or less, and even more preferably 14,000 or less, because the resulting water and oil repellent composition can impart better water repellency to a substrate.

[0137] The content of polyether-modified polydimethylsiloxane (C) is preferably 0.10 mass part or more, more preferably 0.20 mass part or more, further preferably 0.50 mass part or more, particularly preferably 0.90 mass part or more, relative to 100 mass parts of the total of copolymer (A) and copolymer (B). Because it becomes a water and oil repellent composition that can give better oil repellency to substrate.

[0138] The content of polyether-modified polydimethylsiloxane (C) is relative to 100 mass parts of the total of multipolymer (A) and multipolymer (B), preferably below 20 mass parts, more preferably below 10 mass parts, further preferably below 7.0 mass parts, particularly preferably below 3.5 mass parts, most preferably below 1.5 mass parts.Because the feel of the fiber or paper processed using water- and oil-repellent agent composition is good.The content of above-mentioned polyether-modified polydimethylsiloxane (C) can be for example more than 0.10 mass parts and below 5.0 mass parts, more than 0.20 mass parts and below 3.0 mass parts, more than 0.30 mass parts and below 2.0 mass parts, more than 0.40 mass parts and below 1.0 mass parts etc.

[0139] [1-5. Aqueous medium (D)]

[0140] Aqueous medium (D) uses water as an essential component. Aqueous medium (D) can also include a hydrophilic solvent in addition to water. The content of water in the aqueous medium (D) can be arbitrarily selected, but is preferably more than 90 mass %, more preferably more than 95 mass %, further preferably more than 98 mass %, and can be 100 mass %. As hydrophilic solvent, nitrogen-containing organic solvents such as alcohols such as methanol, ethanol, propylene glycol 1-monomethyl ether, n-propyl alcohol, isopropyl alcohol, tert-butyl alcohol, benzyl alcohol, N-methyl pyrrolidone, etc. can be mentioned. The hydrophilic solvent can include only one or more.

[0141] The content of the hydrophilic solvent in the aqueous medium (D) is preferably 10% by mass or less, more preferably 5.0% by mass or less. If the content of the hydrophilic solvent is 10% by mass or less, the cost increase caused by the use of the hydrophilic solvent can be suppressed.

[0142] The content of the aqueous medium (D) contained in the water- and oil-repellent composition is preferably determined so that the non-volatile matter concentration of the water- and oil-repellent composition becomes a desired value.

[0143] The nonvolatile component concentration of the water- and oil-repellent composition is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more. This is because a small amount can effectively impart a water- and oil-repellent composition to a substrate that can repel water and oil.

[0144] The nonvolatile content of the water- and oil-repellent composition is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less, because the composition has good storage stability and can be easily and uniformly applied to a substrate.

[0145] The content of the aqueous medium (D) contained in the water- and oil-repellent composition can be arbitrarily selected, and examples thereof include 2% by mass or more and 95% by mass or less, 5% by mass or more and 90% by mass or less, 10% by mass or more and 80% by mass or less, 30% by mass or more and 70% by mass or less, and 40% by mass or more and 60% by mass or less, but the present invention is not limited to these examples.

[0146] [1-6. Other ingredients]

[0147] The water- and oil-repellent composition of present embodiment can also comprise other compositions as required except multipolymer (A), multipolymer (B), polyether-modified polydimethylsiloxane (C), aqueous medium (D).Other compositions that can comprise as the water- and oil-repellent composition of present embodiment can include resin, cross-linking agent, thickening agent, pH adjusting agent, film-forming aid, plasticizer, preservative, defoamer, surfactant (E) etc.Other compositions can be according to the specification of water- and oil-repellent composition, in the scope that can realize purpose of the present invention, contain 1 kind or more than 2 kinds.

[0148] [1-6-1. Surfactant (E)]

[0149] As surfactant (E), anionic surfactants, nonionic surfactants, and cationic surfactants can be used, and commercially available products can be used. Surfactant (E) does not have an ethylenically unsaturated bond. In this embodiment, a copolymerizable surfactant having an ethylenically unsaturated bond is included in the compound that becomes the source of structural unit (a1).

[0150] Examples of the anionic surfactant include alkylbenzenesulfonates, alkylsulfate ester salts, polyoxyethylene alkyl ether sulfate ester salts, and fatty acid salts.

[0151] Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene polycyclic phenyl ethers, polyoxyalkylene alkyl ethers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters.

[0152] As cationic surfactant, alkyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, lauryl pyridinium chloride etc. can be enumerated.As surfactant (E), preferably comprise cationic surfactant.Because become the high water and oil repellent composition with the close adhesion of base material, and the kind of additive that antibacterial agent etc. can be selected becomes many.As cationic surfactant, preferably use the hydrochloride of the compound with ammonium group, more preferably use quaternary ammonium chloride.

[0153] When the water- and oil-repellent composition of the present embodiment includes surfactant (E), surfactant (E) is preferably more than 0.15 mass part relative to the content of 100 mass parts of the total of multipolymer (A) and multipolymer (B), more preferably more than 0.40 mass part, further preferably more than 0.90 mass part.Because multipolymer (A) and multipolymer (B) can be stably dispersed in the water- and oil-repellent composition.

[0154] In the water- and oil-repellent composition of the present embodiment, surfactant (E) is preferably below 5.0 mass parts relative to the content of 100 mass parts totaling to multipolymer (A) and multipolymer (B), more preferably below 3.0 mass parts, further preferably below 1.5 mass parts.Because can when not damaging water resistance, maintain the base material adhesion of the coating layer obtained by water- and oil-repellent composition.

[0155] The surfactant (E) that the water- and oil-repellent agent composition of present embodiment includes can be partly or entirely for the surfactant used when being used for the manufacture of the polymerization of multipolymer (A) and / or for the surfactant used when being used for the manufacture of the polymerization of multipolymer (B).The surfactant used when being used for the manufacture of the polymerization of multipolymer (A), the surfactant used when being used for the manufacture of the polymerization of multipolymer (B) can be different, also can be identical.

[0156] Furthermore, part or all of the surfactant (E) contained in the water- and oil-repellent composition of the present embodiment may be added after the copolymer (A) and the copolymer (B) are produced.

[0157] <2. Method for producing water- and oil-repellent composition>

[0158] The water- and oil-repellent composition of the present embodiment can be produced, for example, by the method described below. The method for producing the water- and oil-repellent composition according to the present invention is not limited to the method described below.

[0159] First, manufacture the 1st polymerization process of the aqueous emulsion (α) that multipolymer (A) is dispersed in the aqueous medium (D). In addition, manufacture the 2nd polymerization process of the aqueous emulsion (β) that multipolymer (B) is dispersed in the aqueous medium (D). Then, carry out the mixing process that aqueous emulsion (α), aqueous emulsion (β) and polyether-modified polydimethylsiloxane (C) are mixed. By above operation, the water- and oil-repellent composition of present embodiment can be obtained.

[0160] [2-1-1. First polymerization step]

[0161] In the first polymerization step, preferably, monomers containing the compound serving as a source of structural unit (a1) and the compound serving as a source of structural unit (a2), a surfactant (E), an aqueous medium (D), and, if necessary, a polymerization initiator and a chain transfer agent are mixed and emulsion polymerization is carried out. This produces a copolymer (A) obtained by copolymerizing the monomers containing the compound serving as a source of structural unit (a1) and the compound serving as a source of structural unit (a2), and an aqueous emulsion (α) containing the surfactant (E) and in which the copolymer (A) is dispersed in the aqueous medium (D) is obtained.

[0162] In the first polymerization step, emulsion polymerization can be performed at a temperature of, for example, 30 to 85°C.

[0163] As in the example described here, when the chemical structure of the copolymer (A) obtained by polymerization is not changed (however, ion exchange can be performed), each monomer used as a material of the aqueous emulsion (α) also maintains its structure other than the ethylenically unsaturated bond after polymerization (except for ion exchange).

[0164] The amount of the aqueous medium (D) used as a material for the aqueous emulsion (α) is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and even more preferably 100 parts by mass or more, relative to 100 parts by mass of the total of the compound serving as a source of the structural unit (a1) and the compound serving as a source of the structural unit (a2) (total monomers). This is because the compound serving as a source of the structural unit (a1) and the compound serving as a source of the structural unit (a2) can be emulsified in the aqueous medium (D) and emulsion polymerization can be performed efficiently, and the copolymer (A) produced by the emulsion polymerization can be stably dispersed in the aqueous medium (D).

[0165] The amount of the aqueous medium (D) used as a material for the aqueous emulsion (α) is preferably 400 parts by mass or less, more preferably 300 parts by mass or less, and even more preferably 200 parts by mass or less, relative to 100 parts by mass of the total of the compound serving as a source of the structural unit (a1) and the compound serving as a source of the structural unit (a2). By reducing the amount of excess aqueous medium (D), productivity can be improved, and increases in manufacturing and operating costs due to miniaturization of manufacturing equipment and storage facilities can be suppressed. Furthermore, transportation costs can also be suppressed.

[0166] In the present embodiment, the amount of the surfactant (E) used relative to the total mass of monomers used as materials of the aqueous emulsion (α) is the same as the content of the surfactant (E) per 100 parts by mass of the copolymer (A) in the aqueous emulsion (α).

[0167] In the first polymerization step, the above-mentioned polymerization initiator is preferably used. The amount of the polymerization initiator used is preferably 0.01 to 1.0 parts by mass, more preferably 0.05 to 0.80 parts by mass, and even more preferably 0.1 to 0.5 parts by mass, relative to 100 parts by mass of the total of the compound from which the structural unit (a1) originates and the compound from which the structural unit (a2) originates (total monomers), in order to achieve an appropriate polymerization rate.

[0168] In the first polymerization step, each component used as a material for the aqueous emulsion (α) may be added together to carry out emulsion polymerization, or each component may be continuously supplied while emulsion polymerization is carried out. When each component is continuously supplied while emulsion polymerization is carried out, for example, the following method may be used.

[0169] First, a portion of the aqueous medium (D) and a portion of the surfactant (E) are mixed to prepare a mixed solution, and a portion of the polymerization initiator is mixed with the obtained mixed solution to prepare a polymerization initiator solution.

[0170] On the other hand, the compound serving as a source of the structural unit (a1), the compound serving as a source of the structural unit (a2), the remainder of the aqueous medium (D), and the remainder of the surfactant (E) are mixed and emulsified to prepare a mixed emulsion.

[0171] Furthermore, a method of carrying out emulsion polymerization in a polymerization initiator solution by continuously supplying the mixed emulsion and the remaining portion of the polymerization initiator simultaneously with stirring can be used.

[0172] [2-1-2. Second polymerization step]

[0173] In the second polymerization step, preferably, monomers containing the compound serving as a source of structural unit (b1), the compound serving as a source of structural unit (b2), and the compound serving as a source of structural unit (b3), a surfactant (E), an aqueous medium (D), and, if necessary, a polymerization initiator and a chain transfer agent are mixed and emulsion polymerization is carried out. This produces a copolymer (B) obtained by copolymerizing the compound serving as a source of structural unit (b1), the compound serving as a source of structural unit (b2), and the compound serving as a source of structural unit (b3), and an aqueous emulsion (β) containing the surfactant (E) and in which the copolymer (B) is dispersed in the aqueous medium (D).

[0174] In the second polymerization step, emulsion polymerization can be performed at a temperature of, for example, 30 to 85°C.

[0175] The second polymerization step may be performed after the first polymerization step, before the first polymerization step, or simultaneously with the first polymerization step.

[0176] As in the example described here, when the chemical structure of the copolymer (B) obtained by polymerization is not changed (however, ion exchange can be performed), each monomer used as a material for the aqueous emulsion (β) also maintains its structure other than the ethylenically unsaturated bond after polymerization (except for ion exchange).

[0177] The preferred amount of the aqueous medium (D) used as a material for the aqueous emulsion (β) (preferred amount relative to the total amount of monomers) is the same as that used as a material for the aqueous emulsion (α).

[0178] In the present embodiment, the amount of the surfactant (E) used relative to the total mass of monomers used as materials of the aqueous emulsion (β) is the same as the content of the surfactant (E) per 100 parts by mass of the copolymer (B) in the aqueous emulsion (β).

[0179] The preferred amount of the surfactant (E) used as a material for the aqueous emulsion (β) (preferred amount relative to the total amount of monomers) is the same as the preferred amount of the surfactant (E) used as a material for the aqueous emulsion (α).

[0180] In the second polymerization step, the above-mentioned polymerization initiator is preferably used as in the first polymerization step. The amount of the polymerization initiator used (preferably the amount used relative to the total amount of monomers) is the same as that used in the first polymerization step.

[0181] In the second polymerization step, each component used as a material for the aqueous emulsion (β) may be added together to carry out emulsion polymerization, or each component may be continuously supplied while emulsion polymerization is carried out. When emulsion polymerization is carried out while each component is continuously supplied, for example, the same method as that used in the first polymerization step may be used.

[0182] [2-2. Mixing process]

[0183] In the mixing step, the aqueous emulsion (α) obtained in the first polymerization step, the aqueous emulsion (β) obtained in the second polymerization step, and the polyether-modified polydimethylsiloxane (C) are mixed.

[0184] As a mixing method, a known method can be used. For example, as a mixing method, a method of stirring at a temperature of 23° C. and a rotation speed of 500 rpm for 5 minutes using a Homodisper 2.5 (manufactured by PRIMIX) can be mentioned.

[0185] In the manufacture method of the water- and oil-repellent composition of the present embodiment, the case of using a surfactant (E) to manufacture an aqueous emulsion (α) in the first polymerization step and using a surfactant (E) to manufacture an aqueous emulsion (β) in the second polymerization step is cited as an example for description, but the timing of adding the surfactant (E) can be appropriately adjusted according to the purpose of using the surfactant (E).

[0186] Specifically, the surfactant (E) can be used not only in the first polymerization step and the second polymerization step but also, if necessary, added to the aqueous emulsion (α) and / or the aqueous emulsion (β) after the first polymerization step and before the mixing step. In this case, the copolymer (A) can be more stably dispersed in the aqueous emulsion (α), and / or the copolymer (B) can be more stably dispersed in the aqueous emulsion (β).

[0187] In addition, surfactant (E) can be added together with aqueous emulsion (α) and aqueous emulsion (β) in mixing process as needed, and can further add in the water and oil repellent composition obtained after mixing process.In this case, multipolymer (A) and multipolymer (B) can be stably dispersed in the water and oil repellent composition.

[0188] In the manufacture method of the water- and oil-repellent composition of the present embodiment, the case of using an aqueous medium (D) as the material of the aqueous emulsion (α) and the aqueous emulsion (β) is cited as an example for description, but the aqueous medium (D) can be added to the aqueous emulsion (α) and / or the aqueous emulsion (β) as needed after the first polymerization step and the second polymerization step and before the mixing step.

[0189] In addition, aqueous medium (D) can add together with aqueous emulsion (α) and aqueous emulsion (β) in mixing process as required, also can further add in the water and oil repellent composition obtained after mixing process.In addition, can after mixing process, as required water and oil repellent composition is used known method to concentrate, thereby the part for aqueous medium (D) is removed.

[0190] Since the water- and oil-repellent composition of the present embodiment contains the copolymer (A) and the copolymer (B), it can impart high water- and oil-repellency to a substrate.

[0191] In contrast, for example, for not comprising multipolymer (A) and only comprising the water- and oil-repellent agent composition of multipolymer (B), in the case where the containing ratio of structural unit (b3) is identical with the water- and oil-repellent agent composition of present embodiment, the oil repellency that can be given to substrate is poor. It is inferred that this is because, for the water- and oil-repellent agent composition only comprising multipolymer (B), oil is introduced by the structural unit (b3) in multipolymer (B), thus the oil repellency that can be given to substrate is reduced.

[0192] <3. Application of the water- and oil-repellent composition>

[0193] The water- and oil-repellent composition of the present embodiment can give high oil repellency and water repellency to base material, and is good to the adsorptivity of base material.The water- and oil-repellent composition of the present embodiment can give high oil repellency and water repellency to base materials such as fiber, paper, glass.Therefore, as the applicable purposes of the water- and oil-repellent composition of the present embodiment, the material of fiber treatment agent, paper treatment agent, coating agent can be enumerated.

[0194] 〔3-1. Fiber treatment agents〕

[0195] The fiber treatment agent of the present embodiment comprises the water- and oil-repellent composition of the present embodiment, may be composed only of the water- and oil-repellent composition of the present embodiment, or may contain, in addition to the water- and oil-repellent composition, defoaming agents, preservatives, pH regulators, surfactants, cross-linking agents, antistatic agents, wetting agents, thickeners, pigments and other well-known and commonly used additives, as needed, within the scope that can achieve the purpose of the present invention.

[0196] The fiber treatment agent of the present embodiment can give high oil repellency and water repellency to the fiber. In this specification, so-called "fiber" refers to fiber and articles using fiber as raw material. The fiber treated by the fiber treatment agent can be any form such as short fiber (fiber), cotton linters, roving, sliver, yarn, woven fabric, knitted fabric, non-woven fabric, paper, etc. In this specification, paper is also included in the fiber. As the raw material of the fiber treated, cellulose fibers such as cotton, flax, jute, hemp, ramie, regenerated fiber cellulose, rayon, polyvinyl alcohol-based synthetic fibers, pulp, etc. can be mentioned. The fiber treated by the fiber treatment agent preferably contains more than 30% by mass of the above-mentioned raw materials. The fiber treatment agent of the present embodiment can give high oil repellency and water repellency to paper. As the paper treated by the fiber treatment agent, there is no particular limitation, and for example, general paper using pulp cellulose can be mentioned.

[0197] About the water- and oil-repellent fiber processed by the fiber treatment agent of the present embodiment, the fiber treatment agent comprising the water- and oil-repellent composition of the present embodiment is attached to the fiber becoming base material.Above-mentioned water- and oil-repellent composition is preferably more than 1.0 mass parts relative to the total attachment amount of 100 mass parts of the fiber becoming base material, more preferably more than 2.0 mass parts.Because the water repellency and oil repellency of water- and oil-repellent fiber improve.Above-mentioned water- and oil-repellent composition is preferably less than 20 mass parts relative to the attachment amount of 100 mass parts of the fiber becoming base material, more preferably less than 10 mass parts.Because by being attached with fiber treatment agent on fiber, thereby can suppress feel to be damaged, and can suppress quality to increase.

[0198] As a method of treating fibers as a base material using the fiber-treating agent of the present embodiment, that is, a method of producing a fiber-processed product using the fiber-treating agent, for example, the following method can be mentioned.

[0199] First, the fibers serving as the substrate are impregnated or coated with a fiber treatment agent. Examples of impregnation or coating methods include dipping, spraying, and roller coating. After the fibers are impregnated or coated with the fiber treatment agent, the amount of fiber treatment agent adhered to the fibers is adjusted. Examples of methods for adjusting the amount of adherence include, but are not limited to, squeezing using a squeeze roll. Preferably, after impregnation or coating the fibers with the fiber treatment agent, the fibers are dried. The fiber drying temperature is preferably 80°C to 170°C, more preferably 90°C to 150°C.

[0200] The processed fiber product is obtained by impregnating or coating the fiber treatment agent of this embodiment onto fibers and then drying them. In other words, the processed fiber product is an article in which the solid components (non-volatile components) contained in the fiber treatment agent are attached to the fibers.

[0201] [3-3. Coating agent]

[0202] The coating agent of the present embodiment comprises the water- and oil-repellent composition of the present embodiment, and may be composed solely of the water- and oil-repellent composition of the present embodiment, or may conveniently contain known and commonly used additives such as defoaming agents, preservatives, pH regulators, surfactants, cross-linking agents, antistatic agents, wetting agents, thickeners, pigments, etc., in addition to the water- and oil-repellent composition, as needed without prejudice to the purpose of the present invention.

[0203] Examples of substrates to be coated with the coating agent of this embodiment include, but are not limited to, glass, polyolefin resins, polyester resins, polycarbonate resins, acrylonitrile butadiene styrene copolymers (ABS resins), polystyrene resins, or molded products thereof (films, sheets, cups, etc.), metals, and the like.

[0204] As a method of treating the above-mentioned substrate using the coating agent of this embodiment, for example, the following method can be mentioned.

[0205] First, the coating agent is applied to the substrate. Examples of methods for applying the coating agent to the substrate include spraying, brushing, roller coating, trowel coating, dipping, air knife coating, flow coating, bar coating, roller coating, gravure coating, and methods using an applicator.

[0206] After the coating agent is preferably applied to the substrate, the substrate is dried. The drying temperature when the substrate to which the coating agent is applied is dried is preferably 80° C. or more, more preferably 100° C. or more. Because the drying time can be shortened, high productivity can be obtained. The drying temperature when the substrate to which the coating agent is applied is dried is preferably 170° C. or less, more preferably 150° C. or more. If the drying temperature is 170° C. or less, the deterioration of the water- and oil-repellent composition contained in the coating agent can be suppressed. The drying time can be determined according to the coating amount of the coating agent to the substrate, etc., and is not particularly limited.

[0207] Example

[0208] Hereinafter, the present invention will be described in more detail by way of examples and comparative examples. However, the present invention is not limited to the following examples.

[0209] <1. Production of aqueous emulsion (α-1)>

[0210] In a five-necked separable flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, a reflux cooler, and a dropping funnel, 120 g of ion-exchanged water as the aqueous medium (D) and 1 g of Kachiogen (registered trademark) TML as the surfactant (E) were added, and the temperature was raised to 80°C to prepare a mixed solution. The resulting mixed solution was maintained at 80°C, and 10 g of a 3% by mass aqueous solution of AAPH (2,2'-azobis(2-methylpropionamidine) dihydrochloride) was added as a polymerization initiator to prepare a polymerization initiator solution.

[0211] On the other hand, in a 1-liter beaker, the monomer (a1) and the monomer (a2) shown in Table 1 were added in the proportions shown in Table 1, 420 g of ion-exchanged water as an aqueous medium (D) and 15 g of Kachiogen (registered trademark) TML as a surfactant (E) were added, and the mixture was emulsified using a homomixer to prepare a mixed emulsion.

[0212] Furthermore, while the temperature in the five-necked flask containing the polymerization initiator solution was maintained at 80° C., the mixed emulsion and 44 g of a 3% by mass aqueous solution of AAPH as a polymerization initiator were simultaneously added dropwise from a funnel to the polymerization initiator solution over 3 hours while stirring to carry out emulsion polymerization.

[0213] One hour after the completion of the dropwise addition, the temperature in the five-necked flask was maintained at 80° C. while stirring. Then, the five-necked flask was cooled to 30° C. Through the above steps, an aqueous emulsion (α-1) containing copolymer (A) was obtained.

[0214] <2. Production of Aqueous Emulsions (α-2)(β-1) to (β-6)>

[0215] Aqueous emulsion (α-2) containing copolymer (A) was obtained in the same manner as in the preparation of aqueous emulsion (α-1) except that monomer (a1) and monomer (a2) shown in Table 1 were used in the ratio shown in Table 1.

[0216] Aqueous emulsions (β-1) to (β-6) each containing a copolymer (B) were obtained by following the same procedure as for the preparation of the aqueous emulsion (α-1), except that the monomers (b1), (b2), and (b3) shown in Table 1 were used in the proportions shown in Table 1 instead of the monomers (a1) and (a2) shown in Table 1.

[0217]

[0218] In Table 1, monomer (a1) or (b1) is a compound that is a source of structural unit (a1) or (b1). Monomer (a2) or (b2) is a compound that is a source of structural unit (a2) or (b2). Monomer (b3) is a compound that is a source of structural unit (b3).

[0219] The materials used in Table 1 are as follows.

[0220] Monomer (b3); polydimethylsiloxane having an ethylenically unsaturated bond (manufactured by JNC Corporation, サイラプレーン (registered trademark) FM-0725 (a compound represented by formula (1), wherein R 1Represents a methyl group. 2 Represents -CH2CH2CH2-. R 3 represents an n-butyl group. h is 2. j is 125. The number average molecular weight (Mn) is 10,000.

[0221] Surfactant (E); Kachiogen (registered trademark) TML (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.: alkyltrimethylammonium chloride (including lauryltrimethylammonium chloride) (cationic surfactant), 30% by mass aqueous solution)

[0222] Polymerization initiator; AAPH 3 mass % aqueous solution (3 mass % aqueous solution of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (AAPH))

[0223] The values ​​shown in the columns of aqueous medium (D), surfactant (E), and polymerization initiator in Table 1 are the total mass (total of monomers) used as the materials for aqueous emulsions (α-1), (α-2), and aqueous emulsions (β-1) to (β-6). Therefore, the values ​​for aqueous medium (D) shown in Table 1 do not include the water contained in the surfactant (E) and the polymerization initiator.

[0224] <3. Preparation of water- and oil-repellent composition>

[0225] The aqueous emulsion (α-1) or (α-2) shown in Table 1, the aqueous emulsions (β-1) to (β-6) shown in Table 1, and the polyether-modified polydimethylsiloxane (C) were mixed in the proportions shown in Table 2 or Table 3 to obtain water- and oil-repellent compositions of Examples 1 to 12 and Comparative Examples 1 to 8, which contained copolymer (A), copolymer (B), and polyether-modified polydimethylsiloxane (C) in the proportions shown in Table 2 or Table 3.

[0226] The values ​​shown in the copolymer (A) column in Tables 2 and 3 are the masses of the aqueous emulsions (α-1) and (α-2) used in the water- and oil-repellent compositions of Examples 1 to 12 and Comparative Examples 1 to 8, and the values ​​in brackets are the masses of the copolymers (A) contained in the aqueous emulsions (α-1) and (α-2). The content of the copolymers (A) in the aqueous emulsions (α-1) and (α-2) is the ratio of the monomers in Table 1 to the total amount of the monomers, surfactants, polymerization initiators, and aqueous media.

[0227] The values ​​shown in the copolymer (B) column in Tables 2 and 3 are the masses of the aqueous emulsions (β-1) to (β-6) used in the water- and oil-repellent compositions of Examples 1 to 12 and Comparative Examples 1 to 8, and the values ​​in parentheses are the masses of the copolymers (B) contained in the aqueous emulsions (β-1) to (β-6), respectively. The mass of the copolymer (B) in the aqueous emulsions (β-1) to (β-6) is the proportion of the monomers in Table 1 in the total amount of the monomers, surfactants, polymerization initiators, and aqueous media.

[0228]

[0229]

[0230] The polyether-modified polydimethylsiloxane (C) used in Tables 2 and 3 is as follows.

[0231] BYK SILCLEAN 3720: a polyether-modified polydimethylsiloxane having a hydroxyl group at the end of the polyether chain, with a weight-average molecular weight (Mw) of 10,000. The active ingredient is a solvent (methoxypropanol).

[0232] (BYK)

[0233] TEGO (registered trademark) Protect 5100N: Polyether-modified polydimethylsiloxane with hydroxyl groups at the ends of the polyether chain, weight-average molecular weight (Mw) 10,000, containing only the active ingredient and a solvent (water). (Made by Ebonic Co., Ltd.)

[0234] KP-109: Polyether-modified polydimethylsiloxane, weight-average molecular weight (Mw) 10,000, containing only the active ingredient and a solvent (propylene glycol monomethyl ether). (Made by Shin-Etsu Silicone Co., Ltd.)

[0235] <4. Oil repellency evaluation>

[0236] The water- and oil-repellent compositions of Examples 1 to 12 and Comparative Examples 1 to 8 obtained in this manner were subjected to the following first and second tests to evaluate oil repellency.

[0237] [4-1. First Test]

[0238] Water and oil repellent composition is diluted to 2 times of mass reference with ion exchange water.In the water and oil repellent composition after dilution, impregnated the square cotton (muslin No. 3) of vertical 200mm, horizontal 200mm.Then, cotton is dried by heating it for 5 minutes using a baking oven at 130 ℃, making test cloth.Test cloth is made in the mode that the attachment amount of the dried water and oil repellent composition composition becomes the ratio of 20 mass parts relative to cotton 100 mass parts.

[0239] 0.03 ml of a test liquid was dropped onto one side of the obtained test cloth and allowed to stand. The state of the test liquid was visually observed after 1 minute and evaluated according to the following criteria.

[0240] The first test was conducted using a test solution for oil repellency level 1 (liquid paraffin (Nujol)) specified in the AATCC 118 oil repellency test, and a test solution for oil repellency level 2 (liquid paraffin / n-hexadecane = 65 / 35) as the test solution. The test cloth and test solution were both at 23°C. The test solution on the test cloth was allowed to stand and visually observed in a constant temperature chamber at 23°C.

[0241] Evaluation Benchmarks

[0242] Very good: The test liquid retains the ball drop.

[0243] Good: The ball drop of the test liquid collapses, and the test liquid wets and spreads on the test cloth but does not soak into the test cloth.

[0244] Somewhat good: The test liquid soaks into the test cloth within 30 seconds to 1 minute after the test liquid has been left to stand.

[0245] Poor: The test liquid penetrates into the test cloth within 30 seconds after the test liquid is left to stand.

[0246] [4-2. Second Test]

[0247] The water- and oil-repellent composition was applied to a glass plate as a substrate using an applicator to a thickness of 150 μm (undried state), and dried by heat treatment at 130° C. for 5 minutes in an oven to obtain a test body (coated material).

[0248] The surface of the water- and oil-repellent composition coated on the test body obtained was quietly placed on a test solution (liquid paraffin) 2 μl of the oil-repellent 1 grade specified in the oil repellency test of AATCC118 method, and the contact angle of the test solution after 10 seconds was measured using the θ / 2 method using an automatic contact angle meter CA-VP type (Kyowa Interface Science Co., Ltd.). The larger the contact angle, the more excellent the oil repellency.

[0249] <5. Water repellency evaluation>

[0250] The water- and oil-repellent compositions of Examples 1 to 12 and Comparative Examples 1 to 8 were tested according to the water repellency test (spray test) described in JIS L1092 (2009) 7.2. The evaluation criteria are as follows. The larger the grade, the better the water repellency. The test results are shown in Tables 2 and 3.

[0251] Evaluation Benchmarks

[0252] Level 1: The entire surface appears wet.

[0253] Level 2: More than half of the surface area is wet, and only a small amount of moisture permeates the cloth.

[0254] Level 3: The wet area is less than half of the surface, and small water droplets appear on the surface.

[0255] Level 4: The surface does not show moisture, but small water droplets are attached.

[0256] Level 5: There is no moisture or water droplets adhering to the surface.

[0257] <6. Evaluation Results>

[0258] 〔6-1. Oil repellency〕

[0259] As shown in Table 2, about the water- and oil-repellent composition utilizing embodiment 1~embodiment 12 and the base material processed, liquid paraffin and the test solution of liquid paraffin / n-hexadecane=65 / 35 are all difficult for penetration (the 1st test), and the value to the contact angle of the droplet of test solution (liquid paraffin) is also large (the 2nd test).Therefore, it is known that the water- and oil-repellent composition of embodiment 1~embodiment 12 can give high oil repellency to base material.

[0260] In contrast, as shown in Table 3, regarding the substrates treated with the water- and oil-repellent compositions of Comparative Examples 2 to 8 that do not include the aqueous emulsion (α-1) or (α-2) (copolymer (A)), liquid paraffin / n-hexadecane=65 / 35 easily penetrated and could not impart sufficient oil repellency to the substrate.

[0261] 〔6-2. Water repellency〕

[0262] As shown in Table 2, the results of the water repellency test did not show wide-range wetting of the substrates treated with the water- and oil-repellent compositions of Examples 1 to 12. Therefore, it can be seen that the water- and oil-repellent compositions of Examples 1 to 12 can impart high water repellency to the substrate.

[0263] In contrast, as shown in Table 3, about the substrate processed using the water- and oil-repellent compositions of Comparative Example 1, Comparative Example 3, 4, and 8, which do not include aqueous emulsion (β-1) to (β-6) (copolymer (B)), the result of the water- and oil-repellent compositions of Comparative Example 3, 4, and 8, the water- and oil-repellent compositions of Comparative Example 1, 3, 4, and 8, the area more than half of the surface is wetted. Therefore, the water- and oil-repellent compositions of Comparative Example 1, 3, 4, and 8 can not impart sufficient water repellency to substrate.

[0264] Based on the above, it can be seen that the water- and oil-repellent composition according to the present invention can impart high oil repellency and water repellency to a substrate.

[0265] Industrial availability

[0266] The present invention can provide a water- and oil-repellent composition capable of imparting high oil- and water-repellency to a substrate.

Claims

1. A water- and oil-repellent composition comprising: A copolymer (A) that does not contain a structural unit having a siloxane bond; a copolymer (B) comprising a structural unit having a siloxane bond; Polyether modified polydimethylsiloxane (C); as well as Aqueous medium (D), The copolymer (A) consists of: a structural unit (a1) derived from a compound having an ethylenically unsaturated bond and an ester bond and having no amide bond; and It is composed of structural units (a2) derived from a compound having an ethylenically unsaturated bond and an amide bond, The copolymer (B) has: A structural unit (b1) derived from a compound having an ethylenically unsaturated bond and an ester bond and having no amide bond; Structural units (b2) derived from a compound having an ethylenically unsaturated bond and an amide bond; as well as The structural unit (b3) is derived from polydimethylsiloxane having an ethylenically unsaturated bond. 2 . The water- and oil-repellent composition according to claim 1 , wherein the structural unit (a1) and the structural unit (b1) are structural units derived from either or both of a hydrocarbon having an ethylenically unsaturated bond and an alkyl (meth)acrylate. The water- and oil-repellent composition according to claim 1 or 2, wherein the structural unit (a2) and the structural unit (b2) are structural units derived from (meth)acrylamide.

4. The water- and oil-repellent composition according to claim 1 or 2, wherein the structural unit (b3) is a structural unit derived from a compound represented by the following formula (1), In formula (1), R 1 represents a hydrogen atom or a methyl group; R 2 represents a divalent aliphatic group having 1 to 6 carbon atoms which may contain an ether bond; R 3 represents an aliphatic group, an aromatic group, or a hydroxyl group having 1 to 30 carbon atoms; h is any one of 0, 1, and 2; and j represents an integer of 0 to 500. The water- and oil-repellent composition according to claim 1 or 2, wherein the mass ratio of the copolymer (A) to the copolymer (B) is 10 / 90 or more and 90 / 10 or less. The water- and oil-repellent composition according to claim 1 or 2, wherein the copolymer (A) contains the structural unit (a2) in an amount of 0.10% by mass to 20% by mass. The water- and oil-repellent composition according to claim 1 or 2, wherein the copolymer (B) contains the structural unit (b2) in an amount of 0.10% by mass to 20% by mass. The water- and oil-repellent composition according to claim 1 or 2, wherein the copolymer (B) contains 3.0% by mass or more and 50% by mass or less of the structural unit (b3). 9 . The water- and oil-repellent composition according to claim 1 , wherein the polyether-modified polydimethylsiloxane (C) has a hydroxyl group at a terminal of a polyether chain.

10. The water- and oil-repellent composition according to claim 1 or 2, wherein The polyether-modified polydimethylsiloxane (C) is contained in an amount of 0.10 parts by mass to 20 parts by mass based on 100 parts by mass of the total of the copolymer (A) and the copolymer (B). The water- and oil-repellent composition according to claim 1 or 2, further comprising a surfactant (E). The water- and oil-repellent composition according to claim 11 , wherein the surfactant (E) is a cationic surfactant. 13 . A fiber treating agent comprising the water- and oil-repellent composition according to claim 1 .

14. A method for treating fibers, comprising using the fiber treating agent according to claim 13. 15 . A coating agent comprising the water- and oil-repellent composition according to claim 1 .

16. A processed fiber product, wherein the solid component contained in the fiber-treating agent according to claim 13 is attached to fibers.

17. The water- and oil-repellent composition according to claim 1, wherein the structural unit (a1) and the structural unit (b1) are at least one selected from methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, The structural unit (a2) and the structural unit (b2) are at least one selected from acrylamide and methacrylamide, The structural unit (b3) is a structural unit derived from a compound represented by the following formula (1), In formula (1), R 1 represents a hydrogen atom or a methyl group; R 2 represents a divalent aliphatic group having 1 to 6 carbon atoms which may contain an ether bond; R 3 represents an aliphatic group, aromatic group, or hydroxyl group having 1 to 30 carbon atoms; h is any one of 0, 1, and 2; j represents an integer of 0 to 500; The content of the structural unit (a1) in the copolymer (A) is 85% by mass or more and 99% by mass or less, The content of the structural unit (a2) in the copolymer (A) is 0.5% by mass or more and 5.0% by mass or less, The content of the structural unit (b1) in the copolymer (B) is 50% by mass or more and 93% by mass or less, The content of the structural unit (b2) in the copolymer (B) is 0.5% by mass or more and 5.0% by mass or less, The content of the structural unit (b3) in the copolymer (B) is 7.0% by mass or more and 50% by mass or less, The content of the structural unit (b3) in the total amount of the copolymer (A) and the copolymer (B) is 1.5% by mass or more and 30% by mass or less, The ratio represented by the mass of the copolymer (A) / the mass of the copolymer (B) is 10 / 90 to 90 / 10, The weight average molecular weight of the polyether-modified polydimethylsiloxane (C) is 7,000 or more and 14,000 or less.

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