WO2006132385A1 - Polymère hydrosoluble, méthode de synthèse dudit polymère, et application dudit polymère - Google Patents

Polymère hydrosoluble, méthode de synthèse dudit polymère, et application dudit polymère Download PDF

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Publication number
WO2006132385A1
WO2006132385A1 PCT/JP2006/311672 JP2006311672W WO2006132385A1 WO 2006132385 A1 WO2006132385 A1 WO 2006132385A1 JP 2006311672 W JP2006311672 W JP 2006311672W WO 2006132385 A1 WO2006132385 A1 WO 2006132385A1
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water
soluble polymer
weight
vinylpyrrolidone
polymerization
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PCT/JP2006/311672
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English (en)
Inventor
Takahiro Tsumori
Daisuke Imai
Yoshikazu Fujii
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Nippon Shokubai Co., Ltd.
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Publication of WO2006132385A1 publication Critical patent/WO2006132385A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides

Definitions

  • the present invention relates to a water-soluble polymer, a production method thereof, and an application thereof. More preferably, the present invention relates to: a water-soluble polymer used in various applications such as detergent additive, scale inhibitor, dispersant for various inorganic or organic substances, thickener, cohesive agent, adhesive agent, surface-coating agent, cross-linking agent, moisturizer; a production method thereof; a detergent additive using the water-soluble polymer; and a detergent using the detergent additive.
  • Water-soluble polymers have been widely used in various applications such as detergent additive, scale inhibitor, dispersant for various inorganic or organic substances, thickener, cohesive agent, adhesive agent, surface-coating agent, cross-linking agent, and moisturizer.
  • water-soluble polymers polymers produced by polymerizing an unsaturated carboxylic acid monomer such as an acrylic acid or copolymers of such an unsaturated carboxylic acid monomer with another monomer, and graft polymers produced by a graft polymerization of a polyether compound with an unsaturated carboxylic acid monomer such as acrylic acid, vinyl acetate, or (meth) acrylic acidester, havebeenwidelyused conventionally.
  • a graft polymer obtained by a graft polymerization of a polyether compound with a grafting component containing an N-vinylpyrrolidone as an essential component in such a way that 1 part by weight of the polyether compound is copolymerized with 0.1 to 1.2 parts byweight of the grafting component (for example, referring to Japanese Kokai Publication No.2001-106743, pages 2, 8 and 9) .
  • This graft polymer has excellent adsorptivity and dispersibility as well as excellent hydrophilicity.
  • this graft polymer is preferably used in scale inhibitors or detergent additives.
  • this graft polymer itself is highly colored. Therefore, this graft polymer has room for improvement in order to be preferably used in much more applications by being provided with more excellent coloring control ability and by improving the coloring preventing capability.
  • benzoyl peroxide as an initiator, at apolymerization temperature of 105°C.
  • this graft polymer has the followingproblems .
  • the benzoyl peroxide is in a solid state at ordinary temperatures, and therefore the polymerization method is limited to, for example, whether the benzoyl peroxide is dissolved in a solvent and then added dropwise, or the benzoyl peroxide is previously added in one step.
  • the residual amount of the N-vinylpyrrolidone having high toxicity tends to be larger. Therefore, such a graft polymer has room for improvement in the following points.
  • the graft polymerization is efficiently and simply performed, and the graft polymer is provided with a sufficiently satisfying anti-soil redeposition capability for preventing redeposition causedbyhydrophobic soils, and thereby such a graft polymer is preferablyused in, for example, detergent additives .
  • a graft polymer containing: a graft base of a polymer having no monoethylenically unsaturated units; and a side chain of a polymer of an N-vinylpyrrolidone or a copolymer of an N-vinylpyrrolidone and an N-vinylimidazole, the ratio of the side chain in the total polymer being specified to 35% by weight or more (for example, Japanese Kohyo No. 2005-509063, pages 2, 18, and 19, Japanese Kohyo No. 2005-509064, pages 2, 14, and 15, and Japanese Kohyo No. 2005-509065, pages 2, 18 to 21) .
  • Example discloses a technique in which a polyethylene glycol is reacted with an N-vinylpyrrolidone or an N-vinylimmidozole using t-butylpivalate or t-butylhydroperoxide as an initiator in the presence of an aqueous solvent at a polymerization temperature of 80 to 110 0 C.
  • the graft efficiency of the monomer component is insufficient, and the N-vinylpyrrolidone is decomposed to generate a great amount of 2-pyrrolidone.
  • the present invention has been made in view of the above-mentioned state of the art.
  • the present invention has an object to provide: a water-soluble polymer having excellent adsorptivity, dispersibility, and safety as well as excellent hydrophilicity, and capable of preventing coloring sufficiently and being preferably used in a detergent additive application, for example; an application thereof; a production method of the water-soluble polymer, the production method being capable of producing such a water-soluble polymer efficiently in a short time.
  • the present inventors have made various investigations about water-soluble polymers. They have noted that if a water-soluble polymer is produced by polymerizing a polyether compound with a monomer component containing an
  • N-vinylpyrrolidone such a water-soluble polymer is excellent in adsorptivity or dispersibility because of the presence of the pyrrolidone group in the polymer. They have found that if the used amount of the Nrvinylpyrrolidone is specified to a certain amount, the obtained polymer is excellent in safety and less colored. They have also found that if such a water-soluble polymer is used in, for example, a detergent additive application, such a detergent additive can prevent redeposition caused by hydrophobic soils and thereby exhibit high detergency. Therefore, they have resolved the above-mentioned problems. As mentioned above, the above-mentioned polymer is produced using a small amount of N-vinylpyrrolidone.
  • Such a water-soluble polymer can particularlypreferably used in a detergent additive application because such a water-soluble polymer can exhibit dramatically excellent detergency even in a small amount. They have also found that if a water-soluble polymer is produced by polymerizing a polyether compound with a monomer component containing an N-vinylpyrrolidone using an initiator containing an aliphatic organic peroxide at 120 to 14O 0 C, the polymerization can be performed efficiently in a short time, and the residual amount of the N-vinylpyrrolidone in the obtained polymer can be sufficiently reduced and a polymer excellent in coloring preventing capability or anti-soil redeposition capability for preventing redeposition caused by hydrophobic soils . Thereby, the present invention has been completed.
  • the present invention provides a water-soluble polymer capable of exhibiting performances as a detergent additive and the like, even in a smaller amount of such a high priced N-vinylpyrrolidone.
  • the present invention is a water-soluble polymer produced by a polymerization of a polyether compound (A) with a monomer component containing an N-vinylpyrrolidone (B) , wherein the N-vinylpyrrolidone (B) is 0.01 to 0.3 parts by weight to 1 part by weight of the polyether compound (A) .
  • the present invention is also a detergent additive containing the water-soluble polymer.
  • the present invention is further a detergent containing the detergent additive.
  • the water-soluble polymer of the present invention is produced by polymerizing one or two or more species of polyether compound (s) (A) with a monomer component containing an N-vinylpyrrolidone (B) .
  • a graft polymerization of a polyether compound (A) with a monomer component containing an N-vinylpyrrolidone (B) is particularly preferable as a polymerization form, as mentionedbelow.
  • Preferable embodiment of the present invention includes such an embodiment in which the above-mentioned water-soluble polymer is a water-soluble graft polymer.
  • the polyether compound (A) in the above-mentioned water-soluble polymer is preferably produced by polymerizing an alkylene oxide containing an ethylene oxide.
  • the water-soluble polymer can retain excellent hydrophilicity and exhibit more sufficient dispersibility. Therefore, if such a water-solublepolymer is usedin a detergent additive application, deposition of soils to clothes and the like is prevented enough, leading to improvement in detergency.
  • the above-mentioned polyether compound (A) is preferably produced by additionally polymerizing an alkylene oxide with a primary alcohol and/or a secondary alcohol. Thereby, if such a water-soluble polymer is used in, for example, a detergent additive application, the detergency can be more improved.
  • the alkylene oxide additionally polymerized preferably contains an ethylene oxide, as mentioned above.
  • the content of the ethylene oxide in the alkylene oxide used for producing the above-mentioned polyether compound (A) is preferably at least 50% by mole, relative to 100% by mole of all the alkylene oxides. That is, it is preferable that the above-mentioned polyether compound (A) is produced by polymerizing an alkylene oxide containing at least 50% by mole of ethylene oxide. If the content of the ethylene oxide is less than 50% by mole, the obtained water-soluble polymer may exhibit insufficient hydrophilicity and dispersibility. The content thereof is more preferably 70% by mole or more, and still more preferably 80% by mole or more.
  • the above-mentioned alkylene oxide may contain an alkylene oxide other than the ethylene oxide, if necessary.
  • Such an alkylene oxide is not especially limited as long as it is copolymerizable with the ethylene oxide.
  • Examples of such an alkylene oxide include propylene oxide, n-butylene oxide, isobutylene oxide, styrene oxide, epichlorohydrin, allyl glycidyl ether, and phenyl glycidyl ether. One or two or more species of them may be used.
  • the above-mentioned polyether compound (A) has a number average molecular weight of 400 to 5000. Thereby, the polymerization canbe efficiently and easily performed, and the obtained water-soluble polymer can exhibit sufficient dispersibility. If the number average molecular weight is less than 400, the obtained water-soluble polymer has an insufficient molecular weight, possibly failing to exhibit excellent dispersibility. If the number average molecular weight is more than 5000, sufficiently uniform stirring may not be performed during the polymerization when the polymerization is performedwithout a solvent . More preferably, the lower limit of the number average molecular weight is 600 and the upper limit thereof is 4000. Still more preferably, the lower limit thereof is 800 and the upper limit thereof is 3500.
  • the above-mentioned number average molecular weight can be determined by, for example, gel permeation chromatography
  • Detecting element RI Column: produced by Showa Denko K.K.
  • a more preferable embodiment of the above-mentioned polyether compound (A) is an embodiment in which the polyether compound (A) is produced by polymerizing an alkylene oxide containing at least 50%bymole of ethylene oxide andthe polyether compound (A) has a number average molecular weight of 400 to
  • a method for producing the above-mentioned polyether compound (A) is not especially limited.
  • the polyether compound (A) can be produced by polymerizing the above-mentioned alkylene oxide component in the presence of a reacted compound serving as a starting material of the polymerization using a conventional method.
  • the above-mentioned reacted compound is not especially limited as long as it is a compound serving as a polymerization starting material of the cyclic ether.
  • Water, alcohols, hydrogen halides, ammonia, amines, hydroxylamines, and carboxylic acids maybe mentioned as the above-mentioned reacted compound, for example. Among them, water, alcohols, amines are preferable.
  • alcohols include primary aliphatic alcohols containing 1 to 22 carbon atoms such as methanol, ethanol, n-propanol, and n-butanol; aromatic alcohols such as phenol, isopropyl phenol, octyl phenol, tert-butyl phenol, nonyl phenol, andnaphthol; secondary alcohols containing 3 to 18 carbon atoms such as alcohols obtained by oxidizing isopropyl alcohol or n-paraffin; tertiary alcohols such as tert-butanol; diols such as ethylene glycol, diethylene glycol, propanediol, butanediol, and propylene glycol; triols such as glycerin and trimethylol propane; and polyols such as sorbitol. Ethylenediamine, polyethyleneimine may be mentioned as amines, for example. These may be singly or in combination of two or more species of them.
  • the above-mentioned polymerization method is not especially limited.
  • the following methods may be appropriately selected: (1) an anionic polymerization method using a hydroxide of an alkali metal, a strong alkali such as alcoholate, an alkylamine, or the like as a base catalyst; (2) a cationic polymerization method using a halide of a metal or a metalloid, a mineral acid, an acetic acid, or the like as ' a catalyst; and (3) a coordination polymerization method using a combination of an alkoxide of a metal such as aluminum, iron, zinc, or the like, an alkaline earth compound, a Lewis acid, or the like.
  • polyether compound (A) of the present invention can be used as it is as the polyether compound (A) of the present invention, and may be used in a derivative form derived from the polyether compound.
  • a derivative may be, for example, a cross-linked compound obtained by reaction of a cross-linking agent having a plurality of groups such as carboxyl group, isocyanate group, amino group, and halogen group with the above-obtained polyether compound.
  • the obtained water-soluble polymer can be provided with excellent dispersibility and adsorptivity because of the presence of the pyrrolidone group in the obtained water-soluble polymer.
  • a detergent additive for example, such a detergent additive adsorbs to dye eluting intowater froma fiber, andthen disperses it, and thereby can prevent transfer to other fibers.
  • (B) is preferably 0.01 to 0.3- parts by weight, relative to 1 part by weight of the above-mentioned polyether compound (A) . If the used amount the above-mentioned N-vinylpyrrolidone (B) is less than 0.01 parts by weight, the obtained water-soluble polymer may insufficiently exhibit dispersibility and adsorptivity attributed to the pyrrolidone group. If the used amount thereof is more than 0.3 parts by weight, a great amount of the N-vinylpyrrolidone may remain or the polymer may be easily colored, and it is not economically preferable because the N-vinylpyrrolidone is high inprice. More preferably, the lower limit of the used amount is 0.03 parts by weight and the upper limit thereof is 0.27 parts by weight. Still more preferably, the lower limit thereof is 0.05 parts by weight and the upper limit thereof is 0.25 parts by weight.
  • the content of the N-vinylpyrrolidone (B) in 100% byweight (mass %, % by mass) of all the monomer components is preferably 15% by weight or more, for example.
  • the content thereof is more preferably 25% by weight or more, and still more preferably 50% by weight or more.
  • the above-mentionedmonomer component may contain another monomer other than the N-vinylpyrrolidone (B) , if necessary.
  • Amonoethylenically unsaturated monomer may be mentioned as the another monomer, for example. If such a monomer is used in the polymerization, further more excellent dispersibility can be provided with the obtained water-soluble polymer.
  • the above-mentioned monoethylenically unsaturated monomer may be, for example, an unsaturated carboxylic acid monomer (C) or another monomer mentioned below. One or two or more species of them may be used. More preferably, at least an unsaturated carboxylic acidmonomer (C) is used.
  • the unsaturated carboxylic acid monomer (C) may have a structure which can be carboxylic acid (salt) by hydrolysis.
  • Examples of the above-mentioned unsaturated carboxylic acid monomer (C) include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, alkyl-2-hydroxymethyl acrylate, maleic acid, dimethyl maleate, diethyl maleate, dibutylmaleate, maleic anhydride, fumaricacid, dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
  • acrylic acid or ester thereof, maleic acid, andmaleic anhydride are preferred.
  • the used amount of the above-mentioned unsaturated carboxylic acid monomer (C) is preferably 5 parts by weight or less, relative to 1 part by weight of the above-mentioned
  • N-vinylpyrrolidone (B) N-vinylpyrrolidone (B) . If the used amount of the unsaturated carboxylic acidmonomer (C) is more than 5 parts by weight, the amount of the pyrrolidone group present in the obtained water-soluble polymer is insufficient, and thereby the obtained water-soluble polymer may insufficiently exhibit adsorptivity or dispersibility. The used amount thereof is more preferably 3 parts by weight or less.
  • preferable embodiments of the present invention include an embodiment in which the monomer component further contains an unsaturated carboxylic acid monomer (C) , and the unsaturated carboxylic acid monomer (C) is 5 parts by weight or less, relative to 1 part by weight of the N-vinylpyrrolidone (B) .
  • the unsaturated carboxylic acid monomer (C) is used as the monomer component polymerized with the polyether compound (A)
  • the polyether compound (A) is preferably produced by additionally polymerizing an alkylene oxide with a primary alcohol and/or a secondary alcohol, as mentioned above.
  • the above-mentioned another monomer is not especially limited and may be N-vinylacetamides, N-vinylformamides, N-vinylcaprolactams, N-vinylimidazoles, vinylpyridines, alkyl vinyl ethers, and olefins.
  • one or two or more species of the following monomers may be also used as the above-mentioned another monomer: functional group-containing monomers, for example, amide group-containing monomers such as (meth) acrylamide and (meth) acryl acetylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamic acid; alkene monomers such as ethylene and propylene; aromatic vinyl monomers such as styrene and styrene sulfonic acid; trialkyloxysilyl group-containing vinyl monomers such as vinyltrimethoxysilane and vinylethoxysilane; silicon-containing vinyl monomers such as ⁇ (methacryloyloxypropyl) trimethoxysilane; maleimide derivatives such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide
  • the used amount of the above-mentioned another monomer may be appropriately determined depending on applications or needed performances and the like of the obtained water-soluble polymer. It is preferable that the water-soluble polymer of the present inventionhas a residual amount of theN-vinylpyrrolidone of 4000 ppm or less. If the residual amount of the N-vinylpyrrolidone is more than 4000 ppm, the obtained water-soluble polymer may not be excellent in safety, possibly failing to be preferably used in various applications.
  • the residual amount is more preferably 2000 ppm or less, and still more preferably 1000 ppm or less, and particularly preferably 500 ppm or less.
  • the above-mentioned residual amount of the N-vinylpyrrolidone is a value on solid content equivalent basis, and can be determined by liquid chromatography under the following conditions.
  • the water-soluble polymer has abvalue (yellowness degree) of 15.0 or less in anaqueous solution with a solid content of 50% by weight. If the b value is more than 15.0, the polymer may be easily colored, possibly failing to be useful in various applications, particularly in a detergent additive application.
  • the b value is more preferably 10.0 or less and still more preferably 8.0 or less.
  • b value can be determined as follows, for example. ⁇ Measurement method of b value>
  • a polymer (or a polymer aqueous solution) is prepared by being diluted or concentrated with pure water such that the polymer concentration is 50% by weight.
  • the prepared aqueous solution is subjected to transmission measurement using colorimetric difference meter SE-2000 produced by Nippon Denshoku Industries Co., Ltd., to determine b value. The higher positive number the b value shows, the stronger yellowness the aqueous solution shows.
  • a particularly preferable embodiment of the above-mentioned water-soluble polymer is an embodiment in which the water-soluble polymer has a residual amount of the N-vinylpyrrolidone of 4000 ppm or less, and the water-soluble polymer has a b value (yellowness degree) of 15.0 or less in an aqueous solution with a solid content of 50% by weight.
  • the water-soluble polymer has an anti-soil redeposition ratio (an anti-soil redeposition capability) of 73.0% or more.
  • the anti-soil redeposition ratio is more preferably 75.0% by weight or more, and still more preferably 76.0% by weight or more.
  • the anti-soil redeposition ratio is an indicator of performance of preventing redeposition caused by carbon black soil, and canbe determinedby the followingmethod, for example. ⁇ Measurement method of anti-soil redeposition ratio>
  • Whiteness (Z value) of each of the clothes is measured as a reflectance using a colorimetric difference meter (produced by Nippon Denshoku Industries Co., Ltd., SE 2000). The average value of the reflectances is defined as AO.
  • AO average value of the reflectances
  • Atargotmeter is set at 25°C, andhardwater 50OmL, a detergent having the following composition 1.25 g, and a 0.32% by weight aqueous solution of a sample polymer (polymer) on solid content equivalent basis 5 g, carbon black (product of Cleaning Science Association Foundation) 0.5g are put in a pot and stirring is performed at 70 rpm for 1 minute. Thereto is put 1 sheet of the cottoncloth andstirring is performedat 70 rpmfor 10minutes .
  • Table 1 shows the composition of the detergent used in the above-mentioned (3) .
  • the water-soluble polymer of the present invention can be produced by polymerizing the polyether compound (A) with the monomer component containing the N-vinylpyrrolidone (B) in the presence of a polymerization initiator .
  • a graft polymerization of the polyether compound (A) with the monomer component containing the N-vinylpyrrolidone (B) is particularly preferable as a polymerization form.
  • the obtained water-soluble polymer can have further improved anti-soil redeposition capability.
  • the method of the polymerization reaction is not especially limited.
  • the polymerization reaction may be performed by conventional polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization, and precipitation polymerization.
  • the polyether compound (A) may be charged in one step initially or added sequentially, and preferably charged in one step initially in view of shortening of the reaction time, improvement in the productivity, and the like.
  • the monomer component such as the N-vinylpyrrolidone (B) is preferably added sequentially in view of the reaction control, and the like, but the way of the addition is not limited thereto, and may be charged in one step initially.
  • the monomer component such as the N-vinylpyrrolidone (B) may be previously diluted with a solvent mentioned below and then added.
  • the polymerization initiator is not especially limited in the above-mentioned polymerization step.
  • An organic peroxide is preferable as the polymerization initiator.
  • examples of such an organic peroxide include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3, 3, 5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide; hydroperoxides such as tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2, 5-dimethylhexane-2, 5-dihydroperoxide, 1, 1, 3, 3-tetramethylbutyl hydroperoxide, and 2- (4-methylcyclohexyl) -propane hydroperoxide; dialkyl peroxides such as di-tert-butyl peroxide
  • diacyl peroxides such as acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide,
  • an organic peroxide containing at least an aliphatic group is used in the present invention.
  • the graft efficiency is improved enough and thereby the above-mentioned water-soluble polymer can be efficientlyproduced.
  • di-tert-butyl peroxide, tert-butylperoxy-iso-propyl monocarbonate and/or tert-butylperoxy-benzoate are/is particularlypreferably used in view of the reaction temperature in the polymerization step or the temperature control during storage.
  • Another polymerization initiator for example, anorganic peroxide containing an aromatic group
  • a chain transfer agent, or a reducing agent may be used in combination with the above-mentioned organic peroxide containing at least an aliphatic group.
  • the used amount of the another polymerization initiator, the chain transfer agent, or the reducing agent is preferably 300 parts byweight or less, relative to 100 parts by weight of the above-mentioned organic peroxide containing at least an aliphatic group. More preferably, the used amount thereof is 100 parts by weight or less.
  • the used amount of the above-mentioned polymerization initiator is not especially limited. For example, 0.1 to 30 parts by weight of the polymerization initiator is preferably used, relative to 100 parts byweight of all themonomer components used in the polymerization. If the used amount is less than 0.1 parts by weight, the polymerization degree to the polyether compound (A) may be insufficient. If the used amount is more than 30 parts by weight, such a production method may be economically inefficient, for example, if an organic peroxide is used as the polymerization initiator. The used amount of the polymerization initiator is more preferably 0.5 to 20 parts by weight. The way of the addition of the above-mentioned polymerization initiator is not especially limited.
  • the polymerization initiator may be charged in one step initially, or added dropwise, or added sequentially, for example, in portions.
  • a polymerization initiator in liquid state .at ordinary temperatures is preferable because it can be added dropwise without a solvent and therefore the way of the addition is hardly limited.
  • the polymerization initiator may be singly introduced into a reaction container, or may be previously mixed with the polyether compound (A) , the monomer component, the solvent, and the like.
  • Asolventmaybeused in the above-mentionedpolymerization water is not preferable because water resolves the N-vinylpyrrolidone to generate 2-pyrrolidone.
  • a solvent having a chain transfer constant as small as possible to a solvent of a monomer used as a raw material is preferred.
  • Such a solvent examples include alcohols such as isobutyl alcohol, n-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, ethylene glycol monoalkyl ether, and propylene glycol monoalkyl ether; diethers such as ethylene glycol dialkyl ether and propylene glycol dialkyl ether; and acetic acid compounds such as ethyl acetate, propyl acetate, butyl acetate, acetic ester of ethylene glycol monoalkyl ether, and acetic ester of propylene glycol monoalkyl ether. These may be used singly or in combination of two or more species of them.
  • the alkyl group in the above-mentioned alcohols and diethers is not especially limited, and may be methyl group, ethyl group, propyl group, and butyl group, for example.
  • the used amount of the above-mentioned solvent is not especially limited and preferably 20 parts by weight or less, relative to 100 parts by weight of the whole reaction system. If the used amount thereof is more than 20 parts by weight, the graft efficiency of the above-mentioned monomer component may be insufficient. The used amount thereof is more preferably 0 parts by weight. That is, it is more preferable that the polymerization is performed with substantially no solvent. Thereby, the graft efficiencycanbe dramatically improved, which makes it possible to produce a polymer more excellent in various performances .
  • Preferable embodiments of the present invention include such an embodiment in which the polymerization step is performed with no solvent.
  • the above-mentioned solvent may be charged in one step initially or added sequentially.
  • the reaction temperature during the above-mentioned polymerization is not especially limited, and preferably 120 to 140°C. If the reaction temperature is less than 120°C, the residual amount of the N-vinylpyrrolidone in the obtained water-soluble polymer can not be reduced more than enough, and therefore a polymer more excellent in safety can not be produced. If the reaction temperature is more than 140°C, coloring of the polymer can not be prevented and thereby such a polymer may not be preferably used in a detergent additive application. And thermal decomposition of the polyether compound (A) or the obtained water-soluble polymer may be generated.
  • the reaction temperature is more preferably 125 to 140 0 C, and still more preferably 130 to 140 0 C.
  • the reaction pressure during the above-mentioned polymerization is not especially limited, and the reaction may be performed under ordinary pressure (atmospheric pressure) , reduced pressure, or pressurization.
  • the polymerization is preferably performed under ordinary pressure (atmospheric pressure) because the polymerization can be performed simply and at low costs.
  • the above-mentioned polymerization is preferably performed under inert gas atmosphere such as nitrogen gas, argon gas, and CO2 gas.
  • inert gas atmosphere such as nitrogen gas, argon gas, and CO2 gas.
  • the condition is not especially limited to the above.
  • the present invention is also a production method of a water-soluble polymerproducedbyapolymerization of apolyether compound (A) with a monomer component containing an N-vinylpyrrolidone (B) , wherein the productionmethod comprises a step of performing the polymerization using, as an initiator, an organic peroxide containing at least an aliphatic group, at 120 to 140°C.
  • the polymerization is performed at 120 to 140°C in such a production method.
  • the residual amount of the N-vinylpyrrolidone in the obtained water-soluble polymer can be reducedenough in a short time . Therefore, apolymer excellent in safety canbe produced and therefore preferablyused invarious applications.
  • the organic peroxide containing at least an aliphatic group as an initiator (polymerization initiator) makes it possible to improve the graft efficiency sufficiently, for example.
  • the temperature and the polymerization initiator are specified, as mentioned above. Thereby, each functional effect attributed to such specification of the temperature and the polymerization initiator is , jointed and thereby a water-soluble polymer excellent in various performances can be efficiently produced. Therefore, such a production method can be industrially very useful production method.
  • Preferable embodiments and various conditions in the above-mentioned polymerization step are as mentioned above.
  • Particularlypreferable embodiments include, as mentioned above, an embodiment in which di-tert-butyl peroxide, tert-butylperoxy-iso-propyl monocarbonate and/or tert-butylperoxy-benzoate are/is used as the polymerization initiator, and an embodiment in which the above-mentioned polymerization step is performed with no solvent.
  • One or two or more species of conventionally usedpolyether compounds may be used as the polyether compound (A) used in the above-mentioned production method.
  • Preferable form of such polyether compounds are as mentioned above.
  • the used amount of the N-vinylpyrrolidone (B) in the above-mentionedmonomer component is preferably set as mentioned above.
  • the above-mentioned monomer component may contain another monomer other than the N-vinylpyrrolidone (B) .
  • Preferable embodiments of the another monomer, the used amount, and the like are as mentioned above.
  • the above-mentionedproductionmethod is preferred as a production method of the above-mentioned water-soluble polymer of the present invention. That is, preferable embodiments of the present invention include a production method of the above-mentioned water-soluble polymer of thepresent invention, whereintheproductionmethod comprises a step of performing the polymerization using, as an initiator, an organic peroxide containing at least an aliphatic group, at 120 to 140°C.
  • the water-soluble polymer of the present invention and the water-soluble polymer produced by the production method of the present invention have excellent adsorptivity, dispersibility, and safety as well as excellent hydrophilicity. And such water-soluble polymers, can prevent coloring sufficiently and is excellent in various performances. Therefore, such water-soluble polymers can be used in various applications such as detergent additive, scale inhibitor, dispersant for various inorganic or organic substances, thickener, cohesive agent, adhesive agent, surface-coating agent, cross-linking agent, andmoisturizer .
  • water-soluble polymers can be used in anti-redeposition agent for detergents, dye transfer inhibitor for detergents, detergent builder, silica scale inhibitor, dyeing assistant, dye fixing agent, foam stabilizer, emulsion stabilizer, ink dye dispersing agent, water-based ink stabilizer, pigment dispersant for coating materials, thickener for coating materials, thickener for cosmetics, dispersant for cosmetics, binder for cosmetics, moisturizer for cosmetics, cosmetic dispensing additive, hairdressing assistant, hair spray additive, rinse additive, sunscreen composition additive, filler dispersant for resins, coatingagent for recordingpapers, surface treatment agent for ink jet papers, dispersant for photosensitive resins, antistatic agent, moisturizer, raw material for water-absorbing resins, binder for fertilizers, polymer cross-linking agent, resin compatibilizer, photographic additive, pressure sensitive adhesive, paper adhesive, adhesive for medical use, adhesive for patches, stick paste, mud dispersant, heavy metal scavenger, and metal surface treatment agent.
  • water-based ink stabilizer
  • the above-mentioned detergent additive contains the above-mentionedwater-soluble polymer of the present invention .
  • the pyrrolidone group and preferably the oxyethylene chain of the water-soluble polymer adsorb to dye eluting into water from a fiber during washing and then disperse it. Therefore, such a detergent additive containing the water-soluble polymer can effectively prevent transfer to other fibers and also prevent redeposition due to hydrophobic soils or coloring sufficiently, as mentioned above, and thereby to exhibit high detergency sufficiently.
  • the content ratio of the water-soluble polymer of the present invention is preferably 1 to 100% by weight and more preferably 20 to 100% by weight in 100% by weight of the solid content of the detergent additive.
  • the detergent additive of the present invention can be blended to, for example, domestic powder detergents, liquid detergents, softening agents, industrial cleaning agents, and fiber treatments, tobeused.
  • Theblendedamount of the detergent additive in such a case is not especially limited.
  • the blended amount of the detergent additive is preferably set to 0.05 to 20% by weight, and more preferably 0.1 to 10% by weight in 100% by weight of domestic powder detergents, liquid detergents, softening agents, industrial cleaning agents, or fiber treatments.
  • Various blended substrates such as domestic powder detergents, liquid detergents, softening agents, industrial cleaning agents, and fiber treatments may contain acrylic acid polymers or acrylic acid/maleic acid copolymers conventionally used as a detergent additive.
  • the above-mentioned detergent additive is blended to a detergent and then used, as a particularlypreferable embodiment of the above-mentioned detergent additive.
  • the functional effects of the present invention are sufficiently exhibited, that is, such a detergent additive can sufficiently prevent transfer, redeposition due to hydrophobic soils, and coloring, and thereby exhibit high detergency.
  • a detergent (detergent composition) containing the above-mentioned detergent additive is also part of the present invention.
  • the content ratio of the detergent additive of the present invention in the above-mentioned detergent for example, the content ratio of the above-mentioned water-soluble polymer is preferably set to 0.1 to 40% by weight in 100% by weight of the detergent. If the content ratio of the above-mentionedwater-solublepolymer is less than 0.1% byweight, the detergent may insufficiently exhibit detergent performance . If the content ratio thereof is more than 40% by weight, the detergent composition may be economically inefficient. The content ratio is more preferably 0.2 to 30% by weight.
  • the formof the above-mentioneddetergent is not especially limited, and may be in powder or liquid form.
  • the above-mentioned detergent preferably contains a surfactant in addition to the above-mentioneddetergent additive .
  • a surfactant include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. One or two or more species of them may be used.
  • anionic surfactants examples include alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, ⁇ -olefin sulfonates, ⁇ -sulfofatty acids or ester salts thereof, alkane sulfonates, saturated or unsaturated fatty acid salts, alkylor alkenyl ether carboxylates, amino acid surfactants, N-acylamino acid surfactants, and alkyl or alkenyl phosphate or salts thereof.
  • the alkyl group or the alkenyl group of such anionic surfactants may have a branched structure of the alkyl group such as a methyl group.
  • nonionic surfactants examples include polyoxyalkylene alkyl or alkenyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid alkanol amides or alkylene oxide adducts thereof, sucrose fatty acid esters, alkyl glycoxides, fatty acid glycerin monoesters, and alkylamine oxides.
  • the alkyl group or the alkenyl group of such nonionic surfactants may have a branched structure of the alkyl group such as a methyl group .
  • Quarternary ammonium salts and the like may be mentioned as the above-mentioned cationic surfactants.
  • Carboxyl type or sulfobetaine type amphoteric surfactants may be mentioned as the above-mentioned amphoteric surfactants.
  • the content ratio of the surfactant in the above-mentioned detergent is preferably 1 to 70% by weight in 100% by weight of the detergent. If the content ratio is less than 1% by weight, the detergent may insufficiently exhibit detergent performances . If the content ratio is more than 60% by weight, the detergent may be economically inefficient. The content ratio is more preferably 15 to 60% by weight.
  • the above-mentioned detergent preferably contains a detergent builder. The content ratio of the detergent builder in this case is preferably 0.1 to 60% by weight in 100% by weight of the detergent, for example. More preferably, the content ratio is 1 to 10% by weight if the detergent of the present invention is supplied in liquid state, and the content ratio is 1 to 50% by weight if the detergent of the present invention is supplied in powder state.
  • the above-mentioned detergent builder is not especially limited.
  • the detergent builder include organic builders such as alkali metal salts, ammonium salts, substituted ammonium polyacetates, carboxylates, polycarboxylates, and polyhydroxy sulfonates/ inorganic builders such as silicates, aluminosilicates, borates, and carbonates. One or two or more species of them may be used.
  • polyacetates or polycarboxylates in the above-mentioned organic builders include sodium salts, potassium salts, ammonium salts, substituted ammonium salts of ethylenediaminetetraacetic acids, nitrilotriacetic acids, oxydisuccinic acids, mellitic acids, glycolic acids, benzene polycarboxylic acids and citric acids.
  • Preferred examples of the above-mentioned inorganic builders include: sodium salts or potassium salts of carbonic acids, bicarbonic acids, and silicic acids; andaluminosilicates such as zeolites.
  • the above-mentioned detergent may further contain conventionally used additives or solvents such as dye transfer inhibitor, fluorescent whitening agent, foaming agent, foam inhibitor, anticorrosive, antirust, soil suspension, soil release agent, pH adjustor, fungicide, chelating agent, viscosity modifier, enzyme, enzyme stabilizer, perfume, fiber softener, peroxide, peroxide stabilizer, fluorescence agent, coloring agent, foam stabilizer, lustering agent, bleaching agent, anddye. One or two ormore species of themmaybe contained. The content may be appropriately determined depending on needed performance and the like.
  • the water-soluble polymer of the present invention has the above-mentioned configuration, and therefore has excellent adsorptivity, dispersibility, and safety as well as excellent hydrophilicity. Also, the water-soluble polymer can sufficiently prevent coloring. Therefore, the water-soluble polymer can be preferably used in various applications as well as in detergent additives; dispersants for various inorganic or organic substances; scale inhibitors. Particularly if the water-solublepolymer is used in a detergent additive application, the detergent additive can sufficiently prevent transfer, redeposition due to hydrophobic soils, coloring and the like, and thereby exhibit high detergency.
  • the obtained polymer 1 was measured for residual amount of the N-vinylpyrrolidone, b value, and anti-soil redeposition ratio by the above-mentionedmethods .
  • Table 2 shows the results .
  • a polymer 2 was obtained in the same manner as in Example 1, except that polyethylene glycol (product of Wako Pure Chemical Industries, Ltd. ) with a number average molecular weight of 3000 was used in place of the polyethylene glycol (product of Wako Pure Chemical Industries, Ltd. ) with a number average molecular weight of 1000.
  • the obtained polymer 2 was measured for residual amount of the N-vinylpyrrolidone, b value, and anti-soil redeposition ratio by the above-mentionedmethods . Table 2 shows the results .
  • Example 3 A polymer 3 was obtained in the same manner as in Example 1> except that secondary dodecanol to which 50 mole of ethylene oxide was added, was used in place of the polyethylene glycol (product of Wako Pure Chemical Industries, Ltd.) with a number average molecular weight of 1000. The obtained polymer 3 was measured for residual amount of the N-vinylpyrrolidone, b value, and anti-soil redeposition ratio by the above-mentionedmethods . Table 2 shows the results .
  • Example 4 Into apolymerization container equippedwith a condenser, a nitrogen inlet line, and a thermometer was added 400 parts by weight of polyethylene glycol (product of Wako Pure Chemical Industries, Ltd.) with a number average molecular weight of 3000 and 100 parts by weight of N-vinylpyrrolidone. The inside of the polymerization container was made to be nitrogen atmosphere by introduction of nitrogen.. The polymerization container was heated in an oil bath until the temperature inside the polymerization container reached 135°C. Under stirring, 2.25 parts by weight of di-t-butyl peroxide (product of Kayaku Akuzo Corp., trade name "Kayabutyl D”) was added. Then, the stirring was kept for another hour under heating at 135°C to obtain a polymer 4.
  • di-t-butyl peroxide product of Kayaku Akuzo Corp., trade name "Kayabutyl D
  • the obtained polymer 4 was measured for residual amount of the N-vinylpyrrolidone, b value, and anti-soil redeposition ratio by the above-mentionedmethods. Table 2 shows the results.
  • Comparative Example 1 Into apolymerization container equippedwith a condenser, a nitrogen inlet line, and a thermometer was added 400 parts by weight of secondary dodecanol to which 50 mole of ethylene oxide was added. The inside of the polymerization container was made to be nitrogen atmosphere by introduction of nitrogen. The polymerization container was heated in an oil bath until the temperature inside the polymerization container reached
  • the obtained polymer 6 was measured for residual amount of the N-vinylpyrrolidone, b value, and anti-soil redeposition ratio by the above-mentionedmethods. Table 3 shows the results .
  • Apolymer 7 was obtained in the samemanner as in Comparative Example 1, except that the reaction temperature was 150°C.
  • the obtained polymer 7 was measured for residual amount of the N-vinylpyrrolidone, b value, and anti-soil redeposition ratio by the above-mentionedmethods .
  • Table 3 shows the results .
  • the inside of the polymerization container was made to be nitrogen atmosphere by introduction of nitrogen.
  • the polymerization container was heated in an oil bath until the temperature inside the polymerization container reached 105°C. Then, the mixture was stirred for 1 hour to obtain a polymer 8.
  • the obtained polymer 8 was measured for residual amount of the N-vinylpyrrolidone, b value, and anti-soil redeposition ratiobythe above-mentionedmethods .
  • Table 3 shows the results . [Table 2]
  • the water-soluble polymer of the present invention has the above-mentioned configuration, and therefore has excellent adsorptivity, dispersibility, and safety as well as excellent hydrophilicity. Also, the water-soluble polymer can sufficiently prevent coloring. Therefore, the water-soluble polymer can be preferably used in various applications as well as in detergent additives; dispersants for various inorganic or organic substances; scale inhibitors. Particularly if the water-solublepolymer is used in a detergent additive application, the detergent additive can sufficiently prevent transfer, redeposition due to hydrophobic soils, coloring and the like, and thereby exhibit high detergency.

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Abstract

La présente invention a pour objet : un polymère hydrosoluble dont les propriétés de pouvoir adsorbant, de dispersibilité et de sûreté, de même que son caractère hydrophile, sont excellentes, et qui est susceptible d'empêcher de façon suffisante l'apparition d'une coloration, préférentiellement employé, par exemple, en tant qu'adjuvant pour détergents ; une application dudit polymère ; une méthode de synthèse dudit polymère hydrosoluble, ladite méthode de synthèse permettant d'obtenir un tel polymère hydrosoluble de façon efficace. La présente invention a spécifiquement pour objet un polymère hydrosoluble obtenu par une réaction de polymérisation d'un polyéther (A) avec un composant monomère contenant une N-vinylpyrrolidone (B), ladite N-vinylpyrrolidone (B) étant présente à une teneur comprise entre 0,01 et 0,3 parts en masse pour 1 part en masse de polyéther (A).
PCT/JP2006/311672 2005-06-06 2006-06-05 Polymère hydrosoluble, méthode de synthèse dudit polymère, et application dudit polymère WO2006132385A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007111378A1 (fr) * 2006-03-24 2007-10-04 Nippon Shokubai Co., Ltd. Polymère greffé présentant un groupe hydrocarboné et procédé servant à produire celui-ci
US10273185B2 (en) 2014-06-20 2019-04-30 3M Innovative Properties Company Repair compound and methods of use
EP3385313A4 (fr) * 2015-12-02 2019-07-10 Nippon Shokubai Co., Ltd. Film hydrosoluble et son procédé de fabrication

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Publication number Priority date Publication date Assignee Title
JP6986863B2 (ja) * 2017-06-07 2021-12-22 株式会社日本触媒 グラフト重合体
WO2018225680A1 (fr) * 2017-06-07 2018-12-13 株式会社日本触媒 Polymère greffé
JP6990062B2 (ja) * 2017-08-04 2022-01-12 株式会社日本触媒 グラフト重合体
CN116496444B (zh) * 2023-06-28 2023-09-22 上海宇昂水性新材料科技股份有限公司 一种聚乙烯吡咯烷酮共聚物及其制备方法和应用

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JP2001106743A (ja) * 1999-07-30 2001-04-17 Nippon Shokubai Co Ltd グラフト重合体、その製造方法およびそれを用いた用途
JP2001226441A (ja) * 2000-02-14 2001-08-21 Nippon Shokubai Co Ltd 親水性グラフト重合体
JP2001294616A (ja) * 2000-02-10 2001-10-23 Nippon Shokubai Co Ltd アミノ基含有重合体（塩）およびその製造方法
WO2002018526A1 (fr) * 2000-08-30 2002-03-07 Basf Aktiengesellschaft Utilisation d'oxydes de polyalkylene greffes en tant que substances empechant les matieres textiles de grisailler lors du lavage
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JPH03177406A (ja) * 1989-11-22 1991-08-01 Rohm & Haas Co 生分解性の水溶性グラフト共重合体
JP2001106743A (ja) * 1999-07-30 2001-04-17 Nippon Shokubai Co Ltd グラフト重合体、その製造方法およびそれを用いた用途
JP2001294616A (ja) * 2000-02-10 2001-10-23 Nippon Shokubai Co Ltd アミノ基含有重合体（塩）およびその製造方法
JP2001226441A (ja) * 2000-02-14 2001-08-21 Nippon Shokubai Co Ltd 親水性グラフト重合体
WO2002018526A1 (fr) * 2000-08-30 2002-03-07 Basf Aktiengesellschaft Utilisation d'oxydes de polyalkylene greffes en tant que substances empechant les matieres textiles de grisailler lors du lavage
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WO2007111378A1 (fr) * 2006-03-24 2007-10-04 Nippon Shokubai Co., Ltd. Polymère greffé présentant un groupe hydrocarboné et procédé servant à produire celui-ci
US8957163B2 (en) 2006-03-24 2015-02-17 Nippon Shokubai Co., Ltd. Graft polymer with hydrocarbon group and method for producing the same
US10273185B2 (en) 2014-06-20 2019-04-30 3M Innovative Properties Company Repair compound and methods of use
US10894742B2 (en) 2014-06-20 2021-01-19 3M Innovative Properties Company Repair compound and methods of use
US11713278B2 (en) 2014-06-20 2023-08-01 3M Innovative Properties Company Repair compound and methods of use
EP3385313A4 (fr) * 2015-12-02 2019-07-10 Nippon Shokubai Co., Ltd. Film hydrosoluble et son procédé de fabrication

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