CN103890015A - Acrylic acid (salt)-maleic acid (salt) copolymer composition, method for manufacturing same, and cleaning agent composition - Google Patents
Acrylic acid (salt)-maleic acid (salt) copolymer composition, method for manufacturing same, and cleaning agent composition Download PDFInfo
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- CN103890015A CN103890015A CN201280052449.1A CN201280052449A CN103890015A CN 103890015 A CN103890015 A CN 103890015A CN 201280052449 A CN201280052449 A CN 201280052449A CN 103890015 A CN103890015 A CN 103890015A
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- 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
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
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Abstract
Provided are a cleaning agent composition and an acrylic acid (salt)-maleic acid (salt) copolymer composition having excellent calcium scavenging capability and gel resistance. Furthermore, a manufacturing method that can obtain the acrylic acid (salt)-maleic acid (salt) copolymer composition having these excellent properties is provided. The acrylic acid (salt)-maleic acid (salt) copolymer composition is a copolymer composition that contains acrylic acid (salt)-maleic acid (salt) copolymer and a low molecular compound containing a sulfur atom, wherein the copolymer includes a specific structural unit, the weighted average molecular weight of the copolymer is 2000 or higher and 10,000 or lower, the low molecular compound containing a sulfur atom includes 3-sulfopropionic acid (salt), and the amount of the 3-sulfopropionic acid (salt) is 0.01 to 10 mass%, in relation to 100 mass% of the total solid content of the copolymer composition.
Description
Technical field
The present invention relates to vinylformic acid (salt)-toxilic acid (salt) based copolymer composition, its manufacture method and detergent composition.
Background technology
All the time, known vinylformic acid (salt)-toxilic acid (salt) based copolymer can show excellent sequestering action and dissemination, be used to the such as purposes (for example,, referring to patent documentation 1～3) widely such as washing assistant, scale inhibitor, mineral dye dispersion agent.In addition, in patent documentation 4, disclose that a kind of clay dispersion ability in high hardness water is more than 50%, calcium ion capture ability is 270mgCaCO
3vinylformic acid (salt)-toxilic acid (salt) based copolymer more than/g.In patent documentation 4, also disclose: this multipolymer is because the clay dispersion ability in high hardness water is high and calcium ion capture ability is also high, thereby used the detergent composition of this multipolymer also can give play to excellent cleansing power in the high area of the water hardness such as the U.S., China.
Prior art document
Patent documentation
Patent documentation 1: No. 2574144 communique of Japanese Patent
Patent documentation 2: Japanese kokai publication sho 63-235313 communique
Patent documentation 3: Japanese kokai publication sho 58-67706 communique
Patent documentation 4: TOHKEMY 2000-53729 communique
Summary of the invention
The problem that invention will solve
Conventionally, if known to the high water repetitive scrubbing clothing of hardness, thus calcium can deposit to and on clothing, makes clothing dirty (flavescence).On the other hand, because human consumer is for the consciousness raising of environmental problem in recent years, human consumer has got used to by the residue water of having a bath for washing to realize water saving, still, due to the use of residue bath water, can be because of the concentrated problem that produces washing water high rigidity of calcium component.Thereby, for example, for (adding composition in washing composition to, polymkeric substance etc.), in order to be suppressed at the deposition on clothing, require to have catch the performance (calcium capture ability) of the calcium in washing water and in the washing water of high rigidity, be also difficult to the physical property such as thawless performance (gel resistance).As mentioned above, although reported various polymkeric substance, present situation is not yet to develop all extremely good polymkeric substance of calcium capture ability and gel resistance.
The present invention carries out in view of above-mentioned present situation, and its object is to provide all extremely good vinylformic acid (salt)-toxilic acid (salt) based copolymer composition and detergent composition of calcium capture ability and gel resistance.In addition, the object of the present invention is to provide the manufacture method of vinylformic acid (salt)-toxilic acid (salt) based copolymer composition that can suitably obtain having so excellent physical property.
For solving the scheme of problem
The inventor conducts in-depth research for polymkeric substance and the composition thereof that can bring into play well calcium capture ability and gel resistance, found that following copolymer compositions can bring into play extremely good calcium capture ability and gel resistance, be suitable for the various uses such as detergent composition, this copolymer compositions comprises vinylformic acid (salt)-toxilic acid (salt) based copolymer and specific sulfur atom-containing low molecular compound, and the content of this sulfur atom-containing low molecular compound is in specialized range, the weight-average molecular weight of this vinylformic acid (salt)-toxilic acid (salt) based copolymer is in specialized range, and comprise from the structural unit of vinylformic acid (salt) with from the structural unit of toxilic acid (salt) with specific mol ratio.Find in addition, in the time obtaining such copolymer compositions, if adopt following manufacture method, can obtain well having this copolymer compositions of excellent physical property, this manufacture method is included in the operation that will comprise the monomer component polymerization of vinylformic acid (salt) and toxilic acid (salt) under the existence of persulfuric acid (salt) and acidic sulfurous acid (salt).In addition, find that the detergent composition that comprises aforesaid propylene acid (salt)-toxilic acid (salt) based copolymer and specific sulfur atom-containing low molecular compound has very excellent cleansing power.And, find that these copolymer compositions, detergent composition also can give play to excellent cleansing power in the very high areas of water hardness such as the U.S., China, Europe, and expect successfully solving above-mentioned problem, complete thus the present invention.
, the present invention relates to a kind of vinylformic acid (salt)-toxilic acid (salt) based copolymer composition, its copolymer compositions for comprising vinylformic acid (salt)-toxilic acid (salt) based copolymer and sulfur atom-containing low molecular compound, the structural unit (II) that the structural unit (I) that this multipolymer comprises following general formula (1) expression and following general formula (2) represent, this structural unit (I) and structural unit (II) to contain mol ratio (structural unit (I)/structural unit (II)) be 80/20～95/5, the weight-average molecular weight of this multipolymer is more than 2000 and below 10000, this sulfur atom-containing low molecular compound comprises 3-sulfo group propionic acid (salt), with respect to the solids component total amount 100 quality % of this copolymer compositions, the content of this 3-sulfo group propionic acid (salt) is 0.01 quality %～10 quality %.
[Chemical formula 1]
In formula (1), M represents hydrogen atom, atoms metal, ammonium or organic amino group.
[Chemical formula 2]
In formula (2), M
1and M
2identical or different, represent hydrogen atom, atoms metal, ammonium or organic amino group.
In addition, the invention still further relates to the manufacture method of a kind of vinylformic acid (salt)-toxilic acid (salt) based copolymer composition, this manufacture method is to manufacture the method for aforesaid propylene acid (salt)-toxilic acid (salt) based copolymer composition, and this manufacture method is included in the operation that will comprise the monomer component polymerization of vinylformic acid (salt) and toxilic acid (salt) under the existence of persulfuric acid (salt) and acidic sulfurous acid (salt).
In addition, the invention still further relates to a kind of detergent composition, it comprises aforesaid propylene acid (salt)-toxilic acid (salt) based copolymer composition.
In addition, the invention still further relates to a kind of detergent composition, its detergent composition for comprising vinylformic acid (salt)-toxilic acid (salt) based copolymer and sulfur atom-containing low molecular compound, the structural unit (II) that the structural unit (I) that this multipolymer comprises above-mentioned general formula (1) expression and above-mentioned general formula (2) represent, this structural unit (I) and structural unit (II) to contain mol ratio (structural unit (I)/structural unit (II)) be 80/20～95/5, the weight-average molecular weight of this multipolymer is more than 2000 and below 10000, this sulfur atom-containing low molecular compound comprises 3-sulfo group propionic acid (salt), with respect to the solids component total amount 100 quality % of this detergent composition, the content of this 3-sulfo group propionic acid (salt) is 0.0005 quality %～2 quality %.
Describe the present invention below in detail.It should be noted that, be also optimal way of the present invention by each 2 of optimal way combination of the present invention or 3 modes that form above recorded below.
(vinylformic acid (salt)-toxilic acid (salt) based copolymer composition)
Vinylformic acid of the present invention (salt)-toxilic acid (salt) based copolymer composition (hereinafter also referred to as " copolymer compositions ") comprises vinylformic acid (salt)-toxilic acid (salt) based copolymer and sulfur atom-containing low molecular compound, and these contain composition and can use respectively one kind or two or more.In addition, can also further comprise as required one kind or two or more other composition.
Aforesaid propylene acid (salt)-toxilic acid (salt) based copolymer (hereinafter also referred to as " multipolymer ") at least comprises the structural unit (I) of above-mentioned general formula (1) expression and the structural unit (II) that above-mentioned general formula (2) represents.
In above-mentioned general formula (1) and (2), M, M
1and M
2identical or different, represent hydrogen atom, atoms metal, ammonium or organic amino group, as atoms metal, can illustrate the alkali metal atoms such as such as lithium atom, sodium atom, potassium atom; The alkaline earth metal atom such as calcium atom, magnesium atom; The transition metal atoms such as iron; Etc..Wherein be preferably alkali metal atom or alkaline earth metal atom, more preferably alkali metal atom, more preferably sodium atom or potassium atom.In addition, organic amino group refer to primary amine～quaternary amine neutralized in the structure of carboxyl, from the structure division of primary amine～quaternary amine, can illustrate for example group from alkylamines such as methylamine, ethamine, diethylamine, triethylamines; From the group of the alkanolamine such as monoethanolamine, diethanolamine; From the group of the polyamines such as diethyl diamines, diethylenetriamine; Etc..
It should be noted that, if M is ammonium in above-mentioned general formula (1), refer to-CH
2cH (COONH
4the structure of)-represent.
As M, M in above-mentioned general formula (1) and (2)
1and M
2, identical or different, hydrogen atom, sodium atom or potassium atom are applicable to.Thus, above-mentioned multipolymer and copolymer compositions for washing composition purposes etc. in the situation that, can further shown to the raising effect of cleaning force etc.
The structural unit (I) that above-mentioned general formula (1) represents is also referred to as the structural unit from vinylformic acid (salt).Vinylformic acid (salt) refers to vinylformic acid and/or acrylate.
It should be noted that, " comprising the structural unit from vinylformic acid (salt) " refers to that the multipolymer finally obtaining comprises said structure unit (I), is not limited only to by vinylformic acid (salt) polymerization is imported in multipolymer.
As said structure unit (I), preferably by the structural unit under the existence of polymerization starter, the monomer component polymerization that comprises vinylformic acid (salt) being formed.
The structural unit (II) that above-mentioned general formula (2) represents is also referred to as the structural unit from toxilic acid (salt).Toxilic acid (salt) refers to toxilic acid and/or maleate (comprise the form of the salt that two carboxyls are carboxyl and only a form that carboxyl is salt).
It should be noted that, " comprising the structural unit from toxilic acid (salt) " refers to that the multipolymer finally obtaining comprises said structure unit (II), is not limited only to by toxilic acid (salt) polymerization is imported in multipolymer.
As said structure unit (II), preferably by the structural unit under the existence of polymerization starter, the monomer component polymerization that comprises toxilic acid (salt) being formed.
In this specification sheets, salt (for example, the salt in acrylate, maleate etc.) refers to metal-salt, ammonium salt or organic amine salt.As metal-salt, can illustrate an alkali metal salts such as such as lithium salts, sodium salt, sylvite; The alkaline earth salt such as calcium salt, magnesium salts; The transition metal salts such as molysite; Etc..In addition, as organic amine salt, can illustrate the alkylamine salts such as such as methylamine salt, ethylamine salt, diethyl amine salt, triethylamine salt; The alkanolamine salt such as monoethanolamine salt, diethanolamine salt; The polyamines salt such as diethyl diamine salts, diethylenetriamine salt; Etc..In these salt, be preferably an alkali metal salt or alkaline earth salt.More preferably an alkali metal salt, more preferably sodium salt or sylvite.
In above-mentioned multipolymer, the structural unit (II) that structural unit (I) and the above-mentioned general formula (2) that above-mentioned general formula (1) represents represents to contain mol ratio (structural unit (I)/structural unit (II)) be 80/20～95/5., above-mentioned multipolymer comprises said structure unit (I) and structural unit (II) with mol ratio (structural unit (I)/structural unit (II))=80/20～95/5.By making this mol ratio within the scope of this, calcium capture ability and the gel resistance of above-mentioned multipolymer and copolymer compositions are abundant.As above-mentioned mol ratio, be preferably 82/18～92/8, more preferably 85/15～90/10.
In addition, except said structure unit (I) with (II), above-mentioned multipolymer can also further comprise the one kind or two or more structural unit from other monomer (being called " structural unit (III) ").Refer to the structural unit from vinylformic acid (salt) and toxilic acid (salt) monomer (being referred to as " other monomer ") in addition from the structural unit (III) of other monomer.
Herein, " comprising the structural unit from other monomer " refer to that the multipolymer finally obtaining comprises the structural unit (III) from other monomer, is not limited only to by other monomer polymerization is imported in multipolymer.
As said structure unit (III), preferably by the structural unit under the existence of polymerization starter, the monomer component polymerization that comprises other monomer being formed.
It should be noted that, said structure unit (III) is for example during from the structural unit of methyl acrylate, and this structural unit can be with " CH
2-CH (COOCH
3)-", represents., be equivalent to from the structural unit of other monomer the two keys of polymerizability that other monomer has and open the structure (two keys (C=C) become the structure of singly-bound (C-C-)) forming.
Be not particularly limited as above-mentioned other monomer, can enumerate the unsaturated monocarboxylic except vinylformic acid (salt) such as such as methacrylic acid, β-crotonic acid etc. and their salt is monomer, the unsaturated dicarboxylic acid except toxilic acid (salt) such as fumaric acid, methylene-succinic acid, citraconic acid etc. and their salt is monomer, the acid amides such as (methyl) acrylamide, the tertiary butyl (methyl) acrylamide are monomer, the hydrophobic monomers such as (methyl) acrylate, vinylbenzene, 2-methyl styrene, vinyl-acetic ester, the unsaturated sulfonic acids such as vinyl sulfonic acid, allyl sulphonic acid, methallyl sulfonic acid, styrene sulfonic acid, 2-acrylamide-2-methyl propane sulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid, (methyl) vinylformic acid sulphur ethyl ester, (methyl) vinylformic acid sulphur propyl ester, (methyl) vinylformic acid-2-hydroxyl sulphur propyl ester, sulfoethyl maleimide and their salt are monomer, 3-M2BOL (prenol), 3-methyl-3-butene-1-alcohol (isoprenol), 2-M3BOL (isoprene alcohol), (methyl) vinylformic acid-2-hydroxyl ethyl ester, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, polyethyleneglycol isoprene alcohol ether, polypropylene glycol list isoprene alcohol ether, polyoxyethylene glycol mono allyl ether, polypropylene glycol mono allyl ether, allylin, Alpha-hydroxy vinylformic acid, N-methylol (methyl) acrylamide, glycerine list (methyl) acrylate, the hydroxyl unsaturated monomers such as vinyl alcohol, the cationic monomers such as (methyl) dimethylaminoethyl acrylate, dimethylamino-propyl (methyl) acrylamide, the nitriles such as (methyl) vinyl cyanide are monomer, the phosphorous-containing monomers such as (methyl) acrylamide methanephosphonic acid, (methyl) acrylamide methanephosphonic acid methyl esters, 2-(methyl) acrylamide-2-methylpropane phosphonic acids, etc..These monomers can only use a kind, or also two or more can be share.
In above-mentioned multipolymer, said structure unit (I) and total (II) are preferably 100/0～80/20 with the mol ratio (total/structural unit (III) of structural unit (I) and structural unit (II)) that contains of the structural unit from other monomer (III).,, if structural unit (I), (II) and total amount (III) are made as to 100 % by mole, structural unit (III) is preferably below 20 % by mole.If within the scope of this, can further improve calcium capture ability and the gel resistance that above-mentioned multipolymer and copolymer compositions produce.As above-mentioned mol ratio, more preferably 100/0～85/15, more preferably 100/0～90/10.
In addition, above-mentioned multipolymer preferably has (comprising) sulfonic acid (salt) base at least one main chain end.Thus, calcium capture ability and the gel resistance of above-mentioned multipolymer and copolymerization composition further improve, and can further bring into play action effect of the present invention, also can bring into play excellent cleaning force in the region of the water of high rigidity.
It should be noted that, above-mentioned multipolymer has sulfonic acid (salt) base at least one main chain end for example can be passed through
1hNMR analyzes and confirms.
Above-mentioned sulfonic acid (salt) base refers to sulfonic group and/or sulphonate-base, for example, and can be with " SO
3m " (M represents hydrogen atom, atoms metal, ammonium or organic amino group.The preference of atoms metal and organic amino group is described above.) represent.
Sulfonic acid (salt) base of above-mentioned main chain end for example can be as described later by importing monomer component polymerization in the molecule of multipolymer under the existence of acidic sulfurous acid (salt).; preferably by monomer component polymerization being obtained to above-mentioned multipolymer under the existence at acidic sulfurous acid (salt); thus, a part for acidic sulfurous acid (salt) plays a role as chain-transfer agent, at the main chain end of copolymer molecule with sulfonic group (SO
3m) form is introduced.Acidic sulfurous acid (salt) refers to acidic sulfurous acid and/or its salt.
It should be noted that, by the sulfonic acid of above-mentioned main chain end (salt) base also referred to as the structural unit from acidic sulfurous acid (salt).
The weight-average molecular weight (also referred to as Mw) of above-mentioned multipolymer is more than 2000 and below 10000.By making weight-average molecular weight in 2000～10000 scope, above-mentioned multipolymer and copolymer composition can show the good ability that prevents calcium deposition.As the lower value of weight-average molecular weight, be preferably more than 2500, more preferably more than 3000, in addition as higher limit, be preferably below 9000, more preferably below 8000.
In addition, the dispersity of above-mentioned multipolymer (is the value of obtaining by weight-average molecular weight Mw/ number-average molecular weight Mn, also referred to as molecular weight distribution.) be preferably 1.5～10.Thus, can further improve the ability that prevents calcium deposition.More preferably 1.5～5.0, more preferably 1.5～2.7.
In this specification sheets, weight-average molecular weight (Mw) and number-average molecular weight (Mn) can utilize the gimmick of recording in aftermentioned embodiment to measure.
In above-mentioned copolymer compositions, for example, with respect to above-mentioned copolymer compositions 100 quality %, above-mentioned multipolymer containing the proportional 1 quality %～99 quality % that is preferably.
In addition, except above-mentioned multipolymer, above-mentioned copolymer compositions also comprises sulfur atom-containing low molecular compound.Sulfur atom-containing low molecular compound comprises 3-sulfo group propionic acid and/or its salt (being referred to as " 3-sulfo group propionic acid (salt) ").
With respect to the solids component total amount 100 quality % of above-mentioned copolymer compositions, the content of above-mentioned 3-sulfo group propionic acid (salt) is 0.01 quality %～10 quality % (wherein for Na salt type converts).By within the scope of this, can improve calcium capture ability and gel resistance that above-mentioned copolymer compositions produces.As the higher limit (conversion of Na salt type) of the content of above-mentioned 3-sulfo group propionic acid (salt), be preferably 9.5 quality % following, more preferably 9 quality % following, more preferably below 8.5 quality %.The lower value (conversion of Na salt type) of the content to above-mentioned 3-sulfo group propionic acid (salt) is not particularly limited, be for example preferably 0.1 quality % above, more preferably 1 quality % above, more preferably 1.5 quality % above, be particularly preferably 2 quality % above, most preferably be 2.5 quality % more than.
In this specification sheets, " conversion of Na salt type " is to instigate object as sodium salt (Na salt) calculated mass ratio, if for example 3-sulfo group propionic acid (salt), as 3-sulfo group Sodium Propionate calculated mass ratio.
In addition, in this specification sheets, " solids component " refers to whole compositions except volatile component, is in other words nonvolatile component.
In addition, above-mentioned sulfur atom-containing low molecular compound preferably includes 2-sulfo-succinic acid and/or its salt (being referred to as " 2-sulfo-succinic acid (salt) ").
With respect to the solids component total amount 100 quality % of above-mentioned copolymer compositions, the content of above-mentioned 2-sulfo-succinic acid (salt) converts and is preferably 0.01 quality %～4 quality % in Na salt type.Thus, can further improve calcium capture ability and the gel resistance that above-mentioned copolymer compositions produces.As the higher limit (conversion of Na salt type) of the content of above-mentioned 2-sulfo-succinic acid (salt), be preferably below 3.5 quality %.The lower value (conversion of Na salt type) of the content to above-mentioned 2-sulfo-succinic acid (salt) is not particularly limited, for example, more than being preferably 1 quality %.
In addition, above-mentioned sulfur atom-containing low molecular compound preferably includes vitriol.
With respect to the solids component total amount 100 quality % of above-mentioned copolymer compositions, the content of above-mentioned vitriol converts and is preferably 0.01 quality %～5 quality % in Na salt type.Thus, can further improve calcium capture ability and the gel resistance that above-mentioned copolymer compositions produces.As the higher limit of the content of above-mentioned vitriol, be preferably 4.5 quality % following, more preferably below 4 quality %.The lower value of the content to above-mentioned vitriol is not particularly limited, for example, more than being preferably 1 quality %.
In addition, above-mentioned copolymer compositions can comprise remaining monomer, other remaining raw material, mentioned component by product in addition etc.
In above-mentioned copolymer compositions, comprise in the situation of remaining monomer, the content of this remaining monomer is for example preferably 0ppm～1000ppm with respect to the solids component total amount of above-mentioned copolymer compositions.More preferably below 500ppm.
In addition, except situation about mentioning especially, preferably do one's utmost to reduce other remaining raw material, mentioned component by product in addition.
Above-mentioned copolymer compositions can further comprise water equal solvent (also referred to as solvent).In the solvent-laden situation of bag, be preferably the solvent that comprises water.More preferably water.
With respect to above-mentioned copolymer compositions 100 quality %, the content of the solvent in above-mentioned copolymer compositions is preferably 0 quality %～99 quality %.
(manufacture method of vinylformic acid (salt)-toxilic acid (salt) based copolymer composition)
Copolymer compositions of the present invention can obtain by following manufacture method, and this manufacture method is included in the operation that will comprise the monomer component polymerization of vinylformic acid (salt) and toxilic acid (salt) under the existence of persulfuric acid (salt) and acidic sulfurous acid (salt).Such manufacture method is also one of the present invention.By carrying out polyreaction under the share at persulfuric acid (salt) and acidic sulfurous acid (salt), can suitably obtain the above-mentioned copolymer compositions that calcium capture ability and gel resistance are extremely excellent.
< monomer composition >
In above-mentioned monomer component, the usage ratio of vinylformic acid (salt) and toxilic acid (salt) is preferably 80/20～95/5 in mol ratio (vinylformic acid (salt)/toxilic acid (salt)).By selecting this scope, can improve calcium capture ability and gel resistance that above-mentioned multipolymer and copolymer compositions produce, in addition, can carry out polyreaction with high percent polymerization, can efficiently and easily obtain above-mentioned multipolymer and copolymer compositions.More preferably 82/18～92/8, more preferably 85/15～90/10.
In addition, except vinylformic acid (salt) and toxilic acid (salt), above-mentioned monomer component can also further comprise one kind or two or more can with other monomer of any one or both copolymerization in them.About other monomer, as mentioned above.
In above-mentioned monomer component, the ratio of vinylformic acid (salt) and the total consumption of toxilic acid (salt) and the consumption of other monomer is preferably 100/0～80/20 in mol ratio (total amount/other monomer of vinylformic acid (salt) and toxilic acid (salt)).By selecting this scope, can further improve calcium capture ability and gel resistance that above-mentioned multipolymer and copolymer compositions produce.More preferably 100/0～85/15, more preferably 100/0～90/10.
< acidic sulfurous acid (salt) etc., persulfuric acid (salt) >
The polymerization process of above-mentioned monomer component carries out under the existence of persulfuric acid (salt) and acidic sulfurous acid (salt), and the copolymer compositions being obtained by such manufacture method preferably comprises vinylformic acid (salt)-toxilic acid (salt) based copolymer, from the sulfur atom-containing low molecular compound of persulfuric acid (salt) with from the sulfur atom-containing low molecular compound of acidic sulfurous acid (salt).
It should be noted that, as the sulfur atom-containing low molecular compound from persulfuric acid (salt), vitriol is main component, as the sulfur atom-containing low molecular compound from acidic sulfurous acid (salt), 3-sulfo group propionic acid (salt) and 2-sulfo-succinic acid (salt) are main components.
These sulfur atom-containing low molecular compounds are preferably contained in above-mentioned copolymer compositions with the above-mentioned ratio that contains.
In above-mentioned polymerization process, persulfuric acid (salt) and acidic sulfurous acid (salt) can use respectively one kind or two or more.
Above-mentioned persulfuric acid (salt) mainly plays the effect of polymerization starter.As persulfuric acid (salt), for example, be preferably the persulphates such as Sodium Persulfate, Potassium Persulphate, ammonium persulphate.In addition, can also share one kind or two or more other polymerization starter together with persulfuric acid (salt).As other polymerization starter, can enumerate such as hydrogen peroxide, azo-compound, organo-peroxide etc.
Above-mentioned acidic sulfurous acid (salt) mainly plays the effect of chain-transfer agent.It should be noted that, except acidic sulfurous acid (salt), can also further share one kind or two or more other chain-transfer agent.
As above-mentioned acidic sulfurous acid (salt), be preferably the bisul-phites such as sodium acid sulfite, acidic potassium sulfite, acidic ammonium sulfite.
It should be noted that, in the present invention, can or replace above-mentioned acidic sulfurous acid (salt) except above-mentioned acidic sulfurous acid (salt) and use the one kind or two or more compound that can produce acidic sulfurous acid (salt).As the compound that can produce acidic sulfurous acid (salt), for example, be preferably pyrosulphite (salt), SODIUM HYDROSULPHITE (salt), sulfurous acid (salt) etc.
At above-mentioned acidic sulfurous acid (salt) with can produce among the compound of acidic sulfurous acid (salt) preferably acidic sulfurous acid (salt).
In above-mentioned polymerization process, persulfuric acid (salt) is preferably 1/0.5～1/5 with the usage ratio of acidic sulfurous acid (salt) in mass ratio (persulfuric acid (salt)/acidic sulfurous acid (salt)).If within the scope of this, can further prevent that the molecular weight of above-mentioned multipolymer from increasing, in addition, can make molecular weight distribution narrower.More preferably 1/1～1/4.
In addition,, in above-mentioned polymerization process, with respect to 1 mole of the whole monomer component that use in above-mentioned polymerization process, the total consumption of persulfuric acid (salt) and acidic sulfurous acid (salt) is preferably 5g～20g.If within the scope of this, the molecular weight that can further prevent above-mentioned multipolymer increases, can make in addition molecular weight distribution narrower, and can further prevent the generation as the sulfur atom-containing low molecular compound of impurity, can be by the sulfur atom-containing low molecular compound in obtained copolymer compositions contain ratio control in above-mentioned scope.More preferably 10g～15g.
< polyvalent metal ion >
In addition, in order to promote the objects such as polymerization, above-mentioned polymerization process can carry out under the existence of polyvalent metal ion.Polyvalent metal ion can use one kind or two or more.
As above-mentioned polyvalent metal ion, for example, be preferably iron ion (Fe
2+, Fe
3+), vanadium ion (V
2+, V
3+, VO
2+), cupric ion (Cu
2+) etc., wherein preferably at least use iron ion.
Supply form to above-mentioned polyvalent metal ion is not particularly limited, and for example preferably, uses Ionized metal and/or metallic compound in polymerization reaction system, thereby polyvalent metal ion is present in polymerization system in polymerization process.For example, preferably add in polymerization system dissolving the solution (being preferably the aqueous solution or aqueous solution) that such metal and/or metallic compound form.
As Ionized metal in above-mentioned polymerization reaction system, can enumerate such as iron, vanadium, copper etc.
As Ionized metallic compound in above-mentioned polymerization reaction system, can enumerate for example vanadium oxytrichloride, vanadium trichloride, vanadium oxalate, Vanadosulfuric acid, anhydrous vanadic acid, ammonium meta-vanadate, sulfuric acid time vanadium ammonium ((NH
4)
2sO
4vSO
46H
2o), the sub-vanadium ammonium of sulfuric acid ((NH
4) V (SO
4)
212H
2o), venus crystals (II), cupric bromide (II), etheric acid copper (II), cupric chloride, copper carbonate, cupric chloride (II), Cuprocitrol (II), Tubercuprose (II), copper hydroxide (II), cupric oleate (II), toxilic acid copper, cupric phosphate, copper sulfate (II), ferric acetyl acetonade, ferric ammonium citrate, ferric ammonium oxalate, ferrous ammonium sulphate, ferric ammonium sulfate, ironic citrate, ferrous fumarate, toxilic acid iron, iron lactate, iron nitrate (III), pentacarbonyl iron, tertiary iron phosphate (III), the water-soluble metal salts such as ferric pyrophosphate (III), the metal oxides such as vanadium pentoxide, cupric oxide (II), iron protoxide, ferric oxide, the metallic sulfides such as cupric sulfide (II), iron sulphide, etc..
The in the situation that of using polyvalent metal ion in above-mentioned polymerization process, preferably in the early stage 80 quality % in the use total amount 100 quality % of polyvalent metal ion (above-mentioned metallic compound and/or metal) are dropped in reaction vessel above.More preferably drop in the early stage 100 quality %, all measure.
About the consumption of above-mentioned polyvalent metal ion, as the consumption of above-mentioned metallic compound and/or metal, the total mass of the polymerization liquid in the moment of the whole amount monomer components that use with respect to interpolation, is preferably 5ppm～500ppm.If more than 5ppm, there is the tendency of the decomposition efficiency that can further improve the polymerization starters such as persulfuric acid (salt), if in addition below 500ppm, painted possibility is suppressed more fully, and can show more fully additive effect.
< polymer solvent >
Above-mentioned polymerization process preferably carries out in solvent.As solvent, preferably use aqueous solvent.Aqueous solvent refers to the mixed solvent of water or water and organic solvent.In aqueous solvent, with ratios more than 80 quality % comprise water, the aqueous solvent that comprises organic solvent with the ratio below 20 quality % is preferred.More preferably water.
As the organic solvent using in above-mentioned aqueous solvent, can enumerate the lower alcohols such as such as methyl alcohol, ethanol, Virahol; The amidess such as diethyl formaldehyde; The ethers such as diethyl ether; Etc..Organic solvent can use one kind or two or more.
In addition, in above-mentioned polymerization process, other starting material that the consumption of the theoretical solid component concentration (referring to the concentration of nonvolatile component among polymeric solution) of the multipolymer after preferably stopping take polymerization with respect to polymeric solution 100 quality % more than 40 quality % uses monomer component, polymerization starter, aqueous solvent and use as required.Thus, can make the molecular weight distribution of above-mentioned multipolymer narrower.
The theoretical solid component concentration of above-mentioned multipolymer can regulate by utilizing the initial stage to feed intake and dripping the each raw-material quality being supplied in reactor.For example, in the alkali such as vinylformic acid or toxilic acid (acid anhydride) and sodium hydroxide are supplied to reactor respectively and the in the situation that of neutralization in reactor, also must consider to generate water by neutralizing.
< polymerization temperature >
Temperature (also referred to as polymerization temperature) when above-mentioned polyreaction is preferably 25 ℃～150 ℃.More preferably 25 ℃～99 ℃.In the situation that being less than 25 ℃, the likely fully rising of Inhibitory molecules amount and the increase of impurity, polymerization time becomes long in addition, and productivity likely cannot be more abundant.On the other hand, if polymerization temperature is too high, in the situation that using acidic sulfurous acid (salt) as initiator system, acidic sulfurous acid (salt) likely decomposes and produces in a large number sulfurous gas, therefore, likely cannot fully prevent after polymerization that sulfurous gas is dissolved in forms impurity in liquid phase.In addition, in polymerization, sulfurous gas is also likely discharged to outside system and produces and recycle cost, and be discharged from the form of sulfurous gas as the acidic sulfurous acid (salt) of initiator system, thereby cannot obtain and the abundant effect of adding this acidic sulfurous acid (salt) and conforming to, there is the tendency that molecular weight cannot reduce.As the lower limit of polymerization temperature, more preferably 50 ℃ above, be particularly preferably more than 70 ℃.In addition, as the upper limit of polymerization temperature, more preferably 95 ℃ following, be particularly preferably below 90 ℃.
It should be noted that, herein said " polymerization temperature " refer to reaction soln temperature in reaction system (℃).
< polymerization pressure >
In above-mentioned polymerization process, the pressure in reaction system is not particularly limited, can be under normal pressure, under decompression, add under any pressure of depressing.
The addition means > of the each raw material of <
In above-mentioned polymerization process, can also before polymerization causes, part or all of above-mentioned monomer component be added in reaction vessel (reaction solution), the initial stage of carrying out feeds intake.Particularly, consider from the angle of the remaining monomer of further minimizing, preferably before polymerization causes, the toxilic acid of whole consumptions (salt) is added in reaction vessel (reaction solution), but also a part of toxilic acid (salt) can be added after polymerization causes.In addition, preferably after polymerization causes, by it, part or all adds in reaction vessel (reaction solution) vinylformic acid (salt).By interpolation vinylformic acid (salt) after causing in polymerization part or all, can make the molecular weight distribution of obtained multipolymer narrower, and can further improve calcium capture ability and gel resistance that above-mentioned copolymer compositions produces.It should be noted that, monomer component can add separately, also can be dissolved in water equal solvent or with other raw material etc. and mix to add in addition.
In this specification sheets, " before polymerization initiation " referred to before polymerization causes the moment, and " polymerization causes rear " refers to after polymerization causes the moment." polymerization causes the moment " refers to that part or all of polymerization starter and part or all of monomer component are added to the moment in reaction vessel (reaction solution).
Above-mentioned polymerization starter preferably comprises persulfuric acid (salt), can add in reaction vessel disposable whole consumptions of this polymerization starter, also part or all can be added drop-wise in reaction vessel.Preferably part or all of polymerization starter is added drop-wise in reaction vessel, can controls thus and in polymerization, be present in the polymerization starter concentration in reaction system, thereby can make the molecular weight distribution of polymkeric substance narrow etc.More preferably by dripping, 80 quality % in the use total amount of polymerization starter 100 quality % are supplied in reaction vessel above.Further preferably by dripping 100 quality % in the use total amount of polymerization starter 100 quality %, all measuring and be supplied in reaction vessel.
The interpolation time (being preferably time for adding) to above-mentioned polymerization starter in reaction vessel (reaction solution) is not particularly limited, for example, after preferably in the time that the interpolation of vinylformic acid (salt) stops, add, or in front and back in the time that the interpolation of vinylformic acid (salt) stops 20 minutes, end is added.More preferably the interpolation of the above-mentioned polymerization starter of end in front and back in the time that the interpolation of vinylformic acid (salt) stops 10 minutes.Thus, can further reduce the residual volume of the monomer in obtained copolymer compositions.
In above-mentioned polymerization process, in polymerization, at least changing once above-mentioned polymerization starter (being preferably persulfuric acid (salt)) is preferred to the feed speed (adding speed also referred to as polymerization starter) in reaction vessel.Thus, can further suppress the generation of 3-sulfo group propionic acid (salt) and 2-sulfo-succinic acid (salt), can be further by they contain ratio control in above-mentioned scope, therefore can improve calcium capture ability and the gel resistance of obtained copolymer compositions.Like this, following mode is also one of optimal way of the present invention, which is: above-mentioned manufacture method comprises that part or all by polymerization starter add the operation in reaction vessel to, and in polymerization, changes at least one times the interpolation speed of this polymerization starter.
It should be noted that, the in the situation that of changing above-mentioned feed speed at least one times in polymerization, more preferably the polymerization starter at polymerization initial stage is added speed (for example, from polymerization causes the moment 30 minutes with interior V-bar) be set as being greater than (faster than) polymerization starter of time period beyond this adds speed.The mode that the polymerization starter that, the polymerization starter interpolation speed at polymerization initial stage is greater than the time period beyond this adds speed is one of optimal way of the present invention.Thus, can make calcium capture ability and gel resistance more preferably.More preferably the polymerization starter at polymerization initial stage (is for example added to speed, causing the moment 30 minutes with interior V-bar from polymerization) polymerization starter that is set as the time period beyond this adds the speed of 1.1 times～10 times of speed, further be preferably set to the speed of 1.2 times～5 times, particularly preferably be set as the speed of 1.25 times～4.5 times, be most preferably set as the speed of 1.3 times～4 times.
Above-mentioned acidic sulfurous acid (salt) can add in reaction vessel (reaction solution) disposable whole consumptions, also can polymerization cause after by it, part or all is added drop-wise in reaction vessel.Preferably after polymerization causes, part or all of acidic sulfurous acid (salt) added in reaction vessel.More preferably by dripping, 80 quality % in the use total amount of acidic sulfurous acid (salt) 100 quality % are supplied in reaction vessel above, thus, can be by acidic sulfurous acid (salt) more effectively for polyreaction, can fully reduce acidic sulfurous acid (salt) possibility that is decomposed of stage in the early stage.Further preferably by dripping 100 quality % in use total amount 100 quality %, all measuring and be supplied in reaction vessel.
Above-mentioned acidic sulfurous acid (salt) was not particularly limited to the interpolation time in reaction vessel (reaction solution), for example, after preferably in the time that the interpolation of vinylformic acid (salt) stops, add, or in front and back in the time that the interpolation of vinylformic acid (salt) stops 20 minutes, end is added.More preferably the interpolation of end acidic sulfurous acid (salt) in front and back in the time that the interpolation of vinylformic acid (salt) stops 10 minutes.Thus, can further improve calcium capture ability and the gel resistance of obtained copolymer compositions.
In above-mentioned polymerization process, the in the situation that of dripping above-mentioned each composition etc. in polymerization, its time for adding is not particularly limited, for example, for each composition be preferably 40 minutes～420 minutes.More preferably 60 minutes～360 minutes.
It should be noted that, time for adding can be different because of each composition.In addition, except situation about mentioning especially hereinbefore, the rate of addition of each composition is not particularly limited.For example, rate of addition can be certain from dripping beginning to finishing, and also can change as required rate of addition.
Degree of neutralization > in < polymerization
In addition, above-mentioned polymerization process preferably carries out under acidic conditions.By carry out polyreaction under acidic conditions, can fully suppress the viscosity rise of the solution (being preferably the aqueous solution) of polymerization reaction system, can manufacture well low-molecular-weight above-mentioned multipolymer.And, can under than the condition of greater concn in the past, carry out polyreaction, therefore can make to manufacture efficiency and further significantly rise.In addition, by carry out polyreaction under acidic conditions, can with high density and a step carry out polymerization, thereby can also omit in manufacture method in the past according to circumstances needed enrichment process.So the productivity of above-mentioned multipolymer (and copolymer compositions) further significantly improves, and can further suppress the rising of manufacturing cost.
Under above-mentioned acidic conditions, carry out in the mode of polyreaction, preferably make polymerization cause the degree of neutralization while feeding intake at the initial stage (be degree of neutralization) in moment and/or monomer component and drip that to stop the degree of neutralization in moment be 0%～40%.If degree of neutralization is within the scope of this, can further suppress the generation of 3-sulfo group propionic acid (salt) and 2-sulfo-succinic acid (salt), can be further by obtained copolymer compositions they contain ratio control in above-mentioned scope, calcium capture ability and the gel resistance of the copolymer compositions obtaining further improve.As above-mentioned degree of neutralization, more preferably 0%～35%, more preferably 0%～33%, be particularly preferably 0%～30%.In addition, from the point of view, the degree of neutralization (degree of neutralization when initial stage feeds intake) and the monomer component that most preferably make polymerization cause the moment drip the degree of neutralization that stops the moment in above-mentioned scope.
Herein, " polymerization causes the moment " is described above.
In addition, " degree of neutralization " refer to respect to ratio 100 % by mole of the carboxyls in the monomer component containing in reactor (reaction solution), salt type carboxyl (carboxyl being neutralized) (% by mole).For example, cause the moment in polymerization, to having dropped in the reaction solution being equipped with in polymeric kettle (reaction vessel) in the situation of 1 mole of toxilic acid and 1 molar sodium hydroxide, the degree of neutralization that polymerization causes the moment is 50%.
In addition, in above-mentioned polymerization process, be preferably 1～6 by the pH regulator of 25 ℃ of the reaction soln in polymerization.
The > of manufacturing process beyond < polymerization process
Except above-mentioned polymerization process, the manufacture method of above-mentioned copolymer compositions can also comprise 1 or 2 above other operations.For example, the multipolymer obtaining in polymerization process is in acid type or part and when the situation of type etc., in can comprising as required and operation.In addition, can comprise as required following operation: the mixed processes that adds other composition in polymerization process in the copolymer compositions of manufacturing; Part is contained to the refining step that composition is removed or reduced; Dilution operation and the concentrate drying operation of the quantity of solvent of increase and decrease copolymer compositions; Etc..
Like this, following mode is also one of optimal way of the present invention, which is: must be included in the operation that will comprise the monomer component polymerization of vinylformic acid (salt) and toxilic acid (salt) under the existence of persulfuric acid (salt) and acidic sulfurous acid (salt), can comprise alternatively other operation.
(purposes of multipolymer (composition))
Copolymer compositions of the present invention (and multipolymer) can be served as the uses such as such as water conditioner, fibre finish, dispersion agent, washing assistant.As washing assistant, can add to dress material, tableware, house, hair, health, toothpaste with and automobile use etc. in the washing composition of various uses and use.Above-mentioned copolymer compositions can be particularly preferred in the water-soluble polymers purposes such as such washing assistant.Among these purposes, be preferably compounded in detergent composition and use.The detergent composition that, comprises aforesaid propylene acid (salt)-toxilic acid (salt) based copolymer composition is also one of the present invention.Such detergent composition is by comprising aforesaid propylene acid (salt)-toxilic acid (salt) based copolymer, can bring into play extremely good calcium capture ability and gel resistance, therefore also can bring into play excellent cleansing power in the very high areas of water hardness such as the U.S., China, Europe.
In addition, the calcium capture ability value of above-mentioned copolymer compositions is preferably 220mgCaCO
3more than/g, this calcium capture ability value utilizes aftermentioned method to obtain.Thus, even if also can show more excellent cleansing power in high hardness water.More preferably 230mgCaCO
3/ g is above, 240mgCaCO more preferably
3/ g is above, be particularly preferably 250mgCaCO
3/ g is above, most preferably be 260mgCaCO
3more than/g.
In addition, the gel degree of above-mentioned copolymer compositions is preferably less than 0.05, and this gel degree utilizes aftermentioned method to obtain.Thus, even if also can show more excellent cleansing power in high hardness water, can be used as more suitably the additive of washing composition.Be more preferably less than 0.04.
< detergent composition >
Said detergent composition comprises aforesaid propylene acid (salt)-toxilic acid (salt) based copolymer, preferably further comprises tensio-active agent.Thus, can bring into play more excellent cleansing power.Tensio-active agent can use one kind or two or more according to needs.
In said detergent composition, with respect to the solids component total amount 100 quality % of detergent composition, above-mentioned multipolymer containing the proportional 0.1 quality %～20 quality % that is preferably.More preferably 0.5 quality %～15 quality %.In addition, with respect to the solids component total amount 100 quality % of detergent composition, above-mentioned tensio-active agent containing the proportional 5 quality %～99.8995 quality % that are preferably.More preferably 5 quality %～90 quality %, more preferably 5 quality %～70 quality %, be particularly preferably 20 quality %～60 quality %.
As above-mentioned tensio-active agent, can use any one in anion surfactant, nonionogenic tenside, amphoterics, cats product.
As above-mentioned anion surfactant, can enumerate such as alkylbenzene sulfonate, sulfated alkyl ether, alkene ether vitriol, alkyl-sulphate, alkenyl sulfate, sulfonated α-olefin, alpha-sulfo-fatty acid or ester salt, alkane sulfonate, saturated or unsaturated fatty acid salt, alkyl ether carboxy acid salt, alkene ether carboxylate salt, amino acid type surfactant, N-acyl amino acid type tensio-active agent, alkyl phosphate or its salt, thiazolinyl phosphoric acid ester or its salt etc.
As above-mentioned nonionogenic tenside, can enumerate such as polyoxyalkylene alkyl, polyoxyalkylene alkene ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkylolamide or its oxirane affixture, sucrose fatty ester, alkyl glycoside, fatty mono glyceride, alkyl amine oxide etc.
As above-mentioned amphoterics, for example can enumerate carboxyl type amphoterics, sultaine type amphoterics.
As above-mentioned cats product, can enumerate for example quaternary ammonium salt.
As required, can also be in said detergent composition the one kind or two or more enzyme of mixture, alkaline auxiliary lotion, inner complex washing assistant, conventional composition in the detergent composition such as Anti-adhesion agent, fluorescent agent, SYNTHETIC OPTICAL WHITNER, spices again.
With respect to the solids component total amount 100 quality % of this detergent composition, the content of the 3-sulfo group propionic acid (salt) comprising in said detergent composition converts and is preferably 0.0005 quality %～2 quality % in Na salt type.Thus, can bring into play more fully action effect of the present invention.As the content (conversion of Na salt type) of 3-sulfo group propionic acid (salt), be preferably 1.9 quality % following, more preferably 1.8 quality % following, more preferably below 1.7 quality %.The lower value (conversion of Na salt type) of the content to above-mentioned 3-sulfo group propionic acid (salt) is not particularly limited, for example, more than being preferably 0.001 quality %, more preferably more than 0.01 quality %.
It should be noted that, following detergent composition is also one of the present invention, the detergent composition of this detergent composition for comprising aforesaid propylene acid (salt)-toxilic acid (salt) based copolymer and sulfur atom-containing low molecular compound, this sulfur atom-containing low molecular compound comprises 3-sulfo group propionic acid (salt), and the content of this 3-sulfo group propionic acid (salt) is 0.0005 quality %～2 quality % with respect to the solids component total amount 100 quality % of this detergent composition.Such detergent composition can obtain by the copolymer compositions by the invention described above.
The effect of invention
Vinylformic acid of the present invention (salt)-toxilic acid (salt) based copolymer composition is above-mentioned formation, and therefore calcium capture ability and gel resistance are all extremely good, thereby can be compatibly for water-soluble polymers purposes such as washing assistants.In addition, even if the detergent composition that comprises such copolymer compositions and detergent composition of the present invention also can be brought into play very excellent cleansing power in the very high areas of the water hardness such as the U.S., China, Europe, be exceedingly useful.In addition, if use the manufacture method of vinylformic acid of the present invention (salt)-toxilic acid (salt) based copolymer composition, can efficiently and easily obtain all vinylformic acid (salt)-toxilic acid (salt) based copolymer compositions of excellence of calcium capture ability and gel resistance.
Embodiment
Below, enumerate embodiment and illustrate in greater detail the present invention, but the present invention is not limited in these embodiment.Only otherwise special declaration, " part " refers to " weight part ", and " % " refers to " quality % ".
It should be noted that, utilize following method to carry out each analysis and mensuration.
The quantivative approach > of < monomer, 3-sulfo group propionic acid disodium (also referred to as " 3SPA ") and 2-sulfo-succinic acid trisodium (also referred to as " 2SSA ")
The mensuration of the content of monomer etc. is used liquid chromatography to carry out under the following conditions.
Device: society of Hitachi manufactures L-7000 series
Detector: society of Hitachi manufactures UV detector L-7400
Post: Dong Caoshe manufactures ODS-100V4.6 × 250mm2 root
Column temperature: 20 ℃
Flow rate of mobile phase: 0.5ml/ minute
Moving phase: 5mmol/L primary ammonium phosphate (pH2.4)
Detect wavelength: 210nm
< sodium sulfate (Na
2sO
4) quantivative approach >
The mensuration of the content of sodium sulfate is used chromatography of ions to carry out under the following conditions.
Device: Metrohm society manufactures (762Interface)
Detector: Metrohm society manufactures (732IC Detecter)
Ion analysis mode: inhibition method
Post: Shodex IC SI-904E
Guard column: Shodex SI-90G
Column temperature: 40 ℃
Elutriant: NaHCO
3water (being 2000g by 2g dilute with water)
Flow velocity: 1.0mL/ minute
Condition determination (GPC) > of < weight-average molecular weight and number-average molecular weight
Device: society of Hitachi manufactures L-7000 series
Detector: RI
Post: clear and electrician society manufactures SHODEX Asahipak GF-310-HQ, GF-710-HQ, GF-1G7B
Column temperature: 40 ℃
Flow velocity: 0.5ml/ minute
Calibration curve: wound and science society manufacture polyacrylic acid standard
Elutriant: 0.1N aqueous sodium acetate solution
The solids component of < copolymer compositions (multipolymer) is measured >
By copolymer compositions (to the composition that adds water 1.0g in obtained copolymer compositions 1.0g and obtain) under nitrogen atmosphere, be heated to place 1 hour in the baking oven of 170 ℃, carry out drying treatment.Calculate solids component (%) and volatile component (%) by the quality change before and after dry.
The evaluation > of < calcium capture ability (also referred to as Ca capture ability)
The calcium chloride water 50g that gets 0.001mol/L, to the capacity beaker that is 100cc, converts and adds the copolymer compositions of 10mg in solids component.Then be, 9～11 with dilute sodium hydroxide by the pH regulator of this aqueous solution.Afterwards, the potassium chloride solution 1ml that under agitation adds 4mol/L is as calcium ion electrode stablizer.
Use ion analyser (EA920 type, Orion society manufacture) and calcium ion electrode (93-20 type, Orion society manufacture) to measure free calcium ion, obtain with respect to every 1g copolymer compositions with calcium carbonate conversion in respect of the calcium ion of how many mg be chelated (sequestering power a kind---calcium capture ability) by calculating.The unit of calcium capture ability is " mgCaCO
3/ g ".
The evaluation > of < gel resistance
In the conical beaker of 500mL, add successively pure water, boric acid-Sodium Tetraborate pH damping fluid, copolymer compositions and calcium chloride solution, prepare respectively take solid component concentration and comprise this copolymer compositions of 100mg/L, calcium concn as 50mgCaCO
3/ L, pH are 8.5 testing liquid, use afterwards polyvinylidene dichloride film phonograph seal, in the thermostatic bath of 90 ℃, leave standstill 1 hour, evaluate gel resistance according to whether producing precipitation.
In the situation that having produced precipitation, can say that gel resistance is significantly low.
About the situation that does not produce precipitation, after stirring, adding optical length is in the quartz container of 5cm in addition, measures the absorbancy (a) under UV wavelength 380nm.As blank, prepare by the testing liquid of having removed calcium chloride solution in the aqueous solution as above-mentioned testing liquid, carry out same operation and measure absorbancy (b), obtain gel degree by following formula.
Gel degree=(a)-(b)
The numerical value of gel degree is less, can say that gel resistance is higher.
Embodiment 1
In the removable flask of SUS system that is 2.5L to the capacity that possesses reflux exchanger and stirrer, drop into ion exchanged water 180.8g, maleic anhydride (hereinafter also referred to as " MA acid anhydride ") 49.0g, further add 48% aqueous sodium hydroxide solution (hereinafter also referred to as " 48%NaOHaq ") 25.0g.Afterwards, be under agitation warming up to 85 ℃.After interior temperature arrives 85 ℃, maintain 85 ℃, drip respectively 80% acrylic acid aqueous solution (hereinafter also referred to as " 80%AAaq ") 405.0g, 48%NaOH aqueous solution 112.5g, 35% acidic sulfurous acid sodium water solution (hereinafter also referred to as " 35%SBSaq ") 157.1g and 15% sodium persulfate aqueous solution (hereinafter also referred to as " 15%NaPSaq ") 100.0g by different dropping nozzles, 80% vinylformic acid dripped with 180 minutes, 48% aqueous sodium hydroxide solution dripped with 180 minutes, and 35% acidic sulfurous acid sodium water solution dripped with 170 minutes.In addition, about 15% sodium persulfate aqueous solution, within 30 minutes in the early stage, add the amount of 1.3g with respect to every 1 equimolar acid (total amount of vinylformic acid and maleic anhydride), between 30 minutes～190 minutes, drip the amount of 1.7g with respect to every 1 equimolar acid.
Drip after termination, reaction soln is further maintained to 30 minutes at 85 ℃, carry out slaking.After polymerization stops, cooled reaction solution, drips lentamente 48% aqueous sodium hydroxide solution 275.0g and neutralizes.Like this, obtain vinylformic acid (salt)-toxilic acid (salt) based copolymer composition that solid component concentration is 47.5%, finally degree of neutralization is 90%.The each physical property measurement that carries out obtained copolymer compositions, the results are summarized in table 3.
Embodiment 2
In the removable flask of SUS system that is 2.5L to the capacity that possesses reflux exchanger and stirrer, drop into ion exchanged water 180.8g, maleic anhydride 49.0g, further add 48% aqueous sodium hydroxide solution 25.0g.Afterwards, be under agitation warming up to 85 ℃.After interior temperature arrives 85 ℃, maintain 85 ℃, drip respectively 80% acrylic acid aqueous solution 405.0g, 48%NaOH aqueous solution 112.5g, 35% acidic sulfurous acid sodium water solution 157.1g and 15% sodium persulfate aqueous solution 100.0g by different dropping nozzles, 80% vinylformic acid dripped with 180 minutes, 48% aqueous sodium hydroxide solution dripped with 180 minutes, and 35% acidic sulfurous acid sodium water solution dripped with 170 minutes.In addition, 15% sodium persulfate aqueous solution adds the amount of 1.3g for 30 minutes in the early stage with respect to every 1 equimolar acid (total amount of vinylformic acid and maleic anhydride), between 30 minutes～60 minutes, drip the amount of 0.7g with respect to every 1 equimolar acid, between 60 minutes～190 minutes, drip the amount of 1.0g with respect to every 1 equimolar acid.
Drip after termination, reaction soln is further maintained to 30 minutes at 85 ℃, carry out slaking.After polymerization stops, cooled reaction solution, drips lentamente 48% aqueous sodium hydroxide solution 275.0g and neutralizes.Like this, obtain vinylformic acid (salt)-toxilic acid (salt) based copolymer composition that solid component concentration is 47.9%, finally degree of neutralization is 90%.The each physical property measurement that carries out obtained copolymer compositions, the results are summarized in table 3.
Embodiment 3～11
Except initial stage charging capacity, dripping quantity and rear dosis neutralisata are as shown in table 1, utilize method similarly to Example 2 to carry out.Each physical property measurement of obtained copolymer compositions be the results are summarized in to table 3.
Comparative example 1
In the removable flask of SUS system that is 2.5L to the capacity that possesses reflux exchanger and stirrer, drop into ion exchanged water 180.8g, maleic anhydride 49.0g, further add 48% aqueous sodium hydroxide solution 50.0g.Afterwards, be under agitation warming up to 85 ℃.After interior temperature arrives 85 ℃, maintain 85 ℃, drip respectively 80% acrylic acid aqueous solution 405.0g, 48%NaOH aqueous solution 87.5g, 35% acidic sulfurous acid sodium water solution 157.1g and 15% sodium persulfate aqueous solution 100.0g by different dropping nozzles, 80% vinylformic acid dripped with 180 minutes, 48% aqueous sodium hydroxide solution dripped with 180 minutes, 35% acidic sulfurous acid sodium water solution dripped with 170 minutes, and 15% sodium persulfate aqueous solution dripped with 190 minutes.
Drip after termination, reaction soln is further maintained to 30 minutes at 85 ℃, carry out slaking.After polymerization stops, cooled reaction solution, drips lentamente 48% aqueous sodium hydroxide solution 275.0g and neutralizes.Like this, obtain vinylformic acid (salt)-toxilic acid (salt) based copolymer composition that solid component concentration is 47.5%, finally degree of neutralization is 90%.The each physical property measurement that carries out obtained copolymer compositions, the results are summarized in table 3.
Comparative example 2～3
Except initial stage charging capacity, dripping quantity and rear dosis neutralisata are as shown in table 2, utilize the method same with comparative example 1 to carry out.Each physical property measurement of obtained copolymer compositions be the results are summarized in to table 3.
Comparative example 4
In the removable flask of SUS system that is 2.5L to the capacity that possesses reflux exchanger and stirrer, drop into ion exchanged water 111.4g, maleic anhydride 64.7g, further add 48% aqueous sodium hydroxide solution 101.3g.Afterwards, be under agitation warming up to 85 ℃.After interior temperature arrives 85 ℃, maintain 85 ℃, drip respectively 80% acrylic acid aqueous solution 365.6g, 48%NaOH aqueous solution 311.4g, 35% aqueous hydrogen peroxide solution 80.9g and 15% sodium persulfate aqueous solution 157.3g by different dropping nozzles, 80% vinylformic acid dripped with 300 minutes, 48% aqueous sodium hydroxide solution dripped with 300 minutes, 35% aqueous hydrogen peroxide solution dripped with 300 minutes, and 15% sodium persulfate aqueous solution dripped with 320 minutes.
Drip after termination, reaction soln is further maintained to 30 minutes at 85 ℃, carry out slaking, carry out afterwards cooling, vinylformic acid (salt)-toxilic acid (salt) based copolymer composition that obtain solid component concentration and be 41.0%, final degree of neutralization is 92.2%.The each physical property measurement that carries out obtained copolymer compositions, the results are summarized in table 3.
[table 1]
[table 2]
In table 1 and 2, " aq " refers to the aqueous solution.In addition, " 15%NaPSaq is constant " refers to and do not change the rate of addition of the 15%NaPS aqueous solution during the course and be constant.
[table 3]
As shown in Table 3, the calcium capture ability of vinylformic acid of the present invention (salt)-toxilic acid (salt) based copolymer composition all high, be 270mgCaCO
3more than/g, and gel degree all low, be below 0.04, gel resistance is all very excellent.On the other hand, more or completely not containing 3-sulfo group propionic acid (salt), known gel resistance is poor especially than the amount of the present invention's regulation at the content of 3-sulfo group propionic acid (salt).In addition we know, by when the manufacture of copolymer compositions to add in reaction vessel as the persulfuric acid (salt) of polymerization starter part or all, and in polymerization, change at least one times the interpolation speed of this polymerization starter, can preferably obtain vinylformic acid of the present invention (salt)-toxilic acid (salt) based copolymer composition of the high and gel resistance excellence of calcium capture ability.Wherein known, particularly, by making the interpolation speed that causes the moment polymerization starter of 30 minutes from polymerization be greater than the interpolation speed of the polymerization starter of the time period beyond this, calcium capture ability and gel resistance are more excellent.
Claims (4)
1. a vinylformic acid (salt)-toxilic acid (salt) based copolymer composition, its copolymer compositions for comprising vinylformic acid (salt)-toxilic acid (salt) based copolymer and sulfur atom-containing low molecular compound, it is characterized in that
The structural unit (II) that the structural unit (I) that this multipolymer comprises following general formula (1) expression and following general formula (2) represent,
This structural unit (I) is that structural unit (I)/structural unit (II) is 80/20～95/5 with the mol ratio that contains of structural unit (II),
The weight-average molecular weight of this multipolymer is more than 2000 and below 10000,
This sulfur atom-containing low molecular compound comprises 3-sulfo group propionic acid (salt),
With respect to the solids component total amount 100 quality % of this copolymer compositions, the content of this 3-sulfo group propionic acid (salt) is 0.01 quality %～10 quality %,
[Chemical formula 1]
In formula (1), M represents hydrogen atom, atoms metal, ammonium or organic amino group,
[Chemical formula 2]
In formula (2), M
1and M
2identical or different, represent hydrogen atom, atoms metal, ammonium or organic amino group.
2. the manufacture method of a vinylformic acid (salt)-toxilic acid (salt) based copolymer composition, this manufacture method is the method for vinylformic acid (salt)-toxilic acid (salt) based copolymer composition described in manufacture claim 1, it is characterized in that
This manufacture method is included in the operation that will comprise the monomer component polymerization of vinylformic acid (salt) and toxilic acid (salt) under the existence of persulfuric acid (salt) and acidic sulfurous acid (salt).
3. a detergent composition, is characterized in that, it comprises vinylformic acid claimed in claim 1 (salt)-toxilic acid (salt) based copolymer composition.
4. a detergent composition, its detergent composition for comprising vinylformic acid (salt)-toxilic acid (salt) based copolymer and sulfur atom-containing low molecular compound, is characterized in that,
The structural unit (II) that the structural unit (I) that this multipolymer comprises following general formula (1) expression and following general formula (2) represent,
This structural unit (I) is that structural unit (I)/structural unit (II) is 80/20～95/5 with the mol ratio that contains of structural unit (II),
The weight-average molecular weight of this multipolymer is more than 2000 and below 10000,
This sulfur atom-containing low molecular compound comprises 3-sulfo group propionic acid (salt),
With respect to the solids component total amount 100 quality % of this detergent composition, the content of this 3-sulfo group propionic acid (salt) is 0.0005 quality %～2 quality %,
[chemical formula 3]
In formula (1), M represents hydrogen atom, atoms metal, ammonium or organic amino group,
[chemical formula 4]
In formula (2), M
1and M
2identical or different, represent hydrogen atom, atoms metal, ammonium or organic amino group.
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| JP2011267488 | 2011-12-07 | ||
| JP2011-267488 | 2011-12-07 | ||
| PCT/JP2012/080168 WO2013084717A1 (en) | 2011-12-07 | 2012-11-21 | Acrylic acid (salt)-maleic acid (salt) copolymer composition, method for manufacturing same, and cleaning agent composition |
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| JP (1) | JP5722460B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566553A (en) * | 2014-10-13 | 2016-05-11 | 上海东升新材料有限公司 | Maleic anhydride-acrylic acid copolymer for washing agent and preparation method thereof |
| CN110402478A (en) * | 2017-03-06 | 2019-11-01 | 福吉米株式会社 | The manufacturing method of the surface treatment method and semiconductor substrate of surface treating composition and its manufacturing method and use surface treating composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6173736B2 (en) * | 2013-03-28 | 2017-08-02 | 株式会社日本触媒 | Acrylic acid (salt) -maleic acid (salt) polymer composition and method for producing the same |
| JP2015140377A (en) * | 2014-01-28 | 2015-08-03 | 株式会社日本触媒 | Method for manufacturing (meth)acrylic acid-based polymer |
| JP6298646B2 (en) * | 2014-02-12 | 2018-03-20 | 株式会社日本触媒 | Carboxyl group-containing copolymer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63235313A (en) * | 1987-03-25 | 1988-09-30 | Kao Corp | Preparation of maleic acid copolymer |
| CN1528818A (en) * | 1998-03-06 | 2004-09-15 | ��ʽ�����ձ���ý | (Meth) acrylic acid (salt) polymer and manufacturing method thereof |
| JP2007016244A (en) * | 1994-01-14 | 2007-01-25 | Rohm & Haas Co | Cleaning composition |
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| JP4070889B2 (en) * | 1998-03-06 | 2008-04-02 | 株式会社日本触媒 | (Meth) acrylic acid polymer and method for producing the same |
| JP4010921B2 (en) * | 2001-10-03 | 2007-11-21 | 株式会社日本触媒 | (Meth) acrylic acid-based polymer and unsaturated polyalkylene glycol-based copolymer, production method thereof, and detergent using the same |
| JP2004238521A (en) * | 2003-02-06 | 2004-08-26 | Nippon Shokubai Co Ltd | Production method for (meth)acrylic acid copolymer |
-
2012
- 2012-11-21 JP JP2013548172A patent/JP5722460B2/en active Active
- 2012-11-21 CN CN201280052449.1A patent/CN103890015B/en active Active
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63235313A (en) * | 1987-03-25 | 1988-09-30 | Kao Corp | Preparation of maleic acid copolymer |
| JP2007016244A (en) * | 1994-01-14 | 2007-01-25 | Rohm & Haas Co | Cleaning composition |
| CN1528818A (en) * | 1998-03-06 | 2004-09-15 | ��ʽ�����ձ���ý | (Meth) acrylic acid (salt) polymer and manufacturing method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566553A (en) * | 2014-10-13 | 2016-05-11 | 上海东升新材料有限公司 | Maleic anhydride-acrylic acid copolymer for washing agent and preparation method thereof |
| CN110402478A (en) * | 2017-03-06 | 2019-11-01 | 福吉米株式会社 | The manufacturing method of the surface treatment method and semiconductor substrate of surface treating composition and its manufacturing method and use surface treating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2013084717A1 (en) | 2015-04-27 |
| CN103890015B (en) | 2015-09-23 |
| WO2013084717A1 (en) | 2013-06-13 |
| JP5722460B2 (en) | 2015-05-20 |
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