JP2000239326A - Polymer of acrylamide-based copolymer, additive for papermaking and paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an additive for papermaking having the same or higher paper strength in spite of exhibition of excellent drainage and yield. SOLUTION: This additive for papermaking comprises a polymer of an acrylamide-based copolymer obtained by polymerizing monomers containing (a) an acrylamide, (b) an anionic vinyl monomer, (c) a cationic vinyl monomer and (d) tetraallyloxyethane. Consequently papermaking slightly affected by the kind of raw material pulp, papermaking pH and the level of ash content of paper.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer of an acrylamide copolymer having a novel copolymer component, a papermaking additive and paper containing the polymer, and more particularly, to a drainage and retention effect particularly in papermaking. To improve the paper strength despite the fact that it is superior.

[0002]

2. Description of the Related Art Conventionally, the use of virgin pulp in the papermaking process has been limited due to the deterioration of log supply conditions, and the necessity of recycling waste paper for the purpose of energy saving and effective use of resources. And the amount of contaminants contained in the white water is increasing,
BACKGROUND ART Various papermaking additives have been used to improve the productivity as a paper machine speeds up or to improve the quality of paper.

Among the papermaking additives, so-called acrylamide having starch, polyamidepolyamine-epichlorohydrin resin, melamine formaldehyde resin, urea formaldehyde resin, and acrylamide as essential components are used as paper strength agents and drainage improvers. Polymers and the like are used according to the purpose.Among them, acrylamide polymers are advantageous in that they can be easily synthesized, and are easy to obtain predetermined performance, and are easy to handle in use. Most commonly used.

[0004] As papermaking additives comprising acrylamide-based polymers, there are anionic type,
Cationic and amphoteric types are known. As the anion type, acrylamides and vinyl monomers having an anionic group ("anionic vinyl monomers")
Can also be called. ) And, if necessary, a copolymer of a nonionic vinyl monomer that can be copolymerized with these monomers, or a partial hydrolysis of acrylamides or a nonionic acrylamide-based polymer that is a copolymer of this and a nonionic vinyl monomer. There are decomposition products. Also,
As the cationic type, a copolymer of acrylamides, a vinyl monomer having a cationic group (also referred to as a “cationic vinyl monomer”) and, if necessary, a nonionic vinyl monomer copolymerizable with these monomers. There is a Huffman-modified or Mannich-modified nonionic acrylamide-based polymer which is a union or an acrylamide or a copolymer of the acrylamide and a nonionic vinyl monomer. Examples of the amphoteric type include acrylamides, a vinyl monomer having a cationic group, a vinyl monomer having an anionic group, a copolymer of a nonionic vinyl monomer which can be copolymerized with these monomers as necessary, and acrylamides. And a vinyl monomer having an anionic group and, if necessary, a Hoffman-modified product or a Mannich-modified product of an anionic acrylamide-based polymer which is a copolymer of a nonionic vinyl monomer copolymerizable with these monomers.

[0005] However, in the recent papermaking industry, the influence of papermaking conditions such as the deterioration of the raw material conditions of paper as described above, the increase in the amount of impurities in white water generated during the papermaking process, and the fluctuation of papermaking pH are affected. Are increasing. Until now, no known papermaking additive has been found in which a sufficient effect can be obtained by effectively controlling these factors. As a remedy, it is considered to increase the molecular weight by giving a branched structure to the acrylamide-based polymer, and various polyfunctional vinyl monomers have been used for that purpose. Instead of an acrylamide-based polymer that does not increase the molecular weight by having a branched structure, a high-molecular-weight acrylamide-based polymer with a branched structure using a polyfunctional vinyl monomer is used as a papermaking additive. It is considered that when used, there is an effect of improving paper strength or drainage. This effect has a branch structure,
It is considered that increasing the molecular weight increases the number of contact points between the acrylamide polymer and the pulp, increases the hydrogen bonding between cellulose molecules in the pulp, and increases the pulp aggregation.

[0006]

However, when a high molecular weight acrylamide-based polymer having a branched structure using such a polyfunctional vinyl monomer is used, the drainage can be improved by coagulating pulp. On the other hand, it causes the problem that the formation of the formed paper is deteriorated and the paper strength is reduced, and conversely, if the paper strength is not reduced, the drainage cannot be improved. A first object of the present invention is to provide a novel acrylamide-based copolymer polymer which can be used, for example, as a component of a papermaking additive, and a papermaking additive and paper using the copolymer. A second object of the present invention is to
Despite imparting excellent drainage and retention properties, a branched structure is formed using a conventionally known papermaking additive composed of an acrylamide polymer having a relatively low molecular weight or a known polyfunctional vinyl monomer. Acrylamide-based copolymer polymer, which is used as a papermaking additive that can maintain the same or higher paper strength as compared to papermaking additives composed of a high molecular weight acrylamide-based polymer with And a papermaking additive using the same. A third object of the present invention is to affect the conditions for papermaking, such as deterioration of the supply of virgin pulp as a raw material, an increase in the amount of impurities in white water generated during the papermaking process, and fluctuations in papermaking pH. An object of the present invention is to provide a polymer of an acrylamide copolymer used as a papermaking additive that can cope with variations in various factors, and a papermaking additive and paper using the copolymer. A fourth object of the present invention is to provide a polymer of an acrylamide copolymer which is used as a papermaking additive effective for improving productivity due to speeding up of a paper machine or for improving paper quality, and this copolymer. And a papermaking additive using the same.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that acrylamide-based polymers and the like having a high molecular weight using a known polyfunctional vinyl monomer are used for papermaking. Unlike additives, papermaking additives consisting of polymers of acrylamide copolymers having tetraallyloxyethane as a copolymer component are superior to conventional papermaking additives while maintaining the same paper strength. It has been found that the present invention imparts drainage and retention, and the present invention has been completed. That is, the present invention provides (1), (a) an acrylamide, (b) an anionic vinyl monomer, (c) a cationic vinyl monomer,
And (d) an acrylamide copolymer obtained by polymerizing a monomer containing tetraallyloxyethane. Further, the present invention provides (2)
(A) acrylamides 97.995 to 55 mol%,
(B) 1 to 20 mol% of an anionic vinyl monomer,
(C) 1-20 mol% of a cationic vinyl monomer,
(D) Tetraallyloxyethane 0.005 to 5 mol%
An acrylamide copolymer obtained by polymerizing a monomer containing: (3) a papermaking additive containing the acrylamide copolymer polymer of (1) or (2), (4), An object of the present invention is to provide a paper containing a polymer of the acrylamide copolymer (1) or (2).

The polymer of the acrylamide copolymer of the present invention is obtained by polymerizing a monomer containing (a) acrylamides, (b) an anionic vinyl monomer, (c) a cationic vinyl monomer, and (d) tetraallyloxyethane. It is a copolymer obtained by the above. Examples of the “(a) acrylamides” (sometimes referred to as “(a) component”) include, for example, N-methyl (meth) acrylamide, N-ethyl (meth), in addition to acrylamide and methacrylamide. Acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nt
N-substituted (meth) such as octyl (meth) acrylamide
Acrylamide and the like can be mentioned, and these may be used alone or in combination of two or more. Among these, (meth) acrylamide is preferred.

The above-mentioned "(b) anionic vinyl monomer" (sometimes referred to as "component (b)") includes, for example, a carboxyl group-containing vinyl monomer, a sulfonic acid group-containing vinyl monomer and a phosphonic acid group. (-PO
At least one kind of (OH) ₂ ) -containing vinyl monomer can be used. Examples of the carboxyl group-containing vinyl monomer include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated tricarboxylic acids, unsaturated tetracarboxylic acids, and the like, and salts thereof, and the sulfonic acid group-containing vinyl monomers. Examples thereof include unsaturated sulfonic acids and the like and salts thereof. Examples of the phosphonic acid group-containing vinyl monomer include unsaturated phosphonic acids and the like and salts thereof. The species may be used alone, or two or more species may be used in combination.

Examples of the unsaturated monocarboxylic acid include acrylic acid and methacrylic acid, and examples of the salt of the unsaturated monocarboxylic acid include alkali salts such as a sodium salt and a potassium salt of the unsaturated carboxylic acid. Examples thereof include metal salts and ammonium salts.
Specific examples of the unsaturated dicarboxylic acid include, for example, maleic acid, fumaric acid, itaconic acid, and citraconic acid. Specific examples of the unsaturated dicarboxylic acid salts include, for example, unsaturated dicarboxylic acid. And alkali metal salts such as sodium salt and potassium salt, and ammonium salt. Specific examples of the unsaturated tricarboxylic acid include aconitic acid, 3
-Butene-1,2,3-tricarboxylic acid, 4-pentene-1,2,4-tricarboxylic acid and the like,
Specific examples of the unsaturated tricarboxylic acid salts include alkali metal salts such as a sodium salt and a potassium salt of an unsaturated tricarboxylic acid, and ammonium salts. Further, as the unsaturated tetracarboxylic acid, specifically, for example, 1-pentene-1,1,4,4-
Tetracarboxylic acid, 4-pentene-1,2,3,4-tetracarboxylic acid, 3-hexene-1,1,6,6-tetracarboxylic acid and the like, and salts of the unsaturated tetracarboxylic acid Specific examples thereof include alkali metal salts such as a sodium salt and a potassium salt of an unsaturated tetracarboxylic acid, and an ammonium salt.

Specific examples of the unsaturated sulfonic acid include, in addition to those described in the following Examples, vinyl sulfonic acid, styrene sulfonic acid, allyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid Specific examples of the salts of the unsaturated sulfonic acid include alkali metal salts such as sodium salt and potassium salt of the unsaturated sulfonic acid, and ammonium salts. Specific examples of the unsaturated phosphonic acid include, for example, vinylphosphonic acid and α-phenylvinylphosphonic acid.
Specific examples of the unsaturated phosphonic acid salts include alkali metal salts such as the sodium salt and potassium salt of the unsaturated phosphonic acid, and ammonium salts. The anionic vinyl monomer is preferably at least one selected from the group consisting of unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and salts thereof, for example, from the viewpoint of paper quality improving effect and economic efficiency.
Particularly, at least one selected from the group consisting of itaconic acid, acrylic acid and salts thereof is particularly preferred.

In the present invention, "(c) cationic vinyl monomer" (may be referred to as "(c) component").
Examples thereof include dialkylaminoalkyl such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and diethylaminopropyl (meth) acrylate, in addition to those described in Examples described later. Dialkylaminoalkyl (meth) acrylamides such as dialkylaminoalkyl (meth) acrylates, dimethylaminopropyl (meth) acrylamide and diethylaminopropyl (meth) acrylamide, which are esters of alcohol and (meth) acrylic acid, and alkyldiallylamine And amino group-containing vinyl monomers such as allylamines such as dialkylallylamine, diallylamine and allylamine (“tertiary amino group-containing vinyl monomer, 2 Amino group-containing vinyl monomer, and a primary amino group can also contain referred to as vinyl monomer ".), Wherein the amino group-containing vinyl monomer of hydrochloric acid, sulfuric acid, formic acid, salts of inorganic acids or organic acids such as acetic acid, the 3
Secondary amino group-containing vinyl monomer and alkyl halides such as methyl chloride and methyl bromide, aralkyl halides such as benzyl chloride and benzyl bromide, dimethyl sulfate, diethyl sulfate, epichlorohydrin, 3-
Vinyl monomers containing a quaternary ammonium salt obtained by reaction with a quaternizing agent such as chloro-2-hydroxypropyltrimethylammonium chloride and glycidyltrialkylammonium chloride, for example, 2-hydroxyN, N, N, N ', N'-pentamethyl-N'-
[3-{(1-oxo-2-propenyl) amino} propyl] -1,3-propanediaminium dichloride and the like may be used alone or in combination of two or more. You may.

In the present invention, “(d) tetraallyloxyethane” (sometimes referred to as “component (d)”) can be represented by the following chemical formula 1.

[0014]

Embedded image

In addition to the above components (a) to (d), if desired, any nonionic vinyl monomer (e) copolymerizable therewith may be copolymerized. Examples of the (e) nonionic vinyl monomer (sometimes referred to as “component (e)”) include esters of alcohol and (meth) acrylic acid, (meth) acrylonitrile, styrene, styrene derivatives, vinyl acetate, Examples thereof include vinyl propionate and methyl vinyl ether. These may be used alone or in combination of two or more.

When producing the copolymer of the present invention, in addition to the above components (a) to (e), (f) a polyfunctional monomer (sometimes referred to as "(f) component"). Can be used together. Examples of the component (f) include bifunctional vinyl monomers such as di (meth) acrylates, bis (meth) acrylamides and divinyl esters, epoxy acrylates, urethane acrylates, trifunctional vinyl monomers, Functional vinyl monomers, water-soluble aziridinyl compounds and the like,
These may be used alone or in combination of two or more. Examples of the component (f) include, in addition to the above, a water-soluble polyfunctional epoxy compound and a silicon-based compound. These may be used alone or in combination of two or more. You may.

The di (meth) acrylates include:
For example, ethylene glycol di (meth) acrylate,
Examples thereof include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and glycerin di (meth) acrylate, and these may be used alone. Two or more kinds may be used in combination. Examples of the bis (meth) acrylamides include methylenebis (meth) acrylamide, ethylenebis (meth) acrylamide, hexamethylenebis (meth) acrylamide, N, N′-bisacrylamideacetic acid, N, N′-bisacrylamide Methyl acetate,
N, N-benzylidenebisacrylamide and the like can be mentioned, and these may be used alone or in combination of two or more. Examples of the divinyl esters include divinyl adipate and divinyl sebacate. These may be used alone or in combination of two or more. Examples of the bifunctional vinyl monomer other than the above include, for example, allyl (meth) acrylate, diallyl phthalate, diallyl maleate, diallyl succinate, diallyl acrylamide, divinylbenzene, diisopropenylbenzene,
N, N-diallylmethacrylamide, N-methylolacrylamide, diallyldimethylammonium, diallylchlorendate, glycidyl (meth) acrylate, etc., may be used alone or in combination of two or more. You may use together.

The trifunctional vinyl monomers include, for example, 1,3,5-triacryloylhexahydro-S-triazine, triallyl isocyanurate,
N, N-diallylacrylamide, triallylamine,
Triallyl trimellitate and the like can be mentioned, and these may be used alone or in combination of two or more. Examples of the tetrafunctional vinyl monomer include tetramethylol methane tetraacrylate, tetraallyl pyromellitate, N, N, N ', N'-tetraallyl-1,4-diaminobutane, tetraallylamine salt, tetraallylamine Oxyethane and the like can be mentioned,
These may be used alone or in combination of two or more.

The water-soluble aziridinyl compounds include, for example, tetramethylolmethane-tri-β-aziridinylpropionate, trimethylolpropane-
Tri-β-aziridinylpropionate, 4,4′-bis (ethyleneiminecarbonylamino) diphenylmethane and the like can be mentioned. These may be used alone or in combination of two or more. Is also good. Examples of the water-soluble polyfunctional epoxy compound include (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, (poly) glycerin diglycidyl ether, and (poly) glycerin triglycidyl ether. These may be used alone or in combination of two or more. Examples of the silicon-based compound include 3- (meth) acryloxymethyltrimethoxysilane, 3- (meth) acryloxypropyldimethoxymethylsilane,
-(Meth) acryloxypropyltrimethoxysilane,
3- (meth) acryloxypropylmethyldichlorosilane, 3- (meth) acryloxyoctadecyltriacetoxysilane, 3- (meth) acryloxy-2,5-dimethylhexyldiacetoxymethylsilane, vinyldimethylacetoxysilane, etc. And these are 1
The species may be used alone, or two or more species may be used in combination.

In the present invention, the above components (a) to (f)
The copolymerization ratio of each of the components can be determined in consideration of the performance of the obtained copolymer as a papermaking additive, and the following ranges are preferable. (A)
The amounts of components to be copolymerized for component (d) are as follows:
With respect to the total molar amount of the monomer components used, (a)
The component is usually 97.995 to 55 mol%, preferably 9
5.99 to 68 mol%, component (b) is usually 1 to 20 mol%, preferably 2 to 15 mol%, and component (c) is usually 1 to
20 mol%, preferably 2 to 15 mol%, and component (d) is usually in the range of 0.005 to 5 mol%, preferably 0.01 to 2 mol%. When the amount of the component (d) for copolymerization is less than 0.005 mol%, the paper strength enhancing effect and the drainage effect may be low, and the amount of the component (d) is 5 mol%. %, The resulting polymer may be reduced in water solubility to show water insolubility, the viscosity of the polymer may be excessively increased, or gelled.

The amount of component (e) for copolymerization is usually 25 mol% or less, preferably 20 mol% or less, based on the total molar amount of the monomer components used.
Within such a range, when this papermaking additive is used, a sufficient paper strength enhancing effect and a drainage effect can be exhibited more effectively. Further, the compounding amount for copolymerization of the (f) polyfunctional monomer is preferably 5 mol% or less based on the total molar amount of the monomer.

The synthesis of the acrylamide-based copolymer in the present invention can be carried out by various conventionally known methods. For example, the monomer components, for example, the components (a) to (c) may be adjusted to a concentration of 2 to 40% by weight, preferably 5 to 30% by weight in a predetermined reaction vessel.
The components, or the components (a) to (c) and (e), the component (d), and water as a solvent (an organic solvent may be used in combination), a polymerization initiator, For example, a radical polymerization initiator is added, and if necessary, alkyl mercaptans, thioglycolic acid or its esters, isopropyl alcohol, allyl alcohol,
Using a known chain transfer agent such as methallyl sulfonic acid or its sodium salt or ammonium salt as appropriate, under stirring,
It can be performed by heating. of course,
Each of the components (a) to (f) can be mixed and polymerized in a solvent according to the characteristics of the components to be used. , A so-called continuous dropping method (also referred to as “continuous addition”), and a method in which the reaction is carried out.

As the polymerization initiator, known ones can be used, for example, sodium persulfate, potassium persulfate,
Persulfates such as ammonium persulfate, peroxides such as hydrogen peroxide, benzoyl peroxide, tert-butyl hydroperoxide and di-tert-butyl peroxide; bromates such as sodium bromate and potassium bromate; Sodium borate, potassium perborate, perborate such as ammonium perborate, sodium percarbonate, potassium percarbonate, percarbonate such as ammonium percarbonate, sodium perphosphate, potassium perphosphate, and superphosphorus Superphosphates such as ammonium phosphate, and azobisisobutyronitrile;
2,2′-azobis-2-amidinopropane hydrochloride,
Azo compounds such as 2,2'-azobis-2,4-dimethylvaleronitrile, 4,4'-azobis-4-cyanovaleric acid and salts thereof can be exemplified. In this case, 1
A single species can be used, but two or more species may be used in combination, or a redox polymerization initiator may be used in combination with a reducing agent. Examples of the reducing agent include sulfite, hydrogen sulfite, N,
Organic amines such as N, N ', N'-tetramethylethylenediamine; reducing sugars such as aldose; One of these reducing agents may be used alone, or two or more thereof may be used in combination.

By the above polymerization reaction, the polymer of the acrylamide-based copolymer in the present invention can be obtained, for example, as a polymerization reaction product solution of an aqueous solution. From the polymerization reaction product solution, the copolymer is isolated. The copolymer may be purified, and the copolymer may be used for an appropriate purpose.
The copolymer in the present invention thus obtained can be represented by at least the following general formula (Chemical Formula 2). When the above-mentioned components (e) and (f) are used, these are also structural units. , The number of repetitions.

[0025]

## STR2 ##-(acrylamide monomer unit) p- (anionic vinyl monomer unit) q- (cationic vinyl monomer unit) k- (tetraallyloxyethane monomer unit) j- In this formula, acrylamide monomer unit Is
The monomer unit when the acrylamide is incorporated into the main chain of the polymer by polymerization, the anionic vinyl monomer unit is a monomer unit when the anionic vinyl monomer is incorporated into the main chain of the polymer by polymerization The cationic vinyl monomer unit indicates a monomer unit when the cationic vinyl monomer is incorporated into the main chain of the polymer by polymerization, and the tetraallyloxyethane monomer unit is formed by the polymerization of the tetraallyloxyethane. It shows the monomer unit when incorporated into the main chain of the polymer.

In the above formula, p, q, k, and j indicate the number of repeating units, and p is usually 97.
999 to 55, q is usually 1 to 20, k is usually 1 to 20, and j is usually 0.005 to 5. Among the copolymers represented by the general formula (Formula 2), preferred copolymers are at least the following general formulas (Formula 3) to (Formula 5)
(Including the quaternary compound of (Chem. 5)) and a monomer unit incorporated into the main chain of the polymer by polymerizing tetraallyloxyethane.

[0027]

Embedded image However, in the formula, R ¹ represents a hydrogen atom or a methyl group,
R ² represents an -NR ³ R ^4, R ³ represents a hydrogen atom, or a lower alkyl group having a carbon number of 1 to 8, R ⁴ is a hydrogen atom,
Or a lower alkyl group having 1 to 8 carbon atoms, and R ³ and R ⁴ may be the same or different. p has the same meaning as described above.

[0028]

Embedded image However, in the formula, R ⁵ represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms such as a methyl group, and R ⁶ represents a hydrogen atom or-
R ⁷ represents a hydrogen atom, a lower alkyl group having 1 to 5 carbon atoms such as a methyl group, or —CH ₂ COOH. q has the same meaning as described above.

[0029]

Embedded image Wherein R ⁸ represents a hydrogen atom or a methyl group;
⁹ represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms, R ¹⁰ represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms, and R ⁹ and R ¹⁰ are different even if they are the same. May be. X is O or NH, and k has the same meaning as described above. i shows the integer of 1-5.

The quaternary compound of the formula (5) can be obtained by adding the above-mentioned monomer of the formula (5) to an alkyl halide such as methyl chloride or methyl bromide, an aryl halide such as benzyl chloride or benzyl bromide, dimethyl sulfate, diethyl sulfate or epichlorohydride. It can also be obtained by reacting a quaternizing agent such as phosphorus, 3-chloro-2-hydroxypropyltrimethylammonium chloride and glycidyltrialkylammonium chloride.

Since tetraallyloxyethane has four copolymerizable double bonds in the molecule, the monomer unit incorporated into the main chain of the polymer by polymerizing tetraallyloxyethane is uniquely determined. Can not do it. The structure when tetraallyloxyethane is copolymerized with another monomer cannot be unambiguously determined, but is incorporated into the copolymer as a certain monomer unit. The incorporation of tetraallyloxyethane as a monomer unit into the copolymer can be confirmed by an increase in the molecular weight as compared with the case where tetraallyloxyethane is not added. The molecular weight of the copolymer in the present invention, which can be obtained by copolymerizing the above-mentioned various monomers according to the above-mentioned production method, is usually 50,000 to 10,000,000.

The copolymer of the present invention has various uses in addition to the field of papermaking, and particularly when used as an additive for papermaking, the copolymer can exhibit its properties well. As the papermaking additive in the present invention, the polymerization reaction product liquid may be used as it is, and this is preferable, but other components may be added thereto and used, and the paper reaction additive isolated from the polymerization reaction product liquid may be used. The copolymer may be prepared by adding other additive components as needed, or the copolymer isolated from the polymerization reaction product solution may be prepared by adding other additive components as needed. It may also be prepared by dissolving in water so as to have a predetermined concentration. The concentration of the copolymer in the papermaking additive is usually 5 to 40% by weight, preferably 10 to 30% by weight, as a solid concentration.
% By weight. The viscosity of the papermaking additive is generally 1,000 to 100,000 cps (measured at 25 ° C. by a Brookfield rotational viscometer), and preferably 3,000 to 20,000 cps. Note that a sizing agent and other papermaking chemicals can also be included in the papermaking additive, and can be used as one component thereof.

The papermaking additive of the present invention can be added to a wet end portion, for example, in a paper or paperboard manufacturing process. Sulfuric acid bands may be used or not used at all depending on the type of paper. Further, an alkaline substance or an acidic substance may be added to adjust the pH of the paper making as appropriate for use. Also, for example, when producing paper or paperboard in the acidic to neutral or alkaline range, as a pulp raw material, bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, groundwood pulp, mechanical pulp or thermomechanical pulp Bleached or unbleached high yield pulp, newspaper waste, magazine waste,
Any of used paper pulp such as used corrugated paper or deinked used paper can be used. As the pulp raw material,
The pulp raw material, asbestos, polyamide, polyester,
Mixtures with polyolefins and the like can also be used.

In addition to the papermaking additives of the present invention, fillers, dyes, rosin-based sizing agents for acidic papermaking, alkylketene dimer-based sizing agents, alkenylsuccinic anhydride-based sizing agents, and rosin-based sizing agents for neutral papermaking Other papermaking additives such as weakly acidic and neutral to alkaline papermaking sizing agents, dry paper strength improvers, wet strength enhancers, retention improvers, drainage improvers, defoamers, etc. In order to develop physical properties required for paper types, they may be added as needed. Examples of the filler include clay, talc, titanium oxide, heavy or light calcium carbonate, and the like. These may be used alone or in combination of two or more. The amount of the papermaking additive according to the present invention used for the papermaking is usually 0.01 to 8 parts by weight, preferably 0.05 to 2 parts by weight, based on the pulp solids.

Paper containing the acrylamide copolymer polymer of the present invention can be obtained, for example, by papermaking using the above-described papermaking additive of the present invention. Examples of the obtained paper include PPC paper. , Ink-jet recording paper, laser printer paper, foam paper, thermal transfer paper, thermal recording paper, etc., recording paper, art paper, cast coated paper, coated paper such as high quality coated paper, packaging paper such as kraft paper, pure white roll paper, etc. Various types of thick paper, such as notebook paper, book paper, printing paper, newsprint paper, acid paper such as manila ball, white ball, chip ball, paperboard such as high-grade white board, and paperboard such as liner, etc. No.

[0036]

BEST MODE FOR CARRYING OUT THE INVENTION As the above component (a), only acrylamide, acrylamide and methacrylamide (molar ratio: 100: 5 to 15), acrylamide and N, N-dimethylacrylamide (molar 100: 0.2 to 1.2) 3
One kind of a combination of itaconic acid and an alkali salt of methacrylsulfonic acid (molar ratio: 100: 5 to 21) as the component (b), and only acryloyloxyethyldimethylbenzylammonium chloride as the component (c), dimethylaminoethyl In two types of methacrylate and methacryloyloxyethyldimethylbenzylammonium chloride (molar ratio: 100: 50 to 150), all combinations using all of these components (a) to (c), that is, six combinations, Further, the above-mentioned component (d) is copolymerized with various kinds of monomers in a total of 12 combinations of 6 types in which one type of acrylonitrile is added as the component (e). At that time, when the components (a) to (c) and the component (d) are copolymerized, the component (a) is used in a molar ratio of 88.9.
7-94.98, component (b) 2.0-4.0, (c)
The component is 3.0 to 7.0, and the component (d) is 0.020 to 0.1.
030, and when the components (a) to (c) and the component (e) and the component (d) are copolymerized, (a)
83.97 to 93.98 of the component, 2.0 to 2.0 of the component (b)
4.0, component (c) is 3.0 to 7.0, component (e) is 1.0 to 5.0, and component (d) is 0.020 to 0.030.
It is preferable that The mixture of the monomers of each of these combinations is mixed with water, the pH is adjusted to 3 to 4 with a mineral acid, and the mixture is heated and polymerized using a radical polymerization initiator under an inert gas (for example, 50 to 100). ° C, 1-3 hours),
Solid content 10-30%, viscosity 5000-15000 cps
(25 ° C., using a Brookfield rotational viscometer) A copolymer aqueous solution having a molecular weight of 1,000,000 to 3,000,000 (GPC-LALLS method) is produced and used as a papermaking additive.
A paper made using this papermaking additive is obtained. In this manner, the obtained acrylamide-based copolymer polymer can be a high-molecular-weight polymer having a branched structure, and by using a papermaking additive containing the same, the acrylamide-based copolymer can be obtained. By increasing the hydrogen bonding between the polymer polymer and the cellulose molecules in the pulp to increase the pulp aggregation, and by copolymerizing the component (d), it is possible to improve both drainage and retention. Nevertheless, it can have the same or higher paper strength.

[0037]

The present invention will now be described by way of examples, which should not be construed as limiting the invention. In addition,% is based on weight. Example 1 715.97 g of water was placed in a 1-liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube.
269.42 g of a 50% acrylamide aqueous solution (94.7
6 mol%), dimethylaminoethyl methacrylate
72 g (1.5 mol%), 76% methacryloyloxyethyldimethylbenzylammonium chloride aqueous solution 11.20 g (1.5 mol%), itaconic acid 5.20 g
(2.0 mol%), 13.60 g (0.215 mol%) of a 5% aqueous sodium methallylsulfonate solution and 0.127 g (0.025 mol%) of tetraallyloxyethane were charged, and the pH was adjusted with a 15% aqueous sulfuric acid solution. It was adjusted to 3.0. Then, 9.13 g of a 5% ammonium persulfate aqueous solution was added, the temperature was raised to 80 ° C. under nitrogen gas introduction, and the reaction was carried out for 2 hours. 3.9 copolymer aqueous solution was obtained. This was designated as additive A for papermaking.

Example 2 787.76 g of water was placed in a 1-liter four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube.
238.44 g of a 50% acrylamide aqueous solution (83.8
65% by mole), 17.02 g (10% by mole) of methacrylamide, 28.40 g of an aqueous solution of 76% acryloyloxyethyldimethylbenzylammonium chloride (4.
0 mol%), 5.20 g (2.0 mol%) of itaconic acid,
6.96 g of 5% sodium methallyl sulfonate aqueous solution
(0.11 mol%), tetraallyloxyethane 0.1
27 g (0.025 mol%) were charged. Then, 9.13 g of a 5% ammonium persulfate aqueous solution was added, the temperature was raised to 80 ° C. under nitrogen gas introduction, and the reaction was carried out for 2 hours to obtain a solid content of 15.2.
%, A viscosity (at 25 ° C., using a Brookfield rotational viscometer) of 7,800 cps and a pH of 3.6. This was designated as papermaking additive B.

Example 3 747.12 g of water was placed in a 1-liter four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube.
263.15 g of a 50% aqueous acrylamide solution (92.5
55 mol%), 1.98 g of N, N-dimethylacrylamide
(1.0 mol%), 76% aqueous solution of acryloyloxyethyldimethylbenzylammonium chloride 28.4
0 g (4.0 mol%) and 5.20 g (2.0
Mol%), 5% sodium methallylsulfonate aqueous solution 2
6.57 g (0.42 mol%) and 0.127 g (0.025 mol%) of tetraallyloxyethane were charged. Next, 9.13 g of a 5% ammonium persulfate aqueous solution was added,
The temperature was raised to 80 ° C. under introduction of nitrogen gas, and the mixture was reacted for 2 hours to obtain an aqueous copolymer solution having a solid content of 15.2%, a viscosity (25 ° C., using a Brookfield rotational viscometer) of 5,200 cps and a pH of 3.7. This was designated as papermaking additive C.

Example 4 715.46 g of water was added to a 1-liter four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube.
263.78 g of a 0% acrylamide aqueous solution (92.77
5 mol%), acrylonitrile 2.12 g (2.0 mol%), dimethylaminoethyl methacrylate 4.72 g
(1.5 mol%), 76% aqueous methacryloyloxyethyldimethylbenzylammonium chloride solution11.
20 g (1.5 mol%), 5.20 g of itaconic acid (2.
0 mol%), 12.65 g (0.20 mol%) of a 5% aqueous sodium methallylsulfonate solution, and 0.127 g (0.025 mol%) of tetraallyloxyethane were charged.
Next, 9.13 g of a 5% ammonium persulfate aqueous solution was added, the temperature was raised to 80 ° C. under nitrogen gas introduction, and the reaction was performed for 3 hours.
An aqueous copolymer solution having a solid content of 15.1%, a viscosity of 5400 cps (25 ° C., using a Brookfield rotational viscometer) and a pH of 3.8 was obtained. This was designated as Papermaking Additive D.

Comparative Example 1 705.85 g of water was placed in a 1-liter four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube.
269.29 g of a 50% acrylamide aqueous solution (94.7
15 mol%), 4.72 g (1.5 mol%) of dimethylaminoethyl methacrylate, 11.20 g (1.5 mol%) of a 76% aqueous solution of methacryloyloxyethyldimethylbenzylammonium chloride, 5.2 of itaconic acid
0 g (2.0 mol%), a 1% aqueous methylenebisacrylamide solution (7.71 g, 0.025 mol%), and a 5% aqueous sodium methallylsulfonate solution (16.45 g, 0.26 g).
Mol%) and adjusted to pH 3.0 with a 15% aqueous sulfuric acid solution. Then, a 5% aqueous solution of ammonium persulfate 9,13
g, heated to 80 ° C. under nitrogen gas introduction, and reacted for 2 hours. A copolymer aqueous solution having a solid content of 15.2%, a viscosity (25 ° C., using a Brookfield rotational viscometer) of 6050 cps and a pH of 3.7 was added. I got This was used as paper additive a.

Comparative Example 2 715.95 g of water was placed in a 1-liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube.
269.45 g of a 50% aqueous solution of acrylamide (94.7
7 mol%), dimethylaminoethyl methacrylate4.
72 g (1.5 mol%), 76% methacryloyloxyethyldimethylbenzylammonium chloride aqueous solution 11.20 g (1.5 mol%), itaconic acid 5.20 g
(2.0 mol%) 13.60 g (0.215 mol%) of a 5% aqueous solution of sodium methallylsulfonate, 0.11 g (0.01%) of tetramethylolmethanetetraacrylate
5 mol%) and adjusted to pH 3.0 with a 15% aqueous sulfuric acid solution. Then, 5% aqueous ammonium persulfate solution (9.13)
g, and the mixture was heated to 80 ° C. under nitrogen gas introduction and reacted for 2 hours. A copolymer aqueous solution having a solid content of 15.3%, a viscosity (25 ° C., using a Brookfield rotational viscometer) of 6,100 cps and a pH of 3.7 was added. I got This was used as paper additive b.

Comparative Example 3 In a 1-liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, 715.42 g of water was added.
269.49 g of a 50% acrylamide aqueous solution (94.7
85 mol%), 4.72 g (1.5 mol%) of dimethylaminoethyl methacrylate, 76% methacryloyloxyethyl dimethyl ammonium chloride aqueous solution 1
1.20 g (1.5 mol%), 5.20 g of itaconic acid
(2.0 mol%), 13.6 g (0.215 mol%) of a 5% sodium methallylsulfonate aqueous solution was charged, and 15
The pH was adjusted to 3.0 with an aqueous solution of sulfuric acid. Then, 9,13 g of a 5% aqueous solution of ammonium persulfate was added, the temperature was raised to 80 ° C. under nitrogen gas introduction, and the reaction was carried out for 2 hours to obtain a solid content of 15.3.
%, A viscosity (at 25 ° C., using a Brookfield rotational viscometer) of 5,200 cps and a pH of 3.8. This was designated as papermaking additive c.

Table 1 shows the polymer compositions of the papermaking additives (aqueous solutions of acrylamide-based copolymer polymers) obtained in Examples 1 to 4 and Comparative Examples 1 to 3 and the properties of these papermaking additives. Shown in Abbreviations used in the table are as follows. AAm: acrylamide MAAm: methacrylamide DMAAm: N, N-dimethylacrylamide IA: itaconic acid DM: dimethylaminoethyl methacrylate DMBz: methacryloyloxyethyl dimethylbenzylammonium chloride DABz: acryloyloxyethyldimethylbenzylammonium chloride MBAAm: methylenebisacrylamide SMAS: Sodium methallylsulfonate TMMTA: Tetramethylolmethanetetraacrylate AN: Acrylonitrile

Comparative Example 1 (papermaking additive a) is an example in which tetraallyloxyethane of Example 1 (papermaking additive A) was replaced by methylenebisacrylamide, and Comparative Example 2 (papermaking additive a) was used. b) is an example in which tetraallyloxyethane of Example 1 (papermaking additive A) was replaced with tetramethylolmethanetetraacrylate. Comparative Example 3 (papermaking additive c) is an example not containing tetraallyloxyethane of Example 1 (papermaking additive A).

[0046]

[Table 1]

The performance of the papermaking additives obtained in the above Examples and Comparative Examples was evaluated by the following experiments. ~
In this experiment, the types of pulp raw materials and the pH level of papermaking were taken as factors affecting papermaking, and by changing the conditions along with other factors, differences in paper strength, drainage, and yield were mainly determined. It has been examined. Performance Evaluation 1 Sulfuric acid band was added to pulp slurry of 2.4% concentration adjusted to 359 ml of beaten degree (Canadian Standard Freeness, hereinafter abbreviated as CSF) of waste corrugated paper, 1.0% sulfuric acid band was added to pulp, and pH = 6. The pulp slurry was adjusted to 2.0. Next, the respective acrylamide-based polymer aqueous solutions obtained in the above Examples and Comparative Examples, that is, papermaking additives, were added to each pulp slurry in an amount of 0.3% to the pulp.
% And stirred, then the pulp slurry concentration was reduced to 0.6%
And diluted with water at pH = 6.0, and drained (DD)
T) was measured. Further, a sample for paper strength measurement was prepared by using a pulp slurry to which the papermaking additive was added, making paper with a Noble and Wood sheet machine, and drying with a drum dryer at 100 ° C. for 80 seconds. 80
g / m ² of handmade paper was conditioned for 24 hours at 20 ° C. and 65% RH, and then subjected to each measurement. In addition, the addition rate of the above-mentioned chemicals is a solid content weight ratio to the pulp absolute dry weight. Table 2 shows the measurement results.

[0048]

[Table 2]

Performance Evaluation 2 BKP (L / N = 9/1) S. F. A pulp slurry having a pH of 4.5 was prepared by adding 15.0% of talc to pulp and 1.0% of a sulfuric acid band to pulp to a pulp slurry having a concentration of 2.4% adjusted to 425 ml. . Next, the acrylamide-based polymer aqueous solution obtained in the above Examples and Comparative Examples, that is, papermaking additives, was added to the pulp slurry in an amount of 0.5% based on the pulp,
After stirring, the pulp slurry was diluted with water at pH = 4.5 so as to have a pulp slurry concentration of 0.6%, and the drainage (DDT) and the retention (RDDT) were measured. In addition, a sample for paper strength measurement was made using a pulp slurry to which the papermaking additive was added, using a Noble & Wood sheet machine,
It was dried at 100 ° C. for 80 seconds with a drum dryer, and the obtained handmade paper having a basis weight of 80 g / m ² was dried at 20 ° C. and 65% R
After being conditioned for 24 hours under the condition of H, it was subjected to each measurement. The addition ratio of the above chemicals is the weight ratio of the solid content to the absolute dry weight of the pulp. Table 3 shows the measurement results.

[0050]

[Table 3]

Performance Evaluation 3 BKP (L / N = 9/1) S. F. To a pulp slurry having a concentration of 2.4% adjusted to 425 ml, 15.0% of calcium carbonate was added to pulp, and a sulfuric acid band was added to 1.0% of pulp to prepare a pulp slurry having a pH of 7.0. did. Next, the acrylamide-based polymer aqueous solutions obtained in the above Examples and Comparative Examples, that is, papermaking additives, were added to the pulp slurry in an amount of 0.5% with respect to the pulp, and the pulp slurry concentration was reduced to 0.6%. The resulting solution was diluted with water having a pH of 7.0, and the drainage (DDT) and the retention (RDDT) were measured. In addition, the sample for paper strength measurement, using a pulp slurry to which the papermaking additive was added, papermaking with a Noble and Wood sheet machine, and drying with a drum dryer at 100 ° C. for 80 seconds,
The obtained handmade paper having a basis weight of 80 g / m ² was subjected to
After conditioning for 24 hours under the condition of% RH, the sample was subjected to each measurement. The addition ratio of the above chemicals is the weight ratio of the solid content to the absolute dry weight of the pulp. Table 4 shows the measurement results.

[0052]

[Table 4]

The measurement was performed according to the following method. Specific burst strength: Measured in accordance with JIS P8112. The measurement was performed using a Scott Bond Internal Bond Tester (manufactured by Kumagai Riki Kogyo Co., Ltd.) under the conditions of an adhesive pressure of 1 kg / cm ² and 30 seconds. This indicates internal strength. Ash content: JIS P8 except that the temperature was changed to other than 550 ° C
128. DDT Tappi Journal Vol. 56, No. 10 (19
1973), p. 46, "Dynamic
Using a device similar to the “Drainage jar”, pour 500 ml of the pulp slurry into a jar having a diameter of 7.5 cm,
Open the lower cock while stirring at 600 rpm.
It is filtered through a 00 mesh wire net, and the time required for the filtrate to become constant is measured, and can be used for evaluation of drainage. Here, the time required for the filtrate amount to reach 200 ml was measured. The shorter the time required for the filtrate to reach 200 ml, the better the drainage. RDDT Tappi Apparatus similar to the improved Hercules Dynamic Drainage Tester described on page 171 of the Papermakers Conference (1985) (pulp slurry is poured into a 7.5 cm diameter jar and the mat is stirred at 800 rpm). Of the pulp slurry after the addition of the chemical was poured into a jar, and the filtrate 5
0 ml was collected and the transmittance at 620 nm (TM.
(%)). As a parameter of the fast path retention, this T.D. M. (%) Was used. That is, T. M. A higher (%) indicates that the filtrate is more transparent, and indicates a higher yield of the filler and the fine fibers.

From the results shown in Tables 2 to 4, the papermaking additive of the present invention has the same or higher paper strength as the conventional papermaking additive using a polymer while maintaining the paper strength. It can be seen that excellent drainage and retention effects can be provided. It can also be seen that these can be said by changing the pulp raw material and the type of filler, and changing the papermaking pH and filler level. From these facts, in the present invention, papermaking pH is 4.5 to 7, paper ash content is 5.3 to 9.
It may be 1%, and further expanded to the same effect range as paper making pH 4.0-9.0, ash content of the formed paper 5.0- 10.0%.
In that case, a papermaking method using the above-described papermaking additive may be used. Since the polymer having both the components (b) and (c) in the copolymer component is amphoteric,
Components (a) and (d) are contained in the copolymer component, and at least these components (a) to (d) are contained in the copolymer component, and other components (e) and / or (f) ((e) and ( As for the polymer having at least one of f) in the copolymerization component, the above-mentioned “polymer of acrylamide copolymer” may be referred to as “polymer of amphoteric acrylamide copolymer”.

[0055]

According to the present invention, it is possible to provide a novel acrylamide copolymer polymer which can be used, for example, as a component of a papermaking additive. Despite imparting excellent drainage and retention, by using a conventionally known papermaking additive consisting of a relatively low molecular weight acrylamide polymer or the like, using a known polyfunctional vinyl monomer Compared to paper additives made of high molecular weight acrylamide-based polymers having a branched structure. The paper containing the polymer of the acrylamide copolymer can be provided by using the agent. Further, if papermaking is carried out using the papermaking additive containing the acrylamide copolymer of the present invention, the supply of virgin pulp as a raw material is deteriorated, and the amount of impurities in white water generated during the papermaking process is reduced. It is possible to effectively cope with fluctuations in various factors that affect papermaking conditions such as increase and fluctuations in papermaking pH, thereby making it possible to smoothly perform papermaking operations and increasing the speed of papermaking machines. It can make a great contribution to improving productivity or improving paper quality.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Seiji Kono 17-2 Yawata Kaigandori, Ichihara City, Chiba Prefecture F-term within PCMC Corporation (reference) 4J100 AB07Q AE71S AJ02Q AJ08Q AJ09Q AL08R AM15P AM17P AM21R AN03R AN05R AN14R AP00Q AP01Q BA31R BA32R BA56Q BA64Q CA06 JA13 4L055 AG57 AG65 AG70 AG71 AG72 AG74 AH18 EA32 FA10

Claims (4)

[Claims] 1. An acrylamide copolymer obtained by polymerizing (a) acrylamides, (b) anionic vinyl monomer, (c) cationic vinyl monomer, and (d) monomer containing tetraallyloxyethane. polymer. (2) Acrylamides 97.995 to
55 mol%, (b) anionic vinyl monomer 1 to 20
An acrylamide copolymer obtained by polymerizing a monomer containing (c) 1 to 20 mol% of a cationic vinyl monomer and (d) 0.005 to 5 mol% of tetraallyloxyethane. 3. A papermaking additive comprising the acrylamide copolymer polymer according to claim 1. 4. A paper containing the acrylamide-based copolymer polymer according to claim 1.