JP3477932B2 - Rosin-based emulsion sizing agent for papermaking and paper sizing method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rosin emulsion sizing agent for papermaking and a paper sizing method. More specifically, the present invention relates to a rosin emulsion sizing agent for papermaking containing a specific amount of a reinforcing rosin ester containing a sulfone group as a substance to be dispersed, and a paper sizing method using the sizing agent.

[0002]

2. Description of the Related Art In the paper manufacturing industry, there are problems caused by improvement of paper quality, closed papermaking system, etc., and problems associated with the use of waste paper and broke containing calcium carbonate. Neutral papermaking that uses less amount of bun soil has been put to practical use. Conventionally, as a sizing agent for neutral papermaking, a so-called reactive sizing agent in which an alkenyl succinic anhydride or an alkyl ketene dimer is dispersed in water has been widely used. However, all the reactive sizing agents are expensive, the former is in terms of hydrolysis and leaving stability over time, and the latter is liable to cause stains on press rolls during paper making. There is a disadvantage in that the effect rises slowly.

Recently, a rosin-based emulsion sizing agent containing a rosin ester or a reinforced rosin ester, which is lower in price and excellent in operability than the above-mentioned reactive sizing agent, has been attracting attention as a sizing agent for neutral papermaking. (Japanese Patent Laid-Open No. 62-22
3393, JP-A-62-250297, etc.). However, the rosin-based emulsion sizing agent may not be able to exert an excellent sizing effect in a wide range of papermaking pH range, or the emulsion stability may not always be satisfactory when the sizing agent is diluted with hard water having high hardness. No, there is room for improvement.

[0004]

DISCLOSURE OF THE INVENTION An object of the present invention is to improve the size of rosin-based emulsion for papermaking, which is more improved than the prior art in terms of hard water stability of the sizing agent itself and size performance in a wide papermaking pH range. An object is to provide an agent and a paper sizing method.

[0005]

[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventor has conducted extensive studies focusing on a rosin substance as a substance to be dispersed. As a result, a rosin-based emulsion sizing agent for papermaking containing a specific amount of a sulfonic group-containing reinforced rosin ester as the rosin substance was found to be able to solve the above problems, and to complete the present invention. I arrived.

That is, the present invention provides a papermaking emulsion sizing agent comprising a rosin substance, a dispersant and water, wherein the rosin substance is (A) rosin, (B) α, β-unsaturated carboxylic acid, ( The present invention relates to a rosin-based emulsion sizing agent for papermaking, which comprises 20% by weight or more of a reaction product containing C) a sulfocarboxylic acid and (D) a polyhydric alcohol having a valence of 3 or more. The present invention also relates to a paper sizing method, characterized in that the rosin emulsion sizing agent for papermaking is used in a pH range of 4 to 8.

In the emulsion size of the present invention,
It is essential that the rosin substance, which is the substance to be dispersed, contains the reaction product in an amount of 20% by weight or more, preferably 30% by weight or more, in the rosin substance. When the content of the reaction product is less than 20% by weight, the sizing agent obtained is not sufficiently improved in hard water stability and sizing effect in a wide papermaking pH range.

In the present invention, the reaction product contained in the rosin substance to be dispersed is, as described above, rosin (hereinafter referred to as component (A)), α, β-unsaturated carboxylic acid (hereinafter referred to as “component (A)”). , A component (B), a sulfocarboxylic acid (hereinafter, component (C)), and a polyhydric alcohol having 3 or more valences (hereinafter, component (D)).

Specific examples of the component (A) include gum rosin, wood rosin, tall oil rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin and aldehyde-modified rosin, which can be used alone or in combination.

Specific examples of the component (B) include fumaric acid,
Maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, acrylic acid,
Methacrylic acid and the like can be mentioned, and these can be used alone or in combination.

As the component (C), a sulfone group (--SO
₃ M, M is a compound having a hydrogen atom, ammonium or an alkali metal) and a carboxyl group in the same molecule, and is capable of reacting with at least one of the components (A), (B) and (D). It is not particularly limited as long as it is one. Specific examples of the component (C) include sulfosuccinic acid, lower dialkyl ester of sulfosuccinic acid, 2,4-disulfobenzoic acid, 3,5-disulfobenzoic acid, 3-sulfophthalic acid, 4-sulfophthalic acid and 3,5- Disulfophthalic acid, 4-sulfoisophthalic acid, 5-sulfoisophthalic acid, 2-sulfoterephthalic acid; their corresponding acid anhydrides, their corresponding lower alkyl mono- or diesters, their corresponding alkyl-substituted sulfocarboxylic acids, Examples thereof include salts corresponding to these, and these can be used alone or in combination.

Examples of the component (D) include glycerin, trimethylolethane, trimethylolpropane, 3-methylpentane-1,3,5-triol, pentaerythritol, diglycerin and sorbitol.
The dihydric alcohol can be used in combination with the component (D) within a range that does not reduce the size effect of the obtained sizing agent, and usually up to 30 equivalent% of the component (D) can be substituted.

The proportion of each component in the reaction product is not particularly limited, but is usually in the following respective charging ranges. That is, the charging ratio of the components (A) and (B) is in the range of 0 to 1 mol of the component (B), preferably 0.1 to 0.75, relative to 1 mol of the component (A). In addition, the component (A)
The proportion of (C) charged is 0.02 to 0.4 mol, preferably 0.05 to 0.4 mol of the component (C) per 1 mol of the component (A).
It is in the range of 0.3 mol. The charging ratio of the components (A) and (D) is the equivalent ratio of the hydroxyl group of the component (D) to the carboxyl group of the component (A) [-OH (eq) /-COOH.
(Eq)] is 0.2 to 1.5, preferably 0.4 to 1.
The range is 2.

1 mol of the component (B) per 1 mol of the component (A)
If it exceeds the molar amount, improvement of the size effect in the neutral region of the resulting sizing agent is not sufficient. When the amount of the component (C) is less than 0.02 mol with respect to 1 mol of the component (A), the hard water stability of the obtained sizing agent is not sufficiently improved, and when it exceeds 0.4 mol, it is obtained. Since the hydrophilicity of the sizing agent becomes excessive, the sizing effect in the neutral region is not sufficiently improved. When the equivalent ratio of the hydroxyl group of the component (D) to the carboxyl group of the component (A) is less than 0.2, the sizing effect of the resulting sizing agent is not sufficiently improved, and 1.
When it exceeds 5, the size effect tends to decrease due to the residual hydroxyl group in the reaction product.

The method for producing the reaction product is not particularly limited with regard to the order of preparation and the reaction conditions, as long as the usage ratio of each component satisfies the above-mentioned preparation range. For example,
A method of simultaneously charging each component and reacting by heating, by heating the components (A) and (B) to cause Diels-Alder reaction to obtain a so-called reinforced rosin, and then adding the components (C) and (D) to form an ester. Method, ingredient (A)
And (D) are esterified, then components (B) and (C)
Can be appropriately selected and employed, such as a method of further adding and continuing the reaction. In any of the above-mentioned production methods, after charging each predetermined component into a reaction vessel, the reaction vessel is subjected to normal pressure, reduced pressure or increased pressure under the presence or absence of a catalyst.
While stirring at about 50 to 300 ° C for about 3 to 30 hours,
A dehydration reaction may be performed. At this time, benzene, toluene,
The dehydration reaction may be carried out azeotropically using a solvent such as xylene. The end point of the reaction is not particularly limited, but usually, the acid value of the content of the reaction system at the time of initial charging is traced,
It may be confirmed that the esterification reaction rate is 75% or more, preferably 85% or more.

As described above, the rosin emulsion sizing agent for papermaking of the present invention contains a rosin substance which is a substance to be dispersed, and the rosin substance is 20% by weight or more, preferably 30% by weight or more. It is composed of the reaction product and the following residual components. The residual component in the rosin substance is not particularly limited, but is usually rosin such as gum rosin, wood rosin, tall oil rosin; hydrogenated rosin, disproportionated rosin, polymerized rosin, aldehyde-modified rosin, strengthened rosin and the like. Examples include modified rosins; esters such as rosin esters and reinforced rosin esters; waxes such as paraffin wax and microcrystalline wax; petroleum resins, terpene resins, hydrocarbon resins such as hydrides thereof, etc., which may be used alone or Two or more types can be used in combination. For example, in order to enhance the size effect in the weak acidic region where the papermaking pH is around 6, it is necessary to increase the usage ratio of the fortified rosin as a residual component, and to enhance the size effect during neutral papermaking, the residual component should be added. The use ratio of the rosin ester or the fortified rosin ester may be increased.

As the reinforced rosin of the residual components,
Known fortified rosins can be used. For example, gum rosin,
Examples include heating reaction products of 100 parts by weight of rosins such as wood rosin and tall oil rosin, and about 2 to 30 parts by weight, preferably 3 to 20 parts by weight of α, β-unsaturated carboxylic acid. The α, β-unsaturated carboxylic acid is the same as the component (B) in the reaction product. The rosin ester and the reinforced rosin ester among the remaining components are not particularly limited, and various publicly known ones can be appropriately selected and used, but as the former, in particular, JP-A-62-223393.
The one described in JP-A No. 62-250297 is particularly preferable as the latter.

The rosin-based emulsion sizing agent for papermaking of the present invention is obtained by emulsifying and dispersing in water the rosin substance containing the reaction product and the residual component in specified amounts. In the dispersion operation, various well-known emulsifying dispersants such as low molecular weight surfactants and water-soluble polymer compounds may be appropriately selected and used.

The low molecular weight surfactant may be anionic, nonionic or cationic ionic. Examples of the anionic surfactant include dialkyl sulfosuccinic acid ester salts, alkane sulfonic acid salts, α-olefin sulfonic acid salts, polyoxyethylene alkyl ether sulfosuccinic acid ester salts, polyoxyethylene styryl phenyl ether sulfosuccinic acid ester salts, and naphthalene sulfone. Acid formalin condensate, polyoxyethylene alkyl ether sulfate ester salt, polyoxyethylene alkylphenyl ether sulfate ester salt, etc .; as nonionic surfactants, for example, polyoxyethylene alkyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene Sorbitan fatty acid ester and reactive surfactants in which a vinyl group or an allyl group is introduced into these surfactants; examples of the cationic surfactant include Tiger alkyl ammonium chloride, trialkyl benzyl ammonium chloride, alkylamine acetate, alkyl amine hydrochloride can be exemplified polyoxyethylene alkyl amines, polyoxyethylene alkyl amines, etc., respectively, which are alone or possibly in combination.

Examples of the water-soluble polymer compound include casein, lecithin, polyvinyl alcohol, various modified starches, various ionic acrylic acid ester-based copolymers, carboxylic acid vinyl ester-based copolymers, and acrylamide-based copolymers. Examples thereof include polymers. Furthermore, various fixing agents used for reactive neutral sizing agents such as conventional alkyl ketene dimer and alkenyl succinic anhydride,
It can be used as the emulsifying dispersant. Examples of the fixing agent include cationized starch, epichlorohydrin modified product of polyamide polyamine resin, epichlorohydrin modified product of dicyandiamide resin, styrene-dimethylaminoethyl methacrylate copolymer, Hofmann degradation product of polyacrylic amine, dialkyldiallylammonium chloride and dioxide. Examples thereof include copolymers with sulfur.

The method for dispersing the rosin substance in water using the emulsifying dispersant is, for example, Japanese Patent Publication No. 53-48.
Japanese Patent Publication No. 66-53, Japanese Patent Publication No. 53-
Any known method such as a solvent high pressure emulsification method described in JP-A-22090 or an inversion emulsification method described in JP-A-52-77206 and JP-B-58-4938 can be used. In the rosin emulsion sizing agent for papermaking of the present invention, since the reaction product itself has an emulsifying and dispersing ability, the amount of the emulsifying dispersant used can be significantly reduced as compared with known rosin emulsion sizing agents. That is, in the known sizing agent, 5 to 10% by weight of the rosin substance is used, whereas in the present invention, 1 to 4% by weight is sufficient.

The solid content of the rosin emulsion sizing agent for papermaking of the present invention obtained as described above is usually 20 to 6.
It is 0% by weight, preferably 30 to 50% by weight, and the average particle diameter of the rosin substance is usually about 0.4 μm.

The rosin emulsion sizing agent for papermaking of the present invention can be used in the papermaking region of pH 4 to 8 and can impart excellent sizing effect to papermaking. For example, a papermaking system in which a sulfuric acid band cannot be used or the amount of which is limited to a small amount, for example, a neutral pure white roll paper, a neutral liner, an anticorrosion liner, a papermaking system in which calcium carbonate is mixed from a used paper material,
For example, gypsum board base paper, white board, coated base paper, medium quality paper, general liner, core, etc., paper making system using calcium carbonate as a filler, such as neutral printing writing paper, neutral coated base paper, neutral PPC paper, neutral feeling Thermal base paper, neutral pressure-sensitive base paper,
The sizing agent of the present invention exhibits excellent sizing performance not found in conventional rosin emulsion sizing agents, even in paper-making systems such as kraft paper where the use of fixing agents is limited, such as neutral inkjet paper and neutral information paper. To do. Also,
Compared with conventional reactive neutral sizing agents such as alkyl ketene dimer and alkenyl succinic anhydride sizing agent, the sizing effect is excellent for pulp containing high-yield pulp, the sizing effect starts up quickly, and the papermaking machine It has features such as little dirt. Of course, it has excellent size performance even in a papermaking system in which a large amount of sulfuric acid band is used.

The sizing method of the present invention is carried out by adding the rosin emulsion sizing agent for papermaking of the present invention to, for example, the wet end portion in the process of producing paper or paperboard. Specifically, the sizing agent of the present invention is added to an aqueous dispersion of pulp in an amount of 0.05 to 0.05 based on its dry weight.
Add 5 wt% solids.

In the production of the above-mentioned various papers or paperboards, the pulp raw material is bleached or unbleached of kraft pulp, sulfite pulp or the like, or bleached or unbleached of chemical pulp, groundwood pulp, mechanical pulp, thermomechanical pulp, etc. Any of high-yield pulp, waste newspaper, magazine waste paper, corrugated waste paper, waste paper pulp such as deinked waste paper can be used.
Further, a mixture of the above pulp raw material and asbestos, polyamide, polyester, polyolefin or the like can also be used.

Conventionally known additives such as fillers, dyes, dry paper strength improvers, wet paper strength improvers, retention improvers and drainage improvers also exhibit the physical properties required for each paper type. To
Can be used as needed.

The rosin-based emulsion sizing agent for papermaking obtained by the present invention is not only used as a sizing agent to be added internally to an aqueous dispersion of pulp as described above, but also is commonly used for spraying, dipping and coating on wet paper. It can also be used as a surface sizing agent to which a conventional method is applied.

[0028]

EXAMPLES The present invention will be described in more detail with reference to production examples, examples and comparative examples, but the present invention is not limited to these examples. In each example, parts and% are based on weight unless otherwise specified.

Production Example 1 (Production of reaction product) 100 parts of gum rosin having an acid value of 170 and 9 parts of maleic anhydride were placed in a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introducing pipe, a water diverter and a cooler. 5-Sulfoisophthalate sodium 5
And 8 parts of glycerin were charged, and 250
The mixture was heated to 0 ° C. and esterified at the same temperature for 12 hours to obtain a reaction product having an acid value of 122 with a reaction rate of about 90% or more.

Production Examples 2 to 9 (Production of Reaction Product) Reactions were the same as in Production Example 1 except that at least one item of the type of each component and the amount used was changed as shown in Table 1. Esterification up to 90% or more,
Various reaction products were obtained.

Production Example a (Reinforced Rosin as a Remaining Component of Rosin Substance) A strengthened rosin obtained by reacting 100 parts of gum rosin having an acid value of 170 with 9 parts of maleic anhydride at 210 ° C. for 10 hours.

Production Example b (Strengthened Rosin Ester which is the Remaining Component of Rosin Substance) 100 parts of gum rosin having an acid value of 170, 8 parts of glycerin and 9 parts of maleic anhydride were reacted at 250 ° C. for 12 hours to obtain a strengthened rosin ester ( Acid value 117).

Examples 1 to 10 (high pressure emulsification method) 100 parts of each rosin substance (reaction product) shown in Table 1 was dissolved in 100 parts of toluene, and then an emulsifying dispersant (polyoxyethylene (n = 13) di 3 parts of styryl phenyl ether sulfate ester sodium salt) and 103 parts of warm water at 60 ° C. are mixed, and then the shearing force is 300 kg / cm.
Emulsify by passing it twice through a piston type high pressure emulsifier adjusted to ² , and further reduce the pressure to distill off toluene to obtain a nonvolatile content of 50%.
An aqueous emulsion of

Example 11 (inversion method) 100 parts of the reaction product obtained in Production Example 1 was charged 150
After heating and melting at 0 ° C., 3 parts of the emulsifying dispersant and 30 parts of hot water at 95 ° C. were gradually added with stirring to obtain a water-in-oil emulsion. Hot water of 90 ℃ 73 with vigorous stirring
Parts were added over 1 minute and the phases were inverted to give an oil-in-water emulsion with a non-volatile content of 50%.

Comparative Example 1 In Example 1, instead of using the reaction product obtained in Production Example 1 alone, 10% of the reaction product and the remaining components (45% each for Production Example a and Production Example b) High pressure emulsification was carried out in the same manner as in Example 1 except that the mixture consisting of
% Aqueous emulsion was obtained.

Comparative Example 2 In Example 1, the rosin substance was replaced by the reaction product obtained in Production Example 1 by using the reinforced rosin ester of Production Example b, and the amount of the emulsifying dispersant was 8 parts. High pressure emulsification was carried out in the same manner as in Example 1 except that the non-volatile content was 50%.
An aqueous emulsion of

Comparative Example 3 In Example 11, the rosin substance was replaced with the reaction product obtained in Production Example 1 by using the reinforced rosin ester of Production Example b, and the amount of the emulsifying dispersant used was 8 parts. Inversion emulsification was performed in the same manner as in Example 11 except that the non-volatile component was changed to 50%.
% Aqueous emulsion was obtained.

(Evaluation of Sizing Performance) The aqueous emulsions obtained in Examples 1 to 11 and Comparative Examples 1 to 3 were measured for mechanical stability, hard water dilution stability, foamability and size effect by the following methods. evaluated. The results are shown in Table 2.
And 3 are shown.

(1) Mechanical stability 50 g of an aqueous emulsion was weighed in a container of a Marlon type stability tester (manufactured by Shinsei Sangyo Co., Ltd.), temperature 25 ° C., load 2
A mechanical shear was added for 10 minutes at 0 kg and a rotation speed of 1000 rpm. Then, the produced aggregate was filtered through a 200-mesh wire net, and the amount of precipitation with respect to the total solid content was measured and expressed as a percentage.

(2) Hard water stability Hardness 1 so that the solid content concentration of the aqueous emulsion becomes 5%.
After diluting with 00 hard water and allowing it to stand at room temperature for 24 hours, the presence or absence of change in properties such as aggregation, precipitation and separation of the diluted solution was visually judged.

(3) Bleachable bleached kraft pulp with a beating degree of 350 ml (L-BKP / N
1 liter of an aqueous liquid obtained by adding an aqueous emulsion having a solid content of 0.5% to pulp (solid content conversion) and a 0.2% sulfuric acid band to a 2% aqueous slurry of BKP = 2/1), The contents were put into an apparatus specified in JIS K 3362, and the contents were circulated by a pump for 10 minutes (8 liters / minute), then the circulation was stopped and the height (mm) of bubbles was measured.

(4) Size effect evaluation method A (acidic papermaking) Bleached kraft pulp (L-BKP / N) having a beating degree of 350 ml.
-BKP = 2/1) in 2% aqueous slurry, 2% sulfuric acid band based on pulp solids and 0.2% of each aqueous emulsion obtained in Examples 1 to 11 and Comparative Examples 1 to 3 (solids content). (Converted) was added at the same time, and a 1% aqueous slurry adjusted to pH 5 with caustic soda was obtained. Then, a polyamide polyamine-based cationic polymer (manufactured by Arakawa Chemical Industry Co., Ltd., trade name "Arafix-100") as a fixing agent was added to the slurry in an amount of 0.05% (solid content conversion) and uniformly dispersed. Paper was made using a TAPPI standard sheet machine so that the basis weight was 60 g / m ² . The wet paper obtained is dehydrated for 5 minutes by applying a pressure of 5 kg / cm ² .
Dried with a drum dryer at 100 ° C for 1 minute, and further dried at 20 ° C and 65% R.C. H. After conditioning the humidity for 24 hours under
Each size degree (second) was measured by the Steckigt method (JIS P8122).

Evaluation method B (neutral papermaking with low concentration addition of sulfuric acid band) In the same 2% aqueous slurry as in evaluation method A, 0.2% sulfuric acid band based on the pulp solids and 0.4% of each aqueous emulsion.
% Was simultaneously added to obtain a 1% aqueous slurry adjusted to pH 7.5 with caustic soda. Then, 0.05% of the polyamide polyamine-based cationic polymer as a fixing agent was added to the slurry and uniformly dispersed, and then paper was made in the same manner as in Evaluation Method A so that the basis weight was 60 g / m ^2, and then dehydrated and dried. After the humidity control, each size degree (second) was measured.

Evaluation Method C (Neutral Paper Making with High Concentration of Sulfuric Acid Band) In the same 2% aqueous slurry as in Evaluation Method A, 1% of sulfuric acid band and 0.5% of each aqueous emulsion based on pulp solids,
As a fixing agent, 0.2% of the polyamide polyamine-based cationic polymer and 10% of calcium carbonate were added, and a 1% aqueous slurry adjusted to pH 7.5 with caustic soda was obtained. Next, a filler retention agent (made by Allied Colloid Co., Ltd., trade name "Percoll 4
7 ") 0.01% was added and uniformly dispersed, and then paper was made to have a basis weight of 60 g / m ² in the same manner as in the evaluation method A, and then dehydrated, dried, and conditioned. Second) was measured.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

The sizing agent of the present invention is excellent in leaving stability, mechanical stability and hard water stability. In addition, since the sulfone group-containing reaction product contained in the rosin substance itself has excellent emulsification dispersibility, it can be emulsified with a small amount of emulsification dispersant as compared with the conventional rosin emulsion sizing agent, resulting in extremely low foaming property. Excellent size effect. Further, the paper sizing method of the present invention can provide various papers and paperboards having excellent size performance in a wide papermaking range of pH 4 to 8.

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Claims (5)

(57) [Claims] 1. A papermaking emulsion sizing agent comprising a rosin substance, a dispersant and water, wherein the rosin substance comprises:
(A) rosins, (B) α, β-unsaturated carboxylic acids,
A rosin-based emulsion sizing agent for papermaking, comprising 20% by weight or more of a reaction product comprising (C) a sulfocarboxylic acid and (D) a trivalent or higher polyhydric alcohol. 2. The reaction product, wherein the component (B) is 0 to 1 mol per 1 mol of the component (A), and the component (C) is 0.02 to 0.4 mol per 1 mol of the component (A). , And ingredient (A)
The sizing agent according to claim 1, wherein each component is heated and reacted at a use ratio such that the equivalent ratio of the hydroxyl group of component (D) to the carboxyl group of (2) is 0.2 to 1.5. 3. The reaction product contains 0.1 to 0.75 mol of the component (B) per 1 mol of the component (A), and 0.05 to 0 mol of the component (C) to the 1 mol of the component (A). 3. The heat reacting each component at a use ratio of 0.3 mol, and an equivalent ratio of the hydroxyl group of the component (D) to the carboxyl group of the component (A) is 0.4 to 1.2. Sizing agent. 4. The sizing agent according to claim 1, 2 or 3, wherein the content of the reaction product in the rosin substance is 30% by weight or more. 5. A paper sizing method, wherein the rosin emulsion sizing agent for papermaking according to claim 1, 2, 3 or 4 is used in a pH range of 4-8.