TWI688647B - Water repellent - Google Patents

Abstract

A water repellent containing (A1) a repeating unit derived from a non-fluorine (meth) acrylate ester monomer represented by the following formula, and (A2) a repeating unit derived from a silicone macromer having a radical polymerizable group as essential components gives fiber products excellent water repellency, texture and choke mark resistance.

CH₂=CA¹¹-C(=O)-O-A¹² [In the formula, A¹¹ is a hydrogen atom or a methyl group, A¹² is a linear or branched hydrocarbon group having 8 to 30 carbon atoms.]

Description

Water repellent

The present invention relates to a water-repellent agent that does not have a fluorine atom and contains a silicon-containing polymer. Specifically, the present invention can impart excellent water repellency, oil repellency, and antifouling properties to the substrate.

Conventionally, fluorine-containing water- and oil-repellent agents formed from fluorine-containing compounds are known. If the water- and oil-repellent agent is used to treat substrates such as fiber products, it exhibits good water- and oil-repellent properties.

Based on recent research results [EPA REPORT "PRELIMINARY RISK ASSESSMENT OF THE DEVELOPMENTAL TOXICITY ASSOCIATED WITH EXPOSURE TO PERFLUOROOCTANOIC ACID AND ITS SALTS" (http://www.epa.gov/opptintr/pfoa/pfoara.pdf)], etc. PFOA (perfluorooctanoic acid), which is a type of long-chain fluoroalkyl compound, obviously has the potential to cause a load on the environment. On April 14, 2003, the EPA (United States Environmental Protection Agency) published a meeting to strengthen the scientific investigation of PFOA.

On the other hand, Federal Register (FR Vol. 68, No. 73/April 16, 2003 [FRL-2303-8], http://www.epa.gov/opptintr/pfoa/pfoafr.pdf), EPA Environmental News FOR RELEASE: MONDAY APRIL 14,2003 EPA INTENSIFIES SCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID (http://www.epa.gov/opptintr/pfoa/pfoaprs.pdf), and EPA OPPT FACT SHEET April 14,2003 (http:/ /www.epa.gov/opptintr/pfoa/pfoafacts.pdf) discloses that Telomer may generate PFOA by decomposition or metabolism (Telomer refers to long-chain fluoroalkyl). Furthermore, it has been disclosed that Telomer is used in many products such as foam fire extinguishing agents that impart water and oil repellency and antifouling properties, care products, cleaning products, carpets, fabrics, paper, and leather. Fluorine-containing compounds may accumulate in the environment.

In addition, the fluorine-containing water- and oil-repellent agent formed of a fluorine-containing polymer must be heat-treated at a high temperature (for example, 100° C. or higher) after being attached to a substrate such as a fiber product in order to exhibit water- and oil-repellent properties. High temperature heat treatment requires high energy.

In addition, fluoropolymers are expensive.

Therefore, it is desirable not to use fluoropolymer, or to reduce the amount of fluoropolymer.

Japanese Patent Laid-Open No. 2010-500438 (Patent Document 1) discloses a polysiloxane organic copolymer obtained by polymerizing an ethylenically unsaturated organic monomer and a polysiloxane macromonomer. Patent Document 1 does not describe that it can impart good texture and resistance to fine white marks to fiber products.

Japanese Patent Laid-Open No. 5-9248 (Patent Document 2) discloses a method for manufacturing an aqueous resin dispersion, which includes a step of polymerizing a vinyl monomer and a polysiloxane-based macromonomer having a radical polymerizable group . Patent Document 2 does not describe that it can impart good texture and fine white streak resistance to fiber products.

Japanese Patent Laid-Open No. 10-182987 (Patent Document 3) discloses a sliding resin composition obtained by blending a thermoplastic resin, (meth)acrylate, and a radically polymerizable polysiloxane macromonomer. Patent Document 3 does not disclose a water and oil repellent agent (liquid treatment agent).

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2010-500438.

Patent Document 2: Japanese Patent Laid-Open No. 5-9248.

Patent Document 3: Japanese Patent Laid-Open No. 10-182987.

An object of the present invention is to provide a surface treatment agent (water and oil repellent, especially water repellent), which can impart excellent water and oil repellency (especially water repellency), soft texture and good resistance to fiber products Fine white streak.

The present invention provides a water-repellent agent containing a silicon-containing polymer derived from a repeating unit of (A1) derived from a non-fluorine (meth)acrylate monomer represented by the following formula and (A2) derived from The repeating unit of a polysiloxane-based macromonomer having a radical polymerizable group is an essential component.

CH ₂ =CA ¹¹ -C(=O)-OA ¹² [In the formula, A ¹¹ is a hydrogen atom or a methyl group, A ¹² is a linear or branched hydrocarbon group having 8 to 30 carbon atoms]

The water repellent of the present invention imparts excellent water and oil repellency (especially water repellency), soft texture (good texture), and fine white streak resistance to substrates, especially to fiber products.

The water-repellent agent is composed of (A) a silicon-containing polymer, (B) a liquid medium, and (C) other ingredients such as additives that exist as needed. The water repellent may be composed of only the components (A) to (C). The water repellent preferably contains no fluoropolymer.

Silicon-containing polymers do not contain fluorine atoms. The silicon-containing polymer does not contain a fluorine-containing monomer, for example, a fluorine-containing monomer having a fluoroalkyl group.

(A) Silicon-containing polymer

The silicon-containing polymer has: (A1) a repeating unit derived from a non-fluorinated (meth)acrylate monomer, (A2) a repeating unit derived from a polysilicon macromonomer, and (A3) derived from the need Repeating units of other monomers present.

(A1) Non-fluorine (meth)acrylate monomer

The non-fluorine (meth)acrylate monomer is a compound represented by the following formula.

CH ₂ =CA ¹¹ -C(=O)-OA ¹² [In the formula, A ¹¹ is a hydrogen atom or a methyl group, A ¹² is a linear or branched hydrocarbon group having 8 to 30 carbon atoms]

A ^{11 is} preferably a hydrogen atom.

A ¹² is a hydrocarbon group having 6 to 30 carbon atoms. The hydrocarbon group is acyclic (straight chain or branched). The hydrocarbon group may be a linear hydrocarbon group. The carbon number of the hydrocarbon group is 10 to 28, for example, preferably 12 to 26, more preferably 14 to 24, and particularly preferably 18 or 22. The hydrocarbon group may be a general saturated aliphatic hydrocarbon group, especially an alkyl group.

Specific examples of non-fluorine (meth)acrylate monomers are: octyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, (meth Group) tridecyl acrylate, isotridecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, and behenyl (meth) acrylate. Preferred are stearyl (meth)acrylate and behenyl (meth)acrylate.

(A2) Polysilicone macromonomer

The polysiloxane-based macromolecule single system is a high molecular weight monomer with polysiloxane as the backbone. The polysilicon macromolecule single system has a radical polymerizable group at one end or both ends. Examples of radical polymerizable groups are: (meth)acryloyl, styryl, allyl, vinylbenzyl, vinylether, vinylalkylsilyl, vinylketone, and isopropylene base. Preferably, it is (meth)acryloyl, that is, it is preferably acryloyl and methacryloyl. More preferably, it is a polysiloxane-based macromonomer having a methacrylic group (that is, a methacrylic modified polysiloxane-based macromonomer). Particularly preferred is a polysiloxane macromonomer having a methacryloyl group at only one end (a polysiloxane macromonomer modified at one end by methacrylic acid).

The polysiloxane-based macromonomer is preferably a compound represented by the following formula.

[式中，R為相同或相異之碳數1至12之烴基，X為具有自由基聚合性官能基之基，m為5至200之數。]

[In the formula, R is the same or different hydrocarbon group having 1 to 12 carbon atoms, X is a group having a radically polymerizable functional group, and m is a number of 5 to 200. ]

Preferably, more than 50 mole% of the entire R group is methyl. The hydrocarbon group may be substituted.

The X group (radical polymerizable functional group-containing group) is preferably formed by a radical polymerizable functional group and an alkylene group (the alkylene group preferably has 1 to 10 carbon atoms).

Specific examples of polysiloxane-based macromonomers are as follows.

[上述式中，m為5至200之數。]

[In the above formula, m is a number from 5 to 200. ]

The number average molecular weight of the polysilicon macromonomer is generally 1,000 to 100,000, for example, 2,000 to 50,000. The number average molecular weight is determined by colloidal permeation chromatography (in terms of polystyrene).

The polysiloxane-based macromonomer can be produced by a known method. The production method can be exemplified by the following method: using lithium trialkylsilanol as an initiator, anionic polymerization of cyclic silicone to obtain a living polymer, and further reacting γ-methacryloxypropyl di Methyl monochlorosilane, and a method for obtaining a polysiloxane macromonomer (Japanese Patent Laid-Open No. 59-78236); or obtaining a polysiloxane macromonomer as a polysiloxy group containing terminal silanol groups and organic Method for condensate of silicon compound (Japanese Patent Laid-Open No. 58-167606).

(A3) Other monomers

In the present invention, other monomers other than the non-fluorine (meth)acrylate monomer (A1) and the polysiloxane macromonomer (A2) can be used. The other monomers are preferably non-silicon non-fluorine monomers, that is, monomers having no silicon atoms or fluorine atoms.

Examples of other monomers include: (i) halogenated olefins; (ii) non-crosslinkable monomers; and (iii) crosslinkable monomers.

The halogenated olefin may be a halogenated olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms. The halogenated olefin is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms having 1 to 5 chlorine atoms. Preferred specific examples of halogenated olefins are halogenated ethylene, such as vinyl chloride, vinyl bromide, and vinyl iodide; halogenated vinylidene, such as vinylidene chloride, vinylidene bromide, and vinylidene dichloride. Vinyl chloride and vinylidene chloride are preferred, and vinyl chloride is particularly preferred.

The non-crosslinkable monomer is a monomer other than the monomer (A1). Non-crosslinkable monomers are generally non-silicon non-fluorine non-crosslinkable monomers that do not contain silicon atoms and fluorine atoms. The non-crosslinkable monomer is preferably (meth)acrylate.

The non-crosslinkable monomer is preferably a compound represented by the following formula CH ₂ =CA ²¹ -C(=O)-OA ²² [In the formula, A ²¹ is a hydrogen atom or a methyl group, and A ²² is linear or branched Hydrocarbon groups other than hydrocarbon-like groups]

A ²² is a hydrocarbon group other than a linear or branched hydrocarbon group having 8 to 30 carbon atoms. A ²² is a hydrocarbon group having 6 to 30 carbon atoms. The hydrocarbon group is preferably a cyclic hydrocarbon group. The carbon number of the hydrocarbon group is 10 to 28, for example, preferably 12 to 26, more preferably 14 to 24, and particularly preferably 18 or 22.

The non-crosslinkable monomer is preferably a (meth)acrylate monomer having a cyclic hydrocarbon group. A compound having a (meth)acrylate monosystem having a cyclic hydrocarbon group having (preferably a monovalent) cyclic hydrocarbon group and a monovalent (meth)acrylate group. The monovalent cyclic hydrocarbon group is directly bonded to the monovalent (meth)acrylate group. Examples of cyclic hydrocarbon groups include saturated or unsaturated monocyclic groups, polycyclic groups, and cross-linked ring groups. The cyclic hydrocarbon group is preferably saturated. The carbon number of the cyclic hydrocarbon group is preferably 6 to 30. Examples of the cyclic hydrocarbon group include 4 to 20 carbon atoms, especially 5 to 12 cyclic aliphatic groups, 6 to 20 carbon aromatic groups, and 7 to 20 carbon aliphatic aromatic groups. The carbon number of the cyclic hydrocarbon group is 15 or less, and particularly preferably 10 or less. The carbon atom in the ring of the cyclic hydrocarbon group is preferably an ester group directly bonded to the (meth)acrylate group. The cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group.

Specific examples of the cyclic hydrocarbon group are: cyclohexyl group, third butylcyclohexyl group, isobornyl group, dicyclopentyl group, dicyclopentenyl group, and adamantyl group. The acrylate group is preferably an acrylate group or a methacrylate group, particularly preferably a methacrylate group. Specific examples of the monomer having a cyclic hydrocarbon group include cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isocyanate (meth)acrylate Camphenate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, tricyclopentyl (meth)acrylate, (methyl ) Adamantyl acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, etc.

The cross-linkable monomer is generally a non-silicon non-fluorine cross-linkable monomer that does not contain silicon atoms and fluorine atoms. The crosslinkable monomer has at least 2 reactive groups and/or ethylenically unsaturated double bonds, and may be a compound that does not contain fluorine. The crosslinkable monomer is a compound having at least two ethylenically unsaturated double bonds, or may be a compound having at least one ethylenically unsaturated double bond and at least one reactive group. Examples of reactive groups are hydroxy, epoxy, chloromethyl, blocked isocyanate, amine, carboxy, and the like.

Examples of the crosslinkable monomers include diacetone acrylamide, (meth)acrylamide, N-methylolacrylamide, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, (Meth)acrylic acid 3-chloro-2-hydroxypropyl ester, (meth)acrylic acid 2-acetoacetoxyethyl ester, butadiene, isoprene, chloroprene, (meth)acrylic acid Propylene oxide, etc., but not limited to these.

The monomers (A1) to (A3) may be used alone or in combination of two or more.

The amount of non-fluorine (meth)acrylate monomer (A1) relative to the silicon-containing polymer may be 10 to 95% by weight, for example, 50 to 90% by weight, especially 60 to 85% by weight.

The amount of the polysiloxane macromonomer (A2) may be 0.2 to 50 parts by weight relative to 100 parts by weight of the non-fluorine (meth)acrylate monomer (A1), for example, 0.5 to 20 parts by weight, especially 1 to 15 parts by weight.

The amount of the other monomer (A3) may be 200 parts by weight or less relative to 100 parts by weight of the non-fluorine (meth)acrylate monomer (A1), for example, 2 to 50 parts by weight.

The amount of halogenated olefin relative to the silicon-containing polymer may be 50% by weight or less. The amount of halogenated olefin can be more than 10.1% by weight relative to the silicon-containing polymer. The amount of halogenated olefin relative to the silicon-containing polymer may be, for example, 1 to 40% by weight, especially 3 to 30% by weight, preferably 5 to 28% by weight, more preferably 10.1 to 26% by weight, and particularly preferably 12 Up to 24% by weight. By containing the halogenated olefin in such a range, water repellency, water repellency durability (for example, water repellency after washing), good texture, and fine white streak resistance can be satisfactorily achieved.

The amount of the non-crosslinkable monomer relative to the silicon-containing polymer may be 50% by weight or less, for example, 1 to 40% by weight, especially 3 to 30% by weight.

The amount of the crosslinkable monomer relative to the silicon-containing polymer may be 30% by weight or less, for example, 0.1 to 20% by weight, especially 0.5 to 10% by weight.

The number average molecular weight (Mn) of the silicon-containing polymer may generally be 2000 to 1000000, for example, 3000 to 500000, especially 4000 to 200,000. The number average molecular weight (Mn) of the silicon-containing polymer is generally determined by GPC (colloid permeation chromatography).

The amount of the silicon-containing polymer may be 0.1 to 70% by weight relative to the water repellent, for example, 1 to 50% by weight, especially 3 to 40% by weight.

(B) Liquid medium

The liquid medium is water and/or organic solvent. The liquid medium may be only an organic solvent, but it is preferably water alone or a mixture of water and (water-miscible) organic solvent. The amount of the organic solvent may be 30% by weight or less relative to the liquid medium, for example, 10% by weight or less (preferably 0.1% or more). The liquid medium is more preferably water alone. The amount of the liquid medium may be 30 to 99.9% by weight relative to the water repellent, for example, 50 to 99% by weight, especially 55 to 95% by weight.

(C) Other ingredients

The water repellent may contain additives as components other than the silicon-containing polymer and the liquid medium.

Examples of additives are silicon-containing compounds, acrylic emulsions and the like. Other examples of additives are: drying speed adjusters, crosslinking agents, film-forming aids, miscible agents, surfactants, anti-freezing agents, viscosity adjusters, ultraviolet absorbers, antioxidants, pH adjusters, defoamers , Texture adjuster, slip adjuster, antistatic agent, hydrophilizing agent, antibacterial agent, preservative, insect repellent, fragrance, flame retardant, etc. The amount of the additive may be 0.1 to 100 parts by weight relative to 100 parts by weight of the silicon-containing polymer, for example, 1 to 30 parts by weight.

The silicon-containing polymer in the present invention can be produced by any usual polymerization method, and the polymerization reaction conditions can be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization.

In the solution polymerization, a method of dissolving the monomer in an organic solvent in the presence of a polymerization initiator, heating and stirring at 30 to 120° C. for 1 to 10 hours after nitrogen substitution. Examples of the polymerization initiator include: azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, pivalic acid peroxide Oxidized third butyl ester, diisopropyl dicarbonate, etc. The polymerization initiator is used in the range of 0.01 to 20 parts by weight relative to 100 parts by weight of the monomer, for example, 0.01 to 10 parts by weight.

Organic solvents are those that are inert to the monomers and dissolve them. For example, they can be esters (such as esters with a carbon number of 2 to 30, specifically ethyl acetate and butyl acetate), ketones (such as ketones with a carbon number of 2 to 30) , Specifically methyl ethyl ketone, diisobutyl ketone), alcohol (for example, an alcohol having 1 to 30 carbon atoms, specifically isopropyl alcohol). Specific examples of organic solvents include acetone, chloroform, HCHC225, isopropanol, pentane, hexane, heptane, octane, 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-tri Ethylene chloride, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, etc. The organic solvent is used in the range of 10 to 2000 parts by weight, for example, 50 to 1000 parts by weight, relative to 100 parts by weight of the monomer in total.

In the emulsion polymerization, the following method is adopted: the monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen substitution, it is stirred and polymerized in the range of 50 to 80°C for 1 to 10 hours. The polymerization initiator can be used: benzoyl peroxide, lauryl peroxide, tert-butyl benzoate peroxide, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, ethyl peroxide Acyl, azobisisobutylamidine dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate and other water-soluble ones; or azobisisobutyronitrile, benzoyl Peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, third butyl peroxypivalate, diisopropyl dicarbonate and other oil-soluble persons. The polymerization initiator is used in the range of 0.01 to 10 parts by weight relative to 100 parts by weight of the monomer.

In order to obtain an aqueous polymer dispersion with excellent stability, a high-pressure homogenizer, ultrasonic homogenizer, or other emulsifying device that can impart strong crushing energy can be used. Preferably, the monomer is micronized and polymerized in water. In addition, as the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and they are used in the range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the monomer.

The emulsifier may be a nonionic emulsifier. The emulsifier may be a combination of sorbitan ester and other emulsifiers (especially other nonionic emulsifiers) (weight ratio, for example, 5:95 to 95:5). The other emulsifier may be a polyether compound having polyoxyalkylene groups (especially polyoxyethylene groups).

When the monomers are completely immiscible, it is preferable to add a miscible agent that makes the monomers sufficiently compatible, such as a water-soluble organic solvent or a low molecular weight monomer. By adding a miscible agent, emulsification and copolymerization can be improved.

Examples of water-soluble organic solvents include: acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, etc., with respect to 100 parts by weight of water, 1 to 50 parts by weight, For example, it is used in the range of 10 to 40 parts by weight. Examples of low-molecular-weight monomers include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., which can be 1 based on 100 parts by weight of the total amount of monomers. It is used in the range of up to 50 parts by weight, for example, 10 to 40 parts by weight.

A chain transfer agent can be used in the polymerization. The amount of chain transfer agent used can vary depending on the molecular weight of the polymer. Examples of chain transfer agents are: thiol group-containing compounds such as lauryl mercaptan, thioglycol, thioglycerol (especially (for example, alkyl thiol with a carbon number of 1 to 30)), sodium hypophosphite, sodium bisulfite Such as inorganic salts. The use amount of the chain transfer agent is 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, relative to 100 parts by weight of the total amount of monomers.

In the present invention, a polymer can be produced by adding monomers at once.

Alternatively, monomers can be added in portions in the present invention. The silicon-containing polymer can be produced, for example, by the manufacturing method having the following steps (I) and (II).

(I) The step of polymerizing the first monomer and obtaining the first polymer.

(II) The step of obtaining the second polymer by polymerizing the second monomer in the presence of the first polymer.

In step (II) (preferably in both step (I) and step (II)), it is preferable to polymerize the second monomer in the presence of the first polymer and the liquid medium, thereby obtaining the second polymerization Thing.

Preferably, the first monomer is a non-fluorine (meth)acrylate monomer (A1) and a polysiloxane macromonomer (A2), and the second monomer is another monomer (A3), especially a halogenated olefin . The first monomer may contain other monomers (A3), such as halogenated olefins, non-crosslinkable monomers, and crosslinkable monomers.

The halogenated olefin may be either the first monomer or the second monomer, or both the first monomer and the second monomer. When the halogenated olefin is added at once or in portions, the halogenated olefin may be added after polymerizing the monomer (that is, other monomers sometimes containing halogenated olefin). Especially good is to add 100% halogenated olefin afterwards. In other words, it is particularly preferable that the first monomer does not contain halogenated olefin, and the second monomer is composed of halogenated olefin only.

Generally, the first polymer is produced by the polymerization reaction of the liquid containing the first monomer, and then the second polymer is produced by the polymerization reaction of the liquid containing the first polymer and the second monomer. A copolymer composed of a polymer and a second polymer. The polymerization of the second polymer may be started in the polymerization of the first polymer, or the polymerization of the second polymer may be started after the polymerization of the first polymer is completed. This manufacturing method is generally a two-stage polymerization, which has a first polymerization stage of a first polymerization reaction for polymerizing a first monomer, and a second polymerization stage for polymerizing a second monomer. The polymerization of the first polymer reaction (that is, the polymerization reaction of the first monomer) can be more than 10% (that is, 10 to 100%), for example, more than 40% (that is, 40 to 100%), especially more than 70% (That is, 70 to 100%), after the end of the second polymer began to polymerize. The polymerization completion ratio% (that is, the polymerization reaction progress ratio %) refers to the mole% of the monomer (polymerized monomer) completed by the reaction. For example, when the polymerization reaction is completed at 10%, the polymerization completion monomer is 10 mol%, and the unreacted (unpolymerized) monomer is 90 mol%. When the first monomer is a combination of at least two monomers, the mole% of the first monomer is based on the total mole of at least two monomers in the first monomer.

The first polymer polymerization means that the polymerization of the first polymer reaction (that is, the polymerization reaction of the first monomer) is not completely completed. For example, the polymerization of the first polymer may be 10% or more but not more than 40%, 40% or more but not more than 70%, or 70% or more but not more than 100% (especially 80% to 99%, especially 85% to 98%) After the completion, the second polymer will be polymerized.

After the polymerization of the first polymer is completed, it means that the polymerization reaction of the first polymer (that is, the polymerization reaction of the first monomer) is about 100% completed.

When the polymerization of the second polymer is started during the polymerization of the first polymer, the second polymer has repeating units derived from the first monomer and the second monomer. When the polymerization of the second polymer is started after the polymerization of the first polymer is completed, the second polymer has only repeating units derived only from the second monomer.

The amount of the second polymer is 0.1 to 100 parts by weight, 1 to 75 parts by weight, 3 to 60 parts by weight, 6 to 50 parts by weight, or 8 with respect to the total of 100 parts by weight of the first polymer and the second polymer Up to 40 parts by weight.

The addition of the first monomer can be performed at once (short time) or continuously. The addition of the first monomer is preferably carried out in a short time.

The addition of the second monomer can be performed at once or continuously. The continuous addition of the second monomer is preferably performed in such a manner that the pressure of the monomer gas (especially halogenated olefin such as vinyl chloride) is fixed in the polymerization of the second monomer.

In the copolymer of the present invention, the first polymer is chemically bonded or not chemically bonded to the second polymer.

At the time when the polymerization of the second monomer is started, it is preferable that there is substantially no unreacted non-fluorine (meth)acrylate monomer (that is, a long-chain acrylate monomer) in the polymerization system. Substantially absent means that the amount of unreacted long-chain acrylate monomer relative to the added long-chain acrylate monomer is 10 mol% or less, preferably 8 mol, at the time when the second monomer polymerization is started Ear% or less, more preferably 5 mole %, more preferably 3 mole% or less, particularly preferably 1 mole% or less. The long-chain acrylate monomer is substantially absent, and therefore, in the processing treatment of the treatment agent containing the copolymer, the performance of preventing the polymer from adhering to the roller and causing the roller to become dirty is excellent.

The treatment agent of the present invention may be in the form of a solution, an emulsion (especially an aqueous dispersion) or an aerosol, and is preferably an aqueous dispersion. The treatment agent contains a water-repellent oil-repellent polymer (silicon-containing polymer) (the active ingredient of the surface treatment agent) and a liquid medium (especially an aqueous medium, such as an organic solvent and/or water). The amount of the liquid medium relative to the treatment agent may be, for example, 5 to 99.9% by weight, especially 10 to 80% by weight.

In the treatment agent, the concentration of the water- and oil-repellent polymer may be 0.01 to 95% by weight, for example, 5 to 50% by weight.

The treatment agent of the present invention can be applied to the object to be treated by a conventionally known method. Generally, the following method is adopted: a method of dispersing the treatment agent in an organic solvent or water and diluting it, attaching it to the surface of the object to be processed and drying it by known methods such as dip coating, spray coating, foam coating, and the like. Furthermore, if necessary, it can be applied together with an appropriate crosslinking agent (for example, block isocyanate) for curing. In addition, the treatment agent of the present invention may be combined with insecticides, softeners, antibacterial agents, flame retardants, antistatic agents, paint fixing agents, anti-wrinkle agents, and the like. The concentration of the water- and oil-repellent polymer in the treatment liquid in contact with the substrate may be 0.01 to 10% by weight (especially during dip coating), for example, 0.05 to 10% by weight.

The objects to be treated by the treatment agent of the present invention (e.g., water repellent) may include fiber products, stone materials, filters (e.g., electrostatic filters), dust covers, and fuel cell parts (e.g., gas diffusion electrodes and gases) Diffusion support), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, kiln products, plastics, coated surfaces, and gypsum. There are various examples of fiber products. For example, natural fibers such as cotton, hemp, wool, silk, etc., synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, etc., rayon, acetate, etc. Inorganic fibers such as synthetic fibers, glass fibers, carbon fibers, asbestos fibers, or mixed fibers thereof.

The fiber product may be in any form such as fiber and cloth.

The treatment agent of the present invention can also be used as an internal mold release agent or an external mold release agent.

In order to treat the fibrous product with a liquid, the water- and oil-repellent polymer can be applied to the fibrous substrate (eg, fibrous product, etc.) by any known method. When the fiber product is cloth, the cloth may be immersed in the solution, or the cloth may be attached to or sprayed with the solution. The treated fiber product is dried in order to exhibit oil repellency, and is preferably heated at, for example, 100°C to 200°C.

Alternatively, the water- and oil-repellent polymer can be applied to the fiber product by a washing method. For example, it can be applied to the fiber product in a washing application or in a dry cleaning method.

The treated fiber products are typically cloth, including fabrics, knitted fabrics and non-woven fabrics, cloths and carpets in the form of clothing, and may be fibers or silks or intermediate fiber products (e.g. fiber bundles or thick filaments, etc.). The fiber product material can be natural fiber (such as cotton or wool, etc.), chemical fiber (such as viscose rayon (viscose rayon) or lyocell (lyocell), etc.), or synthetic fiber (such as polyester, polyamide) Or acrylic fibers, etc.), or may be a mixture of fibers (such as a mixture of natural fibers and synthetic fibers, etc.). The water-repellent and oil-repellent polymer of the present invention is particularly effective for imparting oleophobicity and oil-repellency to cellulose-based fibers (for example, cotton or rayon). In addition, the method of the present invention generally imparts hydrophobicity and water repellency to fiber products.

Or the fibrous base material may be leather. In order to impart hydrophobicity and oleophobicity to the leather, the water- and oil-repellent polymer is applied to the leather as an aqueous solution or an aqueous emulsion during various stages of leather processing, such as during the wet processing of leather or during the completion of leather.

Or the fibrous substrate can be paper. The water- and oil-repellent polymer can be applied to preformed paper, or to various stages of paper making, such as during the drying period of the paper.

"Treatment" refers to applying a treatment agent to the object by dipping, spraying, coating, or the like. By the treatment, the polymer of the active ingredient of the treatment agent penetrates into the interior of the treatment object and/or adheres to the surface of the treatment object.

(Example)

The following examples illustrate the invention in detail, but the invention is not limited to these examples.

The following parts, %, or ratios indicate parts by weight,% by weight, or weight ratios unless otherwise stated.

The test sequence is as follows.

Spray test

The water repellency of the treated cloth was evaluated according to the spray method of JIS-L-1092 (AATCC-22). In addition, a part of the treated cloth was a test cloth obtained by washing 10 times (HL10) or 20 times (HL20) with a 40°C washing liquid according to JIS L-0217 103, and then drying with a drum (60°C, 30 minutes). The water repellent evaluation results are also shown in Table 4. The water-repellent property is indicated by the water-repellent No. as described below. The higher the score, the better the water repellency. And according to its state, give intermediate values (95, 85, 75).

Rain test

The rain test (Bundesmann test) was performed in accordance with JIS L-1092 Rain Test A method. Rainfall time is 1 minute, 5 minutes and 10 minutes. The evaluation method is represented by the water-repellent No. as shown below in the same manner as the spray test. The larger the number of points, the better the water repellency. Measure the water leakage (g) and water absorption rate (%) after 10 minutes of rain test.

Texture test

Evaluate texture through 5 stages with hand touch. The assessment was made by 5 testers.

1: very hard

2: Hard

3: slightly hard

4: Soft

5: Very soft

Fine white streak test

After processing the cloth, press and move a plastic rod with a diameter of 5 mm at the front end to visually observe whether the mark remains on the cloth (that is, the test of fine white streak), as described in five stages as described below.

1: Confirm obvious traces

2: Traces confirmed

3: A few traces are confirmed

4: There are almost no traces confirmed

5: No trace at all

The meaning of the abbreviation is as follows.

Polymethicone modified with (meth)acrylic acid is a high molecular weight monomer with (meth)acryloyl group at one or both ends of polydimethylsiloxane.

The polysiloxane having a methacryl amide group at one end is shown in the following chemical formula.

The polysiloxane having methacryl acetyl groups at both ends is shown in the following chemical formula.

The polysiloxane having acryl groups at both ends is shown in the following chemical formula.

[上述式中，m為賦予預定數量平均分子量之數]

[In the above formula, m is the number given to the predetermined number average molecular weight]

Manufacturing Example 1

In a 500ml plastic container, add 30g of tripropylene glycol, 76g of stearyl acrylate, 1.5g of N-methylol acrylamide, 2.5g of polysiloxane (number average molecular weight: 4600) modified with methacrylic acid at one end, pure water 180g, dioctadecyl ammonium chloride 3g, sorbitan monooleate 2g, polyoxyethylene tridecyl ether 2.5g, polyoxyethylene lauryl ether 2.5g, heated to 60 ℃, in a homogenizer to After stirring at 2000 rpm for 1 minute, it was emulsified and dispersed with ultrasound for 15 minutes. The emulsified dispersion was transferred to a 500 ml autoclave, and after nitrogen substitution, 0.2 g of lauryl mercaptan and 20 g of vinyl chloride were added. Further, 1 g of 2,2-azobis(2-carboxamidopropane) 2 hydrochloride was added, the temperature was raised to 60°C, and the reaction was carried out for 4 hours to obtain an aqueous dispersion of the polymer. This dispersion liquid was further diluted with pure water to prepare an aqueous dispersion liquid 1 having a solid content concentration of 30%.

Manufacturing Examples 2 to 11 and 23

The compounding shown in Table 1 was polymerized in the same manner as in Production Example 1 and diluted with water, thereby obtaining aqueous dispersions 2 to 11 having a solid content concentration of 30%.

Manufacturing Example 12

In a 500ml plastic container, add 30g of tripropylene glycol, 76g of stearyl acrylate, 1.5g of N-methylol acrylamide, 2.5g of polysiloxane (number average molecular weight: 4600) modified with methacrylic acid at one end, pure water 180g, dioctadecyl ammonium chloride 3g, sorbitan monooleate 2g, polyoxyethylene tridecyl ether 2.5g, polyoxyethylene lauryl ether 2.5g, heated to 60 ℃, in a homogenizer to After stirring at 2000 rpm for 1 minute, it was emulsified and dispersed with ultrasound for 15 minutes. The emulsified dispersion was transferred to a 500 ml autoclave, and after nitrogen substitution, 0.2 g of lauryl mercaptan and 1 g of 2,2-azobis(2-carboxamidopropane) 2 hydrochloride were added and reacted at 60°C for 1 hour. After 1 hour of reaction, it was confirmed that stearyl acrylate had reacted 99 mole% or more. Thereafter, 20 g of filled vinyl chloride was pressed and reacted for 3 hours to obtain an aqueous dispersion of the polymer. The dispersion was further diluted with pure water to obtain an aqueous dispersion 12 with a solid content concentration of 30%.

Manufacturing Examples 13 to 22 and 24

It was blended in the same manner as in Production Example 12 as shown in Table 2 and polymerized and diluted with water, thereby obtaining aqueous dispersions 13 to 22 having a solid content concentration of 30%.

Comparative Manufacturing Examples 1 and 2

By mixing as shown in Table 3 and polymerizing in the same manner as in Manufacturing Example 1 and diluting with water, comparative aqueous dispersions 1 and 2 having a solid content concentration of 30% were obtained.

Comparative Manufacturing Examples 3 to 5

The compounding shown in Table 3 was polymerized in the same manner as in Production Example 12 and diluted with water, thereby obtaining comparative aqueous dispersions 3 to 5 having a solid content concentration of 30%.

Test Example 1

The aqueous dispersion 1 having a solid content concentration of 30% prepared in Production Example 1 was further diluted with tap water to prepare a treatment liquid having a solid content concentration of 1.5%. After impregnating the polyester cloth with the treatment liquid, it was wringed with a rolling machine. The fiber absorption rate is about 55%. The treated cloth was passed through a pin tenter at 170°C for 1 minute, dried and hardened. Test the cloth thus treated. The results are shown in Table 4.

Test Examples 2 to 11 and 23

The same method as in Test Example 1 was repeated except that the aqueous dispersions 2 to 11 and 23 prepared in Production Examples 2 to 11 and 23 were used. The results are shown in Table 4.

Comparative Test Examples 1 and 2

The same method as in Test Example 1 was repeated except that Comparative Water Dispersions 1 and 2 prepared in Comparative Manufacturing Examples 1 and 2 were used. The results are shown in Table 4.

Test Examples 12 to 22 and 24

The same method as in Test Example 1 was repeated except that the water dispersion liquids 12 to 22 and 24 prepared in Production Examples 12 to 22 and 24 were used. The results are shown in Table 5.

Comparative Test Examples 3 to 5

The same method as in Test Example 1 was repeated except that Comparative Water Dispersions 3 to 5 prepared by Comparative Production Examples 3 to 5 were used. The results are shown in Table 5.

Comparative Test Example 6

KF-412 (long-chain alkyl-modified polysiloxane) manufactured by Shin-Etsu Chemical Industry Co., Ltd. 27 g of ethylene oxide with a carbon number of 18 and a molar alcohol adduct of 2 g and a carbon number of 18 1 g of ethylene oxide 20 mole adduct of higher alcohol, mixed at 60°C, further slowly added 70g of deionized water at 60°C, and emulsified with ultrasound for 10 minutes, thereby obtaining an emulsified product of KF-412 (solid Content concentration 30%). 5 parts by weight of the emulsified product was added to 95 parts by weight of the aqueous dispersion liquid synthesized in Comparative Manufacturing Example 1, and adjusted to an aqueous dispersion liquid having a solid content concentration of 30% by mixing polysiloxane. The same method as in Test Example 1 was repeated except that the aqueous dispersion liquid was used. The results are shown in Table 4.

(Industrial availability)

The water repellent of the present invention can be used as a surface treatment agent on various substrates, such as fiber products (such as carpets), paper, non-woven fabrics, stone materials, electrostatic filters, dust covers, and fuel cell parts. The water repellent of the present invention can also function as an antifouling agent and a dirt release agent.

Claims (13)

A water-repellent agent containing a silicon-containing polymer derived from (A1) a repeating unit derived from a non-fluorine (meth)acrylate monomer represented by the following formula, and (A2) derived from a single terminal Or a repeating unit of a polysiloxane macromonomer having radical polymerizable groups at both ends as an essential component, where CH ₂ =CA ¹¹ -C(=O)-OA ¹² , where A ¹¹ is a hydrogen atom or a methyl group, A ¹² is a linear or branched hydrocarbon group having 8 to 30 carbon atoms. The silicon-containing polymer further has a repeating unit derived from at least one halogenated olefin selected from the group consisting of vinyl chloride and vinylidene chloride. For silicon-containing polymers, the amount of halogenated olefin is 10.1% by weight or more. Silicon-containing polymers do not have fluorine atoms. The water repellent as described in item 1 of the patent application, wherein the silicon-containing polymer has a repeating unit derived from a crosslinkable monomer. The water repellent as described in item 1 or 2 of the patent application scope, in which the polysiloxane macromonomer is a compound represented by the following formula,

In the formula, R is the same or different hydrocarbon group having 1 to 12 carbon atoms, X is a group having a radically polymerizable functional group, and m is a number of 5 to 200. The water repellent as described in item 1 or 2 of the patent application scope, wherein the polysiloxane macromonomer is a siloxane-modified polysiloxane macromonomer. The water repellent according to item 1 or 2 of the patent application scope, wherein the polysiloxane macromonomer is a polysiloxane macromonomer modified with methacrylic acid at one end. The water repellent as described in item 1 or 2 of the patent application scope contains at least one liquid medium selected from the group consisting of water and organic solvents. The water repellent according to item 1 or 2 of the patent application scope, wherein the amount of the non-fluorine (meth)acrylate monomer (A1) is 10 to 95% by weight relative to the non-silicon-containing polymer, relative to the non- 100 parts by weight of fluoro (meth) acrylate monomer (A1), the amount of polysilicone macromonomer (A2) is 0.5 to 50 parts by weight, relative to the water repellent, the amount of silicon-containing polymer is 0.1 to 70% by weight. The water repellent as described in item 1 or 2 of the patent application, wherein the amount of halogenated olefin is 12 to 50% by weight relative to the silicon-containing polymer. A method for manufacturing a water-repellent agent is to manufacture the water-repellent agent according to any one of the items 1 to 8 of the patent application scope. The method includes the following steps: the non-fluorine in the presence of a radical polymerization initiator (Meth) acrylate monomer and polysiloxane macromonomer polymerization. The manufacturing method as described in item 9 of the patent application scope, in which the monomer is added at once for polymerization, or the monomer is added in portions for polymerization. The method as described in item 9 or 10 of the patent application scope, wherein after the non-fluorine (meth)acrylate monomer and the polysiloxane macromonomer start to polymerize, the halogenated olefin is added to polymerize the halogenated olefin. A processing method of base material is based on the patent application items 1 to 8. The water repellent treatment base material according to any one of the items. A method for manufacturing a treated substrate includes the following steps: applying the water repellent agent described in any one of claims 1 to 8 to the substrate.