JP3281027B2 - Emulsifying and dispersing agent for rosin substance and rosin-based emulsion sizing agent for paper making containing the dispersing agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an amphoteric complex effective for emulsifying and dispersing a rosin substance when preparing an aqueous emulsion of a rosin substance, and a rosin emulsion for papermaking using the amphoteric complex as an emulsifying dispersant. Agent.

[0002]

2. Description of the Related Art When an aqueous emulsion of a rosin substance is produced, an emulsifying dispersant is generally used. Such an emulsifying dispersant is classified into an anionic emulsifying dispersant and a cationic emulsifying dispersant. Can be classified. Examples of the anionic emulsifying dispersant include, for example, styrene- (meth)
Examples include partially saponified or completely saponified acrylic acid copolymers (see JP-A-61-108796). Examples of cationic emulsifying and dispersing agents include those described in JP-A-63-120198. A partially quaternized product or a fully quaternized product of a copolymer of an alkyl (meth) acrylate and / or styrene and an alkylaminoalkyl (meth) acrylate can be given.

Further, JP-A-3-8893 and JP-A-3-74092 disclose the addition of a poly (meth) acrylamide and a polyvalent metal salt or a cationic vinyl copolymer to an anionic rosin emulsion sizing agent. Thus, it has been proposed to cationize anionic emulsion sizing agents. In the present specification, the description “(meth) acryl” means one or both of acryl and methacryl (the same applies hereinafter).

In general, when a rosin substance is emulsified and dispersed in water using an anionic emulsifying dispersant, an anionic rosin emulsion is obtained. When a cationic emulsifying dispersant is used, a cationic emulsion is obtained. , Any of these emulsions was prepared using a high pH papermaking pH of around 6.
In fact, when used as a sizing agent in a region, satisfactory results cannot always be obtained.

[0005] For these reasons, amphoteric emulsifying and dispersing agents have been developed for the purpose of obtaining a rosin-based emulsion sizing agent that is effective even in neutral papermaking. For example, JP-A-56-16989
No. 8 discloses a modified poly (meth) acrylamide obtained by reacting a poly (meth) acrylamide with a cationic monomer having a tertiary amine structure or a quaternary ammonium salt structure to amphoteric the rosin substance. Has been proposed as an emulsifying dispersant. Also, JP-A-2-33393 discloses that
(Meth) acrylate and anionic monomer
And an amphoteric emulsifier / dispersant comprising a copolymer of a nonionic monomer and a cationic monomer.

[0006]

In the paper industry in recent years, the recovery and reuse of factory water, that is, paper-making
As a result, the amount of dissolved ions in the papermaking water or the temperature of the papermaking water must be increased. Further, for the purpose of effective use of resources, the utilization rate of recovered waste paper has been increased more than ever, and as a result, the amount of calcium carbonate mixed into the papermaking system has also been increased. Since such a situation means worsening of papermaking conditions without any correction, it necessarily inevitably affects the properties of the papermaking, so even if a rosin-based emulsion sizing agent prepared with a conventional amphoteric emulsifying dispersant is used. However, papermaking in a high pH range cannot impart sufficient sizing properties to the papermaking.

Accordingly, an object of the present invention is to provide a novel amphoteric emulsifying and dispersing agent useful for preparing a rosin-based emulsion sizing agent, and to increase the utilization rate of a closed papermaking system and / or recovered waste paper. It is an object of the present invention to provide a rosin-based emulsion sizing agent exhibiting an excellent sizing effect in papermaking at a high pH in a high papermaking system.

[0008]

The amphoteric emulsifying dispersant according to the present invention comprises, based on the weight of the monomer, 50 to 70% of styrene, 10 to 30% of an alkyl acrylate or alkyl methacrylate, An anionic copolymer composed of 10 to 15% of acrylic acid or a salt thereof and 10 to 15% of methacrylic acid or a salt thereof has a cationic formula represented by the following formula (1) or (2): Monomer is an anionic copolymer
The reaction is carried out at a rate of 0.5 to 10 parts by weight per 100 parts by weight, and more preferably, styrene and / or an alkyl (meth) acrylate is added at a rate of 1 to 25 parts by weight per 100 parts by weight of the anionic copolymer. It is characterized by being a complex obtained by the reaction.

[0009]

Wherein R ₁ is H or CH ₃ , R ₂ and R ₃ are individually H, CH ₃ or C ₂ H ₅ , X is O or NH, and Y is C
Shows a ₂ H ₄ or C ₃ H ₆₎

[0010]

Wherein R ₁ is H or CH ₃ , R ₂ and R ₃ are individually H, CH ₃ or C ₂ H ₅ , and R 4 is CH ₃ , C ₂ H ₅ ,
C ₆ H ₅ CH ₂ , (CH ₂ CH ₂ O) _n H [where n = 1
20] or CH ₂ CH (OH) CH ₂ shows the Cl, Z represents an inorganic and organic acids residues such Cl, CH3 -COO)

The amphoteric emulsifying dispersant of the present invention is prepared by first preparing the above-mentioned anionic copolymer and then reacting it with a relatively small amount of a specific cationic monomer alone or with a specific nonionic monomer. Can be manufactured. In preparing the anionic copolymer, it is important to react the above-mentioned four types of monomer components in an amount within the above-mentioned range. Incidentally, a rosin-based emulsion sizing agent excellent in size effect cannot be obtained with a composite in which an anionic copolymer in which the amount of styrene is less than 50% by weight of all monomers is amphoteric. Further, when the amount of the alkyl (meth) acrylate exceeds 30% by weight of all the monomers, the anionic copolymer is amphoteric, and a rosin-based emulsion sizing agent is prepared using this complex.
There is an inconvenience that the pulp slurry to which the sizing agent is added significantly foams. Furthermore, the composite obtained from the anionic copolymer in which the total amount of acrylic acid and methacrylic acid exceeds 30% by weight of the total monomers, the foamability of the rosin-based emulsion sizing agent produced using the same,
On the other hand, in the case of an anionic copolymer whose total amount is less than 20% by weight of the total monomers, a complex obtained by amphoterating the anionic copolymer is expected to have a sufficient emulsifying and dispersing ability. Can not do.

The alkyl (meth) acrylate constituting the anionic copolymer of the present invention generally has an alkyl group having 1 to 18 carbon atoms, preferably 4 to 8 carbon atoms, and the alkyl group is a straight-chain. Or a branched chain. Regarding acrylic acid and methacrylic acid used in the present invention, any of them can use an alkali salt thereof as a monomer component from the beginning, but it is generally preferable to provide the copolymer in an acid form.

The anionic copolymer composed of the above four monomers can be prepared by a usual polymerization method, but it is preferable to employ an emulsion polymerization method. The emulsifier at the time of emulsion polymerization is generally used an anionic or nonionic surfactant having a molecular weight of 1000 or less,
For the preparation of the anionic copolymer of the present invention, a molecular weight of 2000 to 2000
It is recommended to use a surfactant consisting of about 15,000 polyoxyethylene-polyoxypropylene block polymers.

In the emulsion polymerization, a persulfate, hydrogen peroxide or the like is used as a polymerization initiator in the usual manner by adding 1% by weight of the monomer mixture.
~ 5% can be used, and if necessary,
A reducing agent such as a sulfite may be used in combination. In some cases, an oil-soluble peroxide or azo compound may be used in combination. Furthermore, for the purpose of adjusting the molecular weight of the produced copolymer, a chain transfer agent exemplified by mercaptans, thioglycolic esters, carbon tetrachloride, isopropyl alcohol, etc. is added in an appropriate amount according to the polymerization conditions. It is preferred to use. The amount of water for dispersing the monomer mixture at the start of the emulsion polymerization is selected in the range of 65 to 90% by weight, preferably 70 to 75% by weight of the whole reaction mixture. And 50-95
The anionic copolymer of the present invention can be obtained by completing the copolymerization reaction at a temperature of ° C.

The anionic copolymer thus obtained is
If this is in an unsaponified state, as mentioned earlier,
About 40% of the carboxyl groups contained in the copolymer are partially saponified before being subjected to amphoteric conversion. Amphoterization of the anionic copolymer is carried out by adding the cationic monomer represented by the above formula (1) or (2) to 0.5 to 10 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the anionic copolymer. ３3 parts by weight of the reaction. In this case, together with the above-mentioned cationic monomer, styrene and / or alkyl (meth) acrylate are added in an amount of 1 to 25 parts by weight, preferably 2 to 10 parts by weight, per 100 parts by weight of the anionic copolymer. When reacted, an emulsifying dispersant having further excellent performance can be obtained. As the (meth) acrylic acid alkyl ester, an alkyl ester having an alkyl group having 1 to 18, preferably 4 to 8 carbon atoms can be used, and the alkyl group may be linear or branched. No problem.

The cationic monomer used for amphoteric formation is
Any monomer may be used as long as it is included in the above formula (1) or (2), but dimethylaminoethyl acrylate is most preferably used. At the time of amphoteric, the same emulsifier, polymerization initiator and chain transfer agent as those used for preparing the anionic copolymer can be used, and usually at a temperature of about 50 to 90 ° C. for 2 to 5 hours. By carrying out the reaction, the amphoteric reaction is completed. The conjugate thus prepared preferably then saponifies about 30 to 50% of the carboxyl groups remaining in the conjugate. That is, if the saponification rate is indicated based on the anionic copolymer, it is preferable that about 70 to 90% of the carboxyl groups contained in the copolymer are saponified. If the saponification rate based on the anionic copolymer is less than 70%, a composite having excellent emulsifying dispersibility cannot be obtained, and if it exceeds 90%, a rosin-based product obtained using the composite cannot be obtained. The dispersion stability of the emulsion deteriorates.

In preparing the amphoteric emulsifier / dispersant of the present invention, as described above, it is important to take a procedure of preparing an anionic quaternary copolymer and then amphoterating it. Amphoteric copolymers similar to the conjugates of the present invention in terms of monomer construction can be prepared in a one-step process without the procedure described above, but such ampholytic copolymers are It has poor performance as an emulsifying dispersant for rosin substances, and can disperse rosin substances only in coarse particles in water. Further, even when the same procedure as that of the present invention is employed, when an anionic copolymer other than the above-described anionic quaternary copolymer of the present invention is used, an emulsifying dispersant having excellent performance can be obtained. Can not. For example, Japanese Unexamined Patent Publication
108796 teaches that a partially or completely saponified styrene- (meth) acrylic acid copolymer is used as an anionic emulsifier / dispersant for preparing a rosin emulsion. Even when the polymer is reacted with the cationic monomer of the present invention to make it amphoteric, an emulsifying dispersant comparable to the present invention cannot be obtained.

The rosin emulsion sizing agent of the present invention uses the above-mentioned amphoteric emulsifying dispersant in an amount of 5 to 20% by weight, preferably 10 to 15% by weight, based on the rosin substance, based on the solid content. Can be produced by any of the known phase inversion methods (see JP-A-52-77206), solvent methods (see JP-B-54-36242), or mechanical methods (see JP-B-53-32380). it can. A typical composition of the rosin-based emulsion sizing agent according to the present invention is generally 50% by weight of water, 40.0 to 47.5% by weight of rosin substance, preferably 42.5 to 45.0% by weight,
Amphoteric emulsifying dispersant 2.5 to 10.0% by weight, preferably 5 to 7.5%
Although it is in the range of weight%, this composition is not limited to the rosin emulsion size of the present invention.

The above-mentioned rosin substance includes rosin and fortified rosin. Fortified rosin includes rosins such as gum rosin and tall oil rosin, fumaric acid, maleic anhydride,
It means that α, β-unsaturated polybasic acids such as itaconic acid, acrylic acid and methacrylic acid are added in the range of 6 to 15%. In the present invention, a part of the reinforced rosin can be replaced with a phenol resin-modified reinforced rosin, if desired. Also, pheno known as a sizing agent component
Resin, petroleum resin, phenol-modified petroleum resin, and maleated products of these resins can be used in combination with rosin material, but the amount of use can be reduced to 20% by weight or less of rosin material. preferable.

The amphoteric emulsifying dispersant of the present invention is excellent in the ability to emulsify and disperse a rosin substance as fine particles in water. Therefore, when preparing a rosin emulsion, other surfactant-based dispersing agents may be used. However, the present invention does not prevent the combined use of these. Accordingly, polyoxyethylene sulfosuccinic acid half-ester salts of higher alcohols, alkyl phenols, alkyl aryl phenols or polystyrene phenols, alkyl phenols
Surfactants such as polyoxyethylene sulfate, alkylbenzene sulfonate, α-olefin sulfonate and the like of alkyl, alkyl aryl phenol or polystyrene phenol, and the like. ,
It can be used in the range of 0.1 to 1.0% by weight based on the rosin substance.

[0021]

The rosin-based emulsion sizing agent obtained by using the amphoteric emulsifying dispersant of the present invention exhibits excellent sizing effects even when papermaking is performed in a high pH range.
This is presumed to be because the sizing particles emulsified and dispersed in water are fine and amphoteric, so that they are conveniently adsorbed on the pulp fibers in the slurry.

[0022]

Example 1 Preparation of amphoteric emulsifying dispersant (1) Production of anionic copolymer emulsion A polyoxyethylene polyoxypropylene block polymer (trade name: Epan U-) was added as an emulsifier to 288 parts of water in a container. 103, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and 1.9% sodium dodecylbenzenesulfonate aqueous solution 30
Of styrene, 15 parts of butyl acrylate, 12.5 parts of acrylic acid, and 12.5 parts of methacrylic acid.
Of isopropyl alcohol and thioglycolic acid-2 as a chain transfer agent.
-4.5 parts of ethylhexyl was added and stirred. Next, this was heated in a warm bath, and when the temperature in the container reached 30 ° C., 2 parts of ammonium persulfate and 2 parts of sodium bisulfite were added and heating was continued, and the temperature was raised to 80 ° C. in 40 minutes. Polymerization was performed at 80 to 85 ° C for 2 hours. Thereafter, 10.6 parts of a 24% aqueous sodium hydroxide solution and 7.5 parts of a 48% aqueous potassium hydroxide solution were added thereto, and a neutralization reaction was performed for 30 minutes.
Cooled to room temperature. Then, water was added thereto and the solid content concentration was 2
A 5% anionic copolymer emulsion A was obtained. this
The molecular weight of the copolymer contained in the emulsion is 8,000,
The degree of neutralization was 40 mol%.

Further, the amount of the constituent monomer of the copolymer is used,
The copolymer emulsions B to C shown in Table 1 and the copolymer emulsions T to T shown in Table 1 were prepared in accordance with the above-mentioned method except that the type, degree of neutralization, and the like were changed as shown in Table 1.
W was prepared.

[0024]

[Table 1]

(2) Amphoterization of anionic copolymer A container containing 400 parts of anionic copolymer emulsion A, 1.2 parts of dimethylaminoethyl acrylate as a cationic monomer, and a nonionic monomer As
1.6 parts of styrene and 1.2 parts of butyl acrylate were added, an appropriate amount of a suitable chain transfer agent was added, and the mixture was heated in a warm bath. When the temperature in the container reaches 40 ° C, add 0.04 part of ammonium persulfate and 0.04 part of sodium bisulfite, and gradually raise the temperature to 80 ° C in 40 minutes while gradually heating.
The reaction was performed at 85 ° C. for 4 hours. Thereafter, 7.2 parts of a 24% aqueous solution of caustic soda and 5 parts of a 48% aqueous solution of potassium hydroxide were added to neutralize the mixture for 30 minutes.
An emulsifier / dispersant Aa having an emulsion-like appearance having an H of 8.0 and a degree of neutralization of 67 mol% was obtained.

In addition, the type and amount of the cationic monomer and the type and amount of the nonionic monomer used in combination with the amphoteric are changed as shown in Table 2,
Otherwise, in substantially the same manner as the above described amphoteric treatment, the emulsion emulsifying dispersants Ab to Ah shown in Table 2
Ba- Ca and emulsifying dispersants Ta-Wa for comparison were prepared.

[0027]

[Table 2] Cationic monomers- Other monomers- Solid content neutralization degree Aa DMAEA 1.2 parts ST 1.6 parts + BuA 1.2 parts 25% 67% Ab DMAEA 9.6 parts ST 12.8 parts + BuA 9.6 parts 25% 67% Ac Quaternary salt (1) 2.4 part ST 5.6 part 25% 67% Ad Quaternary salt (2) 1.2 part ST 2.8 part 25% 67% Ae DMAEA 2.4 part ST 3.2 part + BuA 2.4 part 25% 67% Af DMAEA 4.8 part ST 11.2 part 25 % 67% Ag DEAEMA 1.2 parts ST 2.8 parts 25% 67% Ah DMAEA 1.2 parts (not used) 25% 67% Ba DMAEA 1.2 parts ST 1.6 parts + BuA 1.2 parts 25% 67% Ca DMAEA 1.2 parts ST 1.6 parts + BuA 1.2 Section 25% 67% Ta DMAEA 1.2 Section ST 1.6 + BuA 1.2 Section 25% 67% Ua DMAEA 1.2 Section ST 1.6 + BuA 1.2 Section 25% 67% Va DMAEA 1.2 Section ST 1.6 + BuA 1.2 Section 25% 67% Wa DMAEA 1.2 Part ST 1.6 parts + BuA 1.2 parts 25% 67% DMAEA = dimethylaminoethyl acrylate ST = styrene, DEAEMA = diethylaminoethyl methacrylate BuA =
Butyl acrylate quaternary salt (1) = benzyl chloride quaternary compound of diethylaminopropyl acrylamide quaternary salt (2) = methyl quaternary chloride of diethylaminopropyl acrylamide

Comparative Example 1 One-Step Preparation of Amphoteric Emulsifier and Dispersant Polyoxyethylene polyoxypropylene block polymer (trade name: Epan U-103, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as an emulsifier in 299 parts of water in a container. 4.5 parts,
1.9% sodium dodecylbenzenesulfonate aqueous solution 30
61.6 parts of styrene, 16.2 parts of butyl acrylate, 12.5 parts of acrylic acid, 12.5 parts of methacrylic acid, and 5.4 parts of isopropyl alcohol and thioglycolic acid as a chain transfer agent. 4.68 parts of 2-ethylhexyl and 1.2 parts of dimethylaminoethyl acrylate as a cationic monomer were added and stirred. Next, this is heated in a warm bath, and the temperature in the container is 30 ° C.
At the time of reaching, 2.04 parts of ammonium persulfate and 2.04 parts of sodium bisulfite were added and heating was continued.
The temperature is raised to 80 ° C. in 0 minutes. Thereafter, polymerization was carried out at 80 to 85 ° C. for 2 hours. Thereafter, 17.8 parts of a 24% aqueous solution of caustic soda and 12.5 parts of a 48% aqueous solution of potassium hydroxide were added thereto, and a neutralization reaction was performed for 30 minutes, followed by cooling to room temperature.
The resulting emulsion had a solid content of 25%, a pH of 8.0, and a degree of neutralization of 67 mol%. This emulsifying dispersant emulsion is designated as X.

Comparative Example 2 Comparative Example According to JP-A-61-108796 5 parts of polyoxyethylene (n = 10) nonylphenyl ether sulfate half ester salt were previously dissolved in 300 parts of water, A monomer mixture consisting of 60 parts of styrene, 25 parts of acrylic acid and 15 parts of 2-ethylhexyl acrylate and 5 parts of dodecyl mercaptan were added to the aqueous solution of the agent and mixed. Next, 3 parts of ammonium persulfate and 3 parts of sodium bisulfite were added at 32 ° C., and the temperature was gradually raised, and emulsion polymerization was carried out at 80 ° C. for 4 hours. The reaction solution was cooled to 60 ° C, and a 48% aqueous potassium hydroxide solution was added.
A liquid obtained by mixing 30.4 parts and 30 parts of water was gradually dropped into the above reaction solution to carry out a neutralization reaction for 30 minutes, and then cooled to obtain an emulsified liquid having a solid content of 25% and a neutralization degree of 75 mol%. Dispersant Y was prepared for comparison.

Comparative Example 3 Comparative Example According to JP-A-63-120198 100 parts of isopropyl alcohol under reflux with stirring, 45 parts of styrene, 25 parts of 2-ethylhexyl acrylate, 25 parts of dimethylaminoethyl acrylate A mixture consisting of 30 parts of late, 2 parts of 2-ethylhexyl thioglycolate and 2 parts of azoisobutyronitrile was added dropwise over 3 hours. After completion of the dropwise addition, the reaction was continued at 85 to 90 ° C. for 2 hours.
An aqueous solution was prepared by adding 9.6 parts and 300 parts of water. Then, isopropyl alcohol was completely distilled off under reduced pressure. Next, 17.7 parts of epichlorohydrin was added thereto, and the mixture was reacted at 80 to 85 ° C. for 2 hours to perform quaternization. The obtained reaction mixture was cooled, and water was added to obtain a copolymer solution having a solid concentration of 30%. This copolymer is a cationic copolymer having a quaternary amino group in the molecule. This copolymer solution is hereinafter referred to as emulsifying dispersant Z.

Example 2 Preparation of a rosin emulsion sizing agent and its size effect (1) Preparation of reinforced rosin 100 parts of rosin is heated and melted, and the temperature is raised to 190 ° C. Under stirring, 11 parts of fumaric acid was added and reacted at 200 ° C.
After confirming that substantially no unreacted fumaric acid was present, the reaction was terminated to obtain a fortified rosin (A). The acid value of this fortified rosin was 241 and the melting point was 100 ° C.

(2) Preparation of emulsion sizing agent 100 parts of the above reinforced rosin (A) was placed in a reactor equipped with a reflux condenser, and heated to 160 ° C. to melt. To this molten rosin, 60 parts of the previously prepared emulsifying dispersant was gradually added, and while the evaporating water was being refluxed, the temperature inside the reactor was maintained at 95 to 98 ° C. to complete the addition of the emulsifying dispersant. Next, 70 parts of 90 ° C. warm water is gradually added thereto. O / O to W / O during dropping
A phase inversion to W occurred, and an aqueous emulsion sizing agent having a fine concentration of dispersed particles of 50% was obtained. The appearance, light transmittance, foamability and size effect of each aqueous emulsion sizing agent thus obtained were evaluated by the following methods, and the results shown in Table 3 were obtained.

Appearance 50cc of a sizing agent is collected in a transparent glass bottle having a capacity of 200cc, and after sealing, the bottle is inverted and allowed to stand.
The state in which the sizing agent flows down in a thin layer on the wall surface of the bottle is visually observed. ：: No coarse particles are present, and a clear feeling appears within 10 seconds. ：: No coarse particles are present, and a clear feeling appears within 20 seconds. Δ: Coarse particles are present, but after 20 seconds, transparency appears. Light transmittance The sizing agent is diluted with deionized water to a solid content concentration of 0.05% by weight, and the diffraction grating photoelectric colorimeter (Spectronic 20) is used.
The light transmittance at a wavelength of 560 nm was measured by Shimadzu Corporation. The light transmittance of each sizing agent is shown as a relative value when the light transmittance of deionized water alone is set to 100%. The higher this value is, the finer the dispersed particles of the sizing agent are.

Foaming property 80 ml of pulp slurry (pulp L-BKP CSF 400 ml) having a concentration of 0.75% is 100 m
The sample is collected in a 1-volume measuring cylinder with a stopper, and 1 ml of a 1% sulfuric acid band is added thereto and shaken 20 times. Then it was further shaken up and down 20 times by the addition of solid concentration of 1% sizing agent dilution 1 ml, and allowed to stand to measure the 浮種 generation amount of 5 minutes after standing. The larger the value, the higher the foaming property. Size effect 2.4% pulp slurry (pulp N
/ L (mixing ratio 3/7) -BKP CSF 400ml)
Then, 30% talc based on the weight of the dried pulp is mixed,
A predetermined amount of the sulfate band was added. Next, the emulsion sizing agent prepared above was added and mixed well to obtain a prepared pulp slurry. This pulp slurry has the same p
H-value water (adjusted with sulfuric acid) was added to dilute to a pulp concentration of 1%, and a cationic polymer PAM as a retention aid was added and mixed with pulp at 0.03%.
Hand-punched with a PI standard sheet machine, press pressure 3.5k
After water squeezing (wet paper moisture 60%) at g / cm ^2, it was dried with a drum dryer (surface temperature 90 ° C.) for 1 minute to prepare a hand-made paper. This hand-made paper has a basis weight of 65 g / m ² and is JIS
The degree of Stekigt sizing was measured according to P8122.

[0035]

TABLE 3 Rosin emulsion sizing agent effervescent Stockigt sizing degree No. used emulsifying dispersant appearance light transmittance ml (Note 1) (Note 2) 1 Aa ◎ 3.0 0 12 12 2 ( Note 3) Aa ◎ 3 0.501 3 133 (Note 4) Aa ◎ 4.2 0 13 13 4 Ab △ 1.50 12 125 Ac ○ 2.60 12 126 Ad ○ 2.2 0 12 127 Ae ○ 4 0 12 12 8 Af ９ 1.9 0 9 10 9 Ag ◎ 3.0 0 10 11 10 Ah ２ 2.9 0 12 12 11 11 Ba ◎ 3.5 1 12 12 12 Ca ９ 2.009 8 13 Ta △ 1.006 514 Ua ○ 2.0 2 10 10 15 Va △ 1.4 16 516 Wa ◎ 3.6 221 2 17 (Note 5) ◎ 6.0 58 88 18 Y △ 1.4 0 7 7 19 Z (Note 6) △ 1.10 5 4 20 X △ 10 5 4 (Note 1) Papermaking conditions = 2% band addition, slurry-pH 4.4, sizing agent addition 0.3% (Note 2) Papermaking conditions = band addition 0.5%, slurry-pH 6.
0, 0.4% of sizing agent added (Note 3) Reinforced rosin (A) 98 instead of 100 parts of fortified rosin (A) 98
Parts + 2 parts of phenolic resin (Note 4) Reinforced rosin (A) 90 instead of 100 parts of reinforced rosin (A)
5 parts + 10 parts of phenolic resin. (Note 5) Instead of 60 parts of the emulsifying and dispersing agent of the present invention, 20% of a sulfosuccinic acid half ester soda salt of polyoxyethylene nonyl phenyl ether (PEG 10 mol) 25 parts of aqueous solution used (Note 6) 50 parts used

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-3-199488 (JP, A) JP-A-3-8893 (JP, A) JP-A-2-33393 (JP, A) International Publication 91/16128 (WO, A1) (58) Field surveyed (Int. Cl. ⁷ , DB name) B01F 17/52 D21H 17 / 62,17 / 37,19 / 44

Claims (4)

(57) [Claims] 1 to 50% to 70% of styrene, 10 to 30% of alkyl acrylate or alkyl methacrylate, 10 to 15% of acrylic acid or a salt thereof, An anionic copolymer composed of 15% of methacrylic acid or a salt thereof has the following formula (1) or
(2) An emulsifying and dispersing agent for a rosin substance comprising a complex obtained by reacting the cationic monomer represented by the formula at a ratio of 0.5 to 10 parts by weight per 100 parts by weight of the anionic copolymer. Embedded image (Wherein R ₁ is H or CH ₃ , R ₂ and R ₃ are individually H, CH ₃ or C ₂ H ₅ , X is O or NH, Y is C
(Indicates ₂ H ₄ or C ₃ H ₆ ) Wherein R ₁ is H or CH ₃ , R ₂ and R ₃ are individually H, CH ₃ or C ₂ H ₅ , and R 4 is CH ₃ , C ₂ H ₅ ,
C ₆ H ₅ CH ₂ , (CH ₂ CH ₂ O) _n H [where n = 1
20] or CH ₂ CH (OH) CH ₂ shows the Cl, Z represents an inorganic and organic acids residues such Cl, CH3 -COO) 2. In addition to the above-mentioned cationic monomer, one or more of styrene, alkyl acrylate and alkyl methacrylate are further added in an amount of 1 to 25 parts by weight per 100 parts by weight of the anionic copolymer. An emulsifying and dispersing agent for a rosin substance, comprising a complex obtained by reacting in a proportion of parts. 3. The alkyl group of the alkyl acrylate or the alkyl methacrylate has 1 carbon atom.
The emulsifying and dispersing agent according to claim 1 or 2, wherein the emulsifying and dispersing agent is an alkyl group. 4. A papermaking emulsion sizing agent containing a rosin substance, an emulsifying dispersant and water, wherein the emulsifying dispersant is 50 to 70% styrene, 10 to 30% Anionic copolymer composed of acrylic acid alkyl ester or methacrylic acid alkyl ester, 10 to 15% of acrylic acid or a salt thereof, and 10 to 15% of methacrylic acid or a salt thereof, the above (1) A cationic monomer represented by the formula or (2) is converted to an anionic copolymer.
An emulsion sizing agent for paper making, characterized in that it is an amphoteric complex which is reacted at a ratio of 0.5 to 10 parts by weight per 100 parts by weight.