JPH08134792A - Additive for papermaking and papermaking method - Google Patents

Abstract

PURPOSE: To provide an additive for papermaking showing excellent freeness, sizing properties and paper strength enhancing effect, comprising a specific polyacrylamide-based copolymer, by making paper in weak acidity to neutrality or alkalinity. CONSTITUTION: This additive for papermaking comprises a water-soluble copolymer obtained by reacting (a) acrylamide with (b) a cationic vinyl monomer such as dimethylaminopropylacrylamide copolymerizable with the component (a), (c) at least one of a vinylphosphonic acid of the formula (R is H, an alkyl, an aryl or an aralkyl) (e.g. α-phenylvinylphosphonic acid) copolymerizable with the components (a) and (b) or its salt, (d) a cross-linkable compound such as methylenebisacrylamide and (e) an anionic vinyl monomer such as itaconic acid or its salt except the compound (c) and/or (f) a nonionic vinyl monomer or its salt. Paper is made in the presence of the additive in weak acidity to neutrality or alkalinity.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyacrylamide papermaking additive and a papermaking method using the same. More specifically, the present invention relates to a papermaking additive that exhibits excellent drainage, retention and paper strength enhancing effects in a papermaking system in the acidic to neutral to alkaline range, and a papermaking method using the same.

[0002]

2. Description of the Related Art Conventionally, in the papermaking process, various papermaking additives have been used in order to improve the productivity and the quality of the paper with the speeding up of the papermaking machine. Above all,
Paper strength enhancers, drainage improvers, retention improvers and the like are important chemicals for improving paper quality and productivity, and the range of use thereof is further widened, and improvements of these chemicals are also in progress. Behind this, there are restrictions on the use of virgin pulp due to the deterioration of raw wood supply conditions, and the need to use recycled paper has become stronger for the purpose of energy saving and effective use of resources, and due to wastewater regulations, etc. The closed rate has increased and the amount of contaminants has increased.

Starch, polyamide polyamine-epichlorohydrin resin, melamine formaldehyde resin, urea formaldehyde resin, and acrylamide-based polymer containing acrylamide as a main component are used as additives for papermaking, depending on the purpose. The system polymers are most widely and commonly used because of their synthetic advantages, performance, ease of use and the like. Due to the hydrogen bonding ability of the carbamoyl group of acrylamide,
It is considered that the dry paper strength is improved because the hydrogen bonds between the cellulose fibers and between the cellulose and the polyacrylamide are strengthened.

As an additive for paper making comprising an acrylamide polymer, an anionic type additive due to its ionic property,
Cationic types and amphoteric types are known. The anion type includes a copolymer of acrylamide and a vinyl monomer having an anion group, a partial hydrolyzate of an acrylamide polymer, and the like. Examples of the cation type include a copolymer of acrylamides and a vinyl monomer having a cation group, a Hoffmann modified product or a Mannich modified product of an acrylamide polymer, and the like.

Examples of the amphoteric type include acrylamides, vinyl monomers having a cation group and vinyl monomers having an anion group, and copolymers of these monomers with a nonionic vinyl monomer and acrylamides. Examples thereof include a Hoffmann modified product of a copolymer with a vinyl monomer having an anion group, or a Mannich modified product. The ionic monomer is introduced to fix the polyacrylamide to the cellulose fiber. The anionic group is fixed to the cellulose fiber by itself through the sulfate band, and the cationic group is fixed by itself.

[0006]

However, in the papermaking industry in recent years, the above-mentioned deterioration of the raw material situation of paper, the speeding up of the papermaking machine, the increase of the amount of impurities in white water generated during the papermaking process and the increase of the papermaking pH. It has various problems related to paper quality such as fluctuation. Further, with the speeding up of paper machines, further drying properties are required. Therefore, the advent of a papermaking additive excellent in drainage, retention, and paper strength enhancing effect, which has not been found in the past, has been awaited.

The present invention has excellent drainage and retention (fine fibers, fillers, sizing agents, paper strength) in the acidic to neutral to alkaline range as compared with conventionally known acrylamide copolymer additives for papermaking. It is an object of the present invention to provide a papermaking additive containing a novel acrylamide copolymer capable of imparting an improving effect and a paper strength enhancing effect, and a papermaking method using the same.

[0008]

Means for Solving the Problems As a result of extensive studies by the present inventors, at least one vinyl phosphonic acid or its salt (c), which has not been used as an additive for papermaking, is used as an acrylamide copolymer. By providing a papermaking additive of the present invention by introducing into the coalescence, by adding the papermaking additive to the pulp slurry, to provide a papermaking method characterized by papermaking in the acidic to neutral to alkaline region Is. That is, the present invention relates to acrylamides (a),
Vinyl monomer having cationic group copolymerizable with component (a) (b), (a), general formula [I] copolymerizable with component (b)

[0009]

Embedded image

At least one of vinylphosphonic acids represented by the formula (wherein R represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group) or a salt thereof (c).
Seeds, a paper-making additive containing a water-soluble copolymer obtained by reacting a crosslinkable compound (d), (a), (b),
A vinyl monomer having an anion group other than (c) component copolymerizable with (c), (d) and the above-mentioned components (a), (b) and (c) or salts thereof (e) are reacted. Papermaking additive containing the obtained water-soluble copolymer, (a), (b), (c), (d) and (a), (b),
A paper-making additive containing a water-soluble copolymer obtained by reacting a nonionic vinyl monomer (f) copolymerizable with the component (c), and (a), (b), (c), (d). ),
A papermaking additive containing a water-soluble copolymer obtained by reacting (e) and (f), and a papermaking method in which the papermaking additive is added to a pulp slurry to make paper in an acidic to neutral or alkaline range. It provides a method.

Copolymers of (meth) acrylamide, a cationic monomer, an α, β-unsaturated carboxylic acid, and a phosphoric acid type monomer are known as papermaking additives containing a phosphorus-containing monomer ( JP-A-2-139495
issue). The phosphoric acid-based monomers disclosed in this publication include 2-hydroxyethyl acrylate and 2-hydroxyethyl acrylate.
Phosphoric acid esters such as hydroxyethyl methacrylate and dimers thereof are mentioned. In this phosphoric acid ester monomer, the phosphoric acid ester functional group is present at a distance of carbon and oxygen or nitrogen atoms from the polymerization active vinyl group.

On the other hand, in the vinylphosphonic acids or salts thereof used in the present invention, the phosphonic acid functional group is directly bonded to the polymerization active vinyl group, and the phosphoric acid ester and the dimer thereof are essentially chemical structures. different. Although the mechanism of action is not clear, in comparison with the performance and effect as an additive for papermaking, the water-soluble copolymer containing the vinylphosphonic acid or salts thereof of the present invention has the above-mentioned phosphoric acid ester and its two amounts. The effect was superior to that of the water-incorporated copolymer in which the polymer was introduced.

Next, the present invention will be described in detail. In the present invention, examples of the acrylamides (a) include N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, in addition to acrylamide and methacrylamide.
N-substituted acrylamides such as N, N-dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nt-octyl (meth) acrylamide and the like can be mentioned, and one of these can be used alone or two or more can be used in combination. Can be used.

Examples of the vinyl monomer (b) having a cation group include dimethylaminoethyl (meth)
Acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate,
Tertiary amino groups such as diethylaminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide or diethylaminopropyl (meth) acrylamide, alkyldiallylamine, dialkylallylamine, diallylamine and allylamine, secondary amino groups,
Vinyl monomers having a primary amino group, or salts thereof with inorganic or organic acids such as hydrochloric acid, sulfuric acid, formic acid and acetic acid,

Alternatively, the above vinyl monomer containing a tertiary amino group and an alkyl halide such as methyl chloride or methyl bromide, an aralkyl halide such as benzyl chloride or benzyl bromide, dimethylsulfate, diethylsulfate,
Vinyl monomers containing a quaternary ammonium salt obtained by reaction with a quaternizing agent such as epichlorohydrin, 3-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 are exemplified, and these can be used alone or in combination of two or more. The above vinylphosphonic acids or salts thereof (c) have the general formula [I]

[0016]

[Chemical 6]

[Wherein R represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group] or a salt thereof, and representative examples thereof include vinylphosphonic acid and isopropenylphosphone. Examples thereof include acids, 1-butene-2-phosphonic acid, α-phenylvinylphosphonic acid, and alkali metal salts such as sodium and potassium salts thereof, ammonium salts and the like. Further, vinylphosphonic acids or salts thereof can be used in combination with one or more vinyl monomers having other anion groups.

Other vinyl monomers having an anion group or salts thereof (e) include monovalent, divalent,
Trivalent, tetravalent unsaturated carboxylic acid or salts thereof,
Monovalent unsaturated carboxylic acids such as (meth) acrylic acid and crotonic acid, divalent unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, muconic acid and citraconic acid, vinyl sulfonic acid, styrene sulfonic acid, Allyl sulfonic acid,
Organic sulfonic acids such as 2-acrylamido-2-methylpropanesulfonic acid or alkali metal salts such as sodium and potassium salts of these various organic acids or ammonium salts, 3-butene-1,2,3-tricarboxylic acid, 4
-Pentene-1,2,4-tricarboxylic acid, aconitic acid, 4-pentene-1,2,3,4-tetracarboxylic acid or their sodium salts, potassium salts, ammonium salts and the like can be mentioned.

Examples of the crosslinkable compound (d) include di (meth) acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate and propylene glycol di (meth) acrylate. Acrylates,
Glycerin di (meth) acrylate, trimethylolpropane / ethylene oxide adduct triacrylate,
Methylenebis (meth) acrylamide, ethylenebis (meth) acrylamide, hexamethylenebis (meth)
Acrylamide, N, N'-bisacrylamide acetic acid,
Bis (meth) acrylamides such as methyl N, N′-bisacrylamide, N, N-benzylidenebisacrylamide, divinyl adipate, divinyl sebacate, divinyl esters, epoxy acrylates, urethane acrylates, allyl (meth) ) Acrylate,
Diallyl phthalate, diallyl malate, diallyl succinate, diallyl acrylamide, divinylbenzene, diisopropylbenzene,

N, N-diallylmethacrylamide, N-
Difunctional vinyl monomers such as methylol acrylamide, diallyl dimethyl ammonium, diallyl chlorendate, glycidyl (meth) acrylate, 1,3,5-
Trifunctional vinyl monomers such as triacryloylhexahydro-S-triazine, triallyl isocyanurate, N, N-diallyl acrylamide, triallylamine, triallyl trimellitate, tetramethylolmethane tetraacrylate, tetraallyl pyromellitate, N ，
N, N ', N'-tetraallyl-1,4-diaminobutane, tetraallylamine salts, tetrafunctional vinyl monomers such as tetraallyloxyethane, tetramethylolmethane-tri-β-aziridinylpropionate, trimethylol Water-soluble aziridinyl compounds such as propane-tri-β-aziridinylpropionate and 4,4′-bis (ethyleneiminecarbonylamino) diphenylmethane,
(Poly) ethylene glycol diglycidyl ether,
(Poly) propylene glycol diglycidyl ether,
Water-soluble polyfunctional epoxy compounds such as (poly) glycerin diglycidyl ether and (poly) glycerin triglycidyl ether,

And 3- (meth) acryloxymethyltrimethoxysilane, 3- (meth) acryloxypropyldimethoxymethylsilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldi Chlorosilane, 3- (meth) acryloxyoctadecyltriacetoxysilane, 3- (meth) acryloxy-2,5-dimethylhexyldiacetoxymethylsilane, 3- (meth) acrylamidopropyltrimethoxysilane, 2- (meth) acrylamidoethyl. Trimethoxysilane, 1- (meth) acrylamidemethyltrimethoxysilane, 2- (meth) acrylamide-2
-Methylpropyltrimethoxysilane, 2- (meth) acrylamido-2-methylethyltrimethoxysilane,
2- (meth) acrylamidoisopropyltrimethoxysilane, 3- (meth) acrylamidopropyltriethoxysilane, N- (2- (meth) acrylamidoethyl) aminopropyltrimethoxysilane, (3- (meth) acrylamidopropyl) oxypropyl Trimethoxysilane,

3- (N-methyl (meth) acrylamide) propyltrimethoxysilane, 3-((meth) acrylamide-methoxy) -3-hydroxypropyltrimethoxysilane, 3-((meth) acrylamide-methoxy) propyltri Methoxysilane, 3- (vinylbenzylaminopropyl) trimethoxysilane, dimethyl-
3- (meth) acrylamido-propyl-3- (trimethoxysilyl) -propylammonium chloride, dimethyl-2- (meth) acrylamido-2-methylpropyl-3- (trimethoxysilyl) -propylammonium chloride, 3- ( (Meth) acrylamidopropylmethyldimethoxysilane, 3- (meth) acrylamidopropyldimethylmethoxysilane, 3- (meth) acrylamidopropylisobutyldimethoxysilane, 2-
(Meth) acrylamidopropylisobutyldimethoxysilane, 2- (meth) acrylamido-2-methylpropylmonochlorodimethoxysilane, 2- (meth) acrylamido-2-methylpropylhydrogendimethoxysilane, 3- (meth) acrylamidopropylbenzyldiethoxy Silane, 3- (meth) acrylamidopropyltriacetoxysilane, 2- (meth) acrylamidoethyltriacetoxysilane,

4- (meth) acrylamidobutyltriacetoxysilane, 2- (meth) acrylamido-2-methylpropyltriacetoxysilane, N- (2- (meth) acrylamidoethyl) aminopropyltriacetoxysilane, 2- (N -Ethyl (meth) acrylamide) ethyltriacetoxysilane, 3- (meth) acrylamidopropyloctyldiacetoxysilane, 1-
(Meth) acrylamidomethylphenyldiacetoxysilane, 3- (meth) acrylamidopropyltripropionyloxysilane, 3- (meth) acrylamidopropyltri (N-methylaminoethoxy) silane, vinyltrichlorosilane, vinylmethyldichlorosilane, divinyldiethyl Chlorosilane, vinylphenyldichlorosilane, vinyldimethylchlorosilane, vinylmethylphenylchlorosilane, vinyldiphenylchlorosilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane,

Vinylisobutyldimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, 3-vinylbenzylaminopropyltriethoxysilane, vinylmethyldiethoxysilane, divinyldiethoxysilane, vinyldimethylethoxysilane, vinyldiphenylethoxysilane, vinyl Triisopropoxysilane, vinyltributoxysilane, vinyldimethylisobutoxysilane, vinyltriphenoxysilane, vinyldimethyl (3-aminophenoxy) silane, vinyldimethyl (4-aminophenoxy) silane, vinyldimethyl (3-methyl-4-) Chlorophenoxy) silane, vinyldimethyl (2-methyl-4-chlorophenoxy) silane, vinyltriacetoxysilane, vinylmethyldiacetoxysilane, vinyl Silicon compounds such as acetoxytrimethylsilane can be exemplified.

By introducing a cross-linking structure with the cross-linking compound (d), the molecules spread and the number of contacts between pulp fibers increases. Therefore, drainage, retention, paper strength effect, etc. are improved. Examples of the nonionic vinyl monomer (f) copolymerizable with the above-mentioned constituent monomers include, for example, esters of alcohol and (meth) acrylic acid, (meth) acrylonitrile, styrene, styrene derivatives, vinyl acetate, vinyl propionate, methyl vinyl ether. Etc. can be illustrated.

In the present invention, the amount of each of the components (a) to (f) to be used must be determined in consideration of the performance of the resulting aqueous copolymerization solution as a papermaking additive. The following ranges are preferable. The amount of component (a) used is 98.95 to 70 mol%, preferably 97.9 to 70 mol%, based on the total molar amount of the monomer components used.
It is 80 mol%. Similarly, the component (b) is 1 to 20 mol%, preferably 2 to 15 mol%, and the amount of the component (c) used is 0.05 to 10 mol%, preferably 0.1 to 5 mol%.
It is in the range of mol%. The component (e) is 0 to 15 mol%,
It is preferably in the range of 0.1 to 10 mol%. The component (f) is 0 to 20 mol%, preferably 0.1 to 10 mol%.
Range. The component (d) is 0.005 to 5 mol% based on the total molar amount of the used monomer components excluding the component (d).
Range.

When the amounts of the components (b) and (c) used are less than the above ranges, the drainage, retention and paper strength enhancing effects are not improved, which is not preferable. On the other hand, when the amount is large, the drainage, the yield and the paper strength are lowered and the cost is increased, which is not preferable. When the amount of the component (d) used is less than 0.005 mol%, drainage, retention and paper strength are not improved, and when it exceeds 5 mol%, the polymer becomes so difficult to handle that it is difficult to have high viscosity or water. It becomes soluble and is not preferable.

The acrylamide polymer used in the present invention can be synthesized by various conventionally known methods. For example, the monomer concentration in a predetermined reaction container is 2 to 4
Charge (a), (b), (c), (d), (e) and (f) components and water so that the amount is 0% by weight, preferably 5 to 30% by weight, and add a radical polymerization initiator. If necessary, a known chain transfer agent such as alkyl mercaptans, thioglycolic acid or its esters, isopropyl alcohol and allyl alcohol is appropriately used and stirred,
The desired acrylamide polymer can be obtained by heating. Of course, (a), (b),
The components (c), (d), (e) and (f) can be subjected to continuous dropping, divided addition, etc. according to the characteristics of the components used.

Examples of the radical polymerization initiator include persulfates such as sodium persulfate, potassium persulfate and ammonium persulfate, hydrogen peroxide, benzoyl peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide and the like. Oxides, bromates such as sodium bromate, potassium bromate, etc., perborates such as sodium perborate, potassium perborate, ammonium perborate, sodium percarbonate, potassium percarbonate, ammonium percarbonate, etc. Examples include percarbonates, sodium perphosphate, potassium perphosphate, ammonium perphosphate and the like. In this case, although it can be used alone, it can also be used as a redox polymerization initiator in combination with a reducing agent.

Examples of the reducing agent include sulfites, hydrogen sulfites, organic amines such as N, N, N ′, N′-tetramethylethylenediamine, and azo compounds such as 2,2′-azobis-2-amidinopropane hydrochloride. And reducing sugars such as aldose and the like. Also, azobisisobutyronitrile, 2,2'-azobis-2-amidinopropane hydrochloride, 2,2'-azobis-2,4-dimethylvaleronitrile, 4,4'-azobis-4-cyanovaleric acid And azo compounds such as salts thereof can also be used. Two or more kinds of these initiators may be used in combination. From the viewpoint of workability, the viscosity of the obtained acrylamide polymer is usually preferably 15,000 cps or less as measured by a Brookfield rotational viscometer.

The papermaking method of the present invention is carried out by adding the papermaking additive of the present invention to, for example, the wet end portion in the process of producing paper or paperboard. Specifically, the papermaking additive of the present invention can be used in an aqueous dispersion of pulp in an amount of 0.01 to 8% by weight of solid content based on the dry weight thereof, and generally 0.05 to 2 Solid content weight% is added. The sulfuric acid band may or may not be used depending on the type of paper. Further, an alkaline substance or an acidic substance may be added to appropriately adjust the papermaking pH before use.

In the present invention, when the papermaking additive is used in a papermaking system using calcium carbonate as a filler, calcium carbonate is generally used in an amount of 5 to 30% based on the dry weight of pulp, and papermaking is carried out at a pH of 7 to 9. . The above-mentioned papermaking additive is added in the same amount as described above in an amount of 0.01 to 8%, generally 0.05 to 2%. The sulfuric acid band can also be added in a papermaking system using calcium carbonate.

According to the papermaking method of the present invention, not only the production of paper / paperboard having excellent paper quality in an acidic papermaking system in which a large amount of sulfuric acid band is added, but also a papermaking system in which calcium carbonate is mixed from a waste paper raw material, for example gypsum Board base paper, coat base paper, medium quality paper,
Can not use general liner, core, sulfuric acid band,
Papermaking system whose use amount is limited to a small amount, for example, neutral pure white roll paper, neutral liner, anticorrosion liner and metal interleaving paper,
It can also be used in papermaking systems where the amount of fixing agent used is limited, such as kraft paper. Papermaking systems using calcium carbonate as a filler, such as neutral printing writing paper, neutral coated base paper, neutral PPC paper, neutral thermosensitive base paper,
It is possible to obtain a paper having the above-mentioned excellent paper quality as a neutral pressure-sensitive base paper, a neutral inkjet paper, and a neutral information paper.

In the production of the above various papers or paperboards in the acidic to neutral or alkaline range, pulp raw materials such as bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, groundwood pulp, mechanical pulp or thermomechanical pulp are used. Any of bleached or unbleached high-yield pulp, used newspaper, used magazine, used corrugated paper, and used paper pulp such as deinked used paper can be used. Further, a mixture of the above pulp raw material and asbestos, polyamide, polyester, polyolefin or the like can also be used.

Fillers, dyes, acidic papermaking rosin-based sizing agents, alkyl ketene dimer-based, alkenyl succinic anhydride-based, specially modified rosin-based sizing agents, etc., weakly acidic and neutral to alkaline papermaking sizing agents, dry paper strength Additives such as improver, wet paper strength improver, retention improver, drainage improver, and defoaming agent may be used as necessary in order to express the physical properties required for each paper type. Good. As a filler,
Examples thereof include clay, talc, titanium oxide, heavy or light calcium carbonate, and one of these may be used alone or two or more thereof may be used in combination.

The papermaking additive of the present invention provides excellent drainage and retention in the papermaking process, and has excellent paper strength and size after papermaking. Further, in particular, when the papermaking additive of the present invention is used in a papermaking method for papermaking in a weakly acidic to neutral to alkaline region, it is revealed that excellent drainage, retention, and paper strength enhancing effects are exhibited. became.

[0037]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. All percentages are by weight. Moreover, the present invention is not limited to the following examples.

Example 1 A 50% acrylamide aqueous solution 13 was placed in a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube.
2.25 g (93.0 mol%), dimethylaminopropylacrylamide 7.8 g (5.0 mol%), 65% vinylphosphonic acid 3.32 g (2.0 mol%), 1% methylenebisacrylamide aqueous solution 1. 54 g (0.01 mol%), isopropyl alcohol 9.02 g, water 31
PH was charged with 8.09 g and 7.28 g of a 15% sulfuric acid aqueous solution.
The temperature was set to 3.0, the temperature was raised to 60 ° C. under introduction of nitrogen gas, and then 5
% Ammonium persulfate aqueous solution 2.28 g and 2% sodium metabisulfite aqueous solution 2.38 g are added, and the mixture is allowed to stand at 80 ° C. for 2 hours.
Reacted for a time, solid content 16.4%, viscosity (25 ° C, Brookfield rotary viscometer used) 7500 cps, pH
An aqueous solution of the copolymer of 3.4 was obtained. This is designated as Papermaking Additive A. The properties of the resulting aqueous copolymer solution are shown in Table 1.

Examples 2 to 6 and Comparative Examples 1 to 5 In Example 1, as shown in Table 1, the types and amounts of the components (a) to (f) were changed, and the types of polymerization initiator and chain transfer agent were changed. , Except that the amount was changed, the same operation as in Example 1 was performed,
An aqueous copolymer solution was obtained. Examples 2-6 and Comparative Examples 1-5
Table 1 shows the properties of the aqueous copolymer solutions obtained in Step 1. In addition, Comparative Example 1 is an example in which acrylic acid is used as the component (e) without containing the components (c) and (f), and Comparative Example 2 is the comparative example 1.
In which the amount of acrylic acid was increased, Comparative example 3 is an example in which itaconic acid was used instead of acrylic acid in Comparative example 1, and Comparative example 4
Is an example in which 2-acryloyloxy acid phosphate is used instead of acrylic acid in Comparative Example 1, and Comparative Example 5 is shown as an example corresponding to JP-A-2-139495.

Application Examples 1-6, Comparative Application Examples 1-5
Papermaking with a pH of 6.5 Corrugated cardboard waste paper
Ratio) and application examples 7 to 12, comparative application examples 6 to 10 (sulfuric acid sulfate).
Papermaking with a pH of 7.0
(Comparison) Beating degree obtained from waste corrugated cardboard (Canadian Standard Freeness, abbreviated as CSF) 350
A pulp slurry having a pH of 6.5 was prepared by adding 1.0% of a sulfuric acid band to pulp to a pulp slurry having a concentration of 2.4% adjusted to ml (Application Examples 1 to 6 and Comparative Application Example 1). For ~ 5). In addition, C.I.
S. F. A pulp slurry having a pH of 7.0 was prepared without adding a sulfuric acid band to a pulp slurry having a concentration of 2.4% adjusted to 350 ml (Application Examples 7 to 12 and Comparative Application Example 6).
For 10).

Then, to each pulp slurry, 0.5% of the aqueous solution of each acrylamide copolymer obtained in the above Examples and Comparative Examples, that is, the papermaking additive was added to the pulp.
%, And sizing agent CC-164 (rosin sizing agent for neutral papermaking, manufactured by Nippon PMC Co., Ltd.) 0.3% were sequentially added and stirred. Dilute the pulp slurry concentration to 0.25% with water with pH 6.5 or pH 7.0,
Paper is made with an Andwood sheet machine, dried with a drum dryer at 110 ° C for 90 seconds, and the basis weight is 80 g /
m ² was obtained (burst strength, tensile strength, Stockigt sizing degree measurement) The two types of hand-made paper and of 170 g / m ² (for compressive strength measurements). The obtained paper has a R.
H. After conditioning the humidity for 24 hours under the conditions described above, each sample was subjected to each measurement. The addition rate of the above chemicals is the weight ratio of solid content to absolutely dry weight of pulp.

The measurement results of the above measurement items are shown in Tables 2 and 3. The measurement items shown in Tables 2 and 3 were performed according to the following methods. Specific compression strength …………………………………………………………………………………………………………………………………… JIS P 8126 Specific burst strength ……………… JIS P 8112 Break length ……………………………………………………………………… 8122 DDT ......... Tap Journal Journal, Vol. 56, No. 10 (1973), p. 46, "D"
Using a device similar to that of the "Dynamic Drainage Jar", a pulp slurry of chemical additives (concentration 0.2
5%) 500 ml is poured into a 7.5 cm diameter jar and 8
Open the lower cock while stirring at 00 rpm, 10
The amount of time required for the amount of filtrate to become constant is measured by filtering with a 0-mesh wire net, and can be used for evaluation of drainage. Here, the time until the amount of filtrate reaches 250 g was measured.

RDDT ..... Tappi Paper
modified Herc, page 171 of the Akers Conference (1985).
ules Dynamic Drainage Tes
Using the same device as ter (a structure in which pulp slurry is poured into a jar with a diameter of 7.5 cm and air is sent from the bottom under stirring at 800 rpm so as not to form a mat, stirring and air supply are stopped and filtration is performed at the same time) Then, 500 ml of pulp slurry (concentration: 0.25%) after addition of chemicals is poured into a jar, 50 ml of this filtrate is collected, and the transmittance (TM.%) At 620 nm is measured. As a parameter of the first pass retention, this T.S. M.
(%) Was used. That is, T. M. The higher (%),
It shows that the filtrate is transparent and that the yield of the filler and the fine fibers is high.

Application Examples 13-18, Comparative Application Examples 11-15
(Comparison with paperboard pH 5.5 papermaking paper system) C.I. S. F. A pulp slurry having a pH of 5.5 was prepared by adding 1.5% of a sulfuric acid band to pulp to a corrugated cardboard waste paper pulp slurry having a concentration of 2.4% adjusted to 360 ml. Then, the pulp slurry was mixed with a rosin sizing agent for acidic papermaking AL-120 (manufactured by Japan PMC Co., Ltd.) with stirring.
0.5%, 0.5% each of the acrylamide copolymer aqueous solutions obtained in the above Examples and Comparative Examples, that is, 0.5% of the papermaking additive was sequentially added to the pulp.

Dilute the pulp slurry concentration to 0.25% with water having a pH of 5.5, make paper with a sheet machine made by Noble and Wood, and dry with a drum dryer at 110 ° C. for 90 seconds. Amount 80 g / m ² (for burst strength, tensile strength, Steckit's size measurement) and 1
Two types of handmade paper of 70 g / m ² (for measuring compression strength) were obtained. The obtained paper has a R. H. After conditioning the humidity for 24 hours under the conditions described above, each sample was subjected to each measurement. The addition rate of the above chemicals is the weight ratio of solid content to dry weight of pulp. The measurement results are shown in Table 4.

Application Examples 19 to 24, Comparative Application Examples 16 to 20
(Papermaking system using a pH 8.0 calcium carbonate
Contrast) C.P. with BKP L / N = 8/2 S. F. 400 ml
Calcium carbonate (Tama Pearl-121S: Okutama Kogyo Co., Ltd.)
And a sulfuric acid band were added to the pulp at 10% and 1.5%, respectively, to prepare a pulp slurry having a pH of 8.0. Then, the pulp slurry was added with the papermaking additive obtained in the above Examples and Comparative Examples at 0.5% with respect to the pulp,
The sizing agent CC-164 was sequentially added at 0.5% and stirred.

Diluted with water having a pH of 8.0 to a pulp slurry concentration of 0.25%, and further stirring the retention agent Hymolok NR-12MLS (manufactured by Hymo Co., Ltd.) 0.0.
1% was added, papermaking was carried out with a sheet machine made by Noble and Wood, and dried with a drum dryer at 100 ° C. for 80 seconds to obtain a handmade paper having a basis weight of 80 g / m ² . The obtained paper has a R. H. After conditioning the humidity for 24 hours under the above conditions, the samples were subjected to each measurement. In addition, the addition rate of the above chemicals is the weight ratio of solid content to absolutely dry weight of pulp.

The measurement results are shown in Table 5. The measurement items shown in Table 5 were performed according to the following methods. Specific rupture degree, breaking length,
The Stoeckigt sizing degree, DDT, and RDDT were measured by the same method as described above. Internal strength (Scott bond) ... An internal bond tester (manufactured by Kumagai Riki Kogyo Co., Ltd.) was used, and the adhesive strength was measured under conditions of 100 kg / cm ² and 30 seconds. Ash content ………… JIS P 8128

Application Examples 25 to 28, Comparative Application Examples 21 and 22
(Papermaking system using a pH 8.0 calcium carbonate
Contrast) C.P. with BKP L / N = 8/2 S. F. 400 ml
Calcium carbonate (Tama Pearl-121S: Okutama Kogyo Co., Ltd.)
And a sulfuric acid band were added to the pulp at 10% and 0.5% respectively to prepare a pulp slurry having a pH of 8.0. Then, the pulp slurry was added with the papermaking additive obtained in the above Examples and Comparative Examples in an amount of 0.25 with respect to the pulp.
%, Amphoteric tapioca starch CATO3210 (manufactured by National Starch and Chemical Co., Ltd.) 0.3%, and sizing agent AS-263 (alkylketene dimer emulsion size agent, manufactured by Japan PMC Co., Ltd.) 0.08% were sequentially added. , Stirred.

Diluted with water having a pH of 8.0 to a pulp slurry concentration of 0.25%, and then stirring retention agent Hymolok NR-12MLS (manufactured by Hymo Co., Ltd.) 0.0.
1% was added, papermaking was carried out with a sheet machine made by Noble and Wood, and dried with a drum dryer at 100 ° C. for 80 seconds to obtain a handmade paper having a basis weight of 80 g / m ² . The obtained paper has a R. H. After conditioning the humidity for 24 hours under the above conditions, the samples were subjected to each measurement. In addition, the addition rate of the above chemicals is the weight ratio of solid content to absolutely dry weight of pulp. The measurement results are shown in Table 6.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

[Table 4]

[0055]

[Table 5]

[0056]

[Table 6]

[0057]

As is clear from the results shown in Tables 2 to 6,
It is clear that the papermaking additive of the present invention has excellent drainage and retention in the papermaking process, and excellent paper strength and size after papermaking, as compared with the chemicals used in Comparative Examples. . In particular, by using the papermaking additive of the present invention in a papermaking method for papermaking in the weakly acidic to neutral to alkaline region, it is clear that excellent drainage, retention, and paper strength enhancing effects are exhibited. Is.

Claims (8)

[Claims] 1. A general formula [I] which is copolymerizable with vinyl monomers (b), (a) and (b) having a cationic group copolymerizable with acrylamides (a) and (a). 1] [Wherein R represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group] and is obtained by reacting at least one kind of vinylphosphonic acids or salts (c) thereof and a crosslinkable compound (d). A papermaking additive containing a water-soluble copolymer. 2. A general formula [I] which is copolymerizable with the vinyl monomers (b), (a) and (b) having a cationic group copolymerizable with the acrylamides (a) and (a). 2] [Wherein R represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group], or at least one of vinylphosphonic acids or salts thereof (c), a crosslinkable compound (d), and the above-mentioned (a). ), (B) and (c) and a water-soluble copolymer obtained by reacting a vinyl monomer having an anion group other than the component (c) and a salt thereof (e) copolymerizable with the component (e). Characteristic papermaking additive. 3. A general formula [I] copolymerizable with the vinyl monomers (b), (a) and (b) having a cationic group copolymerizable with the acrylamides (a) and (a). 3] [Wherein R represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group], or at least one of vinylphosphonic acids or salts thereof (c), a crosslinkable compound (d), and the above-mentioned (a). ), (B), (c) components and a water-soluble copolymer obtained by reacting a nonionic vinyl monomer (f) copolymerizable with the component, a papermaking additive. 4. A general formula [I] which is copolymerizable with the vinyl monomers (b), (a) and (b) having a cationic group copolymerizable with the acrylamides (a) and (a). 4] [Wherein R represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group] or at least one of vinylphosphonic acids or salts thereof (c), a crosslinkable compound (d), and the above (a). , (B), vinyl monomers having an anion group other than the component (c) copolymerizable with the component (c), or salts thereof (e), and (a),
A papermaking additive comprising a water-soluble copolymer obtained by reacting a nonionic vinyl monomer (f) copolymerizable with components (b) and (c). 5. The papermaking machine according to claim 1, wherein the vinylphosphonic acid or salts thereof (c) is vinylphosphonic acid, α-phenylvinylphosphonic acid or salts thereof. Additives. 6. Polymerization of vinylphosphonic acid or a salt thereof (c) in a range of 0.05 to 10 mol% based on the total molar amount of each component used except the component (d) for polymerization. The papermaking additive according to any one of claims 1 to 5, wherein: 7. A papermaking method, which comprises using the papermaking additive according to any one of claims 1 to 6. 8. The papermaking method according to claim 7, wherein the papermaking is performed in a weakly acidic to neutral to alkaline range.