JP2002317394A - Rosin-based emulsion component for newsprint paper, method for manufacturing newsprint paper, and newsprint paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sizing agent consisting of a rosin-based emulsion composition capable of imparting sizing property which is needed by newsprint and resists against wetting water during lithography by a relatively small amount of addition even on the quick drying of high-speed paper making. SOLUTION: A rosin-based emulsion composition for newsprint comprises a dispersing agent containing a copolymer comprising a rosin-based substance and a (meth)acrylic ester monomer as constituting components, and the (meth) acrylic ester is a monomer can constitute a homopolymer having a glass transition temperature of 0 deg.C or lower. A method for manufacturing newsprint by using the composition and newsprint paper.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rosin-based emulsion composition for newsprint, and more particularly to a rosin-based material, a styrene-based monomer, and a glass transition temperature of 0.degree. Containing an anionic copolymer as a component of the copolymer together with a (meth) acrylate monomer and a monomer of (meth) acrylic acid and / or a salt thereof, which are monomers capable of forming a homopolymer. A rosin emulsion composition containing a dispersing agent and a rosin emulsion composition for newsprint that can effectively impart sizing properties suitable for offset printing on newsprint, and a newspaper using the same The present invention relates to a method for manufacturing paper and newsprint using the same.

[0002]

2. Description of the Related Art In the papermaking industry, paper machines for newsprint are operated at higher speeds to improve productivity, and as a result, wet paper webs are often dried rapidly. In recent years, the newspaper printing method has shifted from the conventional letterpress printing method to the offset printing method. In offset printing, a lithographic plate called a PS plate in which a photosensitive resin is applied to an aluminum plate is used. This P
When the film original is brought into close contact with the S plate, exposed and developed, the photosensitive resin other than the image area is removed, the surface of the aluminum plate becomes the non-image area, and the photosensitive resin area becomes the image area. Called edition. When ink is supplied after dampening water has been applied to this printing plate, the ink does not adhere to the surface of the hydrophilic aluminum plate because the dampening water adheres to the plate, resulting in a non-image area,
The ink adheres to the lipophilic photosensitive resin portion to form an image area. Ink is transferred from the printing plate to paper via a blanket, and printing is performed. In such offset printing using a lithographic PS plate, dampening water adheres to the paper surface during printing, so if a paper having a surface with low water resistance is used, the paper surface is peeled off, and this is continued. Then, the paper powder is deposited on the blanket, and the deposit eventually peels off and mixes with the ink, which tends to cause a problem that the printed image of the printed matter is blurred. In order to avoid this, it is important to increase the size (water resistance) with respect to the dampening solution. The sizing required for newspapers is not required to be as high as that required for high-quality paper, but is effective for dampening water (a predetermined sizing effect is achieved with a sizing agent having a low addition rate). Are preferred.

[0003]

However, when a conventional sizing agent, for example, an anionic rosin-based sizing agent, particularly a solution-type rosin sizing agent which is an alkali neutralized reinforced rosin is used, or when a solution-type rosin sizing agent is used. Even when using a conventional dispersion type rosin-based sizing agent (rosin-based emulsion sizing agent) that is superior in size effect to the papermaking agent and has a wide pH range for papermaking, it can be said that the drying conditions are sufficient for papermaking by a high-speed paper machine. Therefore, in order to obtain a predetermined sizing degree, the amount of the sizing agent to be added must be increased, which not only increases the cost but also causes a problem that foaming is remarkable in the paper making process. As described above, a rosin-based emulsion sizing agent using a general fortified rosin does not satisfy the sizing properties required for newsprint unless a large amount of the emulsion sizing agent is added. Foaming trouble easily occurs. In order to solve this problem, for example, JP-A-2000-964
No. 85 discloses an internally added rosin-based emulsion sizing agent for newsprint, but tends to be unable to sufficiently impart the size required by newsprint. From the above, when the papermaking speed is high, such as a newspaper machine for newsprint, and when drying needs to be performed rapidly, the required sizing property (water resistance) is exhibited at a low addition rate. There is a strong demand for the appearance of rosin-based emulsion sizing agents that can be used.

A first object of the present invention is to provide size (water resistance) against dampening water during lithographic printing required for newsprint.
A rosin-based emulsion composition for newsprint that can be achieved at a lower addition rate than conventional rosin emulsion sizing agents, a method for producing newsprint using the same, and newsprint using the same. A second object of the present invention is to provide newsprint papers which can achieve sizing properties (water resistance) at a lower addition rate than conventional rosin emulsion sizing agents even for rapid drying during high speed papermaking required for newsprint. A rosin-based emulsion composition, a method for producing newsprint using the same, and newsprint using the same.
A third object of the present invention is to provide a rosin emulsion composition for newsprint that exhibits an excellent size effect even in a papermaking system in a wide pH range from an acidic pH of 4 to an alkaline pH of 8; An object of the present invention is to provide a manufacturing method and newsprint using the same. A fourth object of the present invention is to provide a rosin-based emulsion composition for newsprint with little foaming in a papermaking process, a method for producing newsprint using the same, and newsprint using the same. A fifth object of the present invention is to provide a rosin emulsion composition for newsprint having excellent storage stability and excellent mechanical stability in a papermaking process, a method for producing newsprint using the same, and a newspaper using the same. To provide paper. A sixth object of the present invention is to provide a rosin-based emulsion composition for newsprint, which is capable of exhibiting an excellent sizing effect at a low addition rate and thereby reducing the cost of a sizing agent in papermaking. The present invention provides a method for manufacturing newsprint and a newsprint using the same.

[0005]

According to the present invention, there is provided a rosin-based emulsion composition containing (1) a rosin-based substance (A) and a dispersant (B). The agent (B) includes a styrene-based monomer (a), a (meth) acrylate-based monomer (b), which is a monomer capable of forming a homopolymer having a glass transition temperature of 0 ° C. even at a high temperature, and (meth) ) Acrylic acid and / or
Another object of the present invention is to provide a rosin emulsion composition for newsprint containing a copolymer obtained by copolymerizing a monomer having the monomer (c) of the salt in the monomer constitution and / or a neutralized product thereof. Further, the present invention provides (2)
In a rosin-based emulsion composition containing a rosin-based material (A) and a dispersant (B), the dispersant (B) has a styrene-based monomer (a) and a styrene-based monomer (a) having a high glass transition temperature of 0%.
(Meth) acrylic acid ester monomer (b), which is a monomer capable of forming a homopolymer having a temperature of ℃
And a monomer (c) having (meth) acrylic acid and / or a salt thereof and a (meth) acrylate monomer (d) other than the (meth) acrylate monomer (b) in the monomer configuration (3) a rosin-based emulsion composition for newsprint, containing a copolymer obtained by copolymerizing the following and / or a neutralized product thereof, (2), wherein the monomer is 2,4-diphenyl-4-methyl-1-pentene ( e) and a rosin emulsion composition for newsprint according to (1) or (2) above, which is copolymerized in the presence of alkyl mercaptan (f) to obtain a copolymer and / or a neutralized product thereof, (4) , (A) component is 10 to 60% by weight,
The component (b) is 20 to 70% by weight, and the component (c) is 20 to 6% by weight.
The rosin emulsion composition for newsprint according to any one of the above (1) to (3), wherein 0% by weight and 0 to 10% by weight of the component (d), components (5) and (a) to (d) 0.1 to 3% by weight of component (e) based on the total weight of
The above (3) or (4), wherein the component is used in an amount of 0.1 to 3% by weight.
Rosin emulsion composition for newsprint of (6),
The above-mentioned (1) to (5), wherein the rosin-based substance (A) is a fortified rosin obtained by reacting a rosin with an α, β-unsaturated carboxylic acid in a weight ratio of 95: 5 to 90.1: 9.9. A rosin emulsion composition for newsprint of any of
(7) A method for producing newsprint paper in which a rosin-based emulsion composition for newsprint paper according to any one of the above (1) to (6) is added to a raw material slurry for newsprint and papermaking is performed to obtain sized paper. (8) A newsprint containing the rosin-based substance (A), the copolymer of any of the above (1) to (6), and / or a neutralized product thereof.

Hereinafter, the present invention will be described in detail. In the present invention, the rosin-based substance (A) refers to rosin itself,
Reaction product using rosin as a reaction component (modified rosin)
And reinforced rosins and rosin esters thereof, which are used alone or as a mixture of two or more. As rosin itself, gum rosin, tall oil rosin,
Wood rosin is used, and these are used alone or as a mixture of two or more. Examples of the rosin-modified product include a partially or substantially completely hydrogenated, disproportionated, polymerized, or formaldehyde-modified rosin.

The above-mentioned fortified rosin is obtained by adding an α, β-unsaturated carboxylic acid to the above-mentioned rosin or a modified rosin. Representative examples of the α, β-unsaturated carboxylic acid used herein include unsaturated dibasic acids such as fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid and citraconic anhydride. And unsaturated monobasic acids such as acrylic acid and methacrylic acid. These may be used alone or in combination of two or more. In the composition of the fortified rosin, the ratio of the rosin to the α, β-unsaturated carboxylic acid is preferably from 95: 5 to 90.1: 9.9, particularly preferably from 93: 7 to 90.5: 9.5.

The above-mentioned rosin esters include reaction products of the above-mentioned rosin and at least one of the rosin-modified or fortified rosins with at least one selected from polyhydric alcohols such as glycerin and pentaerythritol and epoxy compounds. Can be Further, a rosin ester obtained by further adding an α, β-unsaturated carboxylic acid to the above rosin esters is also included. In a current papermaking system for producing newsprint, that is, an acidic papermaking system having a pH of 4 to 6, it is preferable that the rosin-based substance (A) does not contain rosin esters in terms of size effect. When a rosin ester is contained in the rosin-based substance (A), the sizing effect tends to be improved in a weakly acidic or neutral papermaking system having a pH of 6 or more as compared with a rosin ester containing no rosin ester. Preferably contains rosin esters.

In the present invention, among the monomers constituting the copolymer contained in the dispersant (B) and / or its neutralized product, styrene monomers (a) include styrene, α
And styrenes such as methylstyrene, vinyltoluene, and divinylbenzene, and one or more of these are used. Of these, styrene, α-
Methylstyrene is preferred.

[0010] Among the monomers constituting the copolymer and / or the neutralized product thereof contained in the dispersant (B), a (meth) acrylic which can constitute a homopolymer having a glass transition temperature of 0 ° C or lower. As the acid ester monomer (b), specifically, POLYMER HANDBOOK
THIRD EDITION (J. BRANDRU
P, E. H. IMMERGUT, published by AWILEY
-INTERSCIENCE PUBLICATO
N) Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, ethylhexyl acrylate, nonyl acrylate, dodecyl acrylate, methyl butyl acrylate, dimethyl butyl acrylate, etc. And methacrylate monomers such as pentyl methacrylate, hexyl methacrylate, octyl methacrylate, ethylhexyl methacrylate, decyl methacrylate, and dodecyl methacrylate. One or more of these are used. Of these, butyl acrylate, isobutyl acrylate, ethylhexyl acrylate, and ethylhexyl methacrylate are preferred. The glass transition temperature of a homopolymer of each of these monomers is 0 to -70 ° C, and a monomer having a glass transition temperature of the homopolymer of 0 to -60 ° C is preferable.

Among the monomers constituting the copolymer and / or its neutralized product contained in the dispersant (B), (meth)
Examples of the monomer (c) of acrylic acid and / or its salt include acrylic acid, methacrylic acid and at least one of salts obtained by neutralizing these with a basic substance. Examples of the basic substance include sodium, Potassium, ammonium, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, butylamine, monoethanolamine, diethanolamine, triethanolamine, etc., and one or more of these are used. Of these, methacrylic acid and / or its sodium, potassium, ammonium and monoethanolamine salts are preferred.

As the monomer constituting the copolymer contained in the dispersant (B) and / or its neutralized product, a (meth) acrylate monomer (d) other than the monomer (b) is used. The monomer (d) may be methyl (meth) acrylate, ethyl methacrylate, propyl methacrylate, normal butyl methacrylate, isobutyl methacrylate, tertiary butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) Acrylates and the like are mentioned, and one or more of these are used. Of these, methyl (meth) acrylate, normal butyl methacrylate, isobutyl methacrylate, and cyclohexyl methacrylate are preferred.

The rosin emulsion composition of the present invention does not deviate from the object of the present invention when used as a sizing agent, and may contain a dispersant (B) if necessary as long as the effect can be maintained. As the monomers constituting the copolymer and / or the neutralized product thereof, the above (a) to (a)
Other monomers copolymerizable with (c) and (a) to (d) may be used in combination. Examples of such a monomer include hydrophobic monomers such as dialkyl esters of unsaturated dicarboxylic acids such as maleic acid and fumaric acid, vinyl esters such as vinyl acetate and vinyl propionate, crotonic acid,
Α, β-unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid and citraconic acid, monomethyl maleate, monoethyl maleate, monopropyl maleate,
Α, β-unsaturated dicarboxylic acid half esters such as monobutyl maleate, monomethyl fumarate, monoethyl fumarate, monopropyl fumarate, monobutyl fumarate, monomethyl itaconate, monoethyl itaconate, monopropyl itaconate and monobutyl itaconate Sulfonic acid group-containing monomers such as vinylsulfonic acid, (meth) allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid and sulfonated styrene, and phosphoric acid esters of hydroxyalkyl (meth) acrylates And the like, and anionic monomers such as salts thereof with an alkali compound, (mono- or di-alkyl) aminoalkyl (meth) acrylate, (mono- or di-alkyl) aminohydroxyl Cationic monomers such as killed (meth) acrylate, (mono- or di-alkyl) aminoalkyl (meth) acrylamide, vinylpyridine, vinylimidazole and diallylamine, (meth) acrylamide, N-substituted (meth) acrylamide and vinylpyrrolidone Nonionic monomers of the formula (1). The amount of the rosin-based emulsion composition used may be within a range that does not deteriorate the sizing performance of the obtained rosin-based emulsion composition. Specifically, it is usually 10% by weight or less of all monomers, preferably 5% by weight at most. is there.

The above components (a) to (d) comprise 10 to 60% by weight of component (a), 20 to 70% by weight of component (b),
The component (c) is preferably 20 to 60% by weight and the component (d) is preferably 10% by weight or less, more preferably (d).
The component is less than 5% by weight. When the component (d) is not used, the component (a) is 10 to 60% by weight, and the component (b) is 2% by weight.
Preferably, the amount is 0 to 70% by weight and the component (c) is 20 to 60% by weight. In addition, the weight% may be a part by weight.

When a monomer is copolymerized in the presence of 2,4-diphenyl-4-methyl-1-pentene (e) or alkylmercaptan (f), a copolymer and / or a neutralized product thereof is produced. It is known that it is easy to control the molecular weight of the copolymer, but by using a dispersant containing a copolymer obtained by using these chain transfer agents in combination and / or a neutralized product thereof, When a rosin-based material is emulsified and dispersed in water, a finer emulsion of particles can be produced, and a rosin-based emulsion composition in which sediments and agglomerates are more unlikely to occur over time is obtained. It can be suitably used. Examples of the alkyl mercaptan (f) include n-octyl mercaptan, tertiary decyl mercaptan, n-dodecyl mercaptan, n-octadecyl mercaptan, n-hexadecyl mercaptan, and one or more of these are used. Can be Particularly, n-dodecyl mercaptan and tertiary decyl mercaptan are preferred. In synthesizing the copolymer contained in the dispersant (B) and / or a neutralized product thereof, a chain transfer agent other than the components (e) and (f) can be used in combination. For example, thioglycolic acid derivatives, mercaptopropionic acid derivatives, mercaptoethanol, thiomalic acid, mercaptan derivatives such as thiosalicylic acid and the like can be mentioned.
Component (e) is used in an amount of 0.1 to 3% by weight and component (f) is used in an amount of 0.1 to 3% by weight based on the total weight of the components (a) to (d) or the components (a) to (c). Is preferred.

In producing the copolymer contained in the dispersant (B) and / or a neutralized product thereof, the polymerization method may be any of emulsion polymerization, solution polymerization, suspension polymerization and bulk polymerization. Emulsion polymerization is preferred. Known surfactants can be used as the emulsifier for emulsion polymerization. As the surfactant, those which can be generally applied to emulsion polymerization can be used, and examples thereof include nonionic, anionic and amphoteric surfactants. However, a surfactant having a polymerizable group can also be used. These surfactants can be used alone or in combination of two or more.

Examples of the nonionic surfactant include polyoxyalkylene alkylphenyl ether, polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid ester, polyoxypropylene polyoxyethylene glycol glycerin fatty acid ester, sorbitan fatty acid ester, and polyethylene glycol fatty acid. Examples include esters, polyoxyethylene sorbitan fatty acid esters, sucrose fatty acid esters, pentaerythritol fatty acid esters, propylene glycol fatty acid esters, fatty acid diethanolamide, and polyoxypropylene polyoxyethylene glycol. One of these nonionic surfactants can be used alone, or two or more can be used in combination.

Examples of the anionic surfactant include compounds such as polyoxyalkylene alkylphenyl ether, polyoxyalkylene monostyryl phenyl ether, polyoxyalkylene distyryl phenyl ether, polyoxyalkylene alkyl ether and polyoxyalkylene fatty acid ester. Phosphate, sulfonate, succinate and sulfosuccinate, alkylbenzene sulfonate, naphthalene sulfonic acid formalin condensate, alkenyl succinate, rosin salt, reinforced rosin salt and hexyl diphenyl ether disulfonic acid, decyl Alkyl diphenyl ethers such as diphenyl ether disulfonic acid, dodecyl diphenyl ether disulfonic acid and hexadecyl diphenyl ether disulfonic acid Sulfonic acid compounds and can be exemplified salts of these compounds. Examples of the salt include alkali metal salts such as sodium salt and potassium salt, ammonium salt, amine salt and the like. One of these anionic surfactants can be used alone, or two or more can be used in combination.

Examples of the amphoteric surfactant include surfactants having an anionic group and a cationic group, and those in which the anionic group is an alkali metal salt such as a sodium salt or an amine salt. Can be.
These can be used alone or in combination of two or more. The surfactant having a polymerizable group is generally called a reactive emulsifier, and includes a compound having a hydrophobic group, a hydrophilic group, and a polymerizable group in a molecule. Examples of the polymerizable group include (meth)
Examples of the polymerizable group include a functional group having a carbon-carbon double bond, such as an allyl group, a 1-propenyl group, a 2-methyl-1-propenyl group, an isopropenyl group, a vinyl group, and a (meth) acryloyl group. As the surfactant having a polymerizable group, those which can be generally applied to emulsion polymerization can be used, and are not particularly limited. Specific examples include one or more polymerizable groups in a molecule. Polymerizable group-containing polyoxyalkylene ether compounds such as polyoxyalkylene alkyl ethers, polyoxyalkylene aralkyl ethers and polyoxyalkylene phenyl ethers, and polyoxyalkylenes such as polyoxyalkylene monostyryl phenyl ether and polyoxyalkylene distyryl phenyl ether Styryl phenyl ether compounds can be mentioned. In addition, sulfonates, sulfates, phosphates and sulfosuccinates derived from these polymerizable group-containing polyoxyalkylene ether compounds and the polyoxyalkylenestyrylphenyl ether compounds,
Aliphatic carboxylate and aromatic carboxylate derived from the polymerizable group-containing polyoxyalkylene ether compound, acidic phosphoric acid (meth) acrylate compound, rosin-glycidyl (meth) acrylate compound, and the like. Can be illustrated. One of these surfactants can be used alone, or two or more thereof can be used.

In synthesizing the copolymer contained in the dispersant (B) and / or a neutralized product thereof, examples of the solvent include water and organic solvents such as toluene, hexane, benzene, isopropyl alcohol, ethanol, and acetone. Can be The polymerization initiator used in the polymerization includes peroxides such as ammonium persulfate, potassium persulfate and sodium persulfate, peroxides such as tertiary butyl hydroperoxide, and persulfates or peroxides thereof. And a reducing agent in combination with an azo catalyst such as 2,2′-azobisisobutyronitrile and 2,2′-azobis-2-methylpropionamidine dihydrochloride. However, the present invention is not particularly limited thereto, and other known and commonly used polymerization initiators can be used. These polymerization initiators include 1
Species can be used alone, or two or more of them can be used.

The amount of the polymerization initiator used is usually 0.0 with respect to the total amount of the monomers used in the synthesis of the copolymer and / or its neutralized product contained in the dispersant (B).
1 to 5 mol%. The polymerization initiator may be charged together with the monomer into the reaction vessel, or may be continuously dropped. As a method of adding the monomers used in this polymerization, a batch addition polymerization method in which all the monomers are charged into a reaction vessel at one time and polymerization is performed, or a division method in which part or all of the monomers are divided and added to the reaction vessel to perform polymerization. An addition polymerization method, a continuous drop polymerization method in which polymerization is performed while continuously or partially dropping all or a part of a monomer into a reaction vessel, and the like can be used.

The monomer concentration during the polymerization is usually 15 to
50% by weight. It is possible to polymerize at a monomer concentration of less than 15% by weight and obtain a copolymer having a concentration of 15% by weight or more and / or a neutralized product thereof by a concentration operation, but this is not preferable in terms of economy. When the polymerization is carried out at a monomer concentration exceeding 50% by weight, it is difficult to control the heat of polymerization. The polymerization reaction temperature is usually from 40 to 95 ° C, preferably from 50 to 90 ° C, and the reaction time is from 1 to 20 hours. When the copolymer is neutralized, the neutralization reaction at that time generally has a reaction temperature of 60 to 90 ° C. and a reaction time of 0.5 to 4 hours. When the polymer portion corresponding to (meth) acrylic acid of the copolymer is neutralized after completion of the polymerization, 0.6 to 1 with respect to the equivalent of the anionic group of (meth) acrylic acid, that is, the anionic equivalent. Equivalents are preferred.

The above dispersant (B) is the above-mentioned copolymer and / or neutralized product thereof and is usually obtained at a solid content of 15 to 50% by weight, and usually at a solid content of 25% by weight. Viscosity (25 ° C using Brookfield rotational viscometer)
Is 10 to 5000 mPa · s and the pH is 6
~ 11.

The rosin emulsion composition of the present invention comprises:
It comprises at least the above components (A) and (B), and each component is used in an amount of 70 to 99% by weight of the component (A),
The component is preferably 1 to 30% by weight. If the amount of the component (B) is less than 1% by weight, the effect on the sizing performance (size to fountain solution) particularly required for newsprint may be lower than that in the above range, and more than 30% by weight. In addition, the influence on the size performance (size property against dampening solution) particularly required for newsprint tends to level off, which is economically undesirable. In addition, you may use together a well-known high molecular type emulsifying dispersing agent, a low molecular type emulsifying dispersing agent, a high molecular surfactant, a low molecular surfactant, etc. in the range which does not impair the effect of this invention.

The method for producing the rosin emulsion composition of the present invention is not particularly limited. For example, according to the method described in JP-B No. 54-36242, the above-mentioned component (A) is dissolved in a solvent. (E.g., benzene, toluene, methylene chloride, etc.), adding the above-mentioned component (B), and then producing an oil-in-water emulsion through a homogenizer (solvent method), which is described in JP-A-54-77209. According to the method, (A)
A method in which component (B) is mixed with the component to form a water-in-oil emulsion, and inverted water is added to cause a phase transition to an oil-in-water emulsion (phase inversion method), which is described in JP-B-53-32380. After the components (A) and (B) are melted and mixed according to the method described in
(A), (B) according to a method for producing an oil-in-water emulsion through a homogenizer at 150 ° C., 150 to 1000 kg / cm ² ) (mechanical method) and the method described in JP-A-10-226981. A method such as a method of producing an oil-in-water emulsion by passing the components through a high-shear rotary emulsifying and dispersing machine (mechanical method) or the like is used.

The particle size of the obtained emulsion (cumulative 50% size in the weight-based particle size distribution) is 1 μm or less, preferably 0.5 μm or less. If the particle size exceeds 1 μm, precipitation tends to occur during storage, and mechanical stability may not be good. The particle diameter can be measured, for example, with a laser diffraction / scattering particle size distribution analyzer LA-910 (manufactured by Horiba, Ltd.).

When the rosin emulsion composition thus obtained is used as a sizing agent for newsprint, it has excellent storage stability and mechanical stability, and is used in an ultrahigh-speed newsprint machine. In this case, papermaking pH 4 to 6, especially pH 4.5 to 5.0, that is, the so-called acidic papermaking system has excellent performance such as sizing performance as compared with conventional sizing agents, and low addition of sizing properties required for newsprint. It can be given effectively at a rate. In addition, even in a weakly acidic papermaking system having a papermaking pH of 6 to 7 and a neutral papermaking system having a papermaking pH of 7 to 8, the sizing performance is superior to that of a conventional sizing agent.
It can also be used for neutral newsprint that will be made. The rosin emulsion composition for newsprint of the present invention can be used as a sizing agent even if the papermaking pH is less than 4 or the papermaking pH is more than 8, but the above range is preferred from the viewpoint of the size effect. Further, when the rosin emulsion composition for newsprint of the present invention is used as a sizing agent, there is an advantage that stains on paper making tools such as a press roll and a dryer canvas are reduced.

The method for sizing newsprint of the present invention is carried out in the process of manufacturing newsprint, for example, by adding the rosin emulsion composition for newsprint of the present invention to the wet end portion. Specifically, the rosin-based emulsion composition for newsprint of the present invention is used as a sizing agent in an aqueous dispersion (slurry) of newsprint pulp as a sizing agent in an amount of 0.01 to 5% by solid weight based on the dry weight thereof. Preferably, 0.05 to 2% by weight of solid content is added. The rosin-based emulsion composition for newsprint of the present invention can be used as a surface sizing agent. In this case, a conventional surface sizing method such as spraying, dipping, or applying to a wet paper web is applied. Is done. When the rosin-based emulsion composition for newsprint of the present invention is used as a sizing agent, a surface sizing agent is also included in the lower concept.

The newsprint of the present invention contains at least a copolymer containing the rosin-based substance (A) and the dispersant (B) and / or a neutralized product thereof. Using a rosin emulsion composition as a sizing agent, in the presence of bansulfate (in the presence of a cationic chemical such as cationic polyacrylamide, the sulfuric acid band may not necessarily be present), preferably a raw material for newsprint 0.5% to 5% added to the pulp solid content,
It is also obtained by making a paper at H4 to pH 8, and shows superior sizing performance as compared to newsprint sized using a conventional rosin-based sizing agent.

The pulp constituting the newsprint of the present invention includes bleached pulp such as chemical pulp (NBKP, LBKP, etc.).
Semi-bleached pulp with weak bleaching treatment, mechanical pulp (TMP, CTMP, GP, RGP, etc., and bleached pulp), high yield pulp (SCP, CGP, etc.)
And bleached pulp), waste paper pulp, deinked waste paper pulp (DIP) and bleached pulp (B
Collected pulp such as DIP) can be used. Deinked waste paper pulp is pulp obtained by deinking newspapers, flyers, magazines, etc., deinked waste paper pulp that has been bleached to increase its whiteness, and waste paper and collected paper that are usually generated in paper mills. Etc. can be used. These can be used alone or 2
A stock is prepared by appropriately mixing and beating treatments of at least one kind of pulp. Further, in papermaking, the paper material is made of a known material such as white carbon, clay, amorphous silica, talc, titanium dioxide, a filler for papermaking selected from calcium carbonate and the like, and, if necessary, a sulfate band, a paper strength enhancer, a retention aid, and the like. Papermaking chemicals are appropriately added, and the basis weight is 35 to 50 g / m ^2.
Paper is made as a base paper.

[0031]

DETAILED DESCRIPTION OF THE INVENTION As the component (A), rosins reinforced with unsaturated dibasic acids, rosin esters using polyhydric alcohols, and mixtures of both are used. As the component (B), (i) when the component (d) is not used, 10 to 60 parts by weight of styrene and / or α-methylstyrene as the component (a); N-butyl acrylate (Tg (glass transition temperature of the homopolymer; the same applies hereinafter): -45 ° C), isobutyl acrylate (Tg: -15 ° C), 2-ethylhexyl acrylate (Tg: -55 ° C) and 2-ethylhexyl Methacrylate (Tg: -10 ° C) (Tg is-
(Meth) acrylic acid ester monomer having a temperature of 5 to -60 ° C) may be used in an amount of 20 to 70 parts by weight, and as the component (c), (meth) acrylic acid may be used in an amount of 20 to 70 parts by weight.
60 parts by weight, (ii) when using the component (d), 10 to 60 parts by weight of styrene and / or α-methylstyrene as the component (a), and n-butyl acrylate as the component (b) , Isobutyl acrylate,
20-70 parts by weight of at least one of 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate (may be a (meth) acrylate monomer having a Tg of -5 to -60 ° C), and as the component (c), 20 to 60 parts by weight of (meth) acrylic acid, (d)
As a component, methyl methacrylate other than the above (b) (T
g: 104 ° C.), isobutyl methacrylate (Tg: 5
3 ° C.), at least one of n-butyl methacrylate (Tg: 22 ° C.) and cyclohexyl methacrylate (Tg: 83 ° C.) at most 10 parts by weight (10 parts by weight or less)
Used together with these (i) and (ii), alkyl mercaptan and / or 2,4-
Equivalent ratio of 0.6 to 1 using a copolymer obtained by polymerizing in the presence of diphenyl-4-methyl-1-pentene or in combination with mercaptoethanol or at least one of caustic soda, caustic potash and ammonia.
And a dispersant containing a neutralized product of the copolymer obtained by neutralization with the above. A rosin emulsion composition for newsprint is obtained by dispersing 70 to 99% by weight of the component (A) and 1 to 30% by weight of the component (B) in an aqueous dispersion medium (main component is water). The rosin-based emulsion composition for newsprint is added to a raw material slurry for newsprint to obtain newsprint sized by a conventional method.

[0032]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. Also, all parts and percentages in the examples are on a weight basis. Production of rosin-based material (A) Production Example 1 (Production of fumaric acid-reinforced rosin-based material (A-1)) 110 parts of fumaric acid was gradually added to 450 parts of gum rosin in a molten state at 200 ° C, and 2 parts at 200 ° C. After stirring and maintaining the temperature for an hour, 440 parts of a tall oil rosin treated with formaldehyde (denaturation rate: 1%) was further added, and the mixture was melt-stirred and mixed homogeneously. Thereafter, the obtained reaction product was cooled to room temperature. This reaction product is a fumaric acid-reinforced rosin to which fumaric acid is added by 11%, and a fumaric acid-reinforced rosin-based substance (A-1)
And

Production Example 2 (Fumaric acid-reinforced rosin-based material (A
Production of -2)) 80 parts of fumaric acid was gradually added to 450 parts of gum rosin in a molten state at 200 ° C., and the mixture was stirred and kept at 200 ° C. for 2 hours. Then, 470 parts of tall oil rosin treated with formaldehyde (conversion rate 1%) was added. Parts, melt and stir to mix homogeneously,
Thereafter, the obtained reaction product was cooled to room temperature. This reaction product is a fumaric acid-reinforced rosin to which 8% of fumaric acid is added, and is referred to as a fumaric acid-reinforced rosin-based substance (A-2).

Production of Dispersant (B) Synthesis Example 1 (Production of Polymeric Emulsifying Dispersant (B-1) for Example) 1.06 parts of styrene in a flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube. 9.53 parts of butyl acrylate,
13.24 parts of 80% methacrylic acid, 0.21 part of normal dodecyl mercaptan, 0.08 of mercaptoethanol
Parts, sodium dodecylbenzenesulfonate 0.04
And 1.18 parts of ammonium persulfate, and 58.6 parts of water were added to the mixture so that the solid concentration became 27%, and the mixture was stirred and mixed.
Heat at 90 ° C. for 3 hours. Then cooled to 70 ℃, 0.8 equivalent to the anionic equivalent of methacrylic acid,
By gradually dropping 14.23 parts of a 30% aqueous sodium hydroxide solution and 1.88 parts of water so that the solid concentration becomes 25%, the mixture was stirred for 30 minutes, and then cooled to room temperature.
Solid content 25.1%, viscosity 4300 mPa · s, pH 8.
Thus, a polymer emulsifying dispersant (B-1), which is a copolymer polymer dispersion of No. 5, was obtained. Each of the above components used, the equivalent ratio,
Table 1 shows the measured values of the solid content, viscosity, and pH. In addition,
The viscosity is a value measured at 25 ° C. using a Brookfield rotational viscometer.

Synthesis Examples 2 to 16 (Production of Polymeric Emulsifying and Dispersing Agents B-2 to B-16 for Examples) The monomers, chain transfer agents, and alkalis in Synthesis Example 1 described above correspond to those shown in Table 1. In the same manner as in Synthesis Example 1 except that the composition ratio in the column was used, and the charged amount of the alkalis was an amount equivalent to the anion equivalent of (meth) acrylic acid in the corresponding column in Table 1. A copolymer dispersion was prepared, and polymer emulsifying dispersants (B-2 to B-16) were obtained. Table 1 shows the measurement results in the same manner as in Synthesis Example 1.

Comparative Synthesis Examples 1 to 6 (Production of Polymeric Emulsifying and Dispersing Agents B-17 to B-22 for Comparative Example) The monomers, chain transfer agents and alkalis in the above Synthesis Example 1 are shown in Table 1. In the same manner as in Synthesis Example 1, except that the amount of alkalis was adjusted so that the equivalent ratio to the anion equivalent of (meth) acrylic acid in the corresponding column in Table 1 was used. A copolymer dispersion was prepared, and polymer emulsifiers (B-17 to B-22) were obtained. Table 1 shows the measurement results in the same manner as in Synthesis Example 1.

[0037]

[Table 1] The abbreviations in the table are shown in Table 2 below.

[0038]

[Table 2]

Example 1 (Production Example 1 of rosin-based emulsion composition for newsprint) The rosin-based material (A-1) obtained in Production Example 1 of the rosin-based material (A) was heated to about 150 ° C. While melting and stirring, the polymer emulsifying dispersant (B-
1) was added to and mixed with 5% of the total solid content to obtain a water-in-oil emulsion. Under stirring, hot water is gradually added to phase inversion to form an oil-in-water emulsion. Hot water is further quickly added and mixed to form a stable oil-in-water emulsion. An aqueous emulsion composition of a system substance was obtained. The rosin-based emulsion composition thus obtained has a solid content of 50.2%,
The average particle size is 0.47 μm, 0 is 1 μm or more, and the viscosity is 3
1 mPa · s and pH was 5.8. The rosin-based emulsion composition for newsprint is used as it is as a sizing agent. Table 3 shows these measured values. The particle diameter is a value measured by a laser diffraction / scattering type particle size distribution analyzer LA-910 (manufactured by Horiba, Ltd.), and the viscosity is a value measured at 25 ° C. using a Brookfield rotational viscometer.

Examples 2 to 18 (Production Examples 2 to 18 of rosin-based emulsion compositions for newsprint) The rosin-based substances (A) were prepared by fumaric acid-reinforced rosin-based substances (A-1 and A-2) shown in Table 1. ), A polymeric emulsifying dispersant (B-
1) is a polymer emulsifying dispersant (B-2 to B-1) shown in Table 1.
A rosin-based emulsion composition for newsprint was obtained in the same manner as in Example 1, except that 6) was used. Example 1 about the obtained rosin emulsion composition for newsprint
Table 3 shows the measurement results in the same manner as in the case of

Comparative Examples 1 to 6 The rosin-based substance (A) was added to the fumaric acid-reinforced rosin-based substance (A-1) shown in Table 1, and the polymer emulsifier / dispersant (B-1) was added to Table 1.
A rosin emulsion composition for newsprint was obtained in the same manner as in Example 1 except that the polymer emulsifying dispersants (B-17 to B-22) described were replaced. Table 3 shows the measurement results of the obtained rosin-based emulsion composition for newsprint in the same manner as in Example 1.

[0042]

[Table 3]

Using each rosin-based emulsion composition, which is an aqueous emulsion of rosin-based substances for newsprint obtained in the above Examples and Comparative Examples, a size effect test, a mechanical stability test, and a static stability test Table 4, 5 (Examples 1 to 18,
The results are shown in Comparative Examples 1 to 6. (Size effect test) 70 parts of deinked waste paper pulp (DIP)
10 parts of thermomechanical pulp (TMP), 10 parts of ground pulp (GP), and softwood kraft pulp (NB
KP) was mixed at a ratio of 10 parts and defibrated with a refiner to obtain a beating degree of 120. Next, to the obtained pulp slurry (concentration: 2.4%), 2% of pulp relative to white carbon and 2% of pulp to pulp were added.
Rosin emulsion compositions for newsprint obtained from Comparative Examples 1 to 6 and Comparative Examples 1 to 6, respectively.
1% or 0.2% was added. Then, the obtained pulp slurry was diluted to a concentration of 0.25% with dilution water having a pH of 4.5, and cationic polyacrylamide (paper strength enhancer DS43 manufactured by Nippon PMC Co., Ltd.) was used as a fixing agent.
6) was added to pulp at 0.05%, and the paper was made at a papermaking pH of 4.5 using a Noble and Wood paper machine. The obtained wet paper was dried at 80 ° C. for 100 seconds using a drum dryer.
The test was carried out under three conditions of 0 ° C., 80 seconds and 150 ° C., 60 seconds to obtain a test paper having a basis weight of 40 g / m ² . Each of the obtained test papers was conditioned for 24 hours in a constant temperature and humidity (23 ° C., 50% relative humidity) environment, and then 5 μl of deionized water was dropped using a microsyringe, and the water drops were completely absorbed by the test paper. The length of time until the gloss disappeared was measured by a drop size method.

(Stability Stability Test) 100 ml of each of the rosin emulsion compositions for newsprint of the above Examples and Comparative Examples were separately placed in a test tube having a length of 30 cm and an inner diameter of 2.1 cm, and allowed to stand for 2 months. Then, the height of the sediment (c
m) was measured. (Mechanical Stability Test) 50 g of each rosin-based emulsion composition for newsprint of the above Examples and Comparative Examples was separately placed in a cup, and the temperature was 25 ° C., the load was 25 kg, and the rotation speed was 800 rpm.
m for 10 minutes. The aggregate formed in each cup was filtered through a 325 mesh wire net, and the amount of precipitation with respect to the total solid content in each cup was measured and expressed as a percentage.

(Expansion test) Waste ink pulp (DIP)
70 parts, 10 parts of thermomechanical pulp (TMP), 10 parts of ground pulp (GP), and 10 parts of softwood kraft pulp (NBKP) were mixed and defibrated with a refiner to give a beating degree of 120. Then, to the obtained pulp slurry (concentration: 2.4%), 2% of pulp relative to white carbon and 2% of pulp relative to pulp were added, and then the above Examples 1 to 18 and Comparative Examples 1 to 6 were added. The rosin-based emulsion compositions for newsprint obtained from each were individually added to pulp at 0.2%. The resulting pulp slurry was then diluted to a concentration of 0.25% with a dilution of pH 4.5 and placed in a cylindrical container. Then, a cationic polyacrylamide (Paper Strength Enhancer DS43 manufactured by Nippon PMC Co., Ltd.) was used as a fixing agent in the diluted pulp slurry.
6) was added to the pulp at 0.05%, the pulp slurry was circulated by a pump, and the pulp slurry was dropped from a height of 50 cm into a vessel. Expressed as a percentage of the total area.

(Hard Water Dilution Stability Test) An aqueous emulsion of a rosin-based substance was diluted with hard water having a hardness of 300 ppm to a solid content of 5%, and kept at 40 ° C. for 24 hours.
The mixture was filtered with a filter paper, and the remaining amount of the filter with respect to the total solid content was measured and expressed as a percentage.

[0047]

[Table 4]

[0048]

[Table 5]

As can be seen from Table 3, the rosin emulsion composition of the example has a particle size smaller by several tens of percent than that of the comparative example, and the distribution of the particle size does not have a particle size of 1 μm or more. Is remarkable, and it can be said that the dispersion state when the rosin-based substance is emulsified and dispersed is extremely fine in the examples. From this, it can be seen from Table 5 that the examples of the present invention have remarkably excellent standing stability, mechanical stability and hard water dilution stability. Further, from the results in Table 4, the drying conditions of the example were higher than those of the comparative example under any of the drying conditions (80%).
(150 ° C.), the drop sizing degree is particularly remarkably excellent when the amount of the sizing agent used is the same, and the amount of the sizing agent is halved (performed for the sizing agent used amount of 0.2% in the comparative example). It can be seen that the use of the example sizing agent (0.1%) is remarkably excellent. Also, from the results in Table 5, those of Examples have low foaming properties, and have viscosities that are easy to handle.

[0050]

According to the present invention, the size (water resistance) to fountain solution required for lithographic printing required for newsprint can be improved under high-speed papermaking required for newsprint as well as under normal drying conditions. With respect to the rapid drying of rosin emulsion sizing agent, it can be achieved at a lower addition rate than conventional rosin emulsion sizing agents, and also exhibits an excellent sizing effect in a papermaking system in a wide pH range from acidic of pH4 to alkaline of pH8. In addition, there is little bubbling in the papermaking process, and furthermore, it has excellent storage stability and excellent mechanical stability in the papermaking process, reduces dirt on the papermaking machine, and can reduce the cost of a sizing agent in papermaking for newsprint paper. A rosin-based emulsion composition, a method for producing newsprint using the same, and newsprint using the same can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 220/06 C08F 220/06 220/10 220/10 C08L 25/02 C08L 25/02 33/02 33 / 02 33/06 33/06 93/04 93/04 D21H 21/16 D21H 21/16 F term (reference) 4D077 AA05 AB20 AC05 BA07 DC04Z DC26Z DC32Z DD08Z 4J002 AF02W BC01X BC04X BC08X BC09X BG01X BG04X BG05X GK04 HA07 4J0112 NA 4J100 AB02P AB03P AB04P AB16P AJ02R AK01R AK03R AK08R AL03Q AL03S AL04Q AL05Q AL08S BC04S BC43S CA05 CA06 EA07 FA06 JA13 4L055 AG50 AG63 AG70 AG71 AG89 AG97 AH11 AH33 EA20 EA32 FA17 FA30 FA30

Claims (8)

[Claims] 1. A rosin-based emulsion composition containing a rosin-based substance (A) and a dispersant (B), wherein the dispersant (B) is different from the styrene-based monomer (a) even when the glass transition temperature is high. A monomer having a (meth) acrylic ester monomer (b), which is a monomer capable of forming a homopolymer at 0 ° C., and a monomer (c) of (meth) acrylic acid and / or a salt thereof in the monomer constitution A rosin emulsion composition for newsprint containing a copolymer obtained by copolymerization and / or a neutralized product thereof. 2. In a rosin-based emulsion composition containing a rosin-based substance (A) and a dispersant (B), the dispersant (B) is different from the styrene-based monomer (a) even if the glass transition temperature is high. (Meth) acrylic acid ester monomer (b), which is a monomer capable of forming a homopolymer at 0 ° C .; (meth) acrylic acid and / or a salt thereof (c); For a newsprint containing a copolymer obtained by copolymerizing a monomer having a (meth) acrylate monomer (d) other than the acid ester monomer (b) in the monomer constitution and / or a neutralized product thereof. Rosin emulsion composition. 3. The method according to claim 1, wherein the monomer is copolymerized in the presence of 2,4-diphenyl-4-methyl-1-pentene (e) and alkyl mercaptan (f) to obtain a copolymer and / or a neutralized product thereof. Item 4. A rosin emulsion composition for newsprint according to item 1 or 2. 4. Component (a) is 10 to 60% by weight, (b)
The rosin emulsion composition for newsprint paper according to any one of claims 1 to 3, wherein the component is 20 to 70% by weight, the component (c) is 20 to 60% by weight, and the component (d) is 0 to 10% by weight. object. 5. Component (e) is 0.1 to 3% by weight and component (f) is 0.1 to 3% by weight based on the total weight of components (a) to (d).
The rosin emulsion composition for newsprint according to claim 3 or 4 used in an amount of 3% by weight. 6. A rosin-based substance (A) comprising a rosin and α, β
-95: 5 to 90.1: unsaturated carboxylic acid in weight ratio.
The rosin-based emulsion composition for newsprint according to any one of claims 1 to 5, which is a reinforced rosin obtained by 9.9 reaction. 7. A method for producing newsprint, wherein the rosin-based emulsion composition for newsprint according to any one of claims 1 to 6 is added to a raw material slurry for newsprint and the paper is made to obtain sized paper. 8. Newsprint containing the rosin-based substance (A) and the copolymer according to claim 1 and / or a neutralized product thereof.