WO2021241662A1 - 水溶性ポリマー組成物 - Google Patents

水溶性ポリマー組成物 Download PDF

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Publication number
WO2021241662A1
WO2021241662A1 PCT/JP2021/020108 JP2021020108W WO2021241662A1 WO 2021241662 A1 WO2021241662 A1 WO 2021241662A1 JP 2021020108 W JP2021020108 W JP 2021020108W WO 2021241662 A1 WO2021241662 A1 WO 2021241662A1
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Prior art keywords
water
soluble polymer
mass
polymer composition
aqueous solution
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Ceased
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PCT/JP2021/020108
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English (en)
French (fr)
Japanese (ja)
Inventor
直輝 西能
元晴 藤崎
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Sumitomo Seika Chemicals Co Ltd
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Sumitomo Seika Chemicals Co Ltd
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Application filed by Sumitomo Seika Chemicals Co Ltd filed Critical Sumitomo Seika Chemicals Co Ltd
Priority to EP21812568.0A priority Critical patent/EP4159802A4/en
Priority to JP2022526625A priority patent/JP7756080B2/ja
Priority to CN202180030619.5A priority patent/CN115461416A/zh
Priority to KR1020227035629A priority patent/KR20230016615A/ko
Priority to US17/999,761 priority patent/US20230227649A1/en
Publication of WO2021241662A1 publication Critical patent/WO2021241662A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D21H17/375—Poly(meth)acrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
    • 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
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/06—Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/66—Salts, e.g. alums
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06—Paper forming aids
    • D21H21/08—Dispersing agents for fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/262—Alkali metal carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/324—Alkali metal phosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive

Definitions

  • the present invention relates to a water-soluble polymer composition, a water-soluble polymer aqueous solution, an industrial chemical, a method for producing a water-soluble polymer aqueous solution, a kit, and a method for producing paper.
  • Water-soluble polymers such as polyalkylene oxides are used as industrial chemicals (for example, papermaking thickeners, flocculants, dispersants, sedimentation accelerators, etc.) in various industrial applications such as papermaking applications, mining applications, cement applications, and dyeing applications. Widely used (see Patent Document 1). In these fields, the water-soluble polymer is generally used as an aqueous solution of about 1 ppm to 15%.
  • iron ions are contained in the water used for preparing the water-soluble polymer aqueous solution, for example, when industrial water is used or iron rust is formed on the pipe. Sometimes.
  • paper is made by dispersing the paper material in water, diluting it, and then placing it on a wire (net) to remove the water (wire part).
  • a papermaking adhesive such as a water-soluble polymer is blended in the water to increase the viscosity of the water in which the paper material (pulp fiber) is dispersed to uniformly disperse the paper material and prevent sedimentation.
  • the papermaking adhesive is dissolved in water or diluted with water, it takes a predetermined time to be blended in the aqueous dispersion of the paper material and the paper material is made into paper.
  • the present inventors have diligently studied to solve the above-mentioned problems.
  • the water-soluble polymer, the phenolic antioxidant, and the inorganic salt excluding the transition metal salt are contained, and the content of the inorganic salt is 0.001 to 10 parts by mass with respect to 100 parts by mass of the water-soluble polymer. It has been found that when the water-soluble polymer composition set in the range is a water-soluble polymer aqueous solution containing iron ions, the decrease in viscosity of the water-soluble polymer aqueous solution with time is suppressed.
  • the present invention is an invention that has been completed through further diligent studies based on such findings.
  • the present invention provides an invention having the following configuration.
  • Item 1. It contains at least a water-soluble polymer, a phenolic antioxidant, and an inorganic salt excluding transition metal salts.
  • a water-soluble polymer composition having a content of the inorganic salt of 0.001 to 10 parts by mass with respect to 100 parts by mass of the water-soluble polymer.
  • the water-soluble polymer is a group consisting of a (meth) acrylamide homopolymer, a neutralized product of a (meth) acrylamide- (meth) acrylic acid copolymer, polyethylene oxide, polypropylene oxide, and an ethylene oxide-propylene oxide copolymer.
  • the water-soluble polymer composition according to Item 1 which is at least one polymer selected from the above.
  • Item 3. Item 2. The water-soluble polymer composition according to Item 1 or 2, wherein the inorganic salt is neutral or alkaline in the aqueous solution state.
  • Item 4. Item 6. The water-soluble polymer composition according to any one of Items 1 to 3, wherein the content of the phenolic antioxidant is 0.001 to 5 parts by mass with respect to 100 parts by mass of the water-soluble polymer.
  • Item 6. Item 6.
  • Item 8. A water-soluble polymer aqueous solution containing the water-soluble polymer composition according to any one of Items 1 to 6, iron ions, and water.
  • Item 8. An industrial chemical containing the water-soluble polymer composition according to any one of Items 1 to 6.
  • Item 9. A method for producing an aqueous solution of a water-soluble polymer, comprising a step of mixing the water-soluble polymer composition according to any one of Items 1 to 6 with an aqueous solution containing iron ions.
  • Item 11. Item 2. The method for producing a water-soluble polymer aqueous solution using the kit according to Item 10.
  • the step of mixing the mixed solution and the first agent A method for producing a water-soluble polymer aqueous solution.
  • a water-soluble polymer composition in which a decrease in viscosity with time is suppressed when an aqueous solution containing iron ions is used. Further, according to the present invention, it is also possible to provide a water-soluble polymer aqueous solution, an industrial chemical, a method for producing a water-soluble polymer aqueous solution, a kit, and a method for producing paper using the water-soluble polymer composition.
  • Example 3 is a graph showing the evaluation results of the water-soluble polymer compositions of Example 3 and Comparative Example 1 as a papermaking viscous agent (graph showing the relationship between the viscosity of a 0.2% aqueous solution and the degree of anti-water drainage).
  • the water-soluble polymer composition of the present invention is characterized by containing at least a water-soluble polymer, a phenolic antioxidant, and an inorganic salt other than a transition metal salt.
  • the water-soluble polymer composition of the present invention preferably suppresses a decrease in viscosity with time when it is made into an aqueous solution containing iron ions.
  • the water-soluble polymer composition of the present invention a water-soluble polymer aqueous solution, an industrial chemical, a method for producing a water-soluble polymer aqueous solution, a kit, and a method for producing paper using the water-soluble polymer composition will be described in detail.
  • the water-soluble polymer composition of the present invention contains at least a water-soluble polymer, a phenolic antioxidant, and an inorganic salt excluding a transition metal salt, and the content of the inorganic salt is 100 parts by mass of the water-soluble polymer. It is 0.001 to 10 parts by mass.
  • Water-soluble polymer The water-soluble polymer contained in the water-soluble polymer composition of the present invention is not particularly limited as long as it is a water-soluble polymer.
  • water-soluble polymers include water-soluble polyalkylene oxides such as polyethylene oxide, polypropylene oxide, and ethylene oxide-propylene oxide copolymers; neutralized products of (meth) acrylamide- (meth) acrylic acid copolymers; (Meta) acrylamide homopolymer; and the like.
  • the copolymer may be a block copolymer or a random copolymer.
  • 1,2-propylene oxide or 1,3-propylene oxide can be usually used, or both can be used in combination.
  • the water-soluble polyalkylene oxide can be produced by a known method, for example, a method of polymerizing the alkylene oxide in the presence of an alkali or a metal catalyst.
  • water-soluble polyalkylene oxides include the product name "PEO” (registered trademark) series of Sumitomo Seika Chemical Co., Ltd., the product name "POLYOX” series of Dow Chemical Co., Ltd., and the product name of Meisei Chemical Works, Ltd.
  • Commercially available products such as the "Alkox” series or the product name "Zeospan” series of Nippon Zeon Co., Ltd. can also be used.
  • the degree of neutralization of the neutralized product of the (meth) acrylamide- (meth) acrylic acid copolymer is preferably 20 to 100%, preferably 40 to 100%.
  • the molecular weight of the water-soluble polymer is preferably 100,000 to 22 million as a viscosity average molecular weight. , 200,000 to 15 million is more preferable.
  • the method for measuring the viscosity average molecular weight is as follows.
  • the viscosity average molecular weight (Mw) of the neutralized product of the (meth) acrylamide homopolymer and the (meth) acrylamide- (meth) acrylic acid copolymer is the (meth) acrylamide homopolymer or the (meth) acrylamide, respectively.
  • Mw The viscosity average molecular weight
  • the neutralized product of the (meth) acrylic acid copolymer is dissolved in 1N sodium nitrate aqueous solution, the ultimate viscosity [ ⁇ ] is obtained at 30 ° C., and the value is calculated using the following conversion formula.
  • Extreme viscosity formula: [ ⁇ ] 3.73 ⁇ 10 -4 ⁇ (Mw) ⁇ 0.66
  • the viscosity at 25 ° C. when an aqueous solution of 0.5% by mass is 10 to 10 to 4000 mPa.
  • the viscosity at 25 ° C. when made into a 5.0% by mass aqueous solution is 50 to 80,000 mPa.
  • the method for measuring the viscosity of the aqueous solution, in which s is preferable, is as follows.
  • ⁇ Measurement of aqueous solution viscosity> The viscosity of the obtained aqueous solution is immersed in a constant temperature bath at 25 ° C. together with the beaker for 30 minutes or more, and measured with a B-type rotational viscometer (rotation speed 12 r / min, 3 minutes, 25 ° C.).
  • the rotor used for the measurement has a rotor No. If it is 1 and is 500 mPa ⁇ s or more and less than 2,500 mPa ⁇ s, the rotor No. If it is 2 and is 2,500 mPa ⁇ s or more and less than 10,000 mPa ⁇ s, the rotor No. It is 3.
  • the water-soluble polymer contained in the water-soluble polymer composition of the present invention may be one kind or two or more kinds.
  • the content ratio (blending) of the water-soluble polymer in the water-soluble polymer composition of the present invention is preferably 70.00% by mass or more (for example, 70.00 to 99.99% by mass), more preferably 80.00% by mass or more (for example, 80.00 to 99.99% by mass), and 90. More preferably, it is 0.00% by mass or more (for example, 90.00 to 99.99% by mass).
  • the inorganic salt other than the transition metal salt contained in the water-soluble polymer composition of the present invention is an inorganic salt that is not a transition metal salt. That is, the inorganic salt does not include iron salts and the like.
  • the inorganic salt is preferably neutral or alkaline in its aqueous solution state. Specifically, it is preferable that the pH of a 40 mmol% aqueous solution of an inorganic salt is 7 or more (for example, 7 to 13).
  • the pH measuring method is a glass electrode method.
  • the inorganic salt is not particularly limited as long as it is not a transition metal salt, but is preferable from the viewpoint of preferably suppressing a decrease in viscosity over time when the water-soluble polymer composition of the present invention is an aqueous solution containing iron ions.
  • Specific examples include carbonates such as potassium carbonate, lithium carbonate, sodium carbonate, magnesium carbonate and sodium hydrogen carbonate; silicates such as sodium silicate; phosphates such as trisodium phosphate; magnesium sulfate, sodium sulfate and the like.
  • the inorganic salt contained in the water-soluble polymer composition of the present invention may be one kind or two or more kinds.
  • the content (blending amount) of the inorganic salt in the water-soluble polymer composition of the present invention May be 0.001 to 10 parts by mass with respect to 100 parts by mass of the water-soluble polymer.
  • the lower limit is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, and the upper limit is about 100 parts by mass of the water-soluble polymer. Is preferably 5 parts by mass or less, more preferably 2 parts by mass or less.
  • the preferred range of the content is 0.001 to 5 parts by mass, 0.001 to 2 parts by mass, 0.01 to 10 parts by mass, 0.01 to 5 parts by mass, 0.01 to 2 parts by mass, and 0. It is 0.05 to 10 parts by mass, 0.05 to 5 parts by mass, 0.05 to 2 parts by mass, and the like.
  • phenolic antioxidant contained in the water-soluble polymer composition of the present invention, a known phenolic antioxidant can be used.
  • the phenolic antioxidant include dibutylhydroxytoluene (BHT), dibutylhydroxyanisole (BHA), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'.
  • the phenolic antioxidant contained in the water-soluble polymer composition of the present invention may be one kind or two or more kinds.
  • the content of the phenolic antioxidant in the water-soluble polymer composition of the present invention ( The lower limit is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and further preferably 0.05 part by mass or more with respect to 100 parts by mass of the water-soluble polymer.
  • the upper limit is preferably 5 parts by mass or less, more preferably 2 parts by mass or less, and further preferably 1 part by mass or less.
  • the preferred range of the content is 0.001 to 5 parts by mass, 0.001 to 2 parts by mass, 0.001 to 1 part by mass, 0.01 to 5 parts by mass, 0.01 to 2 parts by mass, and 0. 0.01 to 1 part by mass, 0.05 to 5 parts by mass, 0.05 to 2 parts by mass, 0.05 to 1 part by mass, and the like.
  • the phenol-based antioxidant 100 is used in the water-soluble polymer composition of the present invention.
  • the ratio of the inorganic salt to parts by mass is preferably 20 to 10,000 parts by mass.
  • the water-soluble polymer composition of the present invention preferably has a pH of 5 to 13 and preferably 6 to 12 when the concentration of the water-soluble polymer dissolved in ion-exchanged water is an aqueous solution of 0.2%. Is preferable.
  • the method for measuring the pH is as follows.
  • the pH is measured in a room temperature (25 ° C.) environment using a commercially available pH meter (for example, a 3-point calibrated pH meter D-51 manufactured by HORIBA, Ltd.), and the pH value at the time when the indicated value stabilizes is read.
  • a commercially available pH meter for example, a 3-point calibrated pH meter D-51 manufactured by HORIBA, Ltd.
  • the water-soluble polymer composition of the present invention may contain various additives (excluding transition metal salts) in addition to the above-mentioned water-soluble polymer, inorganic salt, and phenolic antioxidant.
  • the additive can be appropriately selected depending on the use of the water-soluble polymer composition of the present invention, and known additives in each use can be used.
  • Additives include, for example, antioxidants other than phenolic antioxidants, UV absorbers, fillers, colorants (eg pigments and dyes, etc.), preservatives, rust inhibitors, surfactants, solvents (eg, eg).
  • Examples include organic solvents), fluidity improvers (eg, silica, etc.), viscosity modifiers (eg, hydrophilic silica, water-soluble polymers, etc.), electrolytes, and the like.
  • the additive contained in the water-soluble polymer composition of the present invention may be one kind or two or more kinds.
  • the content of the additive in the water-soluble polymer composition of the present invention can be appropriately set according to the intended use and the like.
  • the properties of the water-soluble polymer composition of the present invention are not particularly limited, and may be, for example, solid at 25 ° C. and 1 atm (for example, powdery (powdered or granular), lumpy, etc.). However, it may be a liquid or a liquid such as a solution or a dispersion.
  • the water-soluble polymer composition of the present invention is liquefied, it is preferable to use water.
  • the water-soluble polymer, the phenolic antioxidant, the inorganic salt excluding the transition metal salt, and water are used. It becomes a water-soluble polymer composition containing.
  • the water-soluble polymer composition of the present invention can be produced by various methods.
  • a solid water-soluble polymer composition can be prepared, for example, by a method of dry blending the required components at once or stepwise.
  • the liquid water-soluble polymer composition can be used, for example, in a method of adding and mixing a composition prepared by dry-blending a required component into a solvent or a dispersion medium to dissolve or disperse it, or in a solvent or a dispersion medium.
  • it can be prepared by a method in which the required components are individually added and mixed at once or stepwise to dissolve or disperse.
  • a solution or dispersion of a water-soluble polymer is prepared, and the above-mentioned inorganic salt, phenolic antioxidant, etc. are added to the solution or dispersion.
  • the concentration of the liquid water-soluble polymer composition can be adjusted by controlling the solvent or dispersion medium used at the time of preparation, or by appropriately removing the solvent or dispersion medium after preparation.
  • the solid water-soluble polymer composition can also be prepared by removing the solvent or dispersion medium from the liquid water-soluble polymer composition and drying it.
  • the solvent or dispersion medium used to prepare the liquid water-soluble polymer composition is water or various organic media, and is not particularly limited.
  • the water that can be used here is usually preferably purified water such as ion-exchanged water or pure water, but may be tap water or industrial water depending on the use of the water-soluble polymer composition.
  • organic media examples include alcohols such as methanol and ethanol, esters such as ethylene carbonate and propylene carbonate, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran, benzene, toluene and Examples thereof include aromatic hydrocarbons such as xylene, polar solvents such as dimethylformamide, chloroform and dichloroethane.
  • the organic medium used may be one kind or two or more kinds.
  • the water-soluble polymer composition of the present invention can be used for industrial chemicals (for example, papermaking viscous agents, flocculants, dispersants, sedimentation accelerators, etc.) in various industrial applications such as papermaking applications, mining applications, cement applications, and dyeing applications. Can be used.
  • the water-soluble polymer composition of the present invention is particularly suitable as a sticky agent for papermaking.
  • the water-soluble polymer composition of the present invention is used in the production of paper, for example, as a viscous agent for paper making
  • the water-soluble polymer composition of the present invention is granulated and mixed with water at the time of use to obtain a water-soluble polymer.
  • the water-soluble polymer can be used so that the concentration of the water-soluble polymer in the aqueous dispersion containing the paper material is, for example, about 1 to 5000 ppm.
  • a water-soluble polymer aqueous solution (including iron ions) prepared by using the water-soluble polymer composition of the present invention as described above and a paper material are mixed. It is a method including a step of preparing an aqueous dispersion of a paper material and a step of making a paper of the obtained aqueous dispersion of the paper material.
  • the method of using the papermaking adhesive in papermaking is known, and even when the water-soluble polymer composition of the present invention is used as the papermaking adhesive, it can be applied to the known papermaking method (paper manufacturing method). can.
  • the water-soluble polymer composition of the present invention can also be applied to known methods when used for other industrial applications.
  • iron ions may be contained in the water used for preparing the alkylene oxide aqueous solution, for example, when industrial water is used or iron rust is formed on the pipe. May be included.
  • the water-soluble polymer composition of the present invention is a water-soluble polymer aqueous solution containing iron ions, the decrease in viscosity of the water-soluble polymer aqueous solution with time is suppressed. Therefore, an aqueous solution containing iron ions can be used to prepare the aqueous solution of the water-soluble polymer.
  • the water-soluble polymer composition of the present invention can also be a two-agent type kit. That is, the water-soluble polymer composition of the present invention comprises a first agent containing the water-soluble polymer and a phenol-based antioxidant, and a second agent containing an inorganic salt excluding the transition metal salt, and the second agent is an inorganic salt.
  • the ratio of the above is 0.001 to 10 parts by mass with respect to 100 parts by mass of the water-soluble polymer of the first agent.
  • a water-soluble polymer aqueous solution by a method comprising a step of mixing.
  • a method comprising a step of mixing.
  • a water-soluble polymer composition (1) is obtained by dry-blending 1.993 parts by mass of polyethylene oxide having a viscosity average molecular weight of 8 million, 0.0020 parts by mass of dibutylhydroxytoluene (BHT), and 0.0050 parts by mass of potassium carbonate. Manufactured.
  • Example 2 A water-soluble polymer composition (2) is obtained by dry-blending 1.993 parts by mass of polyethylene oxide having a viscosity average molecular weight of 8 million, 0.0020 parts by mass of dibutylhydroxytoluene (BHT), and 0.0050 parts by mass of lithium carbonate. Manufactured. Next, a water-soluble polymer aqueous solution containing iron (II) ions was used in the same manner as in Example 1 except that the water-soluble polymer composition (2) was used instead of the water-soluble polymer composition (1). 2) was manufactured.
  • BHT dibutylhydroxytoluene
  • Example 3 A water-soluble polymer composition (3) is obtained by dry-blending 1.993 parts by mass of polyethylene oxide having a viscosity average molecular weight of 8 million, 0.0020 parts by mass of dibutylhydroxytoluene (BHT), and 0.0050 parts by mass of sodium carbonate. Manufactured. Next, a water-soluble polymer aqueous solution containing iron (II) ions (similar to Example 1) except that the water-soluble polymer composition (3) was used instead of the water-soluble polymer composition (1). 3) was manufactured.
  • BHT dibutylhydroxytoluene
  • Example 4 A water-soluble polymer composition (4) by dry-blending 1.993 parts by mass of polyethylene oxide having a viscosity average molecular weight of 8 million, 0.0020 parts by mass of dibutylhydroxytoluene (BHT), and 0.0050 parts by mass of sodium silicate. Manufactured. Next, a water-soluble polymer aqueous solution containing iron (II) ions was used in the same manner as in Example 1 except that the water-soluble polymer composition (4) was used instead of the water-soluble polymer composition (1). 4) was manufactured.
  • BHT dibutylhydroxytoluene
  • a water-soluble polymer composition (5) is a dry blend of 1.993 parts by mass of polyethylene oxide having a viscosity average molecular weight of 8 million, 0.0020 parts by mass of dibutylhydroxytoluene (BHT), and 0.0050 parts by mass of trisodium phosphate. ) was manufactured.
  • BHT dibutylhydroxytoluene
  • a water-soluble polymer aqueous solution containing iron (II) ions (similar to Example 1) except that the water-soluble polymer composition (5) was used instead of the water-soluble polymer composition (1). 5) was manufactured.
  • Example 6 A water-soluble polymer composition (6) is obtained by dry-blending 1.903 parts by mass of polyethylene oxide having a viscosity average molecular weight of 8 million, 0.0019 parts by mass of dibutylhydroxytoluene (BHT), and 0.0952 parts by mass of lithium carbonate. Manufactured. Next, a water-soluble polymer aqueous solution containing iron (II) ions (similar to Example 1) except that the water-soluble polymer composition (6) was used instead of the water-soluble polymer composition (1). 6) was manufactured.
  • BHT dibutylhydroxytoluene
  • Example 7 A water-soluble polymer composition (7) is obtained by dry-blending 1.816 parts by mass of polyethylene oxide having a viscosity average molecular weight of 8 million, 0.0018 parts by mass of dibutylhydroxytoluene (BHT), and 0.1818 parts by mass of lithium carbonate. Manufactured. Next, a water-soluble polymer aqueous solution containing iron (II) ions (similar to Example 1) except that the water-soluble polymer composition (7) was used instead of the water-soluble polymer composition (1). 7) was manufactured.
  • BHT dibutylhydroxytoluene
  • Example 8 1.993 parts by mass of polyethylene oxide having a viscosity average molecular weight of 8 million and 0.0020 parts by mass of dibutylhydroxytoluene (BHT) were dry-blended to prepare the first agent of the water-soluble polymer composition (8).
  • BHT dibutylhydroxytoluene
  • Example 9 Except for the use of sodium salt of (meth) acrylamide- (meth) acrylic acid copolymer (trade name PAMOL H manufactured by PAM Meisei Kagaku Kogyo Co., Ltd.) instead of 1.993 parts by mass of polyethylene oxide having a viscosity average molecular weight of 8 million. Made a water-soluble polymer composition (9) in the same manner as in Example 2.
  • Example 1 A water-soluble polymer composition (10) was produced in the same manner as in Example 1 except that no inorganic salt was used. Next, a water-soluble polymer aqueous solution containing iron (II) ions (similar to Example 1) except that the water-soluble polymer composition (10) was used instead of the water-soluble polymer composition (1). 10) was manufactured.
  • Example 2 The water-soluble polymer composition (11) was produced in the same manner as in Example 1 except that 0.0050 parts by mass of dibutylhydroxytoluene was used instead of 0.0050 parts by mass of potassium carbonate. Next, a water-soluble polymer aqueous solution containing iron (II) ions (similar to Example 1) except that the water-soluble polymer composition (11) was used instead of the water-soluble polymer composition (1). 11) was manufactured.
  • Example 3 A water-soluble polymer composition (12) was produced in the same manner as in Example 1 except that 0.0050 parts by mass of 2-mercaptobenzothiazole was used instead of 0.0050 parts by mass of potassium carbonate. Next, a water-soluble polymer aqueous solution containing iron (II) ions (similar to Example 1) except that the water-soluble polymer composition (12) was used instead of the water-soluble polymer composition (1). 12) was manufactured.
  • Example 4 A water-soluble polymer composition (13) was produced in the same manner as in Example 1 except that 0.0050 parts by mass of zinc stearate was used instead of 0.0050 parts by mass of potassium carbonate. Next, a water-soluble polymer aqueous solution containing iron (II) ions (similar to Example 1) except that the water-soluble polymer composition (13) was used instead of the water-soluble polymer composition (1). 13) was manufactured.
  • Example 5 A water-soluble polymer composition (14) was produced in the same manner as in Example 1 except that 0.0050 parts by mass of magnesium oxide was used instead of 0.0050 parts by mass of potassium carbonate. Next, a water-soluble polymer aqueous solution containing iron (II) ions (similar to Example 1) except that the water-soluble polymer composition (14) was used instead of the water-soluble polymer composition (1). 14) was manufactured.
  • Example 6 A water-soluble polymer composition (15) was produced in the same manner as in Example 2 except that dibutylhydroxytoluene (BHT) was not used. Next, a water-soluble polymer aqueous solution containing iron (II) ions (similar to Example 1) except that the water-soluble polymer composition (15) was used instead of the water-soluble polymer composition (1). 15) was manufactured.
  • BHT dibutylhydroxytoluene
  • the viscosities of the water-soluble polymer aqueous solutions produced in Examples 1 to 9 and Comparative Examples 1 to 7 immediately after production (aqueous solution storage days 0 days) and the viscosities after 24 hours (aqueous solution storage days 1 day) are as follows. It was measured under the condition of. The viscosity was measured using a B-type rotational viscometer (TOKIMEC Co., Ltd., rotor No. 1, measurement conditions: rotation speed 30 rpm, 3 minutes). The 24-hour storage was carried out by placing a 25 ° C. water-soluble polymer aqueous solution in a glass container containing 500 mL.
  • the glass container was kept sealed in a constant temperature and humidity chamber (model number: ESPEC: PR-2ST) at 40 ° C. and 75% RH.
  • a glass container containing a water-soluble polymer aqueous solution was taken out from a constant temperature and humidity chamber, immersed in a constant temperature bath at room temperature (25 ° C.) for about 60 minutes, and then the viscosity was measured.
  • Table 1 shows the measured viscosity (mPa ⁇ s), viscosity retention rate (%), and pH.
  • the pH was measured using a pH meter D-51 manufactured by HORIBA, Ltd., which had been calibrated at three points, and the pH value at the time when the indicated value became stable was read.
  • Example 9 in which the sodium salt of the (meth) acrylamide- (meth) acrylic acid copolymer was used as the water-soluble polymer, the water-soluble polymer aqueous solution (9) containing the iron (II) ion of Example 9 was used.
  • aqueous solution containing only water and a sodium salt of polyethylene oxide or a (meth) acrylamide- (meth) acrylic acid copolymer without blending iron (II) ions, phenolic antioxidants, and inorganic salts in the composition ( Based on the viscosity of 0).
  • the formula for calculating the viscosity retention rate is as follows. The larger the decrease in viscosity retention rate from immediately after production to 1 day, the greater the decrease in viscosity over time.
  • Viscosity retention rate ( ⁇ Viscosity of polyethylene oxide aqueous solution at each time point [mPa ⁇ s] / Viscosity of polyethylene oxide aqueous solution (0) at day 0 [mPa ⁇ s] ⁇ ⁇ 100)
  • the degree of anti-filtration water indicates the degree of delay in the filtration rate, and is considered to be due to the filter effect due to the pulp being uniformly dispersed and filtered, and the viscosity of the papermaking adhesive fixed on the pulp. Therefore, it can be seen that the water-soluble polymer aqueous solution of Example 3 has a high degree of anti-drainage and is excellent in uniform dispersibility of the paper material in water when used for papermaking.
  • Anti-drainage degree amount of drainage [addition of water-soluble polymer composition 0 ppm] (mL) -amount of drainage [water-soluble polymer composition: amount of addition] (mL))

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