JP7128698B2 - Pitch Inhibitor for Paper/Pulp Manufacturing Process and Pitch Inhibition Method for Paper/Pulp Manufacturing Process - Google Patents

Description

TECHNICAL FIELD The present invention relates to a pitch inhibitor for paper/pulp manufacturing processes and a pitch inhibitor method for paper/pulp manufacturing processes.

In the production of paper and pulp, due to the diversification of raw materials and the increase in papermaking speed, natural resins and fatty acids contained in the raw material wood, and synthetic sticky substances such as adhesives and latex derived from waste paper and waste paper are mixed. Furthermore, pitch troubles due to pitch, which is a hydrophobic sticky substance mainly composed of organic matter derived from additive chemicals such as sizing agents used in the paper manufacturing process, are increasing.

Pitch is normally dispersed in a colloidal form in slurry in the papermaking process. It is believed that they are destroyed, aggregated and coarsened.
Agglomerated and coarsened pitch adheres to manufacturing equipment such as fan pumps, inflow pipes, chests, wires, felts, rolls, etc. due to its adhesiveness, causing contamination of the equipment. It peels off after becoming solid and re-adheres to the pulp or paper, causing paper defects and paper breaks. In addition, when it adheres to wires, felt, etc., clogging reduces the water tightness, and an increase in the moisture content of the wet paper causes paper breakage and an increase in the drying load of the paper in the drying process.
Thus, pitch is a causative substance that causes deterioration of paper product quality and productivity. For this purpose, pitch inhibitors are used.

Pitch inhibitors are roughly classified into internal pitch inhibitors added to the pulp slurry and external pitch inhibitors directly brought into contact with the surfaces of manufacturing equipment such as wires, felts, and rolls by showering or the like.
The internal pitch inhibitor treats the pitch contained in the entire amount of pulp slurry, while the external pitch inhibitor is sprayed, sprayed, immersed, etc. on the surface of any manufacturing equipment such as wires, felts, rolls, etc. , and selectively treats the pitch present near the surface of the equipment.
From this, the external pitch inhibitor does not affect the quality of pulp slurry and paper products compared to the internal pitch inhibitor, and it can be applied to any equipment surface with less chemical usage. There is an advantage that adhesion can be prevented.

Various methods have been conventionally proposed as a pitch suppression method using an externally added pitch suppressor.
As a pitch inhibitor containing two active ingredients, a cationic polymer and a surfactant, Patent Document 1 describes two ingredients, an epichlorohydrin-dimethylamine copolymer and a nonionic surfactant, as active ingredients. A method of using a pitch inhibitor is disclosed.
The pitch inhibitor used in the method of Patent Document 1 is a cationic polymer that exhibits a pitch adhesion prevention action by hydrophilizing the pitch and equipment surfaces. Furthermore, by using a nonionic surfactant in combination, it is possible to further enhance the pitch adhesion prevention effect and prevent the accumulation of deposits caused by the cationic polymer itself on the equipment surface.

Furthermore, as a method for improving the anti-adhesion effect of pitch, a method using a pitch inhibitor having three active ingredients including a cationic polymer, a surfactant and a phosphonic acid compound has been proposed.
For example, in Patent Document 2, a cationic polymer (molecular weight 20,000 to 100,000) selected from polydiallyldimethylammonium salt or epichlorohydrin-dialkylamine copolymer and a higher aliphatic amine with ethylene oxide or Disclosed is a method of using a pitch inhibitor for paper and pulp manufacturing processes containing a nonionic surfactant to which ethylene oxide and propylene oxide are added and 1-hydroxyethane-1,1-diphosphonic acid (HEDP) as active ingredients. It is

Patent Document 3 discloses (A) a dimethyl ester or diethyl ester of a dicarboxylic acid having an alkylene group having 2 to 4 carbon atoms or benzyl alcohol, (B) a glycol compound, and (C) an organic phosphonic acid, an organic carboxylic acid, Low-foaming antifouling agents for paper and pulp manufacturing processes are disclosed which contain organic sulfonic acids, inorganic acids or salts thereof and do not use surfactants.

Patent Document 4 describes papermaking containing (A) a specific polyether ester amide, and (B) at least one of a nonionic surfactant, an ionic surfactant, an ionic polymer, an acidic compound and a basic compound. Disclosed is an antifouling agent composition.

However, problems caused by pitch are increasing due to recent operating conditions such as closed water supply, increased use of recovered paper, more complicated wire and felt weaving structures, and increased dewatering volume due to the spread of shoe press papermaking. There is a tendency. In addition, talc, calcium carbonate, kaolin, clay, etc. have traditionally been added to paper as fillers to improve the compactness, opacity, smoothness, etc. of paper. Neutral papermaking, which allows the use of a large amount of low-cost calcium carbonate, has taken the place of conventional acidic papermaking, and the occurrence of combined soiling of calcium carbonate and pitch is also increasing. The above method is not sufficiently effective in preventing the adhesion of contamination such as pitch to the equipment surface, and a more effective pitch inhibitor and pitch suppression method are desired.

JP-A-2-182995 JP 2004-044067 A JP 2014-221957 A JP 2008-240227 A

Under these circumstances, the problem to be solved by the present invention is to prevent pitch adhesion in the paper manufacturing process, particularly in the process of manufacturing paper from raw materials containing waste paper pulp and in the process of manufacturing neutral paper that uses a lot of calcium carbonate. An object of the present invention is to provide a highly effective pitch suppressing agent and a pitch suppressing method.

As a result of intensive research to solve the above problems, the present inventors have found a pitch containing four active ingredients: a specific cationic polymer, a nonionic surfactant, a phosphonic acid compound, and an organic sulfonic acid compound. The inventors have found that the inhibitor has an excellent effect of preventing adhesion of pitch, and particularly shows an excellent effect on composite pitch derived from calcium carbonate and pitch, and have completed the present invention.

That is, the present invention consists of the following configurations.
(1)
Paper containing nonionic surfactants, phosphonic acid compounds, organic sulfonic acid compounds, and cationic polymers such as epichlorohydrin-ammonia-dialkylamine copolymers or diallyldialkylammonium chloride-acrylamide copolymers as active ingredients. It is a pitch inhibitor for the pulping process.
(2)
In the invention of (1), the pitch inhibitor for a paper/pulp manufacturing process, wherein the epichlorohydrin-ammonia-dialkylamine copolymer has a mass average molecular weight of 10,000 or more and 130,000 or less.
(3)
In the invention of (1) or (2), the pitch inhibitor for the paper/pulp manufacturing process, wherein the epichlorohydrin-ammonia-dialkylamine copolymer is an epichlorohydrin-ammonia-dimethylamine copolymer. be.
(4)
In the invention of any one of (1) to (3), the nonionic surfactant is polyoxyalkylenealkylamine, or a combination of polyoxyalkylenealkylamine and polyoxyalkylene glycol. It is an inhibitor.
(5)
In the invention according to any one of (1) to (4), the phosphonic acid compound is 1-hydroxyethane-1,1-diphosphonic acid, aminotrimethylene phosphonic acid, and 2-phosphonobutane-1,2,4-tricarboxylic acid. A pitch inhibitor for paper and pulp manufacturing processes, which is at least one selected from acids and salts thereof.
(6)
In any one of inventions (1) to (5), the organic sulfonic acid compound is at least one selected from benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, and salts thereof. It is a pitch inhibitor for certain paper and pulp manufacturing processes.
(7)
In any one of inventions (1) to (6), the pitch inhibitor is used in the paper/pulp manufacturing process, wherein the paper/pulp manufacturing process contains waste paper pulp in the raw material of the paper.
(8)
In any one of the inventions (1) to (7), the pitch inhibitor is used in the paper/pulp manufacturing process, wherein the paper/pulp manufacturing process contains calcium carbonate in the paper raw material.
(9)
Pitch in a paper/pulp manufacturing process in which the pitch inhibitor for a paper/pulp manufacturing process according to any one of (1) to (8) is added/diluted to the paper/pulp manufacturing process water and then brought into contact with the paper manufacturing apparatus. It is a suppression method.
(10)
In the invention of (9), the method for suppressing pitch in the paper/pulp manufacturing process, wherein the raw material of the paper in the paper/pulp manufacturing process contains waste paper pulp.
(11)
In the invention of (9) or (10), there is provided the pitch suppression method in the paper/pulp manufacturing process, wherein the raw material of the paper in the paper/pulp manufacturing process contains calcium carbonate.

By using the pitch inhibitor of the present invention, dirt such as pitch can be removed from the surface of manufacturing equipment such as wires, felts, and rolls in the paper/pulp manufacturing process, particularly in the process of manufacturing paper from raw materials containing waste paper pulp and calcium carbonate. Adhesion can be effectively suppressed, and process troubles such as reduction in water tightness of wires and felts, occurrence of paper defects and paper breakage can be prevented, and the quality and productivity of paper products can be improved.

The pitch inhibitor of the present invention and the pitch inhibition method for paper manufacturing equipment using the same include a nonionic surfactant, a phosphonic acid compound, an organic sulfonic acid compound, and epichlorohydrin-ammonia-dialkylamine as a cationic polymer. Copolymer or diallyldialkylammonium chloride-acrylamide copolymer (hereinafter also referred to as "cationic polymer of the present invention") as an active ingredient pitch inhibitor for paper and pulp manufacturing processes, and these pitch inhibitors are used in paper・It is a method of suppressing pitch by adding it to pulp manufacturing process water to suppress staining of pitch.

Specific examples of nonionic surfactants used in the present invention include polyoxyalkylene alkyl ethers that are alkylene oxide adducts to aliphatic alcohols, polyoxyalkylene alkylphenyl ethers that are adducts to alkylphenols, sorbitan fatty acids, Polyoxyalkylene sorbitan fatty acid ester that is an adduct to ester, polyoxyalkylene glycerin fatty acid ester that is an adduct to glycerin fatty acid ester, polyoxyalkylene pentaerythritol fatty acid ester that is an adduct to pentaerythritol fatty acid ester, to fatty acid Polyoxyalkylene fatty acid esters that are adducts of, polyoxyalkylene fatty acid amides that are adducts to fatty acid amides, polyoxyalkylene alkylamines that are adducts to aliphatic amines, polyoxyalkylenes that are adducts to glycol Glycol and the like can be mentioned. The above aliphatic compounds may be either saturated or unsaturated.
Examples of the alkylene oxide to be added include ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof. The alkylene oxide adduct having two or more oxyalkylene groups in the molecule may be either a block copolymer or a random copolymer. These nonionic surfactants can be used singly or in combination of two or more.
Among these, polyoxyalkylenealkylamine alone or in combination with polyoxyalkylene glycol is preferred, and when used in combination, the mixing ratio is preferably 95:5 to 5:95. As the polyoxyalkylenealkylamine, from the viewpoint of pitch adhesion prevention effect, 5 to 30 mol of ethylene oxide is added to a saturated or unsaturated aliphatic amine having 10 to 20 carbon atoms, and 0 to 15 mol of propylene oxide. Added ones are particularly preferred. Specific examples of saturated or unsaturated aliphatic amines having 10 to 20 carbon atoms include decylamine, laurylamine, myristylamine, palmitylamine, stearylamine and oleylamine. As the polyoxyalkylene glycol, one obtained by adding ethylene oxide or propylene oxide to a dihydric alcohol having 2 to 10 carbon atoms is preferable. Examples of dihydric alcohols having 2 to 10 carbon atoms include ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol and 2,3-butane. Diol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 1,3-nonanediol and the like can be mentioned.

Specific examples of the phosphonic acid compound used in the present invention include aminotrimethylenephosphonic acid (ATMP), ethylenediaminetetramethylenephosphonic acid, trimethylenediaminetetramethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, diethylenetriaminepenta(methylene phosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid (HEDP), 1-hydroxypropane-1,1-diphosphonic acid, 1-aminopropane-1,1-diphosphonic acid, and 2-phosphonobutane-1, 2,4-tricarboxylic acid (PBTC) and the like, and salts thereof.
Among these, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotrimethylenephosphonic acid (ATMP), 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and their alkali Metal salts are preferred.
Alkali metal salts include sodium and potassium salts. These phosphonic acid compounds can be used singly or in combination of two or more.
In the blending ratio of each component in the pitch inhibitor of the present invention, preferably 1 to 500 parts by mass of the phosphonic acid compound with respect to 100 parts by mass of the total amount of the cationic polymer and nonionic surfactant of the present invention, more preferably 2 ~50 parts by mass.

Examples of organic sulfonic acid compounds used in the present invention include benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, and salts thereof. , methanesulfonic acid and salts thereof are preferred.
The blending ratio of the organic sulfonic acid compound in the pitch inhibitor of the present invention is 1 to 100 parts by mass of the organic sulfonic acid compound with respect to 100 parts by mass of the total amount of the cationic polymer, nonionic surfactant and phosphonic acid compound of the present invention. , preferably 3 to 50 parts by mass.

式中、Ｒ１、Ｒ２はアルキル基で、互いに同じでも異なってもよく、ｍ、ｎは、整数であってエピクロロヒドリン－アンモニア－ジアルキルアミン共重合体の分子量が１０，０００以上１５０，０００以下に相当する整数、特に分子量が１０，０００以上１３０，０００以下に相当する整数が好ましい）で表される。ここで一般式（１）は構成単位の共重合比を表しており、ブロック共重合体ではない。 The cationic polymer epichlorohydrin-ammonia-dialkylamine copolymer used in the present invention is
General formula (1):

In the formula, R1 and R2 are alkyl groups which may be the same or different, m and n are integers, and the epichlorohydrin-ammonia-dialkylamine copolymer has a molecular weight of 10,000 to 150,000. is preferably an integer corresponding to the following, particularly an integer corresponding to a molecular weight of 10,000 or more and 130,000 or less). Here, the general formula (1) represents the copolymerization ratio of the structural units and is not a block copolymer.

Specific examples of the epichlorohydrin-ammonia-dialkylamine copolymer represented by the general formula (1) include an epichlorohydrin-ammonia-dimethylamine copolymer and an epichlorohydrin-ammonia-diethylamine copolymer. polymers, etc., and epichlorohydrin-ammonia-dimethylamine copolymer is particularly preferred. The weight average molecular weight of the epichlorohydrin-ammonia-dialkylamine copolymer is preferably a weight average molecular weight of 10,000 or more and 150,000 or less, particularly 10, from the viewpoint of pitch suppression effect and aggregation suppression with iron content. ,000 or more and 130,000 or less.

（式中、Ｒ１、Ｒ２はアルキル基で互いに同じでも異なってもよく、ｌ、ｍ、ｎは整数、ｌ≧ｌかつｍ≧１）で表される。
一般式（２）で表されるジアリルジアルキルアンモニウムクロライド－アクリルアミド共重合体として、具体的には、ジアリルジメチルアンモニウムクロライド－アクリルアミドおよびジアリルジエチルアンモニウムクロライド－アクリルアミド共重合体等が挙げられ、ジアリルジメチルアンモニウムクロライド－アクリルアミド共重合体が特に好ましい。ジアリルジアルキルアンモニウムクロライド－アクリルアミド共重合体の質量平均分子量は、ピッチ抑制効果の観点から３０，０００以上１５０，０００以下が好ましい。 The cationic polymer diallyldialkylammonium chloride-acrylamide copolymer used in the present invention has the general formula (2):

(In the formula, R1 and R2 are alkyl groups, which may be the same or different, and l, m, and n are integers, l≧l and m≧1).
Specific examples of the diallyldialkylammonium chloride-acrylamide copolymer represented by the general formula (2) include diallyldimethylammonium chloride-acrylamide and diallyldiethylammonium chloride-acrylamide copolymers. - Acrylamide copolymers are particularly preferred. The weight average molecular weight of the diallyldialkylammonium chloride-acrylamide copolymer is preferably 30,000 or more and 150,000 or less from the viewpoint of pitch suppression effect.

The mass ratio of the epichlorohydrin-ammonia-dialkylamine copolymer or diallyldialkylammonium chloride-acrylamide copolymer, which is the cationic polymer in the pitch inhibitor of the present invention, to the nonionic surfactant is 100 of the cationic polymer. The nonionic surfactant is preferably 25 to 500 parts by mass. More preferably, the nonionic surfactant is 100 to 300 parts by mass with respect to 100 parts by mass of the cationic polymer.

The pitch inhibitor of the present invention may include surfactants, polymers, chelating agents, builders, organic acids, pH adjusters, solvents, antifoaming agents, Bactericides, preservatives, coloring agents, perfumes and the like may be contained.
The pitch inhibitor of the present invention is a drainage improver, a retention aid, a coagulant, a sizing agent, other pitch inhibitors, lubricants, peelability improvers, detergents, and slime inhibitors used in the manufacture of paper. , scale inhibitors, acids and alkalis.

There is no limitation on the type of raw material pulp to which the pitch inhibitor of the present invention is applied, and bleached or unbleached chemical pulp such as kraft pulp and sulfite pulp, bleached mechanical pulp such as groundwood pulp and thermomechanical pulp, or unbleached pulp. Waste paper pulp such as bleached machine pulp, waste newspaper, waste magazine, waste corrugated board and waste deinked paper, and broken pulp such as machine waste and coated waste.
The pitch adhesion prevention effect of the present invention is remarkably exhibited when used paper pulp is used, and the effect is particularly remarkably exhibited when a raw material containing 10% by mass or more of used paper pulp is used.
The pitch inhibitor of the present invention can be applied to the production of paper under acidic, neutral and alkaline conditions, and the type of paper to be produced is not limited, but calcium carbonate is often used as a filler or the like. In particular, in the case of manufacturing neutral paper, the effect of preventing soiling caused by a combination of calcium carbonate and organic pitch is great.
Such paper includes, for example, newsprint, printing paper such as fine paper and lightly coated paper, information paper such as PPC paper for copy paper and thermal base paper, packaging paper such as pure white roll paper and bleached kraft paper, tissue paper, Sanitary paper such as toilet paper, miscellaneous paper such as base paper for food containers and base paper for coating and printing, base paper for corrugated board such as liner and corrugating board, paperboard for paper containers such as white paperboard and colored paperboard, gypsum board and paper tube base paper Miscellaneous paperboard etc. are mentioned.

The pitch inhibitor of the present invention can prevent pitch adhesion to the paper manufacturing equipment by direct contact with the paper manufacturing equipment. When contacting the paper manufacturing equipment, the pitch inhibitor should be diluted with the paper/pulp manufacturing process water such as roll or felt shower water or water doctor added water, and then sprayed, sprayed, or immersed in the paper manufacturing equipment. The amount of the pitch inhibitor added to the paper/pulp manufacturing process water depends on the amount of pitch present, but is usually 5 to 2,000 mg/L in the water to be diluted, preferably , 10 to 500 mg/L.

Examples of manufacturing equipment that contacts the pitch inhibitor of the present invention include wires, felts, center rolls, table rolls, breast rolls, dandy rolls, wire return rolls, couch rolls, press rolls, suction rolls, paper rolls, backing rolls, Slice lip, forming board, foil, doctor, suction box, yule box, canvas, etc. Among these, it is particularly effective for wires and felts containing hydrophobic resins such as polyester resins and nylon resins as main components.

In the paper manufacturing process, the pitch inhibitor of the present invention may be brought into contact with the manufacturing equipment, for example, before or during the operation of the manufacturing equipment, it may be contacted continuously or intermittently, especially during the operation of the manufacturing equipment. Continuous contact is preferred. In addition, as described above, it is preferable to use a method of contacting by spraying, spraying, immersing, etc. as shower water, but by bringing the pitch inhibitor into contact with manufacturing equipment other than the target manufacturing equipment, it is possible to indirectly contact the target manufacturing equipment. can be brought into direct contact.

As the water to which the pitch inhibitor of the present invention is added, any of ground water such as well water, surface water such as river water or lake water, fresh water such as industrial water, recycled water, recycled water such as treated wastewater, Or they can be mixed and used.

The present invention will be described below with reference to examples and test examples, but the present invention is not limited by these examples and test examples.

Table 1 shows the formulations of the pitch inhibitors used in Examples and Comparative Examples and the results of the pitch adhesion prevention test.

［注］ＥＣＨ：エピクロロヒドリン
ＤＭＡ：ジメチルアミン
Ａｍ：アンモニア
ＤＡＤＭＡＣ：ジアリルジメチルアンモニウムクロライド
ＡＡ：アクリルアミド
ｐＤＡＤＭＡＣ：ポリジアリルジメチルアンモニウムクロライド
ＰＯＡＳＡ：ポリオキシアルキレンステアリルアミン（エチレンオキサイド２０モル、プロピレンオキサイド２モルを付加したステアリルアミン）
ＰＯＡＧ：ポリオキシアルキレングリコール
ＨＥＤＰ：１－ヒドロキシエタン－１，１－ジホスホン酸
ＭＳＡ：メタンスルホン酸
ＡＤＢＡＣ：アルキルジメチルベンジルアンモニウムクロライド
（三洋化成工業株式会社「カチオンＧ－５０」）

[Note] ECH: Epichlorohydrin DMA: Dimethylamine Am: Ammonia DADMAC: Diallyldimethylammonium chloride AA: Acrylamide pDADMAC: Polydiallyldimethylammonium chloride POASA: Polyoxyalkylenestearylamine (20 moles of ethylene oxide and 2 moles of propylene oxide stearylamine)
POAG: polyoxyalkylene glycol HEDP: 1-hydroxyethane-1,1-diphosphonic acid MSA: methanesulfonic acid ADBAC: alkyldimethylbenzylammonium chloride (Sanyo Chemical Industries, Ltd. "Cation G-50")

(Pitch adhesion prevention test)
(1) Felt actually used in a kraft paper-making machine that uses only kraft pulp as a raw material (kraft paper machine felt), or actually in a paperboard-making machine that uses waste paper as a raw material (waste paper pulp content of 90% or more) The felt (paperboard machine felt) used in , or the felt actually used in the PPC paper machine using calcium carbonate as a filler (15% by mass of the paper) (PPC paper machine felt) was mixed with ethanol: cyclohexane = Extract with a mixed solvent of 1:2 (volume ratio). The obtained pitch component was again dissolved in ethanol:cyclohexane=1:2 (volume ratio) to prepare a 10% (w/v) pitch solution.
(2) Test water (150 ml) was prepared in a 200 ml tall beaker by diluting each of the pitch inhibitors of the above Examples and Comparative Examples with tap water to a concentration of 100 mg/L. A 60-mesh polyester net (20 mm×60 mm×0.28 mm, mesh size 0.273 mm, thread diameter 0.150 mm) was immersed in test water and stirred at room temperature and 600 rpm.
(3) A 10% (w/v) pitch solution was added to the test water so as to make 100 mg/L, and the mixture was stirred at room temperature and 600 rpm for 2 hours.
(4) The polyester net was taken out, washed thoroughly with pure water, and then Sudan Black B dyeing solution (Sudan Black B was dissolved in 70% (v/v) ethanol to make 0.5% (w/v). ) for 20 minutes, immersed in 50% (v/v) ethanol, washed with pure water, and air-dried.
(5) Using a handy colorimeter NR-11A (manufactured by Nippon Denshoku Industries Co., Ltd.), about the pitch adhesion surface of the dyed polyester net, 3 points on the left half (upper, middle, lower), 3 points on the right half (upper) , middle, and bottom) were measured, and the average value was calculated.
(6) Assuming that the average value of the color difference ΔE(ab) in the case where no pitch inhibitor is added is 10, the pitch relative adhesion amount when each pitch inhibitor is added was calculated from the following equation.

Pitch relative adhesion amount when chemical agent is added = ΔE (ab) average value when chemical agent is added / ΔE (ab) average value when chemical agent is not added × 10

(7) The fractional part of the pitch relative adhesion amount obtained when the agent was added was rounded off to an integer, and the smaller the number, the higher the effect of preventing the adhesion of the agent to the pitch.

(Preventing adhesion of calcium carbonate and pitch composite soil)
(1) Felt (PPC paper machine felt) actually used in a PPC paper machine using calcium carbonate as a filler (15% by mass of paper) was mixed with a mixed solvent of ethanol:cyclohexane = 1:2 (volume ratio). Extract with. The obtained pitch component was again dissolved in ethanol:cyclohexane=1:2 (volume ratio) to prepare a 10% (w/v) pitch solution.
(2) 2,500 mg/L of calcium carbonate (reagent special grade, manufactured by Kishida Chemical Co., Ltd.) and 100 mg/L of each of the pitch inhibitors of the above examples and comparative examples are placed in a 200 ml tall beaker as inorganic soiling components of felt. Test water (150 ml) diluted with tap water was prepared as follows. A weighed 60-mesh polyester net (20 mm×60 mm×0.28 mm, mesh opening 0.273 mm, thread diameter 0.150 mm, weight W1) was immersed in the test water and stirred at room temperature and 600 rpm.
(3) A 10% (w/v) pitch solution was added to the test water so as to make 50 mg/L, and the mixture was stirred at room temperature and 600 rpm for 3 hours.
(4) The polyester net was taken out and dried at room temperature, and then the dry mass W2 was measured.
(5) Calcium carbonate + pitch composite soil adhesion amount W3 when each pitch inhibitor was added was calculated from the following equation.

Calcium carbonate + pitch composite soil adhesion amount W3 (mg) when chemical was added = W2 - W1

(6) The calcium carbonate + pitch composite soil adhesion amount W0 (mg) when the pitch inhibitor was not added was also calculated in the same manner, and the calcium carbonate + pitch composite soil adhesion amount when the chemical was added was calculated from the following equation.

Calcium carbonate + pitch composite soil relative adhesion amount at the time of chemical addition = W3 / W0 × 10

(7) The relative adhesion amount of calcium carbonate + pitch composite soil obtained when the chemical is added is rounded off to the nearest whole number, and the smaller the number, the higher the chemical adhesion prevention effect against the composite soil of calcium carbonate and pitch. and evaluated.

(Examples 1-6 and Comparative Examples 1-6)
Epichlorohydrin-ammonia-dimethylamine (ECH/Am/DMA) copolymer (weight average molecular weight 10,000 , 60,000, 80,000, or 130,000) or a diallyldialkylammonium chloride-acrylamide copolymer (mass average molecular weight 60,000) (Examples 1 to 6) is an organic sulfonic acid ECH / Am / DMA copolymer (mass average molecular weight 60,000) compounded product (Comparative Example 3) and DADMAC / AA copolymer (mass average molecular weight 60,000) compounded product (Comparative Example 4) that does not contain A high pitch adhesion prevention effect was exhibited, and an effect equivalent to that of pDADMAC (mass average molecular weight: 60,000) formulation products (Comparative Examples 1 and 2) was exhibited.
Comparative Example 5 is the same as Example 2 except the ECH/Am/DMA copolymer and MSA, and Comparative Example 6 is the same as Example 2 except that the ECH/Am/DMA copolymer and ADBAC are added. However, the pitch inhibitors of Comparative Examples 5 and 6 were significantly less effective than Example 2 in preventing the adhesion of pitch.
On the other hand, for pitches extracted from paperboard machine felts, the pitch inhibitors of Examples 1-6 were pDADMAC (mass average molecular weight 60,000) formulations (Comparative Examples 1 and 2), ECH/Am/ DMA copolymer (mass average molecular weight 60,000) blended product (Comparative Example 3) and DADMAC/AA copolymer (mass average molecular weight 60,000) blended product (Comparative Example 4) showed a higher pitch adhesion prevention effect. rice field.
Comparative Example 5 is the same as Example 2 except the ECH/Am/DMA copolymer and MSA, and Comparative Example 6 is the same as Example 2 except that the ECH/Am/DMA copolymer and ADBAC are added. However, the pitch inhibitors of Comparative Examples 5 and 6 were significantly less effective than Example 2 in preventing the adhesion of pitch.
For compound soils consisting of calcium carbonate and pitch extracted from PPC paper machine felt, the pitch inhibitors of Examples 1-6 were pDADMAC (weight average molecular weight 60,000) formulations (Comparative Examples 1, 2). ), ECH/Am/DMA copolymer (mass average molecular weight 60,000) formulation (Comparative Example 3), DADMAC/AA copolymer (mass average molecular weight 60,000) formulation (Comparative Example 4) It showed an antifouling effect.
Comparative Example 5 is the same as Example 2 except the ECH/Am/DMA copolymer and MSA, and Comparative Example 6 is the same as Example 2 except that the ECH/Am/DMA copolymer and ADBAC are added. However, the antifouling effect of the pitch inhibitors of Comparative Examples 5 and 6 was significantly lower than that of Example 2.
In Example 5, in which POASA was used alone as a nonionic surfactant, and in Example 2, in which POASA and POAG were used in combination at a blending ratio of 8:2 (w/w), kraft paper machine felt and paperboard machine felt It showed an equally good anti-stick effect against the extracted pitch. It also showed equally good anti-fouling effect against composite soil consisting of calcium carbonate and pitch extracted from PPC paper machine felt.

(Example 7 and Comparative Examples 7 and 8)
The pitch inhibitor (Example 7) in which the content of the nonionic surfactant was reduced from that of Example 2 had a lower pitch adhesion prevention effect than Examples 2 and 5, regardless of the type of pitch.
For the pitch extracted from the kraft paper machine felt, Example 7 is pDADMAC (mass average molecular weight 60,000) blended product (Comparative Example 7), DADMAC/AA copolymer (mass average molecular weight 60,000) blended It showed a higher pitch adhesion prevention effect than the product (Comparative Example 8).
For pitches extracted from paperboard machine felts, the pitch inhibitors of Example 7 were pDADMAC (weight average molecular weight 60,000) formulation (Comparative Example 7), DADMAC/AA copolymer (weight average molecular weight 60,000, 000), exhibiting a significantly higher pitch adhesion prevention effect than the compounded product (Comparative Example 8).
For composite soils consisting of calcium carbonate and pitch extracted from PPC paper machine felt, the pitch inhibitor of Example 7 was the pDADMAC (weight average molecular weight 60,000) formulation (Comparative Example 7), both DADMAC/AA The antifouling effect was significantly higher than that of the polymer (mass average molecular weight 60,000) compounded product (Comparative Example 8).

(Example 8 and Comparative Examples 9 and 10)
The pitch inhibitor (Example 8) in which the content of the nonionic surfactant was increased more than that of Example 2 improved the pitch adhesion prevention effect as compared with Example 2 regardless of the type of pitch.
For pitch extracted from kraft paper machine felt, Example 8 exhibited a higher pitch adhesion prevention effect than the DADMAC/AA copolymer (mass average molecular weight 60,000) formulation (Comparative Example 10), and pDADMAC (Mass-average molecular weight: 60,000).
However, for pitches extracted from paperboard machine felts, the pitch inhibitors of Example 8 were pDADMAC (weight average molecular weight 60,000) formulation (Comparative Example 9), DADMAC/AA copolymer (weight average molecular weight 60,000) showed significantly higher pitch adhesion prevention effect than the compounded product (Comparative Example 10).
For composite soils consisting of calcium carbonate and pitch extracted from PPC paper machine felt, the pitch inhibitor of Example 8 was pDADMAC (weight average molecular weight 60,000), as was pitch extracted from paperboard machine felt. ) compounded product (Comparative Example 9) and DADMAC/AA copolymer (mass average molecular weight 60,000) compounded product (Comparative Example 10) exhibited significantly higher antifouling effect.

(Example 9 and Comparative Examples 11 and 12)
The pitch inhibitor (Example 9) in which the HEDP content was lower than that of Example 2 exhibited a lower pitch adhesion prevention effect than that of Example 2 regardless of the type of pitch.
For pitch extracted from kraft paper machine felt, Example 9 exhibits a higher pitch anti-adhesion effect than the DADMAC/AA copolymer (mass average molecular weight 60,000) formulation (Comparative Example 12), and pDADMAC (Mass-average molecular weight: 60,000).
However, for pitches extracted from paperboard machine felts, the pitch inhibitors of Example 9 were pDADMAC (weight average molecular weight 60,000) formulation (Comparative Example 11), DADMAC/AA copolymer (weight average molecular weight 60,000) showed significantly higher pitch adhesion prevention effect than the compounded product (Comparative Example 12).
For composite soils consisting of calcium carbonate and pitch extracted from PPC paper machine felt, the pitch inhibitor of Example 9 was the pDADMAC (weight average molecular weight 60,000) formulation (Comparative Example 11), both DADMAC/AA It exhibited a significantly higher antifouling effect than the polymer (mass average molecular weight 60,000) compounded product (Comparative Example 12).

(Example 10 and Comparative Examples 13 and 14)
The pitch inhibitor (Example 10) in which the HEDP content was increased more than that of Example 2 improved the pitch adhesion prevention effect as compared with Example 2 regardless of the type of pitch.
For pitch extracted from kraft paper machine felt, Example 10 exhibits a higher pitch adhesion prevention effect than the DADMAC/AA copolymer (mass average molecular weight 60,000) formulation (Comparative Example 14), and pDADMAC (Mass-average molecular weight: 60,000) showed the same effect as the compounded product (Comparative Example 13).
However, for pitches extracted from paperboard machine felts, the pitch inhibitors of Example 10 were pDADMAC (weight average molecular weight 60,000) formulation (Comparative Example 13), DADMAC/AA copolymer (weight average molecular weight 60,000) exhibited a significantly higher pitch adhesion prevention effect than the compounded product (Comparative Example 14).
For composite soils consisting of calcium carbonate and pitch extracted from PPC paper machine felt, the pitch inhibitor of Example 10 was the pDADMAC (weight average molecular weight 60,000) formulation (Comparative Example 13), both DADMAC/AA It showed a much higher antifouling effect than the polymer (mass average molecular weight 60,000) compounded product (Comparative Example 14).

In the pitch inhibitor compositions of Examples 1 to 6 and Comparative Examples 1 to 6, aminotrimethylene phosphonic acid (ATMP) or 2-phosphonobutane-1,2,4-tricarboxylic acid ( PBTC) was prepared and tested for pitch anti-fouling against pitch extracted from kraft and paperboard machine felts.
A soil repellency test was also conducted against a composite soil consisting of calcium carbonate and pitch extracted from PPC paper machine felt.
As a result, even in pitch inhibitors containing ATMP or PBTC, the same pitch inhibitory effect as pitch inhibitors containing HEDP (Examples 1 to 6 and Comparative Examples 1 to 6), and a composite of calcium carbonate and pitch An antifouling effect was obtained.

In the compositions of the pitch inhibitors of Examples 1 to 6 and Comparative Examples 1 to 6, benzenesulfonic acid (BSA), p-toluenesulfonic acid (TSA), ethanesulfonic acid (ESA) were used instead of MSA as organic sulfonic acid compounds. ) were prepared and pitch anti-fouling tests were conducted on pitch extracted from kraft paper machine felts and paperboard machine felts.
A soil repellency test was also conducted against a composite soil consisting of calcium carbonate and pitch extracted from PPC paper machine felt.
As a result, even in pitch inhibitors containing any one of BSA, TSA, and ESA, pitch inhibitors containing MSA (Examples 1 to 6 and Comparative Examples 1 to 6) have the same pitch adhesion prevention effect, and A compound stain adhesion prevention effect of calcium carbonate and pitch was obtained.

(Actual machine test)
In order to evaluate the performance of the pitch inhibitor in an actual machine, the pitch inhibitor described in Example 2 and Comparative Example 2 was felted in a PPC paper manufacturing machine using calcium carbonate as a filler (15% by mass of paper). It was added to the shower water and continuously added to the felt.
When the pitch inhibitor of Comparative Example 2 was used, the felt was clogged with calcium carbonate and pitch, resulting in frequent occurrence of poor dehydration and paper breakage, and the felt had to be replaced after 30 days.
However, when the pitch inhibitor of Example 2 was used, calcium carbonate and pitch stains on the felt were significantly reduced one month after the addition, and no dehydration failure or paper breakage occurred, and the felt could be used continuously for 60 days. was made.

In addition, in the actual paper manufacturing process, adding and diluting a pitch inhibitor, which consists of three components, a cationic polymer, a nonionic surfactant, and a phosphonic acid compound, to the water used in the manufacturing process, such as shower water, was found to be effective in cleaning shower line nozzles. Poor discharge of shower water due to clogging (when undiluted pitch inhibitor is injected into the shower pipe with a chemical injection pump), poor discharge of diluent due to blockage of the discharge port of the chemical injection pump (diluted pitch inhibitor If the shower pipe is pressurized with a pump), clogging of wires, felt, etc., may cause new problems such as poor water constriction and paper breakage.
As a result of investigation of the cause by the present inventors, it was speculated that the three components in the pitch inhibitor reacted with iron and the like in manufacturing process water such as shower water, resulting in the generation of precipitates.

In a tabletop test, the pitch inhibitor used in Examples 1 to 10 and Comparative Examples 1 to 14, in which these three components were mixed with MSA, was added to 1,000 mg / L of the pitch inhibitor. A test piece made of a hot rolled steel plate (SPCC) was immersed, and the amount of precipitates generated was visually evaluated.
As a result, no precipitate was observed in Examples 1 to 10, Comparative Examples 2, 3 and 5, but in Comparative Examples 1, 4 and 7 to 14, the cationic polymer and the phosphonic acid compound Formation of pitch inhibitor-derived precipitates composed of iron was observed. In Comparative Example 6, a cationic surfactant was blended instead of the cationic polymer, but reaction deposits were observed.
From this, the pitch inhibitor of the present invention is not only effective in preventing adhesion of pitch, but also excellent in preventing adhesion of composite stains of calcium carbonate and pitch, and effectively suppresses the generation of precipitates derived from the pitch inhibitor. It was also confirmed that it is possible.

Claims (11)

It contains a nonionic surfactant, a phosphonic acid compound, an organic sulfonic acid compound, and a cationic polymer as active ingredients, and the cationic polymer is epichlorohydrin-ammonia-dialkylamine copolymer or diallyldialkylammonium chloride. - A pitch inhibitor for paper and pulp manufacturing processes, characterized in that it is an acrylamide copolymer. The pitch inhibitor for paper/pulp manufacturing processes according to claim 1, wherein the epichlorohydrin-ammonia-dialkylamine copolymer has a mass average molecular weight of 10,000 or more and 130,000 or less. 3. The pitch inhibitor for paper/pulp manufacturing processes according to claim 1 , wherein the epichlorohydrin-ammonia-dialkylamine copolymer is an epichlorohydrin-ammonia-dimethylamine copolymer. The paper/pulp manufacturing process according to any one of claims 1 to 3, wherein the nonionic surfactant is a polyoxyalkylenealkylamine or a combination of a polyoxyalkylenealkylamine and a polyoxyalkylene glycol. pitch inhibitor. The phosphonic acid compound is at least one selected from 1-hydroxyethane-1,1-diphosphonic acid, aminotrimethylene phosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, and salts thereof. The pitch inhibitor for a paper/pulp manufacturing process according to any one of claims 1 to 4. 6. The method according to any one of claims 1 to 5, wherein the organic sulfonic acid compound is at least one selected from benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, and salts thereof. Pitch inhibitor for paper and pulp manufacturing processes as described. The pitch inhibitor for a paper/pulp manufacturing process according to any one of claims 1 to 6, wherein waste paper pulp is contained in the raw material of the paper in the paper/pulp manufacturing process. 8. The pitch inhibitor for the paper/pulp manufacturing process according to any one of claims 1 to 7, wherein the paper/pulp manufacturing process contains calcium carbonate in the raw material of the paper . The pitch inhibitor for the paper/pulp manufacturing process according to any one of claims 1 to 8 is added to and diluted with the paper/pulp manufacturing process water, and then brought into contact with the paper manufacturing apparatus. Pitch control method for paper and pulp manufacturing processes. 10. The pitch control method in the paper/pulp manufacturing process according to claim 9, wherein waste paper pulp is contained in the raw material of the paper in the paper/pulp manufacturing process. 11. The method for suppressing pitch in a paper/pulp manufacturing process according to claim 9 or 10, wherein the paper/pulp manufacturing process contains calcium carbonate in the raw material of the paper.