WO2011126059A1 - Aqueous solution of poly(meth)acrylic acid polymer and method for producing same - Google Patents
Aqueous solution of poly(meth)acrylic acid polymer and method for producing same Download PDFInfo
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- WO2011126059A1 WO2011126059A1 PCT/JP2011/058740 JP2011058740W WO2011126059A1 WO 2011126059 A1 WO2011126059 A1 WO 2011126059A1 JP 2011058740 W JP2011058740 W JP 2011058740W WO 2011126059 A1 WO2011126059 A1 WO 2011126059A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
- C09D5/027—Dispersing agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
Definitions
- the present invention relates to a poly (meth) acrylic acid polymer aqueous solution and a production method thereof, and an inorganic particle slurry and a production method thereof. More specifically, the poly (meth) acrylic acid polymer aqueous solution, which excels in color tone, pigment dispersion, etc., and low viscosity, little change in viscosity over time, little coloring during drying, and high pH can be maintained.
- the present invention relates to an inorganic particle slurry.
- a carboxyl group-containing polymer typified by sodium poly (meth) acrylate is widely used in applications such as detergent builders, pigment dispersants, water treatment agents (scale component adhesion inhibitors). In these markets, polymers with higher performance are required.
- Patent Document 1 discloses a method for producing a water-soluble polymer in which a chain transfer agent is continuously added for a predetermined period during the polymerization period, which is a monomer of a chain transfer agent.
- a method for producing a water-soluble polymer characterized in that the rate of addition to is changed at least once.
- Patent Document 2 discloses that a monomer component composed of a monocarboxylic acid (salt) monoethylenically unsaturated monomer or the like is polymerized in an aqueous solution at a high concentration using a polymerization catalyst in the presence of an alkaline substance.
- the persulfate and hydrogen peroxide are used in combination as the polymerization catalyst, and the total amount of the alkaline substance used is an amount necessary to neutralize all the acid groups of the monomer component.
- a method for producing a polymer is disclosed.
- a compound containing calcium or the like is reacted in the range of 1 to 70 parts per 100 parts to a polymer of ⁇ , ⁇ monoethylenically unsaturated carboxylic acid, etc.
- a retained polymer is disclosed.
- inorganic particle slurries are widely used in the paper industry and ceramic industry for the purpose of coating and molding inorganic particles.
- Patent Document 3 discloses a compound containing calcium and the like in the range of 1 to 70 parts per 100 parts with respect to a polymer of ⁇ and ⁇ monoethylenically unsaturated carboxylic acids.
- Patent Document 4 discloses a neutralized product of (co) polymer (A) comprising 50 to 100 mol% of ⁇ , ⁇ -unsaturated carboxylic acid and 0 to 50 mol% of other monomers as structural units.
- Patent Document 5 discloses (meth) acrylic acid (co) polymers, etc., and (meth) acrylate units contained in the polymer are (meth) acrylic acid alkali metal salt units 49.9 to Wet pulverization of heavy calcium carbonate using a polymer consisting of 99 mole parts, 0.1 to 10 mole parts of alkaline earth metal salt units of (meth) acrylate and 0 to 10 mole parts of ammonium salt units of (meth) acrylate A heavy calcium carbonate slurry is disclosed that is manufactured including the following steps.
- JP 2005-139469 A Japanese Patent Laid-Open No. 2002-80502 JP 54-82416 A Japanese Patent No. 2984926 International Publication No. 2004/087574
- the polymer obtained by the production method disclosed in Patent Document 1 can reduce the amount of residual monomers, and can narrow the molecular weight distribution of the obtained polymer, thereby further improving calcium carbonate. It is said that the dispersibility of can be shown.
- the polymer obtained by the production method disclosed in Patent Document 2 is said to exhibit good pigment dispersibility.
- the polymer disclosed in Patent Document 3 is said to show a good pigment dispersion effect with a small amount of addition.
- the inorganic particle slurry is usually required to have a high concentration of inorganic particles and a viscosity that is easy to process.
- the slurry disclosed in Patent Document 3 is said to have low viscosity and good temporal stability.
- the dispersion slurry disclosed in Patent Document 4 is said to have a relatively small increase in slurry viscosity after standing for 7 days.
- the slurry disclosed in Patent Document 5 is said to have a low viscosity and a viscosity after 7 days.
- the present invention provides a polymer (aqueous solution) that is excellent in inorganic dispersibility and the like and exhibits sufficient dispersibility over time, and further a polymer (aqueous solution) that also has a good color tone over time, and those It aims at providing the method of manufacturing a polymer (aqueous solution) simply.
- the present invention also provides an inorganic particle slurry that exhibits high inorganic particle concentration and good viscosity, has sufficient viscosity stability over time, has little coloration during drying, and can maintain a high pH, and the inorganic particle slurry. It aims at providing the method of manufacturing simply.
- the inventors of the present invention have conducted intensive studies on the polymer (aqueous solution) and the production method thereof in order to solve the above problems. As a result, it has been found that a specific aqueous solution containing a polyacrylic acid polymer (partially) neutralized with an organic amine exhibits good dispersibility of inorganic substances and sufficient dispersibility with time stability.
- the invention has been completed. That is, the poly (meth) acrylic acid polymer aqueous solution according to the present invention is an aqueous solution containing a poly (meth) acrylic acid polymer, and at least one of the carboxyl groups of the poly (meth) acrylic acid polymer.
- the part is neutralized with an organic amine, and the structure derived from (meth) acrylic acid (salt) and the structure derived from organic amine (salt) contained in the poly (meth) acrylic acid polymer aqueous solution.
- the molar ratio is 100: 10 to 100: 75, and the concentration of inorganic anions containing sulfur atoms or phosphorus atoms contained in the poly (meth) acrylic acid polymer aqueous solution is the poly (meth) An aqueous solution characterized by being 1000 to 10,000 ppm based on the acrylic acid polymer aqueous solution.
- Another aspect of the present invention provides a method for producing an aqueous poly (meth) acrylic acid polymer solution. That is, the method for producing an aqueous poly (meth) acrylic acid polymer solution of the present invention is a method for producing an aqueous solution containing the poly (meth) acrylic acid polymer of the present invention, wherein the acid type and / or part thereof is used.
- a method for producing an aqueous poly (meth) acrylic acid polymer solution comprising a step of neutralizing an aqueous solution containing a Japanese-type poly (meth) acrylic acid polymer with an organic amine.
- a polymer (aqueous solution) having a good color tone over time by producing a specific aqueous solution containing a polyacrylic acid polymer (partially) neutralized with the organic amine by a specific production method. has been found, and the present invention has been completed.
- the molar ratio of the structure derived from (meth) acrylic acid (salt) and the structure derived from organic amine (salt) contained in the acrylic acid polymer aqueous solution is 100: 10 to 100: 75
- the concentration of the inorganic anion containing sulfur atom or phosphorus atom contained in the poly (meth) acrylic acid polymer aqueous solution is 1000 to 10,000 ppm with respect to the poly (meth) acrylic acid polymer aqueous solution.
- the poly (meth) acrylic acid polymer aqueous solution includes (i) a step of neutralizing an aqueous solution containing an acid type and / or partially neutralized poly (meth) acrylic acid polymer with an alkali metal salt; And (ii) a poly (meth) acryl produced essentially comprising a step of neutralizing an aqueous solution containing an acid type and / or partially neutralized poly (meth) acrylic acid polymer with an organic amine.
- An aqueous acid polymer solution is also one aspect of the present invention.
- the molar ratio of the structure derived from (meth) acrylic acid (salt) and the structure derived from organic amine (salt) contained in the acrylic acid polymer aqueous solution is 100: 10 to 100: 75, and
- the concentration of the inorganic anion containing a sulfur atom or phosphorus atom contained in the poly (meth) acrylic acid polymer aqueous solution is 1000 to 10,000 ppm with respect to the poly (meth) acrylic acid polymer aqueous solution.
- the poly (meth) acrylic acid polymer aqueous solution comprises (i) a step of neutralizing an aqueous solution containing an acid type and / or partially neutralized poly (meth) acrylic acid polymer with an alkali metal salt, i) a step of neutralizing an aqueous solution containing a partially neutralized poly (meth) acrylic acid polymer neutralized with an alkali metal salt with an organic amine, A meth) acrylic acid polymer aqueous solution is also one aspect of the present invention.
- Another aspect of the present invention provides a method for producing an aqueous poly (meth) acrylic acid polymer solution. That is, it is a method for producing an aqueous solution containing the poly (meth) acrylic acid polymer of the present invention, and (i) an aqueous solution containing an acid type and / or a partially neutralized poly (meth) acrylic acid polymer. And (ii) a step of neutralizing an aqueous solution containing an acid type and / or partially neutralized poly (meth) acrylic acid polymer with an organic amine as essential components.
- the method for producing a poly (meth) acrylic acid polymer aqueous solution characterized by the above is also one aspect of the present invention.
- the present inventors have conducted intensive studies on the inorganic particle slurry and the production method thereof in order to solve the above problems.
- the inorganic particle slurry containing a specific composition containing a polyacrylic acid polymer (partially) neutralized with an organic amine exhibits good viscosity and sufficient viscosity stability over time, The present inventors have found that there is little coloring during drying and that a high pH can be maintained, and the present invention has been completed. That is, the inorganic particle slurry according to the present invention is an inorganic particle slurry containing a poly (meth) acrylic acid polymer, and at least a part of the carboxyl groups of the poly (meth) acrylic acid polymer is an organic amine.
- the molar ratio of the structure derived from (meth) acrylic acid (salt) and the structure derived from organic amine (salt) contained in the inorganic particle slurry is 100: 10 to 100: 75.
- the concentration of inorganic anions containing sulfur atoms or phosphorus atoms contained in the inorganic particle slurry is 100 to 400 ppm relative to the inorganic particle slurry, and the inorganic particles contained in the inorganic particle slurry are all inorganic. 90-100% by mass of particles having a particle size of 2 ⁇ m or less is included with respect to 100% by mass of the particles, and the solid content concentration of the inorganic particle slurry is 75% by mass or more.
- the method for producing an inorganic particle slurry of the present invention is a method for producing an inorganic particle slurry comprising a step of adding an aqueous solution containing a poly (meth) acrylic acid polymer to inorganic particles and crushing the inorganic particles.
- the carboxyl groups of the poly (meth) acrylic acid polymer is neutralized with an organic amine, and the structure derived from (meth) acrylic acid (salt) and the organic amine contained in the aqueous solution.
- the molar ratio to the structure derived from (salt) is 100: 10 to 100: 75, and the concentration of inorganic anions containing sulfur atoms or phosphorus atoms contained in the aqueous solution is 1000 to 100 It is a manufacturing method of the inorganic particle slurry which is 10000 ppm.
- the aqueous poly (meth) acrylic acid polymer solution of the present invention has excellent dispersibility of inorganic fine particles such as mud stains and inorganic pigments, and can exhibit dispersibility over time. Further, by producing by a specific production method, it has excellent color tone over time. Therefore, when used as a detergent builder or a pigment dispersant, excellent detergency and stable dispersibility of the pigment over time can be obtained. According to the method for producing a poly (meth) acrylic acid polymer aqueous solution of the present invention, the poly (meth) acrylic acid polymer aqueous solution of the present invention can be produced efficiently and simply.
- the inorganic particle slurry of the present invention has the characteristics that the inorganic particle content is high, the viscosity is low, and the change in viscosity over time is low, it exhibits excellent moldability of inorganic particles. Therefore, it is preferably used as a pigment slurry for paper coating in the paper industry and ceramic industries. According to the method for producing an inorganic particle slurry of the present invention, an inorganic particle slurry having excellent viscosity and stability over time can be efficiently produced.
- the poly (meth) acrylic acid polymer aqueous solution of the present invention includes a poly (meth) acrylic acid polymer.
- the poly (meth) acrylic acid polymer represents a polymer containing a structure derived from (meth) acrylic acid (salt), and the structure derived from (meth) acrylic acid (salt) ) A structure formed by radical polymerization of acrylic acid (salt) and represented by —CH 2 CR (COOM) —.
- R represents a hydrogen atom or a methyl group
- M represents a hydrogen atom, a metal atom, an ammonium salt, or an organic amine salt.
- the metal atom examples include alkali metal atoms such as Li, Na, and K, and alkaline earth metal atoms such as Ca and Mg.
- the (meth) acrylic acid (salt) represents acrylic acid, acrylate, methacrylic acid, and methacrylate, and among these, acrylic acid and acrylate are preferable. These (meth) acrylic acids (salts) may be used alone or in combination of two or more.
- the salt in the (meth) acrylic acid (salt) include metal salts, ammonium salts, and organic amine salts. Among these, alkali metal salts are preferable, and sodium salts are more preferable. 1 type may be sufficient as the salt in these (meth) acrylic acid (salt), and 2 or more types may be sufficient as it.
- the carboxyl group possessed by the poly (meth) acrylic acid polymer is characterized in that at least a part thereof is neutralized with an organic amine salt, and all of the carboxyl groups possessed by the poly (meth) acrylic acid polymer Even if the structure is neutralized (neutralized type), a part of the carboxyl groups of the poly (meth) acrylic acid polymer is neutralized and the rest is an acid type structure. (Partial neutralization type) is acceptable.
- the ratio of the salt of is not specifically limited, the structure derived from (meth) acrylic acid (salt), the organic amine and the organic amine salt (this specification) contained in the poly (meth) acrylic acid polymer aqueous solution of the present invention.
- the molar ratio with the structure derived from “organic amine (salt)” is 100: 10 to 100: 75.
- it is 100: 15 to 100: 70, and more preferably 100: 20 to 100: 65.
- the organic amine (salt) may be any of primary amine, secondary amine, tertiary amine, quaternary amine, and salts thereof, and one kind may be used alone, or two or more kinds may be used. You may use together.
- Examples of such organic amines include alkanolamines such as monoethanolamine, monopropanolamine, diethanolamine, and triethanolamine; alkylamines such as methylamine, ethylamine, butylamine, dimethylamine, and diethylamine; cycloalkyl such as cyclohexylamine.
- the aqueous polymer solution preferably contains a structure derived from alkanolamine or a salt thereof.
- the structure derived from the organic amine (salt) is a structure formed by reacting an added organic amine (salt) in the process of producing the poly (meth) acrylic acid polymer aqueous solution of the present invention, and / Or represents an organic amine (salt) that remains unreacted.
- the structure formed by the reaction of the added organic amine (salt) is, for example, (i) an organic amine (salt) in an aqueous solution containing an acid type and / or a partially neutralized polyacrylic acid polymer. ) And the structure contained in the salt of the carboxyl group neutralized with an organic amine, or (ii) an organic compound obtained by neutralizing a monomer such as (meth) acrylic acid in advance with an organic amine.
- Examples include a structure formed by polymerization of an amine salt, and (iii) a structure formed by reacting an added organic amine (salt) with an acidic substance other than a polyacrylic acid polymer.
- the poly (meth) acrylic acid polymer aqueous solution of the present invention is preferably in a form in which the amount of inorganic salt or the like is reduced as much as possible.
- the structure derived from (salt) is preferably a carboxyl group contained in the polymer and neutralized with an organic amine.
- the ratio of carboxyl groups neutralized with organic amines (organic amine salt type carboxyl groups) to 10 mol% to 100 mol% of the carboxyl groups of the poly (meth) acrylic acid polymer is 10 to 75 mol%. Is more preferable, 15 to 70 mol% is more preferable, and 20 to 65 mol% is particularly preferable.
- the poly (meth) acrylic acid polymer of the present invention may have only a structure derived from (meth) acrylic acid (salt), but other copolymerizable with (meth) acrylic acid (salt)
- the structure derived from the monomer may be included.
- Specific examples of the other monomers include monomers containing carboxyl groups other than (meth) acrylic acid, such as maleic acid, fumaric acid, itaconic acid, crotonic acid, 2-methyleneglutaric acid, and salts thereof.
- the poly (meth) acrylic acid polymer of the present invention has a structure derived from all monomers contained in the poly (meth) acrylic acid polymer of the present invention (that is, a structure derived from (meth) acrylic acid (salt)).
- (meth) acrylic acid (salt) -derived structure is preferably contained in an amount of 80% by mass or more in terms of acid type with respect to 100% by mass. If it is 80 mass% or more, it exists in the tendency for the pigment dispersion performance with time of the polymer aqueous solution of this invention to improve more. More preferably, it is 90 mass% or more.
- acid type conversion means calculating a mass ratio using a salt type monomer as a corresponding acid type monomer. For example, if the structure is derived from sodium (meth) acrylate, (meth) The mass ratio is calculated as a structure derived from acrylic acid. The other monomers are similarly calculated in terms of acid type.
- the poly (meth) acrylic acid polymer of the present invention has a structure derived from other monomers with respect to 100% by mass of the structure derived from all monomers contained in the poly (meth) acrylic acid polymer of the present invention.
- the content is preferably 0 to 20% by mass, and more preferably 0 to 10% by mass.
- the weight average molecular weight of the poly (meth) acrylic acid polymer of the present invention is preferably 3,000 to 50,000, more preferably 4,000 to 30,000, and still more preferably. Is 5,000 to 20,000. If the value of the weight average molecular weight is too large, the viscosity becomes high and handling may be complicated. On the other hand, if the value of the weight average molecular weight is too small, the dispersibility of clay, pigment, and the like is lowered, and sufficient performance as a detergent builder or pigment dispersant may not be exhibited. In addition, the value measured by the method as described in the Example mentioned later shall be employ
- the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the poly (meth) acrylic acid polymer of the present invention is specifically preferably 1.1 to 3.0, more preferably. Is 1.5 to 2.8, more preferably 1.8 to 2.6. If the value of this molecular weight distribution is too small, for example, when a poly (meth) acrylic acid polymer is used as an inorganic dispersant, the slurry viscosity immediately after pulverization when the inorganic substance is wet pulverized may increase. Moreover, when too large, there exists a possibility that the viscosity stability with time of a slurry may fall. In addition, the value measured by the method as described in the Example mentioned later shall be employ
- poly (meth) acrylic acid polymer of the present invention or the aqueous solution containing the poly (meth) acrylic acid polymer of the present invention are combined and simply referred to as “poly (meth) acrylic acid system” "Polymer (aqueous solution)” or “polymer (aqueous solution)", as described in [Method for producing poly (meth) acrylic acid polymer (aqueous solution)] (i) ) A step of neutralizing an aqueous solution containing an acid type and / or partially neutralized poly (meth) acrylic acid polymer with an alkali metal salt; and (ii) an acid type and / or partially neutralized poly (meta) ) It is preferable to produce an aqueous solution containing an acrylic acid polymer as an essential step.
- the poly (meth) acrylic acid polymer (aqueous solution) of the present invention thus produced further has a good color tone (less color) over time. More preferably, (i) a step of neutralizing an aqueous solution containing an acid type and / or partially neutralized poly (meth) acrylic acid polymer with an alkali metal salt; and (ii) neutralizing with the alkali metal salt. And the step of neutralizing the aqueous solution containing the partially neutralized poly (meth) acrylic acid polymer with an organic amine.
- the polymer aqueous solution of the present invention essentially contains the poly (meth) acrylic acid polymer of the present invention.
- unreacted (meth) acrylic acid (salt), other unreacted monomers, unreacted polymerization initiator, polymerization initiator decomposition product, and the like may be included.
- the content of unreacted monomers present in the aqueous polymer solution depends on the type of monomer used. Although different, it is preferably less than 1% by mass with respect to 100% by mass of the solid content of the polymer aqueous solution. More preferably, it is less than 0.5 mass%, More preferably, it is less than 0.1 mass%.
- a poly (meth) acrylic-acid type polymer aqueous solution of the present invention includes those concentrated to about 1 to 400% by mass with respect to 100% by mass of the aqueous solution) or concentrated.
- the poly (meth) acrylic acid-based polymer aqueous solution of the present invention contains a solvent in which water is essential in addition to the poly (meth) acrylic acid-based polymer of the present invention.
- the content of the solvent is preferably 50 to 500% by mass, more preferably 60 to 400% by mass, and still more preferably 80 to 300% by mass with respect to 100% by mass of the poly (meth) acrylic acid polymer. 90 to 200% by mass is most preferable.
- the content of the poly (meth) acrylic acid polymer of the present invention in the polymer aqueous solution of the present invention is 16 to 66% by mass with respect to 100% by mass of the poly (meth) acrylic acid polymer aqueous solution. It is preferably 20 to 62% by mass, more preferably 25 to 55% by mass.
- the content of the organic solvent in the polymer aqueous solution of the present invention is preferably reduced as much as possible.
- the content of the organic solvent is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 1% by mass or less.
- the poly (meth) acrylic acid polymer aqueous solution of the present invention is characterized in that the concentration of inorganic anions containing sulfur atoms or phosphorus atoms is 1000 to 10,000 ppm with respect to the polymer aqueous solution of the present invention.
- concentration of the inorganic anion containing a sulfur atom or phosphorus atom exceeds 10,000 ppm, the pigment dispersion performance with time of the polymer aqueous solution tends to deteriorate. If the concentration of the inorganic anion containing a sulfur atom or phosphorus atom is set to less than 1000 ppm, it becomes difficult to produce a polymer aqueous solution having excellent pigment dispersion performance over time.
- the inorganic anion containing sulfur atom or phosphorus atom examples include sulfate ion, sulfite ion, phosphate ion, phosphite ion, hypophosphite ion and the like.
- the aqueous polymer solution preferably has an inorganic anion concentration containing a sulfur atom or a phosphorus atom within the above range when an active ingredient value described later is adjusted to 35 to 45%.
- the poly (meth) acrylic acid polymer aqueous solution of the present invention preferably has a viscosity (25 ° C.) of 400 to 2000 mPa ⁇ s when the solid content (nonvolatile content) concentration is adjusted to 35 to 70 mass%.
- a viscosity 25 ° C.
- the viscosity of the poly (meth) acrylic acid polymer aqueous solution can be easily adjusted by the initiator type and amount used, the neutralizer type and amount used, the degree of neutralization, and the like.
- it is 500-1500 mPa ⁇ s, more preferably 550-1000 mPa ⁇ s, particularly preferably 600-900 mPa ⁇ s, and most preferably 600-800 mPa ⁇ s.
- the viscosity was measured using a B-type viscometer. The value measured at 4, 60 rpm for 5 minutes.
- the poly (meth) acrylic acid polymer aqueous solution of the present invention preferably has a pH of 2.5 to 9.0 when the solid content (nonvolatile content) concentration is adjusted to 35 to 70% by mass.
- the pH of the poly (meth) acrylic acid polymer aqueous solution can be easily adjusted by the type of initiator used, the amount used, the type of neutralizer, the amount used, the degree of neutralization, and the like. More preferably, it is 4.0 to 8.5, and further preferably 4.5 to 8.0. Particularly preferred is 5.0 to 8.0.
- the poly (meth) acrylic acid polymer aqueous solution of the present invention is preferably less colored.
- the hue APHA in a polymer aqueous solution immediately after production and after one month has passed at room temperature (25 ° C.) is 200 or less. It is preferable that it is and it is more preferable that it is 180 or less. More preferably, it is 160 or less.
- the method for producing a poly (meth) acrylic acid polymer aqueous solution of the present invention it is possible to suppress the coloration of the polymer aqueous solution to a low level (make the color tone good). When there is little coloring, it can use preferably for a dispersing agent use or detergent builder use, for example. APHA can be measured with a color difference meter or the like.
- the poly (meth) acrylic acid polymer aqueous solution of the present invention can be used after drying or substitution / dilution with another solvent (referred to as a poly (meth) acrylic acid polymer composition).
- the poly (meth) acrylic acid polymer composition of the present invention includes the polyacrylic acid polymer aqueous solution of the present invention which has been dried and re-dissolved in water, or other optional components added after drying.
- content of the unreacted monomer contained in the poly (meth) acrylic acid polymer composition of the present invention the content of a solvent or an organic solvent, the poly (meth) acrylic acid polymer of the present invention
- the content, concentration of inorganic anion containing sulfur atom or phosphorus atom, viscosity, pH, and APHA are preferably the same as those of the poly (meth) acrylic acid polymer aqueous solution of the present invention described above.
- the poly (meth) acrylic acid polymer of the present invention is preferably produced by polymerizing (meth) acrylic acid (salt) as an essential component.
- the poly (meth) acrylic acid polymer of the present invention may be produced by copolymerizing the above-described other monomers in addition to (meth) acrylic acid (salt).
- (Meth) acrylic acid based on 100% by mass of all monomers referring to the total of (meth) acrylic acid (salt) and other monomers used in the production of the poly (meth) acrylic acid polymer of the present invention
- the ratio of (salt) is preferably 80% by mass or more in terms of acid type.
- acid type conversion means calculating a mass ratio using a salt type monomer as a corresponding acid type monomer. For example, if it is sodium (meth) acrylate, ) Calculate mass percentage as acrylic acid. The other monomers are similarly calculated in terms of acid type.
- a method for producing the poly (meth) acrylic acid polymer (aqueous solution) of the present invention it is preferable to use acrylic acid or acrylate as (meth) acrylic acid (salt).
- the poly (meth) acrylic acid polymer (aqueous solution) of the present invention is a step of neutralizing an aqueous solution containing an acid type and / or partially neutralized poly (meth) acrylic acid polymer with an organic amine (or It is preferable to manufacture by including an organic amine in an aqueous solution containing an acid type and / or a partially neutralized poly (meth) acrylic acid polymer. According to this production method, the color tone of the resulting polymer aqueous solution becomes particularly good, and when used as a pigment (inorganic particle) dispersant, for example, it tends to exhibit particularly good dispersibility.
- the organic amine used in the neutralizing step (or the adding step) include the same organic amines as described above.
- the pigment dispersion performance with time of the aqueous polymer solution is remarkable. Since it improves, it is an alkanolamine.
- the poly (meth) acrylic acid polymer (aqueous solution) of the present invention is produced including a step of neutralizing with the organic amine
- other neutralizing agents may be used in addition to the organic amine.
- an aqueous solution containing an acid-type and / or partially-neutralized poly (meth) acrylic acid polymer is added with another neutralizing agent. It is preferable to perform a step of neutralizing, and then performing a step of neutralizing an aqueous solution containing an acid-type and / or partially neutralized polyacrylic acid polymer with an organic amine because the color tone becomes favorable.
- the reverse process order is also possible.
- neutralizers other than the above organic amines include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate and sodium hydrogen carbonate, alkaline earth metals A salt, ammonia, etc. are mentioned.
- an aqueous poly (meth) acrylic acid polymer solution may be produced by carrying out polymerization with an organic amine salt of (meth) acrylic acid as an essential component. In this case, coloring increases, and it may be difficult to use as a detergent additive or a pigment dispersant.
- the poly (meth) acrylic acid polymer of the present invention is a step of neutralizing an aqueous solution containing an acid type and / or partially neutralized poly (meth) acrylic acid polymer with an organic amine (or acid type and In the case where it is produced by adding an organic amine to an aqueous solution containing a partially neutralized poly (meth) acrylic acid polymer, this step is also referred to as “step N2”), ) A step of producing an aqueous solution containing an acid type and / or partially neutralized poly (meth) acrylic acid polymer by polymerizing acrylic acid (salt) as an essential component (this step is also referred to as “step B”) It is preferable to produce it.
- the neutralization rate (total acid groups (neutralized and unneutralized) of the acid type and / or partially neutralized poly (meth) acrylic acid-based polymer (after step B) produced in step B The ratio of neutralized acid groups to 0) is preferably from 0 to 90%, more preferably from 0 to 85%, and more preferably from 0 to 85%, because the pigment dispersion performance over time and the color tone of aqueous solutions tend to improve. 35% is more preferable, and 0 to 10% is particularly preferable.
- the poly (meth) acrylic acid polymer of the present invention is a step of partially neutralizing an aqueous solution containing an acid type and / or partially neutralized poly (meth) acrylic acid polymer with another neutralizing agent (this It is preferable to manufacture the process including “process C”. Although the order in which the process C is performed is not particularly limited, the process C is particularly preferably performed after the process B.
- the neutralization rate of the partially neutralized poly (meth) acrylic acid polymer produced after Step C (after Step C) is preferably 5 to 90% because the color tone tends to improve. 10 to 85% is more preferable, and 15 to 80% is particularly preferable.
- an aqueous solution containing an acid-type and / or partially neutralized poly (meth) acrylic acid-based polymer is used.
- a step of neutralizing (partially neutralizing) with an alkali metal salt (this step is also referred to as “step N1”) and an aqueous solution containing an acid-type and / or partially-neutralized poly (meth) acrylic acid polymer are organic
- a form including the step of neutralizing with an amine (step N2) as an essential component is particularly preferable.
- Neutralization rate by alkali metal salt of partially neutralized poly (meth) acrylic acid polymer after step N1 Is preferably from 25 to 90 mol%, more preferably from 30 to 85 mol%, particularly preferably from 35 to 80 mol%, since the color tone of the resulting aqueous polymer solution tends to be improved.
- alkali metal salt used in the step N1 examples include hydroxides such as Li, Na, and K, carbonates, bicarbonates, and the like, and lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, Examples thereof include sodium bicarbonate and potassium carbonate.
- an alkali metal salt is used as an essential component, but another alkaline substance (neutralizing agent) such as an alkaline earth metal salt may be used in combination.
- neutralizing agent such as an alkaline earth metal salt may be used in combination.
- an alkali metal salt is 80 mol% or more with respect to 100 mol% of all the neutralizing agents used for process N1.
- the temperature of the step N1 may be appropriately selected according to the type of alkali metal salt to be used, but it is preferably 40 to 100 ° C, more preferably 45 to 95 ° C, and particularly preferably 50 to 90 ° C. . If the neutralization reaction is performed at a temperature exceeding 100 ° C., the color tone of the resulting aqueous polymer solution may be deteriorated, which is not preferable. Moreover, when neutralizing at the temperature lower than 40 degreeC, it is necessary to cool the polymer aqueous solution obtained after superposition
- the neutralization rate by the organic amine of the partially neutralized poly (meth) acrylic acid polymer after Step N2 is: From the aspect of improving the dispersive power of the resulting aqueous polymer solution over time, the poly (meth) acrylic acid polymer aqueous solution, preferably an organic amine (salt) contained in the poly (meth) acrylic acid polymer.
- the molar ratio of the structure derived from is preferably set in the above range.
- Examples of the organic amine used in the step N2 are the same as those exemplified above, but alkanolamine is preferable because the pigment dispersion performance with time of the aqueous polymer solution is remarkably improved. Amines are particularly preferred.
- an organic amine is used as an essential component, but other alkali substances (neutralizing agents) may be used in combination.
- the neutralizing agent is the same as other neutralizing agents other than the organic amine described above. In this case, it is preferable that an organic amine is 80 mol% or more with respect to 100 mol% of all the neutralizing agents used for process N2.
- the temperature of the above step N2 may be appropriately selected according to the type of organic amine to be used, but it is preferably carried out at 40 to 100 ° C., more preferably 45 to 95 ° C., and particularly preferably 50 to 90 ° C. If the neutralization reaction is performed at a temperature exceeding 100 ° C., the color tone of the resulting aqueous polymer solution may be deteriorated, which is not preferable. Moreover, when neutralizing at the temperature lower than 40 degreeC, it is necessary to cool the polymer aqueous solution obtained after superposition
- the time required for the step N2 may be appropriately selected according to the type and amount of the organic amine to be used, but is usually preferably 10 hours or less, more preferably 5 hours or less, and still more preferably 3 hours or less.
- step N1 may be performed first, and the step N2 first.
- the process N1 and the process N2 may be performed simultaneously.
- step N1 is preferably performed first.
- step N1 is performed first, it is possible to perform a part of the steps, for example, at the time when 50 mol% or more of the alkali metal salt added in step N1 is added to the reaction solution. It is also possible to start step N2.
- the step N2 is started when 70 mol% or more of the alkali metal salts added in the step N1 are added, and more preferably, 90% of the alkali metal salts added in the step N1. It is a time when mol% or more is added, and most preferably, the step N2 is started after the addition of the alkali metal salt added in the step N1 is completed.
- the production method including the step N1 and the step N2 as essential, it is preferable to produce the poly (meth) acrylic acid polymer including the step B.
- the poly (meth) acrylic acid polymer of the present invention is preferably produced by solution polymerization.
- water or a mixed solvent of water and an organic solvent is used. be able to.
- a solvent removal step step D is required, but step D may be performed before the neutralization step (steps N1 and N2), or a neutralization step (steps N1 and N2). Or after the neutralization step N1 and the neutralization step N2.
- the coloration of the resulting aqueous poly (meth) acrylic acid polymer solution can be kept low
- the order of the process D, the process N1, and the process N2 may be appropriately selected so as to be able to be performed, and is not particularly limited.
- the organic amine may be colored due to a heat history or the like, the process N2 is performed last. Is more preferable. That is, the order in which the process D is performed first, then the process N1 is performed, and the process N2 is performed last, or the process N1 is performed first, then the process D is performed, and the process N2 is performed finally. preferable.
- the poly (meth) acrylic acid polymer of the present invention is obtained by polymerizing a monomer composition containing (meth) acrylic acid (salt) as an essential component in the presence of a polymerization initiator (also referred to as an initiator). be able to.
- a polymerization initiator also referred to as an initiator
- polymerization initiator those usually used as a polymerization initiator can be used, for example, persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate; hydrogen peroxide; dimethyl 2,2 '-Azobis (2-methylpropionate), 2,2'-azobis (2-amidinopropane) hydrochloride, 4,4'-azobis-4-cyanoparerenic acid, azobisisobutyronitrile, 2,2' -Azo compounds such as azobis (4-methoxy-2,4-dimethylvaleronitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide, cumene hydroperoxide Etc.
- persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate
- hydrogen peroxide dimethyl 2,2 '-Azobis (2-
- polymerization initiators may be used alone or in the form of a mixture of two or more. Since the molecular weight distribution of the polymer tends to be small, it is preferable to use only one kind.
- the amount of the polymerization initiator used is not particularly limited, but is preferably 15 g or less with respect to 1 mol of all monomer components. More preferably, it is 0.1 to 12 g.
- the amount of persulfate used is preferably 1.9 g or less, and preferably 1.6 g or less, based on 1 mol of all monomers. More preferably, it is more preferably 1.2 g or less, and particularly preferably 1.1 g or less. As a minimum of the usage-amount of persulfate, 0.1 g or more is preferable with respect to 1 mol of all the monomers, and 0.5 g or more is more preferable.
- the method for adding the polymerization initiator is not particularly limited, but the amount dripped substantially continuously with respect to the total amount used is preferably 50% by mass or more of the required predetermined amount, and more preferably 80%. Most preferably, the total amount is not less than mass% and the entire amount is dropped. Thus, it is preferable that the polymerization initiator is continuously dropped, but the dropping speed can be set as appropriate.
- the dropping time when the polymerization initiator is continuously dropped is not particularly limited, but ammonium persulfate, potassium persulfate, sodium persulfate under the conditions of polymerization temperature and pH at the time of polymerization described later.
- a relatively quick decomposition initiator such as persulfate, etc.
- the dropping start time is not limited at all and may be set as appropriate.
- the dropping of the initiator may be started before the start of dropping of the monomer.
- one initiator is dropped. May be started, and after a certain period of time has elapsed, or after it has ended, the addition of another initiator may be started. In any case, it may be appropriately set according to the decomposition rate of the initiator and the reactivity of the monomer.
- a chain transfer agent In the method for producing a poly (meth) acrylic acid polymer of the present invention, a chain transfer agent can be used in addition to the polymerization initiator.
- the chain transfer agent that can be used in this case is not particularly limited as long as it is a compound capable of adjusting the molecular weight, and those that are usually used as chain transfer agents can be used.
- the said chain transfer agent may be used independently and may be used with the form of 2 or more types of mixtures.
- the amount of the chain transfer agent added is not particularly limited, but is preferably 1 to 20 g with respect to 1 mol of all monomer components. More preferably, it is 2 to 15 g. If it is less than 1 g, the molecular weight may not be controlled. Conversely, if it exceeds 20 g, the chain transfer agent may remain or the polymer content may decrease.
- hypophosphite, sulfite, and / or bisulfite because the dispersibility of the pigment (inorganic particles) of the resulting poly (meth) acrylic acid polymer aqueous solution is improved.
- hypophosphite, sulfite and bisulfite are used in an amount of 1 mol of all monomers. It is preferably 5.0 g or less, more preferably 4.5 g or less, still more preferably 4.0 g or less, and the lower limit of the amount used is 1 mol of all monomers.
- hypophosphite, sulfite, and / or bisulfite exceeds the above upper limit with respect to 1 mol of all monomers, hypophosphite, sulfite, and Dispersion over time due to an increase in the amount of inorganic anions and / or an increase in bisulfite (hypophosphite, sulfite, and / or bisulfite not incorporated into the polymer ends)
- the force may be reduced, or the hue of the poly (meth) acrylic acid polymer may be deteriorated.
- the method for producing a poly (meth) acrylic acid polymer of the present invention uses a polymerization initiator decomposition catalyst or a reducing compound (also referred to as a reaction accelerator) in addition to the polymerization initiator (added to the polymerization system). May be.
- Examples of the compound that acts as a decomposition catalyst or a reducing compound for the polymerization initiator include heavy metal ions (or heavy metal salts). That is, the method for producing a polyacrylic acid polymer of the present invention may use (add to the polymerization system) heavy metal ions (or heavy metal salts) in addition to the polymerization initiator and the like.
- the heavy metal ion means a metal having a specific gravity of 4 g / cm 3 or more.
- iron, cobalt, manganese, chromium, molybdenum, tungsten, copper, silver, gold, lead, platinum, iridium, osmium, palladium, rhodium, ruthenium etc. are preferable, for example.
- These heavy metals can be used alone or in combination of two or more. Among these, iron is more preferable.
- the ionic valence of the heavy metal ions is not particularly limited.
- the iron ions in the initiator may be Fe 2+ or Fe 3+ , and these may be combined. May be.
- the heavy metal ions are added to the reaction system by adding an aqueous solution or an aqueous solution obtained by dissolving a heavy metal salt (heavy metal compound) to the polymerization system.
- the heavy metal salt used in that case should just contain the heavy metal ion desired to contain in an initiator, and can be determined according to the initiator to be used.
- the mole salt Fe (NH 4 ) 2 (SO 4 ) 2 ⁇ 6H 2 O)
- ferrous sulfate ⁇ 7 hydrate ferrous chloride, ferric chloride, etc. It is preferable to use a heavy metal salt or the like.
- manganese chloride etc. when using manganese as a heavy metal ion, manganese chloride etc. can be used suitably.
- these heavy metal salts since they are water-soluble compounds, they can be used in the form of an aqueous solution and have excellent handleability.
- the solvent of the solution formed by dissolving the heavy metal salt is not limited to water, and must not significantly interfere with the polymerization reaction in the production of the poly (meth) acrylic acid polymer of the present invention. , And can be used as long as the solubility of the heavy metal salt is not impaired.
- the heavy metal ion is added to the polymerization system as an aqueous solution or aqueous solution of a heavy metal salt.
- the heavy metal salt and the carboxyl group-containing compound are added. It is preferable to supply as an aqueous solution containing.
- the effect of the heavy metal ion can be exhibited stably by supplying it as an aqueous solution containing the heavy metal salt and the carboxyl group-containing compound. There is an effect that a polymer having a desired molecular weight can be stably produced.
- the “polymerization system” means the inside of a reaction vessel in which a polymerization reaction is carried out or is carried out, and usually means an initially charged polymerization solvent or a polymerization solution during polymerization.
- the ratio of the heavy metal salt and the carboxyl group-containing compound is preferably 1 to 100 parts by mass of the carboxyl group-containing compound with respect to 100 parts by mass of the heavy metal salt. More preferably, it is 10 to 80 parts by mass.
- the heavy metal salt aqueous solution added to the polymerization system is preferably set so that the pH of the aqueous solution is 8 or less, more preferably 7 or less, and 6 or less. Is particularly preferred.
- the carboxyl group-containing compound is an organic compound having a carboxyl group, for example, acetic acid, propionic acid, butyric acid, formic acid, oxalic acid, succinic acid, glycolic acid, glyoxylic acid, etc., but from the viewpoint of reducing impurities
- a compound having a polymerizable carbon-carbon unsaturated double bond is preferable.
- examples of such a compound include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and 2-methyleneglutaric acid. Etc. and their anhydrides.
- the content of the heavy metal ions is preferably 0.1 to 10 ppm with respect to the total mass of the polymerization reaction solution at the completion of the polymerization reaction. If the content of heavy metal ions is less than 0.1 ppm, the effect of heavy metal ions may not be sufficiently exhibited. On the other hand, if the content of heavy metal ions exceeds 10 ppm, the color tone of the resulting polymer may be deteriorated. Moreover, when there is much content of heavy metal ion, when using the polymer which is a product, for example as a detergent builder, there exists a possibility of causing the stain
- the term “when the polymerization reaction is completed” means a point in time when the polymerization reaction is substantially completed in the polymerization reaction solution and a desired polymer is obtained.
- the content of heavy metal ions is calculated based on the total mass of the polymerization reaction solution after neutralization.
- the total amount of heavy metal ions may be in the above range.
- the concentration of the heavy metal compound in the aqueous solution or aqueous solution obtained by dissolving the heavy metal compound added to the polymerization system is preferably 0.1% by mass to 10% by mass.
- Examples of the polymerization initiator decomposition catalyst other than heavy metal ions include metal halides such as lithium chloride and lithium bromide; metal oxides such as titanium oxide and silicon dioxide; hydrochloric acid, hydrobromic acid, Metal salts of inorganic acids such as perchloric acid, sulfuric acid, nitric acid; carboxylic acids such as formic acid, acetic acid, propionic acid, lactic acid, isolacric acid, benzoic acid, their esters and their metal salts; pyridine, indole, imidazole, And heterocyclic amines such as carbazole and derivatives thereof.
- These decomposition catalysts may be used alone or in combination of two or more.
- reducing compounds other than heavy metal ions include, for example, boron trifluoride ether adducts, inorganic compounds such as perchloric acid; sulfur dioxide, sulfites, sulfate esters, bisulfites, and thiosulfuric acid.
- Sulfur-containing compounds such as salts, sulfoxyacid salts, benzenesulfinic acids and their substitutes, and homologues of cyclic sulfinic acids such as para-toluenesulfinic acid; octyl mercaptan, dodecyl mercaptan, mercaptoethanol, ⁇ -mercaptopropionic acid, thioglycol Mercapto compounds such as acid, thiopropionic acid, ⁇ -thiopropionic acid sodium sulfopropyl ester, ⁇ -thiopropionic acid sodium sulfoethyl ester; nitrogen-containing compounds such as hydrazine, ⁇ -hydroxyethylhydrazine, hydroxylamine; formaldehyde, aceto Aldehyde, propionaldehyde, n- butyraldehyde, isobutyraldehyde, aldehydes such as isovaleralde
- the poly (meth) acrylic acid polymer of the present invention is preferably produced by solution polymerization.
- the solvent that can be used in this case is preferably a mixed solvent in which 50% by mass of water or water is used with respect to the total solvent. When only water is used, it is preferable in that the solvent removal step can be omitted.
- the solvent itself is difficult to chain transfer in order to increase chain transfer efficiency (incorporate more chain transfer agent into the polymer terminal) and reduce inorganic anions as impurities. Those are preferred. From this point of view, it is preferable to use only water as a solvent or to reduce the amount of use as much as possible when an organic solvent is used in combination.
- an organic solvent it is preferably 30% by mass or less, more preferably 20% by mass or less, with respect to 100% by mass of the reaction liquid after completion of polymerization. More preferably, it is 10 mass% or less. It is particularly preferably 5% by mass or less, and most preferably 1% by mass or less.
- a solvent removal step is required. Conditions such as pressure, temperature, and time in the solvent removal step can keep the resulting poly (meth) acrylic acid polymer aqueous solution low in color. Thus, it can be appropriately selected according to the type and amount of the organic solvent to be used. For example, the pressure at the time of solvent removal may be normal pressure, reduced pressure, or increased pressure, and the temperature is 30.
- the time required for solvent removal is preferably 10 hours or less, more preferably 5 hours or less, and particularly preferably 3 hours or less.
- alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; glycerin; polyethylene glycol; amides such as dimethylformaldehyde; ethers such as diethyl ether and dioxane are preferable. It is. These may be used alone or in combination of two or more.
- the polymerization reaction preferably has a solid content concentration after polymerization of 10% by mass to 60% by mass with respect to 100% by mass of the polymerization solution. 15 to 50% by mass is more preferable, and 20 to 45% by mass is even more preferable.
- any of polymerization methods of batch type (batch type), continuous type and semi-continuous type can be adopted.
- conditions for producing the polyacrylic acid polymer of the present invention a method generally known as a polymerization method or a modified method thereof can be used unless otherwise specified.
- the temperature during the polymerization is preferably 70 ° C. or higher, more preferably 75 to 110 ° C., and further preferably 80 to 105 ° C. If the temperature at the time of polymerization is in the above range, the residual monomer component is reduced and the dispersibility of the polymer tends to be improved.
- the temperature at the time of polymerization need not always be kept constant during the progress of the polymerization reaction. For example, the polymerization is started from room temperature, and the temperature is increased to a set temperature at an appropriate temperature increase time or temperature increase rate. Thereafter, the set temperature may be maintained, or the polymerization temperature may be varied (increased or decreased) over time during the course of the polymerization reaction, depending on the dropping method of the monomer component, initiator, and the like. Also good.
- the pressure in the reaction system may be any of normal pressure (atmospheric pressure), reduced pressure, and increased pressure, but from the viewpoint of the molecular weight of the resulting polymer, the reaction system is sealed under normal pressure. However, it is preferably performed under pressure. Moreover, it is preferable to carry out under normal pressure (atmospheric pressure) in terms of equipment such as a pressurizing device, a decompressing device, a pressure-resistant reaction vessel, and piping.
- the atmosphere in the reaction system may be an air atmosphere, but is preferably an inert atmosphere. For example, the inside of the system is preferably replaced with an inert gas such as nitrogen before the start of polymerization.
- the poly (meth) acrylic acid polymer of the present invention are water. It can be used as a treatment agent, a fiber treatment agent, a dispersant, a detergent builder (or a detergent composition) and the like. As a detergent builder, it can be used by adding to detergents for various uses such as clothing, tableware, dwelling, hair, body, toothpaste, and automobile.
- the polymer of the present invention can be used as a water treatment agent.
- the water treatment agent may contain a polymerized phosphate, phosphonate, anticorrosive, slime control agent, and chelating agent as other compounding agents.
- the water treatment agent is useful for scale prevention in a cooling water circulation system, a boiler water circulation system, a seawater desalination apparatus, a pulp digester, a black liquor concentration tank, and the like. Further, any appropriate water-soluble polymer may be included as long as it does not affect the performance and effects.
- the polymer of the present invention can be used as a fiber treatment agent.
- the fiber treatment agent includes at least one selected from the group consisting of a dye, a peroxide, and a surfactant, and the polymer (composition) of the present invention.
- the content of the polymer of the present invention in the fiber treatment agent is preferably 1 to 100% by mass, more preferably 5 to 100% by mass, based on the entire fiber treatment agent. Further, any appropriate water-soluble polymer may be included as long as the performance and effects are not affected.
- This fiber treatment agent can be used in the steps of refining, dyeing, bleaching and soaping in fiber treatment.
- dyeing agents, peroxides, and surfactants include those usually used for fiber treatment agents.
- the blending ratio of the polymer or polymer composition of the present invention to at least one selected from the group consisting of a dye, a peroxide and a surfactant is, for example, the whiteness of the fiber, color unevenness, dyeing tempering degree
- at least one selected from the group consisting of a dye, a peroxide and a surfactant is 0.1 per 1 part by mass of the polymer of the present invention in terms of a pure component of the fiber treatment agent. It is preferable to use a composition blended at a ratio of ⁇ 100 parts by mass as a fiber treatment agent.
- Arbitrary appropriate fiber can be employ
- cellulosic fibers such as cotton and hemp, chemical fibers such as nylon and polyester, animal fibers such as wool and silk, semi-synthetic fibers such as human silk, and woven fabrics and blended products thereof.
- the fiber treatment agent When the fiber treatment agent is applied to the refining process, it is preferable to blend the polymer of the present invention of the present invention with an alkali agent and a surfactant.
- an alkali agent In the case of applying to the bleaching step, it is preferable to blend the polymer composition of the present invention, a peroxide, and a silicic acid-based agent such as sodium silicate as a decomposition inhibitor for the alkaline bleaching agent.
- the polymer of the present invention (polymer, polymer aqueous solution, polymer composition) can be used as a pigment dispersant. That is, the pigment dispersant containing the poly (meth) acrylic acid polymer (aqueous solution) of the present invention is also one aspect of the present invention.
- the polymer of the present invention can be used alone as a pigment dispersant, the pigment dispersant of the present invention includes, as necessary, a solvent such as water and other compounding agents such as condensed phosphoric acid and The salt, phosphonic acid and its salt, and polyvinyl alcohol may be used.
- the content of the polymer of the present invention in the pigment dispersant is preferably 0.5 to 10% by mass with respect to the entire pigment dispersant. Further, any appropriate water-soluble polymer may be included as long as it does not affect the performance and effect. According to the present invention, it is possible to provide a paper slurry having a low viscosity and a viscosity stability with time and having a high concentration. As a result, coating defects are suppressed when coating with the slurry, good base paper coverage, printing gloss, blister resistance, uniform printing surface feeling, and the inherent whiteness and poorness of the pigment are provided. It becomes possible to provide a coated paper for printing having significant points of transparency and ink acceptability.
- the pigment used in the present invention is not particularly limited, and examples thereof include kaolin, clay, heavy calcium carbonate, light calcium carbonate, titanium dioxide, satin white, talc, aluminum hydroxide, and plastic pigment.
- a method for adjusting the pigment a commonly used method can be appropriately referred to or combined, and for example, a method of performing primary dispersion and wet-grinding it can be mentioned. It is done. This method is suitable in that a high-concentration pigment slurry having a low viscosity and excellent dispersion stability can be obtained.
- the adjustment method of the pigment in the present invention is not limited to this wet pulverization method, and it is not limited to take an adjustment method without performing the wet pulverization treatment.
- the primary dispersion method is not particularly limited, but it is preferable to mix with a mixer, for example, a high-speed disper, a homomixer, a ball mill, a coreless mixer, a stirring disper, etc. It is preferable to use a high one.
- a mixer for example, a high-speed disper, a homomixer, a ball mill, a coreless mixer, a stirring disper, etc. It is preferable to use a high one.
- the polymer of the present invention may be charged into a pulverizer and pulverized.
- the polymer also serves as a grinding aid.
- the average particle size of the pigment contained in the slurry is preferably 1.5 ⁇ m or less, more preferably 1.0 ⁇ m or less.
- the average particle size referred to here is a particle size measured by a laser particle size distribution meter or a particle size distribution meter having an X-ray detector as used in Examples described later.
- the desired particle size is preferably 85% or more, more preferably 90% or more.
- the amount of the pigment dispersant used is preferably 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the polymer of the present invention.
- the amount of the pigment dispersant used is within the above range, a sufficient dispersion effect can be obtained, an effect commensurate with the addition amount can be obtained, and this can be economically advantageous.
- the pigment slurry in the present invention preferably has a solid concentration of 60% by mass or more, more preferably 70% by mass or more, and further preferably 75% by mass or more.
- the viscosity of the pigment slurry is not particularly limited, but varies greatly depending on the slurry concentration. Therefore, immediately after adjusting to 75% by mass, it is preferably 1000 mPa ⁇ s or less, more preferably 800 mPa ⁇ s or less.
- the pigment slurry viscosity is measured using a B-type viscometer. The value measured at 4, 60 rpm for 5 minutes.
- the polymer of the present invention can also be added to a detergent composition.
- the content of the polymer of the present invention in the detergent composition is not particularly limited. However, from the viewpoint of exhibiting excellent builder performance, the content of the polymer of the present invention is preferably 0.1 to 15% by mass, more preferably 0%, based on the total amount of the detergent composition. 3 to 10% by mass, more preferably 0.5 to 5% by mass.
- Detergent compositions used in detergent applications usually include surfactants and additives used in detergents. Specific forms of these surfactants and additives are not particularly limited, and knowledge generally known in the detergent field can be appropriately referred to.
- the detergent composition may be a powder detergent composition or a liquid detergent composition.
- the surfactant is one or more selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant.
- the total amount of the anionic surfactant and the nonionic surfactant is preferably 50% by mass or more, more preferably 60% by mass with respect to the total amount of the surfactant. Or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more.
- anionic surfactants include alkylbenzene sulfonate, alkyl ether sulfate, alkenyl ether sulfate, alkyl sulfate, alkenyl sulfate, ⁇ -olefin sulfonate, ⁇ -sulfo fatty acid or ester salt, alkane sulfonate , Saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acyl amino acid type surfactant, alkyl phosphate ester or salt thereof, alkenyl phosphate ester or Its salts are preferred.
- An alkyl group such as a methyl group may be branched from the alkyl group or alkenyl group in these anionic surfactants.
- Nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, alkyl glycoxides, fatty acid glycerin monoesters. Esters, alkylamine oxides and the like are preferred.
- An alkyl group such as a methyl group may be branched from the alkyl group or alkenyl group in these nonionic surfactants.
- a quaternary ammonium salt or the like is suitable.
- amphoteric surfactant a carboxyl type amphoteric surfactant, a sulfobetaine type amphoteric surfactant, and the like are suitable.
- the alkyl group and alkenyl group in these cationic surfactants and amphoteric surfactants may be branched from an alkyl group such as a methyl group.
- the blending ratio of the surfactant is usually 10 to 60% by mass, preferably 15 to 50% by mass, more preferably 20 to 45% by mass, particularly preferably based on the total amount of the detergent composition. Is 25 to 40% by mass.
- Additives include anti-redeposition agent to prevent redeposition of contaminants such as alkali builder, chelate builder, sodium carboxymethyl cellulose, stain inhibitor such as benzotriazole and ethylene-thiourea, soil release agent, color transfer Inhibitors, softeners, alkaline substances for pH adjustment, fragrances, solubilizers, fluorescent agents, colorants, foaming agents, foam stabilizers, polishes, bactericides, bleaching agents, bleaching aids, enzymes, dyes A solvent or the like is preferable.
- the detergent composition may contain other detergent builders in addition to the polymer of the present invention.
- Other detergent builders are not particularly limited, but include, for example, alkali builders such as carbonates, bicarbonates, silicates, tripolyphosphates, pyrophosphates, bow glass, nitrilotriacetate, ethylenediaminetetraacetate, Examples thereof include chelate builders such as acid salts, fumarate salts, and zeolites, and carboxyl derivatives of polysaccharides such as carboxymethyl cellulose.
- the counter salt used in the builder include alkali metals such as sodium and potassium, ammonium and amine.
- the total blending ratio of the additive and other detergent builder is usually preferably 0.1 to 50% by mass with respect to 100% by mass of the cleaning composition. More preferably, it is 0.2 to 40% by mass, further preferably 0.3 to 35% by mass, particularly preferably 0.4 to 30% by mass, and most preferably 0.5 to 20% by mass or less. It is. If the blending ratio of additive / other detergent builder is less than 0.1% by mass, sufficient detergent performance may not be exhibited, and if it exceeds 50% by mass, the economy may be lowered.
- the concept of the above-mentioned detergent composition includes specific detergents such as synthetic detergents for household detergents, textile industry and other industrial detergents, hard surface cleaners, and bleaching detergents that enhance one of the components.
- the amount of water contained in the liquid detergent composition is usually preferably 0.1 to 75% by mass, more preferably based on the total amount of the liquid detergent composition. Is 0.2 to 70% by mass, more preferably 0.5 to 65% by mass, still more preferably 0.7 to 60% by mass, particularly preferably 1 to 55% by mass, The amount is preferably 1.5 to 50% by mass.
- the detergent composition preferably has a kaolin turbidity of 200 mg / L or less, more preferably 150 mg / L or less, and still more preferably 120 mg / L or less.
- the change (difference) in kaolin turbidity when the polymer of the present invention is added to the liquid detergent composition as a detergent builder is preferably 500 mg / L or less, more preferably 400 mg. / L or less, more preferably 300 mg / L or less, particularly preferably 200 mg / L or less, and most preferably 100 mg / L or less.
- the kaolin turbidity value a value measured by the following method is adopted.
- ⁇ Measurement method of kaolin turbidity> A sample (liquid detergent) uniformly stirred in a 50 mm square cell having a thickness of 10 mm was removed and air bubbles were removed. Then, the NDU2000 (trade name, turbidimeter) manufactured by Nippon Denshoku Industries Co., Ltd. was used at 25 ° C. Kaolin turbidity: mg / L) is measured. Proteases, lipases, cellulases, and the like are suitable as enzymes that can be incorporated into the cleaning composition. Of these, proteases, alkaline lipases, and alkaline cellulases that are highly active in an alkaline cleaning solution are preferred.
- the amount of the enzyme added is preferably 5% by mass or less with respect to 100% by mass of the cleaning composition. If it exceeds 5% by mass, improvement in detergency cannot be seen, and the economy may be reduced. Even when the detergent composition is used in an area of hard water (for example, 100 mg / L or more) having a high concentration of calcium ions and magnesium ions, salt precipitation is small and has an excellent cleaning effect. This effect is particularly pronounced when the detergent composition contains an anionic surfactant such as LAS.
- the polymer of the present invention (polymer, polymer aqueous solution, polymer composition) can be used for the inorganic particle slurry. That is, the inorganic particle slurry containing the poly (meth) acrylic acid polymer of the present invention is also one aspect of the present invention.
- ⁇ Poly (meth) acrylic acid polymer> As the poly (meth) acrylic acid polymer contained in the inorganic particle slurry of the present invention, the same ones as described above can be used. Carboxyl groups of the above poly (meth) acrylic acid polymer other than acid type carboxyl groups / carboxyl groups neutralized with organic amines (organic amine salt type carboxyl groups) / carboxyl groups other than organic amine salt type carboxyl groups
- the ratio of the salt is not particularly limited and can be the same as the above-described ratio, but the structure derived from (meth) acrylic acid (salt) and the organic amine (salt) contained in the inorganic particle slurry of the present invention. It is important that the molar ratio with the structure derived from) is 100: 10 to 100: 75. Preferably, it is 100: 15 to 100: 70, and more preferably 100: 20 to 100: 65.
- the structure derived from (meth) acrylic acid (salt) contained in the inorganic particle slurry means a structure derived from (meth) acrylic acid (salt) contained in the compound constituting the inorganic particle slurry.
- the structure derived from the organic amine (salt) contained in the slurry refers to a structure derived from the organic amine (salt) contained in the compound constituting the inorganic particle slurry.
- organic amine examples include those similar to those described above, and among them, the viscosity stability over time of the inorganic particle slurry is remarkably improved and a high pH can be maintained.
- the inorganic particle slurry preferably contains a structure derived from alkanolamine or a salt thereof.
- the structure derived from the organic amine (salt) represents a structure neutralized with any acidic substance and present as an organic amine salt and / or a structure present as an organic amine.
- Examples of the structure neutralized with any acidic substance and existing as an organic amine salt include (i) a structure existing as a salt of the poly (meth) acrylic acid polymer, (ii) (meth) acrylic acid, and the like.
- the structure which exists as a salt of the monomer or other acidic substance is illustrated.
- the inorganic particle slurry of the present invention is preferably in a form in which the amount of inorganic salt or the like is reduced as much as possible, and therefore the above organic amine (salt)
- the structure derived from is preferably a structure that exists as an organic amine salt of a carboxyl group of the poly (meth) acrylic acid polymer. Accordingly, the ratio of carboxyl groups neutralized with organic amines (organic amine salt type carboxyl groups) to 10 mol% to 100 mol% of the carboxyl groups of the poly (meth) acrylic acid polymer is 10 to 75 mol%. Is more preferable, 15 to 70 mol% is more preferable, and 20 to 65 mol% is particularly preferable.
- the poly (meth) acrylic acid polymer has a structure derived from all monomers contained in the poly (meth) acrylic acid polymer (that is, a structure derived from (meth) acrylic acid (salt) and other single quantities. It is preferable that the structure derived from (meth) acrylic acid (salt) is contained in an amount of 80% by mass or more in terms of acid type with respect to 100% by mass (total with the structure derived from the body). If it is 80 mass% or more, the viscosity stability with time of the inorganic particle slurry tends to be further improved. More preferably, it is 90 mass% or more.
- acid type conversion is as described above.
- the structure derived from other monomers is 0 to 20% by mass relative to 100% by mass of the structure derived from all monomers contained in the poly (meth) acrylic acid polymer. Preferably, it is 0 to 10% by mass.
- the weight average molecular weight of the poly (meth) acrylic acid polymer is preferably 3,000 to 50,000, more preferably 4,000 to 30,000, and still more preferably 5 , 20,000 to 20,000. If the value of the weight average molecular weight is too large, the viscosity of the inorganic particle slurry may not be sufficiently lowered. On the other hand, if the value of the weight average molecular weight is too small, the viscosity stability over time of the inorganic particle slurry may not be sufficiently improved.
- a value of the weight average molecular weight of the poly (meth) acrylic acid polymer a value measured by a method described in Examples described later is adopted.
- the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the poly (meth) acrylic acid polymer is preferably 1.1 to 3.0, more preferably 1 0.5 to 2.8, more preferably 1.8 to 2.6. Within this molecular weight distribution range, the viscosity of the inorganic particle slurry and the viscosity stability over time tend to be particularly improved. In addition, the value measured by the method as described in the Example mentioned later shall be employ
- the inorganic particle slurry of the present invention contains inorganic particles, but the inorganic particles used are not particularly limited.
- the inorganic particles used are not particularly limited.
- the inorganic particle slurry of the present invention preferably contains 70% by mass or more of inorganic particles with respect to 100% by mass of the inorganic particle slurry. If the inorganic particles contained in the inorganic particle slurry are less than 70% by mass, for example, when used as a paper coating pigment slurry, the productivity of paper may be reduced. More preferably, it is 73 mass% or more, More preferably, it is 75 mass% or more. Especially preferably, it is 78 mass% or more. Moreover, the upper limit of content of an inorganic particle is 85 mass%, for example.
- the inorganic particle slurry of the present invention preferably contains 0.05 to 10% by mass (as acid type) of poly (meth) acrylic acid polymer with respect to 100% by mass of the inorganic particle slurry. More preferred is 0.1 to 5.0% by mass, still more preferred is 0.15 to 1.0% by mass, and particularly preferred is 0.2 to 0.8% by mass.
- the compound derived from organic amine is such that the molar ratio of the structure derived from (meth) acrylic acid (salt) and the structure derived from organic amine (salt) falls within the above range. Contains in proportions.
- the inorganic particle slurry of the present invention has a solid content concentration of 75% by mass or more. Preferably it is 78 mass% or more as solid content concentration, More preferably, it is 80 mass% or more, More preferably, it is 85 mass% or more. Moreover, the upper limit of the solid content concentration of the inorganic particle slurry is, for example, 90% by mass. In addition, solid content concentration is a value measured by the measuring method mentioned later.
- the inorganic particle slurry of the present invention usually contains water, and the water content in that case is preferably 25% by mass or less, more preferably 22% by mass or less, and still more preferably 20% by mass. Or less, and particularly preferably 15% by mass or less. Moreover, the minimum of content of the water in an inorganic particle slurry is 10 mass%, for example.
- the average particle size of the inorganic particles contained in the inorganic particle slurry of the present invention is preferably 1.5 ⁇ m or less, more preferably 1.0 ⁇ m or less.
- the average particle diameter said here is a particle diameter measured with the laser particle size distribution meter which was used in the below-mentioned Example.
- the inorganic particles contained in the inorganic particle slurry of the present invention contain 90 to 100% by mass of particles having a particle size of 2 ⁇ m or less with respect to 100% by mass of all inorganic particles, preferably 91 to 100% by mass is contained. If the particle diameter is in the above range, the gloss and whiteness of the paper will be good when the inorganic particle slurry of the present invention is used as, for example, a pigment dispersant for paper coating.
- the inorganic particle slurry of the present invention may use condensed phosphoric acid and a salt thereof, phosphonic acid and a salt thereof, and polyvinyl alcohol as an organic solvent and other compounding agents as necessary.
- the inorganic particle slurry of the present invention is characterized in that the concentration of inorganic anions containing sulfur atoms or phosphorus atoms is 100 to 400 ppm with respect to the inorganic particle slurry of the present invention.
- concentration of inorganic anions containing sulfur atoms or phosphorus atoms exceeds 400 ppm, the viscosity stability over time of the inorganic particle slurry tends to decrease.
- the concentration of the inorganic anion containing a sulfur atom or phosphorus atom is set to less than 100 ppm, the combination of the initiator, the chain transfer agent and the solvent becomes expensive, which is not preferable.
- Examples of the inorganic anion containing sulfur atom or phosphorus atom include sulfate ion, sulfite ion, phosphate ion, phosphite ion, hypophosphite ion and the like.
- the viscosity of the inorganic particle slurry of the present invention is not particularly limited and varies greatly depending on the slurry concentration, but immediately after adjusting the solid content concentration of the inorganic particle slurry to 75% by mass, it is preferably 1000 mPa ⁇ s or less, More preferably, it is 900 mPa ⁇ s or less.
- the viscosity of the inorganic particle slurry was measured using a B-type viscometer. The value measured at 4, 60 rpm for 5 minutes.
- the method for producing an inorganic particle slurry of the present invention comprises (i) a poly (meth) acrylic acid polymer aqueous solution containing a structure derived from (meth) acrylic acid (salt) and a structure derived from organic amine (salt), and A method for producing an essential step of mixing inorganic particles, (ii) a poly (meth) acrylic acid polymer aqueous solution containing a poly (meth) acrylic acid polymer, an organic amine (salt), and inorganic particles. It is one of the methods which manufacture by making the process of mixing essential.
- the manufacturing method of the inorganic particle slurry of this invention may include the process of mixing a solvent and another compounding agent, as long as the said mixing process is included.
- the poly (meth) acrylic acid polymer aqueous solution has a structure derived from (meth) acrylic acid (salt) and a structure derived from organic amine (salt) contained in the poly (meth) acrylic acid polymer aqueous solution.
- the molar ratio is preferably 100: 10 to 100: 75.
- the poly (meth) acrylic acid polymer aqueous solution includes a structure derived from an organic amine (salt), a structure derived from an organic amine (salt) contained in the poly (meth) acrylic acid polymer aqueous solution (meta )
- a structure derived from an organic amine (salt) contained in the poly (meth) acrylic acid polymer aqueous solution metala
- the structure derived from the organic amine (salt) contained in the poly (meth) acrylic acid polymer aqueous solution includes, for example, (i) an aqueous solution containing an acid type and / or a partially neutralized polyacrylic acid polymer.
- the structure contained in the carboxyl group salt neutralized with organic amine formed by adding organic amine to (ii) monomers such as (meth) acrylic acid previously neutralized with organic amine examples include a structure formed by polymerization of an organic amine salt, and (iii) a structure existing as an unreacted organic amine. Since the viscosity stability over time of the inorganic particle slurry tends to be improved, the poly (meth) acrylic acid polymer aqueous solution is preferably in a form in which the amount of inorganic salt or the like is reduced as much as possible, and therefore organic
- the structure derived from an amine (salt) is preferably a structure that exists as an organic amine salt of a carboxyl group. The ratio of the carboxyl group neutralized with the organic amine with respect to 100 mol% of the carboxyl group of the poly (meth) acrylic acid polymer is the same as that in the inorganic particle slurry.
- Method for producing poly (meth) acrylic acid polymer (aqueous solution) it can be produced by a method similar to the method for producing the poly (meth) acrylic acid polymer (aqueous solution) of the present invention described above. .
- the production method usually used for producing the inorganic particle slurry can be referred to as appropriate, or it can be carried out by combining, but typically, the primary dispersion And a method of wet pulverizing it.
- This method is suitable in that a high-concentration pigment slurry having a low viscosity and excellent dispersion stability can be obtained.
- the inorganic particle slurry adjusting method in the present invention is not limited to this wet pulverization method, and it is not limited at all to adopt an adjustment method in which the wet pulverization treatment is not performed.
- the primary dispersion method is not particularly limited, but is preferably mixed with a mixer. It is preferable to use one having a high strength.
- the method for producing fine inorganic particles according to the present invention comprises (i) a poly (meth) acrylic acid polymer aqueous solution containing a structure derived from (meth) acrylic acid (salt) and a structure derived from organic amine (salt), and After mixing the inorganic particles, or (ii) after mixing the poly (meth) acrylic acid polymer aqueous solution containing the poly (meth) acrylic acid polymer, the organic amine (salt), and the inorganic particles, It is preferable to include a step of wet-grinding the inorganic particles. In this case, the particle size of the inorganic particles contained in the inorganic particle slurry can be efficiently set within a desired range. In such a case, the poly (meth) acrylic acid polymer (aqueous solution) of the present invention also serves as a grinding aid.
- the inorganic particle slurry of the present invention can be used for paper coating, paper processing, ceramic molding, fiber treatment, emulsion coating, and the like.
- the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.
- the weight average molecular weight, number average molecular weight, unreacted monomer quantification, polymer aqueous solution and polymer composition solid content, and polymer aqueous solution effective component values of the polymer of the present invention are as follows. It was measured.
- Polymer aqueous solution method for measuring solid content of polymer composition>
- the polymer composition (polymer composition 1.0 g + water 3.0 g) was left to dry for 2 hours in an oven heated to 110 ° C. in a nitrogen atmosphere. From the weight change before and after drying, the solid content (%) and the volatile component (%) were calculated.
- the effective component value was measured and calculated as the carboxyl group concentration of the polymer obtained by polymerization using an automatic titrator COM-1500 manufactured by Hiranuma Sangyo Co., Ltd.
- a titration curve is prepared with 1N HCl aqueous solution, and the difference between the second inflection point and the first inflection point of the curve (the amount of 1N HCl solution) ) was calculated as follows.
- Active ingredient value (%) 9.4 ⁇ (1N HCl amount (mass) at the second inflection point ⁇ 1N HCl amount (mass) at the first inflection point) ⁇ HCl titer / analyte amount (mass) .
- the amount of analyte represents the mass of the analyzed poly (meth) acrylic acid polymer aqueous solution.
- Detector HITACHI RI Detector L-2490 Column: Tosoh Corporation TSK-GEL G3000PWXL Column temperature: 40 ° C Flow rate: 0.5 mL / min Calibration curve: POLY SODIUM ACRYLATE STANDARD Eluent: A solution obtained by diluting a mixture of sodium dihydrogen phosphate 12 hydrate / disodium hydrogen phosphate dihydrate (34.5 g / 46.2 g) to 5000 g with pure water.
- ⁇ Anion concentration analysis (ion chromatography analysis)> In the anion concentration analysis, ion chromatography analysis was performed under the following conditions. Apparatus: 762 Interface manufactured by Metrohm Detector: 732 IC Detector manufactured by Metrohm Ion analysis method: suppressor method column: Shodex IC SI-90 4E Guard column: Shodex SI-90 G Column temperature: 40 ° C Eluent: NaHCO 3 water (2 g diluted to 2000 g with water) Flow rate: 1.0 mL / min. When the polymer aqueous solution obtained in the following Example was analyzed, the sulfate ion derived from sodium persulfate and the hypophosphite ion derived from sodium hypophosphite were detected.
- ⁇ Evaluation example> Put 200 parts by weight of commercially available Maruo Calcium Co., Ltd. heavy calcium carbonate powder into a 500 ml SUS container, and attach a stirring seal to the widest mouth at the top of the lid of a glass four-neck separable flask wrapped with a heat insulating material.
- a SUS stirring blade equipped with a three-stage pin is attached to the container, the remaining mouth is covered with a silicone rubber stopper, and the SUS container and the upper part of the glass lid are fixed at two locations with fixing stoppers.
- the SUS stirring blade and a powerful stirring motor were connected, and the entire container was firmly fixed to the support so as not to loosen during the pulverization.
- Example 1 Batch type polymerization kettle (manufactured by SUS, volume 5 m 3 ), thermometer, stirrer (paddle blade), external distillate circulation path and jacket, supply path (for polymerization composition and Polymerization was carried out under the following polymerization prescription and conditions using a reaction apparatus having a reflux cooling apparatus and a neutralizer. First, 362 parts by mass of ion-exchanged water was charged. Thereafter, while stirring the aqueous solution in the polymerization kettle, the temperature of the aqueous solution was raised to reflux with an external jacket at room temperature.
- 85% parts by mass of an 80% by mass acrylic acid aqueous solution for 180 minutes and 49 parts by mass of a 15% by mass sodium persulfate aqueous solution (hereinafter also referred to as “15% NaPS”) 185 minutes, 45% by weight sodium hypophosphite aqueous solution (hereinafter also referred to as “45% SHP”) 17 parts by weight, 20 minutes, and then 70 parts by weight for 160 minutes, each at a two-stage feed rate. It was dripped from the tip nozzle through the supply path. The dropping of each component was continuously performed at a constant dropping rate except for 45% SHP.
- aqueous sodium hydroxide solution 600 parts by mass of a 48% by mass aqueous sodium hydroxide solution (AA neutralization rate of 70%) is dropped into the polymerization kettle from the tip nozzle through the supply path to neutralize the polymer, followed by monoethanolamine. 175 parts by mass (hereinafter also referred to as “MEA”) (AA neutralization rate of 28%) was dropped into the polymerization kettle from the tip nozzle through another supply path to neutralize the polymer.
- MEA aqueous solution of sodium polyacrylate / monoethanolamine salt (1) was obtained.
- the obtained aqueous solution (referred to as polymer aqueous solution (1)) had a solid content value of 52.7% and an active ingredient value of 44.7%.
- the aqueous polymer solution (1) had a Brookfield viscosity of 850 mPa ⁇ s, a weight average molecular weight (Mw) of 5200, and a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 2.15.
- the total concentration of inorganic anions containing sulfur atoms or phosphorus atoms (mainly sulfate ions and hypophosphite ions were detected) in the aqueous polymer solution (1) was 5900 ppm.
- the polymerization prescription is shown in Table 1, and the analysis results are shown in Table 2.
- Example 2 A sodium polyacrylate / monoethanolamine aqueous solution (2) was obtained in the same manner as in Example 1 except that the polymerization conditions were changed to those shown in Table 1.
- the solid content value in the obtained aqueous solution (referred to as polymer aqueous solution (2)) was 59.0%, and the active ingredient value was 45.4%.
- the Brookfield viscosity of the aqueous polymer solution (2) was 990 mPa ⁇ s
- the weight average molecular weight (Mw) was 5400
- the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.14.
- the polymerization prescription is shown in Table 1, and the analysis results of the polymer are shown in Table 2.
- Example 1 when the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 630 mPa ⁇ s, and the slurry viscosity after one week was 2090 mPa ⁇ s.
- Example 3 Batch type polymerization kettle (manufactured by SUS, volume 5 m 3 ), thermometer, stirrer (paddle blade), external distillate circulation path and jacket, supply path (for polymerization composition and Polymerization was carried out under the polymerization prescription and conditions shown below using a reaction apparatus (see FIG. 1) having an external circulation cooling apparatus (for the neutralizing agent) and an external circulation cooling apparatus (external reaction liquid circulation path and heat removal apparatus). 515 parts by mass of ion-exchanged water and 16 parts by mass of a 45% by mass aqueous sodium hypophosphite solution (hereinafter also referred to as “45% SHP”) were charged.
- 45% SHP 45% by mass aqueous sodium hypophosphite solution
- aqueous solution was raised to 82 ° C. with an external jacket at room temperature while stirring the aqueous solution in the polymerization kettle.
- 80% AA 80% by mass acrylic acid aqueous solution
- SHP 67% by mass of 45% SHP
- 15% by mass sodium persulfate aqueous solution hereinafter also referred to as “15% NaPS”.
- each component was continuously performed at a constant dropping rate. Thereafter, 583 parts by mass of a 48% by mass aqueous sodium hydroxide solution (AA neutralization rate of 70%) is dropped into the polymerization kettle from the tip nozzle through the supply path to neutralize the polymer, followed by monoethanolamine. 171 parts by mass (AA neutralization rate of 28%) was dropped into the polymerization kettle from the tip nozzle through another supply path to neutralize the polymer.
- the reaction solution was cooled by a heat removal device while always circulating the reaction solution externally. As described above, an aqueous solution of sodium polyacrylate / monoethanolamine salt (3) was obtained.
- the obtained aqueous solution (3) (referred to as polymer aqueous solution (3)) had a solid content value of 52.4% and an active ingredient value of 40.2%.
- the Brookfield viscosity of the aqueous polymer solution (3) was 800 mPa ⁇ s, the weight average molecular weight (Mw) was 5500, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.15.
- the polymerization prescription is shown in Table 1, and the analysis results of the polymer are shown in Table 2.
- the slurry viscosity of heavy calcium carbonate was evaluated by the above method, the slurry viscosity immediately after pulverization was 1000 mPa ⁇ s, and the slurry viscosity after 1 week was 3450 mPa ⁇ s.
- Example 4 A sodium polyacrylate aqueous solution (4) was obtained in the same manner as in Example 3 except that the polymerization conditions were changed to those described in Table 1.
- the obtained aqueous solution (referred to as polymer aqueous solution (4)) had a solid content value of 56.9% and an active ingredient value of 40.3%.
- the Brookfield viscosity of the aqueous polymer solution (4) was 950 mPa ⁇ s, the weight average molecular weight (Mw) was 5700, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.18.
- the polymerization prescription is shown in Table 1, and the measurement results and evaluation results of the obtained polymers are shown in Table 2.
- Example 1 when the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 890 mPa ⁇ s, and the slurry viscosity after one week was 2210 mPa ⁇ s.
- a sodium polyacrylate aqueous solution (5) was obtained in the same manner as in Example 1, except that the polymerization conditions were changed to those shown in Table 1.
- the obtained aqueous solution (referred to as polymer aqueous solution (5)) had a solid content value of 46.6% and an active ingredient value of 44.5%.
- the Brookfield viscosity of the aqueous polymer solution (5) was 900 mPa ⁇ s, the weight average molecular weight (Mw) was 5900, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.30.
- the polymerization prescription is shown in Table 1, and the analysis results of the obtained polymer are shown in Table 2.
- Example 1 when the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 1800 mPa ⁇ s, and the slurry viscosity after one week was 4700 mPa ⁇ s.
- a sodium polyacrylate aqueous solution (6) was obtained in the same manner as in Example 3, except that the polymerization conditions were changed to those shown in Table 1.
- the obtained aqueous solution (referred to as polymer aqueous solution (6)) had a solid content value of 43.3% and an active ingredient value of 41.3%.
- the Brookfield viscosity of the aqueous polymer solution (6) was 780 mPa ⁇ s, the weight average molecular weight (Mw) was 5500, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.20.
- the polymerization prescription is shown in Table 1, and the analysis results of the obtained polymer are shown in Table 2.
- Example 1 when the slurry viscosity of heavy calcium carbonate was evaluated by the above method, the slurry viscosity immediately after pulverization was 1400 mPa ⁇ s, and the slurry viscosity after 1 week was 3800 mPa ⁇ s.
- the polymer of the present invention has a good initial dispersion force and a temporal dispersion force as compared with the conventional polymer.
- Example 5 Batch type polymerization kettle (manufactured by SUS, volume 5 m 3 ), thermometer, stirrer (paddle blade), external distillate circulation path and jacket, supply path (for polymerization composition and Polymerization was carried out under the polymerization prescription and conditions shown below using a reactor having a neutralizer and an external circulation cooling device (external reaction liquid circulation path and heat removal device). First, 362 parts by mass of ion-exchanged water was charged. Thereafter, while stirring the aqueous solution in the polymerization kettle, the temperature of the aqueous solution was raised to reflux with an external jacket under normal pressure.
- 85% parts by mass of an 80% by mass acrylic acid aqueous solution for 180 minutes and 49 parts by mass of a 15% by mass sodium persulfate aqueous solution (hereinafter also referred to as “15% NaPS”) 185 minutes, 45% by weight sodium hypophosphite aqueous solution (hereinafter also referred to as “45% SHP”) 17 parts by weight, 20 minutes, and then 70 parts by weight for 160 minutes, each at a two-stage feed rate. It was dripped from the tip nozzle through the supply path. The dropping of each component was continuously performed at a constant dropping rate except for 45% SHP.
- the solution was aged for 30 minutes while maintaining the refluxed state of the aqueous solution.
- the temperature of the aqueous solution at this time showed 103 degreeC.
- the temperature of the aqueous solution is cooled to 65 ° C. using an external cooling circulation device, and the aqueous solution temperature is maintained at 65 to 80 ° C., so that 600 parts by mass of the 48% by mass sodium hydroxide aqueous solution (AA neutralization rate) 70%) was dropped from the tip nozzle into the polymerization vessel through the supply path over 60 minutes to neutralize the polymer (step N1), followed by monoethanolamine (hereinafter also referred to as “MEA”).
- MEA monoethanolamine
- polymer aqueous solution (7) 175 parts by mass (AA neutralization rate of 28%) was dropped into the polymerization kettle from the tip nozzle through another supply path over 30 minutes to neutralize the polymer (step N2). The total time required for the steps N1 and N2 was 90 minutes.
- AA neutralization rate of 28%) 175 parts by mass was dropped into the polymerization kettle from the tip nozzle through another supply path over 30 minutes to neutralize the polymer (step N2).
- the total time required for the steps N1 and N2 was 90 minutes.
- an aqueous solution of sodium polyacrylate / monoethanolamine salt (7) was obtained.
- the obtained aqueous solution (referred to as polymer aqueous solution (7)) had a solid content value of 52.7% and an active ingredient value of 44.7%.
- the Brookfield viscosity of the aqueous polymer solution (7) was 850 mPa ⁇ s, the weight average molecular weight (Mw) was 5200, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.15.
- the total concentration of inorganic anions containing sulfur atoms or phosphorus atoms (mainly sulfate ions and hypophosphite ions were detected) in the aqueous polymer solution (7) was 5900 ppm.
- the hue (APHA) in the solid state immediately after manufacture of polymer aqueous solution (7) was 60, and APHA after one-month progress was 140 at room temperature (25 degreeC).
- the polymerization results and the analysis results of the polymer are shown in Table 3, and the evaluation results are shown in Table 4.
- Table 3 the density
- Example 6 A sodium polyacrylate / monoethanolamine aqueous solution (8) was obtained in the same manner as in Example 5 except that the polymerization conditions were changed to those shown in Table 3.
- the solid content value in the obtained aqueous solution (referred to as polymer aqueous solution (8)) was 59.0%, and the active ingredient value was 44.7%.
- the aqueous polymer solution (8) had a Brookfield viscosity of 990 mPa ⁇ s, a weight average molecular weight (Mw) of 5400, and a weight average molecular weight (Mw) / number average molecular weight (Mn) of 2.14.
- the total concentration of inorganic anions containing sulfur atoms or phosphorus atoms (mainly sulfate ions and hypophosphite ions were detected) in the aqueous polymer solution (8) was 6100 ppm.
- the hue (APHA) in the solid state immediately after manufacture of polymer aqueous solution (8) was 70, and APHA after one-month progress was 150 at room temperature (25 degreeC).
- the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 630 mPa ⁇ s, and the slurry viscosity after one week was 2090 mPa ⁇ s.
- the polymerization results and the analysis results of the polymer are shown in Table 3, and the evaluation results are shown in Table 4.
- Example 7 Batch type polymerization kettle (manufactured by SUS, volume 5 m 3 ), thermometer, stirrer (paddle blade), external distillate circulation path and jacket, supply path (for polymerization composition and Polymerization was carried out under the polymerization prescription and conditions shown below using a reactor having a neutralizer and an external circulation cooling device (external reaction liquid circulation path and heat removal device). 515 parts by mass of ion-exchanged water and 16 parts by mass of a 45% by mass aqueous sodium hypophosphite solution (hereinafter also referred to as “45% SHP”) were charged. Thereafter, the temperature of the aqueous solution was raised to 82 ° C.
- 45% SHP 45% by mass aqueous sodium hypophosphite solution
- step N1 After dropping of 15% NaPS, aging was performed for 30 minutes while maintaining the reflux of the aqueous solution. Thereafter, using an external circulation cooling device, the temperature of the aqueous solution is cooled to 65 ° C., and the temperature of the aqueous solution is maintained at 65 to 80 ° C. 70%) was dropped from the tip nozzle into the polymerization kettle through the supply path over 60 minutes to neutralize the polymer (step N1), and then 171 parts by mass of monoethanolamine (AA neutralization rate 28). %) was added dropwise to the polymerization kettle from the tip nozzle through another supply path over 30 minutes to neutralize the polymer (step N2). The total time required for the steps N1 and N2 was 90 minutes.
- an aqueous solution of sodium polyacrylate / monoethanolamine salt (9) was obtained.
- the obtained aqueous solution (referred to as polymer aqueous solution (9)) had a solid content value of 52.4% and an active ingredient value of 40.2%.
- the Brookfield viscosity of the aqueous polymer solution (9) was 800 mPa ⁇ s, the weight average molecular weight (Mw) was 5500, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.15.
- the total concentration of inorganic anions containing sulfur atoms or phosphorus atoms (mainly sulfate ions and hypophosphite ions were detected) in the aqueous polymer solution (9) was 6400 ppm.
- the hue (APHA) in the solid state immediately after manufacture of the polymer aqueous solution (9) was 60, and APHA after one month passed at room temperature (25 ° C.) was 140.
- the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 1000 mPa ⁇ s, and the slurry viscosity after 1 week was 3450 mPa ⁇ s.
- the polymerization results and the analysis results of the polymer are shown in Table 3, and the evaluation results are shown in Table 4.
- Example 8> A sodium polyacrylate aqueous solution (10) was obtained in the same manner as in Example 7 except that the polymerization conditions were changed to those described in Table 3.
- the obtained aqueous solution (referred to as polymer aqueous solution (10)) had a solid content value of 56.9% and an active ingredient value of 40.3%.
- the polymer aqueous solution (10) had a Brookfield viscosity of 950 mPa ⁇ s, a weight average molecular weight (Mw) of 5700, and a weight average molecular weight (Mw) / number average molecular weight (Mn) of 2.18.
- the total concentration of inorganic anions containing sulfur atoms or phosphorus atoms (mainly sulfate ions and hypophosphite ions were detected) in the aqueous polymer solution (10) was 6500 ppm.
- the polymer aqueous solution (10) had a solid hue (APHA) immediately after production of 75 and an APHA of 150 after one month at room temperature (25 ° C.).
- APHA solid hue
- Example 1 when the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 890 mPa ⁇ s, and the slurry viscosity after one week was 2210 mPa ⁇ s.
- the polymerization results and the analysis results of the polymer are shown in Table 3, and the evaluation results are shown in Table 4.
- Example 9 Batch type polymerization kettle (manufactured by SUS, volume 5 m 3 ), thermometer, stirrer (paddle blade), external distillate circulation path and jacket, supply path (for polymerization composition and Polymerization was carried out using a reaction apparatus having a neutralizing agent), an external circulation cooling apparatus (external reaction liquid circulation path and heat removal apparatus), and a solvent distillation apparatus under the following polymerization prescription and conditions. 350 parts by mass of ion-exchanged water and 200 parts by mass of isopropyl alcohol (hereinafter also referred to as “IPA”) were charged.
- IPA isopropyl alcohol
- the dropping was started and dropped over 155 minutes (that is, until 5 minutes after the completion of dropping of 80% AA).
- the dropping of each component was continuously performed at a constant dropping rate.
- aging was performed for 30 minutes while maintaining the reflux of the mixed solution.
- the mixture of IPA and water was distilled off at a temperature of 80 to 103 ° C. over 120 minutes until the IPA in the polymerization vessel disappeared (step D), and then 220 parts by mass of ion-exchanged water was charged into the polymerization vessel.
- the temperature of the aqueous solution was adjusted to 70 ° C.
- the temperature of the aqueous solution is maintained at 70 to 85 ° C., and 583 parts by mass of a 48% by mass sodium hydroxide aqueous solution (AA neutralization rate of 70%) is supplied from the tip nozzle through the supply path.
- AA neutralization rate of 70% 583 parts by mass of a 48% by mass sodium hydroxide aqueous solution
- step N1 171 parts by mass of monoethanolamine (AA neutralization rate of 28%) was then added to the tip through another supply path.
- the solution was dropped from the nozzle into the polymerization kettle over 30 minutes to neutralize the polymer (step N2). The total time required for the steps N1 and N2 was 90 minutes.
- an aqueous solution of sodium polyacrylate / monoethanolamine salt (11) was obtained.
- the obtained aqueous solution (referred to as polymer aqueous solution (11)) had a solid content value of 52.5% and an active ingredient value of 40.3%.
- the Brookfield viscosity of the aqueous polymer solution (11) was 600 mPa ⁇ s, the weight average molecular weight (Mw) was 4500, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.15.
- the total concentration of inorganic anions containing sulfur atoms or phosphorus atoms in the aqueous polymer solution (11) was 6500 ppm.
- the hue (APHA) in the solid immediately after manufacture of polymer aqueous solution (11) was 70, and APHA after one-month progress was 150 at room temperature (25 degreeC).
- the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 900 mPa ⁇ s, and the slurry viscosity after 1 week was 3400 mPa ⁇ s.
- the polymerization results and the analysis results of the polymer are shown in Table 3, and the evaluation results are shown in Table 4.
- Example 10 Batch type polymerization kettle (manufactured by SUS, volume 5 m 3 ), thermometer, stirrer (paddle blade), external distillate circulation path and jacket, supply path (for polymerization composition and Polymerization was carried out using a reaction apparatus having a neutralizing agent), an external circulation cooling apparatus (external reaction liquid circulation path and heat removal apparatus), and a solvent distillation apparatus under the following polymerization prescription and conditions. 350 parts by mass of ion-exchanged water and 200 parts by mass of isopropyl alcohol (hereinafter also referred to as “IPA”) were charged.
- IPA isopropyl alcohol
- the dropping was started and dropped over 155 minutes (that is, until 5 minutes after the completion of dropping of 80% AA).
- the dropping of each component was continuously performed at a constant dropping rate.
- aging was performed for 30 minutes while maintaining the reflux of the mixed solution.
- the external solution is cooled until the temperature of the mixed solution reaches 65 ° C., and the temperature of the mixed solution is maintained at 65 to 80 ° C.
- AA neutralization rate of 70% Part (AA neutralization rate of 70%) is dropped over 60 minutes from the tip nozzle into the polymerization vessel through the supply path to partially neutralize the polymer (step N1), and then monoethanolamine 171 A part by mass (AA neutralization rate of 28%) was dropped into the polymerization kettle from the tip nozzle through another supply path over 30 minutes to neutralize the polymer (step N2).
- the total time required for the steps N1 and N2 was 90 minutes.
- 220 parts by mass of ion-exchanged water was put into the polymerization kettle.
- a sodium polyacrylate / monoethanolamine salt aqueous solution (12) was obtained.
- the obtained aqueous solution (referred to as polymer aqueous solution (12)) had a solid content value of 52.6% and an active ingredient value of 40.4%.
- the Brookfield viscosity of the aqueous polymer solution (12) was 620 mPa ⁇ s, the weight average molecular weight (Mw) was 4600, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.15.
- the total concentration of inorganic anions containing sulfur atoms or phosphorus atoms in the aqueous polymer solution (12) (mainly sulfate ions and hypophosphite ions were detected) was 6400 ppm.
- the hue (APHA) in solid of polymer aqueous solution (12) was 90, and APHA after one-month progress was 160 at room temperature (25 degreeC).
- the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 920 mPa ⁇ s, and the slurry viscosity after 1 week was 3450 mPa ⁇ s.
- the polymerization results and the analysis results of the polymer are shown in Table 3, and the evaluation results are shown in Table 4.
- a sodium polyacrylate aqueous solution (13) was obtained in the same manner as in Example 5 except that the polymerization conditions were changed to those shown in Table 3.
- the obtained aqueous solution (referred to as polymer aqueous solution (13)) had a solid content value of 46.6% and an active ingredient value of 44.5%.
- the Brookfield viscosity of the aqueous polymer solution (13) was 900 mPa ⁇ s, the weight average molecular weight (Mw) was 5900, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.30.
- the total concentration of inorganic anions containing sulfur atoms or phosphorus atoms in the polymer aqueous solution (13) was 5800 ppm.
- the hue (APHA) in the solid state immediately after manufacture of polymer aqueous solution (13) was 60, and APHA after one-month progress was 130 at room temperature (25 degreeC).
- the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 1800 mPa ⁇ s, and the slurry viscosity after one week was 4700 mPa ⁇ s.
- the polymerization results and the analysis results of the polymer are shown in Table 3, and the evaluation results are shown in Table 4.
- a sodium polyacrylate aqueous solution (14) was obtained in the same manner as in Example 7 except that the polymerization conditions were changed to those shown in Table 3.
- the obtained aqueous solution (referred to as polymer aqueous solution (14)) had a solid content value of 43.3% and an active ingredient value of 41.3%.
- the Brookfield viscosity of the aqueous polymer solution (14) was 680 mPa ⁇ s, the weight average molecular weight (Mw) was 5,500, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.20.
- the total concentration of inorganic anions containing sulfur atoms or phosphorus atoms (mainly sulfate ions and hypophosphite ions were detected) in the aqueous polymer solution (14) was 6200 ppm.
- the hue (APHA) in the solid immediately after manufacture of polymer aqueous solution (14) was 70, and APHA after one-month progress was 140 at room temperature (25 degreeC).
- the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 1700 mPa ⁇ s, and the slurry viscosity after 1 week was 4800 mPa ⁇ s.
- the polymerization results and the analysis results of the polymer are shown in Table 3, and the evaluation results are shown in Table 4.
- a sodium polyacrylate aqueous solution (15) was obtained in the same manner as in Example 9, except that the polymerization conditions were changed to those shown in Table 3.
- the obtained aqueous solution (referred to as polymer aqueous solution (15)) had a solid content value of 43.1% and an active ingredient value of 41.1%.
- the Brookfield viscosity of the aqueous polymer solution (15) was 650 mPa ⁇ s, the weight average molecular weight (Mw) was 4500, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.20.
- the total concentration of inorganic anions containing sulfur atoms or phosphorus atoms in the aqueous polymer solution (15) was 6400 ppm.
- the hue (APHA) in the solid state immediately after manufacture of polymer aqueous solution (15) was 75, and APHA after one-month progress was 160 at room temperature (25 degreeC).
- the slurry viscosity of heavy calcium carbonate was 1400 mPa ⁇ s
- the slurry viscosity after 1 week was 4200 mPa ⁇ s.
- the polymerization results and the analysis results of the polymer are shown in Table 3, and the evaluation results are shown in Table 4.
- a sodium polyacrylate / monoethanolamine salt aqueous solution (16) was obtained in the same manner as in Example 5 except that the polymerization conditions were changed to those shown in Table 3.
- the aqueous solution was kept in a reflux state, and the temperature of the aqueous solution at this time was 103 ° C.
- the obtained aqueous solution (referred to as polymer aqueous solution (16)) had a solid content value of 53.2% and an active ingredient value of 44.9%.
- the aqueous polymer solution (16) had a Brookfield viscosity of 900 mPa ⁇ s, a weight average molecular weight (Mw) of 5500, and a weight average molecular weight (Mw) / number average molecular weight (Mn) of 2.17. Further, the total concentration of inorganic anions containing sulfur atoms or phosphorus atoms in the polymer aqueous solution (16) (mainly sulfate ions and hypophosphite ions were detected) was 5500 ppm. Moreover, the hue (APHA) in the solid state immediately after manufacture of polymer aqueous solution (16) was 80, and APHA after one-month progress was 250 at room temperature (25 degreeC).
- Example 1 when the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 1000 mPa ⁇ s, and the slurry viscosity after 1 week was 3500 mPa ⁇ s.
- the polymerization results and the analysis results of the polymer are shown in Table 3, and the evaluation results are shown in Table 4.
- Example 7 A sodium polyacrylate / monoethanolamine salt aqueous solution (17) was obtained in the same manner as in Example 6 except that the polymerization conditions were changed to those shown in Table 3. In addition, at the time of aging and neutralization of the polymerization liquid (step N1 and step N2), the aqueous solution was kept in a reflux state, and the temperature of the aqueous solution at this time was 103 ° C. The obtained aqueous solution (referred to as polymer aqueous solution (17)) had a solid content value of 59.2% and an active ingredient value of 44.9%.
- the aqueous polymer solution (17) had a Brookfield viscosity of 1100 mPa ⁇ s, a weight average molecular weight (Mw) of 5500, and a weight average molecular weight (Mw) / number average molecular weight (Mn) of 2.19. Further, the total concentration of inorganic anions containing sulfur atoms or phosphorus atoms in the aqueous polymer solution (17) (mainly sulfate ions and hypophosphite ions were detected) was 5600 ppm. Moreover, the hue (APHA) in the solid state immediately after manufacture of polymer aqueous solution (17) was 80, and APHA after one-month progress was 300 at room temperature (25 degreeC).
- Example 1 when the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 800 mPa ⁇ s, and the slurry viscosity after 1 week was 2700 mPa ⁇ s.
- the polymerization results and the analysis results of the polymer are shown in Table 3, and the evaluation results are shown in Table 4.
- Tables 5 and 10 and the analysis results of Examples 5 to 10 and Comparative Examples 3 to 7 are summarized in Table 3, and the evaluation results are summarized in Table 4.
- Table 4 in addition to the evaluation results, “a structure derived from (meth) acrylic acid (salt) and a structure derived from organic amine (salt) contained in an aqueous solution containing a poly (meth) acrylic acid polymer” The "molar ratio" is summarized.
- the polymer of the present invention has a good initial dispersive force and a dispersive force over time as compared with the conventional polymer, and (i) the acid type and / or A step of neutralizing an aqueous solution containing a partially neutralized poly (meth) acrylic acid polymer with an alkali metal salt; and (ii) an acid type and / or a partially neutralized poly (meth) acrylic acid polymer. It has been clarified that by producing an aqueous solution containing a solution neutralized with an organic amine, it has a good color tone over time.
- Example 11 Batch type polymerization kettle (manufactured by SUS, volume 5 m 3 ), thermometer, stirrer (paddle blade), external distillate circulation path and jacket, supply path (for polymerization composition and Polymerization was carried out under the following polymerization prescription and conditions using a reaction apparatus having a reflux cooling apparatus and a neutralizer. First, 362 parts by mass of ion-exchanged water was charged. Thereafter, while stirring the aqueous solution in the polymerization kettle, the temperature of the aqueous solution was raised to reflux with an external jacket at room temperature.
- 85% parts by mass of an 80% by mass acrylic acid aqueous solution for 180 minutes and 49 parts by mass of a 15% by mass sodium persulfate aqueous solution (hereinafter also referred to as “15% NaPS”) 185 minutes, 45% by weight sodium hypophosphite aqueous solution (hereinafter also referred to as “45% SHP”) 17 parts by weight, 20 minutes, and then 70 parts by weight for 160 minutes, each at a two-stage feed rate. It was dripped from the tip nozzle through the supply path. The dropping of each component was continuously performed at a constant dropping rate except for 45% SHP.
- AA neutralization rate of 70% 600 parts by mass of a 48% by mass aqueous sodium hydroxide solution (AA neutralization rate of 70%) is dropped into the polymerization kettle from the tip nozzle through the supply path to neutralize the polymer, followed by monoethanolamine. 175 parts by mass (hereinafter also referred to as “MEA”) (AA neutralization rate of 28%) was dropped into the polymerization kettle from the tip nozzle through another supply path to neutralize the polymer.
- MEA aqueous solution of sodium polyacrylate / monoethanolamine salt (18) was obtained.
- the obtained aqueous solution (referred to as polymer aqueous solution (18)) had a solid content value of 52.7% and an active ingredient value of 44.7%.
- the aqueous polymer solution (18) had a Brookfield viscosity of 850 mPa ⁇ s, a weight average molecular weight (Mw) of 5200, and a weight average molecular weight (Mw) / number average molecular weight (Mn) of 2.15.
- the total concentration of inorganic anions containing sulfur atoms or phosphorus atoms (mainly sulfate ions and hypophosphite ions were detected) in the aqueous polymer solution (18) was 5900 ppm. According to the evaluation example, the aqueous polymer solution (18) was used to obtain an inorganic particle slurry (heavy calcium carbonate slurry (18)) of the present invention.
- the proportion of inorganic particles of 2 ⁇ m or less in the heavy calcium carbonate slurry (18) was 90.1% by mass, and the solid content concentration was 77.6% by mass.
- the slurry viscosity of heavy calcium carbonate was evaluated by the above-mentioned method, the slurry viscosity 1 hour after the completion of pulverization was 950 mPa ⁇ s, and the slurry viscosity after 1 week was 3380 mPa ⁇ s.
- Table 5 shows the polymerization formulation and analysis results of the polymer, and Table 6 shows the evaluation results.
- Example 12 A sodium polyacrylate / monoethanolamine salt aqueous solution (19) was obtained in the same manner as in Example 11 except that the polymerization conditions were changed to those shown in Table 5.
- the solid content value in the obtained aqueous solution (referred to as polymer aqueous solution (19)) was 59.0%, and the active ingredient value was 45.4%.
- the aqueous polymer solution (19) had a Brookfield viscosity of 990 mPa ⁇ s, a weight average molecular weight (Mw) of 5400, and a weight average molecular weight (Mw) / number average molecular weight (Mn) of 2.14.
- the inorganic particle slurry (heavy calcium carbonate slurry (19)) of the present invention was obtained using the polymer aqueous solution (19).
- the proportion of the inorganic particles of 2 ⁇ m or less in the heavy calcium carbonate slurry (19) was 90.2% by mass, and the solid content concentration was 77.4% by mass.
- the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 630 mPa ⁇ s, and the slurry viscosity after one week was 2090 mPa ⁇ s.
- Table 5 shows the polymerization formulation and analysis results of the polymer, and Table 6 shows the evaluation results.
- Example 13 Batch type polymerization kettle (manufactured by SUS, volume 5 m 3 ), thermometer, stirrer (paddle blade), external distillate circulation path and jacket, supply path (for polymerization composition and Polymerization was carried out under the polymerization prescription and conditions shown below using a reaction apparatus (see FIG. 1) having an external circulation cooling apparatus (external reaction liquid circulation path and heat removal apparatus). 515 parts by mass of ion-exchanged water and 16 parts by mass of a 45% by mass aqueous sodium hypophosphite solution (hereinafter also referred to as “45% SHP”) were charged. Thereafter, the temperature of the aqueous solution was raised to 82 ° C.
- 45% SHP 45% by mass aqueous sodium hypophosphite solution
- the obtained aqueous solution (referred to as polymer aqueous solution (20)) had a solid content value of 52.4% and an active ingredient value of 40.2%.
- the Brookfield viscosity of the aqueous polymer solution (20) was 800 mPa ⁇ s, the weight average molecular weight (Mw) was 5,500, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.15.
- the inorganic particle slurry (heavy calcium carbonate slurry (20)) of the present invention was obtained using the polymer aqueous solution (20).
- the proportion of inorganic particles of 2 ⁇ m or less in the heavy calcium carbonate slurry (20) was 90.3% by mass, and the solid content concentration was 77.5% by mass.
- the slurry viscosity of heavy calcium carbonate was evaluated by the above method, the slurry viscosity immediately after pulverization was 1000 mPa ⁇ s, and the slurry viscosity after 1 week was 3450 mPa ⁇ s.
- Table 5 shows the polymerization formulation and analysis results of the polymer, and Table 6 shows the evaluation results.
- Example 14 A sodium polyacrylate aqueous solution (21) was obtained in the same manner as in Example 13 except that the polymerization conditions were changed to those shown in Table 5.
- the obtained aqueous solution (referred to as polymer aqueous solution (21)) had a solid content value of 56.9% and an active ingredient value of 40.3%.
- the Brookfield viscosity of the aqueous polymer solution (21) was 950 mPa ⁇ s, the weight average molecular weight (Mw) was 5700, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.18.
- the aqueous polymer solution (21) was used to obtain an inorganic particle slurry (heavy calcium carbonate slurry (21)) of the present invention.
- the proportion of inorganic particles of 2 ⁇ m or less in the heavy calcium carbonate slurry (21) was 90.5% by mass, and the solid content concentration was 77.7% by mass.
- the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 890 mPa ⁇ s, and the slurry viscosity after one week was 2210 mPa ⁇ s.
- the polymerization results and the analysis results of the polymer are shown in Table 5, and the evaluation results are shown in Table 6.
- a sodium polyacrylate aqueous solution (22) was obtained in the same manner as in Example 11 except that the polymerization conditions were changed to those shown in Table 5.
- the obtained aqueous solution (referred to as polymer aqueous solution (22)) had a solid content value of 46.6% and an active ingredient value of 44.5%.
- the Brookfield viscosity of the aqueous polymer solution (22) was 900 mPa ⁇ s, the weight average molecular weight (Mw) was 5900, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.30.
- the aqueous polymer solution (22) was used to obtain an inorganic particle slurry (heavy calcium carbonate slurry (22)) of the present invention.
- the proportion of inorganic particles of 2 ⁇ m or less in the heavy calcium carbonate slurry (22) was 90.2% by mass, and the solid content concentration was 77.3% by mass.
- the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 1800 mPa ⁇ s, and the slurry viscosity after one week was 4700 mPa ⁇ s.
- the polymerization results and the analysis results of the polymer are shown in Table 5, and the evaluation results are shown in Table 6.
- a sodium polyacrylate aqueous solution (23) was obtained in the same manner as in Example 13 except that the polymerization conditions were changed to those shown in Table 5.
- the obtained aqueous solution (referred to as polymer aqueous solution (23)) had a solid content value of 43.3% and an active ingredient value of 41.3%.
- the Brookfield viscosity of the aqueous polymer solution (23) was 780 mPa ⁇ s, the weight average molecular weight (Mw) was 5,500, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.20.
- the aqueous polymer particle (23) was used to obtain the inorganic particle slurry (heavy calcium carbonate slurry (23)) of the present invention.
- the proportion of inorganic particles of 2 ⁇ m or less in the heavy calcium carbonate slurry (23) was 90.1% by mass, and the solid content concentration was 77.6% by mass.
- the slurry viscosity of heavy calcium carbonate was evaluated by the above method, the slurry viscosity immediately after pulverization was 1400 mPa ⁇ s, and the slurry viscosity after 1 week was 3800 mPa ⁇ s.
- the polymerization results and the analysis results of the polymer are shown in Table 5, and the evaluation results are shown in Table 6.
- Table 5 summarizes the polymerization formulations and polymer analysis results in Examples 11 to 14 and Comparative Examples 8 to 9, and Table 6 summarizes the evaluation results.
- “molar ratio of structure” means “a structure derived from (meth) acrylic acid (salt) and a structure derived from organic amine (salt) contained in an aqueous poly (meth) acrylic acid polymer solution” The molar ratio (structure derived from (meth) acrylic acid (salt) / structure derived from organic amine (salt)) ".
- concentration of the inorganic anion containing the sulfur atom or phosphorus atom contained in polymer aqueous solution was described as ion concentration total.
- Molar ratio of structure means “molar ratio of a structure derived from (meth) acrylic acid (salt) and a structure derived from organic amine (salt) contained in the inorganic particle slurry (( Structure derived from (meth) acrylic acid (salt) / structure derived from organic amine (salt) ”.
- concentration of the inorganic anion containing the sulfur atom or phosphorus atom contained in an inorganic particle slurry was described as ion concentration total.
- the inorganic particle slurry of the present invention has a good initial viscosity and viscosity stability over time as compared with the conventional inorganic particle slurry.
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Abstract
Description
また、例えば特許文献2には、モノカルボン酸(塩)モノエチレン性不飽和単量体等からなる単量体成分を、アルカリ物質の存在下で、重合触媒を使用しかつ高濃度で水溶液重合させる方法であって、前記重合触媒として過硫酸塩および過酸化水素を併用し、かつ、前記アルカリ性物質の全使用量は前記単量体成分の全酸基を中和するのに必要な量の99mol%以下とするとともに、前記過酸化水素の滴下を前記単量体成分の滴下終了時間よりも10分以上早く終了するようにすることを特徴とする、低分子量(メタ)アクリル酸(塩)系重合体の製造方法が開示されている。
また、例えば特許文献3には、α、βモノエチレン性不飽和カルボン酸の重合体等に対し、これらの100部当たり1~70部の範囲でカルシウム等を含む化合物を反応させ、pH4以上に維持した重合体が開示されている。 As a method for meeting such a demand, for example, Patent Document 1 discloses a method for producing a water-soluble polymer in which a chain transfer agent is continuously added for a predetermined period during the polymerization period, which is a monomer of a chain transfer agent. Disclosed is a method for producing a water-soluble polymer, characterized in that the rate of addition to is changed at least once.
For example, Patent Document 2 discloses that a monomer component composed of a monocarboxylic acid (salt) monoethylenically unsaturated monomer or the like is polymerized in an aqueous solution at a high concentration using a polymerization catalyst in the presence of an alkaline substance. The persulfate and hydrogen peroxide are used in combination as the polymerization catalyst, and the total amount of the alkaline substance used is an amount necessary to neutralize all the acid groups of the monomer component. Low molecular weight (meth) acrylic acid (salt), characterized in that it is 99 mol% or less, and the dropping of the hydrogen peroxide is finished 10 minutes or more earlier than the dropping end time of the monomer component. A method for producing a polymer is disclosed.
Also, for example, in Patent Document 3, a compound containing calcium or the like is reacted in the range of 1 to 70 parts per 100 parts to a polymer of α, β monoethylenically unsaturated carboxylic acid, etc. A retained polymer is disclosed.
例えば、特許文献1に開示の製造方法によって得られた重合体は、残存単量体量を低減することができると共に、得られる重合体の分子量分布を狭くすることができ、更に良好な炭酸カルシウムの分散能を示すことができるとされている。特許文献2に開示の製造方法によって得られた重合体は、良好な顔料の分散能を示すとされている。また、特許文献3に開示の重合体は、少量の添加で良好な顔料分散効果を示すとされている。
しかしながら、例えば近年の顔料塗工機の高度化、精密化に伴い、従来より厳しい顔料の分散能、とりわけ経時変化の少ない分散性を発現する重合体の要求が高まってきた。
更に、例えば紙処理用顔料スラリーの分散剤用途に使用する場合、上記性能に加えて、紙の白色度に影響しないように、着色の少ない重合体組成物が要求されている。 As described above, various studies have been made on polymers used in detergent builders, pigment dispersants, and the like, and inorganic particle slurries.
For example, the polymer obtained by the production method disclosed in Patent Document 1 can reduce the amount of residual monomers, and can narrow the molecular weight distribution of the obtained polymer, thereby further improving calcium carbonate. It is said that the dispersibility of can be shown. The polymer obtained by the production method disclosed in Patent Document 2 is said to exhibit good pigment dispersibility. Further, the polymer disclosed in Patent Document 3 is said to show a good pigment dispersion effect with a small amount of addition.
However, with the recent advancement and refinement of pigment coating machines, for example, there has been an increasing demand for polymers that exhibit more stringent dispersibility of pigments, especially dispersibility with little change over time.
Further, for example, when used in a dispersant for a paper processing pigment slurry, in addition to the above performance, a polymer composition with less coloring is required so as not to affect the whiteness of the paper.
しかしながら、例えば近年のスラリー塗工機の高速化、精密化に伴い、従来より厳しい無機粒子スラリーの分散性、とりわけ経時変化の少ない粘性を発現する無機粒子スラリーの要求が高まってきた。 Further, the inorganic particle slurry is usually required to have a high concentration of inorganic particles and a viscosity that is easy to process. In addition, since a certain period is required from production to use, it is required to show viscosity stability over time. On the other hand, the slurry disclosed in Patent Document 3 is said to have low viscosity and good temporal stability. The dispersion slurry disclosed in Patent Document 4 is said to have a relatively small increase in slurry viscosity after standing for 7 days. Moreover, the slurry disclosed in Patent Document 5 is said to have a low viscosity and a viscosity after 7 days.
However, for example, with recent increases in the speed and precision of slurry coating machines, there has been an increasing demand for inorganic particle slurries that exhibit more stringent dispersibility of inorganic particle slurries than conventional ones, in particular, viscosity with little change with time.
そこで、本発明は、無機物の分散性等に優れ、充分な経時的な分散性を示す重合体(水溶液)、また、更には経時的に良好な色調をも有する重合体(水溶液)、及びそれら重合体(水溶液)を簡便に製造する方法を提供することを目的とする。
また本発明は、高い無機粒子濃度及び良好な粘性を示し、充分な経時的な粘度安定性を有し、乾燥時の着色が少なく、高pHを維持可能な無機粒子スラリー及びその無機粒子スラリーを簡便に製造する方法を提供することを目的とする。 Thus, although various polymers and inorganic particle slurries have been reported in the past, there is a demand for the development of those that are further adapted to the current needs described above.
Therefore, the present invention provides a polymer (aqueous solution) that is excellent in inorganic dispersibility and the like and exhibits sufficient dispersibility over time, and further a polymer (aqueous solution) that also has a good color tone over time, and those It aims at providing the method of manufacturing a polymer (aqueous solution) simply.
The present invention also provides an inorganic particle slurry that exhibits high inorganic particle concentration and good viscosity, has sufficient viscosity stability over time, has little coloration during drying, and can maintain a high pH, and the inorganic particle slurry. It aims at providing the method of manufacturing simply.
すなわち、本発明にかかるポリ(メタ)アクリル酸系重合体水溶液は、ポリ(メタ)アクリル酸系重合体を含む水溶液であって、上記ポリ(メタ)アクリル酸系重合体のカルボキシル基の少なくとも一部は有機アミンで中和されており、上記ポリ(メタ)アクリル酸系重合体水溶液に含まれる、(メタ)アクリル酸(塩)に由来する構造と有機アミン(塩)に由来する構造とのモル比が100:10~100:75であり、かつ、上記ポリ(メタ)アクリル酸系重合体水溶液に含まれる、硫黄原子又はリン原子を含む無機の陰イオンの濃度が、上記ポリ(メタ)アクリル酸系重合体水溶液に対して1000~10000ppmであることを特徴とする水溶液である。 The inventors of the present invention have conducted intensive studies on the polymer (aqueous solution) and the production method thereof in order to solve the above problems. As a result, it has been found that a specific aqueous solution containing a polyacrylic acid polymer (partially) neutralized with an organic amine exhibits good dispersibility of inorganic substances and sufficient dispersibility with time stability. The invention has been completed.
That is, the poly (meth) acrylic acid polymer aqueous solution according to the present invention is an aqueous solution containing a poly (meth) acrylic acid polymer, and at least one of the carboxyl groups of the poly (meth) acrylic acid polymer. The part is neutralized with an organic amine, and the structure derived from (meth) acrylic acid (salt) and the structure derived from organic amine (salt) contained in the poly (meth) acrylic acid polymer aqueous solution. The molar ratio is 100: 10 to 100: 75, and the concentration of inorganic anions containing sulfur atoms or phosphorus atoms contained in the poly (meth) acrylic acid polymer aqueous solution is the poly (meth) An aqueous solution characterized by being 1000 to 10,000 ppm based on the acrylic acid polymer aqueous solution.
すなわち、ポリ(メタ)アクリル酸系重合体を含む水溶液であって、上記ポリ(メタ)アクリル酸系重合体のカルボキシル基の少なくとも一部は有機アミンで中和されており、上記ポリ(メタ)アクリル酸系重合体水溶液に含まれる、(メタ)アクリル酸(塩)に由来する構造と有機アミン(塩)に由来する構造とのモル比が100:10~100:75であり、かつ、上記ポリ(メタ)アクリル酸系重合体水溶液に含まれる、硫黄原子又はリン原子を含む無機の陰イオンの濃度が、上記ポリ(メタ)アクリル酸系重合体水溶液に対して1000~10000ppmであり、上記ポリ(メタ)アクリル酸系重合体水溶液は、(i)酸型及び/又は部分中和型のポリ(メタ)アクリル酸系重合体を含む水溶液をアルカリ金属塩で中和する工程と、(ii)酸型及び/又は部分中和型のポリ(メタ)アクリル酸系重合体を含む水溶液を有機アミンで中和する工程とを必須として製造されることを特徴とするポリ(メタ)アクリル酸系重合体水溶液もまた、本発明の一つである。 A polymer (aqueous solution) having a good color tone over time by producing a specific aqueous solution containing a polyacrylic acid polymer (partially) neutralized with the organic amine by a specific production method. Has been found, and the present invention has been completed.
That is, an aqueous solution containing a poly (meth) acrylic acid polymer, wherein at least a part of the carboxyl groups of the poly (meth) acrylic acid polymer is neutralized with an organic amine, and the poly (meth) The molar ratio of the structure derived from (meth) acrylic acid (salt) and the structure derived from organic amine (salt) contained in the acrylic acid polymer aqueous solution is 100: 10 to 100: 75, and The concentration of the inorganic anion containing sulfur atom or phosphorus atom contained in the poly (meth) acrylic acid polymer aqueous solution is 1000 to 10,000 ppm with respect to the poly (meth) acrylic acid polymer aqueous solution. The poly (meth) acrylic acid polymer aqueous solution includes (i) a step of neutralizing an aqueous solution containing an acid type and / or partially neutralized poly (meth) acrylic acid polymer with an alkali metal salt; And (ii) a poly (meth) acryl produced essentially comprising a step of neutralizing an aqueous solution containing an acid type and / or partially neutralized poly (meth) acrylic acid polymer with an organic amine. An aqueous acid polymer solution is also one aspect of the present invention.
すなわち、本発明にかかる無機粒子スラリーは、ポリ(メタ)アクリル酸系重合体を含む無機粒子スラリーであって、上記ポリ(メタ)アクリル酸系重合体のカルボキシル基の少なくとも一部は有機アミンで中和されており、上記無機粒子スラリーに含まれる、(メタ)アクリル酸(塩)に由来する構造と有機アミン(塩)に由来する構造とのモル比が100:10~100:75であり、上記無機粒子スラリーに含まれる、硫黄原子又はリン原子を含む無機の陰イオンの濃度が、上記無機粒子スラリーに対して100~400ppmであり、上記無機粒子スラリーに含まれる無機粒子は、全無機粒子100質量%に対して、粒径が2μm以下の粒子が90~100質量%含まれ、上記無機粒子スラリーの固形分濃度が75質量%以上であることを特徴とする無機粒子スラリーである。 In addition, the present inventors have conducted intensive studies on the inorganic particle slurry and the production method thereof in order to solve the above problems. As a result, the inorganic particle slurry containing a specific composition containing a polyacrylic acid polymer (partially) neutralized with an organic amine exhibits good viscosity and sufficient viscosity stability over time, The present inventors have found that there is little coloring during drying and that a high pH can be maintained, and the present invention has been completed.
That is, the inorganic particle slurry according to the present invention is an inorganic particle slurry containing a poly (meth) acrylic acid polymer, and at least a part of the carboxyl groups of the poly (meth) acrylic acid polymer is an organic amine. The molar ratio of the structure derived from (meth) acrylic acid (salt) and the structure derived from organic amine (salt) contained in the inorganic particle slurry is 100: 10 to 100: 75. The concentration of inorganic anions containing sulfur atoms or phosphorus atoms contained in the inorganic particle slurry is 100 to 400 ppm relative to the inorganic particle slurry, and the inorganic particles contained in the inorganic particle slurry are all inorganic. 90-100% by mass of particles having a particle size of 2 μm or less is included with respect to 100% by mass of the particles, and the solid content concentration of the inorganic particle slurry is 75% by mass or more. Inorganic particle slurry, wherein the door.
本発明のポリ(メタ)アクリル酸系重合体水溶液の製造方法によれば、本発明のポリ(メタ)アクリル酸系重合体水溶液を効率良く簡便に製造することができる。
また、本発明の無機粒子スラリーは、無機粒子含有量が高く、低い粘性と経時的な粘性変化が低いという特徴を有している為、優れた無機粒子の成形性を発現する。したがって、製紙工業分野やセラミック工業分野において、特に紙塗工用の顔料スラリーとして好ましく使用される。
本発明の無機粒子スラリーの製造方法によれば、優れた粘性及び経時的粘度安定性を有する無機粒子スラリーを効率良く製造することができる。 The aqueous poly (meth) acrylic acid polymer solution of the present invention has excellent dispersibility of inorganic fine particles such as mud stains and inorganic pigments, and can exhibit dispersibility over time. Further, by producing by a specific production method, it has excellent color tone over time. Therefore, when used as a detergent builder or a pigment dispersant, excellent detergency and stable dispersibility of the pigment over time can be obtained.
According to the method for producing a poly (meth) acrylic acid polymer aqueous solution of the present invention, the poly (meth) acrylic acid polymer aqueous solution of the present invention can be produced efficiently and simply.
Moreover, since the inorganic particle slurry of the present invention has the characteristics that the inorganic particle content is high, the viscosity is low, and the change in viscosity over time is low, it exhibits excellent moldability of inorganic particles. Therefore, it is preferably used as a pigment slurry for paper coating in the paper industry and ceramic industries.
According to the method for producing an inorganic particle slurry of the present invention, an inorganic particle slurry having excellent viscosity and stability over time can be efficiently produced.
本発明のポリ(メタ)アクリル酸系重合体水溶液(本発明の重合体水溶液とも言う。)は、ポリ(メタ)アクリル酸系重合体を含む。
上記ポリ(メタ)アクリル酸系重合体とは、(メタ)アクリル酸(塩)由来の構造を含んでいる重合体を表し、該(メタ)アクリル酸(塩)由来の構造とは、(メタ)アクリル酸(塩)がラジカル重合することにより形成される構造であって、-CH2CR(COOM)-、で表される構造である。該構造中、Rは、水素原子又はメチル基を表し、Mは、水素原子、金属原子、アンモニウム塩、有機アミン塩を表す。上記金属原子としては、Li、Na、K等のアルカリ金属原子、Ca、Mg等のアルカリ土類金属原子等が例示される。
上記(メタ)アクリル酸(塩)とは、アクリル酸、アクリル酸塩、メタクリル酸、メタクリル酸塩を表し、これらの中でも、アクリル酸、アクリル酸塩が好ましい。これら(メタ)アクリル酸(塩)は、1種を用いてもよく、2種以上を用いてもよい。
上記(メタ)アクリル酸(塩)における塩としては、金属塩、アンモニウム塩、有機アミン塩が挙げられる。これらの中でも、アルカリ金属塩が好ましく、より好ましくは、ナトリウム塩である。これら(メタ)アクリル酸(塩)における塩は、1種であってもよいし、2種以上であってもよい。 [Poly (meth) acrylic acid polymer]
The poly (meth) acrylic acid polymer aqueous solution of the present invention (also referred to as the polymer aqueous solution of the present invention) includes a poly (meth) acrylic acid polymer.
The poly (meth) acrylic acid polymer represents a polymer containing a structure derived from (meth) acrylic acid (salt), and the structure derived from (meth) acrylic acid (salt) ) A structure formed by radical polymerization of acrylic acid (salt) and represented by —CH 2 CR (COOM) —. In the structure, R represents a hydrogen atom or a methyl group, and M represents a hydrogen atom, a metal atom, an ammonium salt, or an organic amine salt. Examples of the metal atom include alkali metal atoms such as Li, Na, and K, and alkaline earth metal atoms such as Ca and Mg.
The (meth) acrylic acid (salt) represents acrylic acid, acrylate, methacrylic acid, and methacrylate, and among these, acrylic acid and acrylate are preferable. These (meth) acrylic acids (salts) may be used alone or in combination of two or more.
Examples of the salt in the (meth) acrylic acid (salt) include metal salts, ammonium salts, and organic amine salts. Among these, alkali metal salts are preferable, and sodium salts are more preferable. 1 type may be sufficient as the salt in these (meth) acrylic acid (salt), and 2 or more types may be sufficient as it.
上記ポリ(メタ)アクリル酸系重合体の有するカルボキシル基の、酸型のカルボキシル基/有機アミンで中和されたカルボキシル基(有機アミン塩型カルボキシル基)/有機アミン塩型カルボキシル基以外のカルボキシル基の塩の割合は、特に限定されないが、本発明のポリ(メタ)アクリル酸系重合体水溶液に含まれる、(メタ)アクリル酸(塩)に由来する構造と有機アミン及び有機アミン塩(本明細書においては、「有機アミン(塩)」とも表する。)に由来する構造とのモル比が100:10~100:75であることが重要である。好ましくは、100:15~100:70であり、100:20~100:65であることがより好ましい。 The carboxyl group possessed by the poly (meth) acrylic acid polymer is characterized in that at least a part thereof is neutralized with an organic amine salt, and all of the carboxyl groups possessed by the poly (meth) acrylic acid polymer Even if the structure is neutralized (neutralized type), a part of the carboxyl groups of the poly (meth) acrylic acid polymer is neutralized and the rest is an acid type structure. (Partial neutralization type) is acceptable.
Carboxyl groups of the above poly (meth) acrylic acid polymer other than acid type carboxyl groups / carboxyl groups neutralized with organic amines (organic amine salt type carboxyl groups) / carboxyl groups other than organic amine salt type carboxyl groups Although the ratio of the salt of is not specifically limited, the structure derived from (meth) acrylic acid (salt), the organic amine and the organic amine salt (this specification) contained in the poly (meth) acrylic acid polymer aqueous solution of the present invention. In the document, it is important that the molar ratio with the structure derived from “organic amine (salt)” is 100: 10 to 100: 75. Preferably, it is 100: 15 to 100: 70, and more preferably 100: 20 to 100: 65.
ここで、添加された有機アミン(塩)が反応して形成された構造としては、例えば(i)酸型及び/又は部分中和型のポリアクリル酸系重合体を含む水溶液に有機アミン(塩)を添加することにより形成された、有機アミンで中和されたカルボキシル基の塩に含まれる構造や、(ii)予め(メタ)アクリル酸等の単量体を有機アミンで中和した、有機アミン塩が重合することにより形成される構造、(iii)添加された有機アミン(塩)がポリアクリル酸系重合体以外の酸性物質と反応して形成された構造が例示される。
経時的な顔料分散性能が向上する傾向にあることから、本発明のポリ(メタ)アクリル酸系重合体水溶液は無機塩等の量を極力低減させた形態であることが好ましく、そのため上記有機アミン(塩)に由来する構造は、重合体に含まれる、有機アミンで中和されたカルボキシル基であることが好ましい。したがって、上記ポリ(メタ)アクリル酸系重合体の有するカルボキシル基100モル%に対する、有機アミンで中和されたカルボキシル基(有機アミン塩型カルボキシル基)の割合は、10~75モル%であることが好ましく、15~70モル%であることがより好ましく、20~65モル%であることが特に好ましい。 The structure derived from the organic amine (salt) is a structure formed by reacting an added organic amine (salt) in the process of producing the poly (meth) acrylic acid polymer aqueous solution of the present invention, and / Or represents an organic amine (salt) that remains unreacted.
Here, the structure formed by the reaction of the added organic amine (salt) is, for example, (i) an organic amine (salt) in an aqueous solution containing an acid type and / or a partially neutralized polyacrylic acid polymer. ) And the structure contained in the salt of the carboxyl group neutralized with an organic amine, or (ii) an organic compound obtained by neutralizing a monomer such as (meth) acrylic acid in advance with an organic amine. Examples include a structure formed by polymerization of an amine salt, and (iii) a structure formed by reacting an added organic amine (salt) with an acidic substance other than a polyacrylic acid polymer.
Since the pigment dispersion performance with time tends to be improved, the poly (meth) acrylic acid polymer aqueous solution of the present invention is preferably in a form in which the amount of inorganic salt or the like is reduced as much as possible. The structure derived from (salt) is preferably a carboxyl group contained in the polymer and neutralized with an organic amine. Accordingly, the ratio of carboxyl groups neutralized with organic amines (organic amine salt type carboxyl groups) to 10 mol% to 100 mol% of the carboxyl groups of the poly (meth) acrylic acid polymer is 10 to 75 mol%. Is more preferable, 15 to 70 mol% is more preferable, and 20 to 65 mol% is particularly preferable.
その他の単量体としては、具体的にはマレイン酸、フマル酸、イタコン酸、クロトン酸、2-メチレングルタル酸、及びそれらの塩等の(メタ)アクリル酸以外のカルボキシル基含有単量体及びその塩;2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、3-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、α-ヒドロキシメチルエチル(メタ)アクリレート等の水酸基含有アルキル(メタ)アクリレート類;(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸ブチル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸ラウリル等の(メタ)アクリル酸の炭素数1~18のアルキル基のエステルである、アルキル(メタ)アクリレート類;ジメチルアミノエチル(メタ)アクリレート及びその4級化物等のアミノ基含有アクリレート;(メタ)アクリルアミド、ジメチルアクリルアミド、イソプロピルアクリルアミド等のアミド基含有単量体類;酢酸ビニル等のビニルエステル類;エチレン、プロピレン等のアルケン類;スチレン等の芳香族ビニル系単量体類;マレイミド、フェニルマレイミド、シクロヘキシルマレイミド等のマレイミド誘導体;(メタ)アクリロニトリル等のニトリル基含有ビニル系単量体類;3-アリルオキシ-2-ヒドロキシプロパンスルホン酸、2-アクリルアミド-2-メチルプロパンスルホン酸、スチレンスルホン酸、ビニルスルホン酸等のスルホン酸基を有する単量体及びそれらの塩;ビニルホスホン酸、(メタ)アリルホスホン酸等のホスホン酸基を有する単量体;(メタ)アクロレイン等のアルデヒド基含有ビニル系単量体類;メチルビニルエーテル、エチルビニルエーテル、ブチルビニルエーテル等のアルキルビニルエーテル類;塩化ビニル、塩化ビニリデン、アリルアルコール、ビニルピロリドン等のその他官能基含有単量体類;ポリアルキレングリコール(メタ)アクリレート、モノアルコキシポリアルキレングリコール(メタ)アクリレート、ビニルアルコール、(メタ)アリルアルコール、イソプレノール等の不飽和アルコールにアルキレンオキシドが1~300モル付加した構造を有する単量体等のポリアルキレングリコール鎖含有単量体;等が挙げられる。これらその他の単量体についても、1種のみが単独で用いられてもよいし、2種以上が併用されてもよい。 The poly (meth) acrylic acid polymer of the present invention may have only a structure derived from (meth) acrylic acid (salt), but other copolymerizable with (meth) acrylic acid (salt) The structure derived from the monomer may be included.
Specific examples of the other monomers include monomers containing carboxyl groups other than (meth) acrylic acid, such as maleic acid, fumaric acid, itaconic acid, crotonic acid, 2-methyleneglutaric acid, and salts thereof. Salts thereof: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, α- Hydroxyl group-containing alkyl (meth) acrylates such as hydroxymethylethyl (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid such as lauryl acid having 1 to 18 carbon atoms Alkyl (meth) acrylates which are esters of alkyl groups; amino group-containing acrylates such as dimethylaminoethyl (meth) acrylate and quaternized products thereof; amide group-containing single quantities such as (meth) acrylamide, dimethylacrylamide and isopropylacrylamide Vinyl esters such as vinyl acetate; alkenes such as ethylene and propylene; aromatic vinyl monomers such as styrene; maleimide derivatives such as maleimide, phenylmaleimide and cyclohexylmaleimide; and nitriles such as (meth) acrylonitrile Group-containing vinyl monomers; monomers having a sulfonic acid group such as 3-allyloxy-2-hydroxypropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, vinylsulfonic acid, and the like of Salts: Monomers having phosphonic acid groups such as vinylphosphonic acid and (meth) allylphosphonic acid; Aldehyde group-containing vinyl monomers such as (meth) acrolein; Alkyl such as methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether Vinyl ethers; other functional group-containing monomers such as vinyl chloride, vinylidene chloride, allyl alcohol, vinyl pyrrolidone; polyalkylene glycol (meth) acrylate, monoalkoxy polyalkylene glycol (meth) acrylate, vinyl alcohol, (meth) allyl And a polyalkylene glycol chain-containing monomer such as a monomer having a structure in which 1 to 300 mol of alkylene oxide is added to an unsaturated alcohol such as alcohol or isoprenol. Also about these other monomers, only 1 type may be used independently and 2 or more types may be used together.
ここで、酸型換算とは、塩型の単量体を対応する酸型単量体として質量割合を計算することをいい、例えば(メタ)アクリル酸ナトリウム由来の構造であれば、(メタ)アクリル酸由来の構造として質量割合を計算する。その他の単量体も同様に酸型換算で計算する。 The poly (meth) acrylic acid polymer of the present invention has a structure derived from all monomers contained in the poly (meth) acrylic acid polymer of the present invention (that is, a structure derived from (meth) acrylic acid (salt)). And (meth) acrylic acid (salt) -derived structure is preferably contained in an amount of 80% by mass or more in terms of acid type with respect to 100% by mass. If it is 80 mass% or more, it exists in the tendency for the pigment dispersion performance with time of the polymer aqueous solution of this invention to improve more. More preferably, it is 90 mass% or more.
Here, acid type conversion means calculating a mass ratio using a salt type monomer as a corresponding acid type monomer. For example, if the structure is derived from sodium (meth) acrylate, (meth) The mass ratio is calculated as a structure derived from acrylic acid. The other monomers are similarly calculated in terms of acid type.
なお、本発明のポリ(メタ)アクリル酸系重合体の重量平均分子量の値としては、後述する実施例に記載の手法により測定される値を採用するものとする。 Specifically, the weight average molecular weight of the poly (meth) acrylic acid polymer of the present invention is preferably 3,000 to 50,000, more preferably 4,000 to 30,000, and still more preferably. Is 5,000 to 20,000. If the value of the weight average molecular weight is too large, the viscosity becomes high and handling may be complicated. On the other hand, if the value of the weight average molecular weight is too small, the dispersibility of clay, pigment, and the like is lowered, and sufficient performance as a detergent builder or pigment dispersant may not be exhibited.
In addition, the value measured by the method as described in the Example mentioned later shall be employ | adopted as a value of the weight average molecular weight of the poly (meth) acrylic-acid type polymer of this invention.
なお、本発明のポリ(メタ)アクリル酸系重合体の分子量分布の値としては、後述する実施例に記載の手法により測定される値を採用するものとする。 Further, the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the poly (meth) acrylic acid polymer of the present invention is specifically preferably 1.1 to 3.0, more preferably. Is 1.5 to 2.8, more preferably 1.8 to 2.6. If the value of this molecular weight distribution is too small, for example, when a poly (meth) acrylic acid polymer is used as an inorganic dispersant, the slurry viscosity immediately after pulverization when the inorganic substance is wet pulverized may increase. Moreover, when too large, there exists a possibility that the viscosity stability with time of a slurry may fall.
In addition, the value measured by the method as described in the Example mentioned later shall be employ | adopted as a value of the molecular weight distribution of the poly (meth) acrylic acid-type polymer of this invention.
本発明の重合体水溶液中には、本発明のポリ(メタ)アクリル酸系重合体が必須に含まれる。このほか、未反応の(メタ)アクリル酸(塩)、未反応のその他の単量体、未反応の重合開始剤、重合開始剤分解物等が含まれうる。
上記重合体水溶液中に存在する未反応の単量体の含有量((メタ)アクリル酸(塩)とその他の単量体との合計の含有量)は、使用する単量体の種類によっても異なるが、重合体水溶液の固形分100質量%に対して1質量%未満が好ましい。より好ましくは0.5質量%未満であり、更に好ましくは0.1質量%未満である。 [Poly (meth) acrylic acid polymer aqueous solution]
The polymer aqueous solution of the present invention essentially contains the poly (meth) acrylic acid polymer of the present invention. In addition, unreacted (meth) acrylic acid (salt), other unreacted monomers, unreacted polymerization initiator, polymerization initiator decomposition product, and the like may be included.
The content of unreacted monomers present in the aqueous polymer solution (the total content of (meth) acrylic acid (salt) and other monomers) depends on the type of monomer used. Although different, it is preferably less than 1% by mass with respect to 100% by mass of the solid content of the polymer aqueous solution. More preferably, it is less than 0.5 mass%, More preferably, it is less than 0.1 mass%.
また、本発明の重合体水溶液における、本発明のポリ(メタ)アクリル酸系重合体の含有量は、ポリ(メタ)アクリル酸系重合体水溶液100質量%に対して、16~66質量%が好ましく、20~62質量%がより好ましく、25~55質量%が更に好ましい。 The poly (meth) acrylic acid-based polymer aqueous solution of the present invention contains a solvent in which water is essential in addition to the poly (meth) acrylic acid-based polymer of the present invention. In that case, the content of the solvent is preferably 50 to 500% by mass, more preferably 60 to 400% by mass, and still more preferably 80 to 300% by mass with respect to 100% by mass of the poly (meth) acrylic acid polymer. 90 to 200% by mass is most preferable.
The content of the poly (meth) acrylic acid polymer of the present invention in the polymer aqueous solution of the present invention is 16 to 66% by mass with respect to 100% by mass of the poly (meth) acrylic acid polymer aqueous solution. It is preferably 20 to 62% by mass, more preferably 25 to 55% by mass.
上記硫黄原子又はリン原子を含む無機の陰イオンとしては、硫酸イオン、亜硫酸イオン、リン酸イオン、亜リン酸イオン、次亜リン酸イオン等が例示される。
上記重合体水溶液は、後述する有効成分値を35~45%に調整したときの硫黄原子又はリン原子を含む無機の陰イオンの濃度が上記範囲になるようにすることが好ましい。 The poly (meth) acrylic acid polymer aqueous solution of the present invention is characterized in that the concentration of inorganic anions containing sulfur atoms or phosphorus atoms is 1000 to 10,000 ppm with respect to the polymer aqueous solution of the present invention. When the concentration of the inorganic anion containing a sulfur atom or phosphorus atom exceeds 10,000 ppm, the pigment dispersion performance with time of the polymer aqueous solution tends to deteriorate. If the concentration of the inorganic anion containing a sulfur atom or phosphorus atom is set to less than 1000 ppm, it becomes difficult to produce a polymer aqueous solution having excellent pigment dispersion performance over time.
Examples of the inorganic anion containing sulfur atom or phosphorus atom include sulfate ion, sulfite ion, phosphate ion, phosphite ion, hypophosphite ion and the like.
The aqueous polymer solution preferably has an inorganic anion concentration containing a sulfur atom or a phosphorus atom within the above range when an active ingredient value described later is adjusted to 35 to 45%.
なお、粘度は、B型粘度計を使用し、測定条件としては、ローターNo.4、60rpm、5分間で測定した値をいう。 The poly (meth) acrylic acid polymer aqueous solution of the present invention preferably has a viscosity (25 ° C.) of 400 to 2000 mPa · s when the solid content (nonvolatile content) concentration is adjusted to 35 to 70 mass%. By setting to the above range, the storage stability such as the color tone of the aqueous polymer solution is improved, and the operability on the slurry production facility is improved when used as a pigment dispersant, for example. The viscosity of the poly (meth) acrylic acid polymer aqueous solution can be easily adjusted by the initiator type and amount used, the neutralizer type and amount used, the degree of neutralization, and the like. More preferably, it is 500-1500 mPa · s, more preferably 550-1000 mPa · s, particularly preferably 600-900 mPa · s, and most preferably 600-800 mPa · s.
The viscosity was measured using a B-type viscometer. The value measured at 4, 60 rpm for 5 minutes.
なお、APHAは、色差計等により測定することができる。 The poly (meth) acrylic acid polymer aqueous solution of the present invention is preferably less colored. For example, the hue APHA in a polymer aqueous solution immediately after production and after one month has passed at room temperature (25 ° C.) is 200 or less. It is preferable that it is and it is more preferable that it is 180 or less. More preferably, it is 160 or less. According to the method for producing a poly (meth) acrylic acid polymer aqueous solution of the present invention, it is possible to suppress the coloration of the polymer aqueous solution to a low level (make the color tone good). When there is little coloring, it can use preferably for a dispersing agent use or detergent builder use, for example.
APHA can be measured with a color difference meter or the like.
本発明のポリ(メタ)アクリル酸系重合体水溶液は、乾燥、又は、その他の溶剤で置換・希釈して使用することもできる(ポリ(メタ)アクリル酸系重合体組成物という)。本発明のポリアクリル酸系重合体水溶液を乾燥後水に再溶解したり、乾燥後に他の任意な成分を添加したものも本発明のポリ(メタ)アクリル酸系重合体組成物に含まれる。
なお、本発明のポリ(メタ)アクリル酸系重合体組成物に含まれる未反応の単量体の含有量、溶媒や有機溶剤の含有量、本発明のポリ(メタ)アクリル酸系重合体の含有量、硫黄原子又はリン原子を含む無機の陰イオンの濃度、粘度、pH、及びAPHAは、それぞれ上述した本発明のポリ(メタ)アクリル酸系重合体水溶液と同様であることが好ましい。 [Poly (meth) acrylic acid polymer composition]
The poly (meth) acrylic acid polymer aqueous solution of the present invention can be used after drying or substitution / dilution with another solvent (referred to as a poly (meth) acrylic acid polymer composition). The poly (meth) acrylic acid polymer composition of the present invention includes the polyacrylic acid polymer aqueous solution of the present invention which has been dried and re-dissolved in water, or other optional components added after drying.
In addition, content of the unreacted monomer contained in the poly (meth) acrylic acid polymer composition of the present invention, the content of a solvent or an organic solvent, the poly (meth) acrylic acid polymer of the present invention The content, concentration of inorganic anion containing sulfur atom or phosphorus atom, viscosity, pH, and APHA are preferably the same as those of the poly (meth) acrylic acid polymer aqueous solution of the present invention described above.
本発明のポリ(メタ)アクリル酸系重合体は、(メタ)アクリル酸(塩)を必須として重合することにより製造されることが好ましい。本発明のポリ(メタ)アクリル酸系重合体は、(メタ)アクリル酸(塩)に加えて、上述したその他の単量体を共重合することにより製造しても構わない。本発明のポリ(メタ)アクリル酸系重合体の製造に用いる全単量体((メタ)アクリル酸(塩)とその他の単量体との合計をいう)100質量%に対する(メタ)アクリル酸(塩)の割合は、酸型換算で80質量%以上であることが好ましい。80質量%以上であれば、得られる重合体水溶液の経時的な顔料分散性能が向上する傾向にある。より好ましくは90質量%以上である。
ここで、上記の通り、酸型換算とは、塩型の単量体を対応する酸型単量体として質量割合を計算することをいい、例えば(メタ)アクリル酸ナトリウムであれば、(メタ)アクリル酸として質量割合を計算する。その他の単量体も同様に酸型換算で計算する。
本発明のポリ(メタ)アクリル酸系重合体(水溶液)の製造方法としては、(メタ)アクリル酸(塩)として、アクリル酸、アクリル酸塩を使用することが好ましい。 [Production method of poly (meth) acrylic acid polymer (aqueous solution)]
The poly (meth) acrylic acid polymer of the present invention is preferably produced by polymerizing (meth) acrylic acid (salt) as an essential component. The poly (meth) acrylic acid polymer of the present invention may be produced by copolymerizing the above-described other monomers in addition to (meth) acrylic acid (salt). (Meth) acrylic acid based on 100% by mass of all monomers (referring to the total of (meth) acrylic acid (salt) and other monomers) used in the production of the poly (meth) acrylic acid polymer of the present invention The ratio of (salt) is preferably 80% by mass or more in terms of acid type. If it is 80 mass% or more, it exists in the tendency for the pigment dispersion performance with time of the polymer aqueous solution obtained to improve. More preferably, it is 90 mass% or more.
Here, as described above, acid type conversion means calculating a mass ratio using a salt type monomer as a corresponding acid type monomer. For example, if it is sodium (meth) acrylate, ) Calculate mass percentage as acrylic acid. The other monomers are similarly calculated in terms of acid type.
As a method for producing the poly (meth) acrylic acid polymer (aqueous solution) of the present invention, it is preferable to use acrylic acid or acrylate as (meth) acrylic acid (salt).
上記有機アミン以外のその他の中和剤としては、水酸化ナトリウム、水酸化カリウム等のアルカリ金属の水酸化物、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム等のアルカリ金属の炭酸塩、アルカリ土類金属塩、アンモニア等が挙げられる。
ただし、製造工程の簡略化を目的として、(メタ)アクリル酸の有機アミン塩を必須として重合を行うことによってポリ(メタ)アクリル酸系重合体水溶液を製造しても構わない。この場合、着色が大きくなり、洗剤添加物や顔料分散剤としては使用し難くなる場合がある。 When the poly (meth) acrylic acid polymer (aqueous solution) of the present invention is produced including a step of neutralizing with the organic amine, other neutralizing agents may be used in addition to the organic amine. In that case, in order to reduce coloring during the neutralization reaction, first, an aqueous solution containing an acid-type and / or partially-neutralized poly (meth) acrylic acid polymer is added with another neutralizing agent. It is preferable to perform a step of neutralizing, and then performing a step of neutralizing an aqueous solution containing an acid-type and / or partially neutralized polyacrylic acid polymer with an organic amine because the color tone becomes favorable. However, the reverse process order is also possible. As long as the molar ratio of the structure derived from (meth) acrylic acid (salt) and the structure derived from organic amine (salt) contained in the poly (meth) acrylic acid polymer aqueous solution is in the above-described range, Excess organic amine (salt) may be added beyond the neutralization point. By setting the molar ratio of the structure derived from (meth) acrylic acid (salt) and the structure derived from organic amine (salt) contained in the poly (meth) acrylic acid polymer aqueous solution to the above-mentioned range, The aqueous solution of (meth) acrylic acid polymer will remarkably develop the dispersion power of the pigment over time.
Other neutralizers other than the above organic amines include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate and sodium hydrogen carbonate, alkaline earth metals A salt, ammonia, etc. are mentioned.
However, for the purpose of simplifying the production process, an aqueous poly (meth) acrylic acid polymer solution may be produced by carrying out polymerization with an organic amine salt of (meth) acrylic acid as an essential component. In this case, coloring increases, and it may be difficult to use as a detergent additive or a pigment dispersant.
また、工程N1に要する時間は、使用するアルカリ金属塩の種類や使用量に応じて適宜選択すればよいが、通常、10時間以下が好ましく、5時間以下がより好ましく、3時間以下が更に好ましい。 The temperature of the step N1 may be appropriately selected according to the type of alkali metal salt to be used, but it is preferably 40 to 100 ° C, more preferably 45 to 95 ° C, and particularly preferably 50 to 90 ° C. . If the neutralization reaction is performed at a temperature exceeding 100 ° C., the color tone of the resulting aqueous polymer solution may be deteriorated, which is not preferable. Moreover, when neutralizing at the temperature lower than 40 degreeC, it is necessary to cool the polymer aqueous solution obtained after superposition | polymerization to the temperature lower than 40 degreeC, and it is not preferable from the surface of productivity.
Further, the time required for the step N1 may be appropriately selected according to the type and amount of the alkali metal salt to be used, but is usually preferably 10 hours or less, more preferably 5 hours or less, and further preferably 3 hours or less. .
また、工程N2に要する時間は、使用する有機アミンの種類や使用量に応じて適宜選択すればよいが、通常、10時間以下が好ましく、5時間以下がより好ましく、3時間以下が更に好ましい。 The temperature of the above step N2 may be appropriately selected according to the type of organic amine to be used, but it is preferably carried out at 40 to 100 ° C., more preferably 45 to 95 ° C., and particularly preferably 50 to 90 ° C. If the neutralization reaction is performed at a temperature exceeding 100 ° C., the color tone of the resulting aqueous polymer solution may be deteriorated, which is not preferable. Moreover, when neutralizing at the temperature lower than 40 degreeC, it is necessary to cool the polymer aqueous solution obtained after superposition | polymerization to the temperature lower than 40 degreeC, and it is not preferable from the surface of productivity.
The time required for the step N2 may be appropriately selected according to the type and amount of the organic amine to be used, but is usually preferably 10 hours or less, more preferably 5 hours or less, and still more preferably 3 hours or less.
本発明のポリ(メタ)アクリル酸系重合体は、(メタ)アクリル酸(塩)を必須として含む単量体組成物を、重合開始剤(開始剤とも言う)の存在下に重合して得ることができる。
上記重合開始剤としては、通常重合開始剤として用いられているものを使用することができ、例えば、過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩;過酸化水素;ジメチル2,2’-アゾビス(2-メチルプロピオネート)、2,2’-アゾビス(2-アミジノプロパン)塩酸塩、4,4’-アゾビス-4-シアノパレリン酸、アゾビスイソブチロニトリル、2,2’-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)等のアゾ系化合物;過酸化ベンゾイル、過酸化ラウロイル、過酢酸、ジ-t-ブチルパーオキサイド、クメンヒドロパーオキサイド等の有機過酸化物等が好適である。これらの重合開始剤は、単独で使用されてもよいし、2種以上の混合物の形態で使用されてもよい。重合体の分子量分布が小さくなる傾向にあるので、1種のみを使用することが好ましい。
上記重合開始剤の使用量は、特に制限されないが、全単量体成分1モルに対して、15g以下であることが好ましい。より好ましくは0.1~12gである。 (Polymerization initiator)
The poly (meth) acrylic acid polymer of the present invention is obtained by polymerizing a monomer composition containing (meth) acrylic acid (salt) as an essential component in the presence of a polymerization initiator (also referred to as an initiator). be able to.
As the polymerization initiator, those usually used as a polymerization initiator can be used, for example, persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate; hydrogen peroxide; dimethyl 2,2 '-Azobis (2-methylpropionate), 2,2'-azobis (2-amidinopropane) hydrochloride, 4,4'-azobis-4-cyanoparerenic acid, azobisisobutyronitrile, 2,2' -Azo compounds such as azobis (4-methoxy-2,4-dimethylvaleronitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide, cumene hydroperoxide Etc. are suitable. These polymerization initiators may be used alone or in the form of a mixture of two or more. Since the molecular weight distribution of the polymer tends to be small, it is preferable to use only one kind.
The amount of the polymerization initiator used is not particularly limited, but is preferably 15 g or less with respect to 1 mol of all monomer components. More preferably, it is 0.1 to 12 g.
本発明のポリ(メタ)アクリル酸系重合体の製造方法においては、重合開始剤の他に、連鎖移動剤を使用することも可能である。この際使用できる連鎖移動剤としては、分子量の調節ができる化合物であれば特に制限されず、通常連鎖移動剤として用いられているものを使用することができる。具体的には、メルカプトエタノール、チオグリセロール、チオグリコール酸、2-メルカプトプロピオン際、3-メルカプトプロピオン際、チオリンゴ酸、チオグリコール酸オクチル、3-メルカプトプロピオン酸オクチル、2-メルカプトエタンスルホン酸、n-ドデシルメルカプタン、オクチルメルカプタン、ブチルチオグリコレート等の、チオール系連鎖移動剤;四塩化炭素、塩化メチレン、ブロモホルム、ブロモトリクロロエタン等の、ハロゲン化物;イソプロパノール、グリセリン等の、第2級アルコール;亜リン酸、亜リン酸塩、次亜リン酸、次亜リン酸塩、及びそれらの水和物等;亜硫酸、亜硫酸水素、亜二チオン酸、メタ重亜硫酸、及びそれらの塩(例えば、亜硫酸水素ナトリウム、亜硫酸水素カリウム、亜二チオン酸ナトリウム、亜二チオン酸カリウム、メタ重亜硫酸ナトリウム、メタ重亜硫酸カリウム等)等の、低級酸化物及びそれらの塩等が挙げられる。上記連鎖移動剤は、単独で使用されてもよいし、2種以上の混合物の形態で使用されてもよい。
上記連鎖移動剤の添加量は、特に制限されないが、全単量体成分1モルに対して、1~20gであることが好ましい。より好ましくは2~15gである。1g未満であると、分子量の制御ができないおそれがあり、逆に、20gを超えると、連鎖移動剤が残留したり、重合体純分が低下したりするおそれがある。 (Chain transfer agent)
In the method for producing a poly (meth) acrylic acid polymer of the present invention, a chain transfer agent can be used in addition to the polymerization initiator. The chain transfer agent that can be used in this case is not particularly limited as long as it is a compound capable of adjusting the molecular weight, and those that are usually used as chain transfer agents can be used. Specifically, mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropion, 3-mercaptopropion, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2-mercaptoethanesulfonic acid, n -Thiol chain transfer agents such as dodecyl mercaptan, octyl mercaptan, butyl thioglycolate; halides such as carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane; secondary alcohols such as isopropanol, glycerin; Acid, phosphite, hypophosphorous acid, hypophosphite, and hydrates thereof; sulfurous acid, hydrogen sulfite, dithionic acid, metabisulfite, and salts thereof (for example, sodium bisulfite) , Potassium hydrogen sulfite, sodium dithionite Um, potassium dithionite, sodium metabisulfite, metabisulfite potassium, etc.) and the like, include lower oxides and the like salts thereof. The said chain transfer agent may be used independently and may be used with the form of 2 or more types of mixtures.
The amount of the chain transfer agent added is not particularly limited, but is preferably 1 to 20 g with respect to 1 mol of all monomer components. More preferably, it is 2 to 15 g. If it is less than 1 g, the molecular weight may not be controlled. Conversely, if it exceeds 20 g, the chain transfer agent may remain or the polymer content may decrease.
次亜リン酸塩、亜硫酸塩、及び/又は亜硫酸水素塩の使用量が全単量体1モルに対して、上記上限を超えると、連鎖移動に寄与しない次亜リン酸塩、亜硫酸塩、及び/又は亜硫酸水素塩(重合体末端に取り込まれない次亜リン酸塩、亜硫酸塩、及び/又は亜硫酸水素塩)が増加し、無機陰イオン量が増加することに起因して、経時的な分散力が低下したり、ポリ(メタ)アクリル酸系重合体の色相が悪化したりするおそれがある。 Among the above-mentioned chain transfer agents, hypophosphite, sulfite, and / or bisulfite, because the dispersibility of the pigment (inorganic particles) of the resulting poly (meth) acrylic acid polymer aqueous solution is improved. Is preferably used. However, since the dispersive power of the pigment over time is improved, hypophosphite, sulfite and bisulfite (the total when used in combination) are used in an amount of 1 mol of all monomers. It is preferably 5.0 g or less, more preferably 4.5 g or less, still more preferably 4.0 g or less, and the lower limit of the amount used is 1 mol of all monomers. 1.0 g or more is preferable, and 1.5 g or more is more preferable.
When the amount of use of hypophosphite, sulfite, and / or bisulfite exceeds the above upper limit with respect to 1 mol of all monomers, hypophosphite, sulfite, and Dispersion over time due to an increase in the amount of inorganic anions and / or an increase in bisulfite (hypophosphite, sulfite, and / or bisulfite not incorporated into the polymer ends) There is a possibility that the force may be reduced, or the hue of the poly (meth) acrylic acid polymer may be deteriorated.
本発明のポリ(メタ)アクリル酸系重合体の製造方法は、重合開始剤等の他に、重合開始剤の分解触媒や還元性化合物(反応促進剤ともいう)を使用(重合系に添加)してもよい。 (Decomposition catalyst, reducing compound)
The method for producing a poly (meth) acrylic acid polymer of the present invention uses a polymerization initiator decomposition catalyst or a reducing compound (also referred to as a reaction accelerator) in addition to the polymerization initiator (added to the polymerization system). May be.
なお、本明細書において、重金属イオンとは、比重が4g/cm3以上の金属を意味する。 Examples of the compound that acts as a decomposition catalyst or a reducing compound for the polymerization initiator include heavy metal ions (or heavy metal salts). That is, the method for producing a polyacrylic acid polymer of the present invention may use (add to the polymerization system) heavy metal ions (or heavy metal salts) in addition to the polymerization initiator and the like.
In the present specification, the heavy metal ion means a metal having a specific gravity of 4 g / cm 3 or more.
上記重金属イオンのイオン価は特に限定されるものではなく、例えば、重金属として鉄が用いられる場合、開始剤における鉄イオンとしては、Fe2+であっても、Fe3+であってよく、これらが組み合わされていてもよい。 As said heavy metal ion, iron, cobalt, manganese, chromium, molybdenum, tungsten, copper, silver, gold, lead, platinum, iridium, osmium, palladium, rhodium, ruthenium etc. are preferable, for example. These heavy metals can be used alone or in combination of two or more. Among these, iron is more preferable.
The ionic valence of the heavy metal ions is not particularly limited. For example, when iron is used as the heavy metal, the iron ions in the initiator may be Fe 2+ or Fe 3+ , and these may be combined. May be.
なお、上記重金属塩を溶解してなる溶液の溶媒としては、水に限定されるものではなく、本発明のポリ(メタ)アクリル酸系重合体の製造において、重合反応を著しく妨げるものでなければ、重金属塩の溶解性を損ねない範囲で使用できる。 In the present invention, the heavy metal ions are added to the reaction system by adding an aqueous solution or an aqueous solution obtained by dissolving a heavy metal salt (heavy metal compound) to the polymerization system. The heavy metal salt used in that case should just contain the heavy metal ion desired to contain in an initiator, and can be determined according to the initiator to be used. When iron is used as the heavy metal ion, the mole salt (Fe (NH 4 ) 2 (SO 4 ) 2 · 6H 2 O), ferrous sulfate · 7 hydrate, ferrous chloride, ferric chloride, etc. It is preferable to use a heavy metal salt or the like. Moreover, when using manganese as a heavy metal ion, manganese chloride etc. can be used suitably. In the case where these heavy metal salts are used, since they are water-soluble compounds, they can be used in the form of an aqueous solution and have excellent handleability.
In addition, the solvent of the solution formed by dissolving the heavy metal salt is not limited to water, and must not significantly interfere with the polymerization reaction in the production of the poly (meth) acrylic acid polymer of the present invention. , And can be used as long as the solubility of the heavy metal salt is not impaired.
重合系に添加する、重金属化合物を溶解してなる水溶液又は水性溶液中の重金属化合物の濃度は、0.1質量%~10質量%とすることが好ましい。 The term “when the polymerization reaction is completed” means a point in time when the polymerization reaction is substantially completed in the polymerization reaction solution and a desired polymer is obtained. For example, when the polymer polymerized in the polymerization reaction solution is subsequently neutralized with an alkali component, the content of heavy metal ions is calculated based on the total mass of the polymerization reaction solution after neutralization. When two or more kinds of heavy metal ions are included, the total amount of heavy metal ions may be in the above range.
The concentration of the heavy metal compound in the aqueous solution or aqueous solution obtained by dissolving the heavy metal compound added to the polymerization system is preferably 0.1% by mass to 10% by mass.
本発明のポリ(メタ)アクリル酸系重合体は、溶液重合で製造することが好ましい。この際使用できる溶媒は、全溶媒に対して50質量%が水である混合溶媒又は水であることが好ましい。水のみを使用する場合には、脱溶剤工程を省略できる点で好適である。また、上記連鎖移動剤を使用する場合には、連鎖移動効率を高め(連鎖移動剤を重合体末端により多く取り込む)、不純物である無機陰イオンを低減するために、溶剤自体は連鎖移動しにくいものが好ましい。その観点から、溶媒としては水のみを使用するか、有機溶剤を併用する場合にはその使用量を極力低減することが好ましい。
上記観点から、例えば、有機溶剤を使用する場合であっても、重合終了後の反応液100質量%に対して、30質量%以下にすることが好ましく、20質量%以下にすることがより好ましく、10質量%以下にすることが更に好ましい。特に好ましくは、5質量%以下にすることであり、最も好ましくは、1質量%以下にすることである。
有機溶剤を使用する場合、脱溶剤工程が必要となるが、脱溶剤工程における圧力、温度、時間等の条件は、得られるポリ(メタ)アクリル酸系重合体水溶液の着色を低く抑えることができるように、使用する有機溶媒の種類や使用量に応じて、適宜選択することができ、例えば、脱溶剤時の圧力としては、常圧でもよく、減圧でもよく、加圧でもよく、温度は30~150℃が好ましく、40~130℃がより好ましく、50~110℃が特に好ましい。また脱溶剤に要する時間は10時間以下が好ましく、5時間以下がより好ましく、3時間以下が特に好ましい。
ここで重合の際、水とともに使用できる溶剤としては、メチルアルコール、エチルアルコール、イソプロピルアルコール等のアルコール類;グリセリン;ポリエチレングリコール;ジメチルホルムアルデヒド等のアミド類;ジエチルエーテル、ジオキサン等のエーテル類等が好適である。これらは単独で用いてもよく、2種以上を併用してもよい。 (Polymerization solution)
The poly (meth) acrylic acid polymer of the present invention is preferably produced by solution polymerization. The solvent that can be used in this case is preferably a mixed solvent in which 50% by mass of water or water is used with respect to the total solvent. When only water is used, it is preferable in that the solvent removal step can be omitted. In addition, when the above chain transfer agent is used, the solvent itself is difficult to chain transfer in order to increase chain transfer efficiency (incorporate more chain transfer agent into the polymer terminal) and reduce inorganic anions as impurities. Those are preferred. From this point of view, it is preferable to use only water as a solvent or to reduce the amount of use as much as possible when an organic solvent is used in combination.
From the above viewpoint, for example, even when an organic solvent is used, it is preferably 30% by mass or less, more preferably 20% by mass or less, with respect to 100% by mass of the reaction liquid after completion of polymerization. More preferably, it is 10 mass% or less. It is particularly preferably 5% by mass or less, and most preferably 1% by mass or less.
When an organic solvent is used, a solvent removal step is required. Conditions such as pressure, temperature, and time in the solvent removal step can keep the resulting poly (meth) acrylic acid polymer aqueous solution low in color. Thus, it can be appropriately selected according to the type and amount of the organic solvent to be used. For example, the pressure at the time of solvent removal may be normal pressure, reduced pressure, or increased pressure, and the temperature is 30. Is preferably 150 to 150 ° C, more preferably 40 to 130 ° C, and particularly preferably 50 to 110 ° C. The time required for solvent removal is preferably 10 hours or less, more preferably 5 hours or less, and particularly preferably 3 hours or less.
Here, as a solvent that can be used together with water at the time of polymerization, alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; glycerin; polyethylene glycol; amides such as dimethylformaldehyde; ethers such as diethyl ether and dioxane are preferable. It is. These may be used alone or in combination of two or more.
本発明のポリ(メタ)アクリル酸系重合体は、回分式(バッチ式)、連続式、半連続式のいずれの重合方法も採用することができる。本発明のポリアクリル酸系重合体を製造する条件は、上記の方法の他、特に断りの無い限りは、重合方法として通常知られている方法又はそれを修飾した方法が使用できる。 (Other manufacturing conditions)
For the poly (meth) acrylic acid polymer of the present invention, any of polymerization methods of batch type (batch type), continuous type and semi-continuous type can be adopted. As conditions for producing the polyacrylic acid polymer of the present invention, a method generally known as a polymerization method or a modified method thereof can be used unless otherwise specified.
本発明のポリ(メタ)アクリル酸系重合体、ポリ(メタ)アクリル酸系重合体水溶液、ポリ(メタ)アクリル酸系重合体組成物(以下、本発明の重合体等とも言う)は、水処理剤、繊維処理剤、分散剤、洗剤ビルダー(又は洗剤組成物)等として用いられうる。洗剤ビルダーとしては、衣料用、食器用、住居用、毛髪用、身体用、歯磨き用、及び自動車用等、様々な用途の洗剤に添加されて使用されうる。 [Use of poly (meth) acrylic acid polymer (aqueous solution, composition)]
The poly (meth) acrylic acid polymer of the present invention, the poly (meth) acrylic acid polymer aqueous solution, and the poly (meth) acrylic acid polymer composition (hereinafter also referred to as the polymer of the present invention) are water. It can be used as a treatment agent, a fiber treatment agent, a dispersant, a detergent builder (or a detergent composition) and the like. As a detergent builder, it can be used by adding to detergents for various uses such as clothing, tableware, dwelling, hair, body, toothpaste, and automobile.
本発明の重合体等は、水処理剤に用いることができる。該水処理剤には、必要に応じて、他の配合剤として、重合リン酸塩、ホスホン酸塩、防食剤、スライムコントロール剤、キレート剤を用いても良い。 <Water treatment agent>
The polymer of the present invention can be used as a water treatment agent. If necessary, the water treatment agent may contain a polymerized phosphate, phosphonate, anticorrosive, slime control agent, and chelating agent as other compounding agents.
本発明の重合体等は、繊維処理剤に用いることができる。該繊維処理剤は、染色剤、過酸化物及び界面活性剤からなる群より選ばれる少なくとも1つと、本発明の重合体(組成物)を含む。 <Fiber treatment agent>
The polymer of the present invention can be used as a fiber treatment agent. The fiber treatment agent includes at least one selected from the group consisting of a dye, a peroxide, and a surfactant, and the polymer (composition) of the present invention.
本発明の重合体等(重合体、重合体水溶液、重合体組成物)は、顔料分散剤に用いることができる。すなわち、本発明のポリ(メタ)アクリル酸系重合体(水溶液)を含む顔料分散剤もまた、本発明の一つである。
本発明の重合体等は単独で顔料分散剤として使用することができるが、本発明の顔料分散剤には、必要に応じて、水等の溶媒や、他の配合剤として、縮合リン酸及びその塩、ホスホン酸及びその塩、ポリビニルアルコールを用いても良い。 <Pigment dispersant>
The polymer of the present invention (polymer, polymer aqueous solution, polymer composition) can be used as a pigment dispersant. That is, the pigment dispersant containing the poly (meth) acrylic acid polymer (aqueous solution) of the present invention is also one aspect of the present invention.
Although the polymer of the present invention can be used alone as a pigment dispersant, the pigment dispersant of the present invention includes, as necessary, a solvent such as water and other compounding agents such as condensed phosphoric acid and The salt, phosphonic acid and its salt, and polyvinyl alcohol may be used.
本発明によれば、低粘度で粘性の経時安定性を有し、かつ高濃度の製紙用顔料スラリーを提供することが可能となる。ひいては、該スラリーを用いて塗工した際に塗工欠陥を抑制し、良好な原紙被覆性、印刷光沢、耐ブリスター性、ムラのない印刷面感を与え、かつ顔料が本来持つ白色度、不透明度、インキ受理性の有意点を備えた印刷用塗工紙を提供することが可能となる。 The content of the polymer of the present invention in the pigment dispersant is preferably 0.5 to 10% by mass with respect to the entire pigment dispersant. Further, any appropriate water-soluble polymer may be included as long as it does not affect the performance and effect.
According to the present invention, it is possible to provide a paper slurry having a low viscosity and a viscosity stability with time and having a high concentration. As a result, coating defects are suppressed when coating with the slurry, good base paper coverage, printing gloss, blister resistance, uniform printing surface feeling, and the inherent whiteness and poorness of the pigment are provided. It becomes possible to provide a coated paper for printing having significant points of transparency and ink acceptability.
なお、上記顔料スラリー粘度は、B型粘度計を使用し、測定条件としては、ローターNo.4、60rpm、5分間で測定した値をいう。 The viscosity of the pigment slurry is not particularly limited, but varies greatly depending on the slurry concentration. Therefore, immediately after adjusting to 75% by mass, it is preferably 1000 mPa · s or less, more preferably 800 mPa · s or less.
The pigment slurry viscosity is measured using a B-type viscometer. The value measured at 4, 60 rpm for 5 minutes.
本発明の重合体等は、洗剤組成物にも添加しうる。
洗剤組成物における本発明の重合体の含有量は特に制限されない。ただし、優れたビルダー性能を発揮しうるという観点からは、本発明の重合体の含有量は、洗剤組成物の全量に対して、好ましくは0.1~15質量%であり、より好ましくは0.3~10質量%であり、更に好ましくは0.5~5質量%である。
洗剤用途で用いられる洗剤組成物には、通常、洗剤に用いられる界面活性剤や添加剤が含まれる。これらの界面活性剤や添加剤の具体的な形態は特に制限されず、洗剤分野において通常知られている知見が適宜参照されうる。また、上記洗剤組成物は、粉末洗剤組成物であってもよいし、液体洗剤組成物であってもよい。
界面活性剤は、アニオン性界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤、及び両性界面活性剤からなる群から選択される1種又は2種以上である。2種以上が併用される場合、アニオン性界面活性剤とノニオン性界面活性剤との合計量は、界面活性剤の全量に対して50質量%以上であることが好ましく、より好ましくは60質量%以上であり、更に好ましくは70質量%以上であり、特に好ましくは80質量%以上である。
アニオン性界面活性剤としては、アルキルベンゼンスルホン酸塩、アルキルエーテル硫酸塩、アルケニルエーテル硫酸塩、アルキル硫酸塩、アルケニル硫酸塩、α-オレフィンスルホン酸塩、α-スルホ脂肪酸又はエステル塩、アルカンスルホン酸塩、飽和脂肪酸塩、不飽和脂肪酸塩、アルキルエーテルカルボン酸塩、アルケニルエーテルカルボン酸塩、アミノ酸型界面活性剤、N-アシルアミノ酸型界面活性剤、アルキルリン酸エステル又はその塩、アルケニルリン酸エステル又はその塩等が好適である。これらのアニオン性界面活性剤におけるアルキル基、アルケニル基には、メチル基等のアルキル基が分岐していてもよい。
ノニオン性界面活性剤としては、ポリオキシアルキレンアルキルエーテル、ポリオキシアルキレンアルケニルエーテル、ポリオキシエチレンアルキルフェニルエーテル、高級脂肪酸アルカノールアミド又はそのアルキレンオキサイド付加物、ショ糖脂肪酸エステル、アルキルグリコキシド、脂肪酸グリセリンモノエステル、アルキルアミンオキサイド等が好適である。これらのノニオン性界面活性剤におけるアルキル基、アルケニル基には、メチル基等のアルキル基が分岐していてもよい。
カチオン性界面活性剤としては、第4級アンモニウム塩等が好適である。また、両性界面活性剤としては、カルボキシル型両性界面活性剤、スルホベタイン型両性界面活性剤等が好適である。これらのカチオン性界面活性剤、両性界面活性剤におけるアルキル基、アルケニル基は、メチル基等のアルキル基が分岐していてもよい。
上記界面活性剤の配合割合は、通常、洗剤組成物の全量に対して10~60質量%であり、好ましくは15~50質量%であり、更に好ましくは20~45質量%であり、特に好ましくは25~40質量%である。界面活性剤の配合割合が少なすぎると、充分な洗浄力を発揮できなくなるおそれがあり、界面活性剤の配合割合が多すぎると、経済性が低下するおそれがある。
添加剤としては、アルカリビルダー、キレートビルダー、カルボキシメチルセルロースナトリウム等の汚染物質の再沈着を防止するための再付着防止剤、ベンゾトリアゾールやエチレン-チオ尿素等の汚れ抑制剤、ソイルリリース剤、色移り防止剤、柔軟剤、pH調節のためのアルカリ性物質、香料、可溶化剤、蛍光剤、着色剤、起泡剤、泡安定剤、つや出し剤、殺菌剤、漂白剤、漂白助剤、酵素、染料、溶媒等が好適である。また、粉末洗剤組成物の場合にはゼオライトを配合することが好ましい。
上記洗剤組成物は、本発明の重合体等に加えて、他の洗剤ビルダーを含んでもよい。他の洗剤ビルダーとしては、特に制限されないが、例えば、炭酸塩、炭酸水素塩、珪酸塩等のアルカリビルダーや、トリポリリン酸塩、ピロリン酸塩、ボウ硝、ニトリロトリ酢酸塩、エチレンジアミンテトラ酢酸塩、クエン酸塩、フマル酸塩、ゼオライト等のキレートビルダー、カルボキシメチルセルロース等の多糖類のカルボキシル誘導体等が挙げられる。上記ビルダーに用いられる対塩としては、ナトリウム、カリウム等のアルカリ金属、アンモニウム、アミン等が挙げられる。
上記添加剤と他の洗剤用ビルダーの合計の配合割合は、通常、洗浄剤組成物100質量%に対して0.1~50質量%が好ましい。より好ましくは0.2~40質量%であり、更に好ましくは0.3~35質量%であり、特に好ましくは0.4~30質量%であり、最も好ましくは0.5~20質量%以下である。添加剤/他の洗剤ビルダーの配合割合が0.1質量%未満であると、充分な洗剤性能を発揮できなくなるおそれがあり、50質量%を超えると経済性が低下するおそれがある。
なお、上記洗剤組成物の概念には、家庭用洗剤の合成洗剤、繊維工業その他の工業用洗剤、硬質表面洗浄剤のほか、その成分の1つの働きを高めた漂白洗剤等の特定の用途にのみ用いられる洗剤も含まれる。
上記洗剤組成物が液体洗剤組成物である場合、液体洗剤組成物に含まれる水分量は、通常、液体洗剤組成物の全量に対して0.1~75質量%であることが好ましく、より好ましくは0.2~70質量%であり、更に好ましくは0.5~65質量%であり、更により好ましくは0.7~60質量%であり、特に好ましくは1~55質量%であり、最も好ましくは1.5~50質量%である。
上記洗剤組成物が液体洗剤組成物である場合、当該洗剤組成物は、カオリン濁度が200mg/L以下であることが好ましく、より好ましくは150mg/L以下であり、更に好ましくは120mg/L以下であり、特に好ましくは100mg/L以下であり、最も好ましくは50mg/L以下である。
また、本発明の重合体等を洗剤ビルダーとして液体洗剤組成物に添加する場合としない場合とでのカオリン濁度の変化(差)は、500mg/L以下であることが好ましく、より好ましくは400mg/L以下であり、更に好ましくは300mg/L以下であり、特に好ましくは200mg/L以下であり、最も好ましくは100mg/L以下である。カオリン濁度の値としては、以下の手法により測定される値を採用するものとする。 <Detergent composition>
The polymer of the present invention can also be added to a detergent composition.
The content of the polymer of the present invention in the detergent composition is not particularly limited. However, from the viewpoint of exhibiting excellent builder performance, the content of the polymer of the present invention is preferably 0.1 to 15% by mass, more preferably 0%, based on the total amount of the detergent composition. 3 to 10% by mass, more preferably 0.5 to 5% by mass.
Detergent compositions used in detergent applications usually include surfactants and additives used in detergents. Specific forms of these surfactants and additives are not particularly limited, and knowledge generally known in the detergent field can be appropriately referred to. The detergent composition may be a powder detergent composition or a liquid detergent composition.
The surfactant is one or more selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. When two or more kinds are used in combination, the total amount of the anionic surfactant and the nonionic surfactant is preferably 50% by mass or more, more preferably 60% by mass with respect to the total amount of the surfactant. Or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more.
Examples of anionic surfactants include alkylbenzene sulfonate, alkyl ether sulfate, alkenyl ether sulfate, alkyl sulfate, alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty acid or ester salt, alkane sulfonate , Saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acyl amino acid type surfactant, alkyl phosphate ester or salt thereof, alkenyl phosphate ester or Its salts are preferred. An alkyl group such as a methyl group may be branched from the alkyl group or alkenyl group in these anionic surfactants.
Nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, alkyl glycoxides, fatty acid glycerin monoesters. Esters, alkylamine oxides and the like are preferred. An alkyl group such as a methyl group may be branched from the alkyl group or alkenyl group in these nonionic surfactants.
As the cationic surfactant, a quaternary ammonium salt or the like is suitable. As the amphoteric surfactant, a carboxyl type amphoteric surfactant, a sulfobetaine type amphoteric surfactant, and the like are suitable. The alkyl group and alkenyl group in these cationic surfactants and amphoteric surfactants may be branched from an alkyl group such as a methyl group.
The blending ratio of the surfactant is usually 10 to 60% by mass, preferably 15 to 50% by mass, more preferably 20 to 45% by mass, particularly preferably based on the total amount of the detergent composition. Is 25 to 40% by mass. If the blending ratio of the surfactant is too small, sufficient detergency may not be exhibited, and if the blending ratio of the surfactant is too large, the economy may be lowered.
Additives include anti-redeposition agent to prevent redeposition of contaminants such as alkali builder, chelate builder, sodium carboxymethyl cellulose, stain inhibitor such as benzotriazole and ethylene-thiourea, soil release agent, color transfer Inhibitors, softeners, alkaline substances for pH adjustment, fragrances, solubilizers, fluorescent agents, colorants, foaming agents, foam stabilizers, polishes, bactericides, bleaching agents, bleaching aids, enzymes, dyes A solvent or the like is preferable. In the case of a powder detergent composition, it is preferable to blend zeolite.
The detergent composition may contain other detergent builders in addition to the polymer of the present invention. Other detergent builders are not particularly limited, but include, for example, alkali builders such as carbonates, bicarbonates, silicates, tripolyphosphates, pyrophosphates, bow glass, nitrilotriacetate, ethylenediaminetetraacetate, Examples thereof include chelate builders such as acid salts, fumarate salts, and zeolites, and carboxyl derivatives of polysaccharides such as carboxymethyl cellulose. Examples of the counter salt used in the builder include alkali metals such as sodium and potassium, ammonium and amine.
The total blending ratio of the additive and other detergent builder is usually preferably 0.1 to 50% by mass with respect to 100% by mass of the cleaning composition. More preferably, it is 0.2 to 40% by mass, further preferably 0.3 to 35% by mass, particularly preferably 0.4 to 30% by mass, and most preferably 0.5 to 20% by mass or less. It is. If the blending ratio of additive / other detergent builder is less than 0.1% by mass, sufficient detergent performance may not be exhibited, and if it exceeds 50% by mass, the economy may be lowered.
In addition, the concept of the above-mentioned detergent composition includes specific detergents such as synthetic detergents for household detergents, textile industry and other industrial detergents, hard surface cleaners, and bleaching detergents that enhance one of the components. Detergents that are only used are also included.
When the detergent composition is a liquid detergent composition, the amount of water contained in the liquid detergent composition is usually preferably 0.1 to 75% by mass, more preferably based on the total amount of the liquid detergent composition. Is 0.2 to 70% by mass, more preferably 0.5 to 65% by mass, still more preferably 0.7 to 60% by mass, particularly preferably 1 to 55% by mass, The amount is preferably 1.5 to 50% by mass.
When the detergent composition is a liquid detergent composition, the detergent composition preferably has a kaolin turbidity of 200 mg / L or less, more preferably 150 mg / L or less, and still more preferably 120 mg / L or less. Especially preferably, it is 100 mg / L or less, Most preferably, it is 50 mg / L or less.
Further, the change (difference) in kaolin turbidity when the polymer of the present invention is added to the liquid detergent composition as a detergent builder is preferably 500 mg / L or less, more preferably 400 mg. / L or less, more preferably 300 mg / L or less, particularly preferably 200 mg / L or less, and most preferably 100 mg / L or less. As the kaolin turbidity value, a value measured by the following method is adopted.
厚さ10mmの50mm角セルに均一に攪拌した試料(液体洗剤)を仕込み、気泡を除いた後、日本電色工業社製NDH2000(商品名、濁度計)を用いて25℃でのTubidity(カオリン濁度:mg/L)を測定する。
上記洗浄剤組成物に配合することができる酵素としては、プロテアーゼ、リパーゼ、セルラーゼ等が好適である。中でも、アルカリ洗浄液中で活性が高いプロテアーゼ、アルカリリパーゼ及びアルカリセルラーゼが好ましい。
上記酵素の添加量は、洗浄剤組成物100質量%に対して5質量%以下であることが好ましい。5質量%を超えると、洗浄力の向上が見られなくなり、経済性が低下するおそれがある。
上記洗剤組成物は、カルシウムイオンやマグネシウムイオンの濃度が高い硬水(例えば、100mg/L以上)の地域中で使用しても、塩の析出が少なく、優れた洗浄効果を有する。この効果は、洗剤組成物が、LASのようなアニオン界面活性剤を含む場合に特に顕著である。 <Measurement method of kaolin turbidity>
A sample (liquid detergent) uniformly stirred in a 50 mm square cell having a thickness of 10 mm was removed and air bubbles were removed. Then, the NDU2000 (trade name, turbidimeter) manufactured by Nippon Denshoku Industries Co., Ltd. was used at 25 ° C. Kaolin turbidity: mg / L) is measured.
Proteases, lipases, cellulases, and the like are suitable as enzymes that can be incorporated into the cleaning composition. Of these, proteases, alkaline lipases, and alkaline cellulases that are highly active in an alkaline cleaning solution are preferred.
The amount of the enzyme added is preferably 5% by mass or less with respect to 100% by mass of the cleaning composition. If it exceeds 5% by mass, improvement in detergency cannot be seen, and the economy may be reduced.
Even when the detergent composition is used in an area of hard water (for example, 100 mg / L or more) having a high concentration of calcium ions and magnesium ions, salt precipitation is small and has an excellent cleaning effect. This effect is particularly pronounced when the detergent composition contains an anionic surfactant such as LAS.
また、本発明の重合体等(重合体、重合体水溶液、重合体組成物)は、無機粒子スラリーに用いることができる。すなわち、本発明のポリ(メタ)アクリル酸系重合体を含む無機粒子スラリーもまた、本発明の一つである。 [Inorganic particle slurry]
Moreover, the polymer of the present invention (polymer, polymer aqueous solution, polymer composition) can be used for the inorganic particle slurry. That is, the inorganic particle slurry containing the poly (meth) acrylic acid polymer of the present invention is also one aspect of the present invention.
本発明の無機粒子スラリーに含まれるポリ(メタ)アクリル酸系重合体としては、上述したものと同様のものを用いることができる。
上記ポリ(メタ)アクリル酸系重合体の有するカルボキシル基の、酸型のカルボキシル基/有機アミンで中和されたカルボキシル基(有機アミン塩型カルボキシル基)/有機アミン塩型カルボキシル基以外のカルボキシル基の塩の割合は、特に限定されず、上述した割合と同様とすることができるが、本発明の無機粒子スラリーに含まれる、(メタ)アクリル酸(塩)に由来する構造と有機アミン(塩)に由来する構造とのモル比が100:10~100:75であることが重要である。好ましくは、100:15~100:70であり、100:20~100:65であることがより好ましい。 <Poly (meth) acrylic acid polymer>
As the poly (meth) acrylic acid polymer contained in the inorganic particle slurry of the present invention, the same ones as described above can be used.
Carboxyl groups of the above poly (meth) acrylic acid polymer other than acid type carboxyl groups / carboxyl groups neutralized with organic amines (organic amine salt type carboxyl groups) / carboxyl groups other than organic amine salt type carboxyl groups The ratio of the salt is not particularly limited and can be the same as the above-described ratio, but the structure derived from (meth) acrylic acid (salt) and the organic amine (salt) contained in the inorganic particle slurry of the present invention. It is important that the molar ratio with the structure derived from) is 100: 10 to 100: 75. Preferably, it is 100: 15 to 100: 70, and more preferably 100: 20 to 100: 65.
無機粒子スラリーの経時的な粘度安定性が向上する傾向にあることから、本発明の無機粒子スラリーは無機塩等の量を極力低減させた形態であることが好ましく、そのため上記有機アミン(塩)に由来する構造は、ポリ(メタ)アクリル酸系重合体の有するカルボキシル基の有機アミン塩として存在する構造であることが好ましい。したがって、上記ポリ(メタ)アクリル酸系重合体の有するカルボキシル基100モル%に対する、有機アミンで中和されたカルボキシル基(有機アミン塩型カルボキシル基)の割合は、10~75モル%であることが好ましく、15~70モル%であることがより好ましく、20~65モル%であることが特に好ましい。 The structure derived from the organic amine (salt) represents a structure neutralized with any acidic substance and present as an organic amine salt and / or a structure present as an organic amine. Examples of the structure neutralized with any acidic substance and existing as an organic amine salt include (i) a structure existing as a salt of the poly (meth) acrylic acid polymer, (ii) (meth) acrylic acid, and the like. The structure which exists as a salt of the monomer or other acidic substance is illustrated.
Since the viscosity stability over time of the inorganic particle slurry tends to be improved, the inorganic particle slurry of the present invention is preferably in a form in which the amount of inorganic salt or the like is reduced as much as possible, and therefore the above organic amine (salt) The structure derived from is preferably a structure that exists as an organic amine salt of a carboxyl group of the poly (meth) acrylic acid polymer. Accordingly, the ratio of carboxyl groups neutralized with organic amines (organic amine salt type carboxyl groups) to 10 mol% to 100 mol% of the carboxyl groups of the poly (meth) acrylic acid polymer is 10 to 75 mol%. Is more preferable, 15 to 70 mol% is more preferable, and 20 to 65 mol% is particularly preferable.
ここで、酸型換算とは、上述したとおりである。 The poly (meth) acrylic acid polymer has a structure derived from all monomers contained in the poly (meth) acrylic acid polymer (that is, a structure derived from (meth) acrylic acid (salt) and other single quantities. It is preferable that the structure derived from (meth) acrylic acid (salt) is contained in an amount of 80% by mass or more in terms of acid type with respect to 100% by mass (total with the structure derived from the body). If it is 80 mass% or more, the viscosity stability with time of the inorganic particle slurry tends to be further improved. More preferably, it is 90 mass% or more.
Here, acid type conversion is as described above.
なお、ポリ(メタ)アクリル酸系重合体の重量平均分子量の値としては、後述する実施例に記載の手法により測定される値を採用するものとする。 Specifically, the weight average molecular weight of the poly (meth) acrylic acid polymer is preferably 3,000 to 50,000, more preferably 4,000 to 30,000, and still more preferably 5 , 20,000 to 20,000. If the value of the weight average molecular weight is too large, the viscosity of the inorganic particle slurry may not be sufficiently lowered. On the other hand, if the value of the weight average molecular weight is too small, the viscosity stability over time of the inorganic particle slurry may not be sufficiently improved.
In addition, as a value of the weight average molecular weight of the poly (meth) acrylic acid polymer, a value measured by a method described in Examples described later is adopted.
なお、ポリ(メタ)アクリル酸系重合体の分子量分布の値としては、後述する実施例に記載の手法により測定される値を採用するものとする。 The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the poly (meth) acrylic acid polymer is preferably 1.1 to 3.0, more preferably 1 0.5 to 2.8, more preferably 1.8 to 2.6. Within this molecular weight distribution range, the viscosity of the inorganic particle slurry and the viscosity stability over time tend to be particularly improved.
In addition, the value measured by the method as described in the Example mentioned later shall be employ | adopted as a value of the molecular weight distribution of a poly (meth) acrylic-acid type polymer.
本発明の無機粒子スラリーは、無機粒子を含むものであるが、用いられる無機粒子としては、特に制限されず、例えば、カオリン、クレー、重質炭酸カルシウム、軽質炭酸カルシウム、二酸化チタン、サチンホワイト、タルク、水酸化アルミニウム、プラスティックピグメント等が挙げられる。 <Inorganic particles>
The inorganic particle slurry of the present invention contains inorganic particles, but the inorganic particles used are not particularly limited. For example, kaolin, clay, heavy calcium carbonate, light calcium carbonate, titanium dioxide, satin white, talc, Examples thereof include aluminum hydroxide and plastic pigment.
本発明の無機粒子スラリーは、無機粒子スラリー100質量%に対し、無機粒子を70質量%以上含有することが好ましい。無機粒子スラリーに含まれる無機粒子が70質量%未満であれば、例えば、紙塗工用顔料スラリーとして使用した場合に、紙の生産性が低下するおそれがある。より好ましくは73質量%以上であり、更に好ましくは75質量%以上である。特に好ましくは78質量%以上である。また、無機粒子の含有量の上限は例えば85質量%である。 <Composition of inorganic particle slurry>
The inorganic particle slurry of the present invention preferably contains 70% by mass or more of inorganic particles with respect to 100% by mass of the inorganic particle slurry. If the inorganic particles contained in the inorganic particle slurry are less than 70% by mass, for example, when used as a paper coating pigment slurry, the productivity of paper may be reduced. More preferably, it is 73 mass% or more, More preferably, it is 75 mass% or more. Especially preferably, it is 78 mass% or more. Moreover, the upper limit of content of an inorganic particle is 85 mass%, for example.
なお、固形分濃度は後述する測定方法により測定される値である。 The inorganic particle slurry of the present invention has a solid content concentration of 75% by mass or more. Preferably it is 78 mass% or more as solid content concentration, More preferably, it is 80 mass% or more, More preferably, it is 85 mass% or more. Moreover, the upper limit of the solid content concentration of the inorganic particle slurry is, for example, 90% by mass.
In addition, solid content concentration is a value measured by the measuring method mentioned later.
上記硫黄原子又はリン原子を含む無機の陰イオンとしては、硫酸イオン、亜硫酸イオン、リン酸イオン、亜リン酸イオン、次亜リン酸イオン等が例示される。 The inorganic particle slurry of the present invention is characterized in that the concentration of inorganic anions containing sulfur atoms or phosphorus atoms is 100 to 400 ppm with respect to the inorganic particle slurry of the present invention. When the concentration of inorganic anions containing sulfur atoms or phosphorus atoms exceeds 400 ppm, the viscosity stability over time of the inorganic particle slurry tends to decrease. If the concentration of the inorganic anion containing a sulfur atom or phosphorus atom is set to less than 100 ppm, the combination of the initiator, the chain transfer agent and the solvent becomes expensive, which is not preferable.
Examples of the inorganic anion containing sulfur atom or phosphorus atom include sulfate ion, sulfite ion, phosphate ion, phosphite ion, hypophosphite ion and the like.
本発明の無機粒子スラリーの粘度は、特に制限はされず、スラリー濃度により大きく異なるが、無機粒子スラリーの固形分濃度を75質量%に調整した直後に、1000mPa・s以下であることが好ましく、より好ましくは900mPa・s以下である。
なお、無機粒子スラリーの粘度は、B型粘度計を使用し、測定条件としては、ローターNo.4、60rpm、5分間で測定した値をいう。 <Physical properties of inorganic particle slurry>
The viscosity of the inorganic particle slurry of the present invention is not particularly limited and varies greatly depending on the slurry concentration, but immediately after adjusting the solid content concentration of the inorganic particle slurry to 75% by mass, it is preferably 1000 mPa · s or less, More preferably, it is 900 mPa · s or less.
The viscosity of the inorganic particle slurry was measured using a B-type viscometer. The value measured at 4, 60 rpm for 5 minutes.
本発明の無機粒子スラリーの製造方法は、(i)(メタ)アクリル酸(塩)に由来する構造と有機アミン(塩)に由来する構造とを含むポリ(メタ)アクリル酸系重合体水溶液及び無機粒子を混合する工程を必須として製造する方法、(ii)ポリ(メタ)アクリル酸系重合体を含むポリ(メタ)アクリル酸系重合体水溶液と、有機アミン(塩)と、無機粒子とを混合する工程を必須として製造する方法、のいずれかである。(ii)の製造方法の場合、3つの成分の内2つを予め混合してから残りの1つと混合してもよいし、3つを同時に混合しても構わない。
なお、本発明の無機粒子スラリーの製造方法は、上記混合工程を含む限り、溶媒や他の配合剤を混合する工程を含んでいてもよい。 [Production method of inorganic particle slurry]
The method for producing an inorganic particle slurry of the present invention comprises (i) a poly (meth) acrylic acid polymer aqueous solution containing a structure derived from (meth) acrylic acid (salt) and a structure derived from organic amine (salt), and A method for producing an essential step of mixing inorganic particles, (ii) a poly (meth) acrylic acid polymer aqueous solution containing a poly (meth) acrylic acid polymer, an organic amine (salt), and inorganic particles. It is one of the methods which manufacture by making the process of mixing essential. In the case of the production method (ii), two of the three components may be mixed in advance and then mixed with the remaining one, or three may be mixed simultaneously.
In addition, the manufacturing method of the inorganic particle slurry of this invention may include the process of mixing a solvent and another compounding agent, as long as the said mixing process is included.
上記ポリ(メタ)アクリル酸系重合体水溶液としては、上述した本発明の重合体水溶液と同様のものを用いることができる。
上記ポリ(メタ)アクリル酸系重合体水溶液は、ポリ(メタ)アクリル酸系重合体水溶液に含まれる(メタ)アクリル酸(塩)に由来する構造と有機アミン(塩)に由来する構造とのモル比が100:10~100:75であることが好ましい。別途ポリ(メタ)アクリル酸系重合体や有機アミン(塩)を添加することにより無機粒子スラリーの(メタ)アクリル酸(塩)に由来する構造と有機アミン(塩)に由来する構造とのモル比が上記範囲になるように調整することも可能であるが、無機粒子スラリーの生産効率の点で、ポリ(メタ)アクリル酸系重合体水溶液に含まれる(メタ)アクリル酸(塩)に由来する構造と有機アミン(塩)に由来する構造とのモル比を上記範囲に設定することが好ましい。そのような範囲に設定することにより、無機粒子スラリーの経時的な粘度の安定性を顕著に発現することが可能となる。より好ましくは、100:15~100:70であり、100:20~100:65であることが更に好ましい。 <Poly (meth) acrylic acid polymer aqueous solution>
As said poly (meth) acrylic-acid type polymer aqueous solution, the thing similar to the polymer aqueous solution of this invention mentioned above can be used.
The poly (meth) acrylic acid polymer aqueous solution has a structure derived from (meth) acrylic acid (salt) and a structure derived from organic amine (salt) contained in the poly (meth) acrylic acid polymer aqueous solution. The molar ratio is preferably 100: 10 to 100: 75. Separately adding a poly (meth) acrylic acid polymer or organic amine (salt) to form a mole of the inorganic particle slurry derived from (meth) acrylic acid (salt) and the structure derived from organic amine (salt) Although it is possible to adjust the ratio to be in the above range, it is derived from (meth) acrylic acid (salt) contained in the poly (meth) acrylic acid polymer aqueous solution in terms of production efficiency of the inorganic particle slurry. The molar ratio between the structure to be formed and the structure derived from the organic amine (salt) is preferably set in the above range. By setting to such a range, it becomes possible to remarkably express the stability of the viscosity of the inorganic particle slurry over time. More preferably, it is 100: 15 to 100: 70, and further preferably 100: 20 to 100: 65.
なお、ポリ(メタ)アクリル酸系重合体水溶液に含まれる有機アミン(塩)に由来する構造としては、例えば(i)酸型及び/又は部分中和型のポリアクリル酸系重合体を含む水溶液に有機アミンを添加することにより形成された、有機アミンで中和されたカルボキシル基の塩に含まれる構造や、(ii)予め(メタ)アクリル酸等の単量体を有機アミンで中和した、有機アミン塩が重合することにより形成される構造、(iii)未反応の有機アミンとして存在する構造等が例示される。
無機粒子スラリーの経時的な粘度安定性が向上する傾向にあることから、上記ポリ(メタ)アクリル酸系重合体水溶液は無機塩等の量を極力低減させた形態であることが好ましく、そのため有機アミン(塩)由来の構造は、カルボキシル基の有機アミン塩として存在する構造であることが好ましい。上記ポリ(メタ)アクリル酸系重合体の有するカルボキシル基100モル%に対する、有機アミンで中和されたカルボキシル基の割合は、無機粒子スラリーにおける態様と同様である。 When the poly (meth) acrylic acid polymer aqueous solution includes a structure derived from an organic amine (salt), a structure derived from an organic amine (salt) contained in the poly (meth) acrylic acid polymer aqueous solution (meta ) Aspects of the structure derived from acrylic acid (salt) are the same as those in the inorganic fine particle slurry unless otherwise specified.
The structure derived from the organic amine (salt) contained in the poly (meth) acrylic acid polymer aqueous solution includes, for example, (i) an aqueous solution containing an acid type and / or a partially neutralized polyacrylic acid polymer. The structure contained in the carboxyl group salt neutralized with organic amine formed by adding organic amine to (ii) monomers such as (meth) acrylic acid previously neutralized with organic amine Examples include a structure formed by polymerization of an organic amine salt, and (iii) a structure existing as an unreacted organic amine.
Since the viscosity stability over time of the inorganic particle slurry tends to be improved, the poly (meth) acrylic acid polymer aqueous solution is preferably in a form in which the amount of inorganic salt or the like is reduced as much as possible, and therefore organic The structure derived from an amine (salt) is preferably a structure that exists as an organic amine salt of a carboxyl group. The ratio of the carboxyl group neutralized with the organic amine with respect to 100 mol% of the carboxyl group of the poly (meth) acrylic acid polymer is the same as that in the inorganic particle slurry.
上記ポリ(メタ)アクリル酸系重合体(水溶液)を製造する方法としても、上述した本発明のポリ(メタ)アクリル酸系重合体(水溶液)の製造方法と同様の方法により製造することができる。 <Method for producing poly (meth) acrylic acid polymer (aqueous solution)>
As a method for producing the poly (meth) acrylic acid polymer (aqueous solution), it can be produced by a method similar to the method for producing the poly (meth) acrylic acid polymer (aqueous solution) of the present invention described above. .
本発明の無機粒子スラリーの製造方法としては、通常無機粒子スラリーを製造する際に用いられる製造方法が適宜参照される、又は、組み合わされることにより行うことができるが、典型的には、一次分散を行い、それを湿式粉砕処理する方法が挙げられる。この方法は、低粘度であり、かつ分散安定性に優れた高濃度の顔料スラリーを得ることができる点で好適である。無論、本発明における無機粒子スラリー調整方法は、この湿式粉砕処理法に限定されるものではなく、湿式粉砕処理を施さない調整方法をとることもなんら制限されるものではない。上記無機粒子スラリーの調整方法において、一次分散の方法は特に制限されるものではないが、ミキサーで混合することが好ましく、例えば、高速ディスパー、ホモミキサー、ボールミル、コーレスミキサー、撹拌式ディスパー等の剪断力の高いものを用いることが好適である。 <Manufacturing method of other inorganic particle slurry>
As the method for producing the inorganic particle slurry of the present invention, the production method usually used for producing the inorganic particle slurry can be referred to as appropriate, or it can be carried out by combining, but typically, the primary dispersion And a method of wet pulverizing it. This method is suitable in that a high-concentration pigment slurry having a low viscosity and excellent dispersion stability can be obtained. Of course, the inorganic particle slurry adjusting method in the present invention is not limited to this wet pulverization method, and it is not limited at all to adopt an adjustment method in which the wet pulverization treatment is not performed. In the method for preparing the inorganic particle slurry, the primary dispersion method is not particularly limited, but is preferably mixed with a mixer. It is preferable to use one having a high strength.
本発明の無機粒子スラリーは、紙塗工用、紙加工用、セラミック成型用、繊維処理用、エマルション塗料用等に用いることができる。 [Use of inorganic particle slurry]
The inorganic particle slurry of the present invention can be used for paper coating, paper processing, ceramic molding, fiber treatment, emulsion coating, and the like.
また、本発明の重合体の重量平均分子量、数平均分子量、未反応の単量体の定量、重合体水溶液及び重合体組成物の固形分量、重合体水溶液の有効成分値は、下記の方法に従って測定した。 The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.
In addition, the weight average molecular weight, number average molecular weight, unreacted monomer quantification, polymer aqueous solution and polymer composition solid content, and polymer aqueous solution effective component values of the polymer of the present invention are as follows. It was measured.
窒素雰囲気下、110℃に加熱したオーブンで重合体組成物(重合体組成物1.0g+水3.0g)を2時間放置して乾燥処理した。乾燥前後の重量変化から、固形分(%)と、揮発成分(%)を算出した。 <Polymer aqueous solution, method for measuring solid content of polymer composition>
The polymer composition (polymer composition 1.0 g + water 3.0 g) was left to dry for 2 hours in an oven heated to 110 ° C. in a nitrogen atmosphere. From the weight change before and after drying, the solid content (%) and the volatile component (%) were calculated.
有効成分値は重合して得られたポリマーのカルボキシル基濃度として平沼産業社製 自動滴定装置COM-1500にて測定、算出した。まず1N NaOH水溶液で完全にポリマー中のカルボン酸を中和した後、1N HCl水溶液にて滴定曲線を作成し、その曲線の第二変曲点と第一変曲点の差(1N HCl溶液量)から以下のように算出した。
有効成分値(%)=9.4×(第2変曲点での1N HCl量(質量)-第1変曲点での1N HCl量(質量))×HCl力価/分析物量(質量)。
なお、上記分析物量とは、分析したポリ(メタ)アクリル酸系重合体水溶液の質量を表す。 <Measurement of active ingredients>
The effective component value was measured and calculated as the carboxyl group concentration of the polymer obtained by polymerization using an automatic titrator COM-1500 manufactured by Hiranuma Sangyo Co., Ltd. First, after neutralizing the carboxylic acid in the polymer completely with 1N NaOH aqueous solution, a titration curve is prepared with 1N HCl aqueous solution, and the difference between the second inflection point and the first inflection point of the curve (the amount of 1N HCl solution) ) Was calculated as follows.
Active ingredient value (%) = 9.4 × (1N HCl amount (mass) at the second inflection point−1N HCl amount (mass) at the first inflection point) × HCl titer / analyte amount (mass) .
The amount of analyte represents the mass of the analyzed poly (meth) acrylic acid polymer aqueous solution.
重合体の重量平均分子量及び数平均分子量の測定は、下記条件で、GPC(ゲルパーミエーションクロマトグラフィー)を用いて行った。
装置:日立製作所社製 L-7000シリーズ
検出器:HITACHI RI Detector L-2490
カラム:東ソー社製 TSK-GEL G3000PWXL
カラム温度:40℃
流速:0.5mL/min
検量線:創和科学社製 POLY SODIUM ACRYLATE STANDARD
溶離液:リン酸二水素ナトリウム12水和物/リン酸水素二ナトリウム2水和物(34.5g/46.2g)の混合物を純水にて5000gに希釈した溶液。 <Measurement conditions for weight average molecular weight and number average molecular weight (GPC)>
The weight average molecular weight and number average molecular weight of the polymer were measured using GPC (gel permeation chromatography) under the following conditions.
Apparatus: L-7000 series manufactured by Hitachi, Ltd. Detector: HITACHI RI Detector L-2490
Column: Tosoh Corporation TSK-GEL G3000PWXL
Column temperature: 40 ° C
Flow rate: 0.5 mL / min
Calibration curve: POLY SODIUM ACRYLATE STANDARD
Eluent: A solution obtained by diluting a mixture of sodium dihydrogen phosphate 12 hydrate / disodium hydrogen phosphate dihydrate (34.5 g / 46.2 g) to 5000 g with pure water.
該単量体の測定は、下記条件にて液体クロマトグラフィーを用いて行った。
測定装置:日立製作所社製 L-7000シリーズ
検出器:日立製作所社製 UV検出器 L-7400
カラム:昭和電工社製 SHODEX RSpak DE-413
温度:40.0℃
溶離液:0.1%リン酸水溶液
流速:1.0ml/min。 <Measurement of polymer aqueous solution, monomers in polymer composition>
The monomer was measured using liquid chromatography under the following conditions.
Measuring device: L-7000 series detector manufactured by Hitachi, Ltd .: UV detector L-7400 manufactured by Hitachi, Ltd.
Column: SHODEX RSpak DE-413 manufactured by Showa Denko KK
Temperature: 40.0 ° C
Eluent: 0.1% phosphoric acid aqueous solution Flow rate: 1.0 ml / min.
陰イオン濃度分析は、下記条件にてイオンクロマト分析を行った。
装置 :Metrohm社製 762 Interface
検出器 :Metrohm社製 732 IC Detecter
イオン分析方式:サプレッサー法
カラム :Shodex IC SI-90 4E
ガードカラム :Shodex SI-90 G
カラム温度 :40℃
溶離液 :NaHCO3水(2gを水で2000gに希釈)
流速 :1.0mL/min。
下記実施例で得られた重合体水溶液を分析したところ、過硫酸ナトリウム由来の硫酸イオンと次亜リン酸ナトリウム由来の次亜リン酸イオンとが検出された。 <Anion concentration analysis (ion chromatography analysis)>
In the anion concentration analysis, ion chromatography analysis was performed under the following conditions.
Apparatus: 762 Interface manufactured by Metrohm
Detector: 732 IC Detector manufactured by Metrohm
Ion analysis method: suppressor method column: Shodex IC SI-90 4E
Guard column: Shodex SI-90 G
Column temperature: 40 ° C
Eluent: NaHCO 3 water (2 g diluted to 2000 g with water)
Flow rate: 1.0 mL / min.
When the polymer aqueous solution obtained in the following Example was analyzed, the sulfate ion derived from sodium persulfate and the hypophosphite ion derived from sodium hypophosphite were detected.
空気雰囲気下、150℃に加熱したオーブンで無機粒子スラリーを0.5時間放置して乾燥処理した。乾燥前後の重量変化から、固形分(%)を算出した。 <Measurement of solid content concentration of slurry>
The inorganic particle slurry was left to dry for 0.5 hours in an oven heated to 150 ° C. in an air atmosphere. The solid content (%) was calculated from the weight change before and after drying.
市販の丸尾カルシウム社製、重質炭酸カルシウム粉体200質量部を500mlSUS製容器に投入し、保温材を巻いたガラス製四つ口セパラブルフラスコの蓋上部の一番広い口に撹拌シールを取り付けたものに3段ピンを装着したSUS製攪拌翼を装着、残りの口はシリコーンゴム栓で蓋をして、SUS製容器とガラス製蓋上部を固定用の止め具で2箇所固定する。このSUS製攪拌翼と強力な撹拌モーターを接続し、粉砕途中で緩まないように容器全体を支柱にしっかりと固定した。
続いて、四つ口セパラブルフラスコのシリコーンゴム栓の一つを開けて、ロートを差し込み、撹拌モーターを200~300rpm程度の低速回転の状態で撹拌しながら、ここから、有効成分値10%に調整した(水で希釈又は濃縮等)ポリマー水溶液8質量部と純水46質量部を混合したものと、2mmセラミックビーズ500質量部を順に少しずつ投入していった。すべて投入後、一気に1000rpmまで回転数を上昇させ、ビーズの状態を確認後、更に1500rpmまで回転数をあげた。粉砕開始40分後に10%ポリマー水溶液を4質量部、更に70分後と90分後に2質量部ずつ投入した。この状態で2μm以下の粒径が90%以上に到達するまで粉砕を継続した。最終的には重質炭酸カルシウムに対し0.80質量%のポリマー添加量となった。粉砕後、内容物をセラミックと分離し、回収した。
粒径は日立製作所社製 レーザー式粒度分布測定装置LA-910にて分析した。
スラリーの粘度をB型粘度計で、回転子No.4、60rpm、5分後の粘度を測定し(直後のスラリー粘度)、比較した。なお、回収したスラリーは、測定直前まで25℃の環境下で保存した。 <Evaluation example>
Put 200 parts by weight of commercially available Maruo Calcium Co., Ltd. heavy calcium carbonate powder into a 500 ml SUS container, and attach a stirring seal to the widest mouth at the top of the lid of a glass four-neck separable flask wrapped with a heat insulating material. A SUS stirring blade equipped with a three-stage pin is attached to the container, the remaining mouth is covered with a silicone rubber stopper, and the SUS container and the upper part of the glass lid are fixed at two locations with fixing stoppers. The SUS stirring blade and a powerful stirring motor were connected, and the entire container was firmly fixed to the support so as not to loosen during the pulverization.
Next, open one of the silicone rubber stoppers of the four-neck separable flask, insert a funnel, and stir the stirring motor at a low speed of about 200 to 300 rpm. A mixture prepared by mixing 8 parts by weight of an aqueous polymer solution (diluted or concentrated with water, etc.) and 46 parts by weight of pure water and 500 parts by weight of 2 mm ceramic beads were added little by little. After all the charging, the number of rotations was increased to 1000 rpm at once, and after confirming the state of the beads, the number of rotations was further increased to 1500 rpm. After 40 minutes from the start of pulverization, 4 parts by mass of a 10% polymer aqueous solution was added, and further 2 parts by mass after 70 and 90 minutes. In this state, pulverization was continued until the particle size of 2 μm or less reached 90% or more. Finally, the amount of polymer added was 0.80% by mass with respect to heavy calcium carbonate. After grinding, the contents were separated from the ceramic and collected.
The particle size was analyzed with a laser particle size distribution analyzer LA-910 manufactured by Hitachi, Ltd.
The viscosity of the slurry was measured using a B-type viscometer. Viscosities after 4, 60 rpm and 5 minutes were measured (slurry viscosity immediately after) and compared. The recovered slurry was stored in an environment at 25 ° C. until immediately before the measurement.
バッチ型重合釜(SUS製、容積5m3)と、当該重合釜に備えられた温度計、攪拌器(パドル翼)、外部留出物循環経路及び、ジャケット、供給経路(重合用組成物用及び中和剤用)、並びに、還流冷却装置を有する反応装置を用い、以下に示す重合処方・条件で重合を行った。まずイオン交換水362質量部を仕込んだ。その後、重合釜内の水溶液を撹拌しながら、常温下、外部ジャケットにより水溶液の温度を還流するまでまで昇温させた。
次に、80質量%アクリル酸水溶液(以下、「80%AA」とも称する)925質量部を180分間と、15質量%過硫酸ナトリウム水溶液(以下、「15%NaPS」とも称する)49質量部を185分間、45質量%次亜リン酸ナトリウム水溶液(以下、「45%SHP」とも称する)を17質量部、20分間と更に続いて70質量部を160分間と2段階の供給速度で、それぞれ別々の供給経路を通じて先端ノズルより滴下した。それぞれの成分の滴下は、45%SHP以外は一定の滴下速度で連続的に行った。
その後、48質量%水酸化ナトリウム水溶液600質量部(AA中和率70%分)をその供給経路を通じて先端ノズルより重合釜内に滴下して、重合体を中和し、続いて、モノエタノールアミン(以下、「MEA」とも称する)175質量部(AA中和率28%分)を別の供給経路を通じて先端ノズルより重合釜内に滴下して、重合体を中和した。以上のようにして、ポリアクリル酸ナトリウム・モノエタノールアミン塩水溶液(1)を得た。得られた水溶液(重合体水溶液(1)という)の固形分値は52.7%、有効成分値は44.7%であった。重合体水溶液(1)のブルックフィールド粘度は850mPa・s、重量平均分子量(Mw)は5200、分子量分布(重量平均分子量(Mw)/数平均分子量(Mn))は2.15であった。重合体水溶液(1)中の硫黄原子又はリン原子を含む無機の陰イオンの濃度(主として硫酸イオンと次亜リン酸イオンが検出された)の合計は、5900ppmであった。
当該重合処方を表1に、分析結果を表2に示した。表2において、硫黄原子又はリン原子を含む無機の陰イオンの濃度をイオン濃度合計と記した。
重質炭酸カルシウムのスラリー粘度を上述の方法で評価したところ、粉砕終了1時間後のスラリー粘度は950mPa・sで、1週間後のスラリー粘度は3380mPa・sであった。 <Example 1>
Batch type polymerization kettle (manufactured by SUS, volume 5 m 3 ), thermometer, stirrer (paddle blade), external distillate circulation path and jacket, supply path (for polymerization composition and Polymerization was carried out under the following polymerization prescription and conditions using a reaction apparatus having a reflux cooling apparatus and a neutralizer. First, 362 parts by mass of ion-exchanged water was charged. Thereafter, while stirring the aqueous solution in the polymerization kettle, the temperature of the aqueous solution was raised to reflux with an external jacket at room temperature.
Next, 925 parts by mass of an 80% by mass acrylic acid aqueous solution (hereinafter also referred to as “80% AA”) for 180 minutes and 49 parts by mass of a 15% by mass sodium persulfate aqueous solution (hereinafter also referred to as “15% NaPS”) 185 minutes, 45% by weight sodium hypophosphite aqueous solution (hereinafter also referred to as “45% SHP”) 17 parts by weight, 20 minutes, and then 70 parts by weight for 160 minutes, each at a two-stage feed rate. It was dripped from the tip nozzle through the supply path. The dropping of each component was continuously performed at a constant dropping rate except for 45% SHP.
Thereafter, 600 parts by mass of a 48% by mass aqueous sodium hydroxide solution (AA neutralization rate of 70%) is dropped into the polymerization kettle from the tip nozzle through the supply path to neutralize the polymer, followed by monoethanolamine. 175 parts by mass (hereinafter also referred to as “MEA”) (AA neutralization rate of 28%) was dropped into the polymerization kettle from the tip nozzle through another supply path to neutralize the polymer. As described above, an aqueous solution of sodium polyacrylate / monoethanolamine salt (1) was obtained. The obtained aqueous solution (referred to as polymer aqueous solution (1)) had a solid content value of 52.7% and an active ingredient value of 44.7%. The aqueous polymer solution (1) had a Brookfield viscosity of 850 mPa · s, a weight average molecular weight (Mw) of 5200, and a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 2.15. The total concentration of inorganic anions containing sulfur atoms or phosphorus atoms (mainly sulfate ions and hypophosphite ions were detected) in the aqueous polymer solution (1) was 5900 ppm.
The polymerization prescription is shown in Table 1, and the analysis results are shown in Table 2. In Table 2, the density | concentration of the inorganic anion containing a sulfur atom or a phosphorus atom was described as ion concentration total.
When the slurry viscosity of heavy calcium carbonate was evaluated by the above-mentioned method, the slurry viscosity 1 hour after the completion of pulverization was 950 mPa · s, and the slurry viscosity after 1 week was 3380 mPa · s.
重合条件を表1に記載の方法に変更する以外は、実施例1と同様にしてポリアクリル酸ナトリウム・モノエタノールアミン塩水溶液(2)を得た。得られた水溶液中(重合体水溶液(2)という)の固形分値は59.0%、有効成分値は45.4%であった。また重合体水溶液(2)のブルックフィールド粘度は990mPa・s、重量平均分子量(Mw)は5400、重量平均分子量(Mw)/数平均分子量(Mn)は2.14であった。当該重合処方を表1に、重合体の分析結果を表2に示した。
実施例1と同様に、重質炭酸カルシウムのスラリー粘度を上述の方法で評価したところ、粉砕直後のスラリー粘度は630mPa・sで、1週間後のスラリー粘度は2090mPa・sであった。 <Example 2>
A sodium polyacrylate / monoethanolamine aqueous solution (2) was obtained in the same manner as in Example 1 except that the polymerization conditions were changed to those shown in Table 1. The solid content value in the obtained aqueous solution (referred to as polymer aqueous solution (2)) was 59.0%, and the active ingredient value was 45.4%. In addition, the Brookfield viscosity of the aqueous polymer solution (2) was 990 mPa · s, the weight average molecular weight (Mw) was 5400, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.14. The polymerization prescription is shown in Table 1, and the analysis results of the polymer are shown in Table 2.
As in Example 1, when the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 630 mPa · s, and the slurry viscosity after one week was 2090 mPa · s.
バッチ型重合釜(SUS製、容積5m3)と、当該重合釜に備えられた温度計、攪拌器(パドル翼)、外部留出物循環経路及び、ジャケット、供給経路(重合用組成物用及び中和剤用)、並びに、外部循環冷却装置(外部反応液循環経路及び除熱装置)を有する反応装置(図1を参照)を用い、以下に示す重合処方・条件で重合を行った。イオン交換水515質量部、45質量%次亜リン酸ナトリウム水溶液(以下、「45%SHP」とも称する)16質量部を仕込んだ。その後、重合釜内の水溶液を撹拌しながら、常温下、外部ジャケットにより水溶液の温度を82℃まで昇温させた。
次に、80質量%アクリル酸水溶液(以下、「80%AA」とも称する)900質量部、45%SHPを67質量部、および15質量%過硫酸ナトリウム水溶液(以下、「15%NaPS」とも称する)67質量部をそれぞれ別々の供給経路を通じて先端ノズルより、80%AAおよび45%SHPは150分間に亘って、15%NaPSは80%AAと同時に滴下を開始して155分間に亘って(すなわち、80%AAの滴下終了5分後まで)滴下した。それぞれの成分の滴下は、一定の滴下速度で連続的に行った。
その後、48質量%水酸化ナトリウム水溶液583質量部(AA中和率70%分)をその供給経路を通じて先端ノズルより重合釜内に滴下して、重合体を中和し、続いて、モノエタノールアミン171質量部(AA中和率28%分)を別の供給経路を通じて先端ノズルより重合釜内に滴下して、重合体を中和した。なお、重合体を中和する間、常に反応液を外部循環させながら、除熱装置によって当該反応液を冷却した。
以上のようにして、ポリアクリル酸ナトリウム・モノエタノールアミン塩水溶液(3)を得た。得られた水溶液(3)(重合体水溶液(3)という)の固形分値は52.4%、有効成分値は40.2%であった。重合体水溶液(3)のブルックフィールド粘度は800mPa・s、重量平均分子量(Mw)は5500、重量平均分子量(Mw)/数平均分子量(Mn)は2.15であった。当該重合処方を表1に、重合体の分析結果を表2に示した。
重質炭酸カルシウムのスラリー粘度を上述の方法で評価したところ、粉砕直後のスラリー粘度は1000mPa・sで、1週間後のスラリー粘度は3450mPa・sであった。 <Example 3>
Batch type polymerization kettle (manufactured by SUS, volume 5 m 3 ), thermometer, stirrer (paddle blade), external distillate circulation path and jacket, supply path (for polymerization composition and Polymerization was carried out under the polymerization prescription and conditions shown below using a reaction apparatus (see FIG. 1) having an external circulation cooling apparatus (for the neutralizing agent) and an external circulation cooling apparatus (external reaction liquid circulation path and heat removal apparatus). 515 parts by mass of ion-exchanged water and 16 parts by mass of a 45% by mass aqueous sodium hypophosphite solution (hereinafter also referred to as “45% SHP”) were charged. Thereafter, the temperature of the aqueous solution was raised to 82 ° C. with an external jacket at room temperature while stirring the aqueous solution in the polymerization kettle.
Next, 900 parts by mass of 80% by mass acrylic acid aqueous solution (hereinafter also referred to as “80% AA”), 67% by mass of 45% SHP, and 15% by mass sodium persulfate aqueous solution (hereinafter also referred to as “15% NaPS”). ) 67 parts by mass from the tip nozzles through separate supply paths, 80% AA and 45% SHP for 150 minutes, 15% NaPS starts dropping simultaneously with 80% AA for 155 minutes (ie , Until 5 minutes after the completion of dropping 80% AA). The dropping of each component was continuously performed at a constant dropping rate.
Thereafter, 583 parts by mass of a 48% by mass aqueous sodium hydroxide solution (AA neutralization rate of 70%) is dropped into the polymerization kettle from the tip nozzle through the supply path to neutralize the polymer, followed by monoethanolamine. 171 parts by mass (AA neutralization rate of 28%) was dropped into the polymerization kettle from the tip nozzle through another supply path to neutralize the polymer. During the neutralization of the polymer, the reaction solution was cooled by a heat removal device while always circulating the reaction solution externally.
As described above, an aqueous solution of sodium polyacrylate / monoethanolamine salt (3) was obtained. The obtained aqueous solution (3) (referred to as polymer aqueous solution (3)) had a solid content value of 52.4% and an active ingredient value of 40.2%. The Brookfield viscosity of the aqueous polymer solution (3) was 800 mPa · s, the weight average molecular weight (Mw) was 5500, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.15. The polymerization prescription is shown in Table 1, and the analysis results of the polymer are shown in Table 2.
When the slurry viscosity of heavy calcium carbonate was evaluated by the above method, the slurry viscosity immediately after pulverization was 1000 mPa · s, and the slurry viscosity after 1 week was 3450 mPa · s.
重合条件を表1に記載の方法に変更する以外は、実施例3と同様にしてポリアクリル酸ナトリウム水溶液(4)を得た。得られた水溶液(重合体水溶液(4)という)の固形分値は56.9%、有効成分値は40.3%であった。重合体水溶液(4)のブルックフィールド粘度は950mPa・s、重量平均分子量(Mw)は5700、重量平均分子量(Mw)/数平均分子量(Mn)は2.18であった。当該重合処方を表1に、得られた重合体の測定結果と評価結果を表2に示した。
実施例1と同様に、重質炭酸カルシウムのスラリー粘度を上述の方法で評価したところ、粉砕直後のスラリー粘度は890mPa・sで、1週間後のスラリー粘度は2210mPa・sであった。 <Example 4>
A sodium polyacrylate aqueous solution (4) was obtained in the same manner as in Example 3 except that the polymerization conditions were changed to those described in Table 1. The obtained aqueous solution (referred to as polymer aqueous solution (4)) had a solid content value of 56.9% and an active ingredient value of 40.3%. The Brookfield viscosity of the aqueous polymer solution (4) was 950 mPa · s, the weight average molecular weight (Mw) was 5700, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.18. The polymerization prescription is shown in Table 1, and the measurement results and evaluation results of the obtained polymers are shown in Table 2.
As in Example 1, when the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 890 mPa · s, and the slurry viscosity after one week was 2210 mPa · s.
実施例1と同様に重合条件を表1に記載の方法に変更する以外は、同様の方法でポリアクリル酸ナトリウム水溶液(5)を得た。得られた水溶液(重合体水溶液(5)という)の固形分値は46.6%、有効成分値は44.5%であった。重合体水溶液(5)のブルックフィールド粘度は900mPa・s、重量平均分子量(Mw)は5900、重量平均分子量(Mw)/数平均分子量(Mn)は2.30であった。当該重合処方を表1に、得られた重合体の分析結果を表2に示した。
実施例1と同様に、重質炭酸カルシウムのスラリー粘度を上述の方法で評価したところ、粉砕直後のスラリー粘度は1800mPa・sで、1週間後のスラリー粘度は4700mPa・sであった。 <Comparative Example 1>
A sodium polyacrylate aqueous solution (5) was obtained in the same manner as in Example 1, except that the polymerization conditions were changed to those shown in Table 1. The obtained aqueous solution (referred to as polymer aqueous solution (5)) had a solid content value of 46.6% and an active ingredient value of 44.5%. The Brookfield viscosity of the aqueous polymer solution (5) was 900 mPa · s, the weight average molecular weight (Mw) was 5900, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.30. The polymerization prescription is shown in Table 1, and the analysis results of the obtained polymer are shown in Table 2.
As in Example 1, when the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 1800 mPa · s, and the slurry viscosity after one week was 4700 mPa · s.
実施例3と同様に重合条件を表1に記載の方法に変更する以外は、同様の方法でポリアクリル酸ナトリウム水溶液(6)を得た。得られた水溶液(重合体水溶液(6)という)の固形分値は43.3%、有効成分値は41.3%であった。重合体水溶液(6)のブルックフィールド粘度は780mPa・s、重量平均分子量は(Mw)5500、重量平均分子量(Mw)/数平均分子量(Mn)は2.20であった。当該重合処方を表1に、得られた重合体の分析結果を表2に示した。
実施例1と同様に、重質炭酸カルシウムのスラリー粘度を上述の方法で評価したところ、粉砕直後のスラリー粘度は1400mPa・sで、1週間後のスラリー粘度は3800mPa・sであった。 <Comparative Example 2>
A sodium polyacrylate aqueous solution (6) was obtained in the same manner as in Example 3, except that the polymerization conditions were changed to those shown in Table 1. The obtained aqueous solution (referred to as polymer aqueous solution (6)) had a solid content value of 43.3% and an active ingredient value of 41.3%. The Brookfield viscosity of the aqueous polymer solution (6) was 780 mPa · s, the weight average molecular weight (Mw) was 5500, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.20. The polymerization prescription is shown in Table 1, and the analysis results of the obtained polymer are shown in Table 2.
As in Example 1, when the slurry viscosity of heavy calcium carbonate was evaluated by the above method, the slurry viscosity immediately after pulverization was 1400 mPa · s, and the slurry viscosity after 1 week was 3800 mPa · s.
バッチ型重合釜(SUS製、容積5m3)と、当該重合釜に備えられた温度計、攪拌器(パドル翼)、外部留出物循環経路及び、ジャケット、供給経路(重合用組成物用及び中和剤用)、並びに、外部循環冷却装置(外部反応液循環経路及び除熱装置)を有する反応装置を用い、以下に示す重合処方・条件で重合を行った。まずイオン交換水362質量部を仕込んだ。その後、重合釜内の水溶液を撹拌しながら、常圧下、外部ジャケットにより水溶液の温度を還流するまで昇温させた。
次に、80質量%アクリル酸水溶液(以下、「80%AA」とも称する)925質量部を180分間と、15質量%過硫酸ナトリウム水溶液(以下、「15%NaPS」とも称する)49質量部を185分間、45質量%次亜リン酸ナトリウム水溶液(以下、「45%SHP」とも称する)を17質量部、20分間と更に続いて70質量部を160分間と2段階の供給速度で、それぞれ別々の供給経路を通じて先端ノズルより滴下した。それぞれの成分の滴下は、45%SHP以外は一定の滴下速度で連続的に行った。15%NaPSの滴下終了後、水溶液が還流した状態を保持したまま30分間熟成した。このときの水溶液の温度は103℃を示した。
その後、外部冷却循環装置を用いて、水溶液の温度を65℃まで冷却し、水溶液の温度が65~80℃を維持するようにして、48質量%水酸化ナトリウム水溶液600質量部(AA中和率70%分)をその供給経路を通じて先端ノズルより重合釜内に60分かけて滴下して、重合体を中和し(工程N1)、続いて、モノエタノールアミン(以下、「MEA」とも称する)175質量部(AA中和率28%分)を別の供給経路を通じて先端ノズルより重合釜内に30分かけて滴下して、重合体を中和した(工程N2)。工程N1と工程N2に要した時間の合計は90分であった。以上のようにして、ポリアクリル酸ナトリウム・モノエタノールアミン塩水溶液(7)を得た。得られた水溶液(重合体水溶液(7)という)の固形分値は52.7%、有効成分値は44.7%であった。重合体水溶液(7)のブルックフィールド粘度は850mPa・s、重量平均分子量(Mw)は5200、重量平均分子量(Mw)/数平均分子量(Mn)は2.15であった。重合体水溶液(7)中の硫黄原子又はリン原子を含む無機の陰イオンの濃度(主として硫酸イオンと次亜リン酸イオンが検出された)の合計は、5900ppmであった。
また、重合体水溶液(7)の、製造直後の有姿での色相(APHA)は60であり、室温(25℃)で1ヶ月経過後のAPHAは140であった。当該重合処方及び重合体の分析結果を表3に、評価結果を表4に示した。表3において、硫黄原子又はリン原子を含む無機の陰イオンの濃度をイオン濃度合計と記した。
重質炭酸カルシウムのスラリー粘度を上述の方法で評価したところ、粉砕終了1時間後のスラリー粘度は950mPa・sで、1週間後のスラリー粘度は3380mPa・sであった。 <Example 5>
Batch type polymerization kettle (manufactured by SUS, volume 5 m 3 ), thermometer, stirrer (paddle blade), external distillate circulation path and jacket, supply path (for polymerization composition and Polymerization was carried out under the polymerization prescription and conditions shown below using a reactor having a neutralizer and an external circulation cooling device (external reaction liquid circulation path and heat removal device). First, 362 parts by mass of ion-exchanged water was charged. Thereafter, while stirring the aqueous solution in the polymerization kettle, the temperature of the aqueous solution was raised to reflux with an external jacket under normal pressure.
Next, 925 parts by mass of an 80% by mass acrylic acid aqueous solution (hereinafter also referred to as “80% AA”) for 180 minutes and 49 parts by mass of a 15% by mass sodium persulfate aqueous solution (hereinafter also referred to as “15% NaPS”) 185 minutes, 45% by weight sodium hypophosphite aqueous solution (hereinafter also referred to as “45% SHP”) 17 parts by weight, 20 minutes, and then 70 parts by weight for 160 minutes, each at a two-stage feed rate. It was dripped from the tip nozzle through the supply path. The dropping of each component was continuously performed at a constant dropping rate except for 45% SHP. After completion of the dropwise addition of 15% NaPS, the solution was aged for 30 minutes while maintaining the refluxed state of the aqueous solution. The temperature of the aqueous solution at this time showed 103 degreeC.
Thereafter, the temperature of the aqueous solution is cooled to 65 ° C. using an external cooling circulation device, and the aqueous solution temperature is maintained at 65 to 80 ° C., so that 600 parts by mass of the 48% by mass sodium hydroxide aqueous solution (AA neutralization rate) 70%) was dropped from the tip nozzle into the polymerization vessel through the supply path over 60 minutes to neutralize the polymer (step N1), followed by monoethanolamine (hereinafter also referred to as “MEA”). 175 parts by mass (AA neutralization rate of 28%) was dropped into the polymerization kettle from the tip nozzle through another supply path over 30 minutes to neutralize the polymer (step N2). The total time required for the steps N1 and N2 was 90 minutes. As described above, an aqueous solution of sodium polyacrylate / monoethanolamine salt (7) was obtained. The obtained aqueous solution (referred to as polymer aqueous solution (7)) had a solid content value of 52.7% and an active ingredient value of 44.7%. The Brookfield viscosity of the aqueous polymer solution (7) was 850 mPa · s, the weight average molecular weight (Mw) was 5200, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.15. The total concentration of inorganic anions containing sulfur atoms or phosphorus atoms (mainly sulfate ions and hypophosphite ions were detected) in the aqueous polymer solution (7) was 5900 ppm.
Moreover, the hue (APHA) in the solid state immediately after manufacture of polymer aqueous solution (7) was 60, and APHA after one-month progress was 140 at room temperature (25 degreeC). The polymerization results and the analysis results of the polymer are shown in Table 3, and the evaluation results are shown in Table 4. In Table 3, the density | concentration of the inorganic anion containing a sulfur atom or a phosphorus atom was described as ion concentration total.
When the slurry viscosity of heavy calcium carbonate was evaluated by the above-mentioned method, the slurry viscosity 1 hour after the completion of pulverization was 950 mPa · s, and the slurry viscosity after 1 week was 3380 mPa · s.
重合条件を表3に記載の方法に変更する以外は、実施例5と同様にしてポリアクリル酸ナトリウム・モノエタノールアミン塩水溶液(8)を得た。得られた水溶液中(重合体水溶液(8)という)の固形分値は59.0%、有効成分値は44.7%であった。また重合体水溶液(8)のブルックフィールド粘度は990mPa・s、重量平均分子量(Mw)は5400、重量平均分子量(Mw)/数平均分子量(Mn)は2.14であった。重合体水溶液(8)中の硫黄原子又はリン原子を含む無機の陰イオンの濃度(主として硫酸イオンと次亜リン酸イオンが検出された)の合計は、6100ppmであった。また、重合体水溶液(8)の、製造直後の有姿での色相(APHA)は70であり、室温(25℃)で1ヶ月経過後のAPHAは150であった。
実施例1と同様に、重質炭酸カルシウムのスラリー粘度を上述の方法で評価したところ、粉砕直後のスラリー粘度は630mPa・sで、1週間後のスラリー粘度は2090mPa・sであった。当該重合処方及び重合体の分析結果を表3に、評価結果を表4に示した。 <Example 6>
A sodium polyacrylate / monoethanolamine aqueous solution (8) was obtained in the same manner as in Example 5 except that the polymerization conditions were changed to those shown in Table 3. The solid content value in the obtained aqueous solution (referred to as polymer aqueous solution (8)) was 59.0%, and the active ingredient value was 44.7%. The aqueous polymer solution (8) had a Brookfield viscosity of 990 mPa · s, a weight average molecular weight (Mw) of 5400, and a weight average molecular weight (Mw) / number average molecular weight (Mn) of 2.14. The total concentration of inorganic anions containing sulfur atoms or phosphorus atoms (mainly sulfate ions and hypophosphite ions were detected) in the aqueous polymer solution (8) was 6100 ppm. Moreover, the hue (APHA) in the solid state immediately after manufacture of polymer aqueous solution (8) was 70, and APHA after one-month progress was 150 at room temperature (25 degreeC).
As in Example 1, when the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 630 mPa · s, and the slurry viscosity after one week was 2090 mPa · s. The polymerization results and the analysis results of the polymer are shown in Table 3, and the evaluation results are shown in Table 4.
バッチ型重合釜(SUS製、容積5m3)と、当該重合釜に備えられた温度計、攪拌器(パドル翼)、外部留出物循環経路及び、ジャケット、供給経路(重合用組成物用及び中和剤用)、並びに、外部循環冷却装置(外部反応液循環経路及び除熱装置)を有する反応装置を用い、以下に示す重合処方・条件で重合を行った。イオン交換水515質量部、45質量%次亜リン酸ナトリウム水溶液(以下、「45%SHP」とも称する)16質量部を仕込んだ。その後、重合釜内の水溶液を撹拌しながら、常温下、外部ジャケットにより水溶液の温度を82℃まで昇温させた。
次に、80質量%アクリル酸水溶液(以下、「80%AA」とも称する)900質量部、45%SHPを67質量部、および15質量%過硫酸ナトリウム水溶液(以下、「15%NaPS」とも称する)67質量部をそれぞれ別々の供給経路を通じて先端ノズルより、80%AAおよび45%SHPは150分間に亘って、15%NaPSは80%AAと同時に滴下を開始して155分間に亘って(すなわち、80%AAの滴下終了5分後まで)滴下した。それぞれの成分の滴下は、一定の滴下速度で連続的に行った。15%NaPSの滴下終了後、水溶液の還流を保持した状態で30分間熟成した。
その後、外部循環冷却装置を用いて、水溶液の温度を65℃まで冷却し、水溶液の温度が65~80℃を維持するようにして、48質量%水酸化ナトリウム水溶液583質量部(AA中和率70%分)をその供給経路を通じて先端ノズルより重合釜内に60分かけて滴下して、重合体を中和し(工程N1)、続いて、モノエタノールアミン171質量部(AA中和率28%分)を別の供給経路を通じて先端ノズルより重合釜内に30分かけて滴下して、重合体を中和した(工程N2)。工程N1と工程N2に要した時間の合計は90分であった。
以上のようにして、ポリアクリル酸ナトリウム・モノエタノールアミン塩水溶液(9)を得た。得られた水溶液(重合体水溶液(9)という)の固形分値は52.4%、有効成分値は40.2%であった。重合体水溶液(9)のブルックフィールド粘度は800mPa・s、重量平均分子量(Mw)は5500、重量平均分子量(Mw)/数平均分子量(Mn)は2.15であった。重合体水溶液(9)中の硫黄原子又はリン原子を含む無機の陰イオンの濃度(主として硫酸イオンと次亜リン酸イオンが検出された)の合計は、6400ppmであった。また重合体水溶液(9)の、製造直後の有姿での色相(APHA)は60であり、室温(25℃)で1ヶ月経過後のAPHAは140であった。
実施例1と同様に、重質炭酸カルシウムのスラリー粘度を上述の方法で評価したところ、粉砕直後のスラリー粘度は1000mPa・sで、1週間後のスラリー粘度は3450mPa・sであった。当該重合処方及び重合体の分析結果を表3に、評価結果を表4に示した。 <Example 7>
Batch type polymerization kettle (manufactured by SUS, volume 5 m 3 ), thermometer, stirrer (paddle blade), external distillate circulation path and jacket, supply path (for polymerization composition and Polymerization was carried out under the polymerization prescription and conditions shown below using a reactor having a neutralizer and an external circulation cooling device (external reaction liquid circulation path and heat removal device). 515 parts by mass of ion-exchanged water and 16 parts by mass of a 45% by mass aqueous sodium hypophosphite solution (hereinafter also referred to as “45% SHP”) were charged. Thereafter, the temperature of the aqueous solution was raised to 82 ° C. with an external jacket at room temperature while stirring the aqueous solution in the polymerization kettle.
Next, 900 parts by mass of 80% by mass acrylic acid aqueous solution (hereinafter also referred to as “80% AA”), 67% by mass of 45% SHP, and 15% by mass sodium persulfate aqueous solution (hereinafter also referred to as “15% NaPS”). ) 67 parts by mass from the tip nozzles through separate supply paths, 80% AA and 45% SHP for 150 minutes, 15% NaPS starts dropping simultaneously with 80% AA for 155 minutes (ie , Until 5 minutes after the completion of dropping 80% AA). The dropping of each component was continuously performed at a constant dropping rate. After dropping of 15% NaPS, aging was performed for 30 minutes while maintaining the reflux of the aqueous solution.
Thereafter, using an external circulation cooling device, the temperature of the aqueous solution is cooled to 65 ° C., and the temperature of the aqueous solution is maintained at 65 to 80 ° C. 70%) was dropped from the tip nozzle into the polymerization kettle through the supply path over 60 minutes to neutralize the polymer (step N1), and then 171 parts by mass of monoethanolamine (AA neutralization rate 28). %) Was added dropwise to the polymerization kettle from the tip nozzle through another supply path over 30 minutes to neutralize the polymer (step N2). The total time required for the steps N1 and N2 was 90 minutes.
As described above, an aqueous solution of sodium polyacrylate / monoethanolamine salt (9) was obtained. The obtained aqueous solution (referred to as polymer aqueous solution (9)) had a solid content value of 52.4% and an active ingredient value of 40.2%. The Brookfield viscosity of the aqueous polymer solution (9) was 800 mPa · s, the weight average molecular weight (Mw) was 5500, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.15. The total concentration of inorganic anions containing sulfur atoms or phosphorus atoms (mainly sulfate ions and hypophosphite ions were detected) in the aqueous polymer solution (9) was 6400 ppm. Moreover, the hue (APHA) in the solid state immediately after manufacture of the polymer aqueous solution (9) was 60, and APHA after one month passed at room temperature (25 ° C.) was 140.
As in Example 1, when the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 1000 mPa · s, and the slurry viscosity after 1 week was 3450 mPa · s. The polymerization results and the analysis results of the polymer are shown in Table 3, and the evaluation results are shown in Table 4.
重合条件を表3に記載の方法に変更する以外は、実施例7と同様にしてポリアクリル酸ナトリウム水溶液(10)を得た。得られた水溶液(重合体水溶液(10)という)の固形分値は56.9%、有効成分値は40.3%であった。重合体水溶液(10)のブルックフィールド粘度は950mPa・s、重量平均分子量(Mw)は5700、重量平均分子量(Mw)/数平均分子量(Mn)は2.18であった。重合体水溶液(10)中の硫黄原子又はリン原子を含む無機の陰イオンの濃度(主として硫酸イオンと次亜リン酸イオンが検出された)の合計は、6500ppmであった。また重合体水溶液(10)の、製造直後の有姿での色相(APHA)は75であり、室温(25℃)で1ヶ月経過後のAPHAは150であった。
実施例1と同様に、重質炭酸カルシウムのスラリー粘度を上述の方法で評価したところ、粉砕直後のスラリー粘度は890mPa・sで、1週間後のスラリー粘度は2210mPa・sであった。当該重合処方及び重合体の分析結果を表3に、評価結果を表4に示した。 <Example 8>
A sodium polyacrylate aqueous solution (10) was obtained in the same manner as in Example 7 except that the polymerization conditions were changed to those described in Table 3. The obtained aqueous solution (referred to as polymer aqueous solution (10)) had a solid content value of 56.9% and an active ingredient value of 40.3%. The polymer aqueous solution (10) had a Brookfield viscosity of 950 mPa · s, a weight average molecular weight (Mw) of 5700, and a weight average molecular weight (Mw) / number average molecular weight (Mn) of 2.18. The total concentration of inorganic anions containing sulfur atoms or phosphorus atoms (mainly sulfate ions and hypophosphite ions were detected) in the aqueous polymer solution (10) was 6500 ppm. The polymer aqueous solution (10) had a solid hue (APHA) immediately after production of 75 and an APHA of 150 after one month at room temperature (25 ° C.).
As in Example 1, when the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 890 mPa · s, and the slurry viscosity after one week was 2210 mPa · s. The polymerization results and the analysis results of the polymer are shown in Table 3, and the evaluation results are shown in Table 4.
バッチ型重合釜(SUS製、容積5m3)と、当該重合釜に備えられた温度計、攪拌器(パドル翼)、外部留出物循環経路及び、ジャケット、供給経路(重合用組成物用及び中和剤用)、並びに、外部循環冷却装置(外部反応液循環経路及び除熱装置)、溶媒留去装置を有する反応装置を用い、以下に示す重合処方・条件で重合を行った。イオン交換水350質量部、イソプロピルアルコール(以下、「IPA」とも称する)200質量部を仕込んだ。その後、重合釜内の水溶液を撹拌しながら、常圧下、外部ジャケットにより混合溶液が還流するまで昇温させた(混合溶媒の温度は80℃であった)。
次に、80質量%アクリル酸水溶液(以下、「80%AA」とも称する)900質量部、45%次亜リン酸ナトリウム水溶液(以下、「45%SHP」とも称する)83質量部、および15質量%過硫酸ナトリウム水溶液(以下、「15%NaPS」とも称する)67質量部をそれぞれ別々の供給経路を通じて先端ノズルより、80%AAおよび45%SHPは150分間に亘って、15%NaPSは80%AAと同時に滴下を開始して155分間に亘って(すなわち、80%AAの滴下終了5分後まで)滴下した。それぞれの成分の滴下は、一定の滴下速度で連続的に行った。15%NaPSを滴下終了後、混合溶液の還流を保持した状態で30分間熟成を行った。
熟成終了後、重合釜内のIPAが無くなるまでIPAと水の混合物を80~103℃の温度で120分かけて留去(工程D)した後、イオン交換水220質量部を重合釜内に投入して水溶液の温度が70℃になるようにした。外部循環冷却装置を用いて、水溶液の温度が70~85℃を維持するようにして、48質量%水酸化ナトリウム水溶液583質量部(AA中和率70%分)をその供給経路を通じて先端ノズルより重合釜内に60分かけて滴下して、重合体を部分中和(工程N1)した後、続いて、モノエタノールアミン171質量部(AA中和率28%分)を別の供給経路を通じて先端ノズルより重合釜内に30分かけて滴下して、重合体を中和(工程N2)した。工程N1と工程N2に要した時間の合計は90分であった。以上のようにして、ポリアクリル酸ナトリウム・モノエタノールアミン塩水溶液(11)を得た。
得られた水溶液(重合体水溶液(11)という)の固形分値は52.5%、有効成分値は40.3%であった。重合体水溶液(11)のブルックフィールド粘度は600mPa・s、重量平均分子量(Mw)は4500、重量平均分子量(Mw)/数平均分子量(Mn)は2.15であった。また、重合体水溶液(11)中の硫黄原子又はリン原子を含む無機の陰イオンの濃度(主として硫酸イオンと次亜リン酸イオンが検出された)の合計は、6500ppmであった。また、重合体水溶液(11)の、製造直後の有姿での色相(APHA)は70であり、室温(25℃)で1ヶ月経過後のAPHAは150であった。
実施例1と同様に、重質炭酸カルシウムのスラリー粘度を上述の方法で評価したところ、粉砕直後のスラリー粘度は900mPa・sで、1週間後のスラリー粘度は3400mPa・sであった。当該重合処方及び重合体の分析結果を表3に、評価結果を表4に示した。 <Example 9>
Batch type polymerization kettle (manufactured by SUS, volume 5 m 3 ), thermometer, stirrer (paddle blade), external distillate circulation path and jacket, supply path (for polymerization composition and Polymerization was carried out using a reaction apparatus having a neutralizing agent), an external circulation cooling apparatus (external reaction liquid circulation path and heat removal apparatus), and a solvent distillation apparatus under the following polymerization prescription and conditions. 350 parts by mass of ion-exchanged water and 200 parts by mass of isopropyl alcohol (hereinafter also referred to as “IPA”) were charged. Thereafter, while stirring the aqueous solution in the polymerization kettle, the temperature was raised under normal pressure until the mixed solution was refluxed by an external jacket (the temperature of the mixed solvent was 80 ° C.).
Next, 900 parts by weight of an 80% by weight acrylic acid aqueous solution (hereinafter also referred to as “80% AA”), 83 parts by weight of a 45% sodium hypophosphite aqueous solution (hereinafter also referred to as “45% SHP”), and 15 parts by weight 80% AA and 45% SHP for 150 minutes and 15% NaPS for 80% from the tip nozzle through 67% by mass of a sodium persulfate aqueous solution (hereinafter also referred to as “15% NaPS”) through separate supply paths. At the same time as AA, the dropping was started and dropped over 155 minutes (that is, until 5 minutes after the completion of dropping of 80% AA). The dropping of each component was continuously performed at a constant dropping rate. After completion of the dropwise addition of 15% NaPS, aging was performed for 30 minutes while maintaining the reflux of the mixed solution.
After completion of the aging, the mixture of IPA and water was distilled off at a temperature of 80 to 103 ° C. over 120 minutes until the IPA in the polymerization vessel disappeared (step D), and then 220 parts by mass of ion-exchanged water was charged into the polymerization vessel. Thus, the temperature of the aqueous solution was adjusted to 70 ° C. Using an external circulating cooling device, the temperature of the aqueous solution is maintained at 70 to 85 ° C., and 583 parts by mass of a 48% by mass sodium hydroxide aqueous solution (AA neutralization rate of 70%) is supplied from the tip nozzle through the supply path. After dripping in the polymerization kettle over 60 minutes to partially neutralize the polymer (step N1), 171 parts by mass of monoethanolamine (AA neutralization rate of 28%) was then added to the tip through another supply path. The solution was dropped from the nozzle into the polymerization kettle over 30 minutes to neutralize the polymer (step N2). The total time required for the steps N1 and N2 was 90 minutes. As described above, an aqueous solution of sodium polyacrylate / monoethanolamine salt (11) was obtained.
The obtained aqueous solution (referred to as polymer aqueous solution (11)) had a solid content value of 52.5% and an active ingredient value of 40.3%. The Brookfield viscosity of the aqueous polymer solution (11) was 600 mPa · s, the weight average molecular weight (Mw) was 4500, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.15. The total concentration of inorganic anions containing sulfur atoms or phosphorus atoms in the aqueous polymer solution (11) (mainly sulfate ions and hypophosphite ions were detected) was 6500 ppm. Moreover, the hue (APHA) in the solid immediately after manufacture of polymer aqueous solution (11) was 70, and APHA after one-month progress was 150 at room temperature (25 degreeC).
As in Example 1, when the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 900 mPa · s, and the slurry viscosity after 1 week was 3400 mPa · s. The polymerization results and the analysis results of the polymer are shown in Table 3, and the evaluation results are shown in Table 4.
バッチ型重合釜(SUS製、容積5m3)と、当該重合釜に備えられた温度計、攪拌器(パドル翼)、外部留出物循環経路及び、ジャケット、供給経路(重合用組成物用及び中和剤用)、並びに、外部循環冷却装置(外部反応液循環経路及び除熱装置)、溶媒留去装置を有する反応装置を用い、以下に示す重合処方・条件で重合を行った。イオン交換水350質量部、イソプロピルアルコール(以下、「IPA」とも称する)200質量部を仕込んだ。その後、重合釜内の水溶液を撹拌しながら、常圧下、外部ジャケットにより混合溶液が還流するまで昇温させた(混合溶媒の温度は80℃であった)。
次に、80質量%アクリル酸水溶液(以下、「80%AA」とも称する)900質量部、45%次亜リン酸ナトリウム水溶液(以下、「45%SHP」とも称する)83質量部、および15質量%過硫酸ナトリウム水溶液(以下、「15%NaPS」とも称する)67質量部をそれぞれ別々の供給経路を通じて先端ノズルより、80%AAおよび45%SHPは150分間に亘って、15%NaPSは80%AAと同時に滴下を開始して155分間に亘って(すなわち、80%AAの滴下終了5分後まで)滴下した。それぞれの成分の滴下は、一定の滴下速度で連続的に行った。15%NaPSを滴下終了後、混合溶液の還流を保持した状態で30分間熟成を行った。
熟成終了後、外部循環冷却装置を用いて、混合溶液の温度が65℃になるまで冷却し、混合溶液の温度が65~80℃を維持するようにして、48質量%水酸化ナトリウム水溶液583質量部(AA中和率70%分)をその供給経路を通じて先端ノズルより重合釜内に60分かけて滴下して、重合体を部分中和(工程N1)した後、続いて、モノエタノールアミン171質量部(AA中和率28%分)を別の供給経路を通じて先端ノズルより重合釜内に30分かけて滴下して、重合体を中和(工程N2)した。工程N1と工程N2に要した時間の合計は90分であった。
次に、重合釜内のIPAが無くなるまでIPAと水の混合物を80~103℃で120分かけて留去(工程D)した後、イオン交換水220質量部を重合釜内に投入して、ポリアクリル酸ナトリウム・モノエタノールアミン塩水溶液(12)を得た。
得られた水溶液(重合体水溶液(12)という)の固形分値は52.6%、有効成分値は40.4%であった。重合体水溶液(12)のブルックフィールド粘度は620mPa・s、重量平均分子量(Mw)は4600、重量平均分子量(Mw)/数平均分子量(Mn)は2.15であった。また、重合体水溶液(12)中の硫黄原子又はリン原子を含む無機の陰イオンの濃度(主として硫酸イオンと次亜リン酸イオンが検出された)の合計は、6400ppmであった。また、重合体水溶液(12)の、有姿での色相(APHA)は90であり、室温(25℃)で1ヶ月経過後のAPHAは160であった。
実施例1と同様に、重質炭酸カルシウムのスラリー粘度を上述の方法で評価したところ、粉砕直後のスラリー粘度は920mPa・sで、1週間後のスラリー粘度は3450mPa・sであった。当該重合処方及び重合体の分析結果を表3に、評価結果を表4に示した。 <Example 10>
Batch type polymerization kettle (manufactured by SUS, volume 5 m 3 ), thermometer, stirrer (paddle blade), external distillate circulation path and jacket, supply path (for polymerization composition and Polymerization was carried out using a reaction apparatus having a neutralizing agent), an external circulation cooling apparatus (external reaction liquid circulation path and heat removal apparatus), and a solvent distillation apparatus under the following polymerization prescription and conditions. 350 parts by mass of ion-exchanged water and 200 parts by mass of isopropyl alcohol (hereinafter also referred to as “IPA”) were charged. Thereafter, while stirring the aqueous solution in the polymerization kettle, the temperature was raised under normal pressure until the mixed solution was refluxed by an external jacket (the temperature of the mixed solvent was 80 ° C.).
Next, 900 parts by weight of an 80% by weight acrylic acid aqueous solution (hereinafter also referred to as “80% AA”), 83 parts by weight of a 45% sodium hypophosphite aqueous solution (hereinafter also referred to as “45% SHP”), and 15 parts by weight 80% AA and 45% SHP for 150 minutes and 15% NaPS for 80% from the tip nozzle through 67% by mass of a sodium persulfate aqueous solution (hereinafter also referred to as “15% NaPS”) through separate supply paths. At the same time as AA, the dropping was started and dropped over 155 minutes (that is, until 5 minutes after the completion of dropping of 80% AA). The dropping of each component was continuously performed at a constant dropping rate. After completion of the dropwise addition of 15% NaPS, aging was performed for 30 minutes while maintaining the reflux of the mixed solution.
After completion of the aging, the external solution is cooled until the temperature of the mixed solution reaches 65 ° C., and the temperature of the mixed solution is maintained at 65 to 80 ° C. Part (AA neutralization rate of 70%) is dropped over 60 minutes from the tip nozzle into the polymerization vessel through the supply path to partially neutralize the polymer (step N1), and then monoethanolamine 171 A part by mass (AA neutralization rate of 28%) was dropped into the polymerization kettle from the tip nozzle through another supply path over 30 minutes to neutralize the polymer (step N2). The total time required for the steps N1 and N2 was 90 minutes.
Next, after the IPA and water mixture was distilled off at 80 to 103 ° C. over 120 minutes until the IPA in the polymerization kettle disappeared (step D), 220 parts by mass of ion-exchanged water was put into the polymerization kettle. A sodium polyacrylate / monoethanolamine salt aqueous solution (12) was obtained.
The obtained aqueous solution (referred to as polymer aqueous solution (12)) had a solid content value of 52.6% and an active ingredient value of 40.4%. The Brookfield viscosity of the aqueous polymer solution (12) was 620 mPa · s, the weight average molecular weight (Mw) was 4600, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.15. The total concentration of inorganic anions containing sulfur atoms or phosphorus atoms in the aqueous polymer solution (12) (mainly sulfate ions and hypophosphite ions were detected) was 6400 ppm. Moreover, the hue (APHA) in solid of polymer aqueous solution (12) was 90, and APHA after one-month progress was 160 at room temperature (25 degreeC).
As in Example 1, when the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 920 mPa · s, and the slurry viscosity after 1 week was 3450 mPa · s. The polymerization results and the analysis results of the polymer are shown in Table 3, and the evaluation results are shown in Table 4.
実施例5と同様に重合条件を表3に記載の方法に変更する以外は、同様の方法でポリアクリル酸ナトリウム水溶液(13)を得た。得られた水溶液(重合体水溶液(13)という)の固形分値は46.6%、有効成分値は44.5%であった。重合体水溶液(13)のブルックフィールド粘度は900mPa・s、重量平均分子量(Mw)は5900、重量平均分子量(Mw)/数平均分子量(Mn)は2.30であった。また、重合体水溶液(13)中の硫黄原子又はリン原子を含む無機の陰イオンの濃度(主として硫酸イオンと次亜リン酸イオンが検出された)の合計は、5800ppmであった。また、重合体水溶液(13)の、製造直後の有姿での色相(APHA)は60であり、室温(25℃)で1ヶ月経過後のAPHAは130であった。
実施例1と同様に、重質炭酸カルシウムのスラリー粘度を上述の方法で評価したところ、粉砕直後のスラリー粘度は1800mPa・sで、1週間後のスラリー粘度は4700mPa・sであった。当該重合処方及び重合体の分析結果を表3に、評価結果を表4に示した。 <Comparative Example 3>
A sodium polyacrylate aqueous solution (13) was obtained in the same manner as in Example 5 except that the polymerization conditions were changed to those shown in Table 3. The obtained aqueous solution (referred to as polymer aqueous solution (13)) had a solid content value of 46.6% and an active ingredient value of 44.5%. The Brookfield viscosity of the aqueous polymer solution (13) was 900 mPa · s, the weight average molecular weight (Mw) was 5900, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.30. Further, the total concentration of inorganic anions containing sulfur atoms or phosphorus atoms in the polymer aqueous solution (13) (mainly sulfate ions and hypophosphite ions were detected) was 5800 ppm. Moreover, the hue (APHA) in the solid state immediately after manufacture of polymer aqueous solution (13) was 60, and APHA after one-month progress was 130 at room temperature (25 degreeC).
As in Example 1, when the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 1800 mPa · s, and the slurry viscosity after one week was 4700 mPa · s. The polymerization results and the analysis results of the polymer are shown in Table 3, and the evaluation results are shown in Table 4.
実施例7と同様に重合条件を表3に記載の方法に変更する以外は、同様の方法でポリアクリル酸ナトリウム水溶液(14)を得た。得られた水溶液(重合体水溶液(14)という)の固形分値は43.3%、有効成分値は41.3%であった。重合体水溶液(14)のブルックフィールド粘度は680mPa・s、重量平均分子量(Mw)は5500、重量平均分子量(Mw)/数平均分子量(Mn)は2.20であった。また、重合体水溶液(14)中の硫黄原子又はリン原子を含む無機の陰イオンの濃度(主として硫酸イオンと次亜リン酸イオンが検出された)の合計は、6200ppmであった。また、重合体水溶液(14)の、製造直後の有姿での色相(APHA)は70であり、室温(25℃)で1ヶ月経過後のAPHAは140であった。
実施例1と同様に、重質炭酸カルシウムのスラリー粘度を上述の方法で評価したところ、粉砕直後のスラリー粘度は1700mPa・sで、1週間後のスラリー粘度は4800mPa・sであった。当該重合処方及び重合体の分析結果を表3に、評価結果を表4に示した。 <Comparative Example 4>
A sodium polyacrylate aqueous solution (14) was obtained in the same manner as in Example 7 except that the polymerization conditions were changed to those shown in Table 3. The obtained aqueous solution (referred to as polymer aqueous solution (14)) had a solid content value of 43.3% and an active ingredient value of 41.3%. The Brookfield viscosity of the aqueous polymer solution (14) was 680 mPa · s, the weight average molecular weight (Mw) was 5,500, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.20. Further, the total concentration of inorganic anions containing sulfur atoms or phosphorus atoms (mainly sulfate ions and hypophosphite ions were detected) in the aqueous polymer solution (14) was 6200 ppm. Moreover, the hue (APHA) in the solid immediately after manufacture of polymer aqueous solution (14) was 70, and APHA after one-month progress was 140 at room temperature (25 degreeC).
As in Example 1, when the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 1700 mPa · s, and the slurry viscosity after 1 week was 4800 mPa · s. The polymerization results and the analysis results of the polymer are shown in Table 3, and the evaluation results are shown in Table 4.
実施例9と同様に重合条件を表3に記載の方法に変更する以外は、同様の方法でポリアクリル酸ナトリウム水溶液(15)を得た。得られた水溶液(重合体水溶液(15)という)の固形分値は43.1%、有効成分値は41.1%であった。重合体水溶液(15)のブルックフィールド粘度は650mPa・s、重量平均分子量(Mw)は4500、重量平均分子量(Mw)/数平均分子量(Mn)は2.20であった。また、重合体水溶液(15)中の硫黄原子又はリン原子を含む無機の陰イオンの濃度(主として硫酸イオンと次亜リン酸イオンが検出された)の合計は、6400ppmであった。また、重合体水溶液(15)の、製造直後の有姿での色相(APHA)は75であり、室温(25℃)で1ヶ月経過後のAPHAは160であった。
実施例1と同様に、重質炭酸カルシウムのスラリー粘度を上述の方法で評価したところ、粉砕直後のスラリー粘度は1400mPa・sで、1週間後のスラリー粘度は4200mPa・sであった。当該重合処方及び重合体の分析結果を表3に、評価結果を表4に示した。 <Comparative Example 5>
A sodium polyacrylate aqueous solution (15) was obtained in the same manner as in Example 9, except that the polymerization conditions were changed to those shown in Table 3. The obtained aqueous solution (referred to as polymer aqueous solution (15)) had a solid content value of 43.1% and an active ingredient value of 41.1%. The Brookfield viscosity of the aqueous polymer solution (15) was 650 mPa · s, the weight average molecular weight (Mw) was 4500, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.20. The total concentration of inorganic anions containing sulfur atoms or phosphorus atoms in the aqueous polymer solution (15) (mainly sulfate ions and hypophosphite ions were detected) was 6400 ppm. Moreover, the hue (APHA) in the solid state immediately after manufacture of polymer aqueous solution (15) was 75, and APHA after one-month progress was 160 at room temperature (25 degreeC).
As in Example 1, when the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 1400 mPa · s, and the slurry viscosity after 1 week was 4200 mPa · s. The polymerization results and the analysis results of the polymer are shown in Table 3, and the evaluation results are shown in Table 4.
実施例5と同様に重合条件を表3に記載の方法に変更する以外は、同様の方法でポリアクリル酸ナトリウム・モノエタノールアミン塩水溶液(16)を得た。なお、重合液の熟成時及び中和時(工程N1及び工程N2)には、水溶液が還流した状態を保持し、このときの水溶液の温度は103℃であった。得られた水溶液(重合体水溶液(16)という)の固形分値は53.2%、有効成分値は44.9%であった。重合体水溶液(16)のブルックフィールド粘度は900mPa・s、重量平均分子量(Mw)は5500、重量平均分子量(Mw)/数平均分子量(Mn)は2.17であった。また、重合体水溶液(16)中の硫黄原子又はリン原子を含む無機の陰イオンの濃度(主として硫酸イオンと次亜リン酸イオンが検出された)の合計は、5500ppmであった。また、重合体水溶液(16)の、製造直後の有姿での色相(APHA)は80であり、室温(25℃)で1ヶ月経過後のAPHAは250であった。
実施例1と同様に、重質炭酸カルシウムのスラリー粘度を上述の方法で評価したところ、粉砕直後のスラリー粘度は1000mPa・sで、1週間後のスラリー粘度は3500mPa・sであった。当該重合処方及び重合体の分析結果を表3に、評価結果を表4に示した。 <Comparative Example 6>
A sodium polyacrylate / monoethanolamine salt aqueous solution (16) was obtained in the same manner as in Example 5 except that the polymerization conditions were changed to those shown in Table 3. In addition, at the time of aging and neutralization of the polymerization liquid (step N1 and step N2), the aqueous solution was kept in a reflux state, and the temperature of the aqueous solution at this time was 103 ° C. The obtained aqueous solution (referred to as polymer aqueous solution (16)) had a solid content value of 53.2% and an active ingredient value of 44.9%. The aqueous polymer solution (16) had a Brookfield viscosity of 900 mPa · s, a weight average molecular weight (Mw) of 5500, and a weight average molecular weight (Mw) / number average molecular weight (Mn) of 2.17. Further, the total concentration of inorganic anions containing sulfur atoms or phosphorus atoms in the polymer aqueous solution (16) (mainly sulfate ions and hypophosphite ions were detected) was 5500 ppm. Moreover, the hue (APHA) in the solid state immediately after manufacture of polymer aqueous solution (16) was 80, and APHA after one-month progress was 250 at room temperature (25 degreeC).
As in Example 1, when the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 1000 mPa · s, and the slurry viscosity after 1 week was 3500 mPa · s. The polymerization results and the analysis results of the polymer are shown in Table 3, and the evaluation results are shown in Table 4.
実施例6と同様に重合条件を表3に記載の方法に変更する以外は、同様の方法でポリアクリル酸ナトリウム・モノエタノールアミン塩水溶液(17)を得た。なお、重合液の熟成時及び中和時(工程N1及び工程N2)には、水溶液が還流した状態を保持し、このときの水溶液の温度は103℃であった。得られた水溶液(重合体水溶液(17)という)の固形分値は59.2%、有効成分値は44.9%であった。重合体水溶液(17)のブルックフィールド粘度は1100mPa・s、重量平均分子量(Mw)は5500、重量平均分子量(Mw)/数平均分子量(Mn)は2.19であった。また、重合体水溶液(17)中の硫黄原子又はリン原子を含む無機の陰イオンの濃度(主として硫酸イオンと次亜リン酸イオンが検出された)の合計は、5600ppmであった。また、重合体水溶液(17)の、製造直後の有姿での色相(APHA)は80であり、室温(25℃)で1ヶ月経過後のAPHAは300であった。
実施例1と同様に、重質炭酸カルシウムのスラリー粘度を上述の方法で評価したところ、粉砕直後のスラリー粘度は800mPa・sで、1週間後のスラリー粘度は2700mPa・sであった。当該重合処方及び重合体の分析結果を表3に、評価結果を表4に示した。 <Comparative Example 7>
A sodium polyacrylate / monoethanolamine salt aqueous solution (17) was obtained in the same manner as in Example 6 except that the polymerization conditions were changed to those shown in Table 3. In addition, at the time of aging and neutralization of the polymerization liquid (step N1 and step N2), the aqueous solution was kept in a reflux state, and the temperature of the aqueous solution at this time was 103 ° C. The obtained aqueous solution (referred to as polymer aqueous solution (17)) had a solid content value of 59.2% and an active ingredient value of 44.9%. The aqueous polymer solution (17) had a Brookfield viscosity of 1100 mPa · s, a weight average molecular weight (Mw) of 5500, and a weight average molecular weight (Mw) / number average molecular weight (Mn) of 2.19. Further, the total concentration of inorganic anions containing sulfur atoms or phosphorus atoms in the aqueous polymer solution (17) (mainly sulfate ions and hypophosphite ions were detected) was 5600 ppm. Moreover, the hue (APHA) in the solid state immediately after manufacture of polymer aqueous solution (17) was 80, and APHA after one-month progress was 300 at room temperature (25 degreeC).
As in Example 1, when the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 800 mPa · s, and the slurry viscosity after 1 week was 2700 mPa · s. The polymerization results and the analysis results of the polymer are shown in Table 3, and the evaluation results are shown in Table 4.
バッチ型重合釜(SUS製、容積5m3)と、当該重合釜に備えられた温度計、攪拌器(パドル翼)、外部留出物循環経路及び、ジャケット、供給経路(重合用組成物用及び中和剤用)、並びに、還流冷却装置を有する反応装置を用い、以下に示す重合処方・条件で重合を行った。まずイオン交換水362質量部を仕込んだ。その後、重合釜内の水溶液を撹拌しながら、常温下、外部ジャケットにより水溶液の温度を還流するまで昇温させた。
次に、80質量%アクリル酸水溶液(以下、「80%AA」とも称する)925質量部を180分間と、15質量%過硫酸ナトリウム水溶液(以下、「15%NaPS」とも称する)49質量部を185分間、45質量%次亜リン酸ナトリウム水溶液(以下、「45%SHP」とも称する)を17質量部、20分間と更に続いて70質量部を160分間と2段階の供給速度で、それぞれ別々の供給経路を通じて先端ノズルより滴下した。それぞれの成分の滴下は、45%SHP以外は一定の滴下速度で連続的に行った。
その後、48質量%水酸化ナトリウム水溶液600質量部(AA中和率70%分)をその供給経路を通じて先端ノズルより重合釜内に滴下して、重合体を中和し、続いて、モノエタノールアミン(以下、「MEA」とも称する)175質量部(AA中和率28%分)を別の供給経路を通じて先端ノズルより重合釜内に滴下して、重合体を中和した。以上のようにして、ポリアクリル酸ナトリウム・モノエタノールアミン塩水溶液(18)を得た。得られた水溶液(重合体水溶液(18)という)の固形分値は52.7%、有効成分値は44.7%であった。重合体水溶液(18)のブルックフィールド粘度は850mPa・s、重量平均分子量(Mw)は5200、重量平均分子量(Mw)/数平均分子量(Mn)は2.15であった。重合体水溶液(18)中の硫黄原子又はリン原子を含む無機の陰イオンの濃度(主として硫酸イオンと次亜リン酸イオンが検出された)の合計は、5900ppmであった。
評価例に従い、重合体水溶液(18)を使用して本発明の無機粒子スラリー(重質炭酸カルシウムスラリー(18))を得た。重質炭酸カルシウムスラリー(18)の2μm以下の無機粒子の割合は90.1質量%、固形分濃度は77.6質量%であった。
重質炭酸カルシウムのスラリー粘度を上述の方法で評価したところ、粉砕終了1時間後のスラリー粘度は950mPa・sで、1週間後のスラリー粘度は3380mPa・sであった。
重合処方及び重合体の分析結果を表5に、評価結果を表6に示した。 <Example 11>
Batch type polymerization kettle (manufactured by SUS, volume 5 m 3 ), thermometer, stirrer (paddle blade), external distillate circulation path and jacket, supply path (for polymerization composition and Polymerization was carried out under the following polymerization prescription and conditions using a reaction apparatus having a reflux cooling apparatus and a neutralizer. First, 362 parts by mass of ion-exchanged water was charged. Thereafter, while stirring the aqueous solution in the polymerization kettle, the temperature of the aqueous solution was raised to reflux with an external jacket at room temperature.
Next, 925 parts by mass of an 80% by mass acrylic acid aqueous solution (hereinafter also referred to as “80% AA”) for 180 minutes and 49 parts by mass of a 15% by mass sodium persulfate aqueous solution (hereinafter also referred to as “15% NaPS”) 185 minutes, 45% by weight sodium hypophosphite aqueous solution (hereinafter also referred to as “45% SHP”) 17 parts by weight, 20 minutes, and then 70 parts by weight for 160 minutes, each at a two-stage feed rate. It was dripped from the tip nozzle through the supply path. The dropping of each component was continuously performed at a constant dropping rate except for 45% SHP.
Thereafter, 600 parts by mass of a 48% by mass aqueous sodium hydroxide solution (AA neutralization rate of 70%) is dropped into the polymerization kettle from the tip nozzle through the supply path to neutralize the polymer, followed by monoethanolamine. 175 parts by mass (hereinafter also referred to as “MEA”) (AA neutralization rate of 28%) was dropped into the polymerization kettle from the tip nozzle through another supply path to neutralize the polymer. As described above, an aqueous solution of sodium polyacrylate / monoethanolamine salt (18) was obtained. The obtained aqueous solution (referred to as polymer aqueous solution (18)) had a solid content value of 52.7% and an active ingredient value of 44.7%. The aqueous polymer solution (18) had a Brookfield viscosity of 850 mPa · s, a weight average molecular weight (Mw) of 5200, and a weight average molecular weight (Mw) / number average molecular weight (Mn) of 2.15. The total concentration of inorganic anions containing sulfur atoms or phosphorus atoms (mainly sulfate ions and hypophosphite ions were detected) in the aqueous polymer solution (18) was 5900 ppm.
According to the evaluation example, the aqueous polymer solution (18) was used to obtain an inorganic particle slurry (heavy calcium carbonate slurry (18)) of the present invention. The proportion of inorganic particles of 2 μm or less in the heavy calcium carbonate slurry (18) was 90.1% by mass, and the solid content concentration was 77.6% by mass.
When the slurry viscosity of heavy calcium carbonate was evaluated by the above-mentioned method, the slurry viscosity 1 hour after the completion of pulverization was 950 mPa · s, and the slurry viscosity after 1 week was 3380 mPa · s.
Table 5 shows the polymerization formulation and analysis results of the polymer, and Table 6 shows the evaluation results.
重合条件を表5に記載の方法に変更する以外は、実施例11と同様にしてポリアクリル酸ナトリウム・モノエタノールアミン塩水溶液(19)を得た。得られた水溶液中(重合体水溶液(19)という)の固形分値は59.0%、有効成分値は45.4%であった。また重合体水溶液(19)のブルックフィールド粘度は990mPa・s、重量平均分子量(Mw)は5400、重量平均分子量(Mw)/数平均分子量(Mn)は2.14であった。
評価例に従い、重合体水溶液(19)を使用して本発明の無機粒子スラリー(重質炭酸カルシウムスラリー(19))を得た。重質炭酸カルシウムスラリー(19)の2μm以下の無機粒子の割合は90.2質量%、固形分濃度は77.4質量%であった。
実施例1と同様に、重質炭酸カルシウムのスラリー粘度を上述の方法で評価したところ、粉砕直後のスラリー粘度は630mPa・sで、1週間後のスラリー粘度は2090mPa・sであった。
重合処方及び重合体の分析結果を表5に、評価結果を表6に示した。 <Example 12>
A sodium polyacrylate / monoethanolamine salt aqueous solution (19) was obtained in the same manner as in Example 11 except that the polymerization conditions were changed to those shown in Table 5. The solid content value in the obtained aqueous solution (referred to as polymer aqueous solution (19)) was 59.0%, and the active ingredient value was 45.4%. The aqueous polymer solution (19) had a Brookfield viscosity of 990 mPa · s, a weight average molecular weight (Mw) of 5400, and a weight average molecular weight (Mw) / number average molecular weight (Mn) of 2.14.
According to the evaluation example, the inorganic particle slurry (heavy calcium carbonate slurry (19)) of the present invention was obtained using the polymer aqueous solution (19). The proportion of the inorganic particles of 2 μm or less in the heavy calcium carbonate slurry (19) was 90.2% by mass, and the solid content concentration was 77.4% by mass.
As in Example 1, when the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 630 mPa · s, and the slurry viscosity after one week was 2090 mPa · s.
Table 5 shows the polymerization formulation and analysis results of the polymer, and Table 6 shows the evaluation results.
バッチ型重合釜(SUS製、容積5m3)と、当該重合釜に備えられた温度計、攪拌器(パドル翼)、外部留出物循環経路及び、ジャケット、供給経路(重合用組成物用及び中和剤用)、並びに、外部循環冷却装置(外部反応液循環経路および除熱装置)を有する反応装置(図1を参照)を用い、以下に示す重合処方・条件で重合を行った。イオン交換水515質量部、45質量%次亜リン酸ナトリウム水溶液(以下、「45%SHP」とも称する)16質量部を仕込んだ。その後、重合釜内の水溶液を撹拌しながら、常温下、外部ジャケットにより水溶液の温度を82℃まで昇温させた。
次に、80質量%アクリル酸水溶液(以下、「80%AA」とも称する)900質量部、45%SHPを67質量部、及び15質量%過硫酸ナトリウム水溶液(以下、「15%NaPS」とも称する)67質量部をそれぞれ別々の供給経路を通じて先端ノズルより、80%AA及び45%SHPは150分間に亘って、15%NaPSは80%AAと同時に滴下を開始して155分間に亘って(すなわち、80%AAの滴下終了5分後まで)滴下した。それぞれの成分の滴下は、一定の滴下速度で連続的に行った。
その後、48質量%水酸化ナトリウム水溶液583質量部(AA中和率70%分)をその供給経路を通じて先端ノズルより重合釜内に滴下して、重合体を中和し、続いて、モノエタノールアミン171質量部(AA中和率28%分)を別の供給経路を通じて先端ノズルより重合釜内に滴下して、重合体を中和した。なお、重合体を中和する間、常に反応液を外部循環させながら、除熱装置によって当該反応液を冷却した。
以上のようにして、ポリアクリル酸ナトリウム・モノエタノールアミン塩水溶液(20)を得た。得られた水溶液(重合体水溶液(20)という)の固形分値は52.4%、有効成分値は40.2%であった。重合体水溶液(20)のブルックフィールド粘度は800mPa・s、重量平均分子量(Mw)は5500、重量平均分子量(Mw)/数平均分子量(Mn)は2.15であった。
評価例に従い、重合体水溶液(20)を使用して本発明の無機粒子スラリー(重質炭酸カルシウムスラリー(20))を得た。重質炭酸カルシウムスラリー(20)の2μm以下の無機粒子の割合は90.3質量%、固形分濃度は77.5質量%であった。
重質炭酸カルシウムのスラリー粘度を上述の方法で評価したところ、粉砕直後のスラリー粘度は1000mPa・sで、1週間後のスラリー粘度は3450mPa・sであった。
重合処方及び重合体の分析結果を表5に、評価結果を表6に示した。 <Example 13>
Batch type polymerization kettle (manufactured by SUS, volume 5 m 3 ), thermometer, stirrer (paddle blade), external distillate circulation path and jacket, supply path (for polymerization composition and Polymerization was carried out under the polymerization prescription and conditions shown below using a reaction apparatus (see FIG. 1) having an external circulation cooling apparatus (external reaction liquid circulation path and heat removal apparatus). 515 parts by mass of ion-exchanged water and 16 parts by mass of a 45% by mass aqueous sodium hypophosphite solution (hereinafter also referred to as “45% SHP”) were charged. Thereafter, the temperature of the aqueous solution was raised to 82 ° C. with an external jacket at room temperature while stirring the aqueous solution in the polymerization kettle.
Next, 900 parts by mass of an 80% by mass acrylic acid aqueous solution (hereinafter also referred to as “80% AA”), 67% by mass of 45% SHP, and a 15% by mass sodium persulfate aqueous solution (hereinafter also referred to as “15% NaPS”). ) 67 parts by mass from the tip nozzles through separate supply paths, 80% AA and 45% SHP for 150 minutes, 15% NaPS starts dropping simultaneously with 80% AA for 155 minutes (ie , Until 5 minutes after the completion of dropping 80% AA). The dropping of each component was continuously performed at a constant dropping rate.
Thereafter, 583 parts by mass of a 48% by mass aqueous sodium hydroxide solution (AA neutralization rate of 70%) is dropped into the polymerization kettle from the tip nozzle through the supply path to neutralize the polymer, followed by monoethanolamine. 171 parts by mass (AA neutralization rate of 28%) was dropped into the polymerization kettle from the tip nozzle through another supply path to neutralize the polymer. During the neutralization of the polymer, the reaction solution was cooled by a heat removal device while always circulating the reaction solution externally.
As described above, a sodium polyacrylate / monoethanolamine salt aqueous solution (20) was obtained. The obtained aqueous solution (referred to as polymer aqueous solution (20)) had a solid content value of 52.4% and an active ingredient value of 40.2%. The Brookfield viscosity of the aqueous polymer solution (20) was 800 mPa · s, the weight average molecular weight (Mw) was 5,500, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.15.
According to the evaluation example, the inorganic particle slurry (heavy calcium carbonate slurry (20)) of the present invention was obtained using the polymer aqueous solution (20). The proportion of inorganic particles of 2 μm or less in the heavy calcium carbonate slurry (20) was 90.3% by mass, and the solid content concentration was 77.5% by mass.
When the slurry viscosity of heavy calcium carbonate was evaluated by the above method, the slurry viscosity immediately after pulverization was 1000 mPa · s, and the slurry viscosity after 1 week was 3450 mPa · s.
Table 5 shows the polymerization formulation and analysis results of the polymer, and Table 6 shows the evaluation results.
重合条件を表5に記載の方法に変更する以外は、実施例13と同様にしてポリアクリル酸ナトリウム水溶液(21)を得た。得られた水溶液(重合体水溶液(21)という)の固形分値は56.9%、有効成分値は40.3%であった。重合体水溶液(21)のブルックフィールド粘度は950mPa・s、重量平均分子量(Mw)は5700、重量平均分子量(Mw)/数平均分子量(Mn)は2.18であった。
評価例に従い、重合体水溶液(21)を使用して本発明の無機粒子スラリー(重質炭酸カルシウムスラリー(21))を得た。重質炭酸カルシウムスラリー(21)の2μm以下の無機粒子の割合は90.5質量%、固形分濃度は77.7質量%であった。
実施例1と同様に、重質炭酸カルシウムのスラリー粘度を上述の方法で評価したところ、粉砕直後のスラリー粘度は890mPa・sで、1週間後のスラリー粘度は2210mPa・sであった。
当該重合処方及び重合体の分析結果を表5に、評価結果を表6に示した。 <Example 14>
A sodium polyacrylate aqueous solution (21) was obtained in the same manner as in Example 13 except that the polymerization conditions were changed to those shown in Table 5. The obtained aqueous solution (referred to as polymer aqueous solution (21)) had a solid content value of 56.9% and an active ingredient value of 40.3%. The Brookfield viscosity of the aqueous polymer solution (21) was 950 mPa · s, the weight average molecular weight (Mw) was 5700, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.18.
According to the evaluation example, the aqueous polymer solution (21) was used to obtain an inorganic particle slurry (heavy calcium carbonate slurry (21)) of the present invention. The proportion of inorganic particles of 2 μm or less in the heavy calcium carbonate slurry (21) was 90.5% by mass, and the solid content concentration was 77.7% by mass.
As in Example 1, when the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 890 mPa · s, and the slurry viscosity after one week was 2210 mPa · s.
The polymerization results and the analysis results of the polymer are shown in Table 5, and the evaluation results are shown in Table 6.
実施例11と同様に重合条件を表5に記載の方法に変更する以外は、同様の方法でポリアクリル酸ナトリウム水溶液(22)を得た。得られた水溶液(重合体水溶液(22)という)の固形分値は46.6%、有効成分値は44.5%であった。重合体水溶液(22)のブルックフィールド粘度は900mPa・s、重量平均分子量(Mw)は5900、重量平均分子量(Mw)/数平均分子量(Mn)は2.30であった。
評価例に従い、重合体水溶液(22)を使用して本発明の無機粒子スラリー(重質炭酸カルシウムスラリー(22))を得た。重質炭酸カルシウムスラリー(22)の2μm以下の無機粒子の割合は90.2質量%、固形分濃度は77.3質量%であった。
実施例1と同様に、重質炭酸カルシウムのスラリー粘度を上述の方法で評価したところ、粉砕直後のスラリー粘度は1800mPa・sで、1週間後のスラリー粘度は4700mPa・sであった。
当該重合処方及び重合体の分析結果を表5に、評価結果を表6に示した。 <Comparative Example 8>
A sodium polyacrylate aqueous solution (22) was obtained in the same manner as in Example 11 except that the polymerization conditions were changed to those shown in Table 5. The obtained aqueous solution (referred to as polymer aqueous solution (22)) had a solid content value of 46.6% and an active ingredient value of 44.5%. The Brookfield viscosity of the aqueous polymer solution (22) was 900 mPa · s, the weight average molecular weight (Mw) was 5900, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.30.
According to the evaluation example, the aqueous polymer solution (22) was used to obtain an inorganic particle slurry (heavy calcium carbonate slurry (22)) of the present invention. The proportion of inorganic particles of 2 μm or less in the heavy calcium carbonate slurry (22) was 90.2% by mass, and the solid content concentration was 77.3% by mass.
As in Example 1, when the slurry viscosity of heavy calcium carbonate was evaluated by the above-described method, the slurry viscosity immediately after pulverization was 1800 mPa · s, and the slurry viscosity after one week was 4700 mPa · s.
The polymerization results and the analysis results of the polymer are shown in Table 5, and the evaluation results are shown in Table 6.
実施例13と同様に重合条件を表5に記載の方法に変更する以外は、同様の方法でポリアクリル酸ナトリウム水溶液(23)を得た。得られた水溶液(重合体水溶液(23)という)の固形分値は43.3%、有効成分値は41.3%であった。重合体水溶液(23)のブルックフィールド粘度は780mPa・s、重量平均分子量(Mw)は5500、重量平均分子量(Mw)/数平均分子量(Mn)は2.20であった。
評価例に従い、重合体水溶液(23)を使用して本発明の無機粒子スラリー(重質炭酸カルシウムスラリー(23))を得た。重質炭酸カルシウムスラリー(23)の2μm以下の無機粒子の割合は90.1質量%、固形分濃度は77.6質量%であった。
実施例1と同様に、重質炭酸カルシウムのスラリー粘度を上述の方法で評価したところ、粉砕直後のスラリー粘度は1400mPa・sで、1週間後のスラリー粘度は3800mPa・sであった。
当該重合処方及び重合体の分析結果を表5に、評価結果を表6に示した。 <Comparative Example 9>
A sodium polyacrylate aqueous solution (23) was obtained in the same manner as in Example 13 except that the polymerization conditions were changed to those shown in Table 5. The obtained aqueous solution (referred to as polymer aqueous solution (23)) had a solid content value of 43.3% and an active ingredient value of 41.3%. The Brookfield viscosity of the aqueous polymer solution (23) was 780 mPa · s, the weight average molecular weight (Mw) was 5,500, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.20.
According to the evaluation example, the aqueous polymer particle (23) was used to obtain the inorganic particle slurry (heavy calcium carbonate slurry (23)) of the present invention. The proportion of inorganic particles of 2 μm or less in the heavy calcium carbonate slurry (23) was 90.1% by mass, and the solid content concentration was 77.6% by mass.
As in Example 1, when the slurry viscosity of heavy calcium carbonate was evaluated by the above method, the slurry viscosity immediately after pulverization was 1400 mPa · s, and the slurry viscosity after 1 week was 3800 mPa · s.
The polymerization results and the analysis results of the polymer are shown in Table 5, and the evaluation results are shown in Table 6.
表5において「構造のモル比」とは、「ポリ(メタ)アクリル酸系重合体水溶液に含まれる、(メタ)アクリル酸(塩)に由来する構造と有機アミン(塩)に由来する構造とのモル比((メタ)アクリル酸(塩)に由来する構造/有機アミン(塩)に由来する構造)」を表す。表5において、重合体水溶液に含まれる硫黄原子又はリン原子を含む無機の陰イオンの濃度をイオン濃度合計と記した。
また、表6において「構造のモル比」とは、「無機粒子スラリーに含まれる、(メタ)アクリル酸(塩)に由来する構造と有機アミン(塩)に由来する構造とのモル比((メタ)アクリル酸(塩)に由来する構造/有機アミン(塩)に由来する構造)」を表す。表6において、無機粒子スラリーに含まれる硫黄原子又はリン原子を含む無機の陰イオンの濃度をイオン濃度合計と記した。 Table 5 summarizes the polymerization formulations and polymer analysis results in Examples 11 to 14 and Comparative Examples 8 to 9, and Table 6 summarizes the evaluation results.
In Table 5, “molar ratio of structure” means “a structure derived from (meth) acrylic acid (salt) and a structure derived from organic amine (salt) contained in an aqueous poly (meth) acrylic acid polymer solution” The molar ratio (structure derived from (meth) acrylic acid (salt) / structure derived from organic amine (salt)) ". In Table 5, the density | concentration of the inorganic anion containing the sulfur atom or phosphorus atom contained in polymer aqueous solution was described as ion concentration total.
In Table 6, “Molar ratio of structure” means “molar ratio of a structure derived from (meth) acrylic acid (salt) and a structure derived from organic amine (salt) contained in the inorganic particle slurry (( Structure derived from (meth) acrylic acid (salt) / structure derived from organic amine (salt) ”. In Table 6, the density | concentration of the inorganic anion containing the sulfur atom or phosphorus atom contained in an inorganic particle slurry was described as ion concentration total.
Claims (7)
- ポリ(メタ)アクリル酸系重合体を含む水溶液であって、
該ポリ(メタ)アクリル酸系重合体のカルボキシル基の少なくとも一部は有機アミンで中和されており、
該水溶液に含まれる、(メタ)アクリル酸(塩)に由来する構造と有機アミン(塩)に由来する構造とのモル比が100:10~100:75であり、
該水溶液に含まれる、硫黄原子又はリン原子を含む無機の陰イオンの濃度が、該水溶液に対して1000~10000ppmであることを特徴とする水溶液。 An aqueous solution containing a poly (meth) acrylic acid polymer,
At least a part of the carboxyl groups of the poly (meth) acrylic acid polymer is neutralized with an organic amine;
The molar ratio of the structure derived from (meth) acrylic acid (salt) and the structure derived from organic amine (salt) contained in the aqueous solution is 100: 10 to 100: 75,
An aqueous solution characterized in that the concentration of inorganic anions containing sulfur atoms or phosphorus atoms contained in the aqueous solution is 1000 to 10,000 ppm with respect to the aqueous solution. - 前記ポリ(メタ)アクリル酸系重合体を含む水溶液は、(i)酸型及び/又は部分中和型のポリ(メタ)アクリル酸系重合体を含む水溶液をアルカリ金属塩で中和する工程と、(ii)酸型及び/又は部分中和型のポリ(メタ)アクリル酸系重合体を含む水溶液を有機アミンで中和する工程とを必須として製造されることを特徴とする請求項1に記載のポリ(メタ)アクリル酸系重合体を含む水溶液。 The aqueous solution containing the poly (meth) acrylic acid polymer comprises (i) a step of neutralizing an aqueous solution containing the acid type and / or partially neutralized poly (meth) acrylic acid polymer with an alkali metal salt; And (ii) a step of neutralizing an aqueous solution containing an acid type and / or a partially neutralized poly (meth) acrylic acid polymer with an organic amine. An aqueous solution containing the poly (meth) acrylic acid polymer described.
- 請求項1に記載のポリ(メタ)アクリル酸系重合体を含む水溶液を製造する方法であって、該製造方法は、酸型及び/又は部分中和型のポリ(メタ)アクリル酸系重合体を含む水溶液を、有機アミンで中和する工程を含むことを特徴とするポリ(メタ)アクリル酸系重合体を含む水溶液の製造方法。 A method for producing an aqueous solution containing the poly (meth) acrylic acid polymer according to claim 1, wherein the production method comprises an acid type and / or a partially neutralized poly (meth) acrylic acid polymer. The manufacturing method of the aqueous solution containing the poly (meth) acrylic-acid type polymer characterized by including the process of neutralizing the aqueous solution containing an organic amine.
- 請求項2に記載のポリ(メタ)アクリル酸系重合体を含む水溶液を製造する方法であって、該製造方法は、(i)酸型及び/又は部分中和型のポリ(メタ)アクリル酸系重合体を含む水溶液をアルカリ金属塩で中和する工程と、(ii)酸型及び/又は部分中和型のポリ(メタ)アクリル酸系重合体を含む水溶液を有機アミンで中和する工程とを必須として含むことを特徴とするポリ(メタ)アクリル酸系重合体を含む水溶液の製造方法。 A method for producing an aqueous solution containing the poly (meth) acrylic acid polymer according to claim 2, wherein the production method comprises (i) acid type and / or partially neutralized poly (meth) acrylic acid. A step of neutralizing an aqueous solution containing a polymer with an alkali metal salt, and (ii) a step of neutralizing an aqueous solution containing an acid type and / or partially neutralized poly (meth) acrylic acid type polymer with an organic amine. And a production method of an aqueous solution containing a poly (meth) acrylic acid polymer.
- 請求項1又は2に記載の水溶液を含むことを特徴とする顔料分散剤。 A pigment dispersant comprising the aqueous solution according to claim 1.
- ポリ(メタ)アクリル酸系重合体を含む無機粒子スラリーであって、
該ポリ(メタ)アクリル酸系重合体のカルボキシル基の少なくとも一部は有機アミンで中和されており、
該無機粒子スラリーに含まれる、(メタ)アクリル酸(塩)に由来する構造と有機アミン(塩)に由来する構造とのモル比が100:10~100:75であり、
該無機粒子スラリーに含まれる、硫黄原子又はリン原子を含む無機の陰イオンの濃度が、該無機粒子スラリーに対して100~400ppmであり、
該無機粒子スラリーに含まれる無機粒子は、全無機粒子100質量%に対して、粒径が2μm以下の粒子が90~100質量%含まれ、
該無機粒子スラリーの固形分濃度が75質量%以上であることを特徴とする無機粒子スラリー。 An inorganic particle slurry containing a poly (meth) acrylic acid polymer,
At least a part of the carboxyl groups of the poly (meth) acrylic acid polymer is neutralized with an organic amine;
The molar ratio of the structure derived from (meth) acrylic acid (salt) and the structure derived from organic amine (salt) contained in the inorganic particle slurry is 100: 10 to 100: 75,
The concentration of inorganic anions containing sulfur atoms or phosphorus atoms contained in the inorganic particle slurry is 100 to 400 ppm with respect to the inorganic particle slurry,
The inorganic particles contained in the inorganic particle slurry contain 90 to 100% by mass of particles having a particle size of 2 μm or less with respect to 100% by mass of all inorganic particles.
A solid content concentration of the inorganic particle slurry is 75% by mass or more. - 無機粒子に、ポリ(メタ)アクリル酸系重合体を含む水溶液を添加して無機粒子を粉砕する工程を含む無機粒子スラリーを製造する方法であって、
該ポリ(メタ)アクリル酸系重合体のカルボキシル基の少なくとも一部は有機アミンで中和されており、
該水溶液に含まれる、(メタ)アクリル酸(塩)に由来する構造と有機アミン(塩)に由来する構造とのモル比が100:10~100:75であり、
該水溶液に含まれる、硫黄原子又はリン原子を含む無機の陰イオンの濃度が、該水溶液に対して1000~10000ppmであることを特徴とする無機粒子スラリーの製造方法。
A method for producing an inorganic particle slurry comprising a step of adding an aqueous solution containing a poly (meth) acrylic acid polymer to inorganic particles and pulverizing the inorganic particles,
At least a part of the carboxyl groups of the poly (meth) acrylic acid polymer is neutralized with an organic amine;
The molar ratio of the structure derived from (meth) acrylic acid (salt) and the structure derived from organic amine (salt) contained in the aqueous solution is 100: 10 to 100: 75,
A method for producing an inorganic particle slurry, wherein the concentration of inorganic anions containing sulfur atoms or phosphorus atoms contained in the aqueous solution is 1000 to 10,000 ppm with respect to the aqueous solution.
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JP2013155319A (en) * | 2012-01-31 | 2013-08-15 | Nippon Shokubai Co Ltd | Acrylic acid-based copolymer, and method for producing the same |
JP2013177534A (en) * | 2012-02-10 | 2013-09-09 | Nippon Shokubai Co Ltd | Aqueous poly(meth)acrylic acid-based polymer solution and method for producing the same |
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JP2014208765A (en) * | 2013-03-22 | 2014-11-06 | 株式会社日本触媒 | Poly(meth)acrylic acid-based polymer and method for producing the same |
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