JPH10219590A - Production of paper and paper produced by the method for producing paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impart a prescribed sizing effect in a small amount of a sizing agent and reduce the stains of paper, a paper-making device, etc., by making the paper from a paper-making raw material slurry containing the sizing agent, a phenolic resin-containing sizing auxiliary and a pulp slurry. SOLUTION: This paper is produced from a paper-producing raw material slurry containing (A) a sizing agent (excluding a neutral rosin sizing agent for producing paper), (B) sizing auxiliary containing a phenolic resin and (C) a pulp slurry. The method is useful for producing paper such as printing or writing paper, coated raw paper, PPC paper, ink jet paper, information paper or book paper and for producing paperboards.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a papermaking method and paper produced by the papermaking method, and more particularly, to a papermaking method capable of producing paper having excellent sizing properties and a paper produced by the papermaking method. About paper.

[0002]

2. Description of the Related Art Conventionally, in papermaking methods such as paper or paperboard, sizing has been performed to impart functions such as size, waterproofness, and water resistance to such papers. As the sizing method, for example, using a rosin sizing agent for acidic papermaking having a carboxyl group and a sulfuric acid band,
Acid sizing with sizing in the acid range of 4.5-6.5 has been performed. Further, in recent sizing methods, for example, for the purpose of using waste paper or waste paper containing inexpensive calcium carbonate as a filler, closing water for paper making, imparting the permanent storage of paper, etc., a sizing agent for neutral paper making is used. Neutral sizing using a weakly acidic or weakly alkaline region having a pH of 6 to 9 has been performed.

Examples of the sizing agent used in the sizing method include acid paper sizing agents such as solution rosin sizing agent, acidic rosin emulsion sizing agent, fatty acid soap sizing agent, synthetic sizing agent, ketene dimer sizing agent, and the like.
Neutral papermaking sizing agents such as alkenyl succinic anhydride sizing agents, cationized fatty acid bisamide sizing agents, cationized petroleum resin sizing agents, and cationic polymer sizing agents that can be used in a wide range of acidic to neutral regions Agents and the like are known.

In the sizing agent, if too much sizing agent is used, there are problems such as soiling of paper and devices, adversely affecting paper quality, and adversely affecting other paper making chemicals.

[0005] The acidic papermaking sizing agent has a problem that, for example, if the amount of the sizing agent used is large, the paper and the papermaking apparatus are stained, and foaming occurs in the papermaking process.

[0006] The alkenyl succinic anhydride-based sizing agent for neutral papermaking has a problem that, for example, paper and papermaking equipment are often stained.

The ketene dimer-based sizing agent has a problem that, in addition to stains on paper and paper making equipment, paper is liable to slip, and that printability, toner adhesion, and lamination characteristics of polyethylene and the like are poor. is there.

Further, cationic sizing agents such as the above-mentioned cationized fatty acid bisamide-based sizing agents have a problem of adversely affecting dyes.

[0009] When the amount of the sizing agent is reduced, these problems are reduced. However, when the amount of the sizing agent is too small, the sizing effect is not sufficient. Therefore, the amount of the sizing agent is minimized. Therefore, there is a demand for the development of an effective use method that can obtain a predetermined degree of size.

Conventionally, in order to effectively use such a sizing agent with the smallest possible amount added, for example, cationized starch, cationic polyacrylamide, polyamine-epichlorohydrin resin, polyamine polyamide-epichlorohydrin resin, polyethyleneimine, diallylamine- Cationic sizing aids such as acrylamide copolymers, polyvinylamines and polyamidines have been used in combination with the sizing agents, but have not yet achieved a satisfactory sizing effect.

In addition, the cationic size aid has many problems, for example, the use of the cationized starch has a problem of increasing the drainage load of papermaking water. In the use of epichlorohydrin resin, polyamine polyamide-epichlorohydrin resin, etc., there is a problem in operation such as a decrease in economic efficiency, inferior drying property and disintegration property of broke, or a problem in reducing the effect of other papermaking chemicals such as dyes. Etc.

When the amount of the cationic sizing aid used is increased for the purpose of sufficiently exerting the sizing effect of the sizing agent, it adversely affects the paper quality such as deteriorating the weather resistance of the formed paper. It is preferable to reduce the amount used as much as possible, but if the amount used of the cationic sizing aid is reduced, the sizing effect of the sizing agent cannot be sufficiently exerted.

On the other hand, when the amount of the sizing agent used is increased for the purpose of reducing the amount of the cationic sizing agent used and sufficiently exerting the sizing effect of the sizing agent, the above-described case is considered. Such a sizing agent causes stains on paper and equipment, a decrease in work efficiency in a paper making process, a decrease in paper quality, and the like.

[0014]

As described above, since the conventional sizing agent has various problems, it is possible to reduce the amount of the sizing agent to be used and to produce a paper exhibiting an excellent sizing effect. There is a need for a papermaking method that can be used.

It is an object of the present invention to provide a papermaking method capable of reducing the amount of a sizing agent used and exhibiting an excellent sizing effect, and a paper produced by the papermaking method. .

Another object of the present invention is to provide a papermaking method and a papermaking method capable of preventing a decrease in work efficiency due to dirt on paper and a papermaking apparatus due to a sizing agent and improving workability in a papermaking process. To provide paper manufactured by the company.

[0017]

SUMMARY OF THE INVENTION In order to solve the above problems, the present invention has intensively studied a papermaking method capable of obtaining a predetermined sizing degree by using a small amount of a sizing agent. It has been found that the above object can be achieved by using a size auxiliary agent containing a phenol resin in the production of paper, and the present invention has been completed.

A first means for solving the above-mentioned problems is as follows.
Sizing agent (excluding rosin sizing agent for neutral papermaking)
And a papermaking raw material slurry containing a pulp slurry and a size auxiliary agent containing a phenolic resin, and a second means for solving the above-mentioned problems is as follows. The phenolic resin in the first means is at least a novolak-type resin and / or a resol-type resin obtained by condensation polymerization of (a) formaldehyde and / or paraformaldehyde with (b) phenol and / or substituted phenols, The papermaking method according to the first means, wherein the weight-average molecular weight is from 200 to 10,000, wherein the phenolic resin in the first means is at least (a) Formaldehyde and / or paraformaldehyde, and (b) a substituted phenol represented by the general formula (I) and / or (II) The papermaking method of the first means, which is a novolak resin obtained by condensation polymerization with

[0019]

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(However, R ¹ and R ² are the same or different and represent a linear or branched alkyl group having 1 to 9 carbon atoms, a phenylalkyl group, or a phenyl group.) The means is that the phenolic resin in the first means is polyvinyl phenol and has a weight average molecular weight of 2,000 to 200,000.
0 is the papermaking method of the first means, wherein the phenolic resin in the first means is a copolymer containing a vinylphenol unit, Weight average molecular weight of 2,000 to 20
The papermaking method of the first means, wherein the sizing agent in the first means is a rosin sizing agent for acidic papermaking, a ketene dimer size. Agents, alkenyl succinic anhydride-based sizing agents, cationized fatty acid amide-based sizing agents, cationic polymer-based sizing agents obtained by copolymerizing vinyl monomers, and α-hydroxycarboxylic acid-based sizing agents. Said first to at least one of
A papermaking method according to any one of the fifth means, wherein the sizing agent in the first means is a rosin sizing agent for acidic papermaking, and
PH of the papermaking raw material slurry in the above-mentioned means is 4.5 to 6.5.
The papermaking method according to any one of the first to fifth means, wherein the eighth means for solving the problem is:
The sizing agent in the first means is a ketene dimer-based sizing agent and / or an alkenyl succinic anhydride-based sizing agent, and the papermaking raw material slurry in the first means is adjusted to pH 6 to 9, A ninth means for solving the above-mentioned problems is that the sizing agent in the first means is a cationized fatty acid amide-based sizing agent and a vinyl monomer. And at least one selected from the group consisting of a cationic polymer-based sizing agent and an α-hydroxycarboxylic acid-based sizing agent, and wherein the papermaking raw material slurry in the first means has a pH of 4.5 to 9. An adjusted papermaking method according to any one of the first to fifth means, wherein a tenth means for solving the problem is any one of the first to ninth means. Paper produced by such a papermaking method.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The papermaking method of the present invention is characterized by a sizing agent (excluding a rosin sizing agent for neutral papermaking) and a sizing aid containing a phenolic resin (hereinafter sometimes simply referred to as a phenolic resin). And sizing using a combination of the sizing agent and the phenolic resin, whereby the amount of the sizing agent can be reduced, and a paper exhibiting an excellent sizing effect can be produced. .

(Sizing Agent) As the sizing agent in the present invention, various conventionally known sizing agents other than the rosin sizing agent for neutral papermaking can be used. For example, sizing agents for acidic papermaking and sizing agents for neutral papermaking And acidic to neutral papermaking sizing agents that can be used in a wide range from an acidic region to a neutral region.

The sizing effect can be improved by using any of the sizing agents in combination with the phenol resin-containing sizing aid of the present invention.

Examples of the acidic paper sizing agent include acidic paper rosin sizing agents such as solution rosin sizing agents and acidic rosin emulsion sizing agents, fatty acid soap sizing agents, synthetic sizing agents, and anion-modified petroleum resin sizing agents. Can be mentioned.

The acidic papermaking sizing agent can be added to a pulp slurry as an internal chemical in the acidic papermaking process using a sulfuric acid band, for example.

Examples of the solution rosin sizing agent include rosins such as gum rosin, tall oil rosin and wood rosin, which are reacted with dibasic acids such as maleic acid and fumaric acid, and the like. Aqueous solution partially neutralized or completely neutralized by using one or more of alkalis such as potassium hydroxide, ammonia and the like. Examples of the acidic rosin emulsion sizing agent include, for example, gum rosin, tall oil rosin, rosins such as wood rosin, and mixtures thereof, and maleic acid, fumaric acid, acrylic acid, a reaction product obtained by reacting with an unsaturated carboxylic acid such as itaconic acid. An aqueous liquid produced by emulsifying using a low-molecular surfactant and / or a high-molecular emulsifying dispersant, etc .;
An aqueous liquid produced by emulsifying a mixture obtained by mixing petroleum resins and the like in the same manner as described above (UK Patent No. 8
No. 59787) and the like.

Examples of the fatty acid soap sizing agent include fatty acids having about 8 to 24 carbon atoms, such as palmitic acid and stearic acid, and mixtures thereof with sodium hydroxide,
One or more alkalis such as potassium hydroxide and ammonia may be used in combination to neutralize and form an aqueous solution.

As the synthetic sizing agent, for example, a substituted succinic anhydride obtainable by reacting a dimer to tetramer oligomer of isobutene and a mixture thereof with maleic anhydride may be sodium hydroxide, One or more alkalis such as potassium hydroxide and ammonia may be used in combination to neutralize and form an aqueous solution.

As the anion-modified petroleum resin sizing agent, for example, a petroleum resin is modified with an unsaturated carboxylic acid such as maleic acid, and then, as described above, an alkali, a low molecular surfactant, a polymer emulsifying dispersant, A sizing agent or the like, which is used in combination with an aqueous liquid, may be used. Examples of the petroleum resin include C, such as 1,3-pentadiene and isoprene.
C5 petroleum resin obtained by polymerizing 5-olefin, C9 petroleum resin obtained by polymerizing C9 olefin such as coumarone, indene, C5 / C9 copolymer obtained by copolymerizing C5 olefin and C9 olefin Examples include petroleum resins, dicyclopentadiene-based petroleum resins obtained by polymerizing dicyclopentadiene and derivatives thereof, and the like.

The emulsifiers such as the low-molecular surfactant and / or high-molecular emulsifier can be roughly classified into cationic, anionic, nonionic and amphoteric emulsifiers depending on their ionicity. Irrespective of ionicity, the combined use with the phenolic resin of the present invention has an effect of improving size performance.

As the emulsifier, conventionally known emulsifiers used for a rosin emulsion sizing agent for acids and an anion-modified petroleum resin sizing agent can be used as they are. It is preferable to use a polymer emulsifying dispersant alone or in combination with an alkali or a low molecular surfactant.

Examples of the polymer emulsifying and dispersing agent include natural polymers such as cationized, anionic or amphoteric starch, casein and lecithin, and anionic styrene- (meth) acrylic acid-based copolymers as synthetic polymers. Partially neutralized or fully neutralized polymer, anionic or cationic (meth) acrylate copolymer, anionic or cationic (meth) acrylamide copolymer, cationic Polyaminopolyamide-epichlorohydrin resin, alkylene polyamine-epichlorohydrin resin,
A poly (diallylamine) -epichlorohydrin resin or the like can be suitably used. These polymeric emulsifying and dispersing agents may be used alone or in combination of two or more as protective colloids.

The neutral papermaking sizing agent includes, for example, a ketene dimer sizing agent and an alkenyl succinic anhydride sizing agent.

The ketene dimer sizing agent includes:
For example, a saturated and / or unsaturated fatty acid chloride having about 12 to 24 carbon atoms, such as stearic acid, palmitic acid, lauric acid, oleic acid, and linoleic acid, is dimerized by treating with a base such as triethylamine. And an aqueous liquid which can be produced by emulsifying a ketene dimer or the like obtainable by the above method.

The alkenyl succinic anhydride-based sizing agent includes, for example, a terminal having about 12 to 24 carbon atoms and / or
Or an aqueous liquid which can be produced by emulsifying alkenyl succinic anhydride or the like, which can be obtained by adding maleic anhydride to an internal olefin, and the like.

As the emulsifier, for example, a conventionally known emulsifier used for a ketene dimer sizing agent, an alkenyl succinic anhydride sizing agent, etc. can be used as it is. It is preferable to use a high molecular weight emulsifying dispersant alone or in combination with a low molecular weight surfactant.

Examples of the polymer emulsifying and dispersing agent include starches of any of cationized, anionic and amphoteric types, copolymers of anionic and cationic (meth) acrylate esters, anionic and cationic types. (Meth) acrylamide-based copolymers, and cationic polyaminopolyamide-epichlorohydrin resins, alkylenepolyamine-epichlorohydrin resins,
And any resin such as poly (diallylamine) -epichlorohydrin resin. These polymeric emulsifying and dispersing agents may be used alone or in combination of two or more as protective colloids. In addition, regardless of the ionicity of the emulsifier such as the low-molecular surfactant and / or high-molecular emulsifier / dispersant, the use of the phenol resin in the present invention has an effect of improving the size performance.

Examples of the acidic to neutral papermaking sizing agent which can be used in a wide range from pH 4.5 to 9 in an acidic region to a neutral region include cationized fatty acid bisamide sizing agents and cationized petroleum resins. Examples include a sizing agent, a cationic polymer-based sizing agent, and an α-hydroxycarboxylic acid-based sizing agent.

As the cationized fatty acid bisamide-based sizing agent, for example, a fatty acid having about 12 to 24 carbon atoms is reacted with a polyamine such as diethylenetriamine or triethylenetetramine or a mixture thereof, and then the cationized fatty acid such as epichlorohydrin is used. And a cationized fatty acid bisamide which can be synthesized by reacting with an agent.

Examples of the cationized petroleum resin sizing agent include reacting a maleic acid adduct of petroleum resin with polyamines such as diethylenetriamine and triethylenetetramine and mixtures thereof, and then reacting with a cationizing agent such as epichlorohydrin. A cationized petroleum resin that can be synthesized by reacting can be exemplified.

Examples of the petroleum resin include the C5 petroleum resin, the C9 petroleum resin, the C5 / C9 copolymer petroleum resin, the dicyclopentadiene petroleum resin, and the like.

The cationized fatty acid bisamide and the cationized petroleum resin generally have self-dispersibility. Therefore, an aqueous liquid can be prepared by simply stirring a mixture of these cationized fatty acid bisamides, the cationized petroleum resin, and the like and water without the aid of an emulsifier or a dispersant. Emulsifiers used for sizing agents may be used.

Examples of the cationic polymer sizing agent include cationic vinyl monomers such as dimethylaminoethyl methacrylate and hydrophobic monomers such as styrene, acrylonitrile and alkyl (meth) acrylate in water and / or an organic solvent. And a cationic polymer which can be synthesized by radical copolymerization.

Examples of the α-hydroxycarboxylic acid-based sizing agent include α-hydroxycarboxylic acids which can be produced by reacting a higher alcohol or a higher amine with an oxyacid such as citric acid. JP-B-7-56119, JP-A-1-16899
No. 4).

Among the above sizing agents, ketene dimer sizing agents are preferred.

(Size Aid) As the phenol resin in the present invention, a conventionally known phenol resin can be used.

The method of synthesizing the phenol resin is described, for example, in Shinichi Murayama, “Plastic Materials Course Vol. 15, Phenol Resin” (published by Nikkan Kogyo Shimbun). Examples of the phenol resin include phenol and phenol. And / or substituted phenols and formaldehyde and / or paraformaldehyde, such as phenolic resin, sulfonated phenolic resin, amine-modified phenolic resin, amide-modified phenolic resin, amine-amide-modified phenolic resin, trimethylolphosphine oxide, etc. Examples thereof include a phenol resin using a phosphorus-containing compound as a crosslinking agent, a rosin-modified phenol resin, and an oil-modified rosin phenol resin.

Any of the above phenolic resins can be employed in the present invention as a single kind or as a mixture of plural kinds.

The phenol resin is preferably a phenol resin obtained by polycondensation of phenol and / or a substituted phenol with formaldehyde and / or paraformaldehyde.

Examples of the substituted phenols include:
Examples thereof include phenols having 1 or 2 alkyl groups, alkenyl groups, and aryl groups having 1 to 12 carbon atoms, phenols having other hydroxyl groups, sulfonic acid groups, and the like. Can be adopted.

Specific examples of the above substituted phenols include:
p-cresol and its isomers (isomers are o- or m-
-Means regioisomers such as cresol. The same applies hereinafter. ), P-ethylphenol and its isomers, 3,5
-Xylenol and its isomers, β-naphthol and its isomers, o-cresolsulfonic acid and its isomers,
pt-butylphenol and its isomers, p-phenylphenol and its isomers, p-octylphenol and its isomers, p-nonylphenol and its isomers,
Examples thereof include p-phenolsulfonic acid and isomers thereof.

The phenolic resin obtained by condensation polymerization of phenol and / or substituted phenols with formaldehyde and / or paraformaldehyde is usually prepared in water or in an organic solvent such as toluene or methyl ethyl ketone in the presence of phenol and / or substituted phenols. And formaldehyde and / or paraformaldehyde in a temperature range of about room temperature to about 180 ° C. for about 30 minutes to about 12 hours.

In carrying out this reaction, a catalyst can usually be used. As this catalyst, for example, inorganic acids and organic acids such as sulfuric acid and oxalic acid, magnesium oxide,
Potassium hydroxide, calcium hydroxide, sodium carbonate,
Examples thereof include oxides, hydroxides, carbonates, and chlorides of alkali metals and alkaline earth metals such as sodium chloride.

Depending on the type of the catalyst and reaction conditions such as the reaction temperature, for example, the molar ratio of formalin, the novolak-type phenol resin (hereinafter sometimes referred to as novolak-type resin) or the resol-type phenol resin (hereinafter, referred to as the novolak-type phenol resin). May be referred to as resole type resin).
Either the novolak-type resin or the resol-type resin may be used in the present invention.

The molecular weight of the novolak type resin and the resol type resin is preferably in the range of 200 to 10,000, more preferably in the range of 400 to 6,000.

As the phenol resin, for example, an amine-modified phenol resin, an amide-modified phenol resin, an amine-amide-modified phenol resin and the like can be used.
These modified phenolic resins include, for example, the novolak-type resin and / or the resole-type resin, an amine and / or
Alternatively, it can be obtained by reacting an amide compound with a formaldehyde condensate.

Further, as the phenol resin, a modified phenol resin such as a sulfonated phenol resin obtained by treating the novolak resin and / or the resol resin with sodium sulfite or the like can be used.

In the modified phenolic resin, a modified phenolic resin obtained by reacting the novolak-type resin with a formaldehyde condensate of an amine and / or an amide compound, and the novolak-type resin in the sulfonated phenolic resin are sodium sulfite. The sulfonated phenolic resin obtained by treatment with the above is preferable since the amount of residual formalin in the resin can be further reduced.

The phenolic resin of the present invention can exhibit an excellent sizing effect when used as a size aid, but the phenolic resin and / or substituted phenols are combined with formaldehyde and / or paraformaldehyde. A phenolic resin obtained by condensation polymerization with phenol, a modified phenolic resin obtained by reacting the novolak-type resin and / or the resole-type resin with a formaldehyde condensate of an amine and / or an amide compound, and the sulfonated phenol In resins and the like, it is preferable to reduce the amount of residual formalin in the phenolic resin.When the novolak-type resin and the resole-type resin are used in combination in the phenolic resin, for example, the resole-type resin is usually a base. Using a catalytic catalyst However, since it is obtained by reacting in the presence of excess formaldehyde, by increasing the ratio of the novolak type resin in the composition of the novolak type resin and the resol type resin, the amount of residual formalin in the resin can be further increased Can be reduced.

In contrast to the resol type resin having a large number of highly reactive methylol groups, the novolak type resin obtained by using an acidic catalyst usually has stability with time of the resin itself, and Since the aqueous liquid has excellent stability over time when the resin is converted to an aqueous liquid, the novolak-type resin can be more suitably employed in the present invention.

Further, phenolic resins which can be suitably employed in the present invention include (a) formaldehyde and / or paraformaldehyde, and (b) substituted phenols (I) and / or ( It is preferable to contain a novolak-type resin obtained by reacting with II).

[0063]

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(However, R ¹ and R ² are the same or different and represent a linear or branched alkyl group having 1 to 9 carbon atoms, a phenylalkyl group, or a phenyl group.) Generally, a phenol resin has a substituent. Phenol itself can be synthesized using phenol itself as the main raw material. In this case, the reaction with formalin occurs mainly at the ortho and para positions of the phenol. In other words, phenol can be regarded as a trifunctional cross-linking agent, which makes it difficult to control the reaction with formalin, and when synthesizing a residual phenolic resin having a low content of formalin or residual phenol,
It is difficult to set the charging ratio of formaldehyde and phenol. Therefore, in the present invention, the above-mentioned general formula (I)
And / or in the ortho or para position represented by (II),
Substituted phenols having one substituent can be more preferably employed.

By using the substituted phenols represented by the general formulas (I) and / or (II), the amount of residual formalin and the amount of residual phenol in the obtained phenol resin can be further reduced.

Further, the compounds represented by the general formulas (I) and / or (II)
In the case where the substituted phenol represented by the formula (1) is employed, the size of the obtained phenol resin is reduced as compared with the case where the substituted phenol represented by the formula (I) and / or (II) is not employed. The effect as an agent can be further improved.

Specific examples of the substituted phenols (I) and the substituted phenols (II) include o- or p-cresol, o- or p-ethylphenol, o- or p-
-T-butylphenol, o- or p-phenylphenol, o- or p-octylphenol, o- or p-
Cumylphenol and the like can be mentioned, and these can be used alone or in combination of two or more.

When the substituted phenols (I) and / or (II) or a mixture of these are reacted with formaldehyde and / or paraformaldehyde, the amount of phenols and / or paraformaldehyde is not adversely affected in controlling the residual amount of phenols and formaldehyde. Alternatively, other substituted phenols or phenol may be partially used.

Specific examples of the other substituted phenols include m-cresol having a substituent at the meta position, m-ethylphenol, mt-butylphenol, m-phenylphenol, m-octylphenol, and m-cumyl. 2,3-xylenol, 2,4-xylenol having two substituents such as phenol and m-phenolsulfonic acid;
2,5-xylenol, 2,6-xylenol, 3,4
-Xylenol, 3,5-xylenol, α-naphthol, β-naphthol, o-cresolsulfonic acid, etc., 2,3,5-trimethylphenol having three substituents, catechol having a plurality of phenolic hydroxyl groups, resorcinol, 4-t-butylcatechol, 2-t-butylhydroquinone and the like can be mentioned, and these can be used alone or in combination of two or more.

The respective components used in the synthesis of a novolak phenol resin obtained by reacting the above (a) formaldehyde and / or paraformaldehyde with the above (b) substituted phenols (I) and / or (II) The molar ratio is
It is preferable to make the formaldehyde and / or paraformaldehyde (a) 70 to 150 mol as formaldehyde with respect to 100 mol of the (b) substituted phenols (I) and / or (II).

Further, the above-mentioned other substituted phenols (hereinafter, referred to as “substituted phenols”)
It may be referred to as component (c). )) Is used together with the substituted phenols (b) 10
It is preferable to replace 0.1 to 40 mol of 0 mol with the component (c).

Further, when the above-mentioned phenol (hereinafter sometimes referred to as component (d)) is used in combination, the amount of the phenol used is from 0.1 to 10 per 100 mol of the substituted phenol (b). Preferably, the moles are replaced by component (d).

When the amount of the component (a) is in the range of 70 to 150 moles with respect to 100 moles of the substituted phenol (b), the remaining phenol, the other substituted phenol, and the residual phenol The amount and the remaining amount of formalin can be further reduced.

When the amount of the component (c) exceeds 40 moles with respect to the total of 100 moles of the components (b), (c) and (d), and the amount of the component (d) used Is 10
If more than the mole, the substituted phenols, the other substituted phenols, and the residual amount of the phenol,
In some cases, the residual amount of the formalin cannot be further reduced, and it is sometimes difficult to control the reaction, so that a product having a suitable molecular weight cannot be obtained.

In the present invention, polyvinyl phenol can be used as the phenol resin.

As the polyvinyl phenol, for example, acyloxystyrene such as 4-acetoxystyrene (which is represented by the general formula RCOO—C ₆ H ₄ —C ₂ H ₃ , wherein R is (Indicating an alkyl group.). Polyvinylphenol that can be obtained by hydrolyzing a polymer obtained by polymerizing an alkyl group, polyvinylphenol that can be obtained by homopolymerizing vinylphenol, and the like can be given.

In the present invention, a copolymer containing a vinylphenol unit can be used as the phenol resin.

Examples of the copolymer containing a vinyl phenol unit include copolymers of vinyl phenol and other copolymerizable monomers, acyloxystyrene (which includes:
Represented by the general formula _{RCOO-C 6 H 4 -C 2} H 3. However, in the general formula, R represents an alkyl group. For example, copolymers obtained by hydrolyzing a polymer obtained by copolymerizing 4-acetoxystyrene and other copolymerizable monomers can be used.

The other copolymerizable monomers include styrene, (meth) acrylic acid or salts thereof,
(Meth) acrylic acid esters, styrene sulfonic acid or salts thereof, (meth) acrylonitrile, (meth) acrylamide, vinyl acetate, and the like. Particularly, styrene, (meth) acrylic acid esters, styrene sulfonic acid or the like Salts can be suitably used. The styrene, (meth) acrylic acid esters, styrene sulfonic acid or salts thereof are inexpensive as a copolymerization monomer, and therefore are preferable in terms of cost. The resin obtained by copolymerizing styrene sulfonic acid or salts thereof is converted into water. Is preferred because of its good dispersibility.

When polyvinyl phenols such as the above-mentioned polyvinyl phenol and the copolymer containing the vinyl phenol unit are employed in the present invention, there is an advantage in that a resin substantially free of residual formalin can be obtained.

As the polymerization method of the polyvinyl phenols, for example, Journal of Polymer Science, A-1, 7, 2
175 (1969), Journal of Polymer Science, Ed 12 (9) 20
17-2025 (1974), Chim, Ind, (Milan), 50 (7), 779-782
(1968) and the like.

The molecular weight of the polyvinyl phenol is as follows:
Its weight average molecular weight is preferably from 2,000 to 200,
5,000, more preferably from 5,000 to 10
It is in the range of 0000.

The molecular weight of the phenol resin can be analyzed by, for example, gel permeation chromatography. The weight average molecular weight of the novolak resin and the resol resin is 200 to 1
Preferably, the molecular weight of the polyvinyl phenol is 2,000.
It is preferably in the range of 0 to 200,000. When the molecular weight is lower than this range, the phenol resin may not exhibit sufficient performance as the size aid, and when the molecular weight is higher than this range, for example, the size aid containing the phenol resin When dissolving or dispersing in water to obtain an aqueous liquid, the solubility or dispersibility in water may not be sufficient.

The aqueous liquid of the phenol resin is, for example,
A method of dissolving or dispersing the phenolic resin in water,
A method of adding an alkali such as sodium hydroxide, potassium hydroxide, or ammonia to the phenol resin and dissolving or dispersing the same in water;
Or a method of forming an aqueous dispersion with a polymer emulsifying dispersant, a method of forming an aqueous dispersion by using the phenolic resin, a surfactant and / or a polymer emulsifying dispersant, and the alkali in combination,
And a method of synthesizing a phenolic resin in water to obtain an aqueous liquid in the presence of protective colloids such as polyvinyl alcohol, cellulose and derivatives thereof, gum arabic, guar gum, casein, and gelatin.

The phenolic resin obtained as described above may be directly used in the present invention. However, when an organic solvent is used during the synthesis of the phenolic resin, or when unreacted raw materials such as In the case of containing unreacted phenols, unreacted phenols such as unreacted substituted phenols, formalin, etc., from the viewpoint of environmental protection, for example, under reduced pressure, the organic solvent, unreacted phenols, formalin, etc. are distilled off. Alternatively, it is preferable to precipitate the polymer in a poor solvent for the phenol resin and separate and purify the polymer.

As the phenolic resin in the present invention, a commercially available phenolic resin can be used.
For example, "AV Light" and "Otalite (PP, RX)" manufactured by Asahi Organic Materials Industry Co., Ltd., "Sumicon PM" manufactured by Sumitomo Bakelite Co., Ltd., "Tecolite" manufactured by Toshiba Chemical Co., Ltd., Nippon Gosei "Nikkalite" manufactured by Kako Co., Ltd., "Stand Light" manufactured by Hitachi Chemical Co., Ltd., "Fudolite" manufactured by Fudo Chemical Co., Ltd., "National Light" manufactured by Matsushita Electric Works, Ltd., Dainippon Japan "Phenolite" manufactured by Ink Chemical Industry Co., Ltd. can be mentioned.

(Paper-making method) When sizing is performed using the sizing agent and the phenol resin, the sizing agent and the phenol resin can be used in any of external and internal modes. That is, (a) both the sizing agent and the phenol resin may be added to the pulp slurry as an internal additive (first use mode), and (b) both the sizing agent and the phenol resin may be used as external additives. It may be added to the surface of paper (second use mode), and (c) it is obtained by adding one of the sizing agent and the phenol resin to pulp slurry as an internal additive, and making the resulting papermaking raw material into paper. Any of the above-mentioned sizing agents and phenolic resins which have not been used as internal additives may be added as external additives to the surface of the paper (third mode of use).

The first usage mode (a) will be described.

The pulp slurry can be obtained by beating a pulp raw material in, for example, water.

Examples of the pulp raw materials include bleached or unbleached high-yield pulp such as bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, groundwood pulp, mechanical pulp or thermomechanical pulp, waste paper, corrugated cardboard and the like. Waste paper pulp or the like such as waste paper or deinked waste paper can be used.

The pulp raw material may be a mixture containing natural fibers such as asbestos and synthetic fibers such as polyamide, polyimide, polyester, polyolefin and polyvinyl alcohol.

The sizing agent used as an internal additive can be usually added to the pulp slurry as an aqueous liquid of the sizing agent, and the phenol resin used as the internal additive usually contains the phenol resin. An aqueous liquid of the resin can be added to the pulp slurry.

The aqueous liquid of the sizing agent and the aqueous liquid of the phenol resin may be mixed in advance and added as an integrated liquid. Alternatively, the aqueous liquid of the sizing agent and the aqueous liquid of the phenol resin may be used separately. Alternatively, they may be added at the same time.

The aqueous liquid of the sizing agent and the aqueous liquid of the phenol resin can be added to the pulp slurry having a pH of usually 4.5 to 9, and there are no particular restrictions on the place of addition. , Mixing chest, machine chest, seed box, fan / pump, screen and the like.

When the aqueous solution of the sizing agent and the aqueous solution of the phenol resin are separately added, each of them can be added to the pulp slurry from a separate addition site. The other may be added to the pulp slurry in the surface coating solution.

Next, in the second mode of use (b), the sizing agent and the phenol resin used as external additives are contained in a surface coating solution applied to the surface of paper obtained by papermaking. Used. The surface coating liquid is used for, for example, a size press, a calender, and the like.

Examples of the surface coating solution include starch, a surface sizing agent, a polyacrylamide-based paper strength agent, and polyvinyl alcohol.

In the third mode of use (c), when one of the sizing agent and the phenolic resin is used as an internal additive, it is used as described in the first mode of use, When the remaining one is used as an external additive, it is as described in the second use mode.

The amount of the phenol resin used in the sizing agent and the sizing aid is not particularly limited, and the obtained paper is given a predetermined sizing property.
The amount required to maintain a predetermined degree of sizing in the resulting paper can be the amount of the sizing agent and the amount of the phenol resin used as the sizing aid. Specifically, usually, the sizing agent is used in an amount of 0.
01 to 5.0% by weight, 0.005 to 5.0% by weight of the phenol resin in the size auxiliary agent per dry weight of pulp to be used as the internal additive and as the external additive. In either case, paper having a predetermined size degree can be obtained.

In the present invention, conventional size auxiliaries which have been conventionally used may be partially used in combination within a range that does not adversely affect the operability in the papermaking process or adversely affect the papermaking. Good.

Examples of the conventional size aid include, for example,
Highly modified cationized starch, cationic polyacrylamide, polyamine-epichlorohydrin resin, polyamine polyamide-epichlorohydrin resin, diallylamine-acrylamide copolymer, polyvinylamine, and a cationic size auxiliary such as polyamidine can be mentioned. One or more species can be used in combination.

The conventional size aids can be used in combination, provided that the total weight of the conventional size aids does not exceed 50% by weight based on the weight of the phenolic resin in the present invention.

Further, in the present invention, other papermaking chemicals which can be conventionally used include, for example, water-soluble aluminum salts such as aluminum sulfate, polyaluminum chloride, polyaluminum hydroxide, and polyaluminum silicate sulfate. Fillers such as titanium oxide, clay, talc, calcium carbonate, urea resin, cationized starch, anionized starch and various modified starches, polyacrylamide, polyvinyl alcohol, carboxymethylcellulose, polyamine-epichlorohydrin resin, polyamine polyamide-epichlorohydrin resin, diallylamine- Paper strength enhancers such as acrylamide copolymer, polyvinylamine, chitosan, etc., cationic polyacrylamide, anionic polyacrylamide, amphoteric polyacrylamide, polyamide Use of additives used in the production of paper and paperboard such as polyethyleneimine, bentonite, colloidal silica, retention aids such as polyethylene oxide, dyes, fluorescent dyes, slime control agents, defoamers, etc. Can be.

In the present invention, a papermaking raw material slurry containing the sizing agent, the sizing aid containing the phenolic resin, and the pulp slurry can be made.

When the sizing agent is used in the papermaking raw material slurry, for example, the acidic papermaking sizing agent is used as an internal chemical, the p
H can be adjusted to about 4.5 to 6.5, and when the neutral papermaking sizing agent is employed as an internal additive,
Usually, the pH of the papermaking raw material slurry can be adjusted to about 6 to 9, and when the acid to neutral papermaking sizing agent is employed as an internal chemical, the pH of the papermaking raw material slurry is usually adjusted. Can be prepared in a wide range of about 4.5 to 9.

In the present invention, a size press,
Paper obtained starch, polyvinyl alcohol, dye, coating color, anti-slip agent, surface sizing agent, polyacrylamide surface paper strength agent, etc. as required by adopting gate roll coater, bill blade coater, calender etc. And in this case, the phenolic resin in the sizing agent and the sizing aid, and the starch, polyvinyl alcohol, dye, coating color, anti-slip agent, surface sizing agent, polyacrylamide-based surface. By using together with a paper strength agent or the like, a predetermined sizing degree of the obtained paper and paperboard can be realized.

The papermaking method according to the present invention can be employed in the production of paper and paperboard under acidic and neutral conditions. Examples of the paper and paperboard include printing writing paper, coated base paper, and PPC. Paper, inkjet paper, information paper, book paper, photographic base paper, packaging paper, pure white roll paper, pressure-sensitive base paper, heat-sensitive base paper, medium quality paper, gypsum board base paper, flame retardant paper, newsprint, white board paper, metal interleaf paper, Examples thereof include liners, canned liners, cores, and paper tube base paper.

(Examples) Hereinafter, the effects of the present invention will be specifically described with reference to production examples and examples, but the present invention is not limited to these examples. In the following examples, parts and% mean parts by weight of solid content and% by weight of solid content unless otherwise specified.

Preparation of Aqueous Liquid of Alkenyl Succinic Sizing Agent <Production Example 1> Alkenyl succinic anhydride (AS290,
40 parts of Nippon PMC Co., Ltd.) and an emulsifier (AS280)
P, manufactured by Nippon PMC Co., Ltd.) and 50 parts of water,
The mixture was stirred at 13000 rpm for 3 minutes with a power homogenizer (Model PM-T, manufactured by Nippon Seiki Co., Ltd.) to prepare an aqueous liquid of an alkenyl succinic acid-based sizing agent (hereinafter sometimes referred to as sizing agent D). The solid content of the sizing agent D was 40%.

-Production of Aqueous Solution of α-Hydroxycarboxylic Acid Sizing Agent- <Production Example 2> An α-hydroxycarboxylic acid sizing agent is disclosed in JP-A-5-339896 (hereinafter sometimes referred to as Reference 1). Manufactured according to First, a diamide compound was produced according to Production Example 2 in Document 1. The reaction product had a melting point of 53 ° C. and an acid value of 58.8. Further, a styrene-methacrylic acid-based copolymer having a solid content of 20% was obtained in accordance with Production Example 7 in Document 1.

Next, according to Example 4 in the above-mentioned Document 1, the diamide compound obtained above was emulsified using the styrene-methacrylic acid-based copolymer obtained above, and α-
An aqueous solution of a hydroxycarboxylic acid-based sizing agent (hereinafter sometimes referred to as sizing agent G) was produced. The solid content of the sizing agent G was 40%.

<Production Example 3> AL120 (hereinafter sometimes referred to as sizing agent A) as an aqueous liquid of a rosin-based emulsion sizing agent and P as an aqueous liquid of a rosin-based emulsion sizing agent
FP (hereinafter sometimes referred to as sizing agent B), AS263 (hereinafter sometimes referred to as sizing agent C) as an aqueous liquid of a ketene dimer sizing agent, and AS295 (hereinafter referred to as sizing agent E) as an aqueous liquid of a bisamide epichlorohydrin sizing agent. AS233 (hereinafter sometimes referred to as sizing agent F) was prepared as an aqueous liquid of a cationic polymer-based sizing agent. These are all Japanese P
It is a sizing agent manufactured by MC Corporation.

Table 1 shows the solid contents of the sizing agents A to G.

[0114]

[Table 1]

-Production of Size Aid Aqueous Liquid- <Production Example 4> Novolak type phenol resin MZ301L manufactured by Dainippon Ink and Chemicals, Inc. in a 1 liter flask
(Hereinafter, it may be referred to as phenolic resin H.) 50
Parts, 30 parts of 30% sodium hydroxide and 33 parts of water were mixed to obtain a mixture. Heating the mixture to 70 ° C.,
After stirring for 5 minutes, the mixture was cooled to room temperature and phenol resin H
Of a 50% aqueous liquid was obtained. The pH of this aqueous liquid was 12.1.

<Production Example 5> Instead of the novolak-type phenolic resin MZ301L in Production Example 4, novolak-type cresol resin T manufactured by Dainippon Ink and Chemicals, Inc.
Same as Production Example 4 except that D2699H (hereinafter sometimes referred to as phenolic resin I) was used, and 1 part of phenolic resin I, 0.3 part of 30% sodium hydroxide, and 98.7 parts of water were mixed. And the phenolic resin I
% Aqueous liquid was obtained. The pH of this aqueous liquid was 11.9.

<Production Example 6> A 30% strength aqueous solution of sulfonated phenol resin DP5-produced by Allied Colloid Co., Ltd.
7104B (hereinafter sometimes referred to as an aqueous liquid of phenolic resin J) was prepared.

<Production Example 7> Resol type phenol resin aqueous solution P3 of 40% concentration manufactured by Dainippon Ink and Chemicals, Inc.
98 (hereinafter sometimes referred to as an aqueous liquid of phenolic resin K).

-Production Example of Polyvinylphenol- <Production Example 8> 80 parts of 4-acetoxystyrene was charged into a 1-liter flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a cooler, and heated to 60 ° C. Heated. AIBN
20 parts of a 5% toluene solution of (azoisobutyronitrile) was added, and a polymerization reaction was performed at 60 ° C. for 12 hours.

Thereafter, 200 parts of a 30% sodium hydroxide solution and 200 parts of water were added to the flask, and hydrolysis was performed at 80 ° C. for 2 hours. After the reaction, toluene was removed by distillation under reduced pressure to obtain a 20% aqueous solution of polyvinyl phenol (hereinafter sometimes referred to as phenol resin L). The pH of this solution was adjusted to 12.5 with sulfuric acid.

-Production Example of Copolymer Containing Vinyl Phenol Unit-<Production Example 9> In a 1-liter flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a condenser, 30 parts of water and t
-30 parts of butyl alcohol was charged and heated to 60 ° C.
22.5 parts of 4-acetoxystyrene in which 0.5 part of AIBN is dissolved, 20% aqueous solution of sodium styrene sulfonate 3
7.5 parts were added dropwise over 2 hours, and the mixture was further reacted for 6 hours. Thereafter, the temperature was raised to 98 ° C., and t-butyl alcohol was distilled off. Next, 75 parts of 30% sodium hydroxide was added, and the mixture was hydrolyzed at 80 ° C. for 2 hours to obtain a 20% aqueous solution of vinylphenol / sodium styrenesulfonate copolymer (hereinafter sometimes referred to as phenolic resin M). . This solution was adjusted to pH 11.6 with sulfuric acid.

Table 2 shows the measurement results of the molecular weights of the phenolic resins H to M and the pH of the aqueous liquid of the phenolic resin.

[0123]

[Table 2]

-Papermaking-(Example 1) Acid papermaking L-BKP (hardwood bleached kraft pulp) and N-BKP
(Conifer bleached kraft pulp) mixed pulp having a ratio of 8/2 canadian standard freeness 390
talc ("Talc ND", manufactured by Nippon Talc Co., Ltd.) in 100 parts of the obtained aqueous pulp slurry.
1 part of a cationized starch (manufactured by Oji National Co., Ltd., trade name "CATO-3210") and 1 part of a sulfuric acid band, and then 0.3 parts of the sizing agent A obtained in Production Example 3 were added.
Parts, an aqueous liquid of phenolic resin H obtained in Production Example 4, 0.1 part, a retention agent (Himoloc N, manufactured by Himo Co., Ltd.)
R ¹ 2MLS) 0.01 parts were added and the papermaking material slurry was uniformly dispersed. At this time, the pH of the papermaking raw material slurry was 4.5. The obtained papermaking raw material slurry was weighed to 65 g using a Tappi Standard Sheet Machine.
/ M ^2, and then the obtained wet paper web was subjected to compression dehydration and dried at 100 ° C. for 80 seconds.

The paper obtained by the above-mentioned acidic papermaking method was conditioned for 24 hours under the condition of a relative humidity of 65%, and the sizing effect was measured in terms of sizing degree (seconds) by the Stekicht method (JIS P8122). Table 3 shows the measurement results.

Incidentally, the acidic paper is, for example, printing writing paper,
It may correspond to one manufacturing example of coated base paper, PPC paper, inkjet paper, information paper, book paper, and the like.

[0127]

[Table 3]

(Examples 2 to 6) Instead of the aqueous liquid of phenolic resin H in the above-mentioned Example 1, phenolic resin I
(Example 2), J (Example 3), K (Example 4),
An acidic paper was produced in the same manner as in Example 1 except that the aqueous liquids of L (Example 5) and M (Example 6) were used, and the Stechig sizing degree was measured. Table 3 shows the measurement results.
At this time, the pH of the papermaking raw material slurry was 4.5 to 4.6.

(Examples 7 to 12) Instead of the aqueous liquid of the sizing agent A and the phenolic resin H in Example 1, the aqueous liquid of the sizing agent B and the phenolic resins H, I, J, K, L, or M was used. Was used in the same manner as in Example 1 except that the combination shown in Table 3 was used to produce acidic paper, and the degree of Stigcht sizing was measured. Table 3 shows the measurement results. At this time, the pH of the papermaking raw material slurry was 4.5 to 4.6.

Comparative Examples 1 and 2 0.36 parts of sizing agent A (Comparative Example 1) or sizing agent B 0.3
An acidic paper was made in the same manner as in Example 1 except that 6 parts (Comparative Example 2) was used, and the degree of Stighit sizing was measured. Table 3 shows the measurement results. At this time, the pH of the papermaking raw material slurry was 4.5 to 4.6.

(Example 13) Neutral papermaking Mixed pulp having a ratio of L-BKP to N-BKP of 8/2 was mixed with Canadian Standard Freeness 400 mL.
100 parts of the obtained aqueous pulp slurry was mixed with calcium carbonate (trade name "TP-12" manufactured by Okutama Industry Co., Ltd.).
1 ") 20 parts, cationized starch (Oji National Co., Ltd.)
And 1 part of a sulfuric acid band were added. Then, the sizing agent C obtained in Production Example 3 was added.
0.1 part of the phenolic resin H obtained in Production Example 4 above.
Was added and 0.01 parts of a retention agent (Himoloc NR ¹ 2MLS, manufactured by Himo Co., Ltd.) was added and uniformly dispersed to obtain a papermaking raw material slurry. At this time, the pH of the papermaking raw material slurry was 7.8. The obtained papermaking raw material slurry was paper-made using a Tappi Standard Sheet Machine so as to have a basis weight of 65 g / m ^2, and then the obtained wet paper was subjected to compression dehydration and dried at 100 ° C. for 80 seconds.

The paper obtained by the above neutral papermaking method was humidified for 24 hours under the condition of a relative humidity of 65%, and the size effect was measured in terms of sizing degree (seconds) by the Stekicht method (JIS P8122). Table 4 shows the measurement results.

The neutral paper is, for example, printing writing paper,
It may correspond to one manufacturing example of coated base paper, PPC paper, inkjet paper, information paper, book paper, and the like.

[0134]

[Table 4]

(Examples 14 to 18) Instead of the aqueous liquid of phenolic resin H in Example 13, phenolic resins I (Example 14), J (Example 15), K (Example 16), L (Example 17), M (Example 18)
Neutral paper was manufactured in the same manner as in Example 13 except that the aqueous liquid was used, and the degree of Stigecht sizing was measured. Table 4 shows the measurement results. PH of papermaking raw material slurry at this time
Was 7.8 to 7.9.

(Examples 19 to 42) Instead of 0.1 part of the sizing agent C and the aqueous liquid of the phenol resin H in Example 13, 0.1 part of the sizing agent D, 0.3 part of the sizing agent E, and
0.3 parts or 0.15 parts of the same G and the aqueous liquids of phenolic resins H, I, J, K, L or M in combinations as shown in Tables 4-6 Neutral paper was manufactured in the same manner as in Example 13 except that the measurement was performed, and the degree of Stigecht sizing was measured. Tables 4 to 6 show the measurement results. At this time, the pH of the papermaking raw material slurry was 7.8 to 7.9.

[0137]

[Table 5]

[0138]

[Table 6]

(Comparative Examples 3 to 7) The same procedures as in Example 13 were carried out except that the aqueous liquid of phenol resin H in Example 13 was not used.
Instead of 0.1 part of sizing agent C
0.12 parts (Comparative Example 3), 0.12 parts of sizing agent D (Comparative Example 4), 0.36 parts of sizing agent E (Comparative Example 5), 0.36 parts of sizing agent F (Comparative Example 6), or sizing agent G0 Neutral paper was prepared in the same manner as in Example 13 except that .18 parts (Comparative Example 7) was used, and the Steckigt sizing degree was measured. Tables 4 to 6 show the measurement results. At this time, the pH of the papermaking raw material slurry was 7.8 to 7.9.

[0140]

According to the present invention, by using a sizing agent (excluding a rosin sizing agent for neutral papermaking) and a sizing agent containing a phenol resin, it is possible to use a smaller amount of sizing agent than before. As a result of being able to provide a predetermined degree of size, not only is it economically advantageous, but also it is possible to improve problems such as contamination of the paper making apparatus.

In the present invention, a papermaking raw material slurry comprising a sizing agent (excluding a rosin sizing agent for neutral papermaking), a size aid containing a phenolic resin, and a pulp slurry is prepared by papermaking. (1) Paper capable of reducing the amount of sizing agent used and exhibiting an excellent sizing effect, that is, paper having excellent sizing properties, and (2) paper resulting from the sizing agent In addition, it is possible to improve the problem of soiling of a paper making apparatus and the like, and (3) to prevent a decrease in work efficiency in a paper making process.

Claims (10)

[Claims] 1. A papermaking method comprising the steps of: making a papermaking raw material slurry containing a sizing agent (excluding a rosin sizing agent for neutral papermaking), a size aid containing a phenolic resin, and a pulp slurry. Method. 2. A novolak resin and / or resol obtained by polycondensation of at least (a) formaldehyde and / or paraformaldehyde with (b) phenol and / or substituted phenols. The papermaking method according to claim 1, wherein the papermaking resin is a mold resin having a weight average molecular weight of 200 to 10,000. 3. The phenolic resin according to claim 1, wherein at least (a) formaldehyde and / or paraformaldehyde and (b) general formulas (I) and / or (I)
2. The papermaking method according to claim 1, which is a novolak type resin obtained by condensation polymerization with a substituted phenol represented by I). Embedded image (However, R ¹ and R ² are the same or different and have 1 to 1 carbon atoms.
9 linear or branched alkyl groups, phenylalkyl groups,
Or a phenyl group. ) 4. The papermaking method according to claim 1, wherein the phenol resin in claim 1 is polyvinylphenol, and the weight average molecular weight is 2,000 to 200,000. 5. The phenolic resin according to claim 1, wherein the phenolic resin is a copolymer containing a vinylphenol unit,
The papermaking method according to claim 1, wherein the weight average molecular weight is 2,000 to 200,000. 6. The sizing agent according to claim 1, wherein a rosin sizing agent for acidic papermaking, a ketene dimer sizing agent, an alkenyl succinic anhydride sizing agent, a cationized fatty acid amide sizing agent, and a vinyl monomer are copolymerized. The papermaking method according to any one of claims 1 to 5, wherein the papermaking method is at least one selected from the group consisting of a cationic polymer-based sizing agent obtained by the above method and an α-hydroxycarboxylic acid-based sizing agent. 7. The sizing agent according to claim 1, wherein the sizing agent is a rosin sizing agent for acidic papermaking, and the papermaking raw material slurry according to claim 1 is adjusted to pH 4.5 to 6.5. The papermaking method according to any one of the above. 8. The sizing agent according to claim 1 is a ketene dimer-based sizing agent and / or an alkenyl succinic anhydride-based sizing agent, and the papermaking raw material slurry according to claim 1 is adjusted to pH 6 to 9. Claim 1
A papermaking method according to any one of claims 1 to 5. 9. The sizing agent according to claim 1, comprising a cationized fatty acid amide-based sizing agent, a cationic polymer-based sizing agent obtained by copolymerizing vinyl monomers, and an α-hydroxycarboxylic acid-based sizing agent. The papermaking method according to any one of claims 1 to 5, which is at least one selected from the group, and wherein the papermaking raw material slurry in the above (1) is adjusted to pH 4.5 to 9. 10. A paper produced by the papermaking method according to any one of claims 1 to 9.