JP3175437B2 - Pitch control agent and pitch control 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 pitch control agent for suppressing and preventing pitch disturbance in a pulp and paper manufacturing process, and a method for preventing pitch disturbance using the same.

[0002]

2. Description of the Related Art Generally, pitch in the pulp and paper manufacturing process is a natural resin or gum substance released from wood, pulp or paper, and additive chemicals used in the pulp and paper making process. Is a water-insoluble adhesive substance mainly composed of an organic substance derived from the above. In general,
Pitch is dispersed in the form of colloids in the white water of the pulp and papermaking processes, but the colloids are dispersed by some external action such as a large shear force, a sudden change in pH, and excessive addition of a sulfate band. It is thought that the state is destroyed and agglomerates and enlarges. Agglomeration, huge pitch,
Due to its stickiness, fan pumps, flow pipes, chests,
In addition to adhering to manufacturing equipment such as wires, felts, and rolls, the adhering matter is peeled off and reattached to pulp or paper. As a result, stains and defects of the paper are generated, thereby deteriorating the quality or causing paper breakage, thereby causing pitch disturbances such as a reduction in productivity and workability. In recent years, as the number of chemicals used and the use of closed water used in the process have increased due to the diversification of paper, pitch obstacles have increased more than ever, and the paper has become more complicated.

Conventionally, various methods have been proposed or implemented for this pitch disturbance. For example, as a method of reducing the cause of pitch, a method of seasoning wood or chips to reduce or remove the cause of pitch, strengthen pulp washing, and enhance white water purification.

As a method of dispersing pitch to prevent aggregation and agglomeration, a method of dispersing pitch with a water-soluble anionic polymer (JP-B-59-28676).

As a method for reducing the tackiness and adhesion of the pitch, a method of adding talc (for example, Mistron Vapor (talc from Montana, USA)), clay or other porous inorganic substance (Japanese Patent Laid-Open No. 60-94687) Gazette, Japanese Patent Publication No. 61
-48975), a method of adding a nonionic surfactant (JP-B-62-6039, JP-B-63-23320),
Method of adding a water-soluble cationic polymer
182995).

[0006] As a method of adsorbing the pitch to the pulp in a small state and bringing the pitch out of the system, a method of fixing the pitch to the pulp using a water-soluble cationic polymer (Japanese Patent Laid-Open No.
149592), a method of adding talc (for example, Mythrone vapor (talc produced in Montana, USA)), clay and other porous inorganic substances (Japanese Patent Application Laid-Open No. 60-94687, Japanese Patent Publication No. 61-48975).

As a method of dissolving, dispersing and removing pitch, a method of adding a pitch-soluble organic solvent such as perchlorethane, trichloroethane, and kerosene. And so on.

[0008] However, seasoning is effective for a long period of time, and once used for six months,
Although the seasoning period was one year, the need for a large site and an increase in production volume made it difficult to secure and store logs and chips.
This method has its limitations, forcing it to be reduced to months to five months. Further, as for the strengthening of pulp washing and the strengthening of cleansing of white water, further improvement is difficult and cannot be expected because water is being closed.

The method of dispersing pitch with a water-soluble anionic polymer is a simple and effective method, but when it meets a cationic substance, it agglomerates and loses its effect. Furthermore, since the pitch amount in the system is not reduced, there is always a risk that the dispersion may be poor due to a change in the situation and the pitch may suddenly occur.

On the other hand, the method of adding talc (for example, Mistron Vapor (talc manufactured by Montana, USA)), clay, and other porous inorganic substances is adsorbed on pitch particles to adhere to pitch. It is a method of lowering the properties and adhesion, and further making it into paper as an inorganic filler, and is currently mainstream. These porous inorganic materials are inexpensive but do not always absorb the pitch properly and have low fixation to paper, causing white water pollution and sludge deposition, and causing large wear and damage to the wire, which has been improved. Is strongly desired.

The method of (1) is a method in which pitch particles, which are generally said to have a colloidally negative charge, are fixed to pulp with a cationic polymer to reduce the amount of pitch in the system. If the amount is excessive, the pitch particles are aggregated and enlarged to promote the adhesion of the pitch, and the expected effect cannot be obtained.

According to the method, the pitch is dissolved by adding an organic solvent capable of dissolving the pitch to the place where the pitch is attached to the white water, and the pitch is dissolved in the white water. Today, this method has become less common due to the lack of a fundamental solution and environmental problems due to the solvent used.

Therefore, as a method of using in combination, for example, a method of using a cationic polymer in combination with a nonionic or cationic surfactant (Japanese Patent Application Laid-Open No. 2-182995).
However, effective pitch control has not yet been achieved, and there is still a demand for highly effective chemicals and methods.

[0014]

SUMMARY OF THE INVENTION The present invention solves the drawbacks of the conventional methods for controlling pitch disturbances such as stains, drawbacks, paper breakage and reduced workability of paper in the conventional pulp and paper manufacturing process. It is an object of the present invention to provide a pitch control agent which can be applied in a wide range irrespective of a pitch-causing substance and its situation, and a pitch control method using the same.

[0015]

Means for Solving the Problems The present inventors have conducted a systematic study on pitch suppression in the pulp and paper manufacturing process, and have found that a specific amphoteric surfactant and a water-soluble cationic polymer are used in combination. As a result, the present inventors have found that effective pitch control can be obtained, and have completed the present invention.

That is, the present invention provides the following general formulas [I] and [I
A step of producing a pulp or paper comprising a pitch control agent comprising one or more of the amphoteric surfactants represented by I] and [III] and a water-soluble cationic polymer as active ingredients; The present invention relates to a pitch control method characterized by adding the above-mentioned pitch control agent or spraying the mixture onto a manufacturing apparatus to which the pitch adheres. Hereinafter, the present invention will be described in detail.

[0017]

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[0018]

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[0019]

Embedded image In the amphoteric surfactant represented by the general formula [I], R ¹ is a linear or branched alkyl or alkenyl group having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, and R ² is hydrogen or carbon atom. the number 1 to 12, preferably an amphoteric surfactant alkyl or alkenyl group of a straight-chain or branched-chain C1-8 hydrogen or carbon, more preferably, -NHCH ₂ -CO
OH system glycine type amphoteric surfactants and -NHCH ₂
It is a CH ₂ COOH-based alanine-type amphoteric surfactant.
When R ¹ has 5 or less carbon atoms, sufficient effect cannot be obtained due to insufficient affinity with pitch. When R ¹ has 23 or more carbon atoms, water solubility is reduced, the effect is reduced, and the production is reduced. It is not preferable because it is difficult and not practical. Preferred examples of R ¹ include octyl, nonyl, decyl, dodecyl, myristyl, cetyl, stearyl, isostearyl, oleyl, coconut oil alkyl, tallow alkyl, hardened tallow alkyl, Soybean oil alkyl group,
There are castor oil alkyl groups and hardened castor oil alkyl groups.

When R ² has 13 or more carbon atoms, sufficient water solubility cannot be obtained, so that the effect is undesirably reduced. Preferred examples of R ² include hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, isohexyl, cyclohexyl, octyl, isooctyl,
Examples include a nonyl group, a decyl group, and a dodecyl group. A ¹ is a methylene group in the glycine type amphoteric surfactant, and is an ethylene group in the alanine type amphoteric surfactant. Further, m and n are each an integer of 0 to 3, and preferably, m and n are both 0 in a glycine-type amphoteric surfactant, and m is 1 to 3 in an alanine-type amphoteric surfactant.
And n is 0. When m and n are 4 or more, the effect corresponding to the increase in the number of carbon atoms is not improved, so that it is not preferable. Y
¹ is a -COO or -SO _3.

Examples of the amphoteric surfactant represented by the general formula [I] include hexylglycine, octylglycine, dodecylglycine, octyldiaminoethylglycine, coconut oil alkyldiaminoethylglycine, dioctyldiaminoethylglycine, coconut oil alkyl. Octyl diaminoethyl glycine, lauryl β-alanine, coconut oil alkyl β-alanine, stearyl β-alanine and the like can be mentioned.

The amphoteric surfactants represented by the general formula [II] are betaine-type and sulfobetaine-type amphoteric surfactants, and the amphoteric surfactants represented by the general formula [III] are imidazolium betaine-type amphoteric surfactants. It is a surfactant. R ³ and R ⁶ each have 6 to 30 carbon atoms, preferably a straight or branched alkyl or alkenyl group having 8 to 18 carbon atoms, or 6 to 30, preferably 8 to 18 carbon atoms. It is a fatty acid amide alkyl group comprising a linear or branched fatty acid and an alkylamine having 1 to 3 carbon atoms. When the number of carbon atoms of R ³ is 5 or less, a sufficient effect cannot be obtained due to insufficient affinity with the pitch. Those having 31 or more carbon atoms are not preferred because the water solubility is reduced and the effect is also reduced. Preferred examples of the alkyl group and the alkenyl group include octyl group, nonyl group, decyl group, dodecyl group, myristyl group, cetyl group, stearyl group, isostearyl group, oleyl group, coconut oil alkyl group, tallow alkyl group, and hardened tallow. Alkyl group, soybean oil alkyl group, castor oil alkyl group,
And hardened castor oil alkyl groups. Fatty acids of fatty acid amide alkyl groups include, for example, octanoic acid,
Decanoic acid, lauric acid, palmitic acid, myristic acid,
Stearic acid, isostearic acid, oleic acid, coconut oil fatty acid, tallow fatty acid, hardened tallow fatty acid, soy oil fatty acid,
Castor oil fatty acid, hydrogenated castor oil fatty acid and the like can be mentioned. As the alkyl group, a methylene group, an ethylene group and a propylene group are preferable. A ² has 1 to 6 carbon atoms, preferably 1
To 3 alkylene groups or hydroxyalkylene groups, for example, a methylene group, an ethylene group, a propylene group,
Examples include an isopropylene group, a hydroxyethylene group, and a hydroxypropylene group. If the number of carbon atoms is 7 or more, the production is not easy and the water solubility is lowered, so that the effect is lowered. R ⁴ and R ⁵ are each hydrogen, a methyl group, an ethyl group, or a hydroxyethyl group. Further, both Y ² and Y ³ are -COO or -SO ₃
It is.

Examples of the amphoteric surfactants represented by the general formulas [II] and [III] include dimethyl cocoalkylaminoacetic acid betaine, coconut fatty acid amidopropyldimethylaminoacetic acid betaine, and coconut fatty acid amidopropyldimethylamino- 2-hydroxy-3-propylsulfobetaine, tallow fatty acid amide propyldimethylaminoethylsulfobetaine, oleylsulfotaurine, 2-cocoalkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, 2-coconut fatty acid amide Propyldimethylamino-N-carboxymethyl-N-hydroxyethylimidazolium betaine and the like can be mentioned.

As a method for producing the amphoteric surfactants represented by the general formulas [I], [II] and [III], generally, a higher amine is reacted with sodium chloroacetate to obtain -N ⁺ -
The CH ₂ COO ⁻ form is reacted with a higher amine with 2-chloroethanesulfonic acid to form —N ⁺ —CH ₂ CH
₂ SO ₃ ^- type betaine type surfactant can be easily synthesized.

On the other hand, the water-soluble cationic polymer used in the present invention includes general water-soluble cationic polymers such as polyethyleneimine and dimethyldiallylamine.
Sulfur dioxide copolymers, modified polyacrylamide cations, polyaminoacrylic acid and the like can also be used, but polydimethyldiallylammonium salts represented by the following general formulas (IV) to (VI), epihalohydrin-alkylamine addition polymers and allylamine The hydrochloride or quaternary ammonium salt of the polymer and the water-soluble cationic polymer of dicyandiamide-formaldehyde-ammonium chloride condensation polymer showed higher effects.

Polydimethyldiallylammonium salt

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Epihalohydrin-alkylamine addition polymer

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Salt of allylamine polymer

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The polydimethyldiallylammonium salt represented by the general formula [IV] preferably has a molecular weight of 1,000 to 500,000, more preferably 5,000 to 100,000. X
¹ is a chlorine atom or a bromine atom.

The epihalohydrin-alkylamine addition polymer represented by the general formula [V] preferably has a molar ratio of epihalohydrin to alkylamine of 1: 0.25 to 1: 2.5,
More preferably, the ratio is 1: 0.5 to 1: 2. R
⁷ and R ⁸ are each a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and X ² is a chlorine atom or a bromine atom. Each of R ⁷ and R ⁸ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, and preferably has 1 carbon atom. To 3 are a methyl group, an ethyl group, a propyl group, and an isopropyl group. further,
R ⁷ and R ⁸ may be a hydroxyethyl group or a hydroxypropyl group. Also, a mixture of two or more alkylamines may be used. . The molecular weight is preferably 1,000 to 300,000, and more preferably about 5,000 to 100,000. Examples of the epihalohydrin-alkylamine addition polymer include epichlorohydrin-dimethylamine addition polymer, epichlorohydrin-diethylamine addition polymer, epichlorohydrin-ethylenediamine addition polymer, epichlorohydrin-
Ethylaminoethanol-diethylamine addition polymer,
Examples thereof include an epibromohydrin-dimethylamine addition polymer, an epibromohydrin-diethylamine addition polymer, and an epibromohydrin-isopropylamine-diethylamine addition polymer.

In the salt of the allylamine polymer represented by the general formula [VI], R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, X ³ is a chlorine atom, a bromine atom, a sulfuric acid residue, a nitric acid residue, an organic carboxylic acid residue, and an organic sulfonic acid residue. Molecular weight 1,000-300,0
00 is preferred, and more preferably 5,000 to 100,000. Examples of allylamine polymer salts include polyallylamine hydrochloride, hydrobromide, sulfate, acetate, and propionate. Further, there may be mentioned polymethylallylamine hydrochloride, polyethylallylamine hydrochloride, polypropylallylamine hydrochloride, polyisopropylallylamine hydrobromide, which are salts of polyN-alkylallylamine.

The dicyandiamide-formaldehyde-ammonium chloride condensation polymer is derived from the reaction of dicyandiamide, formaldehyde, formic acid, and ammonium chloride, and has a molecular weight of 1,000 to 300,00.
0, preferably from 5,000 to 100,000.

Each of the general formulas [IV], [V] and [VI] can be synthesized by a known method. General formula (I
V] is obtained by polymerization of dimethyldiallylammonium halide. As a typical example, polydimethyldiallylammonium chloride is PDMDAC (polydimethyldiallylammonium chloride) (Senka Corporation)
) Or AGEFLOC WT POLYMER (C
PS Chem. Co.).

The epihalohydrin-alkylamine addition polymer represented by the general formula [V] includes epichlorohydrin or epibromohydrin, amines such as dimethylamine, diethylamine and ethylenediamine, alkanolamines such as ethylaminoethanol, and ammonia. A polymer obtained by reacting with one or more of these compounds is disclosed in U.S. Pat. No. 3,738,945, and its synthesis method is disclosed in AGELOC A-50, A-50HV (CPS).
Chemical Co., Ltd.) or Weytex (Nagase Sangyo Co., Ltd.).

The allylamine polymer represented by the general formula [VI] is produced by radical polymerization of an allylamine inorganic salt (hydrochloride) (Japanese Patent Application Laid-Open No. 58-201811), and is used as polyallylamine hydrochloride as Nitto Boseki Co., Ltd. ).

The dicyandiamide-formaldehyde-ammonium chloride polycondensate can be obtained by heat-mixing dicyanamide, formaldehyde, formic acid or ammonium chloride and subjecting it to polycondensation (USP 3,582,4).
61, JP-A-62-223394 and JP-A-2-182995), which are commercially available as Tinofix QF (manufactured by Ciba Geigy) and Nikafloc (manufactured by Nippon Carbide Industry Co., Ltd.).

The pitch control agent of the present invention contains the amphoteric surfactants represented by the above general formulas [I], [II] and [III] and a water-soluble cationic polymer as active ingredients. The content ratio of the amphoteric surfactant to the water-soluble cationic polymer is 95: 5 to 5:95 by weight, preferably 70:30 to 50: 5.
30:70. As an addition method, the amphoteric surfactant and the water-soluble cationic polymer may be added separately, but it is preferable that both are dissolved in water or a suitable water-soluble solvent before use. The dissolution concentration is not particularly limited, but generally, about 5 to 30% by weight is appropriate. Further, other process additives such as a surfactant for imparting dispersibility and permeability, a defoaming agent, a scale control agent, a slime control agent, and the like may be added to the pitch control agent of the present invention. . Further, the pitch control agent of the present invention may be blended with a conventionally used pitch control agent such as a nonionic surfactant, a water-soluble cationic polymer, or a cationic surfactant.

The addition of the pitch control agent of the present invention
It is preferable to add to the pulp slurry or white water in the previous stage of the location where the pitch obstacle has occurred or in the previous process,
The amount of addition varies depending on the type of pulp and the type of paper, the conditions of the process, and the occurrence of pitch, but the sum of the amphoteric surfactant and the water-soluble cationic polymer is 0.001 to 2% by weight based on pulp, Preferably it is 0.01 to 0.5% by weight.

In addition to the above-described pitch control method, there is a method of spraying the pitch control agent of the present invention onto manufacturing equipment to which pitch adheres in the step of manufacturing pulp or paper. That is, the pitch control agent of the present invention is used as it is or is diluted to about 1 to 10% by weight, and is pressed into a washing water shower line such as a wire, a felt, or a roll to which the pitch easily adheres and sprayed together with shower water. Or separately, a method of installing and spraying a spray. By this method, the prevention of the adhesion of the pitch and the decrease in the stickiness of the attached pitch are obtained, and the accumulation of the pitch is suppressed. Further, according to this method, the trouble of conventionally stopping the apparatus at the time of regular repair or heavy dirt and cleaning and removing the attached pitch with a cleaning agent is improved.

[0040]

In general, it is said that pitch has a weak negative charge and is dispersed in process water in the form of a colloid, and this agglomerates to cause pitch disturbance due to its adhesiveness or stickiness. On the other hand, the water-soluble amphoteric surfactant used in the present invention has a high affinity for a hydrophobic pitch because of having a large hydrophobic alkyl group in the molecule, and further has a high affinity in the molecule. By having an anionic group and a cationic group as hydrophilic groups, high water solubility can be maintained. Therefore, while having a high affinity for the pitch, the dispersion and stabilization of the colloidal pitch, the decrease in the adhesiveness and the adhesion are obtained, and the pitch obstacle is suppressed or prevented. In addition, the water-soluble cationic polymer used in the present invention has a weak negatively charged colloidal pitch having reduced adhesion and tackiness by the water-soluble amphoteric surfactant used in the present invention due to the cationic group in the polymer. The pitch is dispersed and stabilized by absorbing or surrounding the static electricity, and the pitch is fixed or fixed on the pulp to suppress or prevent pitch disturbance.

[0041]

【Example】

Amphoteric surfactant 1; C ₆ H ₁₃ (NHC ₂ H ₄ ) ₂ NHCH ₂ C
103 g of diethylenetriamine was placed in a 500 cc three-necked round bottom flask equipped with an OOH condenser and a stirrer. This is 180
While heating to 30 ° C, 30 g of n-hexyl chloride was added over about 1 to 2 hours, and the reaction was maintained at 180 ° C for 2 hours. The reaction product was gradually cooled, and diethylenetriamine hydrochloride was filtered off and distilled under reduced pressure to obtain a fraction having a bp of 130 to 180 ° C (15 mmHg). 35 g of this fraction was taken in a 500 cc three-necked round-bottomed flask equipped with a condenser and a stirrer, and an aqueous solution obtained by dissolving an equivalent amount of sodium monochloroacetate (23 g) in 200 ml of water was added to about 100 g of an aqueous solution.
The mixture was added and reacted over about 30 minutes while heating to ° C. After cooling, the precipitate was removed to obtain the desired aqueous solution of hexyldiethylenetriamineacetic acid.

Amphoteric surfactant 2; [C ₈ H ₁₇ (NHC
₂ H ₄ ) ₂ ] ₂ NCH ₂ COOH As in the case of the amphoteric surfactant 1, diethylene triamine, n
-A desired aqueous solution of dioctyldiethylenetriaminoacetic acid was obtained from octyl chloride and sodium monochloroacetate.

Amphoteric surfactant 3; cocoalkyl-NHC
Using the H ₂ CH ₂ COOH Lion Co., Ltd. "Ripomin CA".

Amphoteric surfactant 4; C ₆ H ₁₃ -N ⁺ (CH ₃ ) ₂
CH ₂ COO ^- condenser and sodium monochloroacetate 58g three-necked round bottom flask 1000ml wearing a stirrer, a water 400g were placed,
Dissolved. 107 g of N, N-dimethyldodecylamine (reagent, manufactured by Kanto Kagaku Co., Ltd.) was added thereto, and the mixture was heated to about 100 ° C. and reacted for about 6 hours until water-insoluble matter disappeared and became almost transparent. After cooling, the residue was filtered through a filter to obtain an approximately 20% aqueous solution of the desired betaine dodecyldimethylaminoacetate.

Amphoteric surfactant 5; cocoalkyl-N ⁺ (C
H _{3) 2} CH ₂ COO ^- it was used by Nippon Oil & Fats Co., Ltd. "Nissan Anon BF".

Amphoteric surfactant 6; cocoalkyl-CON
^{_{HC 3 H 6 N + (CH}} 3) 2 CH 2 COO - Using manufactured by NOF Corp. "NISSANANON BDF-R".

Amphoteric surfactant 7; C ₁₂ H ₂₅ N ⁺ (CH ₃ ) ₂
CH ₂ CH ₂ SO ₃ ^- neck round bottom flask sodium 2-chloroethane sulfonic acid 1000ml wearing a condenser and an agitator (Aldrich
Chem.Comp.) 79g to isopropyl alcohol 200g
And 107 g of N, N-dimethyldodecylamine (reagent, manufactured by Kanto Chemical Co., Ltd.) was added thereto, and the mixture was refluxed and heated.
The reaction was performed for about 6 hours. After cooling and filtration, isopropyl alcohol and N, N-dimethyldodecylamine were distilled off under reduced pressure to obtain the target N, N-dimethyl-N-lauryl-N- (2-sulfoethyl) ammonium salt.

Amphoteric surfactant 8; cocoalkyl-CON
^{_{HC 3 H 6 N + (CH}} 3) 2 CH 2 CHOHCH 2 SO 3 - was used manufactured by NOF Corp. "NISSANANON CSB-50".

Amphoteric surfactant 9;

Embedded image "Nissan Anon GLM-R" manufactured by NOF Corporation was used.

Amphoteric surfactant 10; C ₅ H ₁₁ (NHC ₂ H ₄ ) ₂
It was synthesized from pentyl chloride, triethylamine, and sodium chloroacetate in the same manner as in NHCH ₂ COOH amphoteric surfactant 1.

Amphoteric surfactant 11; C ₄ H ₉ N ⁺ (CH ₃ ) ₂ C
H ₂ COO ^- in the same manner as amphoteric surfactants 4 N, was synthesized from N- dimethylbutyl amine with sodium chloroacetate.

Cationic polymer 1; polydimethyldiallylammonium chloride (molecular weight = about 800)

Cationic polymer 2: Polydimethyldiallylammonium chloride (molecular weight = about 2,000) "KZ-63K" manufactured by SENKA CORPORATION was used.

Cationic polymer 3: Polydimethyldiallylammonium chloride (molecular weight = about 45,000) "KZ-106K" manufactured by SENKA CORPORATION was used.

Cationic polymer 4; dimethylamine-
Epichlorohydrin copolymer (molecular weight = about 20,000) "Yustex-T101" manufactured by Nagase & Co., Ltd. was used.

Cationic polymer 5: Polyallylamine hydrochloride (molecular weight = about 10,000) "PAA-HCl-3L" manufactured by Nitto Boseki Co., Ltd. was used.

Cationic polymer 6: Polyallylamine hydrochloride (molecular weight = about 80,000) "PAA-HCl-10L" manufactured by Nitto Boseki Co., Ltd. was used.

Cationic polymer 7: dicyandiamide condensate (molecular weight = about 50,000) "Nikafloc D-300" manufactured by Nippon Carbide Industry Co., Ltd. was used.

Cationic polymer 8; acrylamide-
Amino acrylate copolymer (molecular weight = about 2 million) "Alonfloc C-303L" manufactured by Alonfloc Co., Ltd. was used.

Cationic activator 1; C ₁₂ H ₂₅ N ⁺ (CH ₃ )
₃ Cl ^- was used by Nippon Oil & Fats Co., Ltd. "Nissan cation BB".

Nonionic surfactant 1; C ₁₈ H ₃₇ N [(CH ₂
CH ₂ O) ₁₀ H] ₂ “Nissan Nimeen S-220” manufactured by NOF Corporation.

Anionic polymer 1: pitch control agent, maleic anhydride-diisobutylene copolymer (molecular weight = about 10,000) “Polystar OM” manufactured by NOF Corporation was used.

Anionic polymer 2: pitch control agent, sodium polyacrylate (molecular weight = about 20,000) "AQUALIC DL-423" manufactured by Nippon Shokubai Co., Ltd. was used.

Anionic polymer 3: pitch control agent, maleic anhydride-acrylic acid copolymer (molecular weight =
About 4,000) "Aqualic TL-224" manufactured by Nippon Shokubai Co., Ltd. was used.

Mistron Vapor; Pitch Control Agent "Mistron Vapor" manufactured by Japan Mistron Co., Ltd. was used.

Kerosene: Commercial kerosene was used.

[Test-1] 50 g of pulp obtained by mixing dried LBKP (hardwood bleached kraft pulp) and NBKP (softwood bleached kraft pulp) at a weight ratio of 1: 1 was immersed in 5 l of water, loosened, and then put into a nyagara beater. And CSF
(Canadian Standard Freeness) = Disintegrated to 460 ml. The disintegrated pulp was put into a pitch tester according to J.TAPPI.No. 11, and stirred and mixed at 40 ° C. for 1 hour. The pitch attached to the wire mesh is extracted with chloroform, concentrated,
The weight was measured. This was used as a blank.

Similarly, the pitch control agent of the present invention was added as a component to the pulp in an amount of 0.1% by weight, and the amount of attached pitch was determined. The results are shown in Tables 1 and 2.

[Test-2] In a paper mill producing newsprint, pitch-dispersed maleic anhydride-
Acrylic acid copolymer (1: 1 composition ratio, molecular weight 10,000)
And mistron vapor, a pitch-adsorbing and non-adhesive inorganic mineral-based pitch control agent, were used together, but the paper was frequently cut off due to the sticking of the pitch to the wire, foil, felt, and roll of the paper machine. Therefore, in order to compare the pitch control agent of the present invention with the pitch control agent conventionally used, machine white water and foil, felt,
The pitch was sampled from the roll and used as a sample. This pitch was subjected to Soxhlet extraction with chloroform, and the extract was dissolved in a mixed solvent of chloroform: ethanol = 2: 1 to obtain a 20% concentration pitch sample. Machine white water 1 in 200ml beaker
00ml and the pitch control agent of the present invention as its components
Add 100mg and mix it (TK, manufactured by Tokushu Kika Kogyo Co., Ltd.)
500 mg of the prepared pitch sample was injected with stirring at 9000 rpm using an auto homomixer M type), and the mixture was further stirred for 1 minute. The deposits on the beaker and the mixer were extracted with chloroform, and the deposits were determined. The results are shown in Tables 1 and 2.

[Test-3] In a machine that manufactures toilet paper using waste magazine paper as a raw material, the adhesive pitch derived from the adhesive in the waste magazine paper adheres to wires, rolls, especially felt, and breaks. Paper and perforations were frequent. Therefore, an inorganic mineral-based pitch control agent was added to the raw material chest, and a polydimethyldiallylammonium chloride / quaternary cationic activator-based pitch control agent was sprayed on the wire and felt. It was necessary to wash 1-3 times a day, which hindered production. Therefore, the effect of the pitch control agent of the present invention was compared with that of a conventional product. The pitch attached to the felt is collected and dispersed in a mixed solvent of chloroform: ethanol = 2: 1 to form a 20% concentration pitch solution. 500 mg of this solution is placed on a stainless steel plate (thickness 0.5 mm, length 25 mm, width). (50 mm) was uniformly applied on one side and dried, and this was used as a pitch sample. Machine pitch water using the pitch control agent of the present invention as its active ingredient
300 mg, 100 mg and 50 mg were dissolved in 200 ml, put in a 300 ml tall beaker, and a stainless steel plate coated with a pitch was completely immersed in the solution and stirred at a water temperature of 40 ° C. for 30 minutes. Thereafter, the stainless steel plate on which the pitch was applied was taken out, and the decrease in the adhesiveness was evaluated with a Polyken probe tack tester according to ASTM D-2979. The results are shown in Tables 1 and 2. In the table, ：: tack value = 0
(No tackiness), Δ: tack value = less than 50 gf / cm ² (slightly tacky), ×: tack value = 50 gf / cm ² or more.

[0071]

[Table 1]

[0072]

[Table 2]

[Test-4] In a machine in which a liner and a core base paper are made from KP, GP, and waste magazine paper as a raw material, the sticky pitch adheres to a wire, a roll, particularly a felt as the ratio of the used paper increases. And there were frequent breaks and perforations. Therefore, an inorganic mineral-based pitch control agent (Mistron Vapor) is added to the mixing chest in an amount of 0.1%.
1 to 0.5% (relative to pulp), and an organic pitch control agent A [dimethylamine-epichlorohydrin copolymer (1: 1 polymerization molar ratio, molecular weight of about 20,000) and dodecyltrimethyl quaternary ammonium salt type cation] Diluted with water and 10-40 ml (pitch control agent ml / felt 1m) before the felt suction box.
(Per width) was sprayed with a shower, but it was necessary to wash the wire and felt once every three days, and many paper breaks occurred, which hindered production. Therefore, the effect of the pitch control agent of the present invention was compared with that of a conventional product when the pitch control agent of the present invention was used in the papermaking of a variety having a high ratio of waste paper and many pitch disturbances. Table 3 shows the results. In the table, “Felt pitch adhesion amount” is as follows: ×: The adhesion amount is larger than when using the conventional product, Δ: The adhesion amount is the same as when using the conventional product, ○: The adhesion amount is higher than when using the conventional product It is assumed that the amount is small, and the “addition amount (mg of active ingredient / m width of felt)” is expressed as the effective weight of the pitch control agent sprayed per meter of felt width. , And.

[0074]

[Table 3]

[Test-5] GP and KP were used as main raw materials,
In a machine that produces medium-quality paper by adding waste paper to this, the sticky pitch derived from waste paper has a wire, roll,
Paper breakage and perforation occurred on the felt. Therefore, 0.1 to 0.5% (based on pulp) of an inorganic mineral-based pitch control agent (Mistron Vapor) is added, and an organic pitch control agent B [anionic, which is a 1: 1 copolymer of acrylic acid and maleic anhydride, is added. Although the polymer sodium salt, molecular weight of about 10,000] was used at 0.05 to 0.1% (effective amount relative to pulp), pitch adhesion to the wire could not be controlled and the wire had to be washed frequently. Was. Further, many black spots were formed on the formed paper, which hindered the production. Therefore, in the actual machine,
The pitch control agent of the present invention was spray-sprayed on a wire before the breast roll, and the effect was compared with that of a conventional product. Table 4 shows the results. In the table, "number of spots"
×: The number of formed paper spots is larger than the current state, Δ: The present state, ○: The number of formed paper spots is smaller than the current state. Expressed as the weight of the effective component of the pitch control agent, the “overall evaluation” was evaluated as ×: poor and ○: good.

[0076]

[Table 4]

[0077]

According to the pitch control agent and the pitch control method of the present invention, the pitch adheres to the pulp or paper, and further to the manufacturing equipment such as the fan pump, the inside of the pipe, the chest, the wire, the felt, the roll and the like, and the adhered substance is formed later. Pitch obstruction is improved, for example, paper stains and defects due to separation and reattachment to pulp and paper are eliminated, product quality is improved, and paper breakage is eliminated, and productivity and workability are improved.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-4-300383 (JP, A) JP-A-63-152493 (JP, A) JP-A-62-223394 (JP, A) (58) Investigation Field (Int.Cl. ⁷ , DB name) D21C 9/08

Claims (6)

(57) [Claims] 1. An active ingredient comprising one or more of the amphoteric surfactants represented by the general formulas [I], [II] and [III] and a water-soluble cationic polymer. Pitch control agent used in the pulp or paper manufacturing process Embedded image Embedded image Here, R ¹ is a linear or branched alkyl or alkenyl group having 6 to 22 carbon atoms, R ² is hydrogen or a linear or branched alkyl or alkenyl group having 1 to 12 carbon atoms R ³ , R ⁶ is a linear or branched alkyl or alkenyl group having 6 to 30 carbon atoms, or 6 to 30 carbon atoms.
Linear or fatty acid amidoalkyl radicals R ⁴ consisting of fatty acids and alkyl amines having 1 to 3 carbon atoms branched, R ⁵ are both hydrogen, a methyl group, an ethyl group or a hydroxyethyl group A ^1, are methylene groups Alternatively, the ethylene group A ² is an alkylene group having 1 to 6 carbon atoms or a hydroxyalkylene group Y ¹ , Y ² and Y ³ are each —COO or —SO ₃ m, n is an integer of 0 to 3 Represent each 2. A water-soluble cationic polymer comprising: a polydimethyldiallylammonium salt represented by the general formula [IV]; an epihalohydrin-alkylamine addition polymer represented by the general formula [V]; 2. The pitch control agent according to claim 1, which is at least one selected from the group consisting of a hydrochloride or a quaternary ammonium salt of an allylamine polymer and a dicyandiamide-formaldehyde-ammonium chloride condensation polymer. Epihalohydrin-alkylamine addition polymer Allylamine polymer salt Here, each of X ¹ and X ² is a chlorine atom or a bromine atom. X ³ is a chlorine atom, a bromine atom, a sulfuric acid residue, a nitric acid residue, an organic carboxylic acid residue, an organic sulfonic acid residue R ⁷ , R ⁸ Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 3. The water-soluble cationic polymer has a molar ratio of epihalohydrin to alkylamine of 1: 0.25 to 1: 2.2.
The pitch control agent according to claim 1, which is an epihalohydrin-alkylamine addition polymer represented by the general formula [V] obtained by addition polymerization as 5. 4. The amphoteric surfactant represented by the general formula [I] is an alkyl glycine type amphoteric surfactant or an alkyl alanine type amphoteric surfactant. Pitch control agent 5. A process for producing pulp or paper,
A pitch control method comprising adding the pitch control agent according to claim 1, 2, 3 or 4 as an active ingredient to the pulp in an amount of 0.001 to 2% by weight. 6. A method for producing pulp or paper, comprising spraying the pitch control agent according to claim 1, 2, 3, or 4 onto a production apparatus to which the pitch adheres.