JP3158585B2 - Rosin-based emulsion sizing agent for papermaking and sizing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rosin emulsion sizing agent for papermaking and a sizing method using the same. More specifically, a rosin-based substance containing a predetermined weight% of an ester of at least one of polyhydric alcohols and polyhydric phenols having a valency of 3 or more and a rosin and at least one of the fortified products thereof with a hydrophobic group. Emulsified and dispersed directly in water with a cationic acrylamide-based polymer and / or methacrylamide-based polymer (hereinafter referred to as cationic poly (meth) acrylamide) having excellent mechanical stability and storage stability per se, and acidic The present invention relates to a rosin-based emulsion sizing agent which exhibits an excellent sizing effect in a papermaking system in the range from 1 to neutral and further greatly reduces foaming in the papermaking system, and a sizing method using the same.

[0002]

2. Description of the Related Art In the papermaking industry, measures for improving paper quality and closing papermaking systems have been urgently required.
There are problems such as the problem of using waste paper or broke containing calcium carbonate as a raw material for papermaking, and as a solution to this, try to make paper in the neutral region by reducing the addition rate of bansulfate. The trend is growing.

A conventional rosin sizing agent used in papermaking systems with a high addition rate of bansulfate, particularly a solution-type rosin sizing agent that is an alkali neutralized reinforced rosin, reduces the addition rate of bansulfate. As the papermaking pH is increased to approach the neutral papermaking region, the size effect drops sharply. In particular, when calcium carbonate is mixed in the papermaking system, the tendency becomes remarkable. As a countermeasure to prevent this reduction in size effect, a large amount of bansulfate must be added.As a result, papermaking is performed in an acidic region, resulting in deterioration of paper quality, operation and cost. Was leaving. In addition, the anionic rosin emulsion size which is superior in size effect to the solution type rosin sizing agent and is applied to a papermaking system in a wider pH range (dispersing reinforced rosin as fine particles in water using an anionic emulsifying dispersant). ) Can reduce the addition rate of bansulfate compared to solution-type rosin, but still reduce the bansulfate until the papermaking pH reaches the neutral range, or reduce the papermaking pH. When calcium carbonate was mixed in the system, a large reduction in the size effect was unavoidable and was not satisfactory.

[0004] A rosin emulsion sizing agent having a cationic property (a reinforced rosin is dispersed as fine particles in water using a cationic emulsifying dispersant) has a self-fixing property to pulp fibers and has a predetermined size effect. It has been shown that it is possible to reduce the amount of bansulfate required for the expression of sulphate, and to exhibit an excellent size effect even in a papermaking system in a pH region near neutrality (TAPPI P).
apermakers Conference 1988
pp. 161-188). However, cationic rosin emulsions are more difficult to produce industrially than anionic ones which have been generally used in the past, and also have the stability of products at rest, the size performance of calcium carbonate-containing papermaking systems, and papermaking systems. There is still a problem in the foaming property in the inside, and further improvement is required.

Under these circumstances, sizing agents for neutral papermaking have been developed which are used for papermaking in the neutral region, in which alkenyl succinic anhydride, alkyl ketene dimer and the like are dispersed in a dispersion medium such as water. Sizing agent,
Both of them are expensive, so that not only there is a major problem that the cost of papermaking is increased, but also the workability is poor such as dirt is easily generated on a press roll or the like in the papermaking system, and the rise of the size effect is slow. Have problems such as things. In addition, all of these have a problem that the sizing effect on high-yield pulp such as mechanical pulp is inferior to rosin-based sizing agents.

As a method for improving the sizing effect of a rosin sizing agent in a neutral papermaking system, a sizing agent containing an ester of a trihydric or tetrahydric alcohol and a rosin (Japanese Patent Application Laid-Open No. 62-1987).
223393 and 62-250297) are known, but the content of the esterified product is required to be 20% by weight or more, preferably 40% by weight or more, and the size effect in the acidic papermaking system is not excellent. In some cases, it cannot be used in the pH (4 to 8) region, and there is also a problem that the cost of the sizing agent is increased due to the large amount of rosin ester which is relatively expensive.

[0007]

From the above, it can be seen that not only the acidic pH range, but also the low addition ratio of bansulfate is excellent in the pH range close to neutral, especially in the neutral papermaking system containing calcium carbonate. Development of a rosin-based emulsion sizing agent that rapidly exerts a sizing effect, is excellent in mechanical stability and storage stability, and significantly reduces foaming in papermaking systems, and a sizing method using the same has been desired. .

[0008]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention relates to (A) a method of preparing an alcohol having a trihydric or higher polyhydric alcohol as a main component and a phenol having a polyhydric phenol as a main component. At least one ester of a rosin and at least one of its fortified products with 1.5 to 30
(B) a rosin-based material containing (b) a cationic acrylamide-based polymer and / or a methacrylamide-based polymer having a hydrophobic group, and the component (A) is directly dispersed in water by the component (B). A rosin emulsion sizing agent for papermaking, wherein the zeta potential of the particles of the composition is positive at pH 4 to 8 and the cumulative 50% diameter in the weight-based particle size distribution is 1 μm or less. It is.

In this case, the component (A) is a rosin-based substance containing 4.5 to 25% by weight of at least one of the above-mentioned esters and their fortified products. And / or the molar ratio (-COOH / -OH) to the hydroxyl group of the polyhydric phenol is 0.1.
5 to 50, a reaction product obtained by heating, and the component (B) is (b-1) a cationic monomer in an amount of 2 to 30 mol%, and (b-2) an anionic monomer.
5% by mole or less, (b-3) a polymer obtained using a monomer having a composition of 3 to 50% by mole of a hydrophobic monomer, and (b-4) 15 to 95% by mole of acrylamide and / or methacrylamide. That the component (B) is 0.5 to 20% by weight based on the total solid content;
It is preferably from 0 to 60% by weight.

The present invention also provides a sizing method for sizing using the above-mentioned rosin emulsion sizing agent for papermaking.

In the present invention, an ester of a rosin with at least one of alcohols having a trihydric or higher polyhydric alcohol as a main component and phenols having a polyhydric phenol as a main component (hereinafter referred to as rosin-polyhydric alcohol) The term "isoester") refers to a compound obtained by esterifying a rosin with the above-mentioned alcohols and / or phenols by a dehydration reaction, and includes a completely esterified product, a partially esterified product,
Alternatively, it is a compound comprising a mixture of both. Further, the above-mentioned ester fortification is obtained by reinforcing the above-mentioned ester in the same manner as in obtaining a reinforced rosin described later.

In the present invention, rosins include gum rosin, tall oil rosin, wood rosin, and modified products of these rosins, and these are used alone or as a mixture of two or more. As the rosin modified product,
Examples thereof include partially or substantially completely hydrogenated, disproportionated, polymerized, and formaldehyde-modified ones. Further, for these rosins, fortified rosins obtained by addition reaction of α, β-unsaturated carboxylic acids are also used. Representative examples of the α, β-unsaturated carboxylic acids include fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, acrylic acid and methacrylic acid. These may be used alone or in combination.

In the present invention, the trihydric or higher polyhydric alcohol includes, for example, glycerin, trimethylolethane, trimethylolpropane, 3-methylpropane-
Examples include 1,3,5-triol, pentaerythritol, diglycerin, sorbitol and the like.

Examples of the polyhydric phenol include hydroquinone, pyrogallol, bisphenol A, and phenol resin.

The above-mentioned polyhydric alcohols and polyhydric phenols can be used in combination of two or more of them each or both. Ester of a monohydric or dihydric alcohol or a monohydric phenol and a rosin cannot obtain the effect such as size performance as seen in an ester of a trihydric or higher alcohol or a polyhydric phenol and a rosin, These may be used in combination with polyhydric alcohols and polyhydric phenols.

The method for producing the rosin-polyhydric alcohol ester or the like can be carried out under known esterification conditions. After charging the rosin and the alcohol and / or phenol, normal pressure, reduced pressure or The dehydration reaction may be performed while stirring at a temperature of 150 to 300 ° C. for 3 to 30 hours under the presence or absence of a catalyst under pressure.
At this time, dehydration may be performed azeotropically using a solvent such as benzene, toluene, or xylene.

The charging ratio of the rosin to the polyhydric alcohol and / or the polyhydric phenol is as follows: (a) the ratio at which an ester such as a rosin-polyhydric alcohol can be obtained in a good yield, that is, the carboxyl group of the rosin and the polyhydric alcohol; Or the equivalent ratio [-COOH (eq) /-OH (eq)] to the hydroxyl group of the compound is adjusted to 0.5 to 3 (as described later, a rosin is added later to form a rosin-polyhydric alcohol ester, etc.). Is a rosin-based substance containing 1.5 to 30% by weight), or (a) a ratio in which the rosin contains 1.5 to 30% by weight of an ester such as rosin-polyhydric alcohol, that is, the above equivalent ratio Is preferably 3 to 50, and then a dehydration reaction is performed. In this case, the carboxyl group of the rosin in the equivalent ratio does not include a carboxyl group derived from α, β-unsaturated carboxylic acids added to the rosin such as fortified rosin. When the equivalent ratio is less than 0.5, the amount of residual hydroxyl groups in the rosin-polyhydric alcohol ester is large, and good effects such as size performance may not be obtained. The content of the ester becomes 1.5% by weight or less, which may be undesirable.

In the present invention, the rosin-based material is a mixture of the above-mentioned rosin-polyhydric alcohol ester and the above-mentioned rosin, and the rosin-polyhydric alcohol ester is contained in the rosin-based material, preferably 1.5 to 1.5%. The content is 30% by weight, more preferably 4.5 to 25% by weight. 1.
If the amount is less than 5% by weight, the degree of the size effect in the papermaking system near the neutral pH is not large, and if the amount is more than 30% by weight, the degree of the contribution to the size effect near the neutral pH is small. May reduce the size effect in acidic papermaking systems. In addition, the rosins in the rosin-based material include α,
Fortified rosins obtained by addition reaction of β-unsaturated carboxylic acids are preferred.

In producing the sizing agent of the present invention, the rosin-based material such as a rosin-polyhydric alcohol may be contained in the rosin-based material in the above-mentioned ratio by, for example, the reaction obtained by charging and heating in the above-mentioned ratio (a). The product and rosin are mixed, heated, melted and emulsified and dispersed so that the rosin-polyhydric alcohol or the like ester is contained in the above ratio, or the reaction product obtained by charging and heating in the ratio of (a) above Either as is, or after emulsifying with α, β-unsaturated carboxylic acids and emulsifying and dispersing, it is possible to use either method.

The cationic poly (meth) acrylamide having a hydrophobic group of the component (B) according to the present invention can be used as a monomer component (b-1) as described in JP-A-3-227481. It is a polymer obtained using a monomer having a composition consisting of 2 to 30 mol% of a cationic monomer, (b-2) 5 mol% or less of an anionic monomer, and (b-3) 3 to 50 mol% of a hydrophobic monomer. . When the monomer component composition ratio of the polymer (B) is outside the above range, the emulsifiability is reduced or the storage stability or sizing performance of the obtained papermaking sizing agent is lower than when the composition ratio is within the above range. Tends to decrease.

The (b-1) cationic monomer imparts cationicity to the poly (meth) acrylamide and contributes to the rosin emulsion particles obtained to have a positive zeta potential at pH 4-8. As the cationic monomer,
For example, (mono- or di-alkyl) aminoalkyl (meth) acrylate, (mono- or di-alkyl)
Aminohydroxylalkyl (meth) acrylate,
(Mono- or di-alkyl) aminoalkyl (meth)
Examples thereof include acrylamide, (mono- or di-alkyl) aminohydroxylalkyl vinyl ether, vinylpyridine, vinylimidazole, diallylamine, and the like, and furthermore, quaternary ammonium salts thereof. Used.

Examples of the (b-2) anionic monomer include monomers having a carboxylic acid group such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, vinyl sulfonic acid, and A monomer having a sulfonic acid group such as (meth) allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, or sulfonated styrene; or a monomer having a phosphoric ester group such as a phosphoric acid ester of hydroxyalkyl (meth) acrylate. These can be used alone or in combination of two or more.

The above-mentioned (b-3) hydrophobic monomer is for imparting hydrophobicity to the polymer and for increasing the adsorptivity to rosin particles. By introducing the monomer, remarkable improvements were observed in the emulsifiability of the rosin-based material, the stability of the obtained emulsion and the size performance. It is not clear why hydrophobic monomers contribute to these effects. The following (b-3) can be exemplified as the hydrophobic monomer. The alkyl acrylate or alkyl methacrylate is represented by the following general formula (I)

[0024]

Embedded image

Wherein R1 is H or a methyl group, R2 is an alkyl or alkenyl group having 1 to 22 carbon atoms, cyclohexyl group, phenyl group, benzyl group, glycidyl group,

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image

(Wherein R3 is H or a methyl group, R4 is H
Or a lower alkyl group, a phenyl group, an alkylphenyl group having 1 to 22 carbon atoms, an aralkylphenyl group having 1 to 22 carbon atoms or

[0030]

Embedded image

Is as follows. ) Or

[0032]

Embedded image

Wherein R5 is H or a methyl group;

[0034]

Embedded image

[0035]

Embedded image

(Wherein R6 is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 3 to 22 carbon atoms or

[0037]

Embedded image

Is as follows. ). Indicates｝. Represented by the general formula (II):

[0039]

Embedded image

(Where R7 is H or methyl group, R8 is H or methyl group,

[0041]

Embedded image

[0042]

Embedded image

And a lower alkyl group such as ), Olefins having 6 to 22 carbon atoms, (meth)
Examples thereof include vinyl esters such as acrylonitrile, vinyl acetate and vinyl propionate, and alkyl vinyl ethers having 1 to 22 carbon atoms. These monomers may be used alone or in combination of two or more. When these monomers are used in an amount of more than 50 mol% based on all monomers, the emulsifiability with respect to the rosin-based substance is reduced, so that the stability of the obtained emulsion is reduced. ) Higher amounts of acrylamide may result in reduced sizing performance.

As a method for synthesizing the cationic poly (meth) acrylamide having a hydrophobic group (B), a conventionally known method can be applied. For example, the above (b-1)-
(B-4) a monomer such as lower alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol or tertiary butyl alcohol, acetone,
It is obtained by polymerizing with a radical polymerization catalyst in an organic solvent such as methyl ethyl ketone or dioxane, or in a mixed solution of these organic solvents and water, and distilling off the organic solvent after completion of the polymerization. As the radical polymerization catalyst, for example, ammonium persulfate, potassium persulfate, persulfates such as sodium persulfate, a redox polymerization catalyst by a combination of these persulfates and a reducing agent,
Alternatively, an azo catalyst such as 2,2'-azobisisobutyronitrile can be used. In addition, a known chain transfer agent may be appropriately used as needed.

The polymer solution (B) thus obtained has a viscosity of 10 to 5000 in a 20% by weight aqueous solution.
A centipoise (however, a value measured at 25 ° C. at 60 revolutions per minute by a Brookfield viscometer) is preferable, and a viscosity of 50 to 2,000 centipoise is particularly preferable. When the viscosity is out of the above range, the emulsifying property for the rosin-based substance is reduced, so that it is necessary to use a large amount of the emulsifier, and as a result, the size performance may not be improved.

The sizing agent of the present invention basically contains a rosin-based substance containing an ester such as rosin-polyhydric alcohol and a cationic poly (meth) acrylamide having a hydrophobic group as described above. The use ratio of this rosin-based material and cationic poly (meth) acrylamide having a hydrophobic group is such that the resulting emulsion is stable for a long period of time and stable against the shearing force applied to a papermaking system or applied to papermaking. However, it is preferable that the content be in a range in which the effect as a sizing agent is sufficiently exhibited. Therefore, cationic poly (meth) having a hydrophobic group
The amount of acrylamide used is 0.5 to 0.5% in terms of solid content relative to rosin-based materials in terms of product stability, size performance and economic efficiency.
It is preferably 20% by weight, more preferably 1 to 15% by weight, still more preferably 3 to 10% by weight. If this polymer is used in an amount larger than this range, a stable product can be obtained, but it may not be preferable in terms of economy or size performance.

The sizing agent of the present invention has a total solid content of 20
-60% by weight, more preferably 30-50% by weight.

The sizing agent of the present invention may optionally contain a cationic or nonionic surfactant. As such a surfactant, as a cationic one,
Examples thereof include tetraalkylammonium chloride, trialkylbenzylammonium chloride, alkylamine acetate, alkylamine hydrochloride, oxyethylene alkylamine, and polyoxyethylene alkylamine. Examples of nonionics include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene styryl phenyl ether, polyoxypropylene polyoxyethylene glycol glycerin fatty acid ester, sorbitan fatty acid ester, polyethylene glycol fatty acid ester,
Examples include polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, pentaerythritol fatty acid ester, propylene glycol fatty acid ester, fatty acid diethanolamide and the like.

The method for producing the sizing agent of the present invention is not particularly limited. For example, as described in JP-B-54-36242, the rosin-based substance of the above-mentioned component (A) is previously dissolved in an oil-soluble solvent. After mixing the dissolved solution with the component (B) and water and treating with a homogenizer, the solvent is distilled off to produce an oil-in-water emulsion, as described in the so-called solvent method, Japanese Patent Publication No. 53-32380. Then, the melted rosin-based component (A) is mixed under high temperature and pressure with the component (B) and water, and an oil-in-water emulsion is produced through a homogenizer. As described in the official gazette, the component (B) and a portion of water are mixed with the molten rosin-based material of the component (A) under stirring, and water is added to the rosin-based substance to form a water-in-oil emulsion. Down to form, by adding the inverted water to phase transition to an oil-in-water emulsion, such as a so-called phase inversion method is used.

The rosin emulsion of the present invention has an average particle size (cumulative 50% size in a weight-based particle size distribution) of 1 μm.
Or less, preferably 0.5 μm or less. When the particle size exceeds 1 μm, a precipitate is liable to be formed during storage, and mechanical stability tends to be poor. Average particle size is Master
It can be measured with a Siser (Malvern). Further, the zeta potential of the particles of the rosin emulsion of the present invention is pH
Positive in 4-8. This measurement is LASER ZE
It can be measured by E METER MODEL 501 (manufactured by PEN KEM).

The sizing agent of the present invention is 1.5 to 30% by weight.
By emulsifying and dispersing a rosin-based substance containing a relatively small amount of a rosin-polyhydric alcohol ester such as a cationic poly (meth) acrylamide polymer having a hydrophobic group, It is a papermaking sizing agent having excellent performances beyond those expected from the effects of only the ester such as alcohol and the effects of only the cationic poly (meth) acrylamide polymer dispersant. Specifically, compared with the conventional cationic rosin emulsion sizing agent and rosin sizing agent containing rosin ester, it has extremely excellent storage stability and mechanical stability. In the papermaking system, the sizing agent exhibits an excellent size effect not found in the conventional rosin-based sizing agent, and has the advantage that foaming in the papermaking system is extremely small.

Therefore, papermaking systems in which bansulfate cannot be used or whose usage is limited to a small amount, such as neutral pure white roll paper, neutral liner, rust-proof liner, metal backing, and calcium carbonate mixed from waste paper raw material Papermaking,
For example, gypsum board base paper, white board, coated base paper, medium paper, general liner and core, papermaking system using calcium carbonate as filler, such as neutral printing writing paper, neutral coated base paper, neutral PPC paper, neutral heat Base paper, neutral pressure-sensitive base paper,
Neutral inkjet paper and neutral information paper, the papermaking system in which the amount of the fixing agent used is limited, for example, even in kraft paper, the sizing agent of the present invention has excellent sizing performance that is not available in conventional rosin-based sizing agents. Demonstrate. Also, compared to conventional neutral size, for example, compared to sizing agents such as alkyl ketene dimer and alkenyl succinic anhydride, excellent sizing effect on pulp containing high-yield pulp, rapid rise in size, press roll, It has features such as less contamination of papermaking tools such as dryer campuses. Further, the sizing agent of the present invention exhibits an excellent sizing effect even in a papermaking system in which a large amount of bansulfate is used.

The sizing method of the present invention is carried out by adding the rosin emulsion sizing agent for papermaking of the present invention to, for example, a wet end portion in a paper or paperboard manufacturing process. Specifically, the papermaking sizing agent of the present invention is added to an aqueous dispersion of pulp in an amount of 0.0
It is added in an amount of 0.05 to 10% by solid content, preferably 0.05 to 5% by solid content.

In producing the above various papers or paperboards, pulp raw materials include bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached chemical pulp, mechanical pulp, or thermomechanical pulp. Any of pulp such as yield pulp, used newspaper, used magazine, used corrugated paper, or used deinked paper can be used. In addition, a mixture of the above pulp raw material and asbestos, polyamide, polyester, polyolefin and the like can also be used.

Additives such as fillers, dyes, dry strength agents, wet strength agents, retention improvers, and drainage improvers are also required to develop the physical properties required for each paper type. You may use it according to. Fillers include clay, talc,
Heavy or light calcium carbonate may be used, and these may be used alone or in combination. Examples of the dry paper strength improver include anionic polyacrylamide, cationic polyacrylamide, amphoteric polyacrylamide, and cationized starch, and these may be used alone or in combination. Examples of the wet paper strength improver include polyamide-epichlorohydrin resin, melamine-formalin resin, urea-formalin resin and the like, and these may be used alone or in combination with anionic polyacrylamide. Examples of the retention aid include anionic or cationic high molecular weight polyacrylamide, a combination of silica sol and cationized starch, and a combination of bentonite and cationic high molecular weight polyacrylamide. Examples of the drainage improver include polyethyleneimine and cationic polyacrylamide. In addition, starch, polyvinyl alcohol, dyes, coating colors, surface sizing agents, size presses, gate roll coaters, bill blade coaters, calenders, etc.
An anti-slip agent or the like may be applied as needed. Also, before and after the addition of the sizing agent of the present invention,
Alternatively, they may be added at the same time as needed.

The above-mentioned additives and rosins may be contained in the sizing agent at the same time as or separately from the rosin-based material containing an ester such as rosin-polyhydric alcohol, if necessary. Can also.

The rosin emulsion sizing agent for papermaking of the present invention can also be used as a surface sizing agent. In this case, a conventional method such as spraying, dipping, coating or the like is applied to the formed wet paper.

[0058]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Production Examples, Examples and Comparative Examples of rosin-polyhydric alcohol esters and the like, but the present invention is not limited to these examples. . In addition, in each example, all parts and% are based on weight unless otherwise specified.

Production of Rosin-Polyhydric Alcohol Ester Esters Rosin-polyhydric alcohol equivalent esters (A-1 to A-11) and (A-12 to A-14) were produced as follows. Production of -1 (A-1) In a 1-liter flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, a water separator and a condenser, a gum rosin 60 having an acid value of 170 was added.
0 parts and 55 parts of glycerin (charge equivalent ratio (-COOH /-
OH = 1.0) and 0.2 part of phosphoric acid, and heated to 270 ° C. in a nitrogen stream and kept at the same temperature for 15 hours to obtain a rosin-polyhydric alcohol ester (A-1). Assuming that the acid value of the reaction product is 17 due to gum rosin having an acid value of 170, the content of the unreacted gum rosin in the reaction product is about 10%, and the rosin-multi content contained in the reaction product is about 10%. The content of the hydric alcohol ester is calculated to be about 90%. Hereinafter, the ester content in the reaction product was calculated according to this. -2 (A-2 to A-11) and (A-12 to A-1)
3) Production of rosin-polyhydric alcohol ester (A-ester) in the same manner as in the production method of A-1 above, according to the type of rosin, polyhydric alcohol, and polyhydric phenol shown in Table 1 and the charging ratio.
2 to A-11) and (A-12, A-13). -3 Production of A-14 The production was carried out as follows in accordance with JP-A-62-223393. In a 1-liter flask equipped with a stirrer, thermometer, nitrogen inlet tube, water separator and condenser, 100 parts of gum rosin having an acid value of 170 and 8 parts of glycerin were charged, and reacted at 250 ° C. for 12 hours to obtain a rosin-polyhydric alcohol. Ester A
-14 was obtained.

Production of Fumaric Acid-Enhanced Rosins Fumaric acid-enhanced rosins (F-1 to F-
-4) (for Examples) and F-5 (for Comparative Examples) were produced. -1 Production of F-1 Gum rosin 4 having an acid value of 170 in a molten state at about 200 ° C.
70 parts of fumaric acid was gradually added to 60 parts, and after almost all of the fumaric acid had been reacted, 470 parts of formaldehyde-treated (denatured 3%) tall oil rosin was further added, and the mixture was melt-stirred and homogenized. Thereafter, the reaction product was cooled to room temperature. This fumaration reaction product F-1 was rosin to which 7% of fumaric acid was added. -2 Production of F-2 (Fumarated product of A-1) 465 parts of the reaction product A-1 of the rosin and the polyhydric alcohol obtained in -2 were heated and dissolved up to 200 ° C to obtain fumaric acid 35. The mixture was heated at 200 ° C. for 3 hours to obtain a fumaration reaction product F-2. The content of rosin-polyhydric alcohol ester in this product was about 90%, almost the same as the content of rosin-polyhydric alcohol ester contained in A-1 produced above. -3 F-3 (a fumarate of A-4) and F-4 (A
Preparation of F-5 (Fumarate of A-13) and F-5 (Fumarate of A-13) Using the rosin-polyhydric alcohol esters A-4, A-5, and A-13 obtained in -2, F- 2
Fumification reaction products F-3 to F
-5 were obtained. The rosin-polyhydric alcohol ester content in these products is about 5%, about 2%, respectively.
It was about 1%.

Production of cationic poly (meth) acrylamide dispersant having a hydrophobic group JP-A-3-2274
According to the example described in JP-A-81, cationic poly (meth) acrylamide-based dispersants B-1 to B-2 (for examples) having a hydrophobic group were produced as follows. -1 Production of B-1 1 equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube
31.4 parts of dimethylaminoethyl methacrylate, 50% aqueous solution of acrylamide 8
5.3 parts, styrene 20.8 parts, ion-exchanged water 100.
6 parts, 143.3 parts of isopropyl alcohol and 0.6 part of n-dodecyl mercaptan were charged, and the pH was adjusted to 4.5 with a 20% aqueous acetic acid solution. The mixture was heated to 60 ° C. under a nitrogen gas atmosphere while stirring. 2.3 parts of a 5% aqueous solution of ammonium persulfate was added as a polymerization initiator, the temperature was raised to 80 ° C., and the temperature was maintained for 1.5 hours. Then, 0.7 part of a 5% aqueous solution of ammonium persulfate was added. In addition, 1
After keeping for a time, 100 parts of ion-exchanged water was added, and isopropyl alcohol was distilled off. After the distillation was completed, the solid concentration of the polyacrylamide-based dispersant B-1 in the polymer solution obtained by adding ion-exchanged water was 20.4% and 25%.
Brookfield viscosity (hereinafter referred to as viscosity) measured at 60 ° C. and 60 revolutions per minute is 340 centipoise (cps).
Met. -2 Production of B-2 In the same manner as in the production method of B-1, dimethylaminopropyl methacrylamide 12 parts, methacrylic acid 2 parts, 50% aqueous solution of acrylamide 144 parts, isobutyl methacrylate 8 parts, n-dodecyl mercaptan 0.1 part. A polymerization reaction was carried out with 5 parts of a mixed solvent of isopropyl alcohol and water in the presence of ammonium persulfate as a catalyst, and the solid content was 20.2%.
%, A polyacrylamide-based dispersant B-2 of a polymer aqueous solution having a viscosity of 590 cps.

Production of Anionic Polymer Dispersant B-3 (for Comparative Example) According to the production method of Reference Example 10 of JP-A-61-108796, a styrene-methacrylic acid copolymer A united saponified product dispersant B-3 was produced. 55 parts of styrene, 30 parts of methacrylic acid, 5 parts of itaconic acid, 10 parts of lauryl acrylate, 10 parts of 10% sodium formalin naphthalenesulfonate formalin condensate, 1 part of ammonium persulfate
Parts and 200 parts of water are mixed and stirred.
Heated for 0 minutes. Then cool to 70 ° C., 48.5%
35.5 parts of sodium hydroxide and 7 parts of water are gradually dropped,
After stirring for 30 minutes, the mixture was cooled to room temperature to obtain a saponified styrene-methacrylic acid copolymer dispersant B-3 which is a polymer dispersion having a solid content of 30%.

Production of Papermaking Sizing Agent-1 Rosin-polyhydric alcohol ester obtained in Example 1-1 (A-
1) 20 parts of fumaric acid-enriched rosin (F-
1) 80 parts and heat-melting at about 150 ° C., while stirring vigorously, polyacrylamide dispersant (B-1)
25 parts were added and mixed to obtain a water-in-oil emulsion.
Hot water was gradually added to the resultant to invert the phase to obtain an oil-in-water emulsion. Hot water was quickly added to the emulsion to form a stable oil-in-water emulsion, followed by cooling. The solid content of the emulsion thus obtained is 50.3%,
The cumulative 50% diameter (hereinafter, referred to as an average particle diameter) in the weight-based particle size distribution measured by terSizer (Malvern) was 0.38 μm, which was stable for a long time.

-2 Examples 2-12, 17 The above-mentioned A-1 to A- were prepared at the compounding ratio (solid content weight ratio) shown in Table 2.
3, A-6, A-11, A-12, F-2 to F-4 rosin-polyhydric alcohol ester and fumaric acid-enriched rosin F
The rosin emulsion sizing agents of Examples 2 to 12 and 17 were obtained in the same manner as in Example 1 by using 100 parts of the molten mixture with -1 and 25 parts of the polyacrylamide-based dispersant (B-1). Was.

-3 Examples 13 and 14 30 parts of each of the rosin-polyhydric alcohol esters of A-7 and A-8 and 120 parts of fumaric acid-reinforced rosin (F-1) were melt-mixed at 170 ° C. 39 parts of the polyacrylamide-based dispersant (B-1) and 205 parts of water are mixed under a high temperature and a high pressure, and the mixture is twice mixed with an industrial homogenizer at a pressure of about 150 kg / cm ² (Kg per square centimeter). To obtain a rosin-based emulsion sizing agent having a solid content of about 40%.

-4 Examples 15 and 16 Rosin-polyhydric alcohol ester 3 of A-9 and A-10
0 parts and 120 parts of fumaric acid-reinforced rosin (F-1) were dissolved in 150 parts of toluene, and 39 parts of the polyacrylamide-based dispersant (B-2) and 345 parts of water were mixed.
This mixture was passed twice through an industrial homogenizer at a pressure of about 150 kg / cm ² , and then all toluene was removed by distillation under reduced pressure to obtain a rosin emulsion sizing agent having a solid content of about 35%.

-5 Comparative Examples 1 to 7 Mixing ratio of rosin-polyhydric alcohol ester and fumaric acid-reinforced rosin F-1 shown in Table 2 (total weight: 100 parts)
And the poly (meth) acrylamide-based (B-1) 25
A rosin emulsion sizing agent was obtained in the same manner as in Example 1 using 16 parts of (B-3).

-6 Comparative Example 8 (Example using an anionic dispersant) A total of 150 parts of rosin-polyhydric alcohol ester of A-14 and rosin F-1 reinforced with fumaric acid at the compounding ratio shown in Table 2
Was dissolved in 150 parts of toluene, and 15 parts of a 30% aqueous solution of sodium dodecylbenzenesulfonate (B-4) and 275 parts of water were mixed. About 150 kg of this mixture
Through an industrial homogenizer twice at a pressure of / cm ² and then remove all toluene by vacuum distillation;
A rosin-based emulsion sizing agent having a solid content of 35.1% was obtained. Table 2 shows the composition and properties of the sizing agents of the examples and comparative examples.

Table 3 shows the results of a size effect test using the sizing agents of the above Examples and Comparative Examples under the following test conditions.
Shown in All the added chemicals were shown by the weight ratio of solid content to the absolute dry weight of the pulp. Size effect test -1 Size effect test 1 bleached kraft pulp (pulp ratio of softwood to hardwood is 1: 4
Mixed pulp) is diluted with water for dilution having a pulp concentration of 2.5% and a hardness of 100 ppm using a beater to a concentration of 35%.
Beat to 0 ml Canadian Standard Freeness. Next, 1.2 l of this pulp slurry was weighed into a disintegrator, and 0.2% of the sizing agents of the above Examples and Comparative Examples were used.
0% bansulfate was added simultaneously, the pH was adjusted to 4.5 with caustic soda and then stirred for 30 minutes. Then pH
This pulp slurry is diluted to a concentration of 0.25% with 4.5 dilution water.
And a fixing agent such as cationic polyacrylamide (Epinox DS51 manufactured by Dick Hercules)
0) was added, and the paper was made with a Noble and Wood paper machine (pulp slurry temperature was 40 ° C.).
g / cm ² (g per square centimeter) of test paper was obtained. Drying of the wet paper was performed using a drum dryer at 100 ° C. for 60 seconds. After the obtained test paper was conditioned for 24 hours in a constant temperature and constant humidity (20 ° C., 60% relative humidity) environment, the sizing degree was measured by the Stechich method. This size effect test corresponds to the conditions for papermaking in an acidic papermaking system in which the pH is made acidic using bansulfate.

-2 Size Effect Test 2 1.2 liters of the pulp slurry beaten under the same conditions as in the size effect test 1 above were weighed into a disintegrator, and 0.4% of the sizing agent of each of the above Examples and Comparative Examples was added. At the same time, adjust the pH to 7.5 with caustic soda, then add
Stirred for 0 minutes. Then, the pulp slurry was diluted to a concentration of 0.25% with diluted water having a pH of 7.5, and 0.05% of cationic polyacrylamide (Epinox DS510 manufactured by Dick Hercules) was added as a fixing agent.
Paper making (pulp slurry temperature was 40 ° C.) was performed with a Noble and Wood paper machine to obtain a test paper having a basis weight of 65 g / cm ² (g per square centimeter). Drying of the wet paper was performed using a drum dryer at 100 ° C. for 60 seconds. The obtained test paper was subjected to constant temperature and humidity (20 ° C., 6
(0% relative humidity) After humidifying for 24 hours in an environment, the sizing degree was measured by the Steckigt method. This size effect test corresponds to the conditions for making, for example, neutral pure white roll paper and metal interleaving paper in a papermaking system in which the use of bansulfate is limited to a small amount. -3 Size effect test 3 1.2 l of the pulp slurry beaten under the same conditions as in the size effect test 1 above were weighed into a disintegrator, and 0.5% of the sizing agent of the example and the comparative example was added to 1.0%. Of bansulfate and 0.2% of DS510 as a fixing agent, and then 10%
Stirred for minutes. Next, this pulp slurry was diluted to a concentration of 0.25% with diluted water having a pH of 8, and 10% of light calcium carbonate (Tamapearl 121S manufactured by Okutama Kogyo Kogyo Co., Ltd.) and a high molecular weight cationic polyacrylamide (Dick Hercules Co., Ltd.) as a retention agent were used. No. 104) was added to 0.01%, and papermaking (pulp / slurry temperature: 40 ° C.) was performed on a Noble & Wood paper machine, and the basis weight was 65 g / m ^2.
(G per square meter) of test paper was obtained. Drying of the wet paper was performed at 100 ° C. for 60 seconds using a drum dryer. The obtained test paper was subjected to constant temperature and humidity (20
(° C., 60% relative humidity) for 24 hours, and the sizing degree was measured by the Steicht method. This size effect test was carried out in a papermaking system using calcium carbonate as a filler, for example, neutral printing writing paper, neutral coated paper, neutral PPC.
This corresponds to the conditions for making paper, neutral heat-sensitive base paper, neutral pressure-sensitive base paper, neutral inkjet paper, neutral information paper, and the like.

-4 Size effect test 4 Hardness of the corrugated cardboard waste paper in an amount to give a pulp concentration of 2.5% 10
The mixture was beaten with a beater to 400 ml Canadian standard freeness using 0 ppm dilution water. Next, 1.2 l of the pulp slurry was weighed into a disintegrator, and then 0.2% of the sizing agents of the above Examples and Comparative Examples were added.
Stirred for 10 minutes. Then, the pulp slurry was diluted to a concentration of 0.25% with diluted water having a pH of 7.0, 0.05% of the DS510 was added as a fixing agent, and papermaking was performed with a Noble and Wood paper machine (pulp slurry temperature 40 ° C).
A test paper having a basis weight of 100 g / m ² was obtained. Drying of the wet paper was performed using a drum dryer at 100 ° C. for 80 seconds. After the obtained test paper was conditioned for 24 hours in a constant temperature and humidity (20 ° C., 60% relative humidity) environment, the sizing degree was measured by the Kob method for 1 minute. This size effect test corresponds to the conditions for forming a neutral liner, a rust-proof liner, and the like in a papermaking system in which bansulfate cannot be used.

-4 Size Effect Test 5 A mixture of 2 to 8 bleached kraft pulp of coated paper and hardwood was used to give a pulp concentration of 2.5% and a hardness of 100.
Beated with a beater to 350 ml Canadian Standard Freeness with ppm water for dilution. The amount of calcium carbonate contained in the pulp slurry was 7% based on the pulp. 1.2 l of this pulp slurry
Was weighed into a disintegrator, and 0.5% bansulfate was added.
Stirred for minutes. Then, the pulp slurry was diluted to a concentration of 0.25% with diluting water having a pH of 7.5, 0.5% of the sizing agent of the above-described Example and Comparative Example was added, and then 0.05% of the DS510 was added as a fixing agent. Then, papermaking (pulp slurry temperature: 40 ° C.) was performed using a Noble and Wood paper machine to obtain a test paper having a basis weight of 80 g / m ² . Drying of the wet paper was performed using a drum dryer at 100 ° C. for 70 seconds. After the obtained test paper was conditioned for 24 hours in a constant temperature and humidity (20 ° C., 60% relative humidity) environment, the sizing degree was measured by the Kob method for 1 minute. This size effect test corresponds to conditions for papermaking, for example, gypsum board base paper and white board in a papermaking system in which calcium carbonate is mixed from waste paper raw materials.

Table 4 shows the test results of the foaming property, the mechanical stability test and the static stability test. Foaming test The same pulp slurry as used in the size effect test 1 was used, and 0.6% of the sizing agent of the example and the comparative example was also used.
5% bansulfate was added simultaneously and the pulp slurry was adjusted to pH 7.5 with caustic soda. After stirring for 3 minutes, the pulp slurry was diluted with water for dilution at pH 7.5 to a pH of 0.1.
Diluted to 25%, 0.05% DS510 as fixing agent
After adding and stirring for another 1 minute, the mixture is put into a cylindrical container, a part of this pulp slurry is circulated by a pump, and the pulp slurry is dropped into the container from a height of 1 m and accumulated on the liquid surface after 10 minutes. The area of the foam was determined, and the accumulated foam area relative to the entire liquid surface was expressed as a percentage. The test temperature was 40 ° C. Mechanical Stability Test 50 g of each sizing agent of the above Examples and Comparative Examples was put in a cup, and a Marlon stability test was performed at a temperature of 25 ° C., a load of 20 Kg, and a rotation speed of 800 rpm for 10 minutes. The formed aggregate was filtered through a 325 mesh wire net, and the amount of the precipitate relative to the total solid content was measured and expressed as a percentage. Stationary stability test 100 ml of the sizing samples of the above Examples and Comparative Examples were placed in a test tube having a length of 30 cm and an inner diameter of 2.1 cm, and allowed to stand for 3 months, and then the height of the precipitate deposited on the bottom (mm) Was measured.

[0074]

As described above, according to the present invention, a rosin-based material containing an ester such as rosin-polyhydric alcohol is emulsified and dispersed using cationic poly (meth) acrylamide having a hydrophobic group. The papermaking sizing agent composed of a rosin-based emulsion has excellent mechanical stability and storage stability.In addition to the acidic papermaking system and the neutral papermaking system, it does not meet the conventional anionic and cationic rosin-based sizing agents. It has the advantage of exhibiting an outstanding size effect that could not be obtained, and has less foaming in papermaking systems.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

Continuation of front page (56) References JP-A-3-227481 (JP, A) JP-A-62-223393 (JP, A) JP-A-6-294096 (JP, A) JP-A-53-12951 (JP, A) , A) JP-A-62-250297 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) D21H 11/00-27/42

Claims (7)

(57) [Claims] 1. An ester of a rosin with at least one of (A) an alcohol mainly containing a trihydric or higher polyhydric alcohol and a phenol mainly containing a polyhydric phenol, and at least one kind of an enhanced product thereof. From 1.5 to 30
(B) a rosin-based material containing (b) a cationic acrylamide-based polymer and / or a methacrylamide-based polymer having a hydrophobic group, and the component (A) is directly dispersed in water by the component (B). A rosin-based emulsion sizing agent for papermaking, wherein the zeta potential of the particles of the composition is positive at pH 4 to 8, and the cumulative 50% diameter in the weight-based particle size distribution is 1 μm or less. 2. The rosin-based emulsion sizing agent for papermaking according to claim 1, wherein the component (A) is a rosin-based substance containing 4.5 to 25% by weight of at least one of the above-mentioned esters and their reinforcing substances. 3. The molar ratio of the carboxyl group of the rosin to the hydroxyl group of the polyhydric alcohol and / or polyhydric phenol (-COOH / -OH) in the component (A).
The rosin emulsion sizing agent for papermaking according to claim 1 or 2, which is a reaction product obtained by charging 0.5 to 50 and heating. 4. Component (B) is (b-1) 2 to 30 mol% of cationic monomer (b-2) 5 mol% or less of anionic monomer (b-3) 3 to 50 mol% of hydrophobic monomer (b) -4) The rosin emulsion sizing agent for papermaking according to any one of claims 1 to 3, which is a polymer obtained by using a monomer having a composition of 15 to 95 mol% of acrylamide and / or methacrylamide. 5. Component (B) is 0.5 to 2 parts by weight based on the total solids.
The rosin-based emulsion sizing agent for papermaking according to any one of claims 1 to 4, which is 0% by weight. 6. A rosin emulsion sizing agent for papermaking according to claim 1, wherein the solid content is 20 to 60% by weight. 7. A sizing method using the rosin-based emulsion sizing agent for papermaking according to any one of claims 1 to 6.