JPH09324392A - Sizing agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rosin-based emulsion sizing agent composition capable of exhibiting excellent sizing performance in wide pH region (pH4.5-8.0). SOLUTION: This sizing agent composition is obtained by dispersing an ester of a multifunctional alkanolamine with a rosin or an α,β-unsaturated polybasic acid-added rosin with a dispersing agent comprising a polyoxyethylenealkylphenolsulfonic acid alkanol amine salt or an alkanolamine salt of polyoxyethylene alkylphenol sulfate and mixing the resultant emulsion with a water-soluble aluminum compound or a water soluble cationic resin. A disperse auxiliary agent which is K, Na or alkanolamine salt of a copolymer of styrene and/or a styrene derivative with acrylic acid and/or methacrylic acid and an acrylate and/or methacrylate can be used together with the dispersing agent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel rosin-based emulsion sizing composition, particularly in a wide pH range (papermaking p
The present invention relates to a rosin-based emulsion sizing composition that exhibits excellent sizing performance at H4.5-8.0).

[0002]

2. Description of the Related Art In recent years, neutral papermaking has been increasing due to the quality of paper, the problem of paper recycling accompanying resource saving, or the use of calcium carbonate as a low-cost filler.

As such a situation has progressed more and more, the conventional rosin emulsion sizing agent cannot obtain sufficient sizing performance. Under these circumstances, the size maker has recently launched a rosin emulsion sizing agent for neutral papermaking on the market, but at the development stage, sufficient effects have not been obtained in terms of sizing and operability. In particular, in terms of operation, there are still many problems to be solved such as foaming problem and papermaking system stain problem. As for the problem of stains (blankets, press rolls, etc.), most of the rosin emulsion sizing agents for neutral papermaking currently on the market are esterified by polyhydric alcohols of rosin, as mentioned in the literature. Is dispersed in the mainstream using a surfactant or a polymer-dispersant (styrene / acrylic copolymer), and the calcium carbonate content (or addition amount) in the raw material increases. It becomes difficult to obtain sufficient size performance, so that it is necessary to increase the amount of esterified rosin in order to improve size performance. However, since the esterified rosin which is mainly used at present has the -COOH group blocked, there is a limit to the amount increase from the standpoint of yield or stains.

Other esterified rosins of rosins include rosins or α, β unsaturated polybasic acid-added rosins modified with an alkanolamine.
JP-A-60-161472 and JP-A-4-108
As described in Japanese Patent Publication No. 196, the size performance is not sufficiently obtained with a conventional dispersant even if an alkanolamine ester of rosin is used, and a polyvalent metal such as a water-soluble aluminum compound or a water-soluble aluminum compound is used. When mixed with a cationic resin, a phenomenon of solidification was observed. Therefore, it was found that the pH increase related to calcium carbonate cannot be dealt with by modifying or selecting only the substrate.

Further, Japanese Patent Laid-Open No. 3-8893 discloses that
A method of mixing a polyvalent metal or a cation resin is described, but the effect cannot be expected in the presence of calcium carbonate.

[0006] Conventionally, since a sufficient effect cannot be obtained for waste paper containing calcium carbonate and waste paper for deinking, at present, a large amount of aluminum sulfate is used. Therefore, the precipitation and foaming of gypsum produced as a by-product has become a problem.

Under the above circumstances, a sizing composition having excellent size performance in a wide pH range (papermaking pH 4.5 to 8.0) is still desired in the paper manufacturing industry.

[0008]

SUMMARY OF THE INVENTION The present invention does not have the above-mentioned drawbacks and has a wide pH range (papermaking p
It is an object of the present invention to provide a rosin-based emulsion sizing composition that exhibits excellent sizing performance at H4.5-8.0).

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned conventional problems, the present inventors have found that an ester using an alkanolamine for a rosin or an α, β unsaturated polybasic acid addition rosin. The emulsion obtained by dispersing the rosin chloride with a specific dispersant and mixing the obtained dispersion emulsion with a polyvalent metal compound such as a water-soluble aluminum compound or a water-soluble cationic resin with stirring. It has been found that excellent size performance is exhibited in a wide pH range of pH 4.5 to 8.0. Further, in addition to the above-mentioned specific dispersant, a specific polymer-based dispersion auxiliary agent is also used in combination to obtain a dispersion emulsion, which is also obtained by mixing a polyvalent metal compound or a water-soluble cationic resin with stirring. The emulsion has a wide pH range of 4.5 to 8.0.
It has been found that it exhibits excellent size performance in the H region. As the above specific dispersant, the number of moles of added ethylene oxide of polyoxyethylene alkylphenol is 6 to 15
It has been found that an alkanolamine salt of a sulfonic acid having a molar number of ethylene oxide of 8 to 13 is suitable. By combining this dispersant with an alkanolamine ester of rosin or an α, β unsaturated polybasic acid addition rosin, it is possible to mix not only the water-soluble aluminum compound but also the water-soluble cationic resin in an arbitrary ratio. became. The inventors have completed the present invention based on these findings.

That is, according to the present invention, an ester of an alkanolamine and a rosin or an α, β-unsaturated polybasic acid-added rosin is used as an alkanolamine salt of a polyoxyethylene alkylphenol sulfonic acid alkanolamine salt or a polyoxyethylene alkylphenol sulfate ester. A sizing composition for paper obtained by mixing a water-soluble aluminum compound or a water-soluble cationic resin with an emulsion dispersed with a dispersant consisting of.

Further, according to the present invention, an ester of an alkanolamine and a rosin or an α, β unsaturated polybasic acid-added rosin is used as an alkanolamine salt of a polyoxyethylene alkylphenol sulfonic acid alkanolamine salt or a polyoxyethylene alkylphenol sulfate ester. And a K of a copolymer of styrene and / or a styrene derivative and acrylic acid and / or methacrylic acid and an acrylic ester and / or a methacrylic ester.
A sizing composition for paper, which is obtained by mixing a water-soluble aluminum compound or a water-soluble cationic resin with an emulsion dispersed with a dispersion aid which is Na or an alkanolamine salt. .

As the rosin used in the present invention, gum rosin, wood rosin, tall rosin, disproportionated rosin, hydrogenated rosin and the like are used.

The α, β unsaturated polybasic acids used in the present invention include itaconic acid, maleic acid, maleic anhydride,
Further, fumaric acid or the like is used, and the addition ratio to rosin is preferably 5 to 15% by weight.

Alkanolamines used in the esterification reaction with rosins in the present invention include monoethanolamine, diethanolamine, triethanolamine and the like, with triethanolamine being preferred. The alkanolamine used for the esterification is -COOH / OH.
(Eq / g) is 1 / 0.1 to 1 / 0.8, preferably 1 /
Use around 0.5.

The alkyl of the polyoxyethylene alkylphenol sulfonic acid used in the present invention is octyl,
There are nonyl and the like, and the alkanolamine salt includes monoethanolamine, diethanolamine, triethanolamine salt and the like, and the triethanolamine salt is preferable.

The alkyl of the polyoxyethylene alkylphenol sulfate used in the present invention includes octyl, nonyl, etc., and the alkanolamine salts include monoethanolamine, diethanolamine, triethanolamine salt, etc., and the triethanolamine salt is preferable.

The polyvalent metal compound includes, for example, a water-soluble aluminum compound, and the water-soluble aluminum compound includes aluminum sulfate, aluminum chloride, polyaluminum chloride and the like. Polyamide-for water-soluble cationic resin
There are epichlorohydrin condensates, polyamine-fatty acids-epichlorohydrin fatty acids and the like.

On the other hand, K, Na or an alkanolamine salt of a copolymer of styrene and / or a styrene derivative / acrylic acid and / or methacrylic acid / acrylic acid ester and / or methacrylic acid ester is used as a polymeric dispersion aid. Particularly preferred are alkanolamine salts. The styrene derivative used here includes α-methylstyrene and the like.

If necessary, P may be used as a protective colloid.
VA, MC, PAM starch, cationic starch, casein, etc. can be used.

The rosin ester, dispersant and polyvalent metal compound or water-soluble cationic resin in the sizing composition of the present invention, and optionally the dispersion aid, are added in proportions of 100 parts by weight of rosin ester. On the other hand, it is 1 to 8 parts by weight of the dispersant and 3 to 20 parts by weight of the polyvalent metal compound or the water-soluble cationic resin, and 0 to 7 parts by weight of the dispersion aid.

As a method for esterifying the rosin or the α, β unsaturated polybasic acid addition rosin, a method known in the art can be used. Further, as a method for dispersing the esterified rosin and a method for mixing the polyvalent metallic substance in the dispersion emulsion, methods known in the art can be used.

By adopting the above-mentioned matters specifying the invention, the sizing composition product of the present invention can be used in the presence of calcium carbonate as a filler of paper or against calcium carbonate contained in waste paper. It also has an excellent size effect on deinked waste paper, which has been increasing in recent years.

Further, since the emulsion according to the present invention can freely change the charge from anionic to cationic, the adsorption on pulp fibers is effective in the presence of a very small amount of Al ions, so that the present investigators are in the market. To provide with confidence.

The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the scope.

[0025]

【Example】

Example 1 <Modification of rosin> (1) Gum rosin (900 parts) was charged into a 2-liter four-necked flask, heated and melted, the temperature in the system was adjusted to 160 ° C., and then 100 parts of maleic anhydride was added, 200-2
The reaction was carried out at 10 ° C for 3 hours. After completion of the reaction, the temperature in the system was cooled to 150 ° C., 50 parts of triethanolamine was added, the temperature in the system was gradually raised to 210 to 220 ° C., and the esterification reaction was carried out for 4 hours. It was The acid value of the obtained esterified rosin was 203 and the softening point was 89 ° C.

(2) Gum rosin (920 parts) was charged into a 2-liter four-necked flask, heated and melted, the temperature in the system was adjusted to 150 ° C., and then fumaric acid (80 parts) was added,
The reaction was carried out at 0 to 210 ° C for 3 hours. After completion of the reaction, the temperature in the system was cooled to 150 ° C., and triethanolamine 3 was added.
4.3 parts was added and the temperature in the system was gradually raised to 220 to 2
The temperature was raised to 30 ° C., and the esterification reaction was carried out for 2 hours. The obtained esterified rosin had an acid value of 191 and a softening point of 88 ° C.

<Manufacture of Emulsion> 350 parts of the esterified rosin obtained in the above <Modification of rosin> (1) was charged into an autoclave having a volume of 1 liter, heated and melted, and then the temperature in the system was adjusted to 150 ° C. Next, polyoxyethylene nonylphenol (EO = 11) heated to 70 ° C.
21.4% of sulfonic acid triethanolamine salt
The liquid was gradually added with stirring with 162 parts. Thereafter, 257 parts of water adjusted to 70 ° C. was gradually added to obtain an emulsion having a solid content of 50%. The obtained emulsion is (A)
And

Next, using the esterified rosin obtained in the above <Modification of rosin> (2), emulsification was carried out in the same manner as described above. The obtained emulsion is (B)
And

<Production of Sizing Agent Composition> (1) 1,000 parts of emulsion (A) was placed in an emulsifier, and 588 parts of aluminum sulfate having a solid content of 9.5% was gradually added with stirring to give an emulsion size having a solid content of 35%. A sizing composition was obtained (hereinafter referred to as sizing composition A).

(2) 401 parts of water was added to the emulsion (B), and 56.8 parts of 10% PVA solution was further added (solid content 34.6%). The resulting mixture was designated as (C). Next, 454 parts of a polyamide epichlorohydrin condensate diluted to a solid content of 15% was prepared (referred to as (D)). The liquids (C) and (D) thus obtained were mixed using a high speed mixer to obtain an emulsion sizing composition having a solid content of 30% (hereinafter referred to as sizing composition B).

(3) 91 parts of gum rosin was charged into a reaction vessel, heated and melted, the temperature in the system was adjusted to 160 ° C., 9 parts of fumaric acid was added, and the reaction was carried out at 200 to 210 ° C. for 3 hours.
Then, the modified rosin obtained above is added to a pressure emulsifier 93
After keeping the temperature in the system at 155 ° C., 28 parts (solid content 7 parts) of styrene / acrylic polymer dispersant was added with stirring, and 79 parts of warm water (70 ° C.) was emulsified and dispersed (temperature 70
C.) and then rapidly cooled to obtain an emulsion having a solid content of 50%. This emulsion was used as a comparative sizing composition.

<Size Performance Test> Raw material: Magazine waste paper / DIP = 5/5 (pH 8.0) Beating degree: CSF = 350 ml Basis weight: 90 g / m ² Amount of sizing agent: 0.4% by weight in terms of solid content And 0.6
% By weight (based on pulp weight) Alum addition amount: 2.5% by weight (pH 6.0), 1.8
% By weight (pH 6.5), 1.3% by weight (pH 6.9) and 0.8% by weight (7.3) Drying conditions: 2 minutes at 90 ° C. Papermaking process: Dissociation (5 minutes) → Alum (1 minute ) → size →
(1 minute) → dilution (1 minute) → papermaking Papermaking temperature: 40 ° C. Size measurement method: JIS P 8122 (Steckit method)

<Test results> As can be seen from the above results, the sizing compositions A and B of the present invention exhibited remarkably superior sizing performance as compared with the comparative sizing composition and the emulsions A and B.

Claims (2)

[Claims] 1. An alkanolamine and rosin or α, β
Unsaturated polybasic acid addition ester with rosin is dispersed with a dispersant consisting of alkanolamine salt of polyoxyethylene alkylphenol sulfonic acid or alkanolamine salt of polyoxyethylene alkylphenol sulphate ester. A sizing composition for paper obtained by mixing a cationic resin. 2. Alkanolamine and rosin or α, β
An ester with an unsaturated polybasic acid-added rosin is used as a dispersant comprising a polyoxyethylene alkylphenol sulfonic acid alkanolamine salt or a polyoxyethylene alkylphenol sulfuric acid ester alkanolamine salt, and styrene and / or a styrene derivative with acrylic acid and / or A mixture of a water-soluble aluminum compound or a water-soluble cationic resin with an emulsion dispersed with a dispersion aid which is a K, Na or alkanolamine salt of a copolymer of methacrylic acid and an acrylic ester and / or a methacrylic ester. Paper sizing composition.