JP3491325B2 - Rosin emulsion composition, manufacturing method thereof, sizing agent, sizing method, and sized paper - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION This invention is rosin-based emulsion composition, size agents, relates to a sizing method and size papers, particularly alkenyl succinic anhydride in the emulsion solids rosin-based material and a dispersant A rosin-based emulsion composition containing, which exhibits an excellent size effect in a papermaking system from pH 4 to pH 6.5, especially when the papermaking speed is high and the drying conditions are gentle, that is, the amount of heat applied to the wet paper. Having a relatively low papermaking system, for example, a sizing agent exhibiting an excellent sizing effect even on paper produced under the drying conditions of a paper machine having a Yankee dryer, and having excellent mechanical stability and storage stability of itself. Regarding

[0002]

2. Description of the Related Art In the papermaking industry, papermaking machines are made faster to improve productivity, and as a result, they are often dried rapidly under relatively low temperature conditions. There is a tendency that the degree is not given.

[0003]

For example, when an anionic rosin-based sizing agent, particularly a solution-type rosin-sizing agent which is an alkali-neutralized product of a toughened rosin, is used, the sizing effect is superior to the solution-type rosin-sizing agent When a dispersion type rosin-based sizing agent having a wide pH range applicable to papermaking is used, it cannot be said that the drying conditions are sufficient during papermaking using a high-speed papermaking machine.
In order to obtain a predetermined sizing degree, it is necessary to increase the amount of the sizing agent added, which not only raises the cost but also causes a problem of remarkable foaming in the papermaking process. Under such circumstances, when the papermaking speed is high and the drying conditions are relatively gentle, for example, a paper machine having a Yankee dryer (for example, a paper machine for pure white roll paper) or an ultra-high-speed newsprint paper machine is dried. There is a strong demand for a rosin-based emulsion sizing agent that exerts an excellent sizing effect on paper made under conditions.

The object of the present invention is firstly applied to a papermaking system in which drying conditions are relatively mild, as in the case of making paper in a high speed papermaking machine, and secondly, a papermaking pH from pH 4 to pH 6.5.
Excellent size effect in papermaking system
Which is excellent in mechanical stability and storage stability, and which is capable of achieving these objects, and particularly characterized in achieving the first object, a method for producing the same, a sizing agent containing this composition, and a sizing A method and providing a sized paper.

[0005]

In order to solve the above-mentioned problems, the present invention provides (A) an alkenylsuccinic anhydride,
(B) a rosin-based substance that can contain up to 50% by weight when it does not contain rosin esters or when it contains
(C) A rosin-based emulsion composition in which a dispersoid containing an anionic dispersant is stably dispersed in water,
1 to 30 parts by weight of the component (A) and 50 to 98 parts by weight of the component (B) are melt- mixed, and the mixture is stably dispersed in water by using 1 to 20 parts by weight of the component (C) in a total of 100 parts by weight. Let
It is intended to provide a rosin-based emulsion composition which is a dispersion having a solid content concentration of 20 to 60% by weight.

At this time, the rosin-based emulsion composition according to the above (1), wherein the alkenylsuccinic anhydride (2) or (A) is a reaction product of an olefin having 8 to 20 carbon atoms and maleic anhydride. and a call is preferred.

Further, the present invention is (3), sizing agent containing rosin emulsion composition according to (1) above or (2), (4), according to the above (1) or (2) Sizing method using the rosin-based emulsion composition as a sizing agent in the papermaking pH range from pH 4 to pH 6.5, ( 5 ), the solid content of the rosin-based emulsion composition according to (1) or ( 2) above To provide a sized paper containing.

[0008]

The present invention will be described in detail below. In the present invention, the alkenylsuccinic anhydride (A) refers to a reaction product of an olefin and maleic anhydride, and is represented by the following general formula (I). Therefore, in the present invention, in the above (1) to ( 5 ), "(A) alkenyl succinic anhydride" may be replaced with "(A) alkenyl succinic anhydride represented by the following general formula (I)". it can.

[0010]

[Chemical 1]

(In the formula, R ₁ to R ₅ represent a hydrogen atom or an alkyl group, and may be the same or different.) As the olefin for obtaining the compound of this general formula, a straight chain α olefin and a straight chain olefin are used. Internal olefin, branched olefin,
Although any of the branched internal olefins can be used and a mixture thereof may be used, an olefin having 8 to 20 carbon atoms, preferably 12 to 18 carbon atoms can be mentioned. Specific examples of the alkenyl succinic anhydride include, for example, dodecenyl succinic anhydride, pentadecenyl succinic anhydride, octadecenyl succinic anhydride and the like, and these are used alone or in combination. When alkenylsuccinic acid represented by the following general formula (II), which is a hydrolyzate of alkenylsuccinic anhydride, is used in place of (A) in the composition, sizing agent and sized paper of the present invention. Are inferior in size performance and emulsifying property to those corresponding to these of the present invention, but by using (A) in water, alkenylsuccinic acid coexists with (A). However, the larger the amount of (A), the more preferable. In the present invention, “(A) alkenyl succinic anhydride and (B)
"Containing" of the rosin-based substance and the dispersoid containing the (C) anionic dispersant means at least these (A)
It is shown that the components (B) and (C) are contained as essential components, not that the other components are not contained. For example, alkenyl succinic acid is used within a range not deviating from the object of the present invention. It shows that the additives and other compounds described below may be included as necessary or inevitable.

[0012]

[Chemical 2]

(Wherein R ₁ to R ₅ are the above-mentioned general formula (I)
Is the same as. Further, as the olefin corresponding to the above olefin, those having the above carbon number can be similarly applied, and further, olefins having 6 to 7 and 21 to 30 carbon atoms can also be mentioned.

In the present invention, the component (B) "rosin ester-free rosin-based substance" means rosin itself, a reaction product using rosin as a reaction component (rosin modified product), and a reinforced product thereof. Say, these are alone or 2
Used as a mixture of two or more species. Examples of the rosin itself include gum rosin, tall oil rosin, and wood rosin, which may be used alone or as a mixture of two or more kinds. Examples of the modified rosin include those obtained by partially or substantially completely hydrogenating the above-mentioned rosin, those disproportionated, those polymerized, and those modified with formaldehyde.

The toughened rosin is obtained by adding the α, β-unsaturated carboxylic acid to the above rosin or modified rosin. Typical α, β-unsaturated carboxylic acids used here include unsaturated dibasic acids such as fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, and citraconic anhydride. Unsaturated monobasic acids such as acrylic acid and methacrylic acid are listed,
These may be used alone or in combination of two or more.

Examples of rosin esters include reaction products of at least one of the above rosin and modified rosin or reinforced rosin with at least one selected from polyhydric alcohols such as glycerin and pentaerythritol and epoxy compounds. . Further, it also includes those obtained by further adding the α, β-unsaturated carboxylic acid to the rosin ester. Since such a rosin ester does not sufficiently exhibit the size effect in an acidic papermaking system, it is preferable to use less than 50% by weight of the rosin-based substance as the component (B) in order to obtain a good size effect of the sizing agent. Is preferable, and it is more preferable not to include it.

The anionic dispersant of the component (C) in the present invention is an emulsifying dispersant containing an anionic emulsifying dispersant , or
Is made of the emulsifying and dispersing agent及beauty protection colloid,
Although not particularly limited, various low molecular weight surfactants, polymeric emulsifying dispersants, and casein, lecithin,
Polyvinyl alcohol, can be protected colloids used such as modified starch may also be used in combination of two or more comprising an anionic emulsifying dispersant alone or anionic emulsifying dispersant. However, a cationic dispersant is combined with an anionic dispersant.
It is never used together. As an anionic dispersant
Examples of various low-molecular-weight surfactants include rosin alkali metal salts, reinforced rosin alkali metal salts, alkylbenzene sulfonates, polyoxyethylene alkyl ether sulfate ester salts, polyoxyethylene alkylphenyl ether sulfate ester salts, and polyoxyethylene. Mono and distyryl phenyl ether sulfate ester salt, alkyl sulfate ester salt, alkyl naphthalene sulfonate salt, naphthalene sulfonate formaldehyde condensate, polyoxyethylene alkyl ether sulfosuccinic acid monoester salt, polyoxyethylene alkylphenyl ether sulfosuccinic acid monoester Salt, polyoxyethylene mono and distyryl phenyl ether sulfosuccinic acid monoester salt, alkylphenoxy polyoxyethylene propyl sulfonate Anionic surfactants such as polyoxyethylene sulfophenyl ether salts.
Note that the addition described in paragraph [0011] above may be added.
As other compounds, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene mono- and distyryl phenyl ether, polyoxypropylene polyoxyethylene glycol glycerin fatty acid ester, sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid esters, sucrose fatty acid esters, pentaerythritol fatty acid esters can be exemplified propylene glycol fatty acid esters, fatty acid diethanol amide, a nonionic surfactant such as polyoxypropylene polyoxyethylene glycol.

In addition, the addition described in the above paragraph [0011]
Other compounds that may be used as the polymer-based emulsifying dispersant are not particularly limited , except that a cationic emulsifying dispersant is not used, but basically, a hydrophobic group, a nonionic group and / or an anionic group are used. natural polymeric emulsifying dispersant synthetic polymer or generally having a group can be used, and an anionic dispersing agent
Partially or completely neutralized product of one example as polymeric emulsifying dispersant anionic styrenic ─ (meth) acrylic acid-based copolymer, the anionic (meth) acrylate copolymer or ( meth) acrylamide-based copolymer Ru mentioned. These polymeric emulsifying dispersants may be used alone or in combination of two or more as a protective colloid.

The emulsion composition of the present invention comprises at least the above-mentioned components (A), (B) and (C).
The amount of rosin-based substance used as component (B) is 50
To 98 parts by weight, 1 to 30 parts by weight of the alkenylsuccinic anhydride as the component (A), more preferably 2 to 20 parts by weight, and 1 to 20 parts by weight of the dispersant as the component (C). When the amount of the component (A) is less than 1 part by weight, the effect on the size performance and the like is lower than that in the above range, and 3
If the amount is more than 0 parts by weight, the influence on the size performance tends to reach a peak, which is economically unfavorable. Also,
When the amount of the component (C) is less than 1 part by weight, the action of emulsifying and dispersing the mixture of the rosin-based substance and the alkenylsuccinic anhydride and the storage stability are lower than those in the above range, and even if the amount is more than 20 parts by weight. The emulsifying and dispersing action is not particularly improved, and the size performance and the foamability are not better than those in the above range.

The method of incorporating the component (A) into the solid content of the emulsion is not particularly limited, but a component (A) and a component (B), preferably a rosin-based substance fortified with an α, β-unsaturated carboxylic acid, is used. After melt-mixing, it is emulsified and dispersed with a dispersant of component (C), or a rosin-based substance fortified with component (B), preferably α, β-unsaturated carboxylic acid, is emulsified and dispersed with component (C). And (A) component emulsified and dispersed with (C) component may be mixed, or any of these methods may be used. In the above case, 1 to 30 parts by weight of the component (A) and the component (B), preferably a rosin-based substance 98 to 50 fortified with an α, β-unsaturated carboxylic acid.
After melt-mixing the parts by weight, it is preferred to emulsify and disperse with the dispersant of the component (C). Either 50 parts by weight of the component (C) emulsified and dispersed, or 1 to 30 parts by weight of the component (A) emulsified and dispersed by the component (C) may be mixed, or any method may be used. In these cases, the component (C) is preferably used in an amount of 1 to 20 parts by weight. In the above cases and the above preferable cases, the size performance is excellent, and the emulsion sizing agent is also excellent in mechanical stability. The reason is that the component (A), which is easily hydrolyzed, is not decomposed because the melting point of the mixture is (A) because it is melt-mixed with the component (B).
It is considered that it is higher than the component, and that the component (A) is diluted with the component (B), so that the component (A) is not exposed on the particle surface or the concentration thereof is small, but is not limited to this. is not. The total solid content of the emulsion after emulsified and dispersed is preferably 20 to 60% by weight, more preferably 30.
˜55 wt%. If it is less than 20% by weight, it is economically efficient. If it is more than 60% by weight, the viscosity becomes high.
It is inferior to those in the above range in handling in papermaking.

The method for producing the rosin emulsion composition of the present invention is not particularly limited, but, for example, according to the method described in JP-B No. 54-36242, (B) and (A). A method in which the components are dissolved in a solvent (for example, benzene, toluene, methylene chloride, etc.), the component (C) is added, and then an oil-in-water emulsion is produced through a homogenizer (solvent method) is described in JP-A-54-77209. In accordance with the method described above, the component (A) is mixed with the melted component (B), the component (C) is mixed with this mixture to form a water-in-oil emulsion, and inversion water is added to form an oil-in-water mixture. According to the method of causing phase transition to an emulsion (phase inversion method) and the method described in JP-B-53-32380, the components (A) and (B) are melt-mixed, and then (C).
After mixing the ingredients, under high temperature and high pressure (eg 130-200).
A method (mechanical method) of producing an oil-in-water emulsion through a homogenizer at 150 ° C. and 150 to 1000 kg / cm ² ) is used.

The rosin emulsion composition thus obtained has excellent storage stability and mechanical stability when used as a sizing agent, and is applied to a wet paper under relatively mild drying conditions on a high-speed paper machine. Relatively less heat
For example, in the case of a paper machine having a Yankee dryer or a paper machine for ultra-high speed newsprint, the papermaking pH is 4 to 6.5, particularly pH 4.5 to 5.0, that is, the so-called acidic papermaking system has a size performance higher than that of the conventional sizing agent. Etc. are excellent in performance. The sizing agent of the present invention can be used even if the papermaking pH is less than 4 or the papermaking pH is more than 6.5, but those within the above range are preferable from the viewpoint of sizing effect. Further, the sizing agent of the present invention is characterized in that a papermaking tool such as a press roll or a dryer canvas is less contaminated.

In the sizing method of the present invention, the sizing agent of the present invention is added to, for example, the wet end part in the process of producing various papers and paperboards at a papermaking pH of 4 to 6.5, especially pH of 4.5 to 5.0. It is carried out by Specifically, the sizing agent of the present invention is added to an aqueous dispersion of pulp in an amount of 0.01 to 5% by solid weight, preferably 0.05 to 2% by solid weight, based on its dry weight. Also, (A)
There is also a method of separately adding a component obtained by emulsifying and dispersing the component (C) and a component obtained by emulsifying and dispersing the component (B) with the component (C) to the pulp slurry, but one using the sizing agent of the present invention However, the size effect is remarkably excellent, and the handling is easy.

The sized paper of the present invention has the above (1) or
Using the rosin-based emulsion composition described in ( 2) as a sizing agent, in the presence of vanadium sulfate, preferably in the presence of 0.5% to 5% based on the pulp solid content, the pH is from 4 to pH.
Papermaking p of 6.5, preferably pH 4.5 to pH 5.0
Those sized in the H range, in which case a papermaking pH of 4 to 6 with an alkali or an acid, for example, a strong alkali or a strong acid, specifically NaOH or sulfuric acid, if necessary.
5, preferably the papermaking pH can be 4.5 to 5.0, and exhibits superior sizing performance as compared with paper sized using conventional rosin-based sizing agents.

The sizing agent can also be used as a surface sizing agent. In this case, a conventional surface sizing method such as spraying, dipping or coating is applied to the wet paper made by papermaking. Therefore, the surface sizing agent containing the rosin-based emulsion composition described in (1) or ( 2) above can be used to perform surface sizing on a papermaking paper made at a papermaking pH of 4 to pH 6.5.

The sized paper of the present invention contains at least the component (A), the component (B), and may further contain the component (C), but the content varies depending on the type of paper. , And a range of 0.01 to 5% by solid weight. Each component is identified by analysis. Examples of the analysis method include gas chromatography.

In the production of paper or paperboard, pulp raw materials are bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, groundwood pulp, bleached or unbleached high yield pulp such as mechanical pulp or thermomechanical pulp. Any of used pulp such as used newspaper, used magazine, used corrugated cardboard or deinked used paper can be used. Further, a mixture of the above pulp raw material and synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin and polyvinyl alcohol can also be used.

Additives such as a filler, a dye, a dry paper strength improver, a wet paper strength improver, a retention improver, and a drainage improver are also required in order to exhibit the physical properties required for each paper type. You may use according to it. Examples of the filler include clay and talc, which may be used alone or in combination. Examples of the dry paper strength improver include anionic polyacrylamide, cationic polyacrylamide, amphoteric polyacrylamide, and cationized starch, which may be used alone or in combination. Examples of the wet paper strength improver include polyamide / epichlorohydrin resin, melamine / formaldehyde resin, urea / formaldehyde resin, etc. These may be used alone or in combination with anionic polyacrylamide. As the yield improver, anionic or cationic high molecular weight polyacrylamide, a combination of silica sol and cationized starch,
A combination of bentonite and cationic high molecular weight polyacrylamide may be used. Examples of the drainage improving agent include polyethyleneimine, cationic or amphoteric or anionic polyacrylamide, and the like. Also size press,
If necessary, starch, polyvinyl alcohol, dyes, coating colors, surface sizing agents, anti-slip agents, etc. may be applied using a gate roll coater, bill blade coater, calender or the like. Further, the bansulfate may be used before, after, or simultaneously with the addition of the sizing agent of the present invention.

[0029]

EXAMPLES The present invention will be described in more detail below with reference to production examples of the above components (A), (B) and (C), and examples and comparative examples using the same. It is not limited to the example of. In the examples, parts and% are based on weight unless otherwise specified.

Production of rosin-based substance (B) -1 Production of fumaric acid fortified rosin 90 parts of fumaric acid was gradually added to 450 parts of gum rosin in a molten state at about 200 ° C., and almost all fumaric acid reacted. After the completion, 460 parts of formaldehyde-treated (modification rate 3%) tall oil rosin was added, and the mixture was melted and stirred for homogenization, and then the reaction product was cooled to room temperature. The reaction product (toughened rosin) was rosin with 9% fumaric acid added.

-2 Production of rosin ester To 900 parts of tall oil rosin in a molten state at about 200 ° C, 50 parts of fumaric acid was added, and after reacting at 200 ° C for 3 hours, 18
Cool to 0 ° C. and add ethanediol-1,2 to 11
0 part was added and reacted at 240 ° C. to 260 ° C. for 8 hours to obtain an esterified product of reinforced rosin.

Production of Polymeric Emulsifying Dispersant Polymeric emulsifying dispersants (C-1) and (C- for Examples for stabilizing a rosin-based substance in the following manner for dispersion stabilization.
2) was produced. -1 Anionic Polymer Dispersant for Examples (C-1)
According to the production method of Reference Example 10 of JP-A No. 61-108796, a styrene-methacrylic acid copolymer neutralized product (C-1) was produced as follows. Styrene 55
Parts, methacrylic acid 30 parts, itaconic acid 5 parts, lauryl acrylate 10 parts, 10% sodium naphthalene sulfonate formaldehyde condensate 50 parts, ammonium persulfate 1 part and water 200 parts by mixing and stirring, and under pressure at 150 ° C. 30 Heated for minutes. Then it was cooled to 70 ° C. and 48.5.
By gradually adding 35.5 parts of sodium hydroxide and 7 parts of water, stirring for 30 minutes, and then cooling to room temperature,
An anionic polymer dispersion liquid (C-1) having a solid content of 30% was obtained.

-2 Preparation of Cationic Polymer Dispersant (C-2) for Reference Example Of the cationic poly (meth) acrylamide having a hydrophobic group described in Example 1 of JP-A-2-177534. A polymeric dispersant (C-2) was produced as follows according to the production method. A 1 liter 4-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube was charged with 31.4% of dimethylaminoethyl methacrylate.
Parts, 50% acrylamide aqueous solution 85.3 parts, styrene 20.8 parts, ion-exchanged water 100.6 parts, isopropyl alcohol 143.3 parts, n-dodecyl mercaptan 0.6 parts, and 20% acetic acid aqueous solution pH. To 4.5
Adjusted to. The temperature of this mixed solution was raised to 60 ° C. under a nitrogen gas atmosphere while stirring. 2.3 parts of a 5% ammonium persulfate aqueous solution was added as a polymerization initiator, the temperature was raised to 80 ° C., and the temperature was maintained for 1.5 hours.
% Aqueous solution 0.7 parts was added. After maintaining at the same temperature for another hour, 100 parts of ion-exchanged water was added, then isopropyl alcohol was distilled off, and ion-exchanged water was further added to the aqueous solution of a cationic polymer having a solid content concentration of 20.4% (C-2). Was manufactured.

Production of Rosin-Based Emulsion Composition -1 The fumaric acid-enhanced rosin obtained in Examples 1 to 3 and Reference Example 1 and the alkenylsuccinic anhydride shown in Table 1 were mixed at a ratio shown in the same table, and mixed. 150 ° C
Was melted by heating, and the viscous stirring was carried out, and the dispersant obtained in was added and mixed as shown in the same table to give a water-in-oil emulsion. Hot water was gradually added to this to invert the phase to form an oil-in-water emulsion, and hot water was further quickly added to this to form a stable oil-in-water emulsion, which was then cooled to room temperature. The emulsion thus obtained has a solid content of about 45.
˜50%, cumulative 50% in weight-based particle size distribution measured with MasterSizer (Malvern)
The diameter (hereinafter referred to as the average particle diameter) is 0.23 to 0.38 μ.
m, which was stable for a long period of time.

-2-Comparative Examples 1-2 A rosin emulsion composition (size) was obtained in the same manner as in the above Examples except that the composition shown in Table 1 was used without using the alkenylsuccinic anhydride. .

Comparative Example 3 The alkenylsuccinic anhydride used in Example 1 was completely neutralized with caustic potash to obtain an aqueous solution having a solid content of 40%. The fumaric acid-enhanced rosin obtained in 1 above was melted by heating to about 150 ° C., and the alkenylsuccinic acid neutralized product and the dispersant C-1 were added and mixed under vigorous stirring, and a rosin emulsion was prepared in the same manner as in the above examples. A composition was obtained.

-4 Comparative Example 4 Instead of the fumaric acid fortified rosin used in Example 1, -2
A rosin-based emulsion composition (size) was obtained in the same manner as in Example 1 except that the rosin ester was used. -5 Comparative Example 5 A rosin emulsion composition (size) was obtained in the same manner as in Example 1 except that the alkenylsuccinic acid shown in Table 1 was used instead of the alkenylsuccinic anhydride used in Example 1. It was Table 1 shows the composition and properties of the rosin emulsion compositions of the above Examples, Reference Examples and Comparative Examples.

[0038]

[Table 1]

Table 2 shows the results of a size effect test using the rosin emulsion compositions obtained in the above Examples , Reference Examples and Comparative Examples as sizing agents under the following test conditions. All the added chemicals are shown by the weight ratio of solid content to absolute dry weight of pulp.

-1 Size effect test Bleached kraft pulp (pulp ratio of softwood to hardwood is 1: 4
Was mixed with water for dilution having a hardness of 100 ppm so as to have a pulp concentration of 2.5%, and beaten up to 350 ml of Canadian standard freeness using a beater. 1.2 liters of this pulp slurry was weighed in a disintegrator, and the sizing agents of the above Examples, Reference Examples and Comparative Examples were added in the amounts shown in Table 2 (0.3% or 0.4%) and 1.5.
% Vanadium sulphate was added simultaneously and then stirred for 30 minutes. Next, this pulp slurry is diluted to a concentration of 0.25% with diluting water having a pH of 4.5, and then a cationic polyacrylamide (paper making agent D manufactured by Nippon PMC Co., Ltd.) is used as a fixing agent.
S410) was added at 0.05% and papermaking was carried out at a papermaking pH of 4.5 with a Noble and Wood papermaking machine to obtain a test paper having a basis weight of 65 g / m ² . The wet paper web was dried under a predetermined drying condition using a drum dryer. The obtained test paper was conditioned under a constant temperature and constant humidity environment (20 ° C., 65% relative humidity) for 24 hours, and then the sizing degree was measured by the Steckit method. The results are shown in Table 2. In the table, among the drying conditions, the conditions of 80 ° C. and 100 seconds correspond to “when the drying conditions are relatively gentle”.

[0041]

[Table 2]

Stationary Stability Test 100 ml of the sizing agent of the above-mentioned Examples, Reference Examples and Comparative Examples was put into a test tube having a length of 30 cm and an inner diameter of 2.1 cm, and allowed to stand for 6 months, and then the precipitate deposited on the bottom was removed. The height (cm) was measured. The measurement results are shown in Table 3.

Mechanical Stability Test 50 g of each sizing agent of the above-mentioned Examples, Reference Examples and Comparative Examples was put in a cup, temperature 25 ° C., load 20 Kg, rotation speed 800 r
A Marlon-type stability test was performed at pm for 5 minutes. The generated aggregate was filtered through a wire mesh of 325 mesh and expressed as a percentage of the total solid content. The measurement results are shown in Table 3.

[0044]

[Table 3]

From the above results, the results of the sizing effect test and the stability test of the sizing agent of the example are significantly better than those of the comparative example. For example, if alkenyl succinic anhydride is used, Even in the case of using succinic acid, the remarkable difference in effect is clear,
The alkenyl succinic anhydride, the reinforced rosin, and the anionic polymer dispersant are contained in a weight ratio of 2 to 10 and 85 to 5, respectively.
In the case of using Nos. 93 and 4 to 5 (excluding the case of the above embodiment), good results are obtained as in the corresponding embodiment. Further, in the above example, the alkenyl succinic anhydride was one kind, but the same good result was obtained even if two or more kinds of the compounds shown in Table 1 were used in combination. In addition, you may use together other alkenyl succinic anhydride. Although not shown in the above examples, the results of the sizing effect test and the sizing stability test can be further improved by using a low molecular weight surfactant in combination.

According to the present invention, (A) an alkenyl succinic anhydride, and (B) a rosin-based substance which does not contain rosin esters or can contain up to 50% by weight when (C) ) A rosin-based emulsion composition in which a dispersoid containing an anionic dispersant is stably dispersed in water, wherein the component (A) is 1 to 30 parts by weight and the component (B) is 5.
0 to 98 parts by weight are melt mixed, and the mixture is added to the component (C) 1
Provided are a rosin emulsion composition, a sizing agent, a sizing method, and a sized paper, in which 100 parts by weight in total of 20 to 20 parts by weight are stably dispersed in water to form a dispersion having a solid content concentration of 20 to 60% by weight. Therefore, when sizing is performed using a sizing agent containing this rosin-based emulsion composition, it is possible to obtain a conventional papermaking system having a high papermaking speed of 4 to 6.5 even under conditions of high papermaking speed and mild drying conditions. It is possible to provide a paper exhibiting an excellent sizing effect not found in rosin emulsion sizing agents. Also,
This size is excellent in storage stability and mechanical stability.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-5-140891 (JP, A) JP-A-58-60093 (JP, A) JP-A-6-65891 (JP, A) JP-A-1- 162896 (JP, A) JP 64-68597 (JP, A) JP 64-68596 (JP, A) JP 62-69899 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) D21H 11/00-27/42 B01J 13/00

Claims (5)

(57) [Claims] 1. An (A) alkenyl succinic anhydride,
(B) a rosin-based substance that can contain up to 50% by weight when it does not contain rosin esters or when it contains
(C) A rosin-based emulsion composition in which a dispersoid containing an anionic dispersant is stably dispersed in water,
1 to 30 parts by weight of the component (A) and 50 to 98 parts by weight of the component (B) are melt- mixed, and the mixture is stably dispersed in water by using 1 to 20 parts by weight of the component (C) in a total of 100 parts by weight. Let
A rosin-based emulsion composition, which is a dispersion having a solid content concentration of 20 to 60% by weight. 2. The rosin emulsion composition according to claim 1, wherein the alkenylsuccinic anhydride (A) is a reaction product of an olefin having 8 to 20 carbon atoms and maleic anhydride. 3. A sizing agent containing the rosin-based emulsion composition according to claim 1. 4. The rosin emulsion composition according to claim 1 or 2 is used as a sizing agent from pH 4 to pH 6.
A sizing method of sizing in the papermaking pH range of 5. 5. A sized paper containing solids of the rosin-based emulsion composition of claim 1.