CN103306162A - Rosin-like emulsion-type sizing agent, manufacturing method, and paper - Google Patents
Rosin-like emulsion-type sizing agent, manufacturing method, and paper Download PDFInfo
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Abstract
The invention relates to a rosin-like emulsion-type sizing agent, a manufacturing method, and a piece of paper. The invention provides the rosin-like emulsion-type sizing agent, which is provided with the good stability and the sizing treatment performance, and is provided with the rosin free of the fortified rosin used as the emulsifier. The rosin-like emulsion-type sizing agent contains a copolymer (A) and a rosin (B). The 1.0-3.5 copolymer (A) can be obtained by multiplying the polymerization member (a) containing at least the lyophobic monomer (a1) and the monomer (a2) provided with the anionic functional group (mole number used by the anionic functional group) with the valence number of the anionic functional group of the anionic functional group, and then by being divided by the mole number used by lyophobic monomer (a1). The rosin (B) contains at least 30-100 wt% row rosin (b 1), and is free of the fortified rosin.
Description
Technical field
The paper that the present invention relates to rosin based emulsion-type sizing agent, its manufacture method and use this sizing agent to obtain.
Background technology
Rosin based emulsion-type sizing agent refers to the O/W type emulsion that in the presence of various emulsifying agents and water the emulsification of rosin based material obtained, and the paper that this sizing agent of known use obtains is owing to the emulsion particle that is fixed on the paper pulp fiber demonstrates good applying glue.
In the past, rosin based emulsion-type sizing agent made the unsaturated carboxylic acid such as maleic acid and rosin reaction and the fortified rosin that obtains or the mixture that contains fortified rosin.Compare with common rosin, contain a large amount of carboxyls in the molecule of fortified rosin.Therefore, have following effect: this carboxyl helps to form stable alkali metal salt or stable emulsion, and prevents the crystallization (with reference to the 124th～125 page of non-patent literature 1) of rosin.
The applicant had proposed to utilize specific dispersant that the rosin material is disperseed and the rosin based emulsion-type sizing agent (patent documentation 1) that obtains in the past.According to this invention, can be under the pH of wide region effectively use, degree of sizing does not descend yet in the paper even copy at high temperature, can access the rosin based emulsion-type sizing agent of low foaming, but seek in recent years the further raising of sizing efficiency.But, also specifically study for the rosin based emulsion-type sizing agent that does not use fortified rosin.
Patent documentation 1: Japanese kokai publication hei 6-093595 communique
Non-patent literature 1:Hubbe (2006). and " Paper ' s Resistance to Wetting, " Bio Resource2 (1), 106-145
Summary of the invention
The object of the present invention is to provide all good rosin based emulsion-type sizing agents of stability and applying glue.
The inventor conducts in-depth research, and found that, contains the emulsifying dispersant of specific copolymer by use, can address the above problem, thereby finish the present invention.
Namely, the present invention relates to: a kind of rosin based emulsion-type sizing agent, contain copolymer (A) and rosin based (B), described copolymer (A) uses as 1.0～3.5 mode and obtains take (the use molal quantity with monomer (a2) of anionic property functional group) * (valence mumber with anionic property functional group of containing in the monomer (a2) of anionic property functional group)/(use molal quantity of hydrophobic monomer (a1)) by the polymerization composition (a) that will contain at least hydrophobic monomer (a1) and contain the monomer (a2) of anionic property functional group, and described rosin based (B) contains at least the pine gum (b1) of 30～100 % by weight and do not contain fortified rosin; A kind of manufacture method of rosin based emulsion-type sizing agent, it is characterized in that, use copolymer (A) with rosin based (B) emulsification, described copolymer (A) uses as 1.0～3.5 mode and obtains take (the use molal quantity with monomer (a2) of anionic property functional group) * (valence mumber with anionic property functional group of containing in the monomer (a2) of anionic property functional group)/(use molal quantity of hydrophobic monomer (a1)) by the polymerization composition (a) that will contain at least hydrophobic monomer (a1) and have a monomer (a2) of anionic property functional group, and described rosin based (B) contains at least the pine gum (b1) of 30～100 % by weight and do not contain fortified rosin; A kind of paper, it uses this rosin based emulsion-type sizing agent and obtains.
The invention effect
According to the present invention, even can access the rosin based emulsion-type sizing agent that long preservation does not substantially produce insoluble matter, excellent in stability yet and brings into play good sizing efficiency.
The specific embodiment
sizing agent of the present invention is characterised in that, contain copolymer (A) (hereinafter referred to as composition (A)) and rosin based (B) (hereinafter referred to as composition (B)), described copolymer (A) uses and obtains as 1.0～3.5 mode take (the use molal quantity of composition (a2)) * (valence mumber of the anionic property functional group of containing in composition (a2))/(the use molal quantity of composition (a1)) by the polymerization composition (a) (hereinafter referred to as composition (a)) that will contain at least hydrophobic monomer (a1) (hereinafter referred to as composition (a1)) and have a monomer (a2) (hereinafter referred to as composition (a2)) of anionic property functional group, described rosin based (B) contains at least the pine gum (b1) (hereinafter referred to as composition (b1)) of 30～100 % by weight and does not contain fortified rosin.The hydrophobicity of fortified rosin that has a large amount of carboxyls in the molecule is low, and its contact angle is about 65 degree of 55 degree～approximately, and the contact angle that does not contain the composition (B) of fortified rosin is about 85 degree of 70 degree～approximately, and hydrophobicity is higher than fortified rosin in the past.Therefore, for the hydrophobicity ratio strong composition (B) of fortified rosin in the past stably is distributed to aqueous phase, the hydrophobicity of the composition (A) as emulsifying dispersant is uprised similarly.When the hydrophobicity of composition (A) was weak, the compatibility of the composition strong with hydrophobicity (B) descended, and is difficult to form stable emulsion.(the use molal quantity of composition (a2)) * (valence mumber of the anionic property functional group of containing in the composition (a2)) expression can make the amount of the Ionized functional group of anionic property functional group of containing in the composition (a2), namely represent hydrophilic degree, its value is less, and the hydrophily of composition (A) is more weak.(the use molal quantity of composition (a2)) * (valence mumber of the anionic property functional group of containing in the composition (a2))/(the use molal quantity of composition (a1)) expression is with respect to the hydrophilicity of hydrophobicity component content, when this numerical value became large, it is large that the hydrophily of expression composition (A) becomes.This numerical value surpasses at 3.5 o'clock, and the hydrophobicity of composition (A) dies down, and obtains the large emulsion of particle diameter, and applying glue decline perhaps can't obtain stable emulsion, etc., can't obtain the target emulsion.In addition, (the use molal quantity of composition (a2)) * (valence mumber of the anionic property functional group of containing in the composition (a2))/(the use molal quantity of composition (a1)) is lower than at 1.0 o'clock, the hydrophobicity of composition (A) became strong, can't obtain stable emulsion.Namely, by using (the use molal quantity of composition (a2)) * (valence mumber of the anionic property functional group of containing in the composition (a2))/(the use molal quantity of composition (a1)) to be defined as the composition (A) of 1.0～3.5 scope, become well with the compatibility as the composition (B) that disperses object, emulsion can stably exist.When departing from this scope, composition (A) can't balance be present in the oil-water interfaces place well, emulsibility, applying glue variation, and perhaps the remarkable variation of stability is therefore not preferred.
Need to prove, the value of contact angle for obtaining by the following method to water: each composition that will be dissolved in any solvent is coated on polyethylene terephthalate (PET) film and drying, make thus each test sample, use dynamic absorption tester 1100DAT (manufacturing of Fibro company), drip the water droplet of 1 μ l and measure the contact angle of dropping after 0.1 second at specimen surface.
As composition (a1), as long as be (methyl) alkyl-acrylates, phenylethylene, vinyl esters of carboxylic acids class, unsaturated dicarboxylic acid alkyl esters etc., then be not particularly limited, can use the solubility (g/100g) in water to be the known material of 2.5g/100g of about 0g/100g～approximately.(methyl) alkyl-acrylates is not particularly limited, and usually, the carbon number of alkyl is preferably approximately 1～approximately 18, is particularly preferably 4～8.In addition, this alkyl can be in straight chain shape, chain or the alicyclic ring shape any one.Particularly, can enumerate such as methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-octyl, 2-ethylhexyl, decyl, dodecyl, cetyl, octadecyl, octadecylene base, docosyl, cyclopentyl, cyclohexyl etc.As (methyl) alkyl-acrylates, particularly preferably prop up chain (methyl) alkyl acrylate, alicyclic ring shape (methyl) alkyl acrylate.In addition, as phenylethylene, can enumerate such as styrene, α-methyl styrene, t-butyl styrene, dimethyl styrene, acetoxy-styrene, hydroxy styrenes, vinyltoluene, chlorovinyl toluene etc., particularly preferably styrene, α-methyl styrene.As the vinyl esters of carboxylic acids class, can enumerate: vinyl-acetic ester, vinyl propionate base ester, laurate vinyl esters etc.As the unsaturated dicarboxylic acid alkyl esters, can enumerate such as (two) alkyl esters with abovementioned alkyl of the unsaturated monocarboxylic acid classes such as maleic acid, fumaric acid, itaconic acid etc.These materials can be used alone, and also can mix two or more uses.As composition (a1), from the viewpoint of copolymerization, emulsibility, preferred (methyl) alkyl acrylate and/or the phenylethylene of using.
As composition (a2), so long as have at least the free radical polymerization monomer of the anionic property functional groups such as a carboxyl, sulfonic group, phosphate, then be not particularly limited, can use known free radical polymerization monomer.In addition, composition (a2) can be the neutralized salt such as the alkali metal salts such as lithium salts, sodium salt, sylvite, ammonium salt.Particularly, as the monomer with carboxyl, can enumerate: the unsaturated monocarboxylic acid classes such as (methyl) acrylic acid, crotonic acid; The unsaturated dicarboxylic acid classes such as maleic acid (acid anhydride), fumaric acid, itaconic acid, citraconic acid (acid anhydride).In addition, as having sulfonic monomer, can enumerate: (methyl) propene sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, (methyl) acrylic acid sulphur ethyl ester etc.As the monomer with phosphate, can enumerate: acryloyl phosphoric acid-2-hydroxy methacrylate etc.These monomers can be used alone, and also can mix two or more uses.From with the viewpoint of the copolymerization of (a1) composition, if have the monomer of carboxyl, then preferably use (methyl) acrylic acid, itaconic acid, if having sulfonic monomer, then preferably use (methyl) propene sulfonic acid and/or styrene sulfonic acid.
Composition (a) can use the monomer (a3) (hereinafter referred to as composition (a3)) that has a polymerism functional group in the molecule except composition (a1), composition (a2) as required.As composition (a3), can enumerate (methyl) acrylamide, (methyl) acrylic acid hydroxyalkyl acrylate, unsaturated unary alcohol, ployalkylene glycol class unsaturated monomer class, alhpa olefin class and the nitrile monomer class etc. that replace such as: (methyl) acrylamide, N-.These materials can be used alone, and also can mix two or more uses.
In addition, can further use as required the cross-linkable monomer (a4) (hereinafter referred to as composition (a4)) that has at least two polymerism functional groups in the molecule.As composition (a4), for example can enumerate: divinylbenzene, trivinylbenzene, divinylsulfone, polyethyleneglycol diacrylate, propylene glycol diacrylate, trimethylolpropane triacrylate, tetramethylol methane tetraacrylate, ethylene glycol dimethacrylate, dipropylene glycol dimethylacrylate, hexanediyl ester, N, N '-propylidene bisacrylamide, diacrylamine dimethyl ether, N, N '-methylene-bisacrylamide etc.These materials can be used alone, and also can mix two or more uses.By using composition (a4), the molecular weight of composition (A) increases, and emulsibility improves, and is therefore preferred.
About the use amount of composition (a1) and composition (a2), need to use take (the use molal quantity of composition (a2)) * (valence mumber of the anionic property functional group of containing in the composition (a2))/(the use molal quantity of composition (a1)) as 1.0～3.5 mode.When composition (a) is made of composition (a1) and composition (a2), the use amount of composition (a1) is approximately 35 % by mole～approximately 78 % by mole, preferred 40～65 % by mole in composition (a), and the use amount of composition (a2) is approximately 22 % by mole～approximately 65 % by mole, preferred 35～60 % by mole in composition (a).When composition (a) is made of composition (a1), composition (a2) and composition (a3), the use amount of composition (a1) is approximately 5 % by mole～approximately 20 % by mole, preferred 8～12 % by mole in composition (a), the use amount of composition (a2) is approximately 3 % by mole～approximately 35 % by mole, preferred 5～20 % by mole in composition (a), and the use amount of composition (a3) is approximately 45 % by mole～approximately 90 % by mole, preferred 60～86 % by mole in composition (a).In addition, the use amount of composition (a4) is not particularly limited, and is approximately 0 % by mole～approximately 3 % by mole, preferred 0.1～2 % by mole usually in composition (a).
Composition (A) is by obtaining composition (a) polymerization.The polymerization of composition (a) is not particularly limited, and can use the various known methods such as polymerisation in solution, emulsion polymerisation, suspension polymerization.For example, by make above-mentioned each composition in reaction dissolvent, at radical polymerization initiator and the chain-transferring agent that adds as required, surfactant in the presence of, usually approximately 80 ℃～approximately 180 ℃ of Raolical polymerizables that are generally approximately 1 hour～approximately 10 hours obtain the target copolymer.In addition, this copolymer can utilize various known alkali compoundss to neutralize as required.
As reaction dissolvent, can enumerate: the mixed liquor of organic solvent, water or the organic solvent such as the rudimentary ketone such as the alcohols such as ethanol and propyl alcohol, acetone and MEK, toluene and benzene etc. are aromatic hydrocarbon based, ethyl acetate, chloroform, dimethyl formamide and water.
As radical polymerization initiator, can enumerate such as inorganic peroxide classes such as hydrogen peroxide, ammonium persulfate and potassium peroxydisulfates; The organic peroxide classes such as peroxidized t-butyl perbenzoate, dicumyl peroxide and lauryl peroxide; 2,2 '-azodiisobutyronitrile and 2, the azo compounds such as 2 '-azo-bis-iso-dimethyl etc.
As chain-transferring agent, can enumerate: the oil-soluble chain-transferring agents such as uncle's lauryl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, cumene, bromine chloroform, 2-mercaptobenzothiazole; The water-soluble chain transfer agents such as ethyl mercaptan, propanethiol, TGA, thiomalic acid, dimethyl dithiocarbamic acid etc., isopropyl alcohol etc., hypophosphorous acid sodium salt.
The surfactant that uses when carrying out emulsion polymerisation is not particularly limited, and can use the various surfactants such as anionic surfactant, nonionic surfactant.For example, as the anionic surfactant, can enumerate: dialkyl sulfosuccinates, alkane sulfonate, alpha-alkene sulfonate, polyoxyethylene alkyl ether sulfosuccinate ester salt, polyoxyethylene styryl phenyl ether sulfosuccinate ester salt, naphthalene sulfonic acid-formaldehyde condensation product, polyoxyethylene alkyl ether sulphate salts, polyoxyethylene alkyl phenyl ether sulfuric acid etc.; As nonionic surfactant, can enumerate: polyoxyethylene alkyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitan fatty acid ester and in these surfactants, introduce vinyl or allyl, propenyl and the reactive surfactant that obtains etc.
As the alkali compounds that is used for neutralization, can enumerate: the alkali metal compounds such as NaOH, potassium hydroxide etc., calcium hydroxide and magnesium hydroxide; The organic amines such as monomethyl amine, dimethylamine, trimethylamine, monoethyl amine, diethylamine, a propylamine, di-n-propylamine and tripropyl amine (TPA); Ammonia; Deng.
The physical property of composition (A) is not particularly limited, and weight average molecular weight (refers to the polystyrene conversion value in the gel permeation chromatography (GPC).Lower same.) usually can be approximately 4000～approximately 100000, preferred 5000～50000.Be more than 5000 by making weight average molecular weight, emulsibility is improved, therefore preferred, be below 50000 by making weight average molecular weight, can suppress viscosity lower, become easily thereby make to process, therefore preferred.In addition, (A) composition can obtain with the form of the aqueous solution, and its nonvolatile component is generally approximately 40 % by weight of 20 % by weight～approximately.
Composition (B) contains the composition (b1) of 30～100 % by weight and does not contain fortified rosin.In this manual, composition (b1) refers to the rosin that gathers from Pinaceae Pinus species, preferred use suitably distill, the material behind the purifying.As concrete example, can enumerate: gum rosin, wood rosin, Starex etc.Composition (b1) comprises resin acid and about 10% all the other compositions (in and composition, impurity etc.) more than 90% usually.As resin acid, can enumerate: rosin acid, levopimaric acid, neoabietic acid, palustric acid etc.
As the composition except composition (b1), can enumerate such as the rosin of Foral, disproportionated rosin, newtrex, aldehyde modification, rosin ester etc.As the rosin of aldehyde modification, can enumerate: the rosin of modified formaldehyde (b2) (hereinafter referred to as composition (b2)) etc.Rosin ester refers to the reactant of esterification of mentioned component (b1) and various known alcohols, can use various known rosin esters with being not particularly limited.As polyalcohol, can enumerate: glycerine, trimethylolpropane, trimethylolethane and 3-methylpentane-1,3, the tetrols such as the triols such as 5-triol, pentaerythrite and two glycerine etc.The use amount of pine gum and alcohols is not particularly limited, and (OH/-COOH) being generally approximately, 0.1～approximately 1.5, preferred 0.1～1.0 scope gets final product the mol ratio of the carboxyl of pine gum and the hydroxyl of alcohols.In addition, from the sizing efficiency viewpoint of (also comprising the neutral papermaking field), rosin ester shared weight in composition (B) is generally approximately 50 % by weight of 0 % by weight～approximately, preferred 0～30 % by weight.Wherein, preferably use composition (b2).Use amount when using the composition except composition (b1) is not particularly limited, and is 1～70 % by weight in composition (B) usually, preferred 10～50 % by weight.Especially, when using composition (b2), in composition (B), be preferably set to 1～70 % by weight, particularly preferably be set as 15～50 % by weight.
Composition (B) is to the contact angle (Ang of water
(B)) be not particularly limited, from the viewpoint of sizing efficiency, be generally approximately 85 degree of 65 degree～approximately, preferred 70～85 degree.
Emulsion of the present invention can be by various known method manufacturings.Particularly, for example can adopt disclosed method in high-pressure emulsification method (with reference to Japanese Patent Publication 53-22090 communique), the phase conversion emulsifying (with reference to Japanese kokai publication sho 58-4938 communique).
In the situation that utilize above-mentioned solvent high-pressure emulsification method, at first in the composition (B) that is dissolved in the water-fast organic solvent, add composition (A), water and above-mentioned alkali compounds as required, use homogenizer, piston-type high-pressure emulsification machine, ultrasonic emulsification machine etc. to carry out emulsification, then above-mentioned organic solvent is removed in distillation, obtains thus the target emulsion.
In the situation that utilize above-mentioned phase conversion method, usually composition (B) is heated to approximately 90 ℃～approximately 160 ℃, stir, make its melting, and the hot water of adding ingredient (A) and scheduled volume makes it carry out phase inversion, obtain thus the target emulsion.
When above-mentioned solvent high-pressure emulsification, Phase inversion emulsification, the solid component content of composition (A) is the about scope of 12 weight portions, preferred 6～10 weight portions of 5 weight portions～approximately with respect to 100 weight portion compositions (B).Be more than 5 weight portions by making composition (A), can easily disperse, therefore preferred.In addition, when the use amount of composition (A) surpasses 12 weight portion, the sizing efficiency variation, therefore not preferred.In addition, can regulate by the pH to this emulsion according to expecting water or alkaline water with resulting these emulsions dilutions.
During emulsification, except composition (A), can also be used in combination surfactant foaminess, sizing efficiency not being caused in the dysgenic scope.As this surfactant, also can use the various surfactants that when the emulsion polymerisation of aforesaid copolymer, use.
The physical property of the emulsion that obtains like this is not particularly limited, and from the viewpoint of storage stability, sizing efficiency and the dispersiveness pulp, is generally average grain diameter and (utilizes the measured value of the average grain diameter that the laser diffraction and scattering method obtains.Lower same.) be the about uniform water-based emulsion of 1.2 μ m of 0.1 μ m～approximately.In addition, pH is approximately 2～approximately 7.5, viscosity (nonvolatile component 50%, the measured value of utilizing Brookfield viscometer (No. 1 rotor) to obtain under 25 ℃.Lower same.) be the about 150mPas of 5mPas～approximately.
Can add various additives in this emulsion, such as: the paper power reinforcing agents such as the water soluble polymers such as the cellulose families such as carboxymethyl cellulose, polyvinyl alcohol, polyacrylamide, sodium alginate, antilubricant, preservative agent, rust inhibitor, pH adjusting agent, defoamer (silicone based defoamer etc.), thickener, filler, antioxidant, anti-hydrated agent, membrane producing promoter, pigment, dyestuff etc.
The sizing agent of paper the application of the invention of the present invention and obtaining.When this sizing agent is used as Internal Size, can enumerate the method that above-mentioned emulsion is added in the pulp, approximately carried out applying glue 4～approximately 8 times at pH with fixatives such as aluminum sulfate.In addition, during applying glue, can use the fillers such as talcum, clay, kaolin, titanium dioxide, calcium carbonate.In addition, the use amount of this emulsion is generally approximately 3 % by weight of 0.05 % by weight～approximately with respect to the dry weight of paper pulp.
In addition, when this sizing agent was used as Cypres, it was about 2 % by weight of 0.01 % by weight～approximately that above-mentioned emulsion is diluted to nonvolatile component, and utilized various known methods will dilute after dryer sizing liquid to be applied on the paraffin paper and to get final product.Coating process is not particularly limited, and can enumerate the whole bag of tricks such as: size press method, door roller rubbing method, scraper rubbing method, rolling process, spraying process.As mentioned above, the mechanical stability of surface sizing agent for paper making of the present invention is good, therefore can use in the various coating machines such as double-roll type size press coating method, metering bar type size press coating method or door print roll coating mode.In addition, coating weight (solid constituent) is generally 0.001～2g/m
2, preferred 0.005～0.5g/m
2In addition, paraffin paper is not particularly limited, can example as with the uncoated paper of lumber fibre cellulose fiber as raw material.In addition, as the paraffin paper raw material copy paper paper pulp, can enumerate: the mechanical pulp such as the chemical pulps such as LBKP, NBKP, GP, TMP and old paper stock etc.In addition, can contain the chemicals such as Internal Size, filler, the agent of paper power in this paraffin paper.
Paper of the present invention can be in purposes such as cardboard such as the Western paper such as the package papers such as the coated papers such as the paper used for recording such as foaming body paper using, PPC paper using, thermal photography paraffin paper, pressure sensitive recording paraffin paper, art paper, cast-coated paper, high quality mould coating paper, brown paper, pure white glossy paper, writing folio, books paper using, printing, newspaper paper using, solid bleached paperboard, white board, hardboard, liner sheet.
Embodiment
Below, enumerate embodiment and comparative example is specifically described the present invention, but scope of the present invention is not subjected to the restriction of these examples certainly.In addition, in each example, if not otherwise specified, then part and % are weight basis.
In addition, in each example, weight average molecular weight is for utilizing gel permeation chromatography (operative installations: the HLC8120GPC that TOSOH Co., Ltd makes, chromatographic column: the scaled value of the polyethylene glycol standard substance that the TSK-GEL ALPHA-M that TOSOH Co., Ltd makes) obtains.In the mensuration of viscosity, use Brookfield rotation viscometer VISCOMETER TVK-10 (Co., Ltd.'s east machine industry) under 25 ℃, to measure, in the mensuration of pH, use pH meter F-14 (Horiba Ltd's manufacturing) under 25 ℃, to measure.In addition, the average grain diameter of emulsion obtains by utilizing laser diffraction/scattering method and using particle size determination device laser diffraction granularity analyzer SALD-2000J (Shimadzu Scisakusho Ltd's manufacturing) to measure.
Production Example 1
In the reaction vessel that possesses agitator, thermometer, reflux condenser and nitrogen inlet tube, drop into 25.2 parts of (2.5 % by mole) 2-EHAs, 69.5 parts of (7.5 % by mole) cyclohexyl acrylates, 124.4 parts of (17.5 % by mole) itaconic acids, 281.5 parts of (72.5 % by mole) acrylamides, 738.6 parts of ion exchange waters, 753.7 parts of isopropyl alcohols, 2.6 parts (the total mole with respect to the polymerization composition is 0.6 % by mole) as the 2 mercapto ethanol of chain-transferring agent, be warming up to 50 ℃ when this mixed liquor is stirred under nitrogen bubble.Add 12.5 parts of ammonium persulfates as polymerization initiator (APS) and be warming up to 80 ℃, kept 180 minutes.Then, carry out the distillation of isopropyl alcohol and remove, and add the ion exchange water of scheduled volume, obtain thus weight average molecular weight and be the aqueous solution of 13000 copolymer.In addition, in this aqueous solution, nonvolatile component is that the viscosity under 31.8%, 25 ℃ is 3930mPas, and pH is 4.4.
Production Example 2
At the reaction vessel same with Production Example 1, namely possesses agitator, thermometer, drop into 21.9 parts of (2 % by mole) 2-EHAs in the reaction vessel of reflux condenser and nitrogen inlet tube, 80.8 part (8 % by mole) cyclohexyl acrylate, 38.7 part (5 % by mole) itaconic acid, 359.4 part (85 % by mole) acrylamide, 753.1 part ion exchange water, 750.4 part isopropyl alcohol, 4.6 part (the total mole with respect to the polymerization composition is 1 % by mole) as the 2 mercapto ethanol of chain-transferring agent, is warming up to 50 ℃ when this mixed liquor is stirred under nitrogen bubble.Add 8.1 parts of ammonium persulfates as polymerization initiator (APS) and be warming up to 80 ℃, keep after 120 minutes, add again 5.4 parts of ammonium persulfates as rear catalyst for polymerization (APS) and descend maintenance 60 minutes at 80 ℃.Then, carry out the distillation of isopropyl alcohol and remove, and add the ion exchange water of scheduled volume, obtain thus weight average molecular weight and be the aqueous solution of 7000 copolymer.In addition, in this aqueous solution, nonvolatile component is that the viscosity under 33.8%, 25 ℃ is 700mPas, and pH is 4.4.
Production Example 3
With the same reaction vessel of Production Example 1 in drop into 20.2 parts of (2 % by mole) 2-EHAs, 74.2 parts of (8 % by mole) cyclohexyl acrylates, 71.1 parts of (10 % by mole) itaconic acids, 295.3 parts of (76 % by mole) acrylamides and 17.3 parts of (2 % by mole) methylpropene sodium sulfonates, 25.6 parts of (2 % by mole) Sodium styrene sulfonate, 744.7 parts of ion exchange waters, 742.7 parts of isopropyl alcohols, be warming up to 50 ℃ when this mixed liquor is stirred under nitrogen bubble.Add 7.5 parts of ammonium persulfates as polymerization initiator (APS) and be warming up to 80 ℃, keep further adding 5.0 parts of ammonium persulfates as rear catalyst for polymerization (APS) after 120 minutes, 80 ℃ of lower maintenances 60 minutes.Then, carry out the distillation of isopropyl alcohol and remove, and add the ion exchange water of scheduled volume, obtain thus weight average molecular weight and be the aqueous solution of 11200 copolymer.In addition, in this aqueous solution, nonvolatile component is that the viscosity under 35.3%, 25 ℃ is 1450mPas, and pH is 4.5.
Production Example 4
With the same reaction vessel of Production Example 1 in drop into 32.3 parts of (3 % by mole) 2-EHAs, 49.5 parts of (5 % by mole) cyclohexyl acrylates, 60.8 parts of (8 % by mole) itaconic acids, 346.5 parts of (83.5 % by mole) acrylamides and 11.4 parts of (0.5 % by mole) six glycol diacrylates (Hexaethylene diacrylate), 746.7 parts of ion exchange waters, 743.4 parts of isopropyl alcohols, be warming up to 50 ℃ when this mixed liquor is stirred under nitrogen bubble.Add 8.0 parts of ammonium persulfates as polymerization initiator (APS) and be warming up to 80 ℃, keep further adding 5.3 parts of ammonium persulfates as rear catalyst for polymerization (APS) after 120 minutes, 80 ℃ of lower maintenances 60 minutes.Then, carry out the distillation of isopropyl alcohol and remove, and add the ion exchange water of scheduled volume, obtain thus weight average molecular weight and be the aqueous solution of 11000 copolymer.In addition, in this aqueous solution, nonvolatile component is that the viscosity under 33.3%, 25 ℃ is 1590mPas, and pH is 4.5.
Production Example 5
With the same reaction vessel of Production Example 1 in drop into 5.4g (total amount with respect to the polymerization composition is 1 % by weight) surfactant (Ha イ テ ノ ー Le LA-10, Di-ichi Kogyo Seiyaku Co., Ltd. makes), (144.9g 30 % by mole) styrene, (38.3g 7 % by mole) α-methyl styrene, (20.8g 3.5 % by mole) butyl acrylate, (169.6g 34 % by mole) 80% methacrylic acid, (51.3g 8.5 % by mole) itaconic acid, (36.7g 5 % by mole) methylpropene sodium sulfonate, (72.4g 12 % by mole) acrylic acid hydroxy butyl ester, 1801.9g ion exchange water, 20.0g (total amount with respect to the polymerization composition is 4 % by weight) as the α-methylstyrenedimer of chain-transferring agent, is warming up to 60 ℃ when this mixed liquor is stirred under nitrogen bubble.Add 20.0g as the ammonium persulfate (APS) of polymerization initiator and be warming up to 90 ℃, keep after 100 minutes, further add 5.0g as the ammonium persulfate (APS) of rear catalyst for polymerization, 90 ℃ of lower maintenances 60 minutes.Then, add 48% sodium hydrate aqueous solution 197.0g, carry out the neutralization of methacrylic acid, itaconic acid, and add the ion exchange water of scheduled volume, obtain thus weight average molecular weight and be the aqueous solution of 5100 copolymer.In addition, in this aqueous solution, nonvolatile component is that the viscosity under 25.1%, 25 ℃ is 65mPas, and pH is 8.8.
Compare Production Example 1
With the same reaction vessel of Production Example 1 in drop into 34.3 parts of (3.5 % by mole) 2-EHAs, 67.6 parts of (7.5 % by mole) cyclohexyl acrylates, 138.2 parts of (20 % by mole) itaconic acids, 260.5 parts of (69 % by mole) acrylamides, 739.4 parts of ion exchange waters, 753.1 parts of isopropyl alcohols, 2.5 parts (the total mole with respect to the polymerization composition is 0.6 % by mole) as the 2 mercapto ethanol of chain-transferring agent, be warming up to 50 ℃ when this mixed liquor is stirred under nitrogen bubble.Add 12.1 parts of ammonium persulfates as polymerization initiator (APS) and be warming up to 80 ℃, and kept 180 minutes.Then, carry out the distillation of isopropyl alcohol and remove, and add the ion exchange water of scheduled volume, obtain thus weight average molecular weight and be the aqueous solution of 12900 copolymer.In addition, in this aqueous solution, nonvolatile component is that the viscosity under 32.3%, 25 ℃ is 3900mPas, and pH is 4.4.
Compare Production Example 2
With the same reaction vessel of Production Example 1 in drop into 43.2 parts of (4 % by mole) 2-EHAs, 69.6 parts of (7 % by mole) cyclohexyl acrylates, 38.1 parts of (5 % by mole) itaconic acids, 349.7 parts of (84 % by mole) acrylamides, 753.5 parts of ion exchange waters, 750.1 parts of isopropyl alcohols, 4.6 parts (the total mole with respect to the polymerization composition is 1 % by mole) as the 2 mercapto ethanol of chain-transferring agent, be warming up to 50 ℃ when this mixed liquor is stirred under nitrogen bubble.Add 8.0 parts of ammonium persulfates as polymerization initiator (APS) and be warming up to 80 ℃, keep further adding 5.3 parts of ammonium persulfates as rear catalyst for polymerization (APS) after 120 minutes, 80 ℃ of lower maintenances 60 minutes.Then, carry out the distillation of isopropyl alcohol and remove, and add the ion exchange water of scheduled volume, obtain thus weight average molecular weight and be the aqueous solution of 7600 copolymer.In addition, in this aqueous solution, nonvolatile component is that the viscosity under 32.8%, 25 ℃ is 3900mPas, and pH is 4.4.
Compare Production Example 3
With the same reaction vessel of Production Example 1 in drop into 18.9 parts of (2 % by mole) 2-EHAs, 69.7 parts of (8 % by mole) cyclohexyl acrylates, 133.6 parts of (20 % by mole) itaconic acids, 240.9 parts of (66 % by mole) acrylamides and 16.2 parts of (2 % by mole) methylpropene sodium sulfonates, 24.1 parts of (2 % by mole) Sodium styrene sulfonate, 746.2 parts of ion exchange waters, 742.0 parts of isopropyl alcohols, be warming up to 50 ℃ when this mixed liquor is stirred under nitrogen bubble.Add 7.0 parts of ammonium persulfates as polymerization initiator (APS) and be warming up to 80 ℃, keep further adding 4.7 parts of ammonium persulfates as rear catalyst for polymerization (APS) after 120 minutes, 80 ℃ of lower maintenances 60 minutes.Then, carry out the distillation of isopropyl alcohol and remove, and add the ion exchange water of scheduled volume, obtain thus weight average molecular weight and be the aqueous solution of 12900 copolymer.In addition, in this aqueous solution, nonvolatile component is that the viscosity under 34.5%, 25 ℃ is 540mPas, and pH is 4.4.
Compare Production Example 4
With the same reaction vessel of Production Example 1 in drop into 21.8 parts of (2 % by mole) 2-EHAs, 80.4 parts of (8 % by mole) cyclohexyl acrylates, 23.1 parts of (3 % by mole) itaconic acids, 363.9 parts of (86.5 % by mole) acrylamides and 11.6 parts of (0.5 % by mole) six glycol diacrylates, 746.1 parts of ion exchange waters, 743.6 parts of isopropyl alcohols, be warming up to 50 ℃ when this mixed liquor is stirred under nitrogen bubble.Add 8.1 parts of ammonium persulfates as polymerization initiator (APS) and be warming up to 80 ℃, keep further adding 5.4 parts of ammonium persulfates as rear catalyst for polymerization (APS) after 120 minutes, 80 ℃ of lower maintenances 60 minutes.Then, carry out the distillation of isopropyl alcohol and remove, and add the ion exchange water of scheduled volume, obtain thus weight average molecular weight and be the aqueous solution of 17500 copolymer.In addition, in this aqueous solution, nonvolatile component is that the viscosity under 31.3%, 25 ℃ is 1300mPas, and pH is 4.5.
Compare Production Example 5
With the same reaction vessel of Production Example 1 in drop into 30.5 parts of (5 % by mole) butyl acrylates, 33.8 part (5 % by mole) butyl methacrylate, 142.8 part (30 % by mole) methyl methacrylate, 59.5 part (12 % by mole) styrene, 73.1 part (13 % by mole) α-methyl styrene, 153.5 part (30 % by mole) methacrylic acid, with 37.6 parts of (5 % by mole) methylpropene sodium sulfonates, 1563.6 part ion exchange water, 8.6 part (the total mole with respect to the polymerization composition is 0.9 % by mole) as the n-dodecyl mercaptan of chain-transferring agent, is warming up to 80 ℃ when this mixed liquor is stirred under nitrogen bubble.Add 25.2 parts of ammonium persulfates as polymerization initiator (APS) and be warming up to 90 ℃, keep further adding 10.1 parts of ammonium persulfates as rear catalyst for polymerization (APS) after 100 minutes, 90 ℃ of lower maintenances 60 minutes.Then, add 118.9 parts of neutralizations of carrying out methacrylic acid of sodium hydrate aqueous solution of 48%, and add the ion exchange water of scheduled volume, thus, obtain weight average molecular weight and be the aqueous solution of 5800 copolymer.In addition, in this aqueous solution, nonvolatile component is that the viscosity under 25.2%, 25 ℃ is 23mPas, and pH is 8.7.
Table 1
| ? | R |
| Production Example 1 | 3.5 |
| Production Example 2 | 1.0 |
| Production Example 3 | 2.4 |
| Production Example 4 | 2.0 |
| Production Example 5 | 1.3 |
| Compare Production Example 1 | 3.6 |
| Compare Production Example 2 | 0.9 |
| Compare Production Example 3 | 4.4 |
| Compare Production Example 4 | 0.6 |
| Compare Production Example 5 | 0.5 |
In the table, R represents (having the use molal quantity of the monomer (a2) of anionic property functional group) * (valence mumber with anionic property functional group of containing in the monomer (a2) of anionic property functional group)/(use molal quantity of hydrophobic monomer (a1)).For example, in the Production Example 3, as the anionic property monomer, use the itaconic acid of 10 % by mole divalence, methylpropene sodium sulfonate and the Sodium styrene sulfonate of each monovalence of 2 % by mole, as hydrophobic monomer, use 2 % by mole 2-EHA, 8 % by mole cyclohexyl acrylate, therefore, R is (10 * 2+2 * 1+2 * 1)/(2+8)=2.4.
Production Example 6
In the flask that possesses agitator, thermometer, nitrogen inlet tube, water knockout drum and condenser, drop into approximately 160 ℃ be in 600.0 parts of gum rosin that molten condition and acid number are 170mgKOH/g, 32.4 parts in 37% formaldehyde, as 1.5 parts of the p-methyl benzenesulfonic acid of catalyst, 160 ℃ of lower reactions 2 hours, obtain the rosin that acid number is the modified formaldehyde of 165mgKOH/g when under stream of nitrogen gas, stirring.
Production Example 7
About 150 ℃ be in 600.0 parts of the gum rosin that molten condition and acid number are 170mgKOH/g and add 0.15 part in palladium carbon, 0.25 part of active carbon, be heated to 300 ℃ and reaction 1 hour under this temperature, obtain the disproportionated rosin that acid number is 165mgKOH/g.
Production Example 8
With the same reaction vessel of Production Example 6 in 55.6 parts of 663.2 parts of gum rosin, glycerine that to drop into 663.2 parts of acid numbers be 170mgKOH/g (molar ratio-OH/-COOH=0.90), as 10 parts of the ノ Network ラ ッ Network 300 (manufacturing of the emerging chemical industry of imperial palace Co., Ltd.) of antioxidant, as 0.1 part of the p-methyl benzenesulfonic acid of catalyst, be heated to 270 ℃ when under stream of nitrogen gas, stirring, and under this temperature, reacted 15 hours, obtain the rosin ester compound into acid number 16mgKOH/g.
With reference to Production Example 1
About 200 ℃ be in 600.0 parts of the gum rosin that molten condition and acid number are 170mgKOH/g and add 36.0 parts of fumaric acid, 9.0 parts of maleic anhydrides, and heat tracing reacted in 2 hours under this temperature, obtained the fortified rosin that acid number is 228mgKOH/g.
Embodiment 1
Be that 24 parts of the rosin ester compounds that obtain in 76 parts of the gum rosin of 170mgKOH/g and the Production Example 8 are heated to approximately 160 ℃ and make its melting with acid number, when stirring, slowly drip 8 parts of the aqueous copolymers solutions (converting with solid constituent) that obtain in the Production Example 1, mix, make the W/O form, add hot water in the gains and after making stable O/W type emulsion, be cooled to room temperature.The solid component concentration of resulting rosin based emulsion-type sizing agent is 50.4%, and emulsion viscosity is 82mPas, and average grain diameter is 0.58 μ m.
Embodiment 2～5
The aqueous copolymers solution that obtains in the Production Example 1 of using among the embodiment 1 is changed to the copolymerization aqueous solution shown in the table 2, in addition, similarly to Example 1 operation, preparation rosin based emulsion-type sizing agent.
Embodiment 6～10
(B) composition that uses among the embodiment 3 is changed to the composition shown in the table 2, in addition, similarly to Example 3 operation, preparation rosin based emulsion-type sizing agent.
Comparative example 1, comparative example 2
The aqueous copolymers solution that obtains in the Production Example 1 of using among the embodiment 1 is changed to the copolymerization aqueous solution shown in the table 2, in addition, similarly to Example 1 operation, preparation rosin based emulsion-type sizing agent.
Comparative example 3～5
The aqueous copolymers solution that obtains in the Production Example 1 of using among the embodiment 1 is changed to the copolymerization aqueous solution shown in the table 2, in addition, emulsion is made in similarly to Example 1 operation, but when just finishing manufacturing, just produced a large amount of insoluble matters, therefore do not supplied in follow-up test and machine hand's order.
Comparative example 6
The aqueous copolymers solution that obtains in the Production Example 1 of using among the embodiment 9 is changed to the copolymerization aqueous solution shown in the table 2, in addition, emulsion is made in similarly to Example 9 operation, but when just finishing manufacturing, just produced a large amount of insoluble matters, therefore do not supplied in follow-up test and machine hand's order.
Reference example 1
The gum rosin that uses among the embodiment 2 is changed to the fortified rosin that obtains with reference in the Production Example 1, in addition, similarly to Example 2 operation, preparation rosin based emulsion-type sizing agent, but when just finishing manufacturing, just produced a large amount of insoluble matters, therefore do not supplied in follow-up test and machine hand's order.
Reference example 2
The gum rosin that uses among the embodiment 3 is changed to the fortified rosin that obtains with reference in the Production Example 1, in addition, similarly to Example 3 operation, preparation rosin based emulsion-type sizing agent.
Reference example 3
The gum rosin that uses in the comparative example 4 is changed to the fortified rosin that obtains with reference in the Production Example 1, in addition, operate equally with comparative example 4, preparation rosin based emulsion-type sizing agent.
The proterties of the rosin based emulsion-type sizing agent that in embodiment shown in the table 3 and reference example, obtains.
Table 2
Table 3
In the table, the bad expression of phase inversion can't be carried out emulsification.
(storage-stable test)
Each emulsion 100g of embodiment 1 is put into the mayonnaise bottle, at room temperature left standstill two months, then, it is all filtered with 350 purpose wire nettings, and mensuration is with respect to the filtration residue amount (ppm) of all solids composition.In addition, measure too the filtration residue amount for each emulsion of other embodiment, comparative example and reference example.The results are shown in the table 4.The filtration residue amount is less, and then storage-stable is better.
(making of test paper using)
Add in L-BKP that to make pulp density be the running water of 2.0% amount, use beater to pull an oar to the 300ml Canadian Standard Freeness.Then, the pulp after the making beating further with the running water dilution, is adjusted to 1.0% with pulp density.Then, adding with respect to paper pulp in this pulp is 16.0% (take oven dry weight as benchmark.Lower same.) filler (mixture of calcium carbonate and talcum), be 1.5% aluminum sulfate, be 0.3% commercially available cationic modified starch with respect to paper pulp with respect to paper pulp, then, the emulsion that adds embodiment 1, make it reach 0.2% or 0.3%, utilize paper machine (Tappi Standard Sheet Machine (TAPPI standard page forming machine) (round)) to copy paper, so that basic weight is 80g/m
2In addition, the pH that copies the paper system regulates with the aqueous solution of sulfuric acid or NaOH.Then, resulting write by hand l Water Paper is dewatered with roll squeezer with line pressure 5.5kg/cm, feeding speed 2m/ minute condition, and the use rotary drier is lower dry 150 seconds at 80 ℃.Then, with the damping 24 hours under constant temperature and humidity (23 ℃, 50% relative humidity) environment of resulting dry paper, obtain thus testing paper using.Operate too for each emulsion of other embodiment, comparative example and reference example and obtain testing paper using.
According to JIS-P8122, the test paper using of embodiment 1 is measured these many Jedes (ス テ キ ヒ ト) degree of sizing.Measure too this many Jedes degree of sizing for the test paper using of other embodiment, comparative example and reference example.Show the result in the table 4.
Table 4
(making of test paper using)
Add in secondary corrugating material (containing 12% ash content) that to make pulp density be the running water of 2.0% amount, use beater to pull an oar to the 400ml Canadian Standard Freeness.Then, the pulp after the making beating further with the running water dilution, is adjusted to 1.0% with pulp density.Then, in this pulp, add be 1.0% aluminum sulfate with respect to paper pulp after, add the emulsion of embodiment 1, and utilize paper machine (TAPPI standard page forming machine (round)) to copy paper, so that basic weight is 80g/m
2In addition, the pH that copies the paper system regulates with the aqueous solution of dilute sulfuric acid or NaOH.Then, resulting write by hand l Water Paper is dewatered with roll squeezer with line pressure 5.5kg/cm, feeding speed 2m/ minute condition, and the use rotary drier is lower dry 150 seconds at 80 ℃.Then, with the damping 24 hours under constant temperature and humidity (23 ℃, 50% relative humidity) environment of resulting dry paper, obtain thus testing paper using.Operate too for each emulsion of other embodiment, comparative example and reference example and obtain testing paper using.
According to JIS-P8140, the test paper using of embodiment 1 is measured suddenly (Cobb) absorption of water.Measure too suddenly absorption of water for the test paper using of other embodiment, comparative example and reference example.Show the result in the table 5.
Table 5
Stability and the sizing efficiency of the rosin based emulsion-type sizing agent that obtains according to the present invention are all good.Particularly from the viewpoint of sizing efficiency, compare with 2 with the reference example 1 that uses fortified rosin, irrelevant with the pH that copies the paper system, can confirm significant raising.
Claims (11)
1. rosin based emulsion-type sizing agent, contain copolymer (A) and rosin based (B), described copolymer (A) uses as 1.0～3.5 mode and obtains take (the use molal quantity with monomer (a2) of anionic property functional group) * (valence mumber with anionic property functional group of containing in the monomer (a2) of anionic property functional group)/(use molal quantity of hydrophobic monomer (a1)) by the polymerization composition (a) that will contain at least hydrophobic monomer (a1) and have a monomer (a2) of anionic property functional group, and described rosin based (B) contains at least the pine gum (b1) of 30～100 % by weight and do not contain fortified rosin.
2. rosin based emulsion-type sizing agent as claimed in claim 1, wherein, rosin based (B) contains the rosin (b2) of modified formaldehyde.
3. rosin based emulsion-type sizing agent as claimed in claim 2, wherein, the content of the rosin of modified formaldehyde (b2) is 1～70 % by weight.
4. such as each described rosin based emulsion-type sizing agent in the claim 1～3, wherein, hydrophobic monomer (a1) is (methyl) alkyl acrylate and/or phenylethylene.
5. such as each described rosin based emulsion-type sizing agent in the claim 1～4, wherein, the monomer (a2) with anionic property functional group contains itaconic acid and/or (methyl) acrylic acid.
6. such as each described rosin based emulsion-type sizing agent in the claim 1～5, wherein, the monomer (a2) with anionic property functional group contains (methyl) propene sulfonic acid and/or styrene sulfonic acid.
7. such as each described rosin based emulsion-type sizing agent in the claim 1～6, wherein, polymerization composition (a) contains the cross-linkable monomer (a4) that has at least 2 polymerism functional groups in the molecule.
8. such as each described rosin based emulsion-type sizing agent in the claim 1～7, wherein, with respect to 100 weight portion rosin based (B), (A) composition is counted 5～12 weight portions to be converted into solid constituent.
9. such as each described rosin based emulsion-type sizing agent in the claim 1～8, wherein, the average grain diameter of emulsion particle is 0.1～1.2 μ m.
10. the manufacture method of a rosin based emulsion-type sizing agent, it is characterized in that, use copolymer (A) with rosin based (B) emulsification, described copolymer (A) uses as 1.0～3.5 mode and obtains take (the use molal quantity with monomer (a2) of anionic property functional group) * (valence mumber with anionic property functional group of containing in the monomer (a2) of anionic property functional group)/(use molal quantity of hydrophobic monomer (a1)) by the polymerization composition (a) that will contain at least hydrophobic monomer (a1) and have a monomer (a2) of anionic property functional group, and described rosin based (B) contains at least the pine gum (b1) of 30～100 % by weight and do not contain fortified rosin.
11. a paper, its right to use requires each described rosin based emulsion-type sizing agent in 1～9 and obtains.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105155362A (en) * | 2015-09-07 | 2015-12-16 | 广东华凯科技股份有限公司 | Latex fiberboard for jeans labels and manufacturing process thereof |
| CN105603817A (en) * | 2015-11-29 | 2016-05-25 | 吴滨 | Preparation method for anion rosin surface sizing agent |
| CN105603819A (en) * | 2016-01-15 | 2016-05-25 | 黄家亨 | Sizing agent and preparation method thereof |
| CN110067152A (en) * | 2018-01-22 | 2019-07-30 | 荒川化学工业株式会社 | The manufacturing method and coating paper of paper grade (stock) surface emulsion sizing agent, paper grade (stock) surface emulsion sizing agent |
| CN110318292A (en) * | 2018-03-28 | 2019-10-11 | 荒川化学工业株式会社 | The manufacturing method of surface paper power reinforcing agent, coating liquid, paper |
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| JP7234667B2 (en) * | 2019-02-06 | 2023-03-08 | 星光Pmc株式会社 | paper manufacturing method |
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| CN1109489A (en) * | 1994-03-30 | 1995-10-04 | 近代化学工业株式会社 | Method for preparation of disperser used in glue applying agent and aqueous emulsion |
| JPH10195795A (en) * | 1996-12-27 | 1998-07-28 | Nippon P M C Kk | Papermaking and paper produced by papermaking |
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| JPH01189343A (en) * | 1988-01-20 | 1989-07-28 | Sanyo Chem Ind Ltd | Emulsifying dispersant for aqueous emulsion |
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| CN105603817A (en) * | 2015-11-29 | 2016-05-25 | 吴滨 | Preparation method for anion rosin surface sizing agent |
| CN105603819A (en) * | 2016-01-15 | 2016-05-25 | 黄家亨 | Sizing agent and preparation method thereof |
| CN110067152A (en) * | 2018-01-22 | 2019-07-30 | 荒川化学工业株式会社 | The manufacturing method and coating paper of paper grade (stock) surface emulsion sizing agent, paper grade (stock) surface emulsion sizing agent |
| CN110318292A (en) * | 2018-03-28 | 2019-10-11 | 荒川化学工业株式会社 | The manufacturing method of surface paper power reinforcing agent, coating liquid, paper |
| CN110318292B (en) * | 2018-03-28 | 2022-10-21 | 荒川化学工业株式会社 | Surface paper strength enhancer, coating liquid, and method for producing paper |
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