JP3346643B2 - Water-dispersed water / oil repellent composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-dispersible water / oil repellent composition which can be cured at a low temperature and a method for producing the same.

[0002]

BACKGROUND ART Conventionally, a polymer or a copolymer or compound containing a polyfluoroalkyl group of the polymerizable monomer containing a polyfluoroalkyl group, a textile such as an organic solvent solution or an aqueous dispersion-treated In addition, a technique for imparting water / oil repellency to those surfaces is known.

Conventionally, a monomer having an adhesive group has been copolymerized with a polymerizable monomer having a polyfluoroalkyl group in order to improve the durability of water and oil repellency against washing, dry cleaning, and the like. Attempts have been made to blend a polymer containing a polyfluoroalkyl group with a polymer having high film strength.

[0004]

[SUMMARY OF THE INVENTION However, in the conventional water and oil repellent, in order to firmly express the durability of water and oil repellency, after processing the water-repellent oil-repellent agent to the fabric, 150
It was essential to perform heat treatment at a high temperature of 200 ° C. for 1 to 5 minutes. However, fiber products such as ultrafine synthetic fibers with a fiber diameter of 10 μm or less, irregular shaped yarns, and new synthetic fibers (split yarns)
Or in the case of a water repellent oil repellent treatment on the weak natural fiber product in hot wool, to an essential heat treatment at a high temperature,
There was a problem that the rough hardening of the texture and the decrease in color fastness were caused. For this reason, a processing agent which exhibits high water and oil repellency even at low temperature conditions and has excellent durability has been desired.

Further, in the conventional water and oil repellent, a natural dirt in the environment, problems and water repellency decreases over time, also, the problem of water-repellent, oil-repellent properties Dirt is significantly reduced was there. Since such stains are unavoidable under a practical use environment, a processing agent having excellent durability in water and oil repellency has been demanded.

[0006]

Means for Solving the Problems The present inventors have studied in detail the mechanism of developing the durability of water and oil repellency during low-temperature heat treatment and a method for enhancing the water repellency. As a result, certain water-dispersible water- moistened form a polymer having specific physical properties
Oil composition was found to be capable of solving the above problems. Moreover, the present inventors have found that the composition does not need to be subjected to the high-temperature treatment required for conventional water- and oil-repellents, and can be used under mild processing conditions under water- and oil-repellent rub resistance, washing resistance, and dry resistance. It has been found that the composition is an excellent composition that can maintain practical durability such as cleaning property over a long period of time.

That is, the present invention relates to polymer particles containing at least two kinds of polymers, a first polymer and a second polymer, wherein the first polymer is a polymer containing a polyfluoroalkyl group. Further, the present invention provides a water-dispersed water / oil repellent composition containing polymer particles, wherein the second polymer is a polymer containing a polymerized unit of the following monomer B, and a method for producing the same. Monomer B: a homopolymer having a glass transition point of 30 ° C. or higher and an ester moiety having a cyclic hydrocarbon group, a polycyclic hydrocarbon group, or a branched alkyl group having 5 or more carbon atoms (meth) Acrylate. However, vinyl fluoride
50% to 80% by weight of lidene, 20% to 5% of propylene hexafluoride
0% by weight and other copolymerizable monomers 0 to 30% by weight
% Of a fluoropolymer obtained by polymerizing a monomer consisting of
(T) 40 to 100% by weight of acrylic acid alkyl ester
And 0 to 60% by weight of other copolymerizable monomers
Do not complex with acrylic polymer obtained by polymerizing monomers.
Containing conjugated polymer particles dispersed in an aqueous medium
Excludes aqueous polymer dispersions.

[0008] The water / oil repellent composition of the present invention is characterized by containing polymer particles containing at least two kinds of polymers. One of the at least two polymers is a first polymer containing a polyfluoroalkyl group. Hereinafter, the “polyfluoroalkyl group” is referred to as “R _f group”.

The R _f group is a group in which two or more hydrogen atoms of an alkyl group have been substituted with fluorine atoms. The proportion of fluorine atoms in the R _f group, (the number of fluorine atoms in the R _f group) /
Preferably if (number of hydrogen atom in the number + _the R _f group of fluorine atoms in _the R _f group) is 60% or more, when in particular 80% or more. Further, R _f group all or one <br/> part of hydrogen atoms may be substituted by a chlorine atom.

The R _f 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 terminal of the R _f group. Further, the branched portion is preferably a short chain having about 1 to 4 carbon atoms. The _Rf group has 4 to 20 carbon atoms.
Is particularly preferable, and 6 to 16 are particularly preferable.

Particularly preferred as the R _f group are the aforementioned R _f groups containing a perfluoroalkyl group or a perfluoroalkyl group moiety when the proportion of fluorine atoms 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 of 4 to 20. ] Is preferable.

As the first polymer containing an R _f group in the present invention, a polymer containing a polymerized unit of an R _f group-containing monomer is preferable. The _the R _f group-containing monomer means a compound having the above _the R _f group and a polymerizable unsaturated group. _The R _f group in _the R _f group-containing monomer, showed the same meaning as _the R _f group described above, and their preferred embodiments are also the same. Further, _the R _f group-containing monomer may be a mixture of two or more different compounds of the carbon number of _the R _f group, that case, the average carbon number of the R _f group is 6 or more.

As the R _f group-containing monomer, the aforementioned C _m F
_{2m + 1-} [where m is an integer of 4 to 20. And a compound having a perfluoroalkyl group and a polymerizable unsaturated group. The perfluoroalkyl group-containing monomer may be a mixture of two or more compounds having different numbers of m, but it is preferable that the average of m is 6 or more.
When a resin having a molecular weight of less than 6 is employed, the water / oil repellency eventually decreases, and the desired function may not be exhibited.
The average value of m is preferably in the range of about 6 to 16, particularly 8
The range is preferably from 14 to 14, and more preferably from 9 to 12. Those having an excessively large value of m are solid at ordinary temperature, have high sublimability, and are difficult to handle.

[0014] In _the R _f group-containing monomer and _the R _f group and a polymerizable unsaturated group directly or are indirectly bonded through a linking group, if indirectly bond. The linking group, Ru divalent or higher linking group Der. For example, an alkylene group, an ester bond, an amide bond, urethane bond, ether bond, phenylene group, a sulfonyl group are preferable. These _the R _f group-containing monomer, a known or well known compounds are employed, _the R _f group-containing alcohol, or _the R _f group-containing carboxylic acids may be readily synthesized from _the R _f group-containing acid and the like.

Among these, as the R _f group-containing monomer in the present invention, a compound having a structure in which one R _f group is linked to a polymerizable unsaturated group via a divalent linking group is preferable. . For example, _the R _f group-containing acrylate, _the R _f group-containing methacrylate, _the R _f group-containing styrene, _the R _f group-containing Binirue <br/> stearyl Le us and _the R _f group-containing fumarate and the like are preferable.

Further, as the R _f group-containing monomer in the present invention, acrylate or methacrylate containing the above R _f group is particularly preferable from the viewpoint of versatility.
In this specification , acrylate and methacrylate are collectively referred to as (meth) acrylate, meaning both. The same applies to other compounds.

[0017] Preferred _the R _f group-containing monomer over can be represented by the following formula E.

R _f -Q ¹ -X ... Equation E

In the formula E , R _f represents an R _f group,
¹ is a divalent organic group, and X is a polymerizable unsaturated group-containing 1
It shows a valent organic group.

R _f has the same meaning as the above R _f group,
The preferred embodiment is also the same.

Q ¹ represents a divalent organic group and represents-(CH ₂ )
_{n + p -, - (CH} 2) n C O ONH (CH 2) p -, - (C
_{H 2) n CONH (CH 2} ) p -, - (CH 2) n SO 2 NH
_{(CH 2) p -, -} (CH 2) n NHC O NH (CH 2) p -
Are preferred. Here, n and p represent 0 or an integer of 1 or more, and n + p is an integer of 2 to 22. Among these, Q ¹ _{is, - (CH 2) n +} p -, - (CH 2) n
_{CONH (CH 2) p -,} - (CH 2) n SO 2 NH (C
H ₂ ) _p − and p is an integer of 2 or more;
It is preferred that p is 2 to 6, especially n + p is 2 to 6.
In the case of a _{- (CH 2) n + p} -, i.e., preferably dimethylene group-hexamethylene group.

X represents a monovalent organic group containing a polymerizable unsaturated group, and represents a residue of an olefin, a residue of a vinyl ether, a residue of a vinyl ester, a residue of a (meth) acrylate, Styrene residues are preferred. As the olefin residue, -CR ¹ ＣＨCH ₂ or —OCH ₂ -φ
Preferably -CR ¹ = CH _2, (meth) -OC O CR ¹ = CH ₂ The residue acrylates, -OCR ¹ = CH ₂ The residue of a vinyl ether, a residue of the vinyl esters —C O OCR ¹ ＣＨCH ₂ , and the residues of styrenes include —φ—CH ＝ CH ₂ or —O—φ—CH ＝ C
H ₂ is preferred. Here, R ¹ is a hydrogen atom, a methyl group or a halogen atom, and φ is a phenylene group. Of these, -OC O CR ¹ = CH ₂ in the case as the X residues of (meth) acrylates are preferred, especially R ¹ is a hydrogen atom or a methyl group, i.e., (meth) acrylate <br/> b Iruo alkoxy groups are preferred.

[0023] _the R _f group-containing monomer is one or may be used two or more kinds. Usually, the R _f group-containing monomer is used as a mixture of two or more compounds having different carbon numbers in the R _f group. _The R _f group-containing monomers over the present invention
The was, although Ru include the following examples without limitation.

F (CF ₂ ) ₁₀ (CH ₂ ) ₂ OCOCH = CH ₂ , F (CF ₂ ) ₁₀ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₂ OCOCH = CH ₂ , Cl (CF ₂ ) ₁₀ (CH ₂ ) ₃ OCOCH = CH ₂ , H (CF ₂ ) ₁₀ (CH ₂ ) ₂ OCOCH = CH ₂ , F (CF ₂ ) ₁₀ (CH ₂ ) ₁₁ OCOCH = CH ₂ , F (CF ₂ ) ₁₀ CONH (CH ₂ ) ₅ OCOCH = CH ₂ , F (CF ₂ ) ₈ SO ₂ N (C ₃ H ₇ ) C ₂ H ₄ OCOCH = CH ₂ , F _{(CF 2) 10 OC 2 F} 4 (CH 2) 2 OCOCH = CH 2, F (CF 2) 10 CH 2 COOCH = CH 2, F (CF 2) 10 (CH 2) 2 COOCH = CH 2, F ( CF ₂ ) ₁₀ (CH ₂ ) ₃ OCOCH = CH ₂ ,

F (CF ₂ ) ₈ (CH ₂ ) ₂ OCH = CH ₂ , F (CF ₂ ) ₈ CH ₂ CF ₂ CH ₂ CH ₂ OCOCH = CH ₂ , F (CF ₂ ) ₈ (CH ₂ ) ₄ OCOCH = CH ₂ , F (CF ₂ ) ₈ CONH (CH ₂ ) ₃ CH = CH ₂ , F (CF ₂ ) ₁₀ CONH (CH ₂ ) ₂ CH = CH ₂ , F (CF ₂ ) ₁₄ SO ₂ NH (CH ₂ ) ₂ CH = CH ₂ , F (CF ₂ ) ₁₄ (CH ₂ ) ₆ OCOC (CH ₃ ) = CH ₂ , H (CF ₂ ) ₁₀ CH = CH ₂ , F (CF ₂ ) ₈ (CH ₂ ) ₂ OCH ₂ -φ-CH = CH ₂ , F (CF ₂ ) ₈ (CH ₂ ) ₂ OCH ₂ -φ-CH ₂ CH ₂ OCOCH = CH ₂ .

[0026]

[0027]

The _Rf group-containing monomer in the present invention includes, for example, polymerizability with other monomers, flexibility of a film formed on a fiber, adhesion to a substrate, solubility in a solvent, and ease of emulsion polymerization. In view of the above, (meth) acrylates are particularly preferable.

In addition, the first polymer may contain a polymerized unit of another polymerizable monomer in addition to the polymerized unit of the _Rf group-containing monomer. Is the other polymerizable monomers over, not particularly limited as long as it is a compound containing the above-described _the R _f group-containing monomer and a polymerizable unsaturated group. The other polymerizable monomers one or may be used two or more, in the case of two or more kinds may be used in any proportion. In the following, other polymerizable monomers are referred to as copolymerizable monomers.

Examples of the copolymerizable monomer include (meth) acrylates, (meth) acrylamides, vinyl ethers, vinyl esters, fumarates, and maleates. These copolymerizable monomers preferably have a hydrocarbon group or a benzene ring, and particularly preferably have a hydrocarbon group. Further, the copolymerizable monomer may be vinyl chloride, ethylene, vinylidene chloride, vinyl fluoride, vinylidene fluoride, chlorotrifluoroethylene, styrenes and the like.

When the copolymerizable monomer has a hydrocarbon group, the hydrocarbon group is preferably a long-chain hydrocarbon group.
It is preferable that the number of carbon atoms is 14 or more, especially 14 to 2
4 is preferred. In addition, the hydrocarbon group is linear, branched,
Any structure having a ring may be used , but a straight-chain structure is preferred. As the linear hydrocarbon group, a saturated alkyl group is preferable. When a monomer having a long-chain hydrocarbon group is used as the copolymerizable monomer,
Although Ru can also be included copolymerizable monomer having a 12 degree short chain hydrocarbon group, a copolymerizable monomer having a hydrocarbon group of short-chain, to reduce the water repellency is used at a high rate It is difficult.

As the copolymerizable monomer having a long-chain hydrocarbon group, (meth) acrylates having a straight-chain hydrocarbon group are preferable, and cetyl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate are preferable. Acrylate, lauryl (meth) acrylate and the like are preferred.
When the copolymerizable monomer has a benzene ring, (meth) acrylates having a benzene ring are preferred.
Further, the benzene ring may have a substituent. The having a benzene ring (meth) acrylates, phenyl (meth) acrylate, benzyl (meth) acrylate or methyl these benzene rings, a methoxy group,
Compounds having a chlorine atom or the like bonded thereto are preferred.

In the first polymer, the _Rf group-containing monomer and the copolymerizable monomer include an epoxy group, a halogen atom, a hydroxyl group, an amide group, an amino group, an imino group , an alkoxysilyl group, an N-methylol group, and an N-methylol group. alkyloxyalkyl groups may contain a reactive group other than the polymerizable unsaturated group such as a diisocyanate over preparative group which is blocked. For example, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-methylol (meth)
Acrylamide, diacetone (meth) acrylamide,
N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, 3 -trimethoxysilylpropyl (meth) acrylate, Glycidyl (meth) acrylate is preferred.

Further, as the _the R _f group-containing monomer and a copolymerizable monomer having a blocked diisocyanate over preparative group, a hydroxyl group-containing (meth) acrylate with a polyisocyanate at least one in a ratio isocyanate groups remain A blocked product of the reaction product obtained by the reaction,
Hydroxy group-containing (meth) acrylates and reaction products obtained by reacting a polyisocyanate derivative having at least one blocked isocyanate group with at least one free isocyanate group are preferred.

Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.
Hydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (oxyethylene / oxypropylene) glycol mono (meth) acrylate, glycerin mono (meth) acrylate, trimethylolpropane mono (meth) ) Acrylates and the like are preferred.

Examples of the polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate, and alicyclic groups such as isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate and bis (isocyanatomethyl) cyclohexane. polyisocyanate, and their isocyanurate modified compounds, prepolymer modified compounds, biuret modified compounds, and the like, aliphatic Jiisoshiane Toma other alicyclic diisocyanates are preferred.

As blocking agents, oximes,
Examples thereof include alkyl ketoximes, phenols, β-diketones, malonic esters, lactams, alkanols and the like. Specifically, cyclohexane oxime, methyl ethyl ketoxime, phenol, cresol, acetylacetone, diethyl malonate, isopropyl pin
Ruaruko Lumpur, t-butyl alcohol Lumpur, .epsilon.-caprolactam, imides of maleic acid, sodium bisulfite, and the like, cyclohexane oxime, methyl ethyl ketoxime O Kim like.

[0038] When the first polymer in the present invention is a polymer containing polymerized units of _the R _f group-containing monomer, the amount of _the R _f group-containing monomer is preferably about 50 to 100 wt%, in particular 55-100 % By weight, and 80-100%
But it preferred to express excellent water and oil repellency.

The molecular weight of the first polymer is 1000 to 10
0000 is preferable, and especially 5000 to 10000.
About 0 is preferable. Durability departing ones water and oil repellency of this range or not preferable because the initial performance is poor.
In particular, in the case of a high molecular weight region of 100,000 or more, when heat treatment is performed at a low temperature, high water repellency may not be maintained.

[0040] The synthetic method of the first polymer is not particularly limited, also known polymerizable monomers one of the abovementioned _the R _f group-containing monomer or comprising more than two species polymerizing by known polymerization methods Method . It is preferable to polymerize by an emulsion polymerization method or a dispersion polymerization method.

When polymerizing by an emulsion polymerization method or a dispersion polymerization method, a method of polymerizing the above polymerizable monomer by adding a polymerization initiator in the presence of an emulsifier and a polymerization medium may be exemplified. Is not particularly limited as emulsifiers, nonionic, cationic, anionic, known also <br/> amphoteric type or one known emulsifiers may be employed. The amount of the emulsifier is 0.5 to 100 parts by weight of the polymerizable monomer.
It is preferably 20 parts by weight, and particularly preferably about 1 to 10 parts by weight from the viewpoint of water and oil repellency and stability of the dispersion.

The polymerization medium is a medium containing water,
If desired, an organic solvent may be included. As the organic solvent, a water-soluble organic solvent is preferable, and an organic solvent such as an ester, a ketone, and an ether is preferable. As the ester-based organic solvent, ethyl acetate, butyl acetate, diethyl succinate and the like are preferable, and as the ketone-based organic solvent,
Methyl ethyl ketone, methyl isobutyl ketone, acetone and the like are preferable, as the organic solvent ether, diethylene glycol, dipropylene glycol, triethylene glycol, Contact and these monomethyl ether, dimethyl ether, diethyl ether, and the like are preferable. Among them, the organic solvent is preferably an ether organic solvent from the viewpoint of low flammability. The ratio between water and the organic solvent is not particularly limited, and may be any ratio. As the polymerization initiator, a water-soluble or oil-soluble polymerization initiator is preferable, and a general-purpose initiator such as an azo type, a peroxide type and a redox type can be used according to the polymerization temperature. The polymerization temperature is not particularly limited, but is preferably from 20C to 150C.

In the reaction for obtaining the first polymer, a chain transfer agent may be included for the purpose of controlling the molecular weight. Mercaptans are preferred as the chain transfer agent.
As the mercaptans, compounds represented by the following formulas (1) to (4) and the like are preferable, and in particular, when R ^{2 in the} formula (1) is an alkyl group, alkyl mercaptans are preferable.

[0044]

Embedded image

However, in the formulas (1) to (4), R ²
Represents an alkyl group or an aryl group. R ³ represents an alkylene group. A represents a monovalent organic group containing a mercapto group at the terminal. a shows the integer of 1-3. R ⁴ represents an unsubstituted or substituted monovalent hydrocarbon group having 20 or less carbon atoms. b is an integer of 0 to 3, and 0 <a + b <4.

In the above-mentioned polymerization reaction, a mixture comprising a polymerizable monomer , water and an emulsifier may be treated with a homomixer or a high-pressure emulsifier and pre-dispersed in advance as a stage prior to the start of polymerization.

The first polymer synthesized by the above method is
It is preferably present as fine particles in the medium. The particle diameter of the fine particles is preferably 0.001 to 1 μm. If the particle diameter is too small, stable dispersions large amount of emulsifier is required for obtaining, also decreases water- and oil-repellent properties. 1 μm
In the above case, the polymer fine particles settle in the medium, which is not preferable. A particularly preferred particle size range is 0.01 to 1 μm.
It is. Particle size, dynamic light scattering apparatus, cut with measurement by electron microscope. When polymerization is carried out in the presence of an emulsifier by a usual emulsion polymerization method, the average particle size is usually included in the above preferred range.

The water-dispersed water / oil repellent composition of the present invention is characterized by containing polymer particles containing at least two kinds of the above-mentioned first polymer and second polymer. The second polymer is a polymer containing a polymerized unit of the monomer B. The second polymer has an effect of improving the durability of water repellency and oil repellency even under mild heat treatment conditions, and improving the durability of the above-mentioned practical water repellency.

The second polymer is a polymer containing a polymerized unit of the monomer B , and the glass transition point of the homopolymer is:
The temperature is preferably 40 ° C or higher, particularly preferably 40 to 200 ° C.

[0050]

The ester portion of the monomer B has 5 carbon atoms.
Above, cyclic hydrocarbon group, a polycyclic hydrocarbon group, Ri alkyl group der a branched, particularly preferably 5 or more cyclic hydrocarbon group having a carbon. As the cyclic hydrocarbon group having 5 or more carbon atoms, a cyclohexyl group, a benzyl group, and a phenyl group are preferable. Further, a substituent such as an alkyl group or a halogen may be bonded to these groups. As the polycyclic hydrocarbon group having 5 or more carbon atoms , an isobornyl group or the like is preferable. Carbon number 5
As the alkyl group having the above branch, a 3,3-dimethylbutyl group and the like are preferable.

[0052] As the monomer B, among the above monomers, shea Kurohekishiru (meth) acrylate, cyclododecyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, adamantyl (meth) acrylate, tolyl (meth) acrylate, 3,3-dimethylbutyl (meth) acrylate bets like are preferable.

In the present invention, the second polymer is a monomer
One B or may contain two or more polymerized units. Further, the second polymer may contain a polymerized unit of another polymerizable monomer.

As the other polymerizable monomer, a polymerizable monomer containing no R _f group is preferable, and in particular, the compounds exemplified as the copolymerizable monomer in the first polymer are preferable. However, in the case of employing R _f group-containing motor Nomar as other polymerizable monomer, as compared to the total amount of _the R _f group in the first polymer (parts by weight), _the R _f group of other polymerizable monomers Is preferably such that the total amount is relatively small (parts by weight). R _f group contained
The motor Nomar, exemplified in the first polymer R _f
Compounds similar to the group-containing monomer can be employed.

As the second monomer, a reactive monomer having a reactive group in the molecule may be included. Examples of the group having a reactive epoxy group, a halogen atom, a hydroxyl group, an amide group, an amino group, an alkoxysilyl group, N- methylol group, N- alkyloxy group, an imino group, a blocked diisocyanate over preparative group And the like,
Examples of these include the same examples as those exemplified as monomers containing first the polymer your stomach intramolecular polymerizable unsaturated reactive group other than groups. When the reactive monomer is included, there is an advantage that the adhesiveness to the fiber surface is improved at the time of fiber treatment , and the processing agent can be prevented from falling off during washing or dry cleaning.

In the second polymer, the proportion of the polymerized unit of the monomer B is preferably 1 to 95% by weight in the second polymer.
Properly, it is preferred in particular 5 to 80 wt%, especially 5-7
0% by weight is preferred .

[0057] As a method for synthesizing the second polymer, Write Ru by polymerizing a second monomer containing the above-described monomers B
The method is preferred. Here, the second monomer is a monomer B
One Moshiku two or more, or, even one monomer B
Properly the mixture comprising one or more of two or more with other monomers, is meant.

The method for polymerizing the second monomer in the presence of the first polymer is not particularly limited.
Of the emulsion or dispersion is present polymer as fine particles, the second monomer, collectively or added in portions to several steps, and then a method of polymerizing by adding a polymerization initiator (so-called seed emulsion Polymerization method) is preferred. The polymerization initiator is not particularly limited, and includes a polymerization initiator such as an organic peroxide, an azo compound, a persulfate, or an ionizing radiation such as γ-ray. Salts of the compounds are preferred.

[0059] During the polymerization, the emulsion or dispersion of the first polymer may contain a water or organic solvents. By including water and an organic solvent, the final solid content concentration can be adjusted and the polymerization yield of the second monomer can be increased. As the organic solvent, a water-soluble organic solvent is preferable,
Organic solvents such as ester, ketone and ether are more preferable, and ether organic solvents are particularly preferable. As the ether-based organic solvent, the same organic solvent as that in the first polymer is preferable. The ratio between water and the organic solvent is not particularly limited, and may be any ratio.

It is preferred that the mixture containing the first polymer and the second monomer is thoroughly stirred before the polymerization of the second monomer is started, so that the final yield can be improved. . Further, in the polymerization of the second monomer, a chain transfer agent may be present. As the chain transfer agent, those similar to the above can be exemplified.

The amount of the second monomer relative to the first polymer is preferably such that (weight of the second monomer) / (weight of the solid content of the first polymer) is about 0.05 to 10. Further, the polymerization temperature is not particularly limited, but 20C to 150C
Is preferred.

The polymer particles in the present invention are polymer particles containing at least the first polymer and the second polymer, but may contain other polymers. The first polymer and the second polymer, one or each may be two or more. When the first polymer and the second polymer each contain two or more kinds, a method of synthesizing the above-described seed emulsion polymerization method by sequentially performing the above-described seed emulsion polymerization methods is preferable.

In the polymer particles containing the first polymer and the second polymer, the presence form of the second polymer depends on the amount of the emulsifier coexisting in the first polymer fine particle dispersion and the first polymer. coalescing the hydrophobic of magnitude relationship or second monomer in the second monomer
But is intended to change Ri by the partition coefficient in water phase chromatography, table Menma other particulate of the first polymer is the polymer particles in the form of the second polymer is present therein is preferred. In polymer particles, core first polymer and second polymer layers were separated in layers - but shell is performance preferred, form of a layer sea -
That part of the island structure and the polymer is localized, or,
It may be in a form in which other polymer molecular chains are entangled. By taking such a configuration, excellent water and oil repellent may not possibly be obtained by a technique for mixing a first polymer dispersion and the second polymer dispersion of produced respectively
Is estimated to be obtained.

When the polymer particles are of a core-shell type in which the first polymer and the second polymer are separated into layers, the first polymer containing an _Rf group is formed in the core. Preferably, a second polymer is present in the shell. The second polymer is a case not containing _the R _f group is preferred, if _the R _f group is present, as compared to the first polymer, when the weight percent of _the R _f group is relatively small It is preferred, as compared to the wt% of the value of _the R _f group in the first polymer, a value less wt% of the value of 10 or more second polymer <br/> of _the R _f group is preferred,
It is particularly preferable that the number is 30 or less.

The water-dispersed water / oil repellent composition of the present invention is a composition in which the above-mentioned 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. However, usually, in a polymerization reaction, a water-dispersible water-repellent water-repellent material is used as it is by using a desired medium as a polymerization medium. An oil composition may be prepared. The medium is a medium containing water, and is preferably water or a medium containing water and an organic solvent. When the organic solvent is used, the amount is preferably about 0 to 40 parts by weight based on 100 parts by weight of the polymer particles.

Further, in the water-dispersed water- and oil-repellent composition of the present invention, the amount of the polymer particles is 100% of the medium.
The concentration is preferably about 1 to 50 parts by weight with respect to parts by weight, and it is preferable to adjust the concentration with water or an organic solvent to the concentration. The concentration can be appropriately changed depending on the purpose and the form of the composition. Further, the water-dispersed water / oil repellent composition of the present invention may further contain other additives. For example, other water repellents, oil repellents, crosslinking agents, insect repellents, flame retardants, antistatic agents, Ru can be appropriately added in combination of additives such as anti-wrinkle agent.

The water-dispersed water / oil repellent composition of the present invention can be applied to the article to be treated by any method according to the kind of the article to be treated and the preparation form. For example, a method is employed in which the material is adhered to the surface of the object to be processed by a coating method such as dip coating and dried. The water-dispersed water / oil repellent set of the present invention is also provided.
The product treated with the product shows high water and oil repellency even when subjected to a heat treatment under a mild condition of 150 ° C. or less, and has excellent durability. Usually, the heat treatment temperature is 100 to 13
It is preferably about 0 ° C, particularly preferably about 115 to 125 ° C. Further, the heat treatment time is preferably within 5 minutes, particularly preferably about 30 seconds to 2 minutes. The heat treatment is 150 ° C
It may be a high temperature process described above, in the case of treatment at a high temperature can be shortened than the processing time of the normal.

The products treated with the water-dispersed water- and oil-repellent composition of the present invention include not only fiber products whose materials are natural fibers , synthetic fibers and their blended fibers, but also water- and oil-repellency durability. It can be used without limitation for required articles such as metal, glass and resin. In particular, the water-dispersed water / oil repellent composition of the present invention is suitable for treating textile products. When processed into a textile product, the texture after the treatment is soft, and the fabrics are subjected to initial water / oil repellency, initial antifouling property, initial antifouling property, abrasion resistance, and washing resistance under mild heat treatment conditions, that is, low temperature curing conditions. Practical water / oil repellency such as water resistance, dry cleaning resistance, and rainfall resistance.

[0069]

EXAMPLES The present invention is now described with reference to Synthesis Examples (Examples 1 to 6) and Examples.
(Example 7-15), will be specifically described in the comparative example (Example 16-19), the present invention is Lena had limited to these examples. In addition,
Various evaluations in each example were performed according to the following methods and criteria.

[Method of Evaluating Water Repellency] The water repellency number is shown by a spray method according to JIS-L-1092 (see Table 1). Usually, the shower water temperature was 27 ° C. The evaluation results in which the following water-repellent numbers are indicated by adding + (-) marks indicate that each evaluation is slightly better (lower) than that indicated by the number.

[Evaluation Method of Rainfall Test] According to the method described in JIS-L-1092 (C) method (Bundesman test), the amount of rainfall is 100 cc / min, the temperature of rainwater is 20 ° C., and the rainfall time is 10 minutes. Rain under conditions,
The wetting state of the surface was determined according to the water repellency number in Table 1.

[Evaluation Method of Oil Repellency] A few drops (approximately 4
mm) and discriminated by the permeation state after 30 seconds (AA)
TCC-TM118-1966).

[Method of Measuring Particle Size] The particle size was measured by a laser light scattering method (manufactured by Otsuka Electronics Co., Ltd.).

[Glass transition point of homopolymer] Glass transition point of homopolymer (hereinafter referred to as T _g (° C.))
Is J. Bundrup, etc. “Polymer Handbook No. 3
Edition "(J. Wiley 1989),
And catalog values were adopted.

[0075]

[Table 1]

[0076]

[Table 2]

Example 1 Perfluoroalkylethyl acrylate [C _m F _{2m + 1}
C ₂ H ₄ OCOCH ＝ CH ₂ : m is 6, 8, 10, 1
The average is 9 for a mixture of 2,14,16. ] (Hereinafter referred to as FA) 3013 g, dodecyl mercaptan 5
5.8 g, 155 g of a nonionic emulsifier, polyoxyethylene secondary alkyl ether, 155 g of alkyldimethylamine acetate, and 5032 g of water were pre-dispersed with a homogenizer, and then, using a high-pressure homogenizer (emulsifier manufactured by Menton Goulin Co.). And 400 kg / cm ₂ to obtain an emulsion. 7000 g of the emulsion was placed in a 10-liter stainless steel autoclave, and 39.8 g of azobisisobutyronitrile was added, followed by purging with nitrogen. After the temperature was raised to 60 ° C., polymerization was carried out for 8 hours to give 38.8% solids.
(Polymerization yield 97.0%), F with an average particle size of 0.13 μm
A dispersion of the first polymer containing the polymerized unit of A was obtained. The molecular weight of the polymer obtained by evaporating the polymer dispersion to dryness was about 17000 as a result of GPC measurement.

Examples 2 to 5 100 parts by weight of a monomer having the composition shown in Table 3 and dodecyl mercaptan as a molecular weight modifier were used in the amounts shown in Table 3 to Example 1
In the same manner as in the above, a dispersion of the first polymer was obtained. The abbreviations in Table 3 have the following meanings. CEA: Cetyl acrylate BZMA: Benzyl methacrylate

[0079]

[Table 3]

Example 6 A 10-liter stainless steel autoclave was charged with a polymer dispersion of the first polymer prepared in Example 1 (solids concentration: 3).
5000 g (8.8%) (1940 g solids; 100 parts by weight), 349 g (60 parts by weight) of FA, 175 g of cyclohexyl methacrylate (30 parts by weight: T _{g of} homopolymer = 83 ° C.), 58 of glycidyl methacrylate .2 parts by weight (10 parts by weight) were charged. Further, 252 g of dipropylene glycol monomethyl ether and 359 g of water were added to adjust the total solid content to 40% by weight. After stirring the mixture, 25.0 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added,
After nitrogen replacement, polymerization was carried out at 60 ° C. for 15 hours. After cooling,
The dispersion was removed. The solid concentration was 38.2% by weight. Measurement of the grain terminal size by light scattering method 0.13
μm. As a result of transmission electron microscope observation of the dispersion,
The second polymer core present within the first polymer - present as a shell-type microparticles were also observed some other those polymerized in the aqueous phase.

The solid content concentration of the obtained dispersion was 20% by weight.
To give a latex stock solution. Latex stock solution 1
0 parts by weight of melamine resin (Sumitex Diphen M3 /
0.3 parts by weight of Sumitomo Chemical Co., Ltd.) and 0% of catalyst (Sumitex Accelerator ACX / Sumitomo Chemical Co., Ltd.).
A solution obtained by adding 3 parts by weight and 89.4 parts by weight of water was used as a latex treatment liquid. Oil-repellent properties by using a latex treating solution
Etc. were measured.

The water and oil repellency test was conducted on a polyester skin cloth.
Done as a test cloth, water- and oil-repellent treatment was carried out as follows. That is, a test cloth is immersed in a latex treatment solution,
The test cloth was squeezed between the rubber rollers to adjust the wet pickup to 60% by weight. Then at 110 ° C 9
It was dried for 0 second and further heat-treated at 120 ° C. for 60 seconds.
Measurement of the water and oil repellent properties of the obtained test cloth,
The water repellency number was 100 and the oil repellency number was 6. Further, this test cloth was subjected to JIS-L-0217-103.
After washing repeatedly 20 times according to the method, it was air-dried and subjected to a test. As a result, the water repellency number was 80+ and the oil repellency number was 5.

The rain test was conducted on a high density polyester fabric.
Was carried out as a test cloth, after <br/> treated using the same latex treating solution, and dried for 90 seconds at 110 ° C., further 170
Heat treated at 60 ° C. for 60 seconds. When a rain test was performed on the obtained test cloth, the water repellency number was 100. Further, the test cloth was repeatedly washed 10 times by the same method, then air-dried and subjected to a rainfall test. As a result, the water repellency number was maintained at 80+.

[0084] [Example 7-1 4] using a 1 liter glass autoclave, Examples 1 and 3,
On the dispersion 500g of the first polymer synthesized in 5,
As the second monomer, those shown in Table 4 were used, and the amount of dipropylene glycol monomethyl ether was changed to 2
5.2 g, the amount of water was 35.9 g, the amount of 2,2′-azobis (2-amidinopropane) dihydrochloride was changed to 2.5 g, and the dispersion and latex were prepared in the same manner as in Example 6. A treatment liquid was manufactured. Table 5 shows the results of the same evaluation.

[0085] [Example 15] The dispersion of the first polymer prepared in Example 1 was diluted with water, a material obtained by adjusting the solid concentration to 20% by weight and a latex stock solution, a polyester in the same formulation as Example 6 Doskin fabric and polyester high density fabric. Table 5 shows the results of evaluating the water repellency and oil repellency of the polyester skinned fabric and the rain resistance of the polyester high-density woven fabric.

Example 16 FA 186 g, cyclohexyl methacrylate 93 g,
Glycidyl methacrylate 31 g, a nonionic emulsifier polyoxyethylene secondary alkyl ether 15.5 g,
1.6 g of alkyldimethylamine acetate, water 503.2
g was pre-dispersed with a homogenizer, and then 400 k using a high-pressure homogenizer (emulsifier manufactured by Menton Goulin Co.).
g / cm ² to obtain an emulsion. 700 g of emulsion
After placing in a liter glass autoclave and adding 3.1 g of azobisisobutyronitrile, the atmosphere was replaced with nitrogen.
After raising the temperature to 60 ° C., polymerization was carried out for 8 hours to obtain a solid content of 3
6.0% (polymerization yield 90.0%), average particle size 0.19
A μm dispersion was obtained.

The polymer dispersion of the first polymer synthesized in Example 1 was adjusted to a solid content concentration of 20% by weight, and the polymer dispersion of the first polymer synthesized in Example 1 was adjusted to a solid content concentration of 20% by weight. Was added to make a stock solution. A solution obtained by diluting the stock solution with water (the ratio of the stock solution to water was 6% by weight) was used as a latex treatment solution, and water and oil repellency and the like were measured in the same manner as in Example 6 . Table 5 shows the water / oil repellency of the polyester skinned cloth and the rainfall resistance of the polyester high-density woven fabric.

Example 17 Instead of the cyclohexyl methacrylate of Example 6, 2-
Ethylhexyl methacrylate (homopolymer T _g =
(−10 ° C.) except that the dispersion was used. The resulting dispersion was a latex treating solution in the same formulation as in Example 6, was treated polyester doeskin cloth Contact and polyester dense fabrics was evaluated repellency and耐降rain resistance. Table 5 shows the results.

[0089] [Example 18] 1 liter using a glass autoclave, the dispersion liquid 500g of the first polymer synthesized in Example 1, the second monomer composition FA / ethylene glycol monomethyl ether monomethacrylate (homopolymer T _g = 16
C) / glycidyl methacrylate = 5/4/1 (parts by weight), and the solid concentration in the dispersion of the first polymer / second
Used so as to be 100/30 (parts by weight)
Further, as in Example 6, the amount of dipropylene glycol monomethyl ether was changed to 25.2 g, the amount of water was changed to 35.9 g, and the amount of 2,2′-azobis (2-amidinopropane) dihydrochloride was changed to 2.5 g. A dispersion liquid and a latex treatment liquid were produced by the production method described above, and the same evaluation was performed. Table 5 shows the results.

In Table 4, the meanings of the abbreviations used are as follows:
And the glass transition point (T _g (° C.)) of the homopolymer is as follows. ST: styrene (T _g = 100) DMBMA: 3,3-dimethylbutyl methacrylate (T _g = 45) CYMA: cyclohexyl methacrylate (T _g = 8)
3) IBMA: isobornyl methacrylate (IBMA , manufactured by Kyoei Yushi Co., Ltd.) (T _g = 180 ) H EA: 2-hydroxyethyl acrylate GMA: glycidyl methacrylate HE: 2-hydroxyethyl methacrylate / isophorone diisocyanate / methyl ethyl ketoxime = 1 /
2/1 condensate

[0091]

[Table 4]

[0092]

[Table 5]

[0093]

EFFECT OF THE INVENTION The water-dispersed water / oil repellent composition of the present invention comprises:
And also by containing, as an active ingredient, polymer particles containing two polymers less water and oil repellent and a conventional fluorine-based, two polymers each synthesized water- and oil-repellent composition prepared by mixing with Shows the durability of water and oil repellency that could not be achieved. In the compositions of the present invention, even when the heat treatment at low temperature, excellent to show the water and oil repellency and its durability, even when the processing weak special fibers or natural fibers to a heat treatment, their It has the advantage of not adversely affecting the fiber. In addition, since the composition is excellent in rain resistance and durability, it is an advantageous composition in practical use.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-7-258499 (JP, A) JP-A-3-7784 (JP, A) JP-A-62-32102 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08L 1/00-101/16 C09K 3/18 C08F 2/44

Claims (6)

(57) [Claims] 1. A polymer particle containing at least two kinds of polymers, a first polymer and a second polymer, wherein the first polymer is a polymer containing a polyfluoroalkyl group, and The water-dispersible water / oil repellent composition containing polymer particles, wherein the second polymer is a polymer containing a polymerized unit of the following monomer B. Monomer B: a cyclic hydrocarbon group, a polycyclic hydrocarbon group, or a branched alkyl group having a homopolymer having a glass transition point of 30 ° C. or higher and an ester moiety having 5 or more carbon atoms (meth) Acrylate. However, vinyl fluoride
50% to 80% by weight of lidene, 20% to 5% of propylene hexafluoride
0% by weight and other copolymerizable monomers 0 to 30% by weight
% Of a fluoropolymer obtained by polymerizing a monomer consisting of
(T) 40 to 100% by weight of acrylic acid alkyl ester
And 0 to 60% by weight of other copolymerizable monomers
Do not complex with acrylic polymer obtained by polymerizing monomers.
Containing conjugated polymer particles dispersed in an aqueous medium
Excludes aqueous polymer dispersions. 2. The water-dispersed water / oil repellent composition according to claim 1, wherein the first polymer is a polymer containing polymerized units of a polyfluoroalkyl group-containing monomer. 3. The water-dispersed water / oil repellent composition according to claim 1, wherein the second polymer is a polymer containing no polyfluoroalkyl group. 4. The water-dispersed water-repellent material according to claim 1, wherein the second polymer is a polymer containing a relatively small amount of polyfluoroalkyl group as compared with the first polymer. Oil repellent composition. 5. The aqueous dispersion according to claim 1, wherein the polymer particles are polymer particles in which the second polymer exists on the surface or inside of the particles of the first polymer. Water / oil repellent composition. 6. A second monomer containing the monomer B,
The method for producing a water-dispersed water / oil repellent composition according to any one of claims 1 to 5, wherein the emulsion polymerization is carried out in the presence of particles of the first polymer.