WO2008029484A1 - Additives for a body cleansing agent and body cleansing agents - Google Patents
Additives for a body cleansing agent and body cleansing agents Download PDFInfo
- Publication number
- WO2008029484A1 WO2008029484A1 PCT/JP2006/317918 JP2006317918W WO2008029484A1 WO 2008029484 A1 WO2008029484 A1 WO 2008029484A1 JP 2006317918 W JP2006317918 W JP 2006317918W WO 2008029484 A1 WO2008029484 A1 WO 2008029484A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- cleansing agent
- salt
- additive
- body cleansing
- Prior art date
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
-
- 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
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
-
- 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
Definitions
- the present invention relates to additives for a body cleansing agent" such as shampoo, body soap, hand soap, and soap, wherein the additives for ' the body cleansing agent capture Ca ions in water and are excellent in dispersibility of dirt.
- a body cleansing agent such as shampoo, body soap, hand soap, and soap
- Chelating agents are often added to a body cleansing agent to capture Ca ions in water. Because Ca ions in water bond with surfactants, which are cleansing components, they produce Ca chlorides'which are ' insoluble in water, causing the squeaky feeling of the hair and stiff feeling s o£ the skin at cleansing and after cleansing, and damaging the hair and the ! skin, and further, because the lathering action and cleansing 1 action of the chelated surfactant decrease, the chelating agents, which can prevent bonding of the surfactants and Ca ions, are added.
- ethylene diamine tetraacetic acid (EDTA) and its salt 1 ! are often used as chelating agents, however, EDTA is limited in its ability to' ' ⁇ capture Ca ions, and needless to say, the EDTA has neither a cleansing effect ' itself to clean dirt nor an effect to prevent re-deposition of the dirt by dispersing the cleaned dirt. Further, there are compounds among lowmolecular chelating agents such as EDTA, for which theVe''axe ; cb ⁇ cer ⁇ s about the point of toxicity.
- a dispersant having the roles of preventing ⁇ * ? re-deposition by stably dispersing a dirt component wrapped" wi ' th' a * ! surfactant in water and washing away the dirt component' ⁇ V ⁇ thHva'tef is blended in the body cleansing agent.
- a composition for shampoo using an anionic dispersant such as a polymer c ⁇ ' ⁇ feistMg' ⁇ f' ⁇ crylic' ,acid and 2-methacrylamide-2-propanesulfonic acid is discI ⁇ ' sM' ⁇ W Japanese Patent Application LaidOpen No. 2001-106616 (for example,' [OO ' W Ktt)45] 1 , etc.) .
- the object of the present invention is to discover an optimal ⁇ additive'for ⁇ se in a body cleansing agent which is excellent in dispersibilitybf 'dirtf nas !
- Another object of the presentlnventioto is to provide aibody cleansing agent which lathers well even in u fiWfU w&tS'r a ⁇ rid'is" excellent ,in cleansing characteristics by discovering such. an 'additive.*
- the additive for a body cleansing agent in the present invention is a carboxylic acid-based copolymer having a weight-average molecular weight of 3000 to 30000 including a constituting unit (a) that is originated from an unsaturated monocarboxylic acid (salt) (meaning itself or its' salt from now on) monomer, and a constituting unit (b) that is originated from an unsaturated dicarboxylic acid (salt) monomer, wherein Ca ion-capturing ability of, the carboxylic acid-based copolympr is 300 mg CaCOa/g or more.
- above -described constituting unit (b) is preferably 80 mol% or ⁇ more in a constituting unit of the above-described carboxylic acid-based copolymer d00 > ⁇ mol%, and when the total amount of the above ⁇ described constituting unit (a) and the above-described constituting unit (b) is made to be 100 mol%, the
- above -described constituting unit (b) is preferably from 25 to '60 mol%.
- an additive is a copolymer of acrylic acid >* as an unsaturated monocarboxylic acid (salt) monomer and maleic acid as an unsaturated dicarboxylic acid (salt), monomer is the most preferable embodiment of the present invention.
- the present invention ' includes a body cleansing agent containing the above-described additives for a body cleansing agent.
- thejnresent invention includes a ' method of manufacturing a body cleansing agent containing the
- the above-described carboxylic acid-basedcopolymer shows fgood ' performance as a dispersant in a body cleansing agent and as 'a' Ga ion scavenger. Therefore, the present invention was able to provided body cleansing agent without re-deposition of a dirt component ho the hair and the skin, showing excellent cleansing power, having a good lathering nature, and without the squeaky feeling of the hair and stiff feeling of the skin.”
- the additive for a body cleansing agent in the present invention 1 is a ⁇ carboxylic acid -based copolymer, wherein the main constituting units ⁇ f thecopolymer are a constituting unit (a) that is originated from an" ! unsaturated monocarboxylic acid (salt) monomer, and a constituting unit (b) that is originated from an unsaturated dicarboxylic acid (salt) moiiomer ' '
- the carboxylic ' f acid-based copolymer is preferably 80 mol% or more in the'to'tarconstituting' unit of 100 mol% of the copolymer.
- the total amount'of both units is > less than 80 mol%, the amount of the carboxyl group in the carboxylic ' acid-based copolymer decreases and there is concern that the Gd' ion w capturing ability may not become 300 mg CaCOs/g or more ⁇ ⁇ '
- the total * amount of the constituting unit (a) and the above-described ⁇ constituting unit ' (b) is the more the better, more preferably that the lower limit is !
- the unsaturated monocarboxylic acid (salt) monomer mentioned iii the present invention means a carboxylic acid having one ethylenic double 1 ' bond (unsaturated bond) and one carboxyl group, and its kalt.
- ' Preferred examples are acrylic acid, methacrylic acid, and ⁇ -hydroxyacrylie acid, and two kinds or more may be mixed and used. Among these examples; acrylic acid is the most preferred.
- the unsaturated dicarboxylic acid (salt) monomer mention d in the present invention is a carboxylic acid having one ethylenic 1 double" bond 1 (unsaturated bond) and two carboxyl groups, and its salt, 1 and may be "an l ' anhydride.
- Examples include maleic acid, itaconic acid, fumarid acid,' ⁇ crotonic acid, and citraconic acid, and two kinds or more may be used! Among these examples, maleic acid is the most preferred.
- the carboxyl group in the above -de scribed carboxylic acid'-Based v( 2 copolymer may be free or may be a salt.
- the salt is formed ⁇ it is preferable "to form the salt with compounds including alkali metals such' as Na 1 * and K, ' ' ' organic amines such as ammonia, monoethanolamine and tridtha ⁇ blamine, etc. Furthermore, formation of the salt may be performed at any point of time which is either before polymerization,- during polymerization,' or after polymerization.
- the carboxylic acid-based copolymer when the total amount of the constituting unit (a) originated from an unsaturated mohbiiafboX ⁇ lie acid 15 ⁇ (salt), monomer and the constituting unit ⁇ (b) originated fr ⁇ rtr 1 an unsaturated dicarboxylic acid (salt) monomer is made to be 100 mol%,' the "constituting unit,(b) originated from an unsaturated dicarboxylic acid ( ⁇ alt) monomer is preferably from 25 to 60 mol%.
- the lower limit is more preferably 30 mol%
- the lower limit ' is 'further ⁇ preferably 40 mol%
- the upper limit is more preferably 55 mbl%.
- the preferred range of .the constituting unit (a) originated from an' unsaturated monocarboxylic acid (salt) monomer is from 40 to 75 mol%dn'' ⁇
- the lower 1 limit is more * i( ' > preferably 45 mol%, the upper limit is more preferably 70 mol%, and ! the' > " upper limit is further preferably 60 mol%.
- the total amount of the above-described unsaturated monocarboxylic acid (salt) monomer and the above-described Unsaturated " dicarboxylic acid (salt) monomer is adjusted to be 80 mol ⁇ 'or more 'ill the raw materials mixture of 100 mol% in the synthesis of the copolymer,- and '
- the ( amount of the unsaturated dicarboxylic acid, (salts) monomer is" 'adjusted 1 ' ' to be from 25 to 60 mol% of the total amount of the unsaturated !) monocarboxylic acid (salt) monomer and the unsaturated dicarboxylie acid s • 11 (salt) monomer of 100 mol%.
- ⁇ * dicarboxylie acid (salt) monomer may be used if the amount-is from 0 to QQ "> mol% in the raw materials mixture of 100 mol% in the synthesis ⁇ of the ⁇ s carboxylic acid-based copolymer in the present invention.
- ⁇ ⁇ Examples of . these monomers are kinds of monomers as> follows. '
- Examples include styrene; styrenesulfonic acid! vinyl acetate; ⁇ (meth)acrylonitrile; (meth)acrylamide; methyl(meth)acrylate ⁇ ethyl(meth)acrylate; buthyl(meth)acrylate; 2 w ethylhexyl(m'ethi)acryla n te; . ⁇ t dimethylaminoethyl(meth)acrylate> 'diethylaminoethyKme'tlOacrylate; allyb r > !
- a monomer including polyalkylene glycol can be used.
- Examples ⁇ 1 [ include ,polyalkylene glycol (meth)acrylic ester, allylalcohol polyalkyleneoxide adduct, and 3-methyl-3-butend-l-olalkylene ⁇ xide " add ⁇ cts, and polyethylene glycol and polyethylene oxide are ⁇ preferablfe(as» i polyalkylene glycol or alkyleneoxide.
- the weight-average molecular weight (Mw) of the carboxylic » ' acid -based copolymer in the present invention is from 3000 to 30000. tff it is in this range, the copolymer is easily dissolved in a body cleansing agent, the
- the Ca ion-capturing ability of the carboxylic acid-based ' copolymer in the present invention is 300 mg CaCO ⁇ /g orynore 5 .
- ' ' When > ⁇ thecopolymer has such a high Ca ion-capturing ability, thfecopolymer ⁇ shows excellent performance as a chelating agent. > It is more preferably 310 mg CaC ⁇ 3/g or more, further preferably 320 mg CaOO ⁇ /g or more; and the most ' preferably 350 mg CaCOe/g or more.
- the measuring method of the Ca ion-capturing ability is that the precisely weighted carboxylic acid-based copolymer is added to an aqueous solution of a fixed 1 Ca ion concentration, Ca ions are captured by the copolymer, and 1 after this, the Ca ion concentration remaining in the aqueous solution is obtained with a ⁇ method such as a titration, and the Ca ion-capturing ability is obtained by > ' calculating the decrease.
- the Ca-ionf ⁇ apturing " ability is shown by a mg number calculated in terms 'of calcium” carbonate' as • ; o the captured amount of Ca ions per 1 g ofcopolymer (a sol ⁇ ld 'cb ⁇ erit): ' ⁇ ⁇
- the carboxylic acid "based copolymer in the present 'invention is ⁇ exeellent in dispersibility.
- clay'd ⁇ spersibility evaluated! by 1 a-' measuring method described later is, adopted as a standard of dispersibility;
- the clay dispersibility of the carboxylie acidrbased copolymer in 'the' present invention is preferably 0.3 or more;
- The. clay dispersibility' is 'more . preferably 0.4 or more, further preferably 0.5 or more, 'and' tine ⁇ idst 1 ⁇ ; preferably 0.6 or more.
- the polymerization method of , the above-described carboxyl ⁇ c ' acid-based copolymer is not especially limited,, and for exataple ; a ; methbdH conventionally known can be used.
- examples' of p ⁇ lyti ⁇ eriza-tibnr' l include, in water, in organic solvent, and in a mixed solvent i)f'#ater 'soluble 0 > (J organic solvent and water, and the like.
- the catalyst 1 which can ⁇ be ws : . Used in these polymerizations is not especially limited, examples of theP - .catalyst include persulfate and hydrogen peroxide, and thes# can be' lis'ed I .
- an, accelerator such as sulfurous hydrogen ; saltii ⁇ d a!scbrbi:c ;U; , acid.
- an azoibased initiator and ⁇ an organic ⁇ ' peroxide can be 1 used and, these can be used together with'aln'actfelera'to ⁇ siich ⁇ * as amine compounds.
- a chain transfer agent such as merc ' a'pt ⁇ eth'anol, >. mercap topropionate*.
- sodium hypophosphite may be us ⁇ d ⁇ as a ⁇ mcidifier ⁇ f > ⁇ : .the .molecular weights , r .Because; the: above-described- carboxy lie .acid -based copolymer ! ; i ⁇ -'a#' ⁇ ; ' --*- additive for a body cleansing agent,; itis used .by. being added to ⁇ he ⁇ bddy' : ' ⁇ y l* - ⁇ ef cleansing agent.
- a body cleansing agent to which the additive for a body cleansing agent in the present invention (a carboxylic acidrbased copolymer) was added is also included in the present invention.
- the main component of the body cleansing agent is a surfactant, and it least one kind of surfactant from an»anionic surfactant,? a'noionic ⁇ ⁇ surfactant, a cationic surfactant, and an amphoteric surfactant tcan be used *
- anionic surfactant examples include alkylbenzenesulfonate, alkyl or alkenyl ethersulfate, alkyl 'or alkenyl sulfate, > ⁇ -olefinsulfonate, crsulfofatty acid or ester salt, alkanesulf ⁇ nate, saturated or unsaturated fatty acid salt, alkyl or alkenylethercarboxylate, amino acid ' type surfactant, N-acylamino acid type surfactant, and alkyl or alkenyl phosphoric ester and its salt.
- An alkyl chain and an alkenyl chain of these anionic surfactants may be branched with an additional alkyl group such a's a methyl group, i
- nonionic surfactant examples include polyoxyalkylenealkyl or alkenyl ether, polyoxyethylenealkyiphenylether, higher fatty acid alkanolamide or its alkyleneoxide adduct, sucrose fatty acid ester, alkyl glucoside, fatty acid glycerin monoester, and alkylamffne oxide.
- alkyl group such as a methyl group can be branched in the middle iof an alkyl group and an alkenyl group of these noionic surfactants, i '
- cationic surfactant examples include quaternary ammonium salt and the like.
- an a'mphotexic surfactant ' ⁇ include a betaine type, a glycine type, an alanine type, and 1 a s ⁇ lfobetaine type amphoteric surfactant and the like.
- An alkyl group ⁇ uch as a methyl ? group can be branched in the middle of an alkyl group andean (alkenyl group 1 of these cationic surfactants and amphoteric surfactants. ' '
- the compound ratio of the surfactant included in the body 'cleansing agent in the present invention is preferably from O.L to 50% b ⁇ ma'ssOfthe l body cleansing agent. It is more preferably from 1 to 45% ⁇ 3y mass, and x further preferably from 10 to 40% by mass.
- the compounded ⁇ ratioi of ( the surfactant is less than 0.1% by mass,' there is concern .that' the washing * power becomes insufficient, and when it exceeds 50% by mass, the ( economical efficiency decreases. '
- the additive for a body cleansing agent is preferably from 0;l?to*40 ⁇ % by mass of the body cleansing agent. This is because it can showijus't ' enough of the Ca ion-capturing ability and function as a dispersant if in this range. * It is more preferably from 0.3 to 20% by mass, further preferably, from 0.4 to' 15% by mass, and most preferably from 0.5 to»l ⁇ 0% byimass. ⁇
- the above-described body cleansing agent ordinarily includes water besides, the additive in the present invention and the above-described ⁇ surfactant. Further, any other components known in the ⁇ field of'body cleansing agents such as shampoo, body soap, hand soap, * and soap, may be included. However, because the above-described additive® for. a body? ⁇ cleansing agent in the present invention function as a disptersanfrand ⁇ a chelating agent, there is no need'to add a dispersant and a chelating agent 1 separately, but a small amount of the addition is not excluded?
- cationic (co) polymers such as polypropylene 1 glycol/ saccharides, viscosity adjusters,' antibacterial agents, alkaMne mateial to* , adjust pH, aromaj solubilizing agentsj pigmenting agentSj' €TVI abs'o'rbers, ' !;? ' ⁇ : ⁇ ' ⁇ dandruff inhibitors, and solvents.
- test tube was kep"t ; stl!l;lfin r a''dar]s* • ⁇ * t; place for 20 hours.
- 5 cc. of supernatant of th'e ⁇ test sblt ⁇ iOh- • was taken and the absorbaneei was measured-, with UV spe'c'tfo f gi?a!p'h an ⁇ i Jie H ⁇ ! (manufactured by Shimadzu Corporation! UV- 1200; 1 cm cell and' i ( wavelength 380 run). This absorbance becomes the clay dispetsibility as it
- Example 1 i A'carboxylic acid-based copolymer -having. acylic acid / maleie acid of 1 5OJ 50 in mole ratio was synthesized. , Deionized water 385iO ! ⁇ , 48% NaOH* aqueous solution 333.3 g, and maleic anhydride 196 g were/prepared in 1 a separable flask manufactured by SUS of l f ⁇ ter> capacity equipped with 1 a thermometer ⁇ ant agitator, and' a reflux, condenser, and the aqueous solution in' the flask was raised to a refluxing condition a ⁇ boiling point while being
- a carboxylic acid-based copolymer having acylic acid / maleic acid of 52 / 48 in mole ratio was synthesized.
- Pure water 166.8 -gj 48% 'Na ⁇ H aqueous solution 332.5 g, and maleic anhydride 205.8 g were ⁇ preparedHn a separable flask manufactured by SUS of 2.5 lit ⁇ r capacity equipped'w ⁇ th a thermometer, an agitator, and a reflux condenser, and the ⁇ aq'uebus solution in the flask was raised to a refluxing condition at boiling point While being stirred.
- a polyacrylic acid was ⁇ «sycnthesized. Pure water 56O g was Jpfe ⁇ p'ared in a separable flask manufactured by SUS of 2:5 liter capacity equipped with a thermometer, an agitator, and a reflux condenser, and the 'solution in the flask was raised to a refiuxing condition at boiling point while being stirred. Then, while stirring and keeping the refiuxing condition, using a separate drop nozzle, 80%.acylic.
- a carboxylic ⁇ acid-based copolymer! having acylic acid / maleic acid of 70/ 30, in mole ratio was synthesized.
- Pure water 288.7 g, 48% NaOH aqueous solution 250 g, and maleic anhydride 147 g were -prepared in a .separable flask manufactured by SUS of 2:5 liter capacity equipped with a thermometer, an agitator, and a reflux condenser, and the aqueotts solution , in the flask was raised to a refiuxing condition at boiling poliit while' being' stirred.r : ⁇ Thenj iwhile ; stirring and keeping the refluxing condition, using a separate drop nozzle, 80% acylic acid aqueous solution 3 ⁇ 5 gVl5% Sodium persulfate aqueous solution 66.7 g, and pure water 160 g were 'started 1; ⁇ ?
- Example * ⁇ ! to Example 5 Using the carboxylic acid-based copolymers No. 1 to No. 5 (Example * ⁇ ! to Example 5), No. 6, and No. 7 (Comparative Example 1 and 2) obtained ⁇ he " above-described examples and comparative examples, as described 'above, the Ca ion-capturing ability, the clay dispersib ⁇ ity, and tHe'compktirali ⁇ tyib a' body cleansing agent were evaluated. The result is shown' in Table 1. u !
- Citric acid 3Na ' : 220 o ' ⁇ ' ⁇ • • Example 4 ⁇ ⁇ ,l . ' ⁇ t
- acid -based copolymer) in the present invention is excellent in Ca ion;capj;uring ability and the dispersion effect of dir% it is'useful as ari additive for body cleansmg agents such as a shampoo, body' ⁇ dapy hand soap,.; and soap.
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Dermatology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
To discover an optimal additive for use in a body cleansing agent which is excellent in dispersibility of dirt, has a high Ca ion-capturing ability, and can perform as a dispersant and a chelating agent. Further, by discovering such an additive, a body cleansing agent which lathers well even in hard water and is excellent in cleansing characteristics is provided. The additive for a body cleansing agent in the present invention is a carboxylic acid-based copolymer comprising a constituting unit (a) that is originated from an unsaturated monocarboxylic acid (salt) monomer and a constituting unit (b) that is originated from an unsaturated dicarboxylic acid (salt) monomer, having the weight average molecular weight of 3000 to 30000, wherein the Ca ion-capturing ability of the carboxylic acid-based copolymer is 300 mg CaCO3/g or more.
Description
DESCRIPTION
ADDITIVES FOR A BODY CLEANSING AGENT AND BODY CLEANSING
AGENTS
TECHNICAL FIELD
The present invention relates to additives for a body cleansing agent" such as shampoo, body soap, hand soap, and soap, wherein the additives for ' the body cleansing agent capture Ca ions in water and are excellent in dispersibility of dirt.
BACKGROUND ART
Chelating agents are often added to a body cleansing agent to capture Ca ions in water. Because Ca ions in water bond with surfactants, which are cleansing components, they produce Ca chlorides'which are ' insoluble in water, causing the squeaky feeling of the hair and stiff feeling so£ the skin at cleansing and after cleansing, and damaging the hair and the ! skin, and further, because the lathering action and cleansing1 action of the chelated surfactant decrease, the chelating agents, which can prevent bonding of the surfactants and Ca ions, are added.
Conventionally, ethylene diamine tetraacetic acid (EDTA) and its salt1 ! are often used as chelating agents, however, EDTA is limited in its ability to' '< capture Ca ions, and needless to say, the EDTA has neither a cleansing effect ' itself to clean dirt nor an effect to prevent re-deposition of the dirt by dispersing the cleaned dirt. Further, there are compounds among
lowmolecular chelating agents such as EDTA, for which theVe''axe;cbϋcerώs about the point of toxicity.
Incidentally, a dispersant having the roles of preventing ■* ? re-deposition by stably dispersing a dirt component wrapped" wi'th' a* ! surfactant in water and washing away the dirt component'ΛVϊthHva'tef, is blended in the body cleansing agent. For example, a composition for shampoo using an anionic dispersant such as a polymer cδ'ήfeistMg'όf'έϋcrylic' ,acid and 2-methacrylamide-2-propanesulfonic acid is discIά'sM'ϊW Japanese Patent Application LaidOpen No. 2001-106616 (for example,' [OO'W Ktt)45]1, etc.) . In the Japanese Patent Application Laid-Open NolJ2Oθl- iθ66Ϊ6 J(fόr' ' example, [0040], [0045], etc.), furthermore, a chelating agent1 ύiiϋh. as' EDTA-sodium is added.
DISCLOSURE OF THE INVENTION ! Means for Solving the Problem
In the conventional art as described above, a dispersant ami1 a"3 (" chelating agent are required to be added separately, but wh^n^iPadldltiveΥor a body cleansing agent which can perform as a dispersan1?aή'd' a 'chelating 4'*1 agent is discovered, the only one process is required to blόήd^hό'sό kge'nijs^ and thus reduces raw materials resulting in cost reduction"'1 Accordingly1, ' the object of the present invention is to discover an optimal^additive'for^ύse in a body cleansing agent which is excellent in dispersibilitybf 'dirtf nas!alw high Ca ion-capturing ability, and can perform as a dispersWώ aM !al l chelating agent. Furthermore, another object of the presentlnventioto is to provide aibody cleansing agent which lathers well even inufiWfU w&tS'r a^rid'is"
excellent ,in cleansing characteristics by discovering such. an 'additive.*
The additive for a body cleansing agent in the present invention is a carboxylic acid-based copolymer having a weight-average molecular weight of 3000 to 30000 including a constituting unit (a) that is originated from an unsaturated monocarboxylic acid (salt) (meaning itself or its' salt from now on) monomer, and a constituting unit (b) that is originated from an unsaturated dicarboxylic acid (salt) monomer, wherein Ca ion-capturing ability of, the carboxylic acid-based copolympr is 300 mg CaCOa/g or more. i The total amount of the above-descrihed constituting uniti(a) and the *'
' above -described constituting unit (b) is preferably 80 mol% or<more in a constituting unit of the above-described carboxylic acid-based copolymer d00 > < mol%, and when the total amount of the aboveτdescribed constituting unit (a) and the above-described constituting unit (b) is made to be 100 mol%, the
, above -described constituting unit (b) is preferably from 25 to '60 mol%. Further, an embodiment in which an additive is a copolymer of acrylic acid >* as an unsaturated monocarboxylic acid (salt) monomer and maleic acid as an unsaturated dicarboxylic acid (salt), monomer is the most preferable embodiment of the present invention. Furthermore, the present invention ' includes a body cleansing agent containing the above-described additives for a body cleansing agent. Furthermore, thejnresent invention includes a ' method of manufacturing a body cleansing agent containing the
, above-described additive for a body cleansing agent and surfactant are mixed.
Effect of, the Invention <
The above-described carboxylic acid-basedcopolymer shows fgood ' performance as a dispersant in a body cleansing agent and as 'a' Ga ion scavenger. Therefore, the present invention was able to provided body cleansing agent without re-deposition of a dirt component ho the hair and the skin, showing excellent cleansing power, having a good lathering nature, and without the squeaky feeling of the hair and stiff feeling of the skin."'5
BEST MODE FOR CARRYING OUT THE INVENTION ! < ' ' The additive for a body cleansing agent in the present invention1 is a < carboxylic acid -based copolymer, wherein the main constituting units øf thecopolymer are a constituting unit (a) that is originated from an" ! unsaturated monocarboxylic acid (salt) monomer, and a constituting unit (b) that is originated from an unsaturated dicarboxylic acid (salt) moiiomer ' ' The total amount of the constituting unit (a) originated from an* unsaturated monocarboxylic acid (salt) monomer and the constituting unit (b)*originated ! from an unsaturated dicarboxylic acid (salt) monomer in the carboxylic ' f acid-based copolymer is preferably 80 mol% or more in the'to'tarconstituting' unit of 100 mol% of the copolymer. When the total amount'of both units is > less than 80 mol%, the amount of the carboxyl group in the carboxylic ' acid-based copolymer decreases and there is concern that the Gd' ionwcapturing ability may not become 300 mg CaCOs/g or more\ ■' The total * amount of the constituting unit (a) and the above-described^ constituting unit ' (b) is the more the better, more preferably that the lower limit is!90 mol%, and the most preferably that thecopolymer consists of only the constituting" unit (a) and the constituting unit (b).
The unsaturated monocarboxylic acid (salt) monomer mentioned iii the present invention means a carboxylic acid having one ethylenic double1 ' bond (unsaturated bond) and one carboxyl group, and its kalt. ' Preferred examples are acrylic acid, methacrylic acid, and α-hydroxyacrylie acid, and two kinds or more may be mixed and used. Among these examples; acrylic acid is the most preferred.
The unsaturated dicarboxylic acid (salt) monomer mention d in the present invention is a carboxylic acid having one ethylenic1 double" bond1 (unsaturated bond) and two carboxyl groups, and its salt,1 and may be "an l' anhydride. Examples include maleic acid, itaconic acid, fumarid acid,' ι crotonic acid, and citraconic acid, and two kinds or more may be used! Among these examples, maleic acid is the most preferred.
The carboxyl group in the above -de scribed carboxylic acid'-Based v( 2 copolymer may be free or may be a salt. '.Although it may he* a partial salt type in which a part of the carboxyl group is a salt or a full salt'typέ in3 which all parts of the carboxyl group are a salt, considering the ϊmpOrtance of the* Ca ion-capturing ability of the additives in the present invention', salts 'of Ca' ' and Mg are not preferred. Therefore, if the salt is formed^it is preferable "to form the salt with compounds including alkali metals such' as Na1 *and K, ' ' ' organic amines such as ammonia, monoethanolamine and tridthaήblamine, etc. Furthermore, formation of the salt may be performed at any point of time which is either before polymerization,- during polymerization,' or after polymerization.
As for the carboxylic acid-based copolymer, when the total amount of the constituting unit (a) originated from an unsaturated mohbiiafboX^lie acid15 ^
(salt), monomer and the constituting unit<(b) originated frόrtr1 an unsaturated dicarboxylic acid (salt) monomer is made to be 100 mol%,' the "constituting unit,(b) originated from an unsaturated dicarboxylic acid (δalt) monomer is preferably from 25 to 60 mol%. Although the more the constituting units (b) originated from an unsaturated dicarboxylic acid (salt) monomer there are, the more the amount of the carboxyl group per unit mass of the catffcoxylic < acid-based copolymer there can be, and the< Ca ion-capturing ability'improves, and further, because the unsaturated dicarboxylic acid (salt) monomer is i ! difficult to be polymerized, in order to obtain a carboxylic acid-b'ased copolymer of a preferred molecular weight described later,1 it is desirable to < • adjust the amount of the constituting units (b) to the above-described- range.'1 The lower limit is more preferably 30 mol%, the lower limit' is 'further < preferably 40 mol%, and the upper limit is more preferably 55 mbl%. ( ' The'n, the preferred range of .the constituting unit (a) originated from an' unsaturated monocarboxylic acid (salt) monomer is from 40 to 75 mol%dn'' ■
> the above-described total .amount of 100 mol%. The lower1 limit is more * i( ' > preferably 45 mol%, the upper limit is more preferably 70 mol%, and!the' > " upper limit is further preferably 60 mol%. i In order to set the amount of the constituting unit (a) and (b) in the1 ' carboxylic acid-based copolymer of the present invention to the ' abover described range, the total amount of the above-described unsaturated monocarboxylic acid (salt) monomer and the above-described Unsaturated " dicarboxylic acid (salt) monomer is adjusted to be 80 mol^'or more 'ill the raw materials mixture of 100 mol% in the synthesis of the copolymer,- and '
, the ( amount of the unsaturated dicarboxylic acid, (salts) monomer is" 'adjusted1 '
' to be from 25 to 60 mol% of the total amount of the unsaturated !) monocarboxylic acid (salt) monomer and the unsaturated dicarboxylie acid s • 11 (salt) monomer of 100 mol%.
Further, other monomers which can be polymerized with the unsaturated monocarboxylic acid (salts) monomer and/or ithe unsaturated!, < * dicarboxylie acid (salt) monomer may be used if the amount-is from 0 to QQ "> mol% in the raw materials mixture of 100 mol% in the synthesis <of the \ s carboxylic acid-based copolymer in the present invention. <■ < Examples of . these monomers are kinds of monomers as> follows. '
Examples include styrene; styrenesulfonic acid! vinyl acetate; ύ (meth)acrylonitrile; (meth)acrylamide; methyl(meth)acrylate^ ethyl(meth)acrylate; buthyl(meth)acrylate; 2wethylhexyl(m'ethi)acrylante; . ■ t dimethylaminoethyl(meth)acrylate> 'diethylaminoethyKme'tlOacrylate; allyb r> !< alcohol; 3-methyl-3-butene-l-ol; 3-methyl-2-butene-l-ol>" 2-methyl-3-butene-2"θl; 3-(meth)acryloxyr l,2-dihydroxypropane;r 1 3-(meth)acryloxy-l,2-di(poly)oxyethyleneetherpropane; 3 - (meth) acryloxy- 1,2- di(p oly)oxypropyleneetherpropane >' 3-(meth)acryloxy-l,2-dihydroxypropanephospate and its skltj orlmono iør \ ' diester of alkyl groups having 1 to 4 carbon atoms;
3-(meth)acryloxy-l,2-dihydroxypropanesulfate and its salt or ester> of ^alkyl * groups having 1 to 4 carbon atoms;
3-(meth)acryloxy-2-hydroxypropanesulfonic acid and its saltror tester oftalkyl <ι groups having 1 to 4 carbon atoms! ,
3-(meth)acryloxy2-(poly)oxyethyleneetherpropanesulfonic acidiknd itstsalt" or ester of alkyl groups having ! to 4 carbon atoms;
3-(meth)acryloxy-2-(poly)oxypropyleneetherpropanesulfonic acid and its'Salt ' or ester of alkyl groups having 1 to 4 carbon atoms; 3-allyloxypropane-l,2-dioL* 3-allyloxypropane- 1,2-diolphosp hater " 3-allyloxypropane-l,2-diolsulfonatej' 3-allyloxypropane-l,2-diolsulfate; 3-allyloχyl,2-di(poly)oxyethyleneetherprόpane; 3-allyloxyl,2-di(poly)oxyethyleneetherpropanephosphateJ ' > ^ 3-allyloxyl,2-di(poly)oxyethyleneetherpropanesulfonate; 3 - allyloxy 1,2- di(poly)oxypropyleneetherprop ane>' 3 - allyloxy 1,2- di(poly)oxypropyleneetherprop anephosphate! 3-allyloxyl,2-di(poly)oxypropyleneetherpropanesulfonate; 6-allyloxyhexane-l,2,3,4,5-pentaol; 6-allyloxyhexane-l,2,3,4,5-pentaolphosphate; 6-allyloxyhexane-li,2,3,4,5-pentaolsulfonateJ < > 6-allyloxyihexane- l,2,3,4,5-penta(poly)oxyethyleneetherhexane51 « '> 6-allyloxyhexane-l,2,3,4,5-penta(poly)oxypropyleneetherhexane,' ' 3^allyloxy2-hydroxypropanesulfonic acid and its salt, or phosphoric ester or sulfuric ester, of these compounds and their salts?
3-allyloxy2-(poly)oxyethylenepropanesulfonic acid and its salt, or phosphoric/ ester or sulfuric ester of these compounds and their salts; 3-allyloxy2-(poly)oxypropylenepropanesulfonic acid and its salty or phosphoric ester or sulfuric ester of these compounds and their salts.
, ■> A monomer including polyalkylene glycol can be used. Examples ■ 1 [ include ,polyalkylene glycol (meth)acrylic ester, allylalcohol polyalkyleneoxide adduct, and 3-methyl-3-butend-l-olalkyleneόxide"addύcts, and polyethylene glycol and polyethylene oxide are <preferablfe(as»
i polyalkylene glycol or alkyleneoxide.
■The weight-average molecular weight (Mw) of the carboxylic » ' acid -based copolymer in the present invention is from 3000 to 30000. tff it is in this range, the copolymer is easily dissolved in a body cleansing agent, the
1 dispersion effect of dirt components is shown sufficiently, further, the Ca' * < ion-capturing ability is also better. When Mw is less thani3000'or larger ( < than 20000, the dispersion effect decreases. The lower limit of TVLw is more preferably 4000. The upper limit of Mw is more preferably 20000, even more preferably 15000. Although the measuring method of the weight-average molecular weight is not especially limited, the*ύonverted ' value of sodium polyacrylate measured with GPC is adopted'in the present invention. The measuring method is described in detail later* ' '
Further, the Ca ion-capturing ability of the carboxylic acid-based ' copolymer in the present invention is 300 mg CaCOβ/g orynore5. ' 'When > <■ thecopolymer has such a high Ca ion-capturing ability, thfecopolymer^ shows excellent performance as a chelating agent. > It is more preferably 310 mg CaCθ3/g or more, further preferably 320 mg CaOOβ/g or more; and the most ' preferably 350 mg CaCOe/g or more. The measuring method of the Ca ion-capturing ability, described in detail later, is that the precisely weighted carboxylic acid-based copolymer is added to an aqueous solution of a fixed1 Ca ion concentration, Ca ions are captured by the copolymer, and1 after this, the Ca ion concentration remaining in the aqueous solution is obtained with a ■ method such as a titration, and the Ca ion-capturing ability is obtained by > ' calculating the decrease. In the present invention, the Ca-ionføapturing " ability is shown by a mg number calculated in terms 'of calcium" carbonate' as •
;o the captured amount of Ca ions per 1 g ofcopolymer (a solϊld 'cbήϊerit): ' }~
Further, the carboxylic acid "based copolymer in the present 'invention :; is^exeellent in dispersibility. When clay'dϊspersibility evaluated! by1 a-' , measuring method described later is, adopted as a standard of dispersibility; ' the clay dispersibility of the carboxylie acidrbased copolymer in 'the' present invention is preferably 0.3 or more; The. clay dispersibility'is 'more . preferably 0.4 or more, further preferably 0.5 or more, 'and' tine ήidst1 ■ ; preferably 0.6 or more.
, The polymerization method of , the above-described carboxylϊc ' acid-based copolymer is not especially limited,, and for exataple;a;methbdH conventionally known can be used. I Specifically, examples' of pόlytiϊeriza-tibnr' l include, in water, in organic solvent, and in a mixed solvent i)f'#ater 'soluble0 > (J organic solvent and water, and the like. Although the catalyst1 which can^be ws : . Used in these polymerizations is not especially limited, examples of theP - .catalyst include persulfate and hydrogen peroxide, and thes# can be' lis'ed I . together with an, accelerator (such as sulfurous hydrogen ;saltiiήd a!scbrbi:c;U; , acid). Other examples such as an azoibased initiator and^an organic ι' peroxide can be1 used and, these can be used together with'aln'actfelera'toϊ siich^ * as amine compounds. For the purpose of proceeding the reaction eϊfectϊvelyy^ I a system using persulfate or hydrogen peroxide with ascorbic: acid is ; ' * preferable. Further, a chain transfer agent, such as merc'a'ptόeth'anol, >. mercap topropionate*. and sodium hypophosphite may be us^d^as a^mcidifier όf > ^ : .the .molecular weights , r .Because; the: above-described- carboxy lie .acid -based copolymer !;iή-'a#'^;' --*- additive for a body cleansing agent,; itis used .by. being added to^he^bddy' :'^y l*-^ef
cleansing agent. A body cleansing agent to which the additive for a body cleansing agent in the present invention (a carboxylic acidrbased copolymer) was added is also included in the present invention.
The main component of the body cleansing agent is a surfactant, and it least one kind of surfactant from an»anionic surfactant,? a'noionic η \ surfactant, a cationic surfactant, and an amphoteric surfactant tcan be used*
Specific examples of the anionic surfactant include alkylbenzenesulfonate, alkyl or alkenyl ethersulfate, alkyl 'or alkenyl sulfate, > α-olefinsulfonate, crsulfofatty acid or ester salt, alkanesulfσnate, saturated or unsaturated fatty acid salt, alkyl or alkenylethercarboxylate, amino acid ' type surfactant, N-acylamino acid type surfactant, and alkyl or alkenyl phosphoric ester and its salt. An alkyl chain and an alkenyl chain of these anionic surfactants may be branched with an additional alkyl group such a's a methyl group, i
Specific examples of the nonionic surfactant include polyoxyalkylenealkyl or alkenyl ether, polyoxyethylenealkyiphenylether, higher fatty acid alkanolamide or its alkyleneoxide adduct, sucrose fatty acid ester, alkyl glucoside, fatty acid glycerin monoester, and alkylamffne oxide. ' An» alkyl group such as a methyl group can be branched in the middle iof an alkyl group and an alkenyl group of these noionic surfactants, i '
Specific examples of the cationic surfactant include quaternary ammonium salt and the like. Specific examples of an a'mphotexic surfactant ' < include a betaine type, a glycine type, an alanine type, and1 a sύlfobetaine type amphoteric surfactant and the like. An alkyl group ^uch as a methyl ? group can be branched in the middle of an alkyl group andean (alkenyl group 1
of these cationic surfactants and amphoteric surfactants. ' '
The compound ratio of the surfactant included in the body 'cleansing agent in the present invention is preferably from O.L to 50% b^ ma'ssOfthe l body cleansing agent. It is more preferably from 1 to 45%Λ3y mass, and x further preferably from 10 to 40% by mass. When the compounded <ratioi of ( the surfactant is less than 0.1% by mass,' there is concern .that' the washing * power becomes insufficient, and when it exceeds 50% by mass, the ( economical efficiency decreases. '
The additive for a body cleansing agent is preferably from 0;l?to*40<% by mass of the body cleansing agent. This is because it can showijus't ' enough of the Ca ion-capturing ability and function as a dispersant if in this range. * It is more preferably from 0.3 to 20% by mass, further preferably, from 0.4 to' 15% by mass, and most preferably from 0.5 to»lι0% byimass.Λ
The above-described body cleansing agent ordinarily includes water besides, the additive in the present invention and the above-described < surfactant. Further, any other components known in the<field of'body cleansing agents such as shampoo, body soap, hand soap,* and soap, may be included. However, because the above-described additive® for. a body? Λ cleansing agent in the present invention function as a disptersanfrand^a chelating agent, there is no need'to add a dispersant and a chelating agent1 separately, but a small amount of the addition is not excluded?
Other components which may be added to the body cleansing1 agent include cationic (co) polymers, humectants such as polypropylene1 glycol/ saccharides, viscosity adjusters,' antibacterial agents, alkaMne mateial to* , adjust pH, aromaj solubilizing agentsj pigmenting agentSj'€TVI abs'o'rbers,'!;?
'■: ■ '■ dandruff inhibitors, and solvents.
'■■'• Examples '
Although the present invention is explained concretely by giving : examples below, the present invention is !not«limited to these examples; ' !' Furthermore, "%" indicates "% by mass".
i ^Measuring Method of Weight-Average Molecular Weight (Mw)> : J 1 ; . '''-'"-'-^ ^ ■'■■ " ' ■ • «:< Mw was measured with GPC (Gel: Permeation Chromatography); * Vi '' 1 The column used in the measurement was G-3000 PWXL (Manufactured by ' , ' Tosoh corporation), and the aquέous solutiόϋ was'prepared'by' adding puϊe': ■ : water to disodium hydrogenphosphate 12 hydrate 34.5g 8thd?sddiϋin -""' f dihydrogenphosphate dihydrate 46:2g (both are special grMde rea^eήtέ aϊtd'1 ! >'■ '■' all of the reagents used in the measurement 'are special gra^de^ to make the l : total amount of 500Og; and after this, by filtering the aqueOiis1 -solution witn a ;; ,0.45 μm membrane filter, and was1 used> as a mobile phasei- 5;K-711O;: '
• (manufactured by Hitachi Ltd:) was used as a pump, the flόwrafe of the i: ' ! l mobile phase was set to 0.5-ml/min> and RI ("SHODEX SE^6lJi'maήufactiired'':
'■; by Showa Denko KK) was used as a detector. : At this time, column '"■' ■ ■'• ' «' ' ' temperature was fixed at 35°C. A calibration όurve was produced1 bo using' ■ ' a polyacrylate standard sample (manufactured by Souwa:Kagaku) aϋid'the5 -?/" ( weighttaverage molecular weight (Mw) of the'carboxylic'adid'-Dksdd , ^copolymer was calculated. "•
* <Measurito:g Method of ©alcium lόn-Captύriiig Ability >
, First, a calcium ion standard solution for a calibration curve was ! • prepared. Calcium chloride dihydrate was used as a Ca ions source. ' An i aqueous solution of each concentration of 0.01 mol/L, 0.001 mol/L, and "
, 0.0001 mol/L was produced at 5Og, and the,pH was adjusted in the range of
, pH9,to 11 with a 4.8% NaOH aqueous solution. Furthermore, HmI of a potassium chloride aqueous solution of 4 mol/L (abbreviated below as 1' 1 ' 4M-KC1 aqueous solution) was added to the aqueous solution,' the aqueous ' solution was stirred sufficiently with a magnetic stirrer, and' was made to be ' a sample solution for a calibration curve. A Ca ion electrode (manufactured' by Orion ,KK; 93-20) and a comparative electrode (manufactured by^ Orion
', KK; 90-01) were set in a titrator (manufactured by Hiranuma (Sangyo KK; ' • model number COMTITE-550), a titration of the sample solution for 'a ' * s calibration curve was performed, and the calibration curve^ was "produced: r On the other hand, a necessary amount (5Og per one sample) of an ' aqueous solution of 0.001 mol/L as a Ca ion, standard solution for an ■ > ' > ' ' experiment was prepared using calcium chloride dihydrate iϊi the'sώne
, manner. Then, a carboxylic acid-based copolymer sample weighing 10 mg in terms of solid content and the< above-described Ca ion standard solution for an experiment 5Og were placed in a 100 cc beaker and' the mixed solution was stirred sufficiently with a magnetic stirrer. t The 4.8% NaOH aqueous1 ' < solution was added, the pH was adjusted to pH9, 1 ml of 4M-KC1 aqueous' solution was added, the mixed solution was stirred again, and taade to be a ■ test solution. After the carboxylic acid-based copolymer sample and the da ion standard solution were placed in a beaker for about three minutes', as in < thessame manner described above, the measurement of the Ca ion in the test
, solution was performed with the titrator. :»
Because the Ca ion concentration in the above-described ? ) i experimental solution can be known1 from the calibration curve, 'the1 ; difference from the initial value (0.001 mol/L) was obtain&d by calculation1 , and 'the, capturing amount per lg of the copolymer in a; solid cόhϊeiϊfc'W÷as n% ! calculated. > This value was shown by a mg number calculaledlih terms^ of V i calcium carbonate and made to be a Ga ion-capturing ability valuei' '
• <Glay Dispersibility>
.Pure water was added to Glycine 67.56 g, sodium chloride 52i6^g- and* < , NaOH 2.4 g, and thq mixed solution was made to be 600 g %hϊs;is made" ;tόi be' a buffer (I)), Calcium chloride* dihydrate 0.0817 g was addbd'- ttiUlie'buffer' ! " ; (l) 60 ,gy and further, pure water was added;, !:aήd the mixed solution swas » '-*"e; ; made to be 1000 g (this is made to be a buffer (2». '36 g' of fchfBst %2) Wa!ss '.? added, to 0.1% aqueous (Solution.4 g of the carboxyϋc acid-ba^e'd copolymer! -" sample,, stirredj and the mixed solution was made to be a;test5 solύisiθ'ώ for ! measuring clay dispersibility.,
. -.After placing 0.3 g of clay (manufactured by The Associatibii^f I ^;H;i i !k ■
Powder (Process Industry and EngineeringMl types of powde¥«fόr -testing l:bf ; ι ■ JIS Z8901) in a test tube (manufactured by IWAKI GLASS^ l^'nim diamdter ! ■■' and 180 mm height), 30 g of the above-described test solution fό^ mea'surin-g- ' ;■ dispersing performance was ,added,i sealed, mixed by shakiήf^aήΦ'the elaty'51 -" - : was dispersed uniformly. After, this; the test tube was kep"t;stl!l;lfinra''dar]s* • ■ * t; place for 20 hours. After 20. hours, 5 cc. of supernatant of th'e^test sbltøiOh- •was taken and the absorbaneei was measured-, with UV spe'c'tfofgi?a!p'han^ i Jie H^!
(manufactured by Shimadzu Corporation! UV- 1200; 1 cm cell and' i ( wavelength 380 run). This absorbance becomes the clay dispetsibility as it
. is.
, <Compatibility>.
Water, was added to polyoxyethylene lauryl potassium sulfate (an '■ ' anionic surfactant) 1O g, coconut oil fatty, acid amidepropylbetaine' (an* amphoteric surfactant) 5 g, coconut oil fatty acid diethanolamide (an amphoteric surfactant) 3.0 g, polypropylene glycol (a humectakt and a • dispersant) 2.5 g, and each chelating agent 1.0 g shown in1 Table' lyand<the i mixed solution was made to be 100 g. After stirring and removing air bubbles, the kaolin turbidity (mg/L) was measured with a turbidity meter * . (manufactured by Nippon Denshoku KK; NDH2000) at 25<KV When the' I , kaolin turbidity was 200 mg/L or less, the compatibility was evaluated1 as * O and when the kaolin turbidity exceeded 200 mg/L, the compatibility^ Was ' • v , evaluated as X .
' Example 1 i A'carboxylic acid-based copolymer -having. acylic acid / maleie acid of1 5OJ 50 in mole ratio was synthesized. , Deionized water 385iO!^, 48% NaOH* aqueous solution 333.3 g, and maleic anhydride 196 g were/prepared in1 a separable flask manufactured by SUS of lf ϋter> capacity equipped with1 a thermometer^ant agitator, and' a reflux, condenser, and the aqueous solution in' the flask was raised to a refluxing condition aφ boiling point while being
^ ! stirred, -f Then^ while stirring' and keeping the refluxing conditiόn> using a'
* separate drop nozzle, 60% acylic acid aqueous solution 240 g,'35% hydrogen *f > . peroxide aqueous solution 45.7 gi, and 15% sodium persulfate1 aqueous" solution 53.3 g were started to be dropped into the flask. 'Furthermore, the full amount of the 60% acylic acid aqueous solution, the 3'5%> hydrogens ; ' ' peroxide aqueous solution, and the 15% sodium persulfate^aqueous1 'solution werό dropped continuously at uniform ispeed for 150 minutes-, 120'minutesj and 160 minutes, respectively. Even after all the dropping wa's' completed the refluxing condition at boiling point was kept for 30 minutes,' and then, 48% NaOH aqueous solution 91.7 g was added and the porymesrizatiion was completed. A carboxylic acid -based copolymer No. 1 was' obtained! The - Mw was 5000 and the solid content was 37%.
Example 2
, , ι A carboxylic acid-based copolymer having acylic acid / mal'eic acid 'of 50 / 50'in mole ratio was synthesized. Pure^water 132.8 g;"'48%'NaOH < aqueous solution 400 g, and maleic anhydride 235.2 g werelprep'ared ώa / separable flask manufactured by SUS of 2.5 liter capacity equipped'with aJ thermometer, an agitator, and a reflux condenser, and the1 aqueous solution in the flask was raised to a refluxing condition at boiling point while being stirred. Continuing, while stirring and keeping the refluxing'conditioh, using a separate drop nozzle, 80% acylic acid' aqueous solution-216 g and* 35% hydrogen peroxide aqueous solution 57.6 g were started to be* dropped^ into1 thβiflask.' , Purthermore, ,the full amountlof the 80% acylid'acϊd Aqueous solution and the 35% hydrogen peroxide aqueous solution Were' dropped1- continuously at uniform speed for 180 minutes and 90 minute's* respectively
When 90 minutes past after these droppings started, 15% 'sόdium'persϋlfate ' aqueous solution 96 g and pure water 130 g'were dropped continuously from a separate drop nozzle at uniform speed in > 100 minutes that is 'between 90' minutes and 190 minutes after the dropping started. Even after all the dropping was completed, the refLuxing condition at boiling point was kept' for1 30 minutes, and then, 48% NaOH aqueous Solution' HO.O'g^was added and ( the polymerization was completed. A carboxylic acid-based copolymer No. 2 was obtained. The Mw was1 10000 and the solid content wars 45%! ' * ! '
Example 3
1 A carboxylic acid-based copolymer having acylic acid / maleic acid of
50 / 50 in mole ratio was synthesized. Pure water 118.5 g, 48% NaOH ' ' aqueous solution 316.7 g, and maleic anhydride 196.0 g were prepared^ in a l separable flask manufactured by SUS of 2.5 liter capacity equipjied^with a • ' thermometer, an agitator, and a reflux condenser, and the kq'ueous solution ' in the flask was raised to a refluxing condition at boiling poiiit'while being ' stirred. Then, while stirring and keeping the refluxing condition, using a 4 ' separate drop nozzle, 80% acylic acid aqueous solution 180.0 g, 35% > } ' ' ; ' hydrogen peroxide aqueous solution 48.0 g, 15% sodium persulfate aqueous solution 72.0 g, and pure water 104.0 g were started to be drop'pfed' into the' flask. ' Furthermore, the full amount of the 80% acylic acid aqueous solution, the 35% hydrogen peroxide aqueous solution; 'the* 15% soditiin' persulfate ' l l aqueous solution, and the pure water Were dropped continuously at Uniform < speed for 180 minutes, 150 minutes, 190 minutes, and 180 minutes,' " respectively. Even after all the dropping was 'completed,' the refluxing s v
i condition at boiling point was kept,fori30 mm:ύtes, and then; 48%* NaOH^ ! ■ ' i aqueous ; solution 108.3 gwas added and the polymerizatiόn'was eompfetedi ; i Λcarboxylic acid-based copolymer No. 3 was obtained. ! ' Thfe Mw was 5j200' : and the solid content was 45%.
•Example 4
?, . : • ;,A carboxylic acid-based copolymer having acylic acid / maϊeie acid ό^ v52 /;48,in mole ratio was synthesized. \ Pure water 310.2 g; 48% NaOH' V ;β ϊ t f aqueous solution 350.0 g, and maleic anhydride 205.8 g were 'prepared in a 5'"1' 1 separable flask manufactured by SUS of 2.5 liter capacity equipped -with a iU; 1
•< thermometer, an agitator, and a reflux condenser, and the aqueous solution •• "•' in the flask was raised to a refluxing Condition ;at boiling p%§nt whil£ being ' ;: ; stirred, y. Then, while stirring and. keeping; the 'refluxing condition, using a ' '
> separate: drop nozzle, 80% acylic acid: aqueous solution 204*8rg7:35%: 'i- irr> ">£! hydrogen peroxide aqueous solution 52.5 g, 15% sodium βerέulfatfe aqueous r solution; β 1.3 g, and pure water 80.0 giWerieϊstarted to be dropped; into the f ' I flask, , , Furthermore^ the full amqunt of the|80% acyhci acid 'a'queόus bolutiόnl
,the,35% hydrogen peroxide , aqueous solution, the 15% sόdiύm'persulfate : ' ' aqueous, solution, and the pure water were: dropped continuously ^at -uniform speed for 260 minutes, 260 minutes, 270 minutes, and 180;miήύtes after 95i ¥ t minutes.from the beginning of the polymerization, respectively: • Even after ?
, all, the dropping was completed,' the refluxing condition at' boiling point was ;' kept for SO minuteSj and then, 48,% NaOIJ aqueous solution;^!^© g and'pure !•"'■» water-JQ-O-g were, added and the polymerization was completed. " -A^V-' *i-W:<:-'-& cdrboxylidacid -based copolymer ■ ;Np. ;4 was: obtained. The-Mw;waS δ,'Odθ' ! '; - d
and the solid content was 37%.,
Example 5
A carboxylic acid-based copolymer having acylic acid / maleic acid of 52 / 48 in mole ratio was synthesized. Pure water 166.8 -gj 48% 'NaΘH aqueous solution 332.5 g, and maleic anhydride 205.8 g were^preparedHn a separable flask manufactured by SUS of 2.5 litόr capacity equipped'wϊth a thermometer, an agitator, and a reflux condenser, and the ^aq'uebus solution in the flask was raised to a refluxing condition at boiling point While being stirred. Then, while stirring and keeping the refluxing Condition, using a s separate drop nozzle, 80% acylic acid aqueous solution 204.8 g, '35% hydrogen peroxide aqueous solution 52.5'g, 15% sodium persulfate aqueous solution 78.8 g, and pure water 89.0 g were started to be dropped into the flask. Furthermore, the full amount of the 80% acylic acid} aqueous solution the 35% ^hydrogen peroxide aqueous solution,sthe l5% sodium persulfate! aqueous solution, and the pure water were dropped continuously at uniform speed for. 180 minutes,.150 minutes, 200 minutes, and 180 minutes,
A (respectively. Even after all the dropping was completed, thd refluxing condition fat boiling point was kept for 60 minutes, and thenj 48%' NaOH aqueous solution 71.0 g and pure water 79.0 g^were added ah'dihe ' polymerization was completed. A carboxylic acid-based copolymέr Nb.' was obtained. The Mw was 5,300 and the solid content was' 45%.
Comparative Example 1
A polyacrylic acid was^ «sycnthesized. Pure water 56O g was Jpfe^p'ared
in a separable flask manufactured by SUS of 2:5 liter capacity equipped with a thermometer, an agitator, and a reflux condenser, and the 'solution in the flask was raised to a refiuxing condition at boiling point while being stirred. Then, while stirring and keeping the refiuxing condition, using a separate drop nozzle, 80%.acylic. acid aqueous solution 360 g, 48% NaOH aqueous solution 283 g, 15% sodium persulfate aqueous solution 56*^/ and pure water 6.0Q g were started to be dropped into the flask., ' The acrylic acid aqueous
. solution and the, NaOH aqueous solution wøre dropped continuously at uniform* speed for 240 minutes after the dropping started^ and 'further, the sodium persulfate aqueous solution and the pure water were? dropped .continuously at uniform speed for, 250, minutes after the dropping started: Even after all the dropping was completed, the refluxing condition at boiling pqint was kept for 30 minutes and the polymerization was completed. A carboxylic acid-based copolymer ;No., 6 (for comparison) was obtained. The Mw was 5000. The temperature was adjusted and the solid content was made to.be 45%. .
Comparative Example 2, ,
A carboxylic^ acid-based copolymer! having acylic acid / maleic acid of 70/ 30, in mole ratio was synthesized. Pure water 288.7 g, 48% NaOH aqueous solution 250 g, and maleic anhydride 147 g were -prepared in a .separable flask manufactured by SUS of 2:5 liter capacity equipped with a thermometer, an agitator, and a reflux condenser, and the aqueotts solution , in the flask was raised to a refiuxing condition at boiling poliit while' being' stirred.r : \Thenj iwhile ;stirring and keeping the refluxing condition, using a
separate drop nozzle, 80% acylic acid aqueous solution 3Ϊ5 gVl5% Sodium persulfate aqueous solution 66.7 g, and pure water 160 g were 'started 1;ό?be' dropped into the flask. Furthermore, the 80% acylic acid1 aqueBύs solution was dropped for 120 minutes and the 15% sodium persulfate aqueous solution and pure water was dropped for 130 minutes. Even! after all^the1 dropping was completed, the refluxing condition at boiling point' was kept for 30 minutes, and then, 48% NaOH aqueous solution 210.4 'g wa's'added and' the polymerization was completed. A carboxylic acid'baseα cόpolyMer No.s 7 (for comparison) was obtained. The Mw Was' 70000 and the solict dbntent ' was 40%.
: Experimental Example
Using the carboxylic acid-based copolymers No. 1 to No. 5 (Example* ϊ ! to Example 5), No. 6, and No. 7 (Comparative Example 1 and 2) obtained ϊhe " above-described examples and comparative examples, as described 'above, the Ca ion-capturing ability, the clay dispersibϋity, and tHe'compktiraliϊtyib a' body cleansing agent were evaluated. The result is shown' in Table 1. u ! < Further, also using a Na salt of ethylene diamine tetraacetic acid (expresέed as EDTA • 4Na" Comparative Example 3), which is a known Chelating' agent, '' and a citric acid Na salt (expressed as citric acid • 3Na* Comparative Example 4), the evaluation was performed in the same manner and the result is shown in Table 1. ,
Table 1 ,
! ■ Ca ipn,f capturing
C lay ■ ' Chelating agen^ , ,\ • i . perfprmancb,; ' Cor lpatibilitjr * dispei sibility (mgCaCθ3/g)
• a V"4'--?ϊ'.'"-"
Example 1 AA/MA=50/50mol; Mw: 5,000 370 i K*«~<;
■.. . ' ■ i I 1> J ■
, i ■ '■ • ' • ■ ' . , - , : , ■ . * ; i ' ' !• ' ■'', •' Example 2 AA/MA=50/50mol; Mw: 10,000 400 ] It :
■
, ■ ' ■ I ! ■ | i i '> _
-.'.1I,1' V I- V.1'.-;.'!1
Example 3l AA/MA=50/50mol; Mw': 5;200 380 1 .'.0!"ι-"'!;ι« &■ ' «'' < ■ : ■
Example 4 AA/MA=52/48mol; Mw: 5,000 370 ]
' Example δ: M/MA=52/48mol; Mw:15[300^ ' • ■ ;•■: j i, C.
Comparative
AA/MA=100/0mol;.Mw: 5,000 ■ <' . ,.■'';' 26,0' ' ■;'. ;' ' ■ ■ ■ • ' , ' •' ■] .2 _' ' ' ό;sΛ !,■•-; Example 1 ;.•• i
, Vl . ' '- 11. ' ■: . ' ! '"•• • i ■ '. -
Comparative •■I'!- !'
AA/MA=70/30mol; Mw: 7OjOOO ' ' " ' ' '] .j^'i/'ViΛ" '': Example 2 1, ',
.. I /■(, r : .•■! i ■ ,
Comparative ■ i - * '
• ••' " EDTA*4Na' > ' • '" > '■ 300', '• 0.2 O ' :; Example 3 *r_ ^
, '. ..,i .-..
Comparative
., |-.- v
: Citric acid»3Na ': 220 o ' ■ '■ •• Example 4
■ι,l . ' ■ t
From Table 1, the carboxylic acid-based copolymers No.1 !tό''Nb jδ'ϊn , the present invention were confirmed to be excellent in Ck' ϊόri-cap!ttirin^r ' ability, clay dispersibility, and compatibility to a body cleansing a.gέήϋ}!< Θή;U the other hand, in Comparative Example 1, because carboxylic acid'-ba^ed11 *-
copolymer No. 6 which does not have a maleic acid unit was used, it fell ' behind in the Ca ion-capturing ability." Further, in Comparative' Example 2,; because carboxylic acid-based copolymer Np. 7; having a maleie" acid unit of 30 mol% was used, it had a sufficient Ca ion-capturing ability; but fell "behind in the compatibility to a body cleansing agent because the Mw 'was laf ge. Further, for the known chelating agent, a sufficient value' was: shown M' the .
Ca ion-capturing ability, but it fell behind in clay dispersibility1 aήd,: it was found that it does not have an effect to preyent the re-attachineht of dirt. :
INDUSTRIALAPPLICABILITY
Because the additive for a body cleansing agent (the carbpkylic
! ! acid -based copolymer) in the present invention is excellent in Ca ion;capj;uring ability and the dispersion effect of dir% it is'useful as ari additive for body cleansmg agents such as a shampoo, body' ^dapy hand soap,.; and soap.
Claims
1. An additive for a body cleansing agent is a carboxylic kcid-based* ' copolymer comprising the constituting unit ,(a) that is originated from an unsaturated monocarboxylie acid (salt) monomer and the constituting kinit ,(b) that is originated from an unsaturated dicarboxylic acid (salt) ^monomer, and having the weight average molecular weight of 3000 to 30000,!<whereϊn the Ca ion-capturing ability of the carboxylic 'acid-based copolymer is SOO^mg- < CaCOs/g or more.
2. An additive for a body cleansing agent according to Claim 1\ wherein the total amount of the constituting unit (a) and the1 constituting* * unit ,(b) is 80 mol% or more in 100 mol% of the constitutiiig uriit\>f tb£ -J 'l 'i " carboxylic acid-based copolymer.
3. An additive for a body cleansing agent according to either ClainJ1 1 or 2, wherein the constituting unit (b) is from 25 to 60 mo'l% whe'h th'e'totaϊ amount of the constituting unit (a) and the constituting unit'(b) is made to be 100 mol%.
4. An additive for a body cleansing agent according to an'y one(of ' Claims 1 to 3, wherein the, unsaturated monocarboxylie aciii3 fealt) monomer1 is acylic acid and the unsaturated dicarboxylic acid (salt) monόnieHs'nialeic arirl
5. Abpdy cleansing agent, comprising the additive for a -body ' cleansing agent according to any one of Claims 1 to 4.
. , : . .
6. A method of manufacturing a body cleansing agent, comprising' mixing the additive for aibody cleansing a,gent according tbi airy ipne of €Slaiϊns 1 to 4 and a surfactant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2006/317918 WO2008029484A1 (en) | 2006-09-04 | 2006-09-04 | Additives for a body cleansing agent and body cleansing agents |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2006/317918 WO2008029484A1 (en) | 2006-09-04 | 2006-09-04 | Additives for a body cleansing agent and body cleansing agents |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2008029484A1 true WO2008029484A1 (en) | 2008-03-13 |
Family
ID=39156930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2006/317918 WO2008029484A1 (en) | 2006-09-04 | 2006-09-04 | Additives for a body cleansing agent and body cleansing agents |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2008029484A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016180029A (en) * | 2015-03-23 | 2016-10-13 | 株式会社日本触媒 | Detergent composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10183183A (en) * | 1991-06-15 | 1998-07-14 | Cosmo Chem Kk | Water-repelling type windshield washer liquid for automobile |
| JP2000247926A (en) * | 1998-12-28 | 2000-09-12 | Nippon Shokubai Co Ltd | Production of aqueous solution of maleate having slight impurity and polymer using the same |
| JP2005112756A (en) * | 2003-10-06 | 2005-04-28 | Dai Ichi Kogyo Seiyaku Co Ltd | Cleanser composition for hair or skin |
-
2006
- 2006-09-04 WO PCT/JP2006/317918 patent/WO2008029484A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10183183A (en) * | 1991-06-15 | 1998-07-14 | Cosmo Chem Kk | Water-repelling type windshield washer liquid for automobile |
| JP2000247926A (en) * | 1998-12-28 | 2000-09-12 | Nippon Shokubai Co Ltd | Production of aqueous solution of maleate having slight impurity and polymer using the same |
| JP2005112756A (en) * | 2003-10-06 | 2005-04-28 | Dai Ichi Kogyo Seiyaku Co Ltd | Cleanser composition for hair or skin |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016180029A (en) * | 2015-03-23 | 2016-10-13 | 株式会社日本触媒 | Detergent composition |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5178008B2 (en) | Amino group-containing water-soluble copolymer | |
| JP4846821B2 (en) | Liquid detergent builder and liquid detergent | |
| CN101688160A (en) | Comprise laundry detergent composition based on the amphiphilic graft polymers of polyalkylene oxide and vinyl ester | |
| US11384186B2 (en) | Polymer comprising certain level of bio-based carbon | |
| WO2007135935A1 (en) | Dispersing agent | |
| CN102559409A (en) | Polymers for high-surfactant formulations | |
| CN100393776C (en) | Polyalkylenimine-derived polymer and its production process and uses | |
| JP4323700B2 (en) | Novel water-soluble copolymer, its production method and use | |
| WO2008029484A1 (en) | Additives for a body cleansing agent and body cleansing agents | |
| JP2000053729A (en) | Acrylic acid (salt)-maleic acid (salt)-based copolymer, its production and detergent composition | |
| CN103827153B (en) | Low viscosity suspension ethylenic copolymer | |
| JP4794946B2 (en) | Method for producing emulsion | |
| JPS6286098A (en) | Detergent builder and detergent composition containing the same | |
| JP4634022B2 (en) | Liquid detergent builder and liquid detergent | |
| JP4489422B2 (en) | Liquid detergent composition | |
| EP1505091A1 (en) | Water-soluble copolymer | |
| JP4334749B2 (en) | Liquid detergent builder and liquid detergent composition | |
| CN103379890A (en) | Cosmetic formulation containing a water-insoluble amphiphilic copolymer as a thickener | |
| JP2020182931A (en) | Aqueous dispersant | |
| JPS59108010A (en) | Dispersing agent for inorganic pigment | |
| WO2000059958A1 (en) | Crosslinked copolymer of unsaturated carboxylic acid and process for producing the same, copolymer of unsaturated carboxylic acid, biodegradable builder, and detergent composition | |
| JP2004091635A (en) | Water-soluble polymer and its application | |
| JP4223357B2 (en) | Multiphase liquid detergent composition | |
| JP2006241099A (en) | Additive for body detergent and body detergent | |
| JP2008063233A (en) | Additive for body detergent and body detergent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WWE | Wipo information: entry into national phase |
Ref document number: 2006553008 Country of ref document: JP |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 06797744 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 06797744 Country of ref document: EP Kind code of ref document: A1 |