JPH06101192A - Sizing agent for production of paper - Google Patents

Abstract

PURPOSE:To provide the subject sizing agent excellent in hydrolysis resistance and in sizing effect and improved in stability by emulsifying a specific substituted cyclic dicarboxylic acid anhydride in the presence of an oil-in-water type surfactant and a cationic or amphoteric poly(meth)acrylamide. CONSTITUTION:(A) A substituted cyclic dicarboxylic acid anhydride of the formula (R is >=5C alkyl, alkenyl, aralkyl, aralkenyl; (n) is an integer of 2 or 3) (e.g. hexadecenylcinnamic acid anhydride) is emulsified in the presence of (B) an oil-in-water type surfactant (e.g. polyoxyethylenenonylphenyl sulfate ester ammonium salt) and (C) an amphoteric (meth)acrylamide polymer having <3mol.% of anionic groups to provide the objective paper-sizing agent improved in hydrolysis resistance, excellent in sizing effect, improved in stability, and comprising an aqueous emulsion containing an emulsion.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a papermaking sizing agent comprising an aqueous emulsion of a substituted cyclic dicarboxylic acid anhydride.

[0002]

It is known to use aqueous emulsions of substituted succinic anhydrides as sizing agents for neutral papermaking, including cationized starch, certain polymers and / or
Alternatively, a method is known in which a substituted succinic anhydride is emulsified by using an emulsifier (Japanese Patent Publication No. 39-2305, Japanese Patent Publication No. 53-36044, and Japanese Patent Publication No. 58-45731).

[0003]

However, the aqueous emulsions of substituted succinic anhydrides prepared by these methods have poor physical stability and hydrolysis resistance, and they are not physically stable in the white water circulation system in the papermaking process. Aggregates due to poor stability and hydrolyzed emulsions cause operational problems.

[0004]

In order to solve the above-mentioned problems, the present invention has the general formula (A)

A substituted cyclic dicarboxylic acid anhydride represented by the following formula (R is an alkyl group, an alkenyl group, an aralkyl group, or an aralkenyl group having 5 or more carbon atoms, and n is an integer of 2 to 3) is used as an oil-in-water surfactant. The present invention provides a papermaking sizing agent having improved stability obtained by emulsifying (B) with a cationic or amphoteric poly (meth) acrylamide (C).

The substituted cyclic dicarboxylic acid anhydride used in the present invention is a substituted cyclic dicarboxylic acid anhydride represented by the general formula (A) and having an alkyl group, an alkenyl group, an aralkyl group or an aralkenyl group having 5 or more carbon atoms. There are specifically hexadecyl succinic anhydride, octadecyl succinic anhydride, hexadecenyl succinic anhydride, heptadecenyl succinic anhydride, octadecenyl succinic anhydride, tetrapropenyl succinic anhydride. Compounds, triisobutenyl succinic anhydride, 1-methyl-2-pentadecenyl succinic anhydride, and the like, and substituted glutaric anhydride may be used instead of the substituted succinic anhydride.

The cationic or amphoteric (meth) acrylamide-based polymer used as an emulsifier and / or protective colloid is a water-soluble polymer and is used in an amount of 0.1 to 2 mol%.
With 0 to 3 mol% of anionic groups and 9
It is composed of 5 to 99.9 mol% of acrylamide or methacrylamide. The molecular weight is preferably 10,000 to 1,000,000. Here, the ratio of the cationic group is lowered to 0.1 to 2 mol% when the substituted cyclic dicarboxylic acid anhydride is made into an aqueous emulsion by the same method as in the present invention, the ratio of the cationic group of the polymer is high. And the accelerated hydrolysis of the substituted cyclic dicarboxylic acid anhydride. A primary amino group, a secondary amino group, a tertiary amino group or a quaternary ammonium group can be used as the cationic group of this acrylamide polymer, and a carboxyl group or a sulfonic acid group can be used as the anionic group. it can.

The method for producing the polymer used in the present invention is not particularly limited. For example, the Mannich reaction or Hoffmann rearrangement reaction of polyacrylamide can be applied as a method for introducing a cationic group, and the method for introducing an anionic group can be applied. Can be applied to hydrolysis of an amide group with an alkali or a sulfomethylation reaction, and a cationic group and an anionic group can be introduced by a copolymerization reaction of a cationic monomer, an anionic monomer and acrylamide or methacrylamide. Examples of the cationic monomer in this case include allylamine, diallylamine, monomethyldiallylamine, dimethyldiallylammonium salt, vinylpyridine, aminoalkyl acrylate or methacrylate, mono- or di-alkylaminoalkyl acrylate or methacrylate, mono- or di-alkylaminoalkyl. Methacrylamide or acrylamide, methacryloyloxyalkyl trimethyl ammonium chloride and the like, and the anionic monomer, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, vinyl sulfonic acid, para-styrene sulfonic acid, 2 -Acrylamido-2-Methylpropanesulfonic acid and the like.

As the oil-in-water type surfactant used in the present invention, conventionally known cationic surfactants, anionic surfactants, amphoteric surfactants or nonionic surfactants can be used. Specific examples of the cationic surfactant include long-chain alkylamine salts, modified amine salts, tetraalkyl quaternary ammonium salts, trialkylbenzyl 4 salts.
Examples include primary ammonium salts, alkylpyridinium salts, alkylquinolium salts, alkylphosphonium salts, and alkylsulfonium salts, and amphoteric surfactants include various betaine-based surfactants. As the anionic surfactant, alkyl sulfonate, alkyl sulfate ester salt, alkyl phosphate ester salt, polyoxyalkylene alkyl sulfate ester salt, polyoxyalkylene alkylaryl sulfate ester salt, polyoxyalkylene aralkyl aryl sulfate ester salt, alkyl -Aryl sulfonates and various sulfosuccinic acid ester-based surfactants, and the nonionic surfactants include fatty acid sorbitan ester and its polyalkylene oxide adduct, fatty acid polyglycol ester, various polyalkylene oxide type nonionic Surfactant (
Polyoxyethylene fatty acid ester, polyoxyethylene fatty acid amide, polyoxyethylene aliphatic alcohol, polyoxyethylene aliphatic amine, polyoxyethylene aliphatic mercaptan, polyoxyethylene alkylaryl ether, polyoxyethylene polyoxypropylene block polymer, poly Oxyethylene aralkyl aryl ether, etc.).

Among these, anionic surfactants and
/ Or when using a nonionic surfactant, emulsification and stability are particularly good, and particularly preferred anionic surfactants are alkylaryl sulfonates, polyoxyalkylene alkylaryl sulfates, polyoxyalkylene aralkylaryls. Sulfate salt, (
Examples thereof include polyoxyalkylene) alkyl (aryl) sulfosuccinic acid mono- (or di-) ester salt, and examples of the nonionic surfactant include polyoxyalkylene alkyl aryl ether or polyoxyalkylene aralkyl aryl ether.

The aqueous emulsion of the substituted cyclic dicarboxylic acid anhydride of the present invention comprises the above oil-in-water surfactant and the cationic or amphoteric (meth) acrylamide polymer per 100 parts by weight of the substituted cyclic dicarboxylic acid anhydride. , 0.1 to 5 parts by weight and 1 to 50 parts by weight, respectively, and after mixing in a laboratory, use a universal homogenizer (manufactured by Nippon Seiki Seisakusho), a homomixer, an ultrasonic emulsifier or a household mixer. It is obtained by emulsification, and in a paper mill, it can be emulsified by using a homogenizer or some kind of emulsifying device.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The abbreviations of the monomers used in each table are as follows. AAm; acrylamide DM; dimethylaminoethyl methacrylate DMC; methacryloyloxyethyl trimethyl ammonium chloride DMAPMA; dimethylaminopropyl methacrylamide AA; acrylic acid PSS; parastyrene sulfonic acid

<Production of Cationic or Amphoteric Acrylamide Polymer> Reference Examples 1 to 3 and Comparative Reference Examples 1 to 3 In a 1000 ml four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube. , Dimethylaminoethyl methacrylate 1.7 g, 50% acrylamide aqueous solution 297.1 g, isopropyl alcohol 9.8 g
After water and 431.5 g of water were weighed and added, the pH was adjusted to 4.0 to 4.5 with a 20% sulfuric acid aqueous solution, and oxygen in the reaction system was removed with nitrogen gas. Then, while stirring, 9.6 g of a 5% aqueous solution of ammonium persulfate and 1.6 g of a 5% aqueous solution of sodium acid sulfite were added as a polymerization initiator, and then the temperature was raised from room temperature to 75 ° C over 30 minutes, and at the same temperature. Hold for 3 hours. The resulting cationic copolymer aqueous solution had a solid content of 20.0% and a Brookfield viscosity at 25 ° C (hereinafter simply referred to as viscosity) of 3,
000 cps (estimated molecular weight 150,000), p
H was 4.1. When the amount of ions of the polymer was quantified by the colloid titration method, 0.5 mol% of the cationic group (tertiary amino group) was introduced. The above is referred to as Reference Example 1. Also in Reference Examples 2 and 3 and Comparative Reference Examples 1, 2, and 3, the same operation as in Reference Example 1 was performed except that the composition of the constituent monomer components shown in Table 1 was followed. The amount of isopropyl alcohol for adjusting the molecular weight and the amount of 20% sulfuric acid aqueous solution for adjusting the polymerization pH in each Reference Example and Comparative Reference Example were changed each time. Table 1 shows the property values of the copolymers obtained in each of the reference examples and comparative reference examples.

[0013]

[Table 1]

Reference Examples 4 to 9 and Comparative Reference Examples 4 and 5, except that the constituent monomer components were changed as shown in Table 2.
By the same operation as in Reference Example 1, an aqueous solution of a cationic and amphoteric acrylamide polymer was obtained. Table 2 shows the property values of the copolymers obtained in each Reference Example and Comparative Reference Example.

[0015]

[Table 2]

Reference Example 10 300 ml of 3 equipped with a stirrer, thermometer and dropping funnel
Add a 15% polyacrylamide aqueous solution (2
5 ° C 1000 cps, estimated molecular weight 150,000) 1
42.2 g was added, and 4.51 g of a mixed solution of 4.00 g of sodium hypochlorite having an effective chlorine concentration of 12% and 0.51 g of a 50% sodium hydroxide aqueous solution was added dropwise to the mixture under cooling with stirring. The temperature was maintained at 0 ° C., and 1.80 g of 50% choline chloride aqueous solution was further added. After this mixed solution was kept at 20 ° C. for 2 hours while stirring, the amount of residual chlorine was quantified, and a 20% aqueous sodium thiosulfate solution equivalent to that value was added. After that, adjust the pH to 4.5 with 15% hydrochloric acid.
The Huffman reaction product aqueous solution having an effective concentration of 10% was obtained. According to the colloid titration method, the cationic groups (primary amino group and quaternary ammonium group) in the polymer are 1.
5 mol% was introduced.

Reference Example 11 1000 ml equipped with a stirrer, thermometer and reflux condenser
15% polyacrylamide (25 ℃
Viscosity at 1,000 cps, estimated molecular weight 150,000
0) 600 g was added and heated to 40 ° C. Next, while stirring, 2.44 g of a 50% dimethylamine aqueous solution and 37%
After adding 1.76 g of formalin aqueous solution and adjusting the pH to 10 with 30% sodium hydroxide, the mixture was kept at 40 ° C for 2 hours and the solid content was 15.2% and the viscosity at 25 ° C was 1050.
An aqueous Mannich reaction product having a cps and a pH of 10.2 was obtained. According to the colloid titration method, 1.5 mol% of the cationic group (tertiary amino group) was introduced into the polymer.

<Production of Aqueous Emulsion of Substituted Cyclic Dicarboxylic Acid Anhydride and Stability and Size Effect of the Aqueous Emulsion> Examples 1 to 11 and Comparative Examples 1 to 5 Aqueous emulsions of hexadecenyl succinic anhydride were prepared. It was manufactured by the method shown below. First, the concentration of 20 shown in Reference Example 1
% Polymer, 2 parts by weight of polyoxyethylene alkylphenyl sulfate ammonium salt (Hitenol No7 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and 48 parts by weight of water were mixed and homogenized with hexadecenyl. Add 100 parts by weight of succinic anhydride and use a universal homogenizer (manufactured by Nippon Seiki Co., Ltd.) to rotate at 10,000 rpm for 3 times.
The emulsification operation is performed for 0 seconds, and the average particle size is 0.5 to 1 μm.
An aqueous emulsion of This was diluted with water so that the concentration of hexadecenyl succinic anhydride was 1%, and used for the subsequent tests.

The above is the same as Example 1 except that Examples 2 to 15 and Comparative Examples 1 to 5 are blended with the components shown in Table 3 and the amount of water added is changed each time. The aqueous emulsion was prepared by various methods.

[0020]

[Table 3]

Comparative Example 6 150 parts by weight of 10% by weight of cationized starch (Cato 15 manufactured by Oji National Co., Ltd.) after cooking and 10 parts of a commercially available alkenylsuccinic anhydride were used for 15 minutes per minute using a universal homogenizer. The emulsification operation was performed at 000 rpm for 3 minutes to obtain an aqueous emulsion having an average particle diameter of 0.5 to 1 μm. Water was added to this, and the mixture was diluted with water so that the alkenylsuccinic anhydride concentration was 1%, and used for the subsequent experiments.

Comparative Example 7 The same operation as in Comparative Example 6 was carried out using hexadecenyl succinic anhydride instead of the commercially available alkenyl succinic anhydride, and the alkenyl succinic anhydride having an average particle diameter of 0.5 to 1 μm. An aqueous emulsion of the product was obtained. Water was added to this to dilute it so that the alkenylsuccinic anhydride concentration was 1%, and the mixture was used in the subsequent experiments.

Table 4 shows the results of stability and sizing tests of the aqueous emulsions of the substituted cyclic dicarboxylic acid anhydrides obtained in the respective Examples and Comparative Examples.

[0024]

[Table 4]

As shown in Table 4, the acrylamide polymer used has a strong cationic property (Comparative Examples 1, 2,
3) has a high hydrolysis rate, and those having a strong anionic property (Comparative Examples 4 and 5) are inferior in size effect. Further, the substituted cyclic dicarboxylic acid anhydride according to the present invention has excellent emulsion storage stability (physical stability), for example, a concentration of 1
% Emulsion was left at 30 ° C. and Comparative Example 6,
The emulsion obtained by emulsifying with the cationized starch shown in 7 aggregates in a few hours, whereas the aggregates of the particles and the free floating of the substituted cyclic dicarboxylic acid anhydride or its hydrolyzate, etc., even if left for several days. Did not occur.

Note 3) Stability (hydrolysis rate) The concentration of an aqueous emulsion of a substituted cyclic dicarboxylic acid anhydride is diluted to 0.5% and the pH is adjusted to 7.0. 50 ° C
This aqueous emulsion is kept for 2 hours in a constant temperature water bath.
After freeze-drying a sample of 1 to 5 g, the hydrolyzate and unhydrolyzate of the substituted cyclic dicarboxylic acid anhydride were extracted with diethyl ether to a certain concentration, and then the hydrolyzate was analyzed with an infrared spectroscope. And the weight ratio of unhydrolyzed product was determined.

Note 4) Sizing test on carbon charcoal paper Test pulp: LBKP (Canadian Standard
Freeness 375 ml) Reagents and addition rate (solid dry pulp solids ratio) Heavy calcium carbonate Escalon 1500 (manufactured by Sankyo Milling Co., Ltd.): 20% Cationized starch Cato 102 (manufactured by Oji National Corporation): 0.75 % Alum: 0.5% Substituted cyclic dicarboxylic acid anhydride emulsion: 0.1%
(Active ingredient) Yield improver Hileten 102 (manufactured by Dick Hercules): 0.02% Paper making pH: 7.5 Paper making method: White water circulating hand-made machine made by Noble and Wood, USA Basis weight: 60 g / m ² Drying: Drum dryer 100 ° C 40 seconds Size test: Steckigt method (JIS P-8122)

Note 5) Sizing degree test when used corrugated cardboard waste paper Pulp: Corrugated cardboard waste paper (Canadian Standard Freeness 340 ml) Reagent product and addition rate (solid dry pulp solids ratio) Alum: 0. 25% Substituted cyclic dicarboxylic acid anhydride emulsion: 0.05%
(Active ingredient) Retention improver Reten HM159 (manufactured by Dick Hercules): 0.03% Paper making pH: 6.5 Paper making method: White water circulating hand-made machine made by Noble and Wood Co., USA Basis weight: 80 g / m ² Drying: Drum dryer 100 ° C, 80 seconds Size test: Steckit method (JIS P-8122)

[0029]

The papermaking sizing agent of the present invention exhibits excellent physical stability and hydrolysis resistance, and also has an excellent sizing effect, so that the emulsion stability in the white water circulation system of an actual paper machine is good. In addition to reducing operational troubles, it is possible to produce paper having excellent paper quality.

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[Procedure amendment]

[Submission date] March 18, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] Full text

[Correction method] Change

[Correction content]

[Document name] Statement

[Title of Invention] Sizing agent for papermaking

[Claims]

[Chemical 1] ( Wherein R represents an alkyl group, an alkenyl group, an aralkyl group or an aralkenyl group having 5 or more carbon atoms, and n represents an integer of 2 to 3 ) , and a substituted cyclic dicarboxylic acid anhydride (A) represented by Oil-in-water surfactant (B) and click
The on group is 0.1 to 2 mol%, and the anionic group is 3
Less than mol% both of (meth) acrylamide poly
Water containing an emulsified liquid obtained by emulsification using Marr (C)
Sizing agent made from a water-soluble emulsion .

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a papermaking sizing agent comprising an aqueous emulsion of a substituted cyclic dicarboxylic acid anhydride.

[0002]

It is known to use aqueous emulsions of substituted succinic anhydrides as sizing agents for neutral papermaking, including cationized starch, certain polymers and / or
Alternatively, a method is known in which a substituted succinic anhydride is emulsified by using an emulsifier (Japanese Patent Publication No. 39-2305, Japanese Patent Publication No. 53-36044, and Japanese Patent Publication No. 58-45731).

[0003]

However, the aqueous emulsions of substituted succinic anhydrides prepared by these methods have poor physical stability and hydrolysis resistance, and they are not physically stable in the white water circulation system in the papermaking process. Aggregates due to poor stability and hydrolyzed emulsions cause operational problems. Especially water resistant
If the degradability is poor, the hydrolyzate will stick to the rolls of the paper machine.
And this causes troubles such as breaking the paper being made.
Sometimes . The object of the present invention is, for example, a substituted succinic anhydride.
Aqueous emulsion of substituted cyclic dicarboxylic acid anhydrides such as
Is a paper-making sizing agent that is physically stable.
To improve operational performance and hydrolysis resistance.
It is possible to reduce the number of bulls and the size is excellent.
It is to provide an anti-bacterial agent .

[0004]

In order to solve the above-mentioned problems, the present invention provides the following general formula [I]

[Chemical 2] (Wherein, R 5 or more alkyl groups carbon atoms, an alkenyl group, an aralkyl group or an aralkenyl group, n represents an integer of 2-3.) Substituted cyclic dicarboxylic acid anhydride represented by the (A) Oil-in-water surfactant ( B) and click
The on group is 0.1 to 2 mol%, and the anionic group is 3
Less than mol% both of (meth) acrylamide poly
Water containing an emulsified liquid obtained by emulsification using Marr (C)
The present invention provides a papermaking sizing agent comprising a water-soluble emulsion .

At this time, the above-mentioned amphoteric (meth) acrylamido
Depolymer (C), the oil-in-water surfactant (B)
Substituted cyclic dicarbo each represented by the above general formula [I]
1 to 50 parts by weight per 100 parts by weight of acid anhydride (A)
Parts, and 0.1 to 5 parts by weight is also preferable .

The substituted cyclic dicarboxylic acid anhydride (A) used in the present invention is a substituted cyclic dicarboxylic acid having an alkyl group, an alkenyl group, an aralkyl group or an aralkenyl group having 5 or more carbon atoms represented by the general formula [I]. Anhydrous , specifically hexadecyl succinic anhydride, octadecyl succinic anhydride, hexadecenyl succinic anhydride, heptadecenyl succinic anhydride, octadecenyl succinic anhydride, tetra Examples include propenyl succinic anhydride, triisobutenyl succinic anhydride, 1-methyl-2-pentadecenyl succinic anhydride, and substituted glutaric anhydride can be used instead of substituted succinic anhydride. .

[0007] Both properties to use as emulsifiers and / or protective colloid (meth) acrylamide-based polymer (C)
Is a water-soluble polymer : 0.1 to 2 mol% cationic groups and less than 3 mol% anionic groups and a total of 10
It consists of 0 mol% acrylamide or methacrylamide. The molecular weight is preferably 10,000 to 1,000,000.
Here, the ratio of the cationic group is lowered to 0.1 to 2 mol% when the substituted cyclic dicarboxylic acid anhydride is made into an aqueous emulsion by the same method as in the present invention, the ratio of the cationic group of the polymer is high. And the accelerated hydrolysis of the substituted cyclic dicarboxylic acid anhydride. Amphoteric (meth) primary amino group as a cationic group of acrylamide polymer (C), 2 amino groups, it may be used a tertiary amino group or quaternary ammonium group, these alone also
You may use 2 or more types together. Further, the anionic As the group a carboxyl group, a sulfonic acid group can be used, these
They may be used alone or in combination of two or more.

[0008] amphoteric used in the present invention (meth) acrylic
The method for producing the amide polymer (C) is not particularly limited, but for example, the Mannich reaction of a polyacrylamide or the Hoffmann rearrangement reaction can be applied as a method of introducing a cationic group, and the method of introducing an anionic group is an alkali group. The hydrolysis of the amide group by the above or the sulfomethylation reaction can be applied, and the cationic group and the anionic group can be introduced also by the copolymerization reaction of the cationic monomer, the anionic monomer and acrylamide or methacrylamide. Examples of the cationic monomer in this case include allylamine, diallylamine, monomethyldiallylamine, dimethyldiallylammonium salt, vinylpyridine, aminoalkyl acrylate or methacrylate, mono-
Or di ─ alkylaminoalkyl acrylates or methacrylates, mono- ─ or di ─ alkylaminoalkyl methacrylamide or acrylamide, methacryloyloxy alkyl trimethylammonium chloride and the Ru mentioned. In addition, these cationic monomers
Of which, inorganic or organic acids and salts, quaternary ammonium
They can also be used as the salts that form the murine salts. Examples of the anionic monomer include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, vinylsulfonic acid, para-styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid and the like.

[0009] Oil-in-water surfactant used in the present invention
As (B) , a conventionally known cationic surfactant, anionic surfactant, amphoteric surfactant or nonionic surfactant can be used. Specific examples of the cationic surfactant include long-chain alkylamine salts, modified amine salts, tetraalkyl quaternary ammonium salts, trialkylbenzyl quaternary ammonium salts, alkylpyridinium salts, alkylquinolium salts, alkylphosphonium salts,
Examples thereof include alkylsulfonium salts, and examples of the amphoteric surfactant include various betaine surfactants. As the anionic surfactant, alkyl sulfonate, alkyl sulfate ester salt, alkyl phosphate ester salt, polyoxyalkylene alkyl sulfate ester salt, polyoxyalkylene alkylaryl sulfate ester salt, polyoxyalkylene aralkyl aryl sulfate ester salt, alkyl -Aryl sulfonates and various sulfosuccinic acid ester-based surfactants, and the nonionic surfactants include fatty acid sorbitan ester and its polyalkylene oxide adduct, fatty acid polyglycol ester, various polyalkylene oxide type nonionic surfactants. Surfactant (polyoxyethylene fatty acid ester, polyoxyethylene fatty acid amide, polyoxyethylene fatty alcohol, polyoxyethylene fatty amine, polyoxyethylene Emissions aliphatic mercaptans, polyoxyethylene alkyl aryl ethers, polyoxyethylene polyoxypropylene block polymers, polyoxyethylene aralkyl aryl ether, etc.).

[0010] Anionic surfactant and among these
/ Or when using a nonionic surfactant, emulsification and stability are particularly good, and particularly preferred anionic surfactants are alkylaryl sulfonates, polyoxyalkylene alkylaryl sulfates, polyoxyalkylene aralkylaryls. Sulfate salt, (
Examples thereof include polyoxyalkylene) alkyl (aryl) sulfosuccinic acid mono- (or di-) ester salt, and examples of the nonionic surfactant include polyoxyalkylene alkyl aryl ether or polyoxyalkylene aralkyl aryl ether.

[0011] The papermaking sizing agents of the present invention, the above-mentioned general formula
Substituted cyclic dicarboxylic acid anhydride (A ) 1 represented by [I]
00 parts by weight based on the upper Symbol of oil-in-water surfactant (B) 0.1 to 5 parts by weight, and the amphoteric a (meth) acrylamide-based polymer (C) used respectively 1 to 50 parts by weight
Emulsification obtained by emulsifying the above substituted cyclic dicarboxylic acid anhydride (A)
The liquid itself or an aqueous emulsion prepared by diluting it with water
The emulsion comprises (A), (B),
Obtained by mixing component (C) in water and then emulsifying it using a universal homogenizer (manufactured by Nippon Seiki Seisakusho Co., Ltd.), a homomixer, an ultrasonic emulsifier or a household mixer in a laboratory. It can be obtained by emulsification by using a homogenizer or some kind of emulsifying device.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The abbreviations of the monomers used in each table are as follows. AAm; acrylamide DM; dimethylaminoethyl methacrylate DMC; methacryloyloxyethyl trimethyl ammonium chloride DMAPMA; dimethylaminopropyl methacrylamide AA; acrylic acid PSS; parastyrene sulfonic acid

[0013] <Production of amphoteric acrylamide polymer> Comparative Reference Example 1-3 stirrer, a thermometer, a four-necked flask 1000ml equipped with a reflux condenser and a nitrogen gas inlet tube, dimethylaminoethyl methacrylate 12.6 g, 50% acrylamide aqueous solution 273.0 g, isopropyl alcohol 8.2
g and 441.1 g of water are weighed and added, and then 20%
The pH was adjusted to 4.0 to 4.5 with an aqueous sulfuric acid solution, and oxygen in the reaction system was removed with nitrogen gas. Then, while stirring, 9.1 g of a 5% ammonium persulfate aqueous solution as a polymerization initiator
And 1.5 g of a 5% aqueous sodium sulfite solution were added, and the temperature was raised from room temperature to 75 ° C. in 30 minutes,
Furthermore, the same temperature was maintained for 3 hours. The resulting aqueous solution of the cationic copolymer had a solid content of 20.3 % and a Brookfield viscosity at 25 ° C. (hereinafter simply referred to as viscosity).
Was 3,000 cps (estimated molecular weight 150,000) and pH was 4.3 . By the colloid titration method,
When the ionic group of the polymer was quantified, the cationic group (3
The primary amino group) was introduced at 4 mol%. The above is referred to as Comparative Reference Example 1. Also in Comparative Reference Examples 2 and 3, the same operation as in Comparative Reference Example 1 was performed except that the composition monomer components shown in Table 1 were followed. When these cationic groups were quantified in the same manner as in Comparative Reference Example 1, mol% equal to the mol% of the constituent monomer (DM) was obtained as in Comparative Reference Example 1. The amount of isopropyl alcohol for adjusting the molecular weight and the pH at the time of polymerization for each comparative reference example.
The amount of the 20% sulfuric acid aqueous solution for adjustment was changed each time.
The property values of the copolymers obtained in each comparative reference example are summarized in Table 1.

[0014]

[Table 1]

[0015] except that the Reference Examples 1 to 4 and Comparative Reference Examples 4 and 5 constituting monomer components was changed as shown in Table 2,
An aqueous solution of an amphoteric acrylamide polymer was obtained in the same manner as in Comparative Reference Example 1 above. Table 2 shows the property values of the copolymers obtained in each Reference Example and Comparative Reference Example.

[0016]

[Table 2]

[0017] The aqueous emulsion of <manufacture and stability of the aqueous emulsion of the aqueous emulsion and the size effect of the substituted cyclic dicarboxylic acid anhydrides> Examples 1-4 and Comparative Examples 1-5 hexadecenylsuccinic anhydride It was manufactured by the method shown below. First, the concentration 2 shown in Reference Example 1
99 parts by weight of a 0.2 % polymer, 2 parts by weight of polyoxyethylene nonylphenyl sulfate ammonium salt (Hitenol NO7 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and 48 parts by weight of water were mixed and homogenized to give hexa. 100 parts by weight of decenyl succinic anhydride was added, and an emulsification operation was performed at 10,000 rpm for 30 seconds using a universal homogenizer (manufactured by Nippon Seiki Co., Ltd.) to obtain an average particle size of 0.5 to 1 μm.
m aqueous emulsion was obtained. This was diluted with water so that the concentration of hexadecenyl succinic anhydride was 1%, and used for the subsequent tests.

The above is the same as Example 1 except that Examples 1 to 4 and Comparative Examples 1 to 5 are based on the composition of the components shown in Table 3 and the amount of water added is changed each time. The aqueous emulsion was prepared by various methods.

[0019]

[Table 3]

Comparative Example 6 150 parts by weight of 10% by weight of cationized starch (Cato 15 manufactured by Oji National Co., Ltd.) after cooking and 10 parts of a commercially available alkenylsuccinic anhydride were used for 15 minutes per minute using a universal homogenizer. The emulsification operation was performed at 000 rpm for 3 minutes to obtain an aqueous emulsion having an average particle diameter of 0.5 to 1 μm. Water was added to this, and the mixture was diluted with water so that the alkenylsuccinic anhydride concentration was 1%, and used for the subsequent experiments.

COMPARATIVE EXAMPLE 7 Hexadecenyl succinic anhydride was used in place of the commercially available alkenyl succinic anhydride, and the same operation as in Comparative Example 6 was carried out to obtain hexadecenyl having an average particle diameter of 0.5 to 1 μm. An aqueous emulsion of succinic anhydride was obtained. Water was added to this to dilute it to a hexadecenyl succinic anhydride concentration of 1%, and the mixture was used in the subsequent experiments.

Table 4 shows the results of stability and sizing test of the aqueous emulsions of the substituted cyclic dicarboxylic acid anhydrides obtained in the respective Examples and Comparative Examples.

[0023]

[Table 4]

As shown in Table 4, the acrylamide polymer used has a strong cationic property (Comparative Examples 1, 2,
3) has a high hydrolysis rate, and amphoteric amphoteric ones (Comparative Examples 4 and 5) have poor size effect. Further, the emulsion stability of the substituted cyclic dicarboxylic acid anhydride according to the present invention (physical stability) is excellent,
For example, when an emulsion having a concentration of 1% is left at 30 ° C., the emulsions obtained by emulsification with the cationized starch shown in Comparative Examples 6 and 7 aggregate in a few hours, whereas the emulsions agglomerated even after left for a few days. The phenomenon such as free floating of the substituted cyclic dicarboxylic acid anhydride or its hydrolyzate did not occur.

Note 3) Stability (hydrolysis rate) The concentration of the substituted cyclic dicarboxylic acid anhydride aqueous emulsion is diluted to 0.5% and the pH is adjusted to 7.0. 50 ° C
This aqueous emulsion is kept for 2 hours in a constant temperature water bath.
After freeze-drying a sample of 1 to 5 g, the hydrolyzate and unhydrolyzate of the substituted cyclic dicarboxylic acid anhydride were extracted with diethyl ether to a certain concentration, and then the hydrolyzate was analyzed with an infrared spectroscope. And the weight ratio of unhydrolyzed product was determined.

Note 4) Sizing test on carbon charcoal paper Test pulp: LBKP (Canadian Standard
Freeness 375 ml) Reagents and addition rate (solid dry pulp solids ratio) Heavy calcium carbonate Escalon 1500 (manufactured by Sankyo Milling Co., Ltd.): 20% Cationized starch Cato 102 (manufactured by Oji National Corporation): 0.75 % Alum: 0.5% Substituted cyclic dicarboxylic acid anhydride emulsion: 0.1%
(Active ingredient) Yield improver Hileten 102 (manufactured by Dick Hercules): 0.02% Paper making pH: 7.5 Paper making method: White water circulating hand-made machine made by Noble and Wood, USA Basis weight: 60 g / m ² Drying: Drum dryer 100 ° C 40 seconds Size test: Steckigt method (JIS P-8122)

Note 5) Sizing test when used corrugated cardboard waste paper Pulp: Corrugated cardboard waste paper (Canadian Standard Freeness 340 ml) Reagents and addition ratio (solid dry pulp solids ratio) Alum: 0. 25% Substituted cyclic dicarboxylic acid anhydride emulsion: 0.05%
(Active ingredient) Yield improver Reten HM159 (manufactured by Dick Hercules): 0.03% Paper making pH: 6.5 Paper making method: White water circulating hand-made machine made by US Noble and Wood Co. Basis weight: 80 g / m ² Drying: Drum dryer 100 ° C 80 seconds Size test: Steckit method (JIS P-8122)

[0028]

According to the present invention , the cationic group is 0.1
~ 2 mol% and an anionic group of less than 3 mol% amphoteric
A) acrylamide polymer and oil-in-water surfactant
According to the above-mentioned substituted cyclic dicarboxylic acid anhydride of the general formula [I]
The paper-making sizing agent obtained by emulsifying the
Hydrolysis resistance is significantly improved by limiting the amount of on-groups.
Let this substituted cyclic dicarboxylic acid be applied to the roll of a paper machine, for example.
Operations such as tearing the paper during paper making due to the attachment of anhydride hydrolysates
You can avoid business troubles and its excellent physical stability
Together, the emergy in the white water circulation of an actual paper machine.
Stability and reduce other operational problems.
Not only can it be reduced, but the latter anionic group
The size effect can be improved by limiting the amount of
it can.

Claims (3)

[Claims] 1. A compound represented by the general formula (A): A substituted cyclic dicarboxylic acid anhydride represented by
The above alkyl group, alkenyl group, aralkyl group, or aralkenyl group, n is an integer of 2 to 3) is emulsified with an oil-in-water surfactant (B) and a cationic or amphoteric poly (meth) acrylamide (C). A papermaking sizing product with improved stability. 2. Paper making with improved stability according to claim 1, wherein the cationic or amphoteric poly (meth) acrylamide has 0.1 to 2 mol% of cationic groups and 0 to 3 mol% of anionic groups. Sizing agent. 3. The poly (meth) acrylamide according to claim 2 is added in an amount of 1 to 50 parts by weight and the oil-in-water surfactant is added in an amount of 0.1 to 100 parts by weight of the substituted cyclic dicarboxylic acid anhydride.
A papermaking sizing product with improved stability according to claim 1, which is used in an amount of 5 parts by weight.