JP2000080592A - Sizing of paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of sizing paper in an acidic paper-making region of pH 4-5.5 by which an excellent size effect is manifested even if the total hardness of the water for the papermaking is high, and a dissolved electrolyte is present abundantly in the water. SOLUTION: A rosin based emulsion sizing agent obtained by dispersing a mixture of (A) a rosin ester obtained by heating and reacting (a) an alkenyl- substituted succinic acid with (b) rosins and (c) a polyhydric alcohol, with (B) a fortified rosin, or (C) a fortified rosin ester obtained by heating and reacting (a) the alkenyl-substituted succinic acid with (b) the rosins, (c) the polyhydric alcohol and (d) α,β-unsaturated carboxylic acids, in water in the presence of (D) an emulsification dispersant is used in an acidic paper-making region in the method for sizing a paper.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for sizing paper using a rosin-based emulsion sizing agent containing a mixture of a specific rosin ester and a reinforced rosin or a specific rosin ester as a main resin component.
An object of the present invention is to provide a sizing method in which the total hardness of papermaking water is high in an acidic papermaking region of less than 5.5 and an excellent size effect is exhibited even when a large amount of dissolved electrolyte is present.

[0002]

2. Description of the Related Art In recent years, in the papermaking industry, from the viewpoint of strengthening regulations on industrial wastewater and reducing water costs, the papermaking process has been closed in order to recover and use papermaking wastewater as much as possible. If the dissolved electrolyte in the papermaking water is increased or the papermaking temperature is forced to increase, the deterioration of the papermaking conditions is inevitable, and the total hardness of seawater is high, and water containing a large amount of dissolved electrolyte must be used as the papermaking water. There are many cases that do not. Under such papermaking conditions, it is extremely difficult for a saponified rosin-based sizing agent, which has been widely used in the past, to give a sufficient size effect to the formed paper. Is taking a bath. For example, a sizing agent obtained by emulsifying and dispersing a reinforced rosin with a specific modified polyacrylamide resin (Japanese Unexamined Patent Publication No.
No. 169898), a sizing agent emulsified and dispersed with a dissolved polyoxyethylene tristyrylphenyl ether sulfosuccinic acid half-ester salt (Japanese Patent Publication No. 7-88470), a mixture of reinforced rosin and phenolic resin, or a rosin-based substance and aromatic petroleum Sizing agent obtained by emulsifying and dispersing a resin mixture with a styrene-acrylic copolymer salt (JP-A-3-1992)
488, JP-A-6-330496), a sizing agent containing an alkenylsuccinic acid derivative, a rosin-based substance, and a dispersant (JP-A-7-189174, JP-A-7-243191) and the like. A proposal has been made.
The rosin-based emulsion sizing agents disclosed in each of these publications show a modest effect in the acidic papermaking region, but are still insufficient, and the total hardness of papermaking water is high, and a large amount of dissolved electrolyte is present. In this case, the size effect is further deteriorated. Therefore, in the papermaking industry, there is a strong demand for a paper sizing method that exhibits high sizing effects even in the acidic papermaking region, where the total hardness of papermaking water is high and a large amount of dissolved electrolyte is present.

[0003]

DISCLOSURE OF THE INVENTION The present inventors have developed a paper which exhibits an excellent size effect even in the acidic range of pH 4 to less than 5.5, in which the total hardness of papermaking water is high and a large amount of dissolved electrolyte is present. As a result of intensive research on providing a sizing method as described above, the present invention has been completed as follows.

[0004]

That is, the present invention relates to a rosin ester (A) obtained by heating and reacting an alkenyl-substituted succinic acid (a), a rosin (b) and a polyhydric alcohol (c) with a reinforced resin. A method for sizing paper, wherein a rosin-based emulsion sizing agent obtained by dispersing a mixture with rosin (B) in water in the presence of an emulsifying dispersant (D) is used in an acidic papermaking region having a pH of less than 4 to less than 5.5, and , Alkenyl-substituted succinic acids (a), rosins (b), polyhydric alcohols (c), and α, β-unsaturated carboxylic acids (d)
A rosin-based emulsion sizing agent obtained by dispersing a strengthened rosin ester (C) obtained by heat-reacting with water in the presence of an emulsifying dispersant (D) is used in an acidic papermaking region having a pH of 4 to less than 5.5. This is a method for sizing paper.

The alkenyl-substituted succinic acids (a) used in the rosin ester (A) or the fortified rosin ester (C) in the present invention include C6-C36 internal olefins, ethylene oligomers, propylene oligomers, and butylene oligomers. Alternatively, it can be obtained by an addition reaction of a mixture thereof with maleic anhydride and / or maleic acid. Particularly preferably, it has 12 to 1 carbon atoms.
6 and the addition product of propylene tetramer and / or propylene pentamer with maleic anhydride.

The production of the alkenyl-substituted succinic acids (a) may be carried out according to a conventional method. For example, maleic anhydride and / or maleic acid are added to the olefins, and the olefins are added at 150 to 250 ° C. in an autoclave reactor at 10 to 250 ° C. Obtained by reacting for 24 hours.

The rosins (b) used in the rosin ester (A), the fortified rosin (B) or the fortified rosin ester (C) in the present invention include gum rosin, tall rosin, wood rosin, hydrogenated rosin, polymerized rosin, (alkyl) ) Various rosins such as phenol / formalin resin-modified rosin, xylene resin-modified rosin, aldehyde-modified rosin, and styrene-modified rosin.

The polyhydric alcohol (c) used in the rosin ester (A) or the fortified rosin ester (C) in the present invention includes ethylene glycol, propylene glycol, butanediol, pentyl glycol, hexanediol, glycerin, and trimethylolpropane. , Trimethylolethane, pentaerythritol, sorbitol and the like. These may be used alone or in combination of two or more.

The production of the rosin ester (A) may be carried out in accordance with a conventional method. For example, alkenyl-substituted succinic acids (a), rosins (b) and polyhydric alcohols (c) may be prepared in two steps.
It is obtained by heating and reacting at 00 to 280 ° C for 10 to 24 hours.

The mixing ratio of the alkenyl-substituted succinic acids (a) and the rosins (b) in the rosin ester (A) is (a) :( b) = 1: 99 to 20:80 parts by weight,
More preferably, (a) :( b) = 3: 97 to 10:90
Parts by weight. Alkenyl-substituted succinic acids (a)
And the ratio of the hydroxyl equivalent of the polyhydric alcohol (c) to the total carboxyl equivalent of the rosins (b) is from 0.2 to 1.
5, more preferably from 0.7 to 1.0 by a heating reaction.

The fortified rosin (B) according to the present invention means that the rosin (b) is an α, β-unsaturated carboxylic acid (d).
Means an addition reaction. Α, β used here
-Typical unsaturated carboxylic acids (d) include fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, unsaturated dibasic acids such as citraconic anhydride, acrylic acid, methacrylic acid and the like. Unsaturated monobasic acids and the like can be mentioned, and these may be used alone or in combination of two or more. The α, β-unsaturated carboxylic acid (d) to be added is 5 to 20% by weight, preferably 1%, based on the rosin (b).
0 to 17%.

The production of the fortified rosin (B) may be carried out according to a conventional method, for example, heating the rosin (b) with an α, β-unsaturated carboxylic acid (d) at 180 to 250 ° C. for 1 to 5 hours. Obtained by reaction.

In the present invention, the mixing ratio of the rosin ester (A) and the fortified rosin (B) is (A) :( B) = 1.
0:90 to 80:20 parts by weight, more preferably (A) :( B) = 20: 80 to 50:50 parts by weight.

The reinforced rosin ester (C) according to the present invention
May be produced according to a conventional method. For example, after reacting an alkenyl-substituted succinic acid (a), a rosin (b) and a polyhydric alcohol (c) at 200 to 280 ° C. for 10 to 24 hours, α , β-unsaturated carboxylic acids (d) may be added and reacted at 180 to 250 ° C. for 1 to 5 hours, and rosins (b) and α, β-unsaturated carboxylic acids (d) may be reacted at 180 to 250 ° C. After the reaction for 1 to 5 hours, the alkenyl-substituted succinic acids (a) and the polyhydric alcohol (c) may be added and reacted at 200 to 280 ° C. for 10 to 24 hours. ), Rosins (b), polyhydric alcohols (c) and α, β-unsaturated carboxylic acids (d) at the same time.
You may make it react at 00-280 degreeC for 10 to 24 hours.

The reinforcing rosin ester (C) has an alkenyl-substituted succinic acid (a) and a rosin (b) in a proportion of (a) :( b) = 0.5: 99.5 to 10:90 parts by weight. , More preferably (a) :( b) = 1: 99 to 5: 9
5 parts by weight, and the ratio of the hydroxyl equivalent of the polyhydric alcohol (c) to the total carboxyl equivalent of the alkenyl-substituted succinic acids (a) and rosins (b) is 0.2 to 1.5, more preferably 0.1 to 1.5. 7 to 1.0, and the α, β-unsaturated carboxylic acids (d) to be added are rosins (b)
1 to 15% by weight, more preferably 5 to 10%
It is obtained by a heating reaction at a charge ratio as follows.

[0016] Incidentally, a mixture of rosin ester without impairing the effect of the present invention (A) and fortified rosin (B), or, in addition to fortified rosin ester (C), C ₅ or more aliphatic, aromatic A phenolic resin such as a petroleum resin obtained by polymerizing residual olefins, an alkylphenyl formalin addition condensate, and a phenol-modified petroleum resin may be used.

As the emulsifying dispersant (D) in the present invention, various low molecular surfactants, high molecular emulsifying dispersants, and protective colloids such as casein, polyvinyl alcohol and modified starch can be used. You may use it in combination of 2 or more types. Various low molecular surfactants include alkali metal salts of rosin, alkyl benzene sulfonate, polyoxyethylene alkyl phenyl ether sulfate, alkyl naphthalene sulfonate, polyoxyethylene alkyl ether sulfosuccinate monoester salt, polyoxy Anionic surfactants such as ethylene alkyl phenyl ether sulfosuccinic acid monoester salt, polyoxyethylene mono and distyryl phenyl ether sulfosuccinic acid monoester salt, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene mono and Distyryl phenyl ether, propylene glycol fatty acid ester, fatty acid diethanolamide, polyoxypropylene polyoxyethylene glycol Nonionic surfactants, more can be exemplified tetraalkylammonium chlorides, trialkyl benzyl ammonium chloride, alkyl amines, cationic surfactants such as mono- and polyoxyethylene alkylamine.

As the polymer emulsifying and dispersing agent, a synthetic polymer having a hydrophobic group, a nonionic group and / or an ionic group or a general natural polymer emulsifying and dispersing agent can be used. Or cationic styrene-
Partially or completely neutralized (meth) acrylic acid copolymer, anionic or cationic (meth) acrylic ester copolymer, or (meth) acrylamide copolymer, cationic polyaminopolyamide- Examples include epichlorohydrin resin, poly (diallylamine) -epichlorohydrin resin, and the like. In addition,
These polymeric emulsifying and dispersing agents may be used alone or in combination of two or more as protective colloids.

In particular, as the emulsifying dispersant (D) in the present invention, a carboxyl group-containing monomer and / or its salt (a), (meth) acrylamide (b), a sulfo group-containing monomer and / or its salt (c), and a hydrophobic compound When the anionic copolymer obtained by copolymerizing the monomer mixture containing the acidic monomer (d) is used, the effect of the present invention is more effectively exhibited.

The preferred mol% of each monomer constituting the anionic copolymer which is the emulsifying dispersant (D) in the present invention is 21 to 29 mol% of a carboxyl group-containing monomer and / or a salt thereof (a), ) 48-68 mol% of acrylamide (b), a sulfo group-containing monomer and / or
Alternatively, it is in the range of 3 to 10 mol% of the salt (c) and 8 to 13 mol% of the hydrophobic monomer (d).

The carboxyl group-containing monomer and / or its salt (a) is used for improving the emulsifying property and for reducing the particle size of the rosin-based emulsion sizing agent. Since the emulsifying dispersibility is deteriorated, the particle size of the obtained rosin-based emulsion sizing agent is increased, and the sizing effect and the stability over time are deteriorated. On the other hand, if it exceeds 29 mol%, the foaming property becomes large.

Specific examples of the carboxyl group-containing monomer and / or its salt (a) include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid and / or their potassium salts and sodium salts. And the like, and these may be used alone or in combination of two or more. Among these, acrylic acid, methacrylic acid, and maleic anhydride are more preferable.

(Meth) acrylamide (b) is used to improve the stability of the rosin emulsion sizing agent in hard water dilution, and its amount is from 48 to 68 mol% of the total monomers constituting the emulsifying dispersant. Preferably 55-6
5 mol%. When the amount is less than 48 mol%, the stability in dilution with hard water is deteriorated. C), the content of the hydrophobic monomer (d) decreases, and the particle size of the rosin-based emulsion sizing agent increases.

The sulfo group-containing monomer and / or its salt (c) contributes to the stability of the rosin-based emulsion sizing agent in hard water dilution and the emulsifying property, and its use amount is 3 to 10 of the total monomers constituting the emulsifying dispersant. Mol%. If the amount is less than 3 mol%, the stability in hard water dilution and the emulsifying property deteriorate, and
If the amount exceeds mol%, the cohesive strength becomes strong, and the rosin-based emulsion sizing agent is unevenly fixed on the pulp, which adversely affects the sizing effect.

Specific examples of the sulfo group-containing monomer and / or its salt (c) include styrene sulfonic acid (salt),
Vinyl sulfonic acid (salt), 2- (meth) acrylamide-2-methylpropane sulfonic acid (salt), sulfoethyl (meth) acrylate (salt), sulfopropyl (meth) acrylate (salt), (meth) allyl sulfone Sulfonic acid (salt) monomers such as acid (salt), sulfate (salt) of hydroxypropyl (meth) acrylate, sulfate (salt) of hydroxyethyl (meth) acrylate, (meth)
Sulfuric ester (salt) monomers such as polyoxyalkylene sulphate (salt) and polyoxyethylene alkylpropenyl ether sulphate (salt) can be used. These may be used alone or in combination of two or more. Among them, styrene sulfonic acid (salt),
2- (meth) acrylamide-2-methylpropanesulfonic acid (salt), sulfoethyl (meth) acrylate (salt)
Is more preferred.

The hydrophobic monomer (d) is used for imparting hydrophobicity to the emulsifying dispersant, and its amount is 8 to 13 mol% of the total monomers constituting the emulsifying dispersant. If it is less than 8 mol% or more than 13 mol%, the emulsifiability becomes poor.

Specific examples of the hydrophobic monomer (d) include:
Ethyl (meth) acrylate, methyl (meth) acrylate, (meth) acrylate having 1 to 20 carbon atoms in the alkyl group such as butyl (meth) acrylate, styrene, α
Styrenes such as methylstyrene, monomers of styrene compounds having an alkyl group having 1 to 4 carbon atoms in the aromatic ring of these styrenes, vinyl acetate, vinyl carboxylate such as vinyl propionate, carbon number 6-22 α-
Examples thereof include olefins, alkyl vinyl ethers having 1 to 22 carbon atoms, and vinylpyrrolidone. Among these, (meth) acrylic acid esters are particularly preferable in view of emulsifiability.

As a method for producing the anionic copolymer which is the emulsifying dispersant (D) in the present invention, various known methods such as solution polymerization, emulsion polymerization and suspension polymerization can be adopted. Solvents such as isopropyl alcohol and methyl ethyl ketone can be used. The emulsifier used in the case of the emulsion polymerization is not particularly limited, and various surfactants can be used. For example, alkali metal salts of fortified rosin, alkyl benzene sulfonate, polyoxyethylene alkyl phenyl ether sulfate, alkyl naphthalene Anionic surfactants such as sulfonates, polyoxyethylene alkyl ether sulfosuccinate monoester salts, polyoxyethylene alkylphenyl ether sulfosuccinate monoester salts, polyoxyethylene mono- and distyrylphenyl ether sulfosuccinate monoester salts, Polyoxyethylene alkyl ether,
Uses nonionic surfactants such as polyoxyethylene alkyl phenyl ether, polyoxyethylene mono and distyryl phenyl ether, propylene glycol fatty acid ester, fatty acid diethanolamide, polyoxypropylene polyoxyethylene glycol, and polyoxyethylene polyoxypropylene These can be used alone or in combination of two or more. The amount of use is about 0.5 to 10% by weight based on all charged monomers.

The polymerization initiator used in each of the above polymerization methods is not particularly limited, and various known ones such as persulfates, peroxides, azo compounds and redox initiators can be used, and the molecular weight is adjusted. Known chain transfer agents such as isopropyl alcohol, carbon tetrachloride, cumene, thioglycolate, alkyl mercaptan, 2-mercaptoethanol, and 2,4-diphenyl-4-methyl-1
-Pentenes and the like can be used as appropriate.

Since the molecular weight of the anionic copolymer as the emulsifying dispersant is directly correlated with the emulsifying property of the rosin-based material, the weight average molecular weight is usually 500 to 500,000,
More preferably, it is 1,000 to 100,000. 50
If it is less than 0, the stability over time of the emulsion will be poor, and
If it exceeds 0000, the product viscosity will be high.

The rosin-based emulsion sizing agent in the present invention comprises a mixture of a rosin ester (A) and a reinforced rosin (B) or a rosin ester (C), a emulsified dispersant (D) and water. A mixture of the component (A) and the component (B), or the component (D) is 3 to 20 parts by weight, more preferably 5 to 10 parts by weight, based on 100 parts by weight of the component (C).
Parts by weight.

The production method of the rosin emulsion sizing agent in the present invention is not particularly limited. For example, according to the method described in JP-B-54-36242, the component (A) and the After dissolving the component (B) or the component (C) with a solvent (eg, benzene, toluene, methylene chloride, etc.) and adding the emulsifying dispersant (D), an oil-in-water emulsion is produced through a homogenizer. (Solvent method), JP-A-54-7720
According to the method described in JP-A No. 9, the component (A) and the component (B) or the component (C) are melted, and the emulsified dispersant (D) is added to the melt. A water-in-oil emulsion to form a water-in-oil emulsion, adding inverted water to cause a phase transition to an oil-in-water emulsion (phase inversion method),
According to the method described in JP-B-53-32380, the component (A) and the component (B) or the component (C) are melted, and the emulsifying dispersant (D After the addition of the components, a method (mechanical method) of producing an oil-in-water emulsion through a homogenizer under high temperature and high pressure is used.

The method for sizing paper according to the present invention comprises the steps of:
An aqueous dispersion of pulp is produced by, for example, adding a rosin-based emulsion sizing agent according to the present invention to a wet end portion in a process for producing various papers and paperboards in an acidic papermaking region of 4 to less than 5.5. The rosin-based emulsion sizing agent of the present invention is used in an amount of 0.01 to 5% by solid content, preferably 0.05 to 5% by weight based on the dry weight of the pulp.
Add 2% solids by weight.

In the paper making step, a fixing aid and / or an aluminum salt such as aluminum sulfate is used according to a conventional method.

The filler that can be used in the paper sizing method according to the present invention is not particularly limited, and any of those conventionally used in the acidic papermaking area can be used. For example, talc, clay, titanium oxide, white carbon and the like can be mentioned.

As the fixing agent used in the paper sizing method of the present invention, known fixing agents conventionally used in the acidic papermaking area can be used as they are. For example, cationic starch, Mannich-modified polyacrylamide, Hoffmann-modified polyacrylamide, anionic, cationic and zwitterionic copolymers obtained by copolymerizing acrylamide with a cationic monomer and / or anionic monomer And modified epichlorohydrin of polyamide polyamine resin.

In the paper sizing method using a rosin-based emulsion sizing agent according to the present invention, the amount of the sulfate band used can be reduced because of good fixability to pulp. Furthermore, when the papermaking process is closed, impurities due to the use of waste paper and the like, increase in various dissolved electrolytes, or when the total hardness such as seawater is high and water containing a large amount of dissolved electrolyte must be used as papermaking water, it is excellent. Develop size effect.

The paper sizing method according to the present invention includes printing paper such as high-quality paper, medium-quality paper, and coated paper, information paper such as PPC paper, foam paper, heat-sensitive paper, pressure-sensitive paper, packaging paper, cardboard base paper, and white board. It can be applied to paperboard such as paper and gypsum board paper. Furthermore, as well as papermaking of cellulose fibers, cellulose fibers and mineral fibers, such as asbestos, rock wool, and synthetic fibers,
For example, it can be advantageously applied to papermaking of a mixture with polyamide, polyester, polyolefin and the like to produce paper, paperboard, fiberboard and the like.

[0039]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention are as follows.

Production of alkenyl-substituted succinic acids (a): A predetermined amount of an olefin oligomer and maleic anhydride are charged into an autoclave reactor, and charged under a nitrogen atmosphere.
After reaction at 0 to 250 ° C. for 10 to 24 hours, vacuum distillation was performed to obtain sticky alkenyl-substituted succinic anhydride.

Production of rosin ester (A): stirrer,
A predetermined amount of gum rosin and a predetermined amount of the above-mentioned alkenyl-substituted succinic anhydride and glycerin were charged into a reactor equipped with a thermometer, a distilling tube, and a nitrogen introducing tube.
The mixture was heated to 0 ° C and reacted at the same temperature for 10 to 24 hours to obtain a rosin ester.

Production of fortified rosin (B): about 200 in a reactor equipped with a stirrer, thermometer, distilling tube and nitrogen introducing tube.
C. A predetermined amount of maleic anhydride is gradually added to a predetermined amount of gum rosin in a molten state at a temperature of 180.degree.
An addition reaction was performed at 1 ° C. for 1 to 5 hours to obtain a reinforced rosin.

Production of fortified rosin ester (C): A predetermined amount of the alkenyl-substituted succinic acid (a), gum rosin and glycerin was charged into a reactor equipped with a stirrer, thermometer, distilling tube and nitrogen introducing tube, and nitrogen was added. 200-280 under air flow
° C, and after reacting at the same temperature for 10 to 24 hours,
A predetermined amount of maleic anhydride was charged and reacted at 180 to 250 ° C. for 1 to 5 hours to obtain a reinforced rosin ester (C). As another method, the reaction order of glycerin and maleic anhydride was reversed to obtain a fortified rosin ester (C). As still another method, the above-mentioned glycerin and maleic anhydride were simultaneously charged and reacted at 200 to 280 ° C for 10 to 24 hours to obtain a reinforced rosin ester (C).

Production of emulsifying and dispersing agent (D): Soft water and an anionic copolymer are formed in a reactor equipped with a stirrer, thermometer, distilling tube, nitrogen introducing tube, and condenser. (D)
Each monomer, a predetermined amount of a chain transfer agent is added and mixed and stirred, and then a predetermined amount of a polymerization initiator is added under a nitrogen atmosphere,
The reaction was carried out at 75 to 85 ° C. for 3 to 6 hours to obtain an anionic copolymer as an emulsifying dispersant (D).

・ Rosin emulsion size agent (RE)
Production: A predetermined amount of the mixture of the rosin ester (A) and the fortified rosin (B) obtained here or the predetermined amount of the fortified rosin ester (C) obtained here is heated and melted at about 150 ° C. While stirring, add the emulsifying dispersant (D)
Is added and mixed to form a water-in-oil emulsion, and a predetermined amount of hot water is further quickly added thereto to form a stable oil-in-water emulsion. After cooling to room temperature, a rosin emulsion sizing agent (RE ) Got.

Performance evaluation of rosin emulsion sizing agent: [Method 1] Pulp slurry (2.5% concentration) (L-BKP C
SF; 470 ml), aluminum sulfate was 2.0% in terms of solid content with respect to absolutely dry pulp, and the rosin emulsion sizing agent (RE) was 0.3% in terms of solid content with respect to absolutely dry pulp. Was added to the absolutely dry pulp in terms of solid content, and then Pearl Floc FR-C (trade name: filler retention agent manufactured by Seiko Chemical Co., Ltd.) was added to the absolutely dry pulp at 500 ppm in terms of solid content. TAP according to the usual law
Paper was made with a PI standard sheet machine. The water for papermaking at this time had a total hardness of 100 ppm and a specific conductivity of 500 μm.
hos / cm water was used, and the pH of the pulp slurry was 4.
It was 5. The wet paper was dehydrated under a pressure of 3.5 kg / cm ² for 5 minutes, and then dried for 1 minute with a rotary drier at a temperature of 90 ° C. to obtain a paper having a basis weight of 60 g / m ² . After conditioning for 24 hours at a temperature of 20 ° C. and a humidity of 65%, the size of each paper
ISP8112: Measured by the Steckigt method. [Method 2] 2.5% pulp slurry (L-BKP)
CSF (470 ml), aluminum sulfate was 1.5% in terms of solid content based on absolutely dry pulp, and the rosin-based emulsion sizing agent (RE) was 0.3% in terms of solid content based on absolutely dry pulp. 20% was added to the absolutely dry pulp in terms of solid content, and then Pearl Floc FR-C was added to the absolutely dry pulp in an amount of 500 ppm in terms of solid content,
Paper was made using a TAPPI standard sheet machine according to a conventional method. At this time, the papermaking water used was water having a total hardness of 200 ppm and a specific conductivity of 800 μmhos / cm, and the pH of the pulp slurry was 5.0. 3.5 kg / cm ^{2 for} wet paper
After drying for 5 minutes under a pressure of 90 ° C., drying was performed for 1 minute with a rotary drier at a temperature of 90 ° C. to obtain a paper having a basis weight of 60 g / m ² . After humidity control at a temperature of 20 ° C. and a humidity of 65% for 24 hours, the sizing degree of each formed paper was measured by JIS P8112; Total hardness and specific conductivity of papermaking water (indicating the amount of electrolyte components)
Analysis ・ Total hardness: according to the chelate titration method of JIS K0101. (The content of calcium ion and magnesium ion in water expressed in terms of calcium carbonate)-Specific conductivity: Measured with a specific conductivity meter. (LASER ZEE
Model 501. PEN. KEM INC. (Unit: μmhos / cm)

[0047]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Production Examples, Examples, and Comparative Examples, but the present invention is not limited to each of these examples. In addition, in each example, all parts and% are based on weight unless otherwise specified.

Production of alkenyl-substituted succinic acids (a): [Production Example a-1] In an autoclave reactor, 144 parts of a high mass polymer (trade name: Nippon Oil Co., Ltd .: propylene oligomer: 15 carbon atoms), anhydrous After 68 parts of maleic acid was charged and reacted at 200 ° C. for 24 hours under a nitrogen atmosphere, vacuum distillation was performed to obtain a sticky alkenyl-substituted succinic anhydride having an acid value of 230.

Production of rosin ester (A): [Production Example A-1] 800 parts of gum rosin having an acid value of 170 were placed in a reactor equipped with a stirrer, a thermometer, a distilling tube, and a nitrogen introducing tube.
13 parts of the alkenyl-substituted succinic anhydride obtained in [Production Example a-1] and 83 parts of glycerin were charged, heated to 250 ° C. in a nitrogen stream, and reacted at the same temperature for 24 hours to obtain an acid value of 1
A rosin ester of 0 was obtained.

[Production Example A-2] In Production Example A-1, 800 parts of gum rosin having an acid value of 170, [Production Example a-
26 parts of the alkenyl-substituted succinic anhydride obtained in 1),
A rosin ester having an acid value of 11 was obtained in the same manner as in [Production Example A-1] except that glycerin was changed to 86 parts.

[Production Example A-3] In Production Example A-1, 800 parts of gum rosin having an acid value of 170 were prepared.
1] The alkenyl-substituted succinic anhydride 103 obtained in [1]
And Production Example A-
In the same manner as in [1], a rosin ester having an acid value of 10 was obtained.

[Production Example A-4] In Production Example A-2, MSP was used in place of the alkenyl-substituted succinic anhydride.
(Mitsubishi Petroleum Co., Ltd .: addition reaction product of propylene oligomer having 12 carbon atoms and maleic anhydride)
A rosin ester having an acid value of 12 was obtained in the same manner as in [Production Example A-2].

[Production Example A-5] In Production Example A-2, instead of the alkenyl-substituted succinic anhydride, Coropearl Z-100S (trade name: manufactured by Hoshi Photo Chemical Industry Co., Ltd .: internal olefin having 16 carbon atoms) And the addition of maleic anhydride) in the same manner as in [Production Example A-2].
A rosin ester having an acid value of 10 was obtained.

[Production Example A-6] A reaction was carried out in the same manner as in [Production Example A-2] except that 65 parts of pentaerythritol was used instead of glycerin in [Production Example A-2].
A rosin ester having an acid value of 11 was obtained.

[Production Example A-7] The same procedure as in [Production Example A-1] was carried out except that [Alkaline Substituted Succinic Anhydride [Production Example a-1]] was not used. Thus, a rosin ester having an acid value of 9 was obtained.

[Production Example A-8] The same procedure as in [Production Example A-3] was carried out except that the alkenyl-substituted succinic anhydride [Production Example a-1] was not used in [Production Example A-3]. Thus, a rosin ester having an acid value of 8 was obtained.

Production of fortified rosin (B): [Production Example B-1] Gum rosin 800 in a molten state at about 200 ° C. in a reaction vessel equipped with a stirrer, a thermometer, a distilling tube, and a nitrogen introducing tube. 136 parts of maleic anhydride was gradually added to the mixture, and an addition reaction was performed at 200 ° C. for 5 hours under a nitrogen stream.
A reinforced rosin with an acid value of 230 was obtained. [Production Example B-2]

A reinforced rosin having an acid value of 215 was obtained in the same manner as in [Production Example B-1] except that 96 parts of maleic anhydride was used in [Production Example B-1].

[Preparation Example B-3] [Preparation Example B-1] was the same as [Preparation Example B-1] except that 80 parts of fumaric acid was used.
In the same manner as described above, a reinforced rosin having an acid value of 210 was obtained.

Production of reinforced rosin ester (C): [Production Example C-1] 800 parts of gum rosin in a molten state at 200 ° C. in a reaction vessel equipped with a stirrer, a thermometer, a distilling tube and a nitrogen introducing tube. After adding 70 parts of maleic anhydride and reacting at 200 ° C. for 5 hours under a nitrogen stream, [Production Example a-1]
10 parts of the alkenyl-substituted succinic anhydride obtained above and 36 parts of glycerin were charged, heated to 250 ° C. and reacted at the same temperature for 24 hours to obtain a reinforced rosin ester having an acid value of 120.

[Production Example C-2] 800 parts of gum rosin in a molten state at 200 ° C. in a reaction vessel equipped with a stirrer, a thermometer, a distilling tube, and a nitrogen introducing tube were obtained in [Production Example a-1]. 10 parts of alkenyl-substituted succinic anhydride and glycerin 3
After charging 6 parts and reacting at 250 ° C. for 24 hours under a nitrogen stream, 36 parts of maleic anhydride was charged and reacted at 200 ° C. for 5 hours to obtain a reinforced rosin ester having an acid value of 130.

[Production Example C-3] 800 parts of gum rosin in a molten state at 200 ° C. in a reaction vessel equipped with a stirrer, a thermometer, a distilling tube, and a nitrogen introducing tube were obtained in [Production Example a-1]. 10 parts of alkenyl-substituted succinic anhydride and glycerin 3
After charging 6 parts, 70 parts of maleic anhydride were added and reacted at 250 ° C. for 24 hours under a nitrogen stream to obtain a reinforced rosin ester having an acid value of 115.

Production of emulsifying dispersant (D) [Production Example D-1] 40 parts of styrene and 40 parts of methacrylic acid were placed in a reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube and a cooler.
Parts, 20 parts of n-butyl methacrylate, 6 parts of isopropyl alcohol, 4 parts of dodecyl mercaptan, 4 parts of Coropearl E-5 (trade name: rosin-based emulsion sizing agent, manufactured by Hoshiko Chemical Co., Ltd.), and 450 parts of water are mixed and stirred. Then, 6 parts of ammonium persulfate and 6 parts of sodium hydrogen sulfite were added, and the mixture was heated and reacted at 80 ° C. for 4 hours. After adding 80 parts of 24% sodium hydroxide, the mixture was cooled to room temperature, and anionic copolymer having a solid content of 20% was added. A combined emulsified dispersant was obtained. The properties are shown in Table 1.

[Production Example D-2] A reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a cooler was charged with 55 parts of styrene,
Ethylhexyl acrylate 15 parts, acrylic acid 15
Parts, methacrylic acid 15 parts, isopropyl alcohol 10
Parts and 320 parts of soft water in a polyoxyethylene polyoxypropylene block polymer (trade name: Epan U-103)
A solution prepared by dissolving 5 parts of Daiichi Kogyo Seiyaku Co., Ltd. and 3 parts of 2-ethylhexyl thioglycolate were mixed and stirred, and 3 parts of ammonium persulfate and 3 parts of sodium bisulfite were added.
After reacting at 70 to 80 ° C. for 5 hours, 20 parts of 24% sodium hydroxide was added, and then soft water was added to a concentration of 25% to obtain an emulsifying dispersant of an anionic copolymer. The properties are shown in Table 1.

[Production Example D-3] 150 parts of isopropyl alcohol, 70 parts of soft water, and 28.5 parts of methacrylic acid (2 parts) were placed in a reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a cooler.
9 mol%), 40% acrylamide 116.6 parts (5
7.5 mol%), 16.3 parts (10 mol%) of isobutyl methacrylate, 8.6 parts (3.5 mol%) of sodium sulfoethyl methacrylate, 1 part of n-dodecyl mercaptan, 1 part of 2-mercaptoethanol After mixing and stirring 8 parts, the mixture was heated to an internal temperature of 50 ° C. under a nitrogen atmosphere, 0.5 parts of azobisisobutyronitrile was added, and the temperature was raised to 80 ° C.
After keeping the temperature for 5 hours, 120 parts of water was added and distillation under reduced pressure was performed to distill off isopropyl alcohol. After the distillation was completed, the mixture was cooled to obtain an emulsifying dispersant of an anionic copolymer. The properties are shown in Table 1.

[Production Examples D-4 to 6] In [Production Example D-3], the composition of the carboxyl group-containing monomer, acrylamide, sulfo group-containing monomer, and 2-mercaptoethanol was changed as shown in Table 1. Except for the above, the reaction was carried out in the same manner as in [Production Example D-3] to obtain an anionic copolymer as each emulsifying dispersant. Table 1 shows the product properties.

[0067]

[Table 1]

Rosin emulsion sizing agent (RE)
Production: Rosin ester 40 of [Production Example RE-1] [Production Example A-1]
Of the reinforced rosin of [Production Example B-1] and about 60 parts of the reinforced rosin at about 150 ° C., and 9 parts of the emulsifying dispersant of [Production Example D-1] as a solid content was added and mixed with vigorous stirring. Then, a water-in-oil emulsion was added, and 95 parts of hot water was added thereto to form a stable oil-in-water emulsion, and then cooled to room temperature to obtain a rosin-based emulsion sizing agent. The properties are shown in Table 2.

[Production Example RE-2 to 15] [Production Example RE-1]
In the same manner as in [Production Example RE-1], except that the mixing ratio and the type of the rosin ester and the fortified rosin, the fortified rosin ester and the emulsifying dispersant were changed as shown in Table 2, 15] was obtained. The properties are shown in Table 2.

Comparative Production Example of Rosin Emulsifier (CRE) [Comparative Production Example CRE-1-8] [Comparative Production Example CRE-1-8] [Comparative Production Example C] in the same manner as in [Production Example RE-1] except that the type was changed as shown in Table 2.
RE-1 to 8] were obtained. The properties are shown in Table 2.

[0071]

[Table 2]

[Examples 1 to 15] [Production Examples RE-1 to 1]
Using the rosin emulsion sizing agent of the present invention obtained in [5], papermaking is performed according to the method 1 and method 2 for evaluating the performance of the rosin emulsion sizing agent of the embodiment of the present invention, and the size effect is measured. did. Table 3 shows the results.

Comparative Examples 1 to 8 In Example 1, except that the rosin emulsion sizing agent of [Comparative Production Example CRE-1 to 8] was used instead of [Production Example RE-1]. Papermaking was performed in the same manner as in [Example 1], and the size effect was measured. Table 3 shows the results.

[0074]

[Table 3]

[0075]

According to the present invention, as shown in the Examples, pH 4 to
An excellent sizing effect is exhibited in an acidic papermaking region of less than 5.5 and when the papermaking water has a high total hardness and a large amount of dissolved electrolyte.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4D077 AA05 AB20 AC03 BA05 BA07 BA13 CA02 CA03 CA04 CA14 CA15 DA02Y DA02Z DC02Y DC02Z DC16Z DC28Z DD03Y DD13Z DD14Z DD17Y DD17Z DD18Z DD19Y DD19Z DD32Z DD49Z DE02Y DE09Y DE09Z DE09Y DE09Z AB22Y AB35Y BA03 BB06 CA03 DA07 EA01 EA06 4L055 AG50 AG63 AG71 AG72 AG89 AH11 AH33 AH50 EA17 EA31

Claims (3)

[Claims] An emulsifying dispersant comprising a mixture of a rosin ester (A) obtained by heating and reacting an alkenyl-substituted succinic acid (a), a rosin (b) and a polyhydric alcohol (c) with a reinforced rosin (B). A rosin-based emulsion sizing agent obtained by dispersing in water in the presence of (D) has a pH of 4 to 5.5.
A method for sizing paper, wherein the method is used in an acidic papermaking area of less than. 2. A reinforced rosin ester (C) obtained by heating and reacting an alkenyl-substituted succinic acid (a), a rosin (b), a polyhydric alcohol (c) and an α, β-unsaturated carboxylic acid (d). Is dispersed in water in the presence of an emulsifying dispersant (D) to obtain a rosin emulsion sizing agent having a pH of
A method for sizing paper, wherein the method is used in an acidic papermaking area of 4 to less than 5.5. 3. An emulsifying dispersant (D) comprising a carboxyl group-containing monomer and / or a salt thereof (a), (meth) acrylamide (b), a sulfo group-containing monomer and / or a salt thereof (c), and a hydrophobic monomer 3. The paper sizing method according to claim 1, comprising an anionic copolymer obtained by copolymerizing a monomer mixture containing (d).