CN111663366A - Dispersion for papermaking chemicals, paper strength enhancer containing the same, drainage enhancer, and yield enhancer - Google Patents
Dispersion for papermaking chemicals, paper strength enhancer containing the same, drainage enhancer, and yield enhancer Download PDFInfo
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- CN111663366A CN111663366A CN202010139600.1A CN202010139600A CN111663366A CN 111663366 A CN111663366 A CN 111663366A CN 202010139600 A CN202010139600 A CN 202010139600A CN 111663366 A CN111663366 A CN 111663366A
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- 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
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- 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
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- 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
- D21H21/18—Reinforcing agents
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Abstract
The present invention relates to a dispersion liquid for papermaking chemicals, a paper strength enhancing agent, a drainage improving agent, and a yield improving agent each containing the dispersion liquid for papermaking chemicals. The purpose of the present invention is to provide a dispersion for papermaking chemicals which does not generate aggregates during polymerization and has excellent paper strength effects, drainage effects, and yield effects. The invention uses a dispersion liquid for a papermaking chemical, which comprises a (meth) acrylamide polymer (A), the dispersion liquid comprising at least 2 inorganic salts (B), the component (B) comprising at least 2 kinds selected from inorganic ammonium salts, inorganic sodium salts and inorganic potassium salts, the dispersion liquid having a tensile viscosity of 40 to 200mm when made into a 0.5 wt% aqueous solution by the concentration of the solid component of the component (A), and the intrinsic viscosity (temperature 25 ℃) of a liquid obtained by diluting the dispersion liquid with 1 equivalent of NaCl aqueous solution being 10 to 30 dl/g.
Description
Technical Field
The present invention relates to a dispersion liquid for papermaking chemicals, a paper strength enhancing agent, a drainage improving agent, and a yield improving agent each containing the dispersion liquid for papermaking chemicals.
Background
In the papermaking process, various papermaking chemicals are added to raw pulp depending on the desired performance and application, and for example, a paper strength enhancer is used to improve the strength of paper, a drainage enhancer is used to improve the drainage effect, and a yield enhancer is used to improve the yield effect of pulp fines in paper, papermaking chemicals/ash, and the like.
There are various forms of such papermaking chemicals. For example, as chemicals having paper strength enhancing, drainage and yield effects, there are a dispersion liquid obtained by dispersion-polymerizing a monomer component mainly containing acrylamide in an aqueous salt solution (patent document 1). As such a dispersion liquid for a papermaking chemical, a dispersion liquid having a high intrinsic viscosity is suitable in order to improve the effect of improving the yield of pulp fines in paper, papermaking internal chemicals/ash, and the like.
As a dispersion liquid for papermaking chemicals having a high intrinsic viscosity, for example, a dispersion liquid containing a high molecular weight water-soluble polymer having an intrinsic viscosity in a range of 18 to 25dl/g under specific conditions, which is obtained by adding a specific amount of a polymerization-delaying substance together with a vinyl monomer or a vinyl monomer mixture and stirring the mixture to disperse and polymerize the mixture, in the coexistence of a high molecular weight dispersant soluble in a salt water solution, is disclosed (patent document 2). However, in this dispersion, the produced particles may be aggregated to cause dispersion failure, or the paper-making effect, drainage effect, and yield effect may be deteriorated.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2003-73566
Patent document 2: japanese patent laid-open No. 2008-56752
Disclosure of Invention
Problems to be solved by the invention
The invention aims to provide a dispersion liquid for papermaking chemicals, which does not generate aggregates during polymerization and has excellent paper force effect, water filtration effect and yield effect.
Means for solving the problems
The present inventors have conducted intensive studies and, as a result, have found that: the present inventors have completed the present invention by solving the above problems by using a combination of a plurality of specific salts and a dispersion liquid for papermaking chemicals to exhibit a predetermined extensional viscosity. That is, the present invention relates to the following dispersion liquid for a papermaking chemical, a paper strength enhancer, a drainage enhancer and a yield enhancer each comprising the dispersion liquid for a papermaking chemical.
1. A dispersion for a papermaking chemical, which comprises a (meth) acrylamide polymer (A),
the dispersion contains 2 or more salts (B) selected from ammonium salts, sodium salts and potassium salts,
the extensional viscosity of the dispersion when it is made into a 0.5 wt% aqueous solution based on the solid content concentration of the component (A) is 40 to 200mm,
the intrinsic viscosity (temperature 25 ℃) of a liquid obtained by diluting the dispersion with 1 equivalent of NaCl aqueous solution is 10 to 30 dl/g.
2. The dispersion liquid for papermaking chemicals according to claim 1, wherein the component (A) comprises a polymer of a monomer component containing (meth) acrylamide (a1) and a cationic unsaturated monomer (a 2).
3. The dispersion liquid for a papermaking chemical according to the above 2, wherein the component (a2) is a tertiary amino group-containing (meth) acrylic acid ester and/or a quaternary salt of the (meth) acrylic acid ester.
4. The dispersion liquid for a papermaking chemical according to claim 2 or 3, wherein the monomer component further contains an anionic unsaturated monomer (a 3).
5. The dispersion liquid for papermaking chemicals according to claim 4, wherein the component (a3) is at least 1 selected from the group consisting of acrylic acid, itaconic acid, and itaconic anhydride.
6. The dispersion liquid for a papermaking chemical as described in any one of the above 1 to 5, wherein the component (B) contains ammonium sulfate and further contains sodium sulfate and/or sodium chloride.
7. The dispersion for papermaking chemicals according to any one of 1 to 6, wherein the content of the component (B) is 15 to 45% by weight based on 100% by weight of the dispersion for papermaking chemicals.
8. The dispersion liquid for a papermaking chemical as described in any one of the above 1 to 7, further comprising a polymeric dispersant (C) and/or a polyol (D).
9. A paper strength enhancing agent comprising the dispersion for papermaking chemicals according to any one of 1 to 8.
10. A drainage enhancer comprising the dispersion for papermaking chemicals according to any one of 1 to 8.
11. A yield improver comprising the dispersion for a papermaking chemical according to any one of 1 to 8.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the dispersion liquid for papermaking chemicals of the present invention, since 2 kinds of specific salts are contained in the liquid, the particles produced at the time of polymerization are favorably dispersed without being incorporated or the like, and no aggregates are produced. The dispersion liquid for a papermaking chemical is adjusted to have a specific elongational viscosity in addition to the intrinsic viscosity, thereby exhibiting excellent paper strength effects, drainage effects, and yield effects.
Detailed Description
The dispersion liquid for papermaking chemicals of the present invention contains a (meth) acrylamide polymer (a) (hereinafter referred to as component (a)), and the dispersion liquid contains a specific 2 or more kinds of salts (B) (hereinafter referred to as component (B)).
< composition of (A) >
The component (a) is not particularly limited as long as it is a (meth) acrylamide polymer, and is preferably a polymer of a monomer component containing (meth) acrylamide (a1) (hereinafter referred to as a (a1) component) and a cationic unsaturated monomer (a2) (hereinafter referred to as a (a2) component) in terms of improving self-adsorption of the component (a) to pulp. The term "unsaturated monomer" refers to a monomer having one or more double or triple bonds in the molecule of the monomer 1 (the same applies hereinafter).
(a1) Examples of the component (B) include acrylamide and methacrylamide.
The content of the component (a1) is not particularly limited, and is usually about 10 to 99 mol%, preferably about 15 to 95 mol%, and more preferably 50 to 90 mol%, based on 100 mol% of the total of all monomer components.
The component (a2) is not particularly limited, and various known materials can be used, including, for example, unsaturated monomers containing secondary amino groups, unsaturated monomers containing tertiary amino groups, and quaternary salts of these unsaturated monomers.
The secondary amino group-containing unsaturated monomer is not particularly limited, and examples thereof include diallylamine. The tertiary amino group-containing unsaturated monomer is not particularly limited, and examples thereof include tertiary amino group-containing (meth) acrylic esters such as N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate; and tertiary amino group-containing (meth) acrylamides such as N, N-dimethylaminopropyl (meth) acrylamide and N, N-diethylaminopropyl (meth) acrylamide. The quaternary salt of these monomers is a quaternary salt obtained by reacting the above-mentioned unsaturated monomer containing a secondary amino group or unsaturated monomer containing a tertiary amino group with a quaternary salinization agent, and the quaternary salt may be an inorganic acid salt such as a hydrochloride or a sulfate, or an organic acid salt such as an acetate. The quaternizing agent may be methyl chloride, benzyl chloride, dimethyl sulfuric acid, epichlorohydrin, or the like. These may be used alone, or 2 or more of them may be used in combination. Among them, the (meth) acrylic acid ester containing a tertiary amino group and/or a quaternary salt of the (meth) acrylic acid ester are preferably contained, and the chloromethane salt of N, N-dimethylaminoethyl acrylate and the benzylchloride salt of N, N-dimethylaminoethyl acrylate are more preferably contained, from the viewpoint that the produced component (a) has a high extensional viscosity and a moderate hydrophobicity, thereby being easily made into particles and being easily dispersed in an aqueous solution containing the component (B). The term (meth) acrylate refers to methacrylate or acrylate (the same applies hereinafter).
(a2) The content of the component (a) is not particularly limited, and is usually about 1 to 45 mol%, preferably about 5 to 40 mol%, and more preferably about 10 to 30 mol% based on 100 mol% of the total monomer components, in terms of molar ratio, from the viewpoint of obtaining the component (a) having a higher molecular weight and exhibiting excellent paper strength effect, drainage effect, and yield effect.
The monomer component preferably further contains an anionic unsaturated monomer (a3) (hereinafter referred to as (a3) component). By including the component (a3), the produced component (a) can be easily dispersed in an aqueous solution containing the component (B).
The component (a3) is not particularly limited, and various known substances can be used, and examples thereof include α, β -unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; α, β -unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, muconic acid, and citraconic acid; unsaturated carboxylic acid anhydrides such as (meth) acrylic anhydride, maleic anhydride and itaconic anhydride; organic sulfonic acids such as vinylsulfonic acid and styrenesulfonic acid; sodium salts, potassium salts, etc. of these acids. These may be used alone, or 2 or more of them may be used in combination. Among these, α, β -unsaturated monocarboxylic acid, α, β -unsaturated dicarboxylic acid, and unsaturated carboxylic acid anhydride are preferable, and at least 1 selected from acrylic acid, itaconic acid, and itaconic anhydride is more preferable, from the viewpoint of obtaining component (a) having a higher molecular weight and exhibiting excellent paper strength effect, drainage effect, and yield effect.
(a3) The content of the component (a) is not particularly limited, and is usually 40 mol% or less, preferably 30 mol% or less, and more preferably 25 mol% or less, based on 100 mol% of the total monomer components, in terms of molar ratio, in order to obtain a component (a) having a higher molecular weight and exhibit excellent paper strength effect, drainage effect, and yield effect.
The monomer component may contain an unsaturated monomer (a4) (hereinafter referred to as component (a 4)) other than components (a1) to (a 3).
The component (a4) is not particularly limited, and various known substances can be used. Examples of the component (a4) include N-alkyl (meth) acrylamides such as N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, and N-isopropyl (meth) acrylamide; n, N-dialkyl (meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N, N-diethyl (meth) acrylamide; n, N ' -alkylenebis (meth) acrylamides such as N, N ' -methylenebis (meth) acrylamide and N, N ' -ethylenebis (meth) acrylamide; alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylate; (meth) acrylates having polyalkylene glycol groups such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, polytrimethylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, polyethylene glycol propylene glycol mono (meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate; unsaturated monomers having an allyl group such as allyl (meth) acrylate, triallyl trimellitate, triallyl isocyanurate, triallylamine, tetraallyl pyromellitate, N-allyl (meth) acrylamide, and N, N-diallyl (meth) acrylamide; aromatic unsaturated monomers such as divinylbenzene, styrene, α -methylstyrene and vinyltoluene; monovinyl esters such as vinyl acetate and vinyl propionate; divinyl esters such as divinyl adipate and divinyl sebacate; triazines having a (meth) acryloyl group such as 1, 3, 5-tri (meth) acryloyl-1, 3, 5-triazine, 1, 3, 5-tri (meth) acryloyl hexahydro-1, 3, 5-triazine, and the like; diacetone (meth) acrylamide, N-methylol (meth) acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, and the like.
The amount of the component (a4) used is not particularly limited, and the total amount of all monomer components is 100 mol%, preferably 5 mol% or less in terms of molar ratio.
Further, other components not belonging to the monomer component may be used. Examples of the other component include thiols such as 2-mercaptoethanol and n-dodecylmercaptan; methallyl sulfonates such as sodium methallyl sulfonate, potassium methallyl sulfonate and ammonium methallyl sulfonate; aliphatic alcohols such as ethanol, isopropanol and pentanol; chain transfer agents such as alpha-methylstyrene dimer, carbon tetrachloride, ethylbenzene, cumene, 2, 4-diphenyl-4-methyl-1-pentene and the like; organic acids such as citric acid, succinic acid, and oxalic acid; inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide and the like; defoaming agents, antioxidants, preservatives, and the like. These may be used alone, or 2 or more of them may be used in combination. The content is not particularly limited, and is preferably 5% by weight or less based on 100% by weight of the dispersion for papermaking chemicals containing a solvent such as water.
(B) The component is more than 2 kinds of salts selected from ammonium salt, sodium salt and potassium salt. Since the salting-out effect is enhanced by containing 2 or more kinds of salts, the produced component (a) becomes particulate without being combined or the like, and is easily dispersed in an aqueous solution containing the component (B).
The content of the component (B) is not particularly limited, and is preferably 15 to 45 wt%, more preferably 15 to 40 wt%, and particularly preferably 15 to 35 wt% with respect to 100 wt% of the dispersion for papermaking chemicals, in order to obtain particles of the component (a) without coalescence or gelation and to exhibit excellent paper strength effect, drainage effect, and yield effect.
The ammonium salt is not particularly limited, and examples thereof include organic ammonium salts such as ammonium acetate, ammonium propionate, ammonium oxalate, ammonium citrate, ammonium succinate and tetramethylammonium chloride; inorganic ammonium salts such as ammonium chloride, ammonium bromide, ammonium iodide, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium hydrogen carbonate and ammonium carbonate. These may be used alone, or 2 or more of them may be used in combination.
The sodium salt is not particularly limited, and examples thereof include organic sodium salts such as sodium acetate, sodium propionate, sodium oxalate, sodium citrate, and sodium succinate; and inorganic sodium salts such as sodium chloride, sodium bromide, sodium iodide, sodium nitrate, sodium sulfate, sodium phosphate, sodium hydrogen carbonate, and sodium carbonate. These may be used alone, or 2 or more of them may be used in combination.
The potassium salt is not particularly limited, and examples thereof include organic potassium salts such as potassium acetate, potassium propionate, potassium oxalate, potassium citrate, and potassium succinate; and inorganic potassium salts such as potassium chloride, potassium bromide, potassium iodide, potassium nitrate, potassium sulfate, potassium phosphate, potassium hydrogen carbonate, and potassium carbonate. These may be used alone, or 2 or more of them may be used in combination.
Among them, from the viewpoint of promoting granulation of the component (a) produced during polymerization and good dispersion, inorganic ammonium salts and inorganic sodium salts are preferable, and sodium sulfate and/or sodium chloride containing ammonium sulfate is more preferable.
The content of the inorganic ammonium salt and the inorganic sodium salt is not particularly limited, and in order to obtain the component (a) having a higher molecular weight and to exhibit excellent paper strength effect, drainage effect and yield effect, the ratio of (inorganic ammonium salt)/(inorganic sodium salt) is preferably about 99/1 to 10/90, more preferably 97/3 to 25/75, and particularly preferably 95/5 to 40/60, in terms of the weight ratio of the solid content.
The dispersion liquid for papermaking chemicals of the present invention can be obtained by various known production methods, and from the viewpoint of obtaining a component (a) having a higher molecular weight and exhibiting excellent paper strength effect, drainage effect and yield effect, a method of performing dispersion polymerization of the components (a1) and (a2) and, if necessary, the components (a3), the component (a4) and the component (a5) in a saline solution having a saturated concentration or less of the component (B) (hereinafter, also simply referred to as "saline solution") in the presence of a polymerization initiator is preferable. The monomer component may be added dropwise, and further, 1 or more kinds of salts may be added during or after the polymerization. Further, the polymerization initiator may be added at once, or may be added in portions.
The conditions for the dispersion polymerization are not particularly limited, and the temperature is, for example, preferably about 15 to 70 ℃ and more preferably about 30 to 60 ℃. The time is preferably about 3 to 30 hours, and more preferably about 6 to 18 hours.
The concentration of the aqueous salt solution is not more than the saturation concentration. This allows the component (a) produced by dispersion polymerization to precipitate as particles, thereby producing a dispersion liquid for papermaking chemicals. From the same viewpoint, the concentration is preferably 15% by weight or more and not more than the saturation concentration.
The polymerization initiator is not particularly limited, and examples thereof include persulfates such as ammonium persulfate, potassium persulfate, and calcium persulfate; azo polymerization initiators such as 2, 2 '-azobis (2-amidinopropane) hydrochloride and 2, 2' -azobis [2- (2-imidazolin-2-yl) propane ] hydrochloride. Among these, 2 '-azobis (2-amidinopropane) hydrochloride and 2, 2' -azobis [2- (2-imidazolin-2-yl) propane ] hydrochloride are preferable because they hardly cause a crosslinking reaction in dispersion polymerization.
The amount of the polymerization initiator used is not particularly limited, but is usually about 0.02 to 0.3 parts by weight, preferably about 0.04 to 0.2 parts by weight, based on 100 parts by weight of the total monomer components (solid components).
In the dispersion polymerization, it is preferable to contain a polymer dispersant (C) (hereinafter referred to as component (C)) and/or a polyol (D) (hereinafter referred to as component (D)) in order that the particles of the component (a) to be produced are well dispersed in an aqueous solution containing the component (B).
(C) The component (c) is not particularly limited as long as it is a polymer dispersant, and examples thereof include a copolymer containing 30 to 99.99 mol% of a cationic radical polymerizable monomer (c1) (hereinafter also referred to as a (c1) component) and 0.01 to 1 mol% of a sulfonic acid group-containing monomer and/or a salt thereof (c2) (hereinafter also referred to as a (c2) component). By using the component (C), the component (a) can be easily dispersed in an aqueous solution.
The component (c1) is not particularly limited, and examples thereof include tertiary amino group-containing unsaturated monomers such as N, N-dimethylaminoethyl (meth) acrylate, N-diethylaminoethyl (meth) acrylate, N-dimethylaminopropyl (meth) acrylamide, and N, N-diethylaminopropyl (meth) acrylamide; salts of unsaturated monomers having a tertiary amino group, quaternary salt compounds obtained by reacting unsaturated monomers having a tertiary amino group with a quaternizing agent, and the like. The salt may be an inorganic acid salt such as a hydrochloride or a sulfate, or an organic acid salt such as an acetate. The quaternizing agent may be methyl chloride, benzyl chloride, dimethyl sulfuric acid, epichlorohydrin, or the like. These may be used alone, or 2 or more of them may be used in combination. Among them, preferred are a quaternary salt of N, N-dimethylaminoethyl acrylate and a quaternary salt of N, N-dimethylaminoethyl methacrylate, from the viewpoint of maintaining the solubility of the component (a) in the aqueous solution containing the component (B) and dispersing it well.
The component (c2) is not particularly limited as long as it is a monomer and/or a salt thereof having at least one sulfonic acid group and one unsaturated double bond. Examples thereof include unsaturated monomers having a (meth) allyl group and a sulfonic acid group such as allylsulfonic acid, calcium allylsulfonate, methallylsulfonic acid, calcium methallylsulfonate, and ammonium methallylsulfonate, and salts thereof; vinylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and the like. These may be used alone, or 2 or more of them may be used in combination. Among them, from the viewpoint of facilitating the generation of movement of radicals (chain transfer) and the adjustment of molecular weight and crosslinking structure, an unsaturated monomer having a (meth) allyl group and a sulfonic acid group or a salt thereof is preferable, and sodium (meth) allylsulfonate is more preferable.
The reactant of component (C) may contain, if necessary, unsaturated monomers (C3) other than components (C1) to (C2) (hereinafter also referred to as component (C3)) as long as components (C1) and (C2) are contained in the above-described usage amount range. The component (c3) is not particularly limited, and examples thereof include N, N-dialkyl (meth) acrylamides such as N, N-dimethylacrylamide, N-diethyl (meth) acrylamide, and N, N-diisopropyl (meth) acrylamide; n-alkyl (meth) acrylamides such as N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N-tert-butyl (meth) acrylamide; n, N ' -alkylenebis (meth) acrylamides such as N, N ' -methylenebis (meth) acrylamide and N, N ' -ethylenebis (meth) acrylamide; triazines having a (meth) acryloyl group such as 1, 3, 5-triacryloylhexahydro-1, 3, 5-triazine; aromatic unsaturated monomers such as styrene, alpha-methylstyrene and vinyltoluene; alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylate; vinyl esters such as vinyl acetate and vinyl propionate; unsaturated carboxylic acids such as (meth) acrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, and citraconic anhydride; acrylamide, methacrylamide, and the like. These may be used alone, or 2 or more of them may be used in combination. Among them, acrylamide, N-dimethylacrylamide and N, N-methylenebisacrylamide are preferable in terms of high copolymerizability with the components (c1) and (c 2). (c3) The amount of component (c) used is less than 50 mol% based on 100 mol% of the total amount of components (c1) to (c 3).
(C) The amount of the component (a) used is not particularly limited, but is preferably about 1 to 15 parts by weight, more preferably about 1 to 13 parts by weight, and still more preferably about 1 to 10 parts by weight, based on 100 parts by weight of the component (a), from the viewpoint of assisting the dispersion of the particles of the component (a) to be produced and increasing the molecular weight of the particles.
(D) Component (b) is used to disperse the particles of component (a) produced. The component (D) is not particularly limited, and examples thereof include ethylene glycol, propylene glycol, glycerin, pentaerythritol, polyethylene glycol, polypropylene glycol, sorbitol, and the like. These may be used alone, or 2 or more of them may be used in combination. Among these, from the viewpoint of solubility in water and reduction in environmental load, a polyhydric alcohol having 2 to 10 carbon atoms is preferable, and ethylene glycol is more preferable.
(D) The amount of the component (a) used is not particularly limited, but is preferably about 1 to 15 parts by weight, more preferably about 1 to 10 parts by weight, based on 100 parts by weight of the component (a), from the viewpoint of assisting the dispersion of the particles of the component (a) to be produced.
As the physical properties of the dispersion liquid for papermaking chemicals containing the obtained component (a), the extensional viscosity (hereinafter, simply referred to as "extensional viscosity") when the solid content concentration of the component (a) is made into a 0.5 wt% aqueous solution is important. The elongational viscosity is an index indicating the drawability of an aqueous solution obtained by diluting a so-called dispersion liquid for a papermaking chemical, and is a value obtained by measuring the length of a yarn drawn from the liquid surface of the aqueous solution. In the present invention, the higher the extensional viscosity, the higher the drainage effect and yield effect of the dispersion.
In the present invention, a dispersion liquid for a papermaking chemical is prepared into an aqueous solution of 0.5 wt% in terms of the solid content concentration of the component (A), and the aqueous solution is placed in a special rod, pulled up at a constant speed using a material testing machine (manufactured by Roid Corporation) or the like, and the length (unit: mm) of the filament stretched at that time is taken as the value of the elongational viscosity. The solid content concentration of component (a) can be calculated from the following (formula 1) using the total solid content weight of the monomer components (a1) to (a4) constituting component (a) and the weight of the entire dispersion for a papermaking chemical (the same applies hereinafter).
(formula 1) { (A) component solid concentration } (%)
(total of solid contents of monomer components constituting component (a))/(total weight of dispersion liquid for papermaking chemicals) ] × 100
The extensional viscosity is usually 40 to 200 mm. If the extensional viscosity is less than 40mm, the coagulation of pulp becomes weak when the dispersion for papermaking chemicals containing the component (a) is added, and the drainage effect and yield effect also become liable to be lowered. When the particle size exceeds 200mm, the pulp is excessively coagulated and paper breakage is likely to occur or the texture is disturbed when the dispersion liquid for papermaking chemicals containing the component (a) is added, and the paper strength effect is also likely to deteriorate. From the same viewpoint, the extensional viscosity is preferably 40 to 200mm, more preferably 50 to 180 mm.
Further, as the physical properties of the dispersion liquid for a papermaking chemical, the intrinsic viscosity (temperature 25 ℃) of a liquid obtained by diluting with 1 equivalent of an aqueous NaCl solution (hereinafter, also referred to as "intrinsic viscosity") is also an important parameter in order to exhibit excellent paper strength effect, drainage effect, and yield effect. In the present invention, a dispersion for a papermaking chemical is diluted with a 1-equivalent aqueous NaCl solution to prepare a plurality of dilutions having different solid content concentrations of component (a), and the falling time (t) is measured for each dilution using a UBBELOHDE viscometer. Next, the falling time (t0) was measured similarly with only 1 equivalent of NaCl aqueous solution, the specific viscosity (η sp) was obtained by (equation 2), the value obtained by dividing the specific viscosity by the solid content concentration of component (a) was plotted on the vertical axis, the solid content concentration of component (a) was plotted on the horizontal axis, and the intercept of the obtained straight line was taken as the measured value of the intrinsic viscosity. The NaCl was sodium chloride (the same applies hereinafter).
(formula 2) specific viscosity (. eta.sp) (t/t0) -1
The intrinsic viscosity is usually 10 to 30 dl/g. When the intrinsic viscosity is less than 10dl/g, the coagulation of pulp is weak when the dispersion liquid for papermaking chemicals containing the component (a) is added, and the drainage effect and the yield effect are difficult to be exhibited. If the amount exceeds 30dl/g, the pulp tends to excessively coagulate and to cause paper breakage or a disorder in texture, and the paper strength effect tends to be deteriorated when the dispersion liquid for papermaking chemicals containing the component (a) is added. For the same reason as above, the intrinsic viscosity is preferably 10 to 30dl/g, more preferably 12 to 25 dl/g.
Other physical properties of the dispersion for a papermaking chemical are not particularly limited, and for example, the viscosity of a diluted solution (at 25 ℃) obtained by diluting the dispersion with 0.5 equivalent of an aqueous solution of NaCl so that the solid content concentration of the component (a) is 0.5% is preferably about 20 to 300mPa · s, and more preferably about 50 to 200mPa · s.
The particle size of the dispersion for papermaking chemicals is preferably about 0.1 to 150 μm, and more preferably about 0.1 to 100 μm, from the viewpoint of satisfactory dispersion in an aqueous solution containing component (B) and excellent paper strength effect, drainage effect and yield effect.
For the present invention, a paper strength enhancer comprising a dispersion for papermaking chemicals is also one of the present invention. Thus, the paper produced by the papermaking process can exhibit a good paper strength effect.
In the present invention, a drainage enhancer comprising the dispersion for papermaking chemicals is also one aspect of the present invention. This makes it possible to remove water satisfactorily in the dewatering step in the paper making process.
The present invention also provides a yield improving agent for papermaking, which comprises the dispersion liquid for papermaking chemicals. This makes it possible to retain the paper-making chemicals such as pulp fines, paper strength enhancers, sizing agents, and ash in the paper, and to exert the excellent effects of the paper-making chemicals.
The dispersion liquid for papermaking chemicals of the present invention can be added to chemical pulp such as hardwood tree pulp (LBKP), softwood tree pulp (NBKP), and the like, regardless of western paper and horse dung paper; mechanical pulp such as wood pulp (GP), Refiner Ground Pulp (RGP), thermomechanical pulp (TMP), and the like; pulp slurry such as waste paper pulp such as corrugated paper waste paper. The above pulps may be combined in 2 or more kinds. Further, a papermaking chemical such as a sizing agent, a paper strength agent, starch, aluminum sulfate, calcium carbonate, talc or the like may be added to the pulp slurry.
Examples
The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited thereto. In the examples, "%" is based on weight unless otherwise specified. For convenience, monomers and the like are represented by the following abbreviations.
AM: acrylamide
DMAEA-Q: chloromethane salt of N, N-dimethylaminoethyl acrylate
DMAEA-BQ: benzyl chloride salt of N, N-dimethylaminoethyl acrylate
IA: itaconic acid AA: acrylic acid
EG: ethylene glycol IPA: isopropanol (I-propanol)
MBAA: n, N-methylenebisacrylamide
DMAA: n, N-dimethylacrylamide
SMAS: sodium methallyl sulfonate
V-50: 2, 2' -azobis (2-amidinopropane) hydrochloride
[ extensional viscosity ]
An aqueous solution was prepared by diluting a dispersion for a papermaking chemical with ion-exchanged water in advance so that the solid content concentration of the component (a) became 0.5%. 100g of the aqueous solution was put into a 140ml glass container having an inner diameter of 4.5cm, and the temperature was maintained at 25 ℃. Using a rod (material: stainless steel, length 140mm, diameter 2mm) having a ball with a diameter of 10mm attached to the tip, the rod was placed 20mm from the liquid surface in the above aqueous solution with the ball side down, and the rod was lifted up at a speed of 1000 mm/min using an LRX type material tester (manufactured by Roid corporation), and the length (unit: mm) of the filament drawn from the liquid surface was measured.
[ intrinsic viscosity ]
The dispersion liquid for a papermaking chemical was diluted with 1 equivalent of an aqueous NaCl solution so that the concentration of the solid content of component (A) became 0.02g/dl, 0.04g/dl, 0.06g/dl, and 0.08g/dl, and the resulting liquid was kept at 25 ℃ to measure the falling time (t) with a UBBELOHDE viscometer. Similarly, the falling time (t0) of 1 equivalent of the NaCl aqueous solution was also measured, and the specific viscosity (η sp) was calculated by the formula 2.
(formula 2) η sp ═ t/t0) -1
The value (. eta.sp/c) obtained by dividing the obtained eta.sp by the solid content concentration (c) of the component (A) is plotted on the vertical axis, the solid content concentration (c) of the component (A) is plotted on the horizontal axis, and the intercept of the obtained straight line is taken as the intrinsic viscosity (unit: dl/g).
[ viscosity of salt ]
The dispersion for a papermaking chemical was diluted with 0.5 equivalent of an aqueous NaCl solution so that the solid content concentration of the component (a) reached 0.5%, and the viscosity of the thus obtained diluted solution (25 ℃) was measured using a B-type viscometer (manufactured by philips systems).
(preparation of Polymer dispersant (C-1))
Production example 1
A2 liter five-necked separable flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen inlet was charged with 249.98g (solid content 199.98 g; 99.99 mol%) of an 80% DMAEA-Q aqueous solution, 0.02g (0.01 mol%) of SMAS, and 529.6g of ion-exchanged water, and the mixture was heated to 60 ℃ while nitrogen substitution was carried out. 20g of a 2% V-50 aqueous solution was added thereto as a polymerization initiator, and polymerization was carried out under stirring. The polymer dispersant (C-1) was obtained by polymerization at 80 ℃ for 1 hour while raising the temperature by self-heating. The resulting polymer dispersant (C-1) was adjusted to a solid content of 20%. The results are shown in table 1 (the same applies hereinafter).
Production examples 2 and 3
Polymer dispersants (C-2) and (C-3) were obtained by synthesizing the polymer dispersant according to preparation example 1 except for changing the compositions to the compositions shown in Table 1.
[ Table 1]
(preparation of (meth) acrylamide Polymer (A-1))
Example 1
In a2 liter five-neck separable flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube, 100.0g (solid content concentration: 20% to 5g based on 100g of the obtained dispersion liquid for a papermaking chemical (solid content of component (a)) as component (C), 400.0g of ammonium sulfate and 100.0g of sodium sulfate were dissolved in 721.93g of ion-exchanged water. 389.06g of a 50% AM aqueous solution (194.53 g as a solid content; 73.0 mol%), 181.47g of an 80% DMAEA-Q aqueous solution (145.18 g as a solid content; 20.0 mol%), 67.39g of a 75% DMAEA-BQ aqueous solution (50.54 g as a solid content; 5.0 mol%), IA9.75g (2.0 mol%), and 10.0g of EGG as the component (D) (0.5% based on the amount of reaction charge at the time of charging the polymerization initiator) were added thereto, and the temperature was raised to 55 ℃ while replacing the nitrogen gas. To this was added 20.0g of a 2% V-50 aqueous solution as a polymerization initiator, and polymerization was carried out for 7 hours under stirring to obtain (meth) acrylamide polymer (A-1). The compositions and physical properties (the same applies hereinafter) are shown in table 2.
Examples 2 to 22 and comparative examples 1 to 7
(meth) acrylamide polymers (A-2) to (A-22) and (E-1) to (E-3) were obtained in the same manner as in example 1, according to the compositions shown in Table 2. In comparative examples 4 to 7, thickening and solidification occurred during production, and therefore, the following evaluation was not performed.
(preparation of Diluent of Dispersion for papermaking chemical)
The (meth) acrylamide polymers (A-1) to (A-22) and (E-1) to (E-3) were diluted with ion-exchanged water so that the solid content concentration of component (A) became 0.1% by weight, to prepare a diluted solution of a dispersion liquid for a papermaking chemical.
(evaluation of papermaking)
Corrugated wastepaper was beaten with a NIAGARA type heater and adjusted to 350ml of canadian standard freeness (c.s.f) to obtain a pulp slurry having a solid content of 1.0 wt%. Next, 1.0 wt% of aluminum sulfate was added to the solid content of the pulp slurry to prepare a pulp slurry having a ph of 7.0, and then 0.02 wt% of a diluted solution of a dispersion liquid for papermaking chemicals was added to the solid content of the pulp slurry to dehydrate the pulp slurry with TAPPI SHEET MACHINE. The obtained wet paper was charged at a rate of 5kg/cm2Extruding for 2 min, drying for 4 min with a rotary drier at 105 deg.C, and regulating humidity at 23 deg.C and 50% for 24 hr to obtain 150g/m of paper per square meter2The paper of (1). The coefficient of fracture of the resulting paper was measured by the following method.
(coefficient of rupture)
Measured according to JIS P8131.
In the above papermaking, 500ml of the pulp slurry to which all the chemicals were added was put into DDJ (dynamic drainage machine, 40 mesh), 100ml of the drainage was collected from the lower hole while stirring at 2000rpm using a stirrer equipped with a turbine blade, and the weight thereof was measured, followed by suction filtration using No2 filter paper. The resulting mixture was dried for 60 minutes by a circulating air dryer at a temperature of 110 ℃ and the weight of the dried mixture was measured to determine the concentration of the filtrate collected from the lower hole. Further, the pulp slurry concentration after chemical addition was calculated in advance by the same method, and the total product yield (OPR) was obtained by the formula (3).
(formula 3) OPR (%) { (Y1-Y2)/Y1} × 100
(Y1: concentration of pulp slurry after adding all chemicals, Y2: concentration of filtrate collected from lower hole)
As described above, the drainage of the pulp slurry to which all the chemicals were added was measured according to JIS P8121. The results are shown in table 2.
[ Table 2]
Claims (11)
1. A dispersion for a papermaking chemical, which comprises a (meth) acrylamide polymer (A),
the dispersion contains 2 or more salts (B) selected from ammonium salts, sodium salts and potassium salts,
the extensional viscosity of the dispersion when it is made into a 0.5 wt% aqueous solution based on the solid content concentration of the component (A) is from 40mm to 200mm,
the intrinsic viscosity of a liquid obtained by diluting this dispersion with a 1-equivalent NaCl aqueous solution is 10dl/g to 30dl/g at a temperature of 25 ℃.
2. The dispersion liquid for papermaking chemicals according to claim 1, wherein component (A) comprises a polymer of a monomer component containing (meth) acrylamide (a1) and a cationic unsaturated monomer (a 2).
3. The dispersion liquid for papermaking chemicals according to claim 2, wherein the component (a2) is a tertiary amino group-containing (meth) acrylate and/or a quaternary salt of the (meth) acrylate.
4. The dispersion liquid for papermaking chemicals according to claim 2 or 3, wherein the monomer component further comprises an anionic unsaturated monomer (a 3).
5. The dispersion liquid for papermaking chemicals according to claim 4, wherein the component (a3) is at least 1 selected from the group consisting of acrylic acid, itaconic acid, and itaconic anhydride.
6. The dispersion for a papermaking chemical according to any one of claims 1 to 5, wherein the component (B) comprises ammonium sulfate and further comprises sodium sulfate and/or sodium chloride.
7. The dispersion liquid for a papermaking chemical according to any one of claims 1 to 6, wherein the content of the component (B) is 15 to 45% by weight based on 100% by weight of the dispersion liquid for a papermaking chemical.
8. The dispersion liquid for papermaking chemicals according to any one of claims 1 to 7, further comprising a polymeric dispersant (C) and/or a polyol (D).
9. A paper strength enhancing agent comprising the dispersion for a papermaking chemical according to any one of claims 1 to 8.
10. A drainage enhancer comprising the dispersion for a papermaking chemical according to any one of claims 1 to 8.
11. A yield improver comprising the dispersion liquid for a papermaking chemical according to any one of claims 1 to 8.
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| JP7445859B2 (en) | 2019-12-16 | 2024-03-08 | ハイモ株式会社 | Pitch control agent made of amphoteric water-soluble polymer |
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