JP2009155591A - Aqueous polymer dispersion composition and water- and oil-repellent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a water-dispersed water- and oil-repellent composition exerting high water- and oil-repellency and durability in spite of using a substantially decreased amount of a Rf-containing monomer. <P>SOLUTION: The water-dispersed water- and oil-repellent composition comprises a multilayer-structured polymer particle comprising at least two polymers, i.e. a first polymer and a second polymer. Here, the first polymer is a polymer containing a halogen atom in its main chain, and the second polymer is a polymer containing a fluoroalkyl group. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a water-dispersed polymer composition and a method for producing the same. The water-dispersed polymer composition of the present invention can be used as a water / oil repellent.

Conventionally, a polymer or copolymer of a polymerizable monomer containing a fluoroalkyl, or a compound containing a fluoroalkyl is treated as an organic solvent solution or an aqueous dispersion into a fiber product, etc., and the surface thereof is water- and oil-repellent. A technique for imparting is known.
Conventionally, for the purpose of improving durability of water and oil repellency against washing, dry cleaning, etc., a monomer having an adhesive group is copolymerized with a fluoroalkyl-containing polymerizable monomer, or a fluoroalkyl-containing polymer is used. Attempts have been made to blend coalesced polymers with high film strength.
In the field of coating materials (coating agents), the use of a particle polymer having a multilayer structure has succeeded in maintaining the properties of fluorine and imparting new properties such as processability (Patent Documents 1 to 3).
In order to impart properties such as durability and low temperature cure to water and oil repellents, a composition of a multilayer structure particle polymer has been proposed (Patent Documents 4 to 7).
In addition, Patent Document 8 discloses that a fluorinated monomer is composed of a dispersion of fluorinated structured particles or a latex composed of a blend of fluorinated structured particles or fluorinated random particles and random particles not containing fluorine. It is described that the content can be reduced, the water wettability of the coating can be reduced and the wet abrasion resistance can be maintained.
Furthermore, a method of producing an excellent hydrophobic material while forming core-shell structured particles by various polymerization methods and containing a smaller amount of fluorine-containing monomer is disclosed (Patent Documents 9 to 10).

JP 06-56944 JP-A-62-135531 JP 64-40510 JP 02-001795 JP 07-278422 JP-A-11-172126 JP2007-291373 JP 08-208936 JP 06-192352 JP2003-171607

In conventional water and oil repellents, for the purpose of improving durability of water and oil repellency for washing and dry cleaning, copolymerization with a monomer having an adhesive group together with a fluoroalkyl-containing polymerizable monomer, Attempts have been made to blend a polymer containing fluoroalkyl with a polymer having high film strength. However, durability and water / oil repellency are relative to each other depending on the introduction ratio of the fluorinated monomer and the monomer having an adhesive group. That is, high water and oil repellency can be achieved by introducing a large amount of the fluorinated monomer, but this results in insufficient durability. Conversely, sufficient durability can be imparted by introducing a large amount of the monomer having an adhesive group, but the water and oil repellency becomes poor. Moreover, in order to exhibit sufficient water and oil repellency, it is necessary to introduce a large amount of fluorine monomer, and the cost is high because the fluorine monomer is very expensive.
There has been a demand for a processing agent that exhibits high water and oil repellency and excellent durability in water and oil repellency even when the amount of fluorine monomer used is reduced.

  In order to solve the above problems, the present inventors provide a water and oil repellent composition that exhibits high water and oil repellency even when the amount of fluorine monomer used is reduced and is excellent in durability. We conducted intensive studies for the purpose. As a result, a polymer having a polymer unit having a specific chemical structure and a multi-layered polymer particle having a polymer unit of a monomer containing a fluoroalkyl group have remarkable water and oil repellency and durability. It has been found that it can be achieved, and the present invention has been completed.

  That is, the present invention is a polymer particle containing at least two polymers of a first polymer and a second polymer, and the first polymer is a polymer containing a halogen atom in the main chain, The bipolymer provides a water-dispersed water / oil repellent composition containing multilayer structure polymer particles which are polymers containing polymer units of a monomer containing a fluoroalkyl group, and a method for producing the same.

  According to the present invention, a polymer having a polymer unit having a specific chemical structure and a multilayer structure polymer particle having a polymer unit of a monomer containing fluoroalkyl have remarkable water and oil repellency and durability. For this reason, this invention can reduce cost by reducing the usage-amount of a fluorine monomer, and can provide the water / oil repellent which exhibits high water / oil repellency and is excellent also in durability.

Hereinafter, the present invention will be described in detail.
The water / oil repellent composition of the present invention has multilayer structure polymer particles comprising at least two kinds of polymers, that is, (A) a first polymer and (B) a second polymer.
The multilayer structure polymer particles preferably have an inner layer of the first polymer (A) and an outer layer of the second polymer (B). The multi-layered polymer particles may have unclear layer separation like a sea-island structure, but in general, it is preferable to have a core / shell structure with clear layer separation.
In general, in multi-layered polymer particles, the first polymer forms the core of the particle and the second polymer forms the shell of the particle.
There may be other polymers other than the first polymer and the second polymer, for example, the third polymer (intermediate layer) is between the first polymer (core) and the second polymer (shell). May be present. The third polymer may be one or more polymer layers, may be a polymer included in the range of the first polymer or the second polymer, and may be the first polymer or the second polymer. It may be a polymer not included in the range of coalescence.

(A) First polymer The first polymer generally forms the inner layer (particularly the core) in the multilayer structure polymer particles.
The first polymer contains a halogen atom in the main chain. “The main chain contains a halogen atom” means that the halogen atom is directly bonded to the carbon atom constituting the main chain. As for the monomer which comprises a 1st polymer, it is preferable that the glass transition point of a homopolymer is -80-120 degreeC, for example, -20-100 degreeC. In the first polymer, there is a repeating unit in which a halogen atom is directly bonded to a carbon atom constituting the main chain. Such a repeating unit can be derived from a monomer in which a halogen atom is directly bonded to a carbon atom forming a carbon-carbon double bond (hereinafter referred to as “main chain monomer having a halogen atom”). Examples of halogen atoms are fluorine, chlorine, bromine and iodine.
Examples of main chain monomers having a halogen atom include vinyl halides such as vinyl chloride and vinyl fluoride, vinylidene halides such as vinylidene chloride and vinylidene fluoride, chlorotrifluoroethylene, α-chloro having a hydrocarbon group ( And (meth) acrylate. Vinyl chloride and vinylidene chloride are preferred. The main chain monomer having a halogen atom may be one kind or a combination of two or more kinds.
In addition to the main chain monomer having a halogen atom, the first polymer may contain another polymerizable monomer that can be copolymerized.
Another example of the polymerizable monomer is a monomer having a homopolymer glass transition point of −80 ° C. or higher. Other examples of other polymerizable monomers are (meth) acrylates, (meth) acrylamides, vinyl ethers, vinyl esters, fumarates, maleates and the like. These copolymerizable monomers preferably have a hydrocarbon group, a benzene ring or a reactive group, and particularly preferably have a hydrocarbon group or a reactive group. Still another example of the other polymerizable monomer may be ethylene, styrenes, or the like.
The other polymerizable monomer may be a silicone having a reactive group such as a (meth) acryloxy group. Furthermore, although it may be a monomer having fluoroalkyl (Rf) described in detail in the second polymer (B), it is preferably a monomer not having fluoroalkyl. The first polymer preferably has no fluorine atom. When a monomer containing an Rf group is adopted as another polymerizable monomer in the first polymer, the total amount (weight) of Rf groups in the first polymer is the total amount (weight) of Rf groups in the second polymer. The amount is preferably small compared to

  As the copolymerizable monomer having a hydrocarbon group, (meth) acrylates having a linear hydrocarbon group (in particular, an alkyl group (for example, having 1 to 30 carbon atoms)) are preferred. The hydrocarbon group may be interrupted by an oxygen atom. Specific examples of the copolymerizable monomer having a hydrocarbon group include ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Isodecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, lauryl (meth) acrylate, n-butoxyethyl (meth) acrylate, butoxydiethylene glycol (meth) acrylate, cyclohexyl (meth) Acrylate and the like are preferable.

  As the copolymerizable monomer having a benzene ring, (meth) acrylates having a benzene ring are preferable. The benzene ring may have a substituent (for example, an alkyl or alkoxy group having 1 to 10 carbon atoms, or a halogen atom). As the (meth) acrylate having a benzene ring, phenyl (meth) acrylate, benzyl (meth) acrylate, or a compound in which a methyl group, a methoxy group, a chlorine atom or the like is bonded to these benzene rings is preferable.

  Copolymerizable monomers are polymerizable such as epoxy group, halogen atom, hydroxyl group, amide group, amino group, imino group, alkoxysilyl group, N-methylol group, N-alkyloxyalkyl group, blocked isocyanate group, etc. A reactive group other than the unsaturated bond may be contained (hereinafter referred to as “reactive group-containing monomer”). Examples of the reactive group-containing monomer include 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-methylol (meth) acrylamide, and diacetone (meth) acrylamide. N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, γ-trimethoxysilylpropyl (meth) acrylate , Glycidyl (meth) acrylate and the like are preferable.

  Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and poly (oxyethylene / oxy). Propylene) glycol mono (meth) acrylate, glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate and the like are preferable.

  As a copolymerizable monomer having a blocked isocyanate group, a blocked product of a reaction product obtained by reacting a hydroxyl group-containing (meth) acrylate and a polyisocyanate in a ratio in which at least one isocyanate group remains, A reaction product obtained by reacting a hydroxyl group-containing (meth) acrylate and a polyisocyanate derivative having at least one blocked isocyanate group and at least one free isocyanate group is preferred.

  Examples of the polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate, or alicyclic polyisocyanates such as isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, and bis (isocyanate methyl) cyclohexane, and These nurate modified bodies, prepolymer modified bodies, burette modified bodies and the like can be mentioned, and aliphatic diisocyanates or alicyclic diisocyanates are preferable.

Examples of the blocking agent for obtaining a blocked isocyanate group include oximes, alkyl ketoximes, phenols, β-diketones, malonic esters, lactams, alkanols and the like. Specific examples of the blocking agent include cyclohexane oxime, methyl ethyl ketoxime, phenol, cresol, acetylacetone, diethyl malonate, isopropanol, t-butanol, ε-caprolactam, maleic imide, sodium bisulfite and the like. Cyclohexane oxime, methyl ethyl keto oxime and the like are preferable.
As silicones having a reactive group such as a (meth) acryloxy group, silicones modified with a (meth) acryloxy group can be suitably used.

In the first polymer, the proportion of the main chain monomer having a halogen atom is 10 to 100% by weight in the first polymer. For example, it may be 15 to 90% by weight, in particular 20 to 85% by weight, especially 30 to 80% by weight. The proportion of main chain monomers having halogen atoms is preferably at least 20% by weight, in particular at least 30% by weight.
The molecular weight of the first polymer is preferably in the range of 1,000 to 100,000, particularly preferably about 5,000 to 100,000. Within this range, the durability or initial performance of water / oil repellency is high, and the effect of maintaining high water repellency can be obtained even when heat treatment is performed at a low temperature.

The method for synthesizing the first polymer is not particularly limited, and examples thereof include a method in which the polymerizable monomer including the main chain monomer having a halogen atom is polymerized by a known or well-known polymerization method. Polymerization is preferably performed by emulsion polymerization or dispersion (suspension) polymerization.
In the case of polymerization by emulsion polymerization or dispersion polymerization, a method of polymerizing the above polymerizable monomer by adding a polymerization initiator in the presence of an emulsifier and a polymerization medium can be exemplified. The emulsifier is not particularly limited, and one or more known or well-known emulsifiers of nonionic type, cationic type, anionic type and amphoteric type may be employed. The amount of the emulsifier is preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the polymerizable monomer, and particularly preferably about 1 to 10 parts by weight from the viewpoint of water / oil repellency and dispersion stability.

  The polymerization medium is a medium containing water, and an organic solvent may be included if desired. As the organic solvent, water-soluble organic solvents are preferable, and organic solvents such as esters, ketones, and ethers (alcohols) are preferable. As the ester-based organic solvent, ethyl acetate, butyl acetate, diethyl succinate and the like are preferable. As the ketone-based organic solvent, methyl ethyl ketone, methyl isobutyl ketone, acetone and the like are preferable, and as the ether-based (alcohol-based) organic solvent. Are preferably diethylene glycol, dipropylene glycol, tripropylene glycol, triethylene glycol, glycol, and monomethyl ether, dimethyl ether or diethyl ether thereof. Among these, the organic solvent is preferably an ether-based (alcohol-based) organic solvent from the viewpoint of low flammability. The ratio of water and organic solvent is not particularly limited, and any ratio may be used. The amount of the organic solvent may be 100 parts by weight or less, for example, 1 to 10 parts by weight with respect to 100 parts by weight of water. The amount of the polymerization medium may be 0.5 to 100 parts by weight, for example 1 to 20 parts by weight with respect to 1 part by weight of the polymerizable monomer.

As the polymerization initiator, a water-soluble or oil-soluble polymerization initiator is preferable, and general-purpose initiators such as persulfate-based, azo-based, peroxide-based, and redox-based initiators can be used depending on the polymerization temperature. Although polymerization temperature is not specifically limited, 20 to 150 degreeC is preferable.
In the polymerization reaction of the first polymer, a chain transfer agent may be included for the purpose of controlling the molecular weight. As the chain transfer agent, mercaptans are preferable, a chain transfer agent containing silicone can also be used, and mercapto group-modified alkyl silicone, mercapto group-modified aminoalkyl silicone and the like can be preferably used.

In the polymerization reaction, as a pre-stage for initiating polymerization, a mixture comprising a polymerizable monomer, water, and an emulsifier may be treated with a homomixer or a high-pressure emulsifier, and predispersed in advance.
The first polymer synthesized by the above method is preferably present as fine particles in the medium. The particle diameter of the fine particles of the first polymer is preferably 0.001 to 1 μm, for example 0.01 to 0.5 μm. Within this range, the amount of the emulsifier may be small in order to obtain a stable dispersion, the water / oil repellency is high, and the polymer fine particles are stably present in the medium. The particle diameter can be measured with a dynamic light scattering device, an electron microscope, or the like. When the polymerization is carried out in the presence of an emulsifier by the usual emulsion polymerization method, the average particle size is usually included in the above preferred range.

(B) Second polymer The second polymer generally forms an outer layer (particularly a shell) in the multilayered polymer particles.
The second polymer is a polymer having a fluoroalkyl group (Rf group). The second polymer includes polymerized units derived from a monomer having a fluoroalkyl group (Rf group). Since the second polymer is present on the particle surface, it is easily oriented on the fiber surface and exhibits water and oil repellency.
The monomer constituting the second polymer (hereinafter referred to as “second monomer”) comprises an Rf group-containing monomer and other monomers present if necessary.

The Rf group is a group in which two or more hydrogen atoms of a saturated alkyl group are substituted with fluorine atoms. The ratio of fluorine atoms in the Rf group is preferably such that (number of fluorine atoms in the Rf group) / (number of fluorine atoms in the Rf group + number of hydrogen atoms in the Rf group) is 40% or more. In particular, the case of 60% or more is preferable. In the Rf group, part or all of the hydrogen atoms may be substituted with chlorine atoms.
The Rf group preferably has a linear or branched structure, and particularly preferably has a linear structure. In the case of a branched structure, the branched portion is preferably present near the end of the Rf group. The branched portion is preferably a short chain having about 1 to 4 carbon atoms. The preferred number of carbon atoms for the Rf group is 1 to 12, particularly 4 or 6.
Particularly preferred as the Rf group is a Rf group containing a perfluoroalkyl group or a perfluoroalkyl group moiety when the proportion of the fluorine atom is substantially 100%. The perfluoroalkyl group also preferably has a linear structure. The perfluoroalkyl group _{linear, C m F 2m + 1 -} [ however, m is an integer from 2 to 20. ] Is preferable.

A monomer containing an Rf group means a compound having an Rf group and a polymerizable unsaturated group (particularly a carbon-carbon double bond). The Rf group of the Rf group-containing monomer has the same meaning as the above Rf group, and the preferred embodiment is also the same. Further, the Rf group-containing monomer may be a mixture of two or more compounds having different carbon numbers of the Rf group. In this case, the average carbon number of the Rf group is preferably 4 or more (for example, 4 or 6).
The Rf group-containing monomer, wherein the C _m F _{2m + 1} - [however, m is an integer from 2 to 20. A compound having a perfluoroalkyl group and a polymerizable unsaturated group represented by the formula: The perfluoroalkyl group-containing monomer may be a mixture of two or more compounds having different numbers of m, but the average of m is preferably 4 or more.

  In the Rf group-containing monomer, the Rf group and the polymerizable unsaturated group are bonded directly or indirectly through a bonding group, and are preferably bonded indirectly. The linking group is a divalent or higher linking group, and is preferably an alkylene group, an ester group, an amide group, an amino group, a urethane group, an ether group, a phenyleneoxy group, a sulfonyl group, or a linking group containing these structures. These Rf group-containing monomers employ known or well-known compounds, and can be easily synthesized from Rf group-containing alcohols, Rf group-containing carboxylic acids, Rf group-containing sulfonic acids, or the like.

  Of these, the Rf group-containing monomer in the present invention is preferably a compound having a structure in which one Rf group is linked to a polymerizable unsaturated group via a divalent linking group. For example, Rf group-containing acrylate, Rf group-containing methacrylate, Rf group-containing styrene, Rf group-containing vinyl ester, and Rf group-containing fumarate are preferable.

  Further, the Rf group-containing monomer in the present invention is particularly preferably an acrylate or methacrylate containing an Rf group from the viewpoint of versatility. In the following, acrylate and methacrylate are collectively referred to as (meth) acrylate, which means both. The same applies to other compounds.

Preferred Rf group-containing monomers have the general formula:
Rf-Q ¹ -X ¹
[Wherein, Rf represents a fluoroalkyl group, Q ¹ represents a divalent organic group, and X ¹ represents a monovalent organic group containing a polymerizable unsaturated group. ]
Can be expressed as

Q ¹ represents a divalent organic group, and — (CH ₂ ) _{n + p} −, — (CH ₂ ) _n C (O) ONH (CH ₂ ) _p —, — (CH ₂ ) _n CONH (CH _{2 ) p -, - (CH 2} ) n SO 2 NH (CH 2) p -, - (CH 2) n NHC (O) NH (CH 2) p - , and the like are preferable. However, n and p show 0 or an integer greater than or equal to 1, and n + p is an integer of 2-22. Among these, Q ¹ _{is, - (CH 2) n +} p -, - (CH 2) n C (O) ONH (CH 2) p -, - (CH 2) n SO 2 NH (CH 2) -(CH ₂ ) _{n + p} − in the case where _p − and p is an integer of 2 or more and n + p is 2 to 6, particularly n + p is 2 to 6, that is, dimethylene Group to hexamethylene group is preferred.

X ¹ represents a monovalent organic group containing a polymerizable unsaturated group, a residue of an olefin, a residue of a vinyl ether, a residue of a vinyl ester, a residue of a (meth) acrylate, a styrene These residues are preferred. Preferably -CR ¹ = CH ₂ or ^{_{-OCH 2 -φ-CR 1 = CH}} 2 as residues of olefins, (meth) residues acrylates ^{-OC (O) CR 1 = CH} 2, a vinyl ether -OCR ¹ = CH ₂ as a residue of a group, -C (O) OCR ¹ = CH ₂ as a residue of a vinyl ester, -φ-CH = CH ₂ or -O- as a residue of a styrene φ−CH═CH ₂ is preferred. Where R ¹ is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX ¹ X ² group (where X ¹ and X ² are A hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.), A cyano group, a linear or branched fluoroalkyl having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or non-substituted group It is a substituted phenyl group, and φ is a phenylene group. Among these, X ¹ is preferably a residue of (meth) acrylates, and in particular when —R ¹ is a hydrogen atom or a methyl group —OC (O) CR ¹ ═CH ₂ , that is, an acryloxy group or a methacryloxy group. Is preferred. As the Rf group-containing monomer, in particular, from the viewpoint of polymerizability with other monomers, flexibility of the film formed on the fiber, adhesion to the substrate, solubility in a solvent, ease of emulsion polymerization, etc. ) Acrylates are preferred.
One or two or more Rf group-containing monomers can be used. Usually, the Rf group-containing monomer is used as a mixture of two or more compounds having different Rf group carbon numbers.

Examples of Rf group-containing monomers may be of the general formula:
General formula:
_{CH 2 = C (-X) -C} (= O) -Y-Z-Rf
[Wherein, X represents a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (where X ¹ and X ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.), A cyano group, a linear or branched fluoroalkyl having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted Or an unsubstituted phenyl group;
Y is —O— or —NH—;
Z is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms or a cyclic aliphatic group,
CH (R ¹ ) SO ₂ — group (where R ¹ is an alkyl group having 1 to 4 carbon atoms) or
—CH ₂ CCH (OZ ¹ ) CH ₂ — group (where Z ¹ is a hydrogen atom or an acetyl group) or — (CH ₂ ) _m —SO ₂ — (CH ₂ ) _n — group or — (CH ₂ ) _m —S— (CH ₂ ) _n — group (where m is 1 to 10 and n is 0 to 10),
Rf is a linear or branched fluoroalkyl having 1 to 21 carbon atoms. ]
A compound represented by

  Specific examples of the Rf group-containing monomer include the following, but are not limited thereto.

CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ −Rf
CH ₂ = C (−H) −C (= O) −O−C ₆ H ₄ −Rf
CH ₂ = C (−Cl) −C (= O) −O− (CH ₂ ) ₂ −Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ N (−CH ₃ ) SO ₂ −Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ N (−C ₂ H ₅ ) SO ₂ −Rf
CH ₂ = C (-H) -C (= O) -O-CH ₂ CH (-OH) CH ₂ -Rf

CH ₂ = C (-H) -C (= O) -O-CH ₂ CH (-OCOCH ₃ ) CH ₂ -Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (-H) -C (= O) -NH- (CH ₂ ) ₂ -Rf
CH ₂ = C (−CH ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−CH ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CH ₃ ) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−CH ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (-CH ₃ ) -C (= O) -NH- (CH ₂ ) ₂ -Rf

CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (-F) -C (= O) -NH- (CH ₂ ) ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -S-Rf
CH ₂ = C (−Cl) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -SO ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CH ₂ ) ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -NH- (CH ₂ ) ₂ -Rf

CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (-CF ₃ ) -C (= O) -NH- (CH ₂ ) ₂ -Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (-CF ₂ H) -C (= O) -NH- (CH ₂ ) ₂ -Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (-CN) -C (= O) -NH- (CH ₂ ) ₂ -Rf

CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (-CF ₂ CF ₃ ) -C (= O) -NH- (CH ₂ ) ₂ -Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₃ −S−Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (-F) -C (= O) -NH- (CH ₂ ) ₃ -Rf

CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₃ -S-Rf
CH ₂ = C (−Cl) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₃ -SO ₂ -Rf
CH ₂ = C (−Cl) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −S−Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₃ −S−Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ − (CH ₂ ) ₂ −Rf

CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₃ −S−Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −S−Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
[In the above formula, Rf is a fluoroalkyl having 1 to 21, especially 1 to 6 carbon atoms. ]
The Rf group-containing monomer may be a mixture of two or more.
The amount of the Rf group-containing monomer may be 5 to 95% by weight, for example 20 to 80% by weight, based on the fluoropolymer.

  The second polymer may contain other monomers (that is, copolymerizable monomers) other than the fluorine-containing monomer. Other monomers generally do not contain fluorine atoms.

  When the copolymerizable monomer has a hydrocarbon group, there is no particular limitation, but the hydrocarbon group is preferably a hydrocarbon group having 2 or more carbon atoms, particularly preferably a hydrocarbon group having 4 to 24 carbon atoms. Further, the hydrocarbon group may have any of a straight chain structure, a branched structure, and a ring structure. As the linear hydrocarbon group, a (saturated) alkyl group is preferable.

The other monomer may be a non-crosslinkable monomer or a crosslinkable monomer.
The non-crosslinkable monomer preferably does not contain fluorine and has a carbon-carbon double bond. The non-crosslinkable monomer is preferably a vinyl monomer that does not contain fluorine. Non-crosslinkable monomers are generally compounds having one carbon-carbon double bond.

Non-crosslinkable monomers include butadiene, chloroprene, maleic acid derivatives, vinyl halides such as vinyl chloride, ethylene, vinylidene halides such as vinylidene chloride, vinyl alkyl ethers, styrene, alkyl (meth) acrylates, vinyl pyrrolidone, These are exemplified, but not limited thereto.
Since washing resistance is improved, it is preferable to use vinyl halide such as vinyl chloride or vinylidene halide such as vinylidene chloride.
The other monomer is preferably a monomer mixture containing vinyl chloride and / or vinylidene chloride. The preferred content of vinyl chloride and vinylidene chloride is not more than 80% by weight, for example 1 to 50% by weight, in particular 5 to 40% by weight, based on the other monomers.

The non-crosslinkable monomer may be a (meth) acrylic acid ester containing an alkyl group. Carbon number of an alkyl group may be 1-30, for example, 6-30, for example, 10-30. For example, the non-crosslinkable monomer has the general formula:
CH ₂ = CA ¹ COOA ²
[Wherein, A ¹ is a hydrogen atom or a methyl group, and A ² is an alkyl group represented by C _n H _{2n + 1} (n = 1 to 30). ]
It may be an acrylate represented by

  The second polymer may include a crosslinkable monomer. The crosslinkable monomer may be a compound having at least two reactive groups and / or carbon-carbon double bonds and not containing fluorine. The crosslinkable monomer may be a compound having at least two carbon-carbon double bonds, or a compound having at least one carbon-carbon double bond and at least one reactive group. Examples of reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanates, amino groups, carboxyl groups, and the like.

Examples of crosslinkable monomers include diacetone acrylamide, (meth) acrylamide, N-methylol acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, N , N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, butadiene, chloroprene, glycidyl (meth) acrylate, and the like, but are not limited thereto.
Other examples of the crosslinking monomer include isocyanate groups containing (meth) acrylates such as glycerol (meth) acrylate, acetoacetoxyethyl (meth) acrylate, 2-isocyanatoethyl methacrylate or blocking agents such as methyl ethyl ketoxime. Examples thereof include those (meth) acrylates in which the group is blocked.

  The second polymer may include a reactive monomer containing a reactive group in the molecule. Examples of the reactive group include an epoxy group, a halogen atom, a hydroxyl group, an amide group, an amino group, an alkoxysilyl group, an N-methylol group, an N-alkyloxy group, an imino group blocked isocyanate group, and the like. It is done. Examples thereof include the same examples as those exemplified as the monomer containing a reactive group other than the polymerizable unsaturated bond in the first polymer. When the reactive monomer is contained, there is an advantage that adhesion to the fiber surface can be improved during fiber processing, and the processing agent can be prevented from falling off during washing or dry cleaning.

Examples of the other monomer in the second polymer include the same examples as those exemplified as the monomer in the first polymer. A monomer containing a halogen atom in the main chain, which is an essential component in the first polymer, can also be used. Examples of the monomer containing a halogen atom in the main chain include the same examples as those exemplified in the first polymer.
In the second polymer, the proportion of the Rf group-containing monomer may be 30 to 100% by weight, preferably 40 to 90% by weight, and more preferably 50 to 80% by weight with respect to the second polymer. The proportion of the Rf group-containing monomer is particularly preferably 50 to 100% by weight. In the multilayer structure polymer particles including the first polymer and the second polymer, the proportion of the Rf group-containing monomer is 25 to 65% by weight, preferably 30 to 60% by weight, more preferably, based on the multilayer structure polymer particle. May be 35-55% by weight.
In other monomers than the Rf group-containing monomer, the amount of the non-crosslinkable monomer is 50% by weight or more, for example, 80% by weight or more, particularly 90% by weight or more, especially 100%, relative to the other monomers. It's okay.

As a method for synthesizing the second polymer, it is preferable to polymerize the second monomer containing the Rf group-containing monomer. Here, the second monomer is composed of only one or more of Rf group-containing monomers, or a mixture containing one or more of Rf group-containing monomers and one or more of other monomers. Means.
The method for polymerizing the second monomer in the presence of the first polymer is not particularly limited, but the second monomer is added to the emulsion or dispersion in which the first polymer is present as fine particles in one step or several steps. A method of adding a polymerization initiator and polymerizing it (so-called seed emulsion polymerization method) is preferred. The polymerization method is a general seed polymerization method, but any method may be used. It may be re-emulsified after the second-stage dropping and the addition of the second-stage monomer, or may be polymerized after the first-stage resin is impregnated for a certain time at a predetermined temperature after the addition of the second-stage monomer. The polymerization initiator is not particularly limited, and examples thereof include organic peroxides, azo compounds, polymerization initiators such as persulfates, and ionizing radiation such as γ-rays, but azo compounds or azo compounds. Compound salts are preferred.

During the polymerization, water, an organic solvent, or the like may be included in the emulsion or dispersion of the first polymer. By including water or an organic solvent, the final solid content concentration can be adjusted, or the polymerization yield of the second monomer can be increased. The organic solvent is preferably a water-soluble organic solvent, preferably an organic solvent such as an ester, ketone, ether, or alcohol, and particularly preferably an ether or alcohol. As the ether-based or alcohol-based organic solvent, the same organic solvent as that in the first polymer is preferable. The ratio of water and organic solvent is not particularly limited, and any ratio may be used.
Prior to initiating polymerization of the second monomer, it is preferable to stir the mixture containing the first polymer and the second monomer well, thereby improving the final yield. Further, a chain transfer agent may be present in the polymerization of the second monomer. Examples of the chain transfer agent may be the same as those in the first polymer.

  The weight ratio of the second monomer to the first polymer, that is, (weight of the second monomer) / (weight of the solid content of the first polymer) is 0.05: 1 to 10: 1, for example, 0.1: 1 to It is preferably 8: 1. Moreover, although superposition | polymerization temperature is not specifically limited, 20 to 150 degreeC is preferable.

  The polymer particles in the present invention are polymer particles containing at least a first polymer and a second polymer, but may contain other polymers. In addition, the first polymer and the second polymer may each be one type or two or more types. When two or more types of the first polymer and the second polymer are included, respectively, a method of synthesizing by sequentially performing the seed emulsion polymerization method described above is desirable.

  In the polymer particles containing the first polymer and the second polymer, the presence form of the second polymer depends on the amount of emulsifier coexisting in the first polymer fine particle dispersion and the hydrophobicity of the first polymer and the second monomer. However, polymer particles in a form in which the second polymer is present on the surface or inside of the fine particles of the first polymer are preferable. In the polymer particles, a core-shell type in which the first polymer and the second polymer are separated into layers is preferable in terms of performance, but the layer separation form is a sea-island structure or a part of the polymer is localized. Or a form in which another polymer molecular chain or the like is entangled. By adopting such a form, even when the amount of the Rf group-containing monomer is greatly reduced, it is still possible to produce and mix the first polymer dispersion and the second polymer dispersion, respectively. It is estimated that excellent water and oil repellency that cannot be obtained is obtained.

When the polymer particle is a core-shell type in which the first polymer and the second polymer are separated into layers, the core contains a first polymer containing a monomer having a halogen atom in the main chain. And it is preferable that the 2nd polymer containing a Rf containing monomer exists in a shell part. The first polymer preferably does not contain an Rf group, but when the Rf group is present, the amount of Rf group (parts by weight) is preferably relatively small compared to the second polymer. Compared with 100 parts by weight of the Rf group of the second polymer, the value of the parts by weight of the Rf group of the first polymer is preferably 10 parts by weight or more, and more preferably 30 parts by weight or less.
The particle diameter of the multilayer structure polymer particles including the first polymer and the second polymer may be 0.001 to 1 μm, for example, 0.01 to 0.50 μm.

  The water-dispersed water / oil repellent composition of the present invention is a composition in which the polymer particles are dispersed in a medium containing water. The composition may be prepared by dispersing the polymer particles in a desired medium containing water. Usually, in the polymerization reaction, the dispersion medium is used as it is by using the polymerization medium as the desired medium. An oil composition may be prepared. As a medium, it is a medium containing water, and the medium containing water or water and an organic solvent is preferable. The amount of the organic solvent used is preferably about 0 to 40 parts by weight with respect to 100 parts by weight of the polymer particles.

  Furthermore, in the water-dispersed water / oil repellent composition of the present invention, the amount of the polymer particles is preferably about 1 to 50 parts by weight with respect to 100 parts by weight of the medium. It is preferable to adjust with water or an organic solvent. The concentration can be appropriately changed depending on the purpose and the form of the composition. Furthermore, the water / oil repellent composition of the present invention may contain other additive components. If necessary, a blender can be used together. For example, water / oil repellent, wrinkle preventive, anti-shrink agent, flame retardant, crosslinking agent, antistatic agent, softener, water-soluble polymer such as polyethylene glycol and polyvinyl alcohol, wax emulsion, antibacterial agent, pigment, paint, etc. is there. These blenders may be used by being added to the object to be treated and the treatment bath at the time of treatment, or in advance, if possible, mixed with the composition of the present invention.

  The water-dispersed water / oil repellent composition of the present invention is applied to the article to be treated by any method depending on the type of article to be treated, the preparation form, and the like. For example, a method of adhering to the surface of the object to be processed by a coating method such as dip coating and drying is employed. Further, the product treated with the water / oil repellent of the present invention exhibits high water / oil repellency even when heat-treated under mild conditions of 180 ° C. or less, and is excellent in durability. In general, the heat treatment temperature is preferably about 100 to 170 ° C. Further, the heat treatment time is preferably within 5 minutes, particularly preferably about 30 seconds to 2 minutes. Further, the heat treatment may be a high-temperature treatment at 150 ° C. or higher, and the treatment time can be shortened compared with a normal case when the treatment is performed at a high temperature.

  The article to be treated is not particularly limited, but besides textiles, stones, filters (for example, electrostatic filters), dust masks, glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, Mention may be made of ceramic products, plastics, painted surfaces and plasters. It is particularly useful for textile products. Various examples can be given as textile products. For example, natural animal and vegetable fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, glass fibers, and carbon fibers , Inorganic fibers such as asbestos fibers, or mixed fibers thereof. The fiber product may be in the form of fiber, yarn, cloth or the like. In particular, the water-dispersed water / oil repellent composition of the present invention is suitable for the treatment of textile products. When processed into textile products, the fabric has water and oil repellency, antifouling properties, abrasion resistance, washing resistance, dry cleaning resistance, rain resistance, etc. A practical water / oil repellent function can be imparted.

In the present invention, the article to be treated is treated with a soil release agent. “Treatment” means that a treatment agent is applied to an object to be treated by dipping, spraying, coating, or the like. By the treatment, the fluoropolymer which is an active ingredient of the treatment agent penetrates into the treatment object and / or adheres to the surface of the treatment object.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
The characteristics were measured as follows.
Water and oil repellency
When treating T / C fabric, the polymer dispersion is diluted with water so that the solid concentration is 30% by weight, and diluted with water so that the concentration of the 30% by weight dispersion is 3.2%. Prepare a treatment solution. After immersing T / C cloth (twill, 200 g / m ² , undyed cloth) in the treatment liquid, squeezing with mangle at 4 kg / cm ² , 4 m / min and heat-treating at 170 ° C. for 1 minute, Evaluate water and oil repellency. Similarly, the treatment liquid is prepared by diluting with water so that the concentration of the 30 wt% dispersion becomes 4.8%. When processing a cotton cloth, after immersing a cotton cloth (twill, 160 g / m ² , undyed cloth) in the treatment liquid, squeezing with a mangle at 4 kg / cm ² , 4 m / min, and heat-treating at 170 ° C. for 2 minutes. The water and oil repellency of the treated fabric is evaluated. Similarly, the treatment liquid is prepared by diluting with water so that the concentration of the 30 wt% dispersion becomes 4.8%. When processing polyester fabric, immerse the polyester fabric (microfiber navy) in the processing solution, squeeze it with 4kg / cm ² , 4m / min with mangle and heat-treat at 170 ° C for 2 minutes, then water and oil repellency of the treated fabric To evaluate. The water repellency was measured according to AATCC-21 spraying method No. (See Table 1 below). For oil repellency, 3 drops of the test solution shown in Table 2 below on AATCC-118 were placed on the test cloth, the penetration state after 30 seconds was observed, and the highest oil repellency given by the test solution showing no soaking was the oil repellency. And In the case of the same grade, when water / oil repellency is higher, it is evaluated as +, and when it is lower, it is evaluated as −.

Water and oil repellent washing durability
According to the JIS L-0217-103 method, washing with a washing solution at 40 ° C for 25 minutes (5 minutes x HL, 5 consecutive times), dehydration 3 minutes, rinsing 2 minutes, dehydration 3 minutes, rinsing 2 minutes, dehydration 3 minutes Then, tumbler drying is performed, and the subsequent water and oil repellency is evaluated (HL-5).

A storage-stable aqueous dispersion (solid content 30% by weight) is stored at 40 ° C. for 1 month, and the occurrence of sedimentation is observed.
○: No sedimentation □: Slight sedimentation ×: Many sedimentation

Average particle size The average particle size of the dispersed particles is measured using a laser light scattering method (Fiber-Optics Particle Analyzer FPAR-1000 manufactured by Otsuka Electronics Co., Ltd.).

[Core / Shell Polymer]
Synthesis example 1
In a 500 mL container, as a polymerizable monomer, n-butyl acrylate (hereinafter referred to as n-BA) 11.16 g, N-methylolacrylamide (hereinafter referred to as N-MAM) 1.07 g, 3-chloro- 0.53 g of 2-hydroxypropyl methacrylate (hereinafter referred to as TM), 0.49 g of lauryl mercaptan (hereinafter referred to as L-SH), di-cured tallow alkyldimethylammonium chloride (hereinafter referred to as C2ABT) as an emulsifier 41 g, sorbitan monopalmitate (hereinafter referred to as PP-40R) 1.89 g, polyethylene glycol lauryl ether (hereinafter referred to as K220) 8.15 g, polyoxyethylene oleyl ether (hereinafter referred to as BO50) 2.02 g, water 87. 56 g, tripropylene glycol (hereinafter referred to as TPG) 12.60 After adding g and pre-dispersing with a homomixer, the mixture was treated with an ultrasonic emulsifier while cooling for 5 minutes to obtain an emulsion of the first monomer.
This emulsion was placed in a 500 mL stainless steel autoclave, purged with nitrogen, and charged with 44.04 g of vinyl chloride (hereinafter referred to as VCl). Next, 0.65 g of 2,2′-azobis (2-amidinopropane) dihydrochloride (hereinafter referred to as NC-32W) as an initiator was dissolved in 4 g of water and added, and then the temperature was raised to 60 ° C. Polymerization was performed for 3 hours to obtain a dispersion of first polymer particles having a solid content of 34.2% and an average particle size of 0.159 μm (167.5 g).

Synthesis Examples 2-15
A dispersion of first polymer particles having the composition of the first monomer shown in Tables 3 to 5 was obtained in the same manner as in Synthesis Example 1. For polymerization using VCl, a stainless steel autoclave was used. A separable flask was used for the polymerization without using VCl. When polymerization was performed using a separable flask, a cooling tube, a thermometer, and a nitrogen introduction tube were provided.
Hereinafter, 2-ethylhexyl methacrylate is HEMA, n-butyl methacrylate is n-BMA, cyclohexyl methacrylate is CHMA, t-butyl methacrylate is TBMA, stearyl acrylate is StA, lauryl acrylate is LA, 2-ethylhexyl acrylate is 2EHA, 3, 3 , 4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl methacrylate was designated as 13FMA. 2,2,3,3,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoro-nonyl acrylate was designated 17FA.

Example 1
13FMA (28.59 g), StA (3.61 g) as the second monomer with respect to the dispersion of the first polymer particles produced in Synthesis Example 1 (solid content concentration 34.2%, 110.29 g) in a 500 mL container , N-MAM (0.89 g), TM (0.42 g), TPG (12.6 g) and water (69.97 g) were added, and the mixture was stirred at 60 ° C. for 5 minutes. After pre-dispersing, the mixture was processed with an ultrasonic emulsifier for 3 minutes while cooling to obtain an emulsion.
This emulsion was placed in a 500 mL stainless steel autoclave, purged with nitrogen, and charged with VCl (10.48 g). Thereafter, NC-32W (0.2 g) was dissolved in water (4 g) and added, and polymerized at 60 ° C. for 3 hours. The aqueous solvent dispersion after cooling had a solid content concentration of 32.7% and an average particle size of 0.154 μm. As a result of observation of the aqueous solvent dispersion with a transmission electron microscope, the second polymer formed core / shell type fine particles present on the surface of the first polymer particles.

Examples 2-6
A dispersion of polymer particles was obtained in the same manner as in Example 1, using a combination of the second monomer mixture having the composition of the second monomer shown in Tables 6 to 7 and the first polymer particle dispersion.

Comparative Examples 1-11
A dispersion of polymer particles was obtained in the same manner as in Example 1 using a combination of the second monomer mixture having the composition of the second monomer shown in Tables 8 to 10 and the first polymer particle dispersion.

Test Examples 1-6 and Comparative Test Examples 1-11
The polymer particle dispersions obtained in the above examples were evaluated for water / oil repellency and storage stability. The evaluation results are shown in Tables 11-12.

表１１と表１２を比較すると、１段目（コア）にVClを含有したエマルジョンを用いると良好な結果が得られることがわかる。

Comparing Table 11 and Table 12, it can be seen that good results can be obtained by using an emulsion containing VCl in the first stage (core).

Synthesis Example 16
In a 500 mL container, as a polymerizable monomer, n-BA (23.25 g), N-MAM (1.88 g), TM (0.93 g), L-SH (0.72 g), emulsifier C2ABT (4.15 g), PP-40R (5.64 g), K220 (23.66 g), BO50 (6.02 g), water (157.23 g), TPG (28.13 g) were added, and the mixture was mixed with a homomixer. After the dispersion, the mixture was treated for 5 minutes while cooling using an ultrasonic emulsifier to obtain an emulsion of the first monomer.
This emulsion was placed in a 500 mL stainless steel autoclave, purged with nitrogen, and charged with VCl (73.00 g). Next, after adding NC-32W (1.16 g) of an initiator dissolved in water (4 g), the temperature was raised to 60 ° C. and polymerized for 3 hours to obtain a solid content of 40.4% and an average particle size of 0. A dispersion of .226 μm first polymer particles was obtained (299.4 g).

Synthesis Example 17
A dispersion of first polymer particles having the composition of the first monomer shown in Table 13 was obtained in the same manner as in Synthesis Example 16.

Example 7
13FMA (28.59 g), StA (3.61 g) as a second monomer with respect to 110.29 g of the first polymer particle dispersion (solid content concentration 34.3%) produced in Synthesis Example 1 in a 500 mL container, N-MAM (0.89 g), T-M (0.42 g), TPG (12.6 g), and water (62.96 g) were added, and the mixture was stirred at 60 ° C. for 5 minutes. After the dispersion, the mixture was processed with an ultrasonic emulsifier while cooling for 3 minutes to obtain an emulsion.
This emulsion was placed in a 500 mL stainless steel autoclave, purged with nitrogen, and charged with VCl (10.48 g). Thereafter, NC-32W (0.2 g) was dissolved in 4 g of water and added, and polymerized at 60 ° C. for 3 hours. The aqueous solvent dispersion after cooling had a solid content concentration of 32.7% and an average particle size of 0.154 μm. As a result of observation of the aqueous solvent dispersion with a transmission electron microscope, the second polymer was a core / shell type fine particle present on the surface of the first polymer particle.

Examples 8-13
A dispersion of polymer particles was obtained in the same manner as in Example 7 using a combination of the second monomer mixture having the composition of the second monomer shown in Tables 14 to 15 and the first polymer particle dispersion.
Mercapto group-modified aminodimethylsilicone was denoted as Si-SH.

Test Examples 7 to 13
The polymer particle dispersions obtained in Examples 7 to 13 were evaluated for water / oil repellency and storage stability.
The evaluation results are shown in Table 16.

Example 14
13FMA (30.19 g) as a second monomer and StA (3.86 g) with respect to 117.36 g of the dispersion (solid content concentration 34.3%) of the first polymer particles produced in Synthesis Example 1 in a 500 mL stainless steel autoclave ), N-MAM (0.95 g), T-M (0.45 g), TPG (13.38 g) and water (74.27 g) were added, and after purging with nitrogen, VCl (11.23 g) was charged. . Thereafter, the mixture was stirred at 60 ° C. for 1 hour, and after cooling to 40 ° C., NC-32W (0.25 g) was dissolved in water (4 g) and added, followed by polymerization at 60 ° C. for 3 hours. The aqueous solvent dispersion after cooling had a solid content concentration of 33.6% and an average particle size of 0.229 μm. As a result of observation of the aqueous solvent dispersion with a transmission electron microscope, the second polymer was a core / shell type fine particle present on the surface of the first polymer particle.

Synthesis Example 18
In a 500 mL container, as a polymerizable monomer, n-BA (12.78 g), N-MAM (1.06 g), TM (0.53 g), L-SH (0.38 g), emulsifier C2ABT (0.64 g), PP-40R (0.85 g), K220 (3.68 g), BO50 (0.91 g), water (87.00 g), TPG (15.67 g) were added, and the mixture was mixed with a homomixer. After the dispersion, the mixture was treated for 5 minutes while cooling using an ultrasonic emulsifier to obtain an emulsion of the first monomer.
This emulsion was placed in a 500 mL stainless steel autoclave, purged with nitrogen, and charged with VCl (40.32 g). Next, after adding NC-32W (0.64 g) of an initiator dissolved in water (4 g), the temperature was raised to 60 ° C., followed by polymerization for 3 hours to obtain a solid content of 34.3% and an average particle size of 0. A dispersion of .184 μm first polymer particles was obtained (156.3 g).

Example 15
13FMA (30.00 g), StA (3.84 g) as the second monomer with respect to 117.48 g of the first polymer particle dispersion (solid concentration 34.1%) produced in Synthesis Example 18 in a 500 mL stainless steel autoclave ), N-MAM (0.94 g), TM (0.45 g), emulsifiers C2ABT (0.54 g) and PP-40R (0.72 g), K220 (3.12 g), BO50 (0.77 g) ), Water (73.8 g), TPG (13.29 g), pre-dispersed with a homomixer, and then treated with an ultrasonic emulsifier while cooling for 5 minutes to obtain an emulsion of the second monomer It was. This emulsion was placed in a 500 mL stainless steel autoclave, purged with nitrogen, and charged with VCl (11.16 g). Thereafter, NC-32W (0.27 g) was dissolved in water (4 g) and added to the first polymer particle dispersion, and after heating to 60 ° C., an emulsion of the second monomer was added dropwise over 1 hour. It is. After completion of the dropwise addition, polymerization was further performed for 3 hours. The aqueous solvent dispersion after cooling had a solid content concentration of 34.1% and an average particle size of 0.187 μm. As a result of observation of the aqueous solvent dispersion with a transmission electron microscope, the second polymer was a core / shell type fine particle present on the surface of the first polymer particle.

Test Examples 14-15
The polymer particle dispersions obtained in Examples 14 to 15 were evaluated for water / oil repellency and storage stability.
The evaluation results are shown in Table 17.

[Polymer blend]
Synthesis Example 19
In a 500 mL container, n-BA (63.11 g), N-MAM (1.26 g), T-M (0.63 g), L-SH (0.9 g), and emulsifier as polymerizable monomers C2ABT (0.91 g), PP-40R (1.22 g), K220 (5.25 g), BO50 (1.3 g), water (103.4 g), TPG (18.62 g) were added, and the mixture was mixed with a homomixer. After the dispersion, the mixture was treated with an ultrasonic emulsifier while cooling for 5 minutes to obtain an emulsion of the monomer mixture.
This emulsion is put into a 500 mL separable flask equipped with a cooling tube, a nitrogen introduction tube, and a thermometer, and after nitrogen substitution, the initiator NC-32W (0.38 g) is dissolved in water (4 g) and added. Thereafter, the temperature was raised to 60 ° C., followed by polymerization for 3 hours to obtain a dispersion of non-fluorinated polymer particles having a solid content of 35.3% and an average particle size of 0.109 μm (207.1 g).

Synthesis Examples 20-23
The monomer mixture shown in Table 18 is emulsified in the same manner as in Synthesis Example 19, and polymerized in a 500 mL stainless steel autoclave or 500 mL separable flask equipped with a cooling tube, a nitrogen introduction tube, and a thermometer. Combined particles were obtained.

Synthesis Example 24
In a 500 mL container, 13FMA (49.98 g), StA (12.97 g), N-MAM (1.39 g), T-M (0.66 g), and C2ABT (0.47 g) as an emulsifier as polymerizable monomers PP-40R (0.63 g), K220 (2.74 g), BO50 (0.68 g), TPG (18.62 g) and water (103.4 g) were added, and the mixture was stirred at 60 ° C. for 5 minutes. After pre-dispersing with a homomixer, the mixture was processed with an ultrasonic emulsifier while cooling for 3 minutes to obtain an emulsion.
After this emulsion was put into a 500 mL separable flask and purged with nitrogen, NC-32W (0.38 g) as an initiator was dissolved in water (4 g) and added, and the temperature was raised to 60 ° C. for 3 hours. Polymerization was performed to obtain a dispersion of fluoropolymer particles having a solid content of 34.4% and an average particle size of 0.134 μm (195.0 g).

Synthesis Example 25
In the same manner as in Synthesis Example 24, the monomer mixture solution other than VCl was emulsified in the preparation shown in Table 19, and placed in a 500 mL stainless steel autoclave. After purging with nitrogen, a predetermined amount of VCl was charged. Thereafter, NC-32W as an initiator was added after being dissolved in water, heated to 60 ° C. and polymerized for 3 hours to obtain a dispersion of fluorine-containing polymer particles.

Synthesis Example 26
In the same manner as in Synthesis Example 25, the monomer mixture solution other than VCl was emulsified in the preparation shown in Table 19, and placed in a 500 mL stainless steel autoclave. After purging with nitrogen, a predetermined amount of VCl was charged. Thereafter, NC-32W as an initiator was added after being dissolved in water, heated to 60 ° C. and polymerized for 3 hours to obtain a dispersion of fluorine-containing polymer particles.

Comparative Examples 12-19
Dispersion obtained by diluting the non-fluorinated polymer particle dispersions obtained in Synthesis Examples 19 to 23 and the fluorinated polymer particle dispersions obtained in Synthesis Examples 24 to 26 with water so that the solid content concentration is 30% by weight. A dispersion mixture was obtained by blending the liquids at the mixing ratios shown in Table 20 and Table 21.

Comparative Test Examples 12-19
The polymer particle dispersions obtained in the above Comparative Examples 12 to 19 were evaluated for water / oil repellency and storage stability.
The evaluation results are shown in Table 22.

[Random copolymer]
Comparative Example 20
In a 500 mL container, 13FMA (37.68 g), StA (25.15 g), emulsifiers C2ABT (0.74 g) and PP40R (0.98 g), K220 (4.39 g), BO50 as polymerizable monomers. (1.08 g), water (102.12 g), and TPG (18.51 g) were added and pre-dispersed with a homomixer, and then treated with an ultrasonic emulsifier while cooling for 5 minutes to obtain an emulsion. It was.
After this emulsion was put into a 500 mL separable flask and purged with nitrogen, NC-32W (0.38 g) as an initiator was dissolved in water (4 g) and added, and the temperature was raised to 60 ° C. for 3 hours. Polymerized. As a result, a random copolymer particle dispersion having a solid content of 36.6% and an average particle size of 0.118 μm was obtained (190.6 g).

Comparative Examples 21-26
The monomer mixtures shown in Table 23 and Table 24 were emulsified in the same manner as in Comparative Example 20, and those using no VCl were polymerized using a separable flask to obtain a dispersion of random copolymer particles. For those using VCl, the emulsion is put into a stainless steel autoclave, and after substitution with nitrogen, VCl is introduced, an initiator dissolved in water is added, polymerization is performed at 60 ° C. for 3 hours, and random copolymer particles A dispersion was obtained.

Comparative Test Examples 20 to 26
The polymer particle dispersions obtained in the above Comparative Examples 20 to 26 were evaluated for water / oil repellency and storage stability.
The evaluation results are shown in Table 25.

Test Examples 16-23 and Comparative Test Examples 27-40
With respect to various fabrics obtained by treating the aqueous resin dispersion shown in Table 26 by the method shown in Test Example 1, the water and oil repellency washing durability was evaluated.
The evaluation results are shown in Tables 26 to 27.

Claims (20)

A multi-layer structure polymer particle comprising at least two polymers of a first polymer and a second polymer, wherein the first polymer is a polymer containing a halogen atom in the main chain; Is a water-dispersed water / oil repellent composition comprising multi-layered polymer particles which are polymers containing a fluoroalkyl group. The water-dispersed water / oil repellent composition according to claim 1, wherein the first polymer contains vinyl chloride and / or vinylidene chloride as a polymerized unit. The water-dispersed water / oil repellent composition according to claim 2, wherein the first polymer is a polymer containing 10 to 100% by weight of vinyl chloride and / or vinylidene chloride polymer units. The water-dispersed water / oil repellent composition according to any one of claims 1 to 3, wherein the first polymer does not contain fluoroalkyl. The water-dispersed water / oil repellent composition according to any one of claims 1 to 4, wherein the first polymer has no fluorine atom. The water-dispersed water / oil repellent composition according to any one of claims 1 to 5, wherein the second polymer is a polymer containing a polymer unit of a fluoroalkyl group-containing monomer. The water-dispersed water / oil repellent composition according to claim 6, wherein the second polymer is a polymer containing 50 to 100% by weight of a polymer unit of a fluoroalkyl group-containing monomer. Fluoroalkyl group, the general formula C _m F _{2m + 1} - (however, m is an integer from 2 to 20.), Or _{(CF 3) 2 CF (CF} 2 CF 2) n - ( where, n is It is an integer of 0-10.) The water-dispersed water / oil repellent composition according to any one of claims 1 to 7 is represented. The fluoroalkyl group-containing monomer has the general formula:
Rf-Q ¹ -X ¹
[Wherein, Rf represents a fluoroalkyl group, Q ¹ represents a divalent organic group, and X ¹ represents a monovalent organic group containing a polymerizable unsaturated group. ]
The water-dispersed water / oil repellent composition according to claim 6 or 7, represented by: The fluoroalkyl group-containing monomer has the general formula:
_{CH 2 = C (-X) -C} (= O) -Y-Z-Rf
[Wherein, X represents a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (where X ¹ and X ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.), A cyano group, a linear or branched fluoroalkyl having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted Or an unsubstituted phenyl group;
Y is —O— or —NH—;
Z is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms or a cyclic aliphatic group,
—CH ₂ CH ₂ N (R ¹ ) SO ₂ — group (where R ¹ is an alkyl group having 1 to 4 carbon atoms) or —CH ₂ CH (OZ ¹ ) CH ₂ — group (where Z ¹ Is a hydrogen atom or an acetyl group.) Or — (CH ₂ ) _m —SO ₂ — (CH ₂ ) _n — group or — (CH ₂ ) _m —S— (CH ₂ ) _n — group (where m is 1 to 10, n is 0 to 10, and Rf is a linear or branched fluoroalkyl having 1 to 21 carbon atoms. ]
The water-dispersed water / oil repellent composition according to claim 6 or 7, which is a compound represented by the formula: The water-dispersed water / oil repellent composition according to claim 6 or 7, wherein the second polymer contains 10 to 50% by weight of a monomer other than the fluoroalkyl-containing monomer. The water-dispersed water / oil repellent composition according to claim 11, wherein the other monomer is a monomer mixture containing vinyl chloride and / or vinylidene chloride. The water-dispersed water / oil repellent composition according to any one of claims 1 to 12, wherein the multilayer polymer particles are polymer particles in which a second polymer is present on the surface or inside of the first polymer particles. . The water-dispersed water / oil repellent composition according to claim 13, wherein the first polymer has a particle size of 0.001 to 1 μm. The water-dispersed water / oil repellent composition according to any one of claims 1 to 14, wherein the particle diameter of the multilayer structure polymer particles is 0.001 to 1 µm. The method for producing a water-dispersed water / oil repellent composition according to any one of claims 1 to 15, wherein the second monomer is polymerized in the presence of particles of the first polymer. The production method according to claim 16, wherein the particle size of the first polymer is 0.001 to 1 µm. The production method according to claim 16 or 17, wherein the polymerization reaction for forming the second polymer is carried out in the presence of a chain transfer agent. The production method according to any one of claims 16 to 18, wherein particles of the first polymer are obtained by polymerizing a polymerizable monomer containing a monomer having a halogen atom bonded to an unsaturated double bond in the presence of a chain transfer agent. . A multi-layer structure polymer particle comprising at least two polymers of a first polymer and a second polymer, wherein the first polymer is a polymer containing a halogen atom in the main chain; Is a multilayer structure polymer particle which is a polymer containing a fluoroalkyl group.