Method of producing water and oil repellent agent

FIELD: chemistry.

SUBSTANCE: proposed method of producing a water and oil repellent agent involves emulsification of (a) 15-85 wt % perfluoroalkylethylacrylate, (b1) 5-65 wt % 2-ethylhexylmethacrylate and (b2) 1-40 wt % benzyl methacrylate in the presence of (c) a cation surface active substance of the polyethylene oxide adduct type, or neutralised organic acid compound of an amine, with polyethylene oxide chains, and (d) compounds based on polypropylene glycol, with molecular weight 300-3000, or hexylene glycol, with subsequent copolymerisation reaction in the presence of a polymerisation initiator, and mixing the obtained aqueous dispersion with (e) blocked isocyanate.

EFFECT: satisfactory water and oil repellent for synthetic and natural fibre.

5 cl, 22 ex, 5 tbl

 

The technical FIELD

This invention relates to a method for producing a water - and oil-repellent agent, and more specifically to a method for producing water - and oil-repellent agent with considerable resistance to the sink.

The LEVEL of TECHNOLOGY

Water and malatjalian currently can be imparted to the fibers by the use of water - and oil-repellent agent containing as an effective component, a copolymer of (meth)acrylic acid containing poliferation group. In patent literature 1 proposed water - and oil-repellent agents type water dispersion, effective to impart to the fibers as water resistance and malatjalian and baristanet against repeated washes. Water - and oil-repellent agent type aqueous dispersion contains a mixture of the product of emulsion polymerization, obtained from a mixture of mixed performancerelated containing performanceline group with 6 to 16 carbon atoms, polymerized monomer, such as dioctylmaleate, 2-hydroxyethylacrylate, N,N-dimethylacrylamide etc., surfactant and solvent, emulsion blocked isocyanate, but (he) is unable to give a satisfactory water and malatjalian not only synthetic fibers, but also natural fibers.

Patent literature 1: WO 00/58416

DISCLOSURE of INVENTIONS

The PROBLEM WHICH MUST BE SOLVED by the INVENTION

One of the objects of this invention is a method of obtaining a water - and oil-repellent agent, capable of giving satisfactory water and malatjalian not only synthetic fibers, but also natural fibers, as well as having a significant resistance to the sink.

Part of the SOLUTION

The objective of the present invention can be solved by the method of obtaining water - and oil-repellent agent, which provides emulsification (a) (meth)acrylate containing poliferation group, and (b) of the polymerized monomer containing no fluorine atoms, in the presence of (C) cationic surfactants of the type of polyethylene oxide adduct or as cationic surfactants, and nonionic surfactants of the type adduct of polyethylene oxide and (d) compounds based on glycol followed by reaction of copolymerization in the presence of a polymerization initiator and mixing the resulting aqueous dispersion (e) blocked isocyanate.

The EFFECT of the INVENTION

Water - and oil-repellent agent obtained according to this method, has improved resistance to washing with the optional addition of the blocked isocyanate to the water dispersion is AI, which can give a satisfactory water and malatjalian not only synthetic fibers, but also natural fibers.

The BEST OPTION of carrying out the INVENTION

Can be used(a) (meth)acrylate containing performanceline group represented by the following General formula:

CH2=CRCOOR1(NR2SO2)mRf,

in which R represents a hydrogen atom or methyl group;

R1represents a divalent organic group containing 1-12 carbon atoms;

R2represents a lower alkyl group containing 1-12 carbon atoms;

Rf represents poliferation group containing 4-20 carbon atoms;

m is 0 or 1;

these include, for example, the following (meth)acrylates containing politcially group,

CH2=CHCOOCH2CnF2nH

CH2=C(CH3)COOCH2CnF2nH

CH2=CHCOOCH2CnF2n+1

CH2=C(CH3)COOCH2CnF2n+1

CH2=CHCOOC2H4CnF2n+1

CH2=C(CH3)COOC2H4CnF2n+1

CH2=CHCOOC3H6CnF2n+1

CH2=C(CH3)COOC3H6CnF2n+1

CH2=CHCOOC4H8CnF2n+1

CH2=C(CH3 )COOC4H8CnF2n+1

CH2=CHCOOC2H4N(CH3)SO2CnF2n+1

CH2=C(CH3)COOC2H4N(CH3)SO2CnF2n+1

CH2=CHCOOC2H4N(C2H5)SO2CnH2n+1

CH2=C(CH3)COOC2H4N(C2H5)SO2CnH2n+1

CH2=CHCOOC2H4N(C3H7)SO2CnF2n+1

CH2=C(CH3)COOC2H4N(C3H7)SO2CnF2n+1

CH2=CHCOOC2H4CnF2nCF(CF3)2

CH2=C(CH3)COOC2H4CnF2nCF(CF3)2

Performanceline group in (meth)acrylates containing performanceline group may be a mixture of groups WithnF2n+1in which n has different values (usually n=6-10). Even if you use the copolymers of (meth)acrylates containing a mixture of performanceline groups, including performanceline group with 12 or more carbon atoms, or if at all with 16 or more carbon atoms, the invention is able to provide the aqueous dispersion with good emulsion stability. (Meth)acrylates containing performanceline group, is subjected to copolymerization in the ratio of 10 wt.% or more, preferably 25-75 wt.% in the calculation of the copolymer, IP is alsoany when obtaining a water dispersion, achieving significant water and malatjalian.

Containing no fluorine atom curable monomer, which must be copolymerizate (a) (meth)acrylate containing poliferation group may submit themselves, for example, esters of acrylic acid or esters of methacrylic acid, such as esterified alkyl group such as methyl, ethyl, propyl, isopropyl, n-butyl, n-hexyl, 2-ethylhexyl, n-octyl, lauryl, stearyl etc., cycloalkyl group, such as cyclohexyl, etc., aranceles group, such as benzyl, etc. and alkoxyalkyl group, such as methoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 3-ethoxyethyl etc., complex dialkyl ethers such as dimethyl, diethyl, dipropylamine, dibutylamine, dioctyloxy etc. (esters) of fumaric acid or maleic acid, and complex vinyl esters such as vinyl acetate, vinylcaprolactam etc. From the point of view of water and malatjalian preferred combination of alkyl(meth)acrylate with a long-chain alkyl group containing 8 or more carbon atoms, particularly esters of acrylic acid, such as esterified alkyl group, such as 2-ethylhexyl n-octyl, lauryl, stearyl etc., cycloalkyl group, such as cyclohexyl, etc., aranceles group, such as benzyl, etc. and more predpochtitel is s combination of acrylic ester, such as esterified alkyl group, such as 2-ethylhexyl, stearyl etc. with ether (meth)acrylic acid, esterified aranceles group, such as benzyl, etc. When obtaining a water dispersion of the polymerized monomer containing no fluorine atom may be used in a ratio of 90 wt.% or less, preferably 75-25 wt.% in the calculation of the copolymer.

In this invention, in particular, preferably can be used terpolymer of perftorpolietilena, 2-ethylhexylacrylate and benzylmethylamine. The composition of terpolymer consists of from about 15 to about 85 wt.%, preferably from about 25 to about 75 wt.% perftorpolietilena, from about 5 to about 65 wt.%, preferably from about 10 to about 45 wt.% 2-ethylhexylacrylate and from about 1 to about 40 wt.%, preferably from about 5 to about 30 wt.% bezelmaterial.

The copolymer may be further copolymerization with other copolymerization monomer within such limits as not to impair the characteristics of, for example, in the proportion of 30 wt.% or less in the calculation of the resulting copolymer. Such copolymerizable monomers can be, for example, vinyl compounds, which differ from esters of (meth)acrylic acid diesters of fumaric acid or maleic acid and complex wine is gross esters, such as mentioned above as component (b), such as styrene, vinyltoluene, α-methylsterol, vinylnaphthalene, Acrylonitrile, Methacrylonitrile, arylamidase, 2-hydroxyethylacrylate, 4-hydroxyethylacrylate, 2-hydroxy-3-chloropropyl(meth)acrylate, mono(meth)acrylate of polyethylene glycol mono(meth)acrylate of polypropylenglycol, viniferin, vinylidenefluoride, simple hydroxyethylimino ether, simple hydroxybutylidene ether, etc. and diene compounds such as isoprene, pentadiene, butadiene, etc.

If necessary, a polyfunctional monomer or oligomer can be copolymerizable in the proportion of 30 wt.% or less in the calculation of the resulting copolymer. Such polyfunctional monomers or oligomers are, for example, di(meth)acrylate of ethylene glycol, di(meth)acrylate of propylene glycol, di(meth)acrylate 1,4-butanediol di(meth)acrylate 1,6-hexanediol, di(meth)acrylate 1,9-nonanediol, di(meth)acrylate neopentyl glycol, di(meth)great tetraethyleneglycol, di(meth)acrylate of tripropyleneglycol, di(meth)acrylate of polypropylenglycol, diacrylate adduct of bisphenol a and ethylene oxide, diacrylate of dimethylpolysiloxane, acrylate methacrylate glycerin, monomethacrylate 3-acryloyloxyhexyloxy etc.

All of these individual polymerized monomers are subjected to copolymerization in the presence of surface-act the main emulsifier, cationic surfactants on the basis of polyethylene oxide or cationic surfactants, and nonionic surface-active substances and auxiliary emulsifier glycol-based.

For surfactant acts as an emulsifier, a cationic surfactant type adduct of polyethylene oxide or as a cationic surfactant and nonionic surfactant type adduct of polyethylene oxide can be used in a ratio of 1-20 wt.%, preferably 1-10 wt.% calculated on the total weight of the copolymer. Cationic surface-active agent based on polyethylene oxide is a surface-active agents based on Quaternary ammonium salts, such as chlorides of alkylamine or salt alkylpyridine containing 1-3 polyoxyethylene groups, such as the higher alkyl chlorides(12-18 carbon atoms)dimethylammonio, the higher chlorides of allylmethylamine, acetate of dodecylbenzenesulfonic and so on, which are adducts of polyethylene oxide. In this case, the cationic surfactant without adduct with polyethylene oxide, such as chloride of stearylamine, acetate of dodecyltrimethylammonium, chloride of dodecyltrimethylammonium, tetradecanol trimethylammonium, Gex is deciphered trimethylammonium and octadecylsilane trimethylammonium, can be used simultaneously in a ratio of from about 0.1 to about 2 mass parts per mass fraction of surfactant type adduct of polyethylene oxide.

Nonionic surface-active agent based on polyethylene oxide, which must be used together with a cationic surface-active agent, represents the reaction products of polyethylene oxide with a simple alkilany ether or alcohol, such as hexylene, op, Nonylphenol, simple polycyclic phenyl ether, dodecanol, hexadecanol, octadecanol, alerby alcohol, etc., oleic acid, With12-C18-alkylamino, (ether) sorbitol with monogynous acid, etc. is Preferably the reaction product of polyethylene oxide with an alcohol, such as op, Nonylphenol, dodecanol or hexadecanol, can be used in a ratio of 80 wt.% or less, preferably from about 30 to about 80 wt.% calculated on the total weight surfactant-type adduct of polyethylene oxide.

Instead cationic surfactants can also be used amine-containing chain polyethylene oxide, neutralized organic acid, such as acetic acid, etc. Specified applicable Amin is polyoxyethyleneglycol (for example, Amete 30, the product of Kao), polyoxyethylenesorbitan, represented by the following formula:

H(OCH2CH2)xNRCH2CH2CH2N[(CH2CH2O)yH](CH2CH2O)zH

(for example, Esoduomin T/25, a product of Lion), polyoxyethylenated (for example, Nymin L-207, a product of NOF), etc.

Connection glycol-based, which should be used as an auxiliary emulsifying agents in combination with an emulsifier, represents, for example, ethylene glycol, diethylene glycol, simple onomatology ether of diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropyleneglycol, tripropyleneglycol, tetrapropenyl, simple onomatology broadcast dipropyleneglycol, simple onomatology broadcast tripropyleneglycol, hexyleneglycol, polypropylenglycol or end a simple onomatology ether adduct of propylene glycol with glycerol, etc. Preferably a compound based on polypropylenglycol with a molecular weight of 300 to 3000 or hexyleneglycol can be used in the ratio of 10-100 wt.%, preferably 15-70 wt.% calculated on the total weight of the comonomers.

Before the copolymerization reaction mixture of the polymerized monomers containing (meth)acrylate containing poliferation group, and the polymerized monomer containing no fluorine, is subjected to emulsification in the presence on Ernesto-active emulsifier and an auxiliary emulsifying substances glycol-based. The emulsification may be carried out carefully using a homogenizer high pressure, etc.

The copolymerization reaction emulsified polymerized monomers is carried out in the presence of added radical polymerization initiator. As the radical polymerization initiator may be used any organic peroxide, uzasadnienie, salt persulfate, etc. and preferably can be used water-soluble radical polymerization initiator such as potassium persulfate, ammonium persulfate, dihydrochloride 2,2'-azobis(2-amidinopropane) and so the Reaction is conducted in aqueous medium at from about 40° up to about 80°C for from about 1 to about 10 hours prior to the formation of undiluted water dispersion (water emulsion) with a concentration of solids of from about 15 to about 35 wt.%.

During the reaction copolymerizate monomer containing a cross stitched group such as (meth)acrylamide, N-methylol(meth)acrylamide, N-methoxyethylamine, N-butoxyaniline, glycidyl(meth)acrylamide, etc. may be added together with the initiator radical copolymerization and copolymerizate a ratio of about 10 wt.% or less, preferably from about 0.5 to 7 wt.% in the calculation of the resulting copolymer. Additional copolymerization of a monomer containing a cross sshi is aimie group, can improve the resistance of water and malatjalian due to cross-linking of hydroxyl groups on the surfaces of the fibers or by samosiuk.

The blocked isocyanate is added to the obtained water dispersion (water emulsion) in the ratio of 0.15 to 3.0 mass parts, preferably of 0.3-2.0 mass parts per mass fraction of solids in the aqueous dispersion. The blocked isocyanate may give significant hydrophobic (water resistant) and high resistance to washing well as natural fibers such as cotton, etc. If the blocked isocyanate is used in a ratio of less than 0.15 mass parts, resistance to washing can be reduced, while a ratio of more than 3.0 mass parts may impair the texture of the fabric.

Used herein, the term " blocked isocyanate means a compound containing at least one blocked isocyanate group and depolymerizing carbon-carbon unsaturated bond, i.e. a compound in which the structure of the isocyanate group blocked by a blocking agent. The specified blocked isocyanate is preferably a compound obtained by the MDI interaction with a compound containing at least two active hydrogen atoms in the molecule; the resulting compound has such a structure to the th scienta group blocked by a blocking agent.

The polyisocyanates are, for example, aromatic isocyanates, such as 4,4'-diphenylmethanediisocyanate, 2,4'-diphenylmethanediisocyanate, colorization etc., aliphatic isocyanates, such as trimethylenediamine, tetramethyldisilane, pentamethyldisiloxane, hexamethylenediisocyanate, 1,2-propertisation, 1,2-butanedisulfonate, trimethylhexamethylenediamine, isophoronediisocyanate, 4,4'-dicyclohexylmethane, cyclohexanediethanol etc. and their isocyanurate - modified compounds, prepolymers modified compounds biuret-modified compounds, allophanate-modified compounds, etc.

The compound containing at least two active hydrogen atoms in the molecule, preferably represents a polyhydric alcohol or polybasic amine. Polyhydric alcohols are, for example, at least one of ethylene glycol, propylene glycol, butandiol, pentandiol, hexanediol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, neopentyl glycol, bisphenol a, xilinguole etc. or modified alcohols. Polybasic amines are, for example, hexamethylenediamine were, 3,3'-aminobiphenyl etc. Polyhydric alcohol can be a difficult politicophobia. Complex politicophobia to use the here is a, which contains an ester bond, obtained by the interaction of a polyhydric alcohol with a polybasic carboxylic acid, such as phthalic acid, adipic acid, fumaric acid, pyromellitate acid, trimellitate acid, aliphatic dicarboxylic acid, etc. or its derivatives.

Blocking agents for isocyanate can be, for example, oximes of alkylthiol, phenols, alcohols, β-diketones and lactams, preferably methyl ethyl ketone oxime, ε-caprolactam, phenol, cresol, acetylacetone, diethylmalonate, isopropyl alcohol, tert-butyl smirt, the imide of maleic acid and so on, more preferred compounds having a temperature of dissociation 120-180°usually oximes of dialkylamino, such as methyl ethyl ketone oxime, etc., lactams, such as ε-caprolactam, etc

Blocked isocyanates can be obtained by the interaction of the isocyanate with a polyhydric alcohol, followed by reaction with a blocking agent, as described above, and it is preferable to carry out these reactions in nonaqueous solvents, such as ketones, ethers, hydrocarbons, etc. Additionally, it is preferable that after all the reactions of the equivalent weight of each of the isocyanates, compounds containing at least two active hydrogen atoms in the molecule, and blocking agent steel is quivalente each other.

After the reaction block preferably, the blocked isocyanate was emulsiable with water and non-ionic emulsifier, nonionic/cationic emulsifier or nonionic/anionic emulsifier, in particular, nonionic/cationic emulsifier. After the esterification solvent, if necessary, removed.

Blocked isocyanate commercially available. For example, as such can be used Guard named ruco XTS, product a Rudolf; named ruco Guard WEB, product a Rudolf; NK Assist-NY, product a Nikka Chemical; NK Assist-V product a Nikka Chemical; NK Assist-FU, product a Nikka Chemical; Prominate XC-830, a product Gantsu Chemical; Prominate XC-915, product a Gantsu Chemical; Prominate XC-950, a product Gantsu Chemical; Elastron BN-69, the product Daichi Kogyo Seiaku etc.

Aqueous dispersion may optionally contain other additives, such as other cross linking agents, different from the blocked isocyanate, for example, melamine resin, urea resin, etc., the filler polymer, other means, which imparts hydrophobicity, such as silicone resin or oil, wax, etc. and other necessary additives for use in water - and oil-repellent agent, for example, an insecticide, an antistatic agent, a dye stabilizer, a tool that reduces wrinkling blocker staining, etc.

Thus obtained aqueous dispersion, mixed with the blocked isocyanate can be effectively COI is used as water and oil resistant agent for paper, films, fibers, fabrics, woven nets, carpets or woven products made from filaments, fibers, woven threads, etc. the Usual methods of application are coating, dipping, spraying, padding, lining shaft or combinations thereof. For example, a bath with a concentration of solids of from about 0.1 to about 10 wt.% can be predostavlena for use as an impregnating bath. Designed to handle material impregnated in the impregnating bath and the excess dispersion in the material removed from the pressing shaft, followed by drying to hold from about 0.01 to about 10 wt.% copolymer in the material; the material is then dried, typically at from about 100° up to about 200°C for from about one minute to about 2 hours, depending on the type of material, concluding that water and oil repellent processing.

The invention will be described in detail below, referring to examples.

EXAMPLES

REFERENCE EXAMPLE 1

Mass part
Perftorpolietilena133,5
(a mixture of n=6:6%, 8:52%, 10:24%, 12:7% and 14:2%, amounting to 91%, from 8.8 carbon atoms in average)
2-Ethylhexylacrylate99,5
Benzilate is relat 49,0
Laurylsarcosine0,9
Polypropylenglycol57,0
(Uniol D-400, a product of NOF; molecular weight:400)
Chloride polyoxyethylene(n:15)alkylamine18,0
(Esoguard C/25, the product of a Lion)
Ionoobmennaya water400,7

All these components were placed in a reactor and subjected to emulsification at 60 MPa high-pressure homogenizer, and the resulting emulsion was purged with gaseous nitrogen. Then the reactor temperature was slowly increased to 40°and sequentially loaded with a solution containing 11,8 mass parts of N-methylolacrylamide 100 mass parts of ionized water, and a solution containing 5,9 massowah parts dihydrochloride 2,2'-azobis(2-amidinopropane) 100 mass parts of ionized water, and then slowly raised the internal temperature to 70°for the reaction for 4 hours. After completion of the reaction by cooling the received 961 mass aqueous dispersion with a concentration of solids of 30 wt.%.

REFERENCE EXAMPLE 2

In the reference example 1, the amount of chloride polyoxyethylene(n:15)alkylamine as a surfactant was changed to 12 mass parts and will complement the flax used 12 mass parts simple Olkiluoto ether of polyoxyethylene(n:20) (Nonion S-220, the product of NOF).

REFERENCE EXAMPLE 3

In reference example 1 instead of the chloride polyoxyethylene(n:15)alkylamine as surfactants used 11 mass parts simple polyoxyethylene(n:20)Olkiluoto ether (Nonion S-220), 8 mass parts of chloride of stearylamine (Coatamine 86P Conc., the product of Kao) and 15 mass parts of the neutralized acid polyoxyethylene(n:20)alkylamine (Ameat 320).

REFERENCE EXAMPLE 4

In the reference example 1, the amount of chloride polyoxyethylene(n:15)alkylamine as a surfactant was changed to 16 mass parts and in addition used 11 mass parts simple polyoxyethylene(n:20)Olkiluoto ether (Nonion S-220) and 15 mass parts of the neutralized acid polyoxyethylene(n:20)alkylamine (Ameat 320).

REFERENCE EXAMPLE 5

In reference example 1 instead of the chloride polyoxyethylene(n:20)alkylamine as surfactants used 18 mass parts of the neutralized acid polyoxyethylene(n:15)alkylamino (Esoduomine T/25).

REFERENCE EXAMPLE 6

In example 1 instead of the polyethylene glycol used 57 mass parts of hexyleneglycol (HEG, product Godo Solvent).

COMPARATIVE EXAMPLE 1

In the reference example 1 2-ethylhexylacrylate and benzylmercaptan changed to 124 mass parts and 24.5 mass parts, respectively is instead chloride polyoxyethylene(n:15)alkylamine as surfactants used chloride of stearylamine (Coatamin 86P Conc.).

COMPARATIVE EXAMPLE 2

In reference example 1 instead of the chloride polyoxyethylene(n:15)alkylamine as surfactants used the same amount of chloride of stearylamine (Coatamin 86P Conc.).

COMPARATIVE EXAMPLE 3

In reference example 1 instead of the chloride polyoxyethylene(n:15)alkylamine as surfactants used 11 mass parts of chloride of stearylamine (Coatamin 86P Conc.), 16 mass parts of chloride of distearyldimethylammonium (Coatamin D86P, product of Kao) and 11 mass parts simple polyoxyethylene(n:20)octylphenols ether (Nonion HS-220, a product of NOF).

COMPARATIVE EXAMPLE 4

In reference example 1 instead of the chloride polyoxyethylene(n:15)alkylamine as surfactants used 11 mass parts of chloride of stearylamine (Coatamin 86P Conz.), 16 mass parts of chloride of distearyldimethylammonium (Coatamin D86P) and 11 mass parts simple polyoxyethylene(n:20)octylphenols ether (Nonion HS-220).

COMPARATIVE EXAMPLE 5

In reference example 1 instead of 2-ethoxyacrylate used the same amount of lauriemittiet. Instead chloride polyoxyethylene(n:15)alkylamine used the same amount of chloride of stearylamine (Coatamin 86P Conc.).

Water dispersion obtained in the previous reference examples and compare what lnyh examples diluted ionoobmennoi water, each to a concentration of solids of 0.9 wt.% and received in a separate dilute aqueous dispersion dipped cotton fabric, mixed spun cotton-polyester fabric, polifemo fabric and nylon fabric to determine vodootlivnye (according to JIS L1092) and malatjalian (according to AATCC-TM118-1966), for which values were found moisturize after push-UPS 100% cotton fabric, 65% for mixed spun cotton-polyester fabric, 60% for polyester fabric and 40% for Polimeni tissue. The conditions of drying and curing were 165°C for 3 minutes for cotton and cotton-polyester fabric and 185°C for 1.5 minutes for polyester fabric and nylon fabric on chirillo-drying machine hot drying.

The results are shown in table 1.

Table 1
Reference example No.Compare. example No.
12345612345
[Water resistant]
Cotton fabric100100901001001007070808080
Mixed spun cotton-polyester fabric100100100100100100100100100100100
Polyester fabric100100100100100100100100100100100
Polyamide cloth100100100100100100100100100100100
[Malatjalian]
Cotton fabric66566655555
Mixed spun cotton-polyester fabric65788666666
Polyester fabric56667756766
Polyamide cloth68888677877

These treated fabrics were subjected to 5-fold test for resistance to washing and it was found that water resistant cotton fabrics decreased to 50-70 in all reference examples and comparative examples and the initial water resistant could not be saved.

The test for resistance to washing: 1 kg each wash fabric wash (in) 30 l of warm water at 40°and 21 g of detergent (Attack, a product of Kao) in the following conditions is: washing for 12 minutes dehydration for 3 minutes - rinse in running water for 6 minutes - dehydration for 5 minutes and drying in a rotary drum.

EXAMPLE 1

2,3 mass parts (corresponding to 0.69 mass parts solids) aqueous dispersion (solids content was adjusted to 30%)obtained in referential example 1 was mixed with 0.7 mass parts of the emulsion blocked isocyanate, diphenylmethanediisocyanate etc.(named ruco Guard XTS) and diluted 97 mass parts ionoobmennoi water to obtain a water - and oil-repellent agent.

EXAMPLE 2

In example 1, instead of a Guard named ruco XTS used the same number of NK Assist V, the product of Nikka Chemical, as a blocked isocyanate, diphenylmethanediisocyanate etc.

EXAMPLE 3

In example 1, instead of a Guard named ruco XTS used is 0.5 mass parts of the emulsion blocked isocyanate colordistance etc. (Prominate XC-915) as emulsions of blocked isocyanate and the number ionoobmennoi water was changed to 97,2 mass parts.

EXAMPLE 4

In example 1 instead of the aqueous dispersion obtained in reference example 1 used the same amount of water dispersion obtained in reference example 2.

EXAMPLE 5

In example 1 instead of the aqueous dispersion obtained in reference example 1 used the same amount of water dispersion obtained in ssy is face-to-face example 3.

EXAMPLE 6

In example 1 instead of the aqueous dispersion obtained in reference example 1 used the same amount of water dispersion obtained in reference example 6.

COMPARATIVE EXAMPLE 6

In example 1 instead of the aqueous dispersion obtained in reference example 1 used the same amount of water dispersion obtained in comparative example 1.

COMPARATIVE EXAMPLE 7

In example 1 instead of the aqueous dispersion obtained in reference example 1 used the same amount of water dispersion obtained in comparative example 2.

COMPARATIVE EXAMPLE 8

In example 1 instead of the aqueous dispersion obtained in reference example 1 used the same amount of water dispersion obtained in comparative example 3.

COMPARATIVE EXAMPLE 9

In example 1 instead of the aqueous dispersion obtained in reference example 1 used the same amount of water dispersion obtained in comparative example 4.

COMPARATIVE EXAMPLE 10

In example 1 instead of the aqueous dispersion obtained in reference example 1 used the same amount of water dispersion obtained in comparative example 5.

Water - and oil-repellent agents obtained in the foregoing examples 1 to 6 and comparative examples 6 to 10 (which is hereinafter referred to as "undiluted dispersions of water and oil is repulsive agent", water dispersion obtained by diluting the undiluted aqueous dispersions twice ionoobmennoi water (hereinafter referred to as "2-fold diluted dispersions of water - and oil-repellent agent"), and water dispersion, similarly diluted four times (which are hereinafter referred to as "4-hkrati diluted dispersion of water - and oil-repellent agent"), used for dipping cotton, mixed spun cotton-polyester fabric, polyester fabric and nylon fabric to determine water and malatjalian in the same manner as in reference example 1. The results are shown in table 2 for undiluted dispersions of water - and oil-repellent agents, in table 3 for the 2-fold diluted dispersions of water - and oil-repellent agents and in table 4 for the 4-fold diluted dispersions of water - and oil-repellent agents.

Table 2
(Undiluted dispersions of water - and oil-repellent agent)
Example No.Compare. example No.
123456 678910
[Water resistant]
Cotton fabric1001001001001001008080808080
Mixed spun cotton-polyester fabric100100100100100100100100100100100
Polyester fabric100100100100100100100100100100100
Polyamide cloth100100100100100100100100100100100
[Malatjalian]
Cotton fabric66666655555
Mixed spun cotton-polyester fabric76777776665
Polyester fabric67676666666
Polyamide cloth88887887877

Table 3
(Twice-diluted dispersions of water - and oil-repellent agent)
Example No.Compare. example No.
123456678910
[Water resistant]
Cotton fabric100100901001001008080808080
Mixed spun cotton-polyester fabric1001001001001001009080909090
Polyester fabric100100100100100100100100100100100
Polyamide cloth10010010010010010010090100 90100
[Malatjalian]
Cotton fabric44444433443
Mixed spun cotton-polyester fabric56667576665
Polyester fabric55566566666
Polyamide cloth67777687877

Table 4
(Fourfold diluted dispersion of water - and oil-repellent agent
Example No.Compare. example No.
123456678910
[Water resistant]
Cotton fabric8080808080807070707070
Mixed spun cotton-polyester fabric1009090100100908080809080
Polyester fabric100100100100100100100100100100100
Polyamide cloth100100/td> 100100100100100909010090
[Malatjalian]
Cotton fabric22122211010
Mixed spun cotton-polyester fabric44444343343
Polyester fabric55555454445
Polyamide cloth55555555455

Fabric treated with undiluted dispersions of water and oil repellent and the clients in examples 1 to 6 and comparative examples 6 to 10, were subjected to a test for resistance to 5-fold the washing, and the results are shown in table 5.

Table 5
Example No.Compare. example No.
123456678910
[Water resistant]
Cotton fabric1001001001001001007070808080
Mixed spun cotton-polyester fabric100100100100100100100100100100100
Polyester fabric100100 100100100100100100100100100
Polyamide cloth100100100100100100100100100100100
[Malatjalian]
Cotton fabric55555554542
Mixed spun cotton-polyester fabric76767655554
Polyester fabric55566555555
Polyamide cloth777 77667676

1. A method of obtaining a water - and oil-repellent agent, providing emulsification (a) 15-85 wt.% perftorpolietilena, (b1) 5-65 wt.% 2-ethylhexylacrylate and (b2) 1-40 wt.% bezelmaterial in the presence of (C) cationic surfactants of the type of polyethylene oxide adduct or as specified cationic surfactants, and nonionic surfactants of the type of polyethylene oxide adduct, or neutralized organic acid amine compounds having polietilenoksidnoy chain, and (d) connections on the basis of polypropyleneglycol having a molecular weight of 300 to 3000, or hexyleneglycol, with subsequent reaction of copolymerization in the presence of a polymerization initiator, and the mixture obtained water dispersion from (e) blocked isocyanate.

2. The method according to claim 1, wherein the blocked isocyanate is used in a ratio of 0.15 to 3.0 wt. hours per mass fraction solids in water dispersion.

3. The method according to claim 1, wherein the polymerized monomer containing a cross stitched group, additionally copolymerized during copolymerization with comonomers components (a), (b1) and (b2).

4. Water - and oil-repellent agent, the floor is obtained according to the method of claim 1, which has a satisfactory water - and malatjalian for synthetic fibers and natural fibers.

5. Water - and oil-repellent agent obtained according to the method of claim 3, which has a satisfactory water - and malatjalian for synthetic fibers and natural fibers.



 

Same patents:

FIELD: chemistry; production methods of composition for thread coating.

SUBSTANCE: composition includes x) = 10-50 mass.% of polyethylene wax with melting temperature from 110 to 150°C, y) = 10-50 mass.% compound ether compositions of conjoint polymer produced from α-olefine containing from 10 to 24 carbon atoms and unsaturated dicarboxylic acid selected from maleinic acid, fumaric acid, itaconic acid and citraconic acid z) = 100-(x+y) mass.% of silicon oil composition with 100 to 100- MPa-c viscosity at 20°C. Threads, fibres or filaments produced by spinning, stretching and texturing, if necessary, are subject to treatment with the specified composition.

EFFECT: items are ensured with high resistance property.

17 cl, 2 tbl, 3 ex

The invention relates to the technology of yarn supplied overabsorbed material that can be used to obtain waterproof cables optical communications as reinforcing elements

FIELD: chemistry.

SUBSTANCE: invention refers to technology of hull-kernel particles which can be used to modify impact strength of poly(met)akrylate moulding compositions. According to method a) water and emulsifier b) are added with 25.0 to 45.0 mass fractions of the first composition containing A) alkylmetacrylate 50.0 to 99.9 mass fractions, B) alkylakrylate 0.0 to 40 mass fractions, C) cohesive monomers 0.1 to 10.0 mass fractions, and D) styrene monomers 0.0 to 8.0 mass fractions, and polymerised, c) added 35.0 to 55.0 mass fractions of the second composition containing E) (met)akrylates 80.0 to 100.0 mass fractions, F) cohesive monomers 0.05 to 10.0 mass fractions, and G) styrene monomers 0.0 to 20.0 mass fractions, and polymerised, d) added 10.0 to 30.0 mass fractions of the third composition containing H) alkylmetakrylates 50.0 to 100.0 mass fractions I) alkylakrylates 0.0 to 40.0 mass fractions and J) styrene monomers 0.0 to 10.0 mass fractions, and polymerised. Method is distinctive in that e) each polymerisation cycle is performed at temperature within 60 to 90°C and f) fractional content of all substances is selected so that total weight A) to J) per total weight of aqueous dispersion exceeds 50.0 mass %. Presented method is used to produce impact strength modifiers minimum content of which provides sufficient improvement of impact strength when tested on cut moulding composition samples, not degrading at the same time other important properties of moulding composition.

EFFECT: production of impact strength modifiers minimum content of which provides sufficient improvement of impact strength when tested on cut moulding composition samples, not degrading at the same time other important properties of moulding composition.

17 cl, 8 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to impregnation and hermetisation of porous products with thermally hardened compositions based on (meth)acrylic monomers. Claimed is thermally hardened composition for impregnation and hermetisation of porous products, containing (in mass fraction): 100 (meth)acrylic monomer, 0.1-0.5 nitronitrile, 0.01-0.04 hydrohynone, 0.004-0.03 disodium salt of ethylendiaminetetraacetic acid, 0.001-0.03 2,2,6,6-tetramethyl-4-oxopiperidin-1-oxyl and 0.5-5.0 non-ionogenic emulsifying agent. Method of impregnation and hermetisation of porous products includes their vacuum processing with further impregnation under vacuum and atmospheric pressure with abovementioned composition and hardening at temperature ≥90°C. Thermally-hardened composition has higher serviceability and allows to increase productivity of impregnation and hermetisation method essentially.

EFFECT: increasing productivity of method of impregnation and hermetisation of porous products by means of thermally-hardened compositions.

2 cl, 1 tbl, 15 ex

FIELD: technological processes.

SUBSTANCE: present invention relates to the technology of modifiers production on the basis of nuclear-shell type particles used for production of molding such as films, pipes, mirror housings etc. from poly(meth)acrylates. The nuclear-shell type particle consists of a nucleus, the first shell and, if required, the second shell that on every single case consist of alkylmetacrylate and styrene recurring units with minimum glass-transition temperature of 30°C. The said particles are produced by multistage emulsion polymerisation.

EFFECT: invention ensures implementation of the process with minimum labour costs and small investments for commercial deployment.

15 cl, 2 tbl

FIELD: physics.

SUBSTANCE: invention concerns manufacturing of integrated microcircuits and other electronic devices using planar technology based on photolithographic processes. The technical task was to develop a photoactivated composition for silicon dioxide film etching for photolithographic purposes, which would allow reduce technological process of photolithographical drawing in silicon layer. The offered composition contains (mass%): polymethylmethacrylate (3.2-3.9) as polymeric substrate, ammonium fluoride (3.0-3.7) as photosensitive component, and pyridine (75.0-80.3) and trifluoroacetic acid (12.1-18.8) as solvents.

EFFECT: application of the offered composition simplifies the technological process and decreases the number of flaws of production drastically.

1 cl, 2 ex

FIELD: heat-curable sealing compositions.

SUBSTANCE: composition is proposed, containing the following mass components: 100 (meth)acrylic monomer or its mixture with an allyic monomer, 0.5-2.5 initiator, 0.01-0.32 hydroquinone, 0.01-0.13 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl, 0.004-0.05 disodium salt of ethylenediaminetetraacetic acid, 20-125 filler and 5-30 functional additives. The proposed composition has polymerising activity at 100-250°C for 3-8 minutes and breaking stress of 605-15.5 MPa. This adhesive strength is sufficient for withstanding steam pressure of up to 4 MPa. Use of the proposed composition allows for repairing steam pipes with constant supply of steam.

EFFECT: design of a heat-curable sealing composition for repairing steam pipes without interruption of steam supply.

1 cl, 1 tbl, 5 ex

FIELD: textile industry.

SUBSTANCE: invention relates to manufacture of nonwoven fabrics possessing sorption ability and can be used in making various-modification filters suitable for cleaning liquid media. Impregnating composition contains blend constituted by latexes based on rigid chain- and flexible chain-nature copolymers taken at ratio between 95:5 and 50:5, respectively, solid filler, and water, wherein ratio of all components is expressed as 1:(2.5-3.0):1. Composition is obtained by mixing and vibration action in resonance mode at frequency 50-150 Hz and action time 5-15 min.

EFFECT: increased aggregative stability of composition and physicomechanical properties of material with no additional components added.

2 cl, 2 tbl, 6 ex

FIELD: composite polymer biomedicine materials containing polymer binder, biocompatible filler and carbon reinforcing filler.

SUBSTANCE: claimed composition contains polymer binder, namely mixture of polymethylmethacrylate or methylmethacrylate copolymer with methylacrylate and monomer methylmethacrylate in ratio of polymer part to monomer from 1:0.3 to 1:0.5 mass pts (50-72 mass pts); peroxide initiator (0.05-0.5 mass pts): carbon continuous fibers of 200-1000 filaments made of hydratcellulose fiber of polyacrylonitrile fiber (2-10 mass pts); and hydroxyapatite as filler (25-40 mass pts). Method for production of material from claimed composition useful in manufacturing of jowl implants also is disclosed.

EFFECT: polymer material having natural bone-like properties.

3 cl, 10 ex, 1 tbl

The invention relates to the field of solid state ionic conductors, namely, polymer electrolytes

The invention relates to the qualitative and quantitative composition of composite materials for the combination of crumb rubber, which is obtained by grinding waste rubber with other ingredients such rubber mixtures, which are intended for forming of new rubber products

FIELD: chemistry.

SUBSTANCE: invention refers to technology of hull-kernel particles which can be used to modify impact strength of poly(met)akrylate moulding compositions. According to method a) water and emulsifier b) are added with 25.0 to 45.0 mass fractions of the first composition containing A) alkylmetacrylate 50.0 to 99.9 mass fractions, B) alkylakrylate 0.0 to 40 mass fractions, C) cohesive monomers 0.1 to 10.0 mass fractions, and D) styrene monomers 0.0 to 8.0 mass fractions, and polymerised, c) added 35.0 to 55.0 mass fractions of the second composition containing E) (met)akrylates 80.0 to 100.0 mass fractions, F) cohesive monomers 0.05 to 10.0 mass fractions, and G) styrene monomers 0.0 to 20.0 mass fractions, and polymerised, d) added 10.0 to 30.0 mass fractions of the third composition containing H) alkylmetakrylates 50.0 to 100.0 mass fractions I) alkylakrylates 0.0 to 40.0 mass fractions and J) styrene monomers 0.0 to 10.0 mass fractions, and polymerised. Method is distinctive in that e) each polymerisation cycle is performed at temperature within 60 to 90°C and f) fractional content of all substances is selected so that total weight A) to J) per total weight of aqueous dispersion exceeds 50.0 mass %. Presented method is used to produce impact strength modifiers minimum content of which provides sufficient improvement of impact strength when tested on cut moulding composition samples, not degrading at the same time other important properties of moulding composition.

EFFECT: production of impact strength modifiers minimum content of which provides sufficient improvement of impact strength when tested on cut moulding composition samples, not degrading at the same time other important properties of moulding composition.

17 cl, 8 tbl

FIELD: heat-curable sealing compositions.

SUBSTANCE: composition is proposed, containing the following mass components: 100 (meth)acrylic monomer or its mixture with an allyic monomer, 0.5-2.5 initiator, 0.01-0.32 hydroquinone, 0.01-0.13 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl, 0.004-0.05 disodium salt of ethylenediaminetetraacetic acid, 20-125 filler and 5-30 functional additives. The proposed composition has polymerising activity at 100-250°C for 3-8 minutes and breaking stress of 605-15.5 MPa. This adhesive strength is sufficient for withstanding steam pressure of up to 4 MPa. Use of the proposed composition allows for repairing steam pipes with constant supply of steam.

EFFECT: design of a heat-curable sealing composition for repairing steam pipes without interruption of steam supply.

1 cl, 1 tbl, 5 ex

FIELD: physics, photographic material.

SUBSTANCE: invention pertains to polymer cholesteric photoactive compounds, which can independently generate laser emission when irradiated with laser light. Such a compound can be used, for example, in photonics, optoelectronics and telecommunication systems. The cholesteric photoactive compound for generating laser emission consists of cholesteric liquid crystal, photoactive additive and laser dye. The liquid crystal used contains conjoint polymer n-(6-acrylyl oxycapril hydroxyphenyl)-n-methoxy benzoate with cholesterine-11-acrylyl undecanoate, containing molar quantities between 30% and 25% of the cholesterine-11-acrylyl undecanoate links. Photoactive additive used is 2.5-bis(4-methoxy cynnamoyl)-1.4;3.6-dianhydro-B-sorbitol, while the laser dye used is 4-(dicyano methylene)-2-methyl-6-(4-dimethyl amino styryl)-4H-pyran. The invention improves the temporal and thermal stability of the compound, and allows for its use at room temperatures and at lower temperatures as well. Sensitivity of the compound to external effects is also lowered.

EFFECT: increased thermal stability of photoactive compounds and lower sensitivity to external effects.

2 ex, 1 dwg

FIELD: rubber industry; production of the vulcanizable rubber mixture on the basis of the hydrogenated butadiene-nitrile caoutchouck.

SUBSTANCE: the invention is pertaining to production of the vulcanizable rubber mixture on the basis of the hydrogenated butadiene-nitrile caoutchouck used for manufacture of rubber-technical products efficient at the temperatures up to 150°С. The vulcanizable rubber mixture contains (in mass): the hydrogenated butadiene-nitrile caoutchouck - 70-95, the acrylate caoutchouck - 30-50, sulfur - 0.5-1.2, quaternary ammonium base - 2-6, sulfonamide Ц - 0.5-1.5, thiuram Д - 1-2, metallic stearate - 2-4, zinc oxide - 3-5, industrial carbon - 40-50, the stearic acid - 1-2, the antioxidant - 3.0-3.8. The technical result of the invention consists in reduction of the mixture viscosity, increase of the heat-resistance and the aggressive mediums-resistant properties with the simultaneous decrease of the residual compressive deformation.

EFFECT: the invention ensures the reduced mixture viscosity, the increased heat-resistant and the aggressive mediums-resistant properties at the simultaneously decreased of the residual compressive deformation.

3 cl, 2 tbl

FIELD: rubber industry; chemical industry; production of the vulcanized rubber mixture made on the basis of an acrylate rubber and partially on the hydrogenated butadiene-nitril caoutchoucks.

SUBSTANCE: the invention is pertaining to production of the vulcanized rubber mixture made on the basis of the acrylate rubber and partially on the basis of the hydrogenated butadiene-nitril caoutchoucks, which is used for manufacture of the hardware products operable at the temperatures up to 150°С and having the heightened wear resistance and which may be used in production of the industrial rubber products - the rings, the sleeves gaskets, the drive belts operating in the friction pairs at the heightened temperatures. The vulcanized rubber mixture made on the basis of the acrylate rubber of the heightened wear resistance includes the mineral filler, the engineering carbon, the antioxidant, the plasticizer, the partially hydrogenated butadiene-nitril caoutchouck, the quaternary ammonium base, the metallic stearate, the brimstone, the vulcanization accelerators, zinc oxide, the anti-adhesive agent, the anti-scorching agent. The rubber mixture made on the basis of the acrylate rubber of the heightened wear resistance allows to increase the level of the values of the indexes: the wear resistance, the tensile strength, the frost hardiness, the resistance to the action of the aggressive mediums of the aromatic series.

EFFECT: the invention ensures the increased level of the values of the indexes of the rubber mixture made on the basis of the acrylate rubber of the heightened wear resistance: the wear resistance, the tensile strength, the frost hardiness, the resistance to the action of the aggressive mediums of the aromatic series.

3 cl, 2 tbl

FIELD: antifriction materials.

SUBSTANCE: invention relates to antifriction self-hardening covers based on polymeric binding agent. Proposed composition comprises the following components, wt.-%: molybdenum disulfide, 10.0-18.0; crystalline iodine, 0.2-0.6 and polyacryl lacquer. For improving antifriction properties ultradispersed β-sialone in the amount 0.2-0.5 wt.-% can be added to composition additionally. Composition is prepared by mechanical mixing components. Ready composition is applied on working surface of unit friction article by spraying, immersion method or by a brush. Prepared cover is dried at temperature 20 ± 5°C for 0.5-2 h. Prepared covers are especially effective for applying on articles that can't be heated or in case of difficult heating. Proposed composition is used in machine engineering for applying on friction unit articles working without lubrication. Invention provides enhancing antifriction properties of composition, adhesion to steel and exclusion the necessity of temperature effect.

EFFECT: improved and valuable technical properties of composition.

1 cl, 3 tbl, 12 ex

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