JPH07189174A - Rosin emulsion composition, its production, sizing agent and sizing method - Google Patents

Abstract

PURPOSE:To obtain a composition comprising a rosin emulsion containing an alkenylsuccinic acid derivative, a rosin substance and a dispersant, applicable both to an acidic paper making process and a neutral paper making process, exhibiting excellent sizing effect and having excellent stability. CONSTITUTION:This rosin emulsion composition having excellent stability is obtained by dispersing a mixture of (A) an alkenylsuccinic acid derivative, e.g. a reaction product of a kind selected from among primary and secondary amines, polyamines and aminoalcohols with a kind selected from among alkenylsuccinic anhydrides and alkenylsuccinic acids, (B) a rosin material (e.g. a gum rosin or a tall-oil rosin) and (C) a dispersant consisting of a known emulsifying agent and a protective colloid substance, e.g. a casein or a PVA, in water. This composition is added, as a sizing agent, to an aqueous dispersion of pulp to obtain a sizing composition. The obtained sizing composition exhibits better sizing effect than a known sizing composition when applied to sizing, especially under a condition of a high sizing speed and even under mild drying conditions. This sizing composition has excellent preservative and mechanical stabilities.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rosin emulsion composition, a process for producing the same, a sizing agent and a sizing method, and more particularly to a rosin containing an alkenylsuccinic acid derivative, a rosin substance and a dispersant in the emulsion solids. A system emulsion composition, which exhibits an excellent size effect not only in an acidic system but also in a papermaking system in a neutral region, particularly when the papermaking speed is high and the drying conditions are mild, that is, the amount of heat applied to the wet paper is The present invention relates to a sizing agent that exhibits excellent sizing effect even on paper produced under the drying conditions of a paper machine having a relatively low papermaking system, for example, a Yankee dryer, and has excellent mechanical stability and storage stability of itself. .

[0002]

2. Description of the Related Art In the papermaking industry, there are problems associated with improving paper quality, closing papermaking systems, and using waste paper and broke containing calcium carbonate as a raw material for papermaking.
On the other hand, in order to improve productivity, paper machines have been made faster, and as a result, drying has been often performed rapidly under relatively low temperature conditions. Regarding the latter, there is a tendency that conventional sizing agents cannot give sufficient sizing degree to paper.

[0003]

For example, when an anionic rosin-based sizing agent, particularly a solution-type rosin-sizing agent which is an alkali-neutralized product of a toughened rosin, is used, it is also superior in size effect to the solution-type rosin-sizing agent. When a dispersion type rosin-based sizing agent having a wide pH range applicable to papermaking is used, it cannot be said that the drying conditions are sufficient during papermaking using a high-speed papermaking machine.
In order to obtain a predetermined sizing degree, it is necessary to increase the amount of the sizing agent added, which not only raises the cost but also causes a problem of remarkable foaming in the papermaking process. Under such circumstances, when the papermaking speed is high and the drying conditions are relatively gentle, for example, a paper machine having a Yankee dryer (for example, a paper machine for pure white roll paper) or an ultra-high speed paper machine for newsprint is used. There is a strong demand for a rosin-based emulsion sizing agent that exerts an excellent sizing effect on paper made under dry conditions.

The object of the present invention is not only to make paper in a papermaking system in which drying conditions are relatively mild, as in the case of making paper in a high-speed papermaking machine, but also to a wide range of papermaking pH from acidic to neutral.
Rosin emulsion composition exhibiting excellent sizing effect on paper produced in the papermaking system of the domain, and having excellent mechanical stability and storage stability, a method for producing the same, a sizing agent containing this composition, and sizing To provide a method.

[0005]

In order to solve the above problems, the present invention provides (A) an alkenylsuccinic acid derivative,
It is intended to provide a rosin-based emulsion composition in which a dispersoid containing (B) a rosin-based substance and (C) a dispersant is stably dispersed in water.

The present invention also provides a method for producing these rosin emulsion compositions, a sizing agent containing this composition, and a sizing method.

The present invention will be described in detail below. The alkenylsuccinic acid derivative (A) that constitutes the present invention is
Reaction product of at least one selected from the group consisting of primary amines, secondary amines, polyvalent amines and amino alcohols with at least one of alkenyl succinic anhydride and alkenyl succinic acid, secondary Amines,
The reaction product of at least one selected from the group consisting of polyhydric amines and amino alcohols with at least one of alkenyl succinic anhydride and alkenyl succinic acid is further added to monohydric alcohols, polyhydric alcohols, and A reaction product obtained by reacting at least one selected from the group consisting of primary carboxylic acids, a reaction product of a monohydric alcohol with at least one of alkenyl succinic anhydride and alkenyl succinic acid, monovalent Reaction product obtained by reacting polyhydric alcohol with reaction product of alcohol and at least one of alkenyl succinic anhydride and alkenyl succinic acid, polyhydric alcohol, alkenyl succinic anhydride and alkenyl Reaction products with at least one succinic acid, polyhydric alcohols, alkenyl succinic anhydride and And a reaction product of at least one kind of alkenyl succinic acid with at least one kind of a monohydric alcohol and a primary carboxylic acid, and these are reaction products obtained individually or in combination of two or more kinds in each group. Alternatively, at least one of each of two or more groups may be used in combination.

Here, the alkenylsuccinic anhydride and the alkenylsuccinic acid are reaction products of an olefin having 6 to 30 carbon atoms and maleic anhydride, and an olefin having 6 to 30 carbon atoms and maleic acid, respectively. Although they are used alone, they may be used in combination. The olefin preferably has 8 to 20 carbon atoms, and more preferably 1 carbon atom.
2-18. As typical olefins, any of linear α-olefins, linear internal olefins, and branched olefins can be used.
It may be a mixture of two or more species. The alkenylsuccinic anhydride is represented by the following general formula, and the alkenylsuccinic acid is a ring-opened product thereof.

[0009]

[Chemical 1]

In the formula, R ⁸ to R ¹² each represent a hydrogen atom or a linear or branched alkyl group having 1 to 27 carbon atoms which may be the same or different.

In producing the alkenylsuccinic acid derivative, it is preferable to use the former of the alkenylsuccinic anhydride and the alkenylsuccinic acid in terms of easiness of reaction. The above reaction product is a compound obtained by amidation reaction, imidization reaction, esterification reaction or a combination of these reactions.
In practice, each of the above amines is mixed with at least one of alkenylsuccinic anhydride and alkenylsuccinic acid, or one component is added dropwise while the other component is added at room temperature to about 200 ° C. 30 minutes to 24
It is produced by adding addition and / or dehydration reaction for about time. Generally, since the reaction is exothermic, the method of dropping the other component in one component is preferable. Two or more kinds of these amines may be used in combination, and in this case, two or more kinds of amines may be simultaneously reacted with at least one of alkenylsuccinic anhydride and alkenylsuccinic acid, or one kind of amine. The reaction may be carried out in a stepwise manner so that the following amine is reacted.

The primary amines used in the present invention are represented by the general formula R ¹ NH ₂ , and the secondary amines are represented by the general formula R ² R ³ NH, R ¹ , R ² and R ³ is preferably a compound which is the same or different and represents a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms. Specific examples of R ¹ , R ² and R ³ include methyl, ethyl, propyl, isopropyl, allyl, butyl, isobutyl, s-butyl,
t-butyl, hexyl, cyclohexyl, octyl, 2
—Chain hydrocarbon groups such as ethylhexyl, nonyl, decyl, lauryl, myristyl, palmityl, stearyl, oleyl, phenyl, naphthyl, dehydroabietyl, etc.

Further, as the polyvalent amine, general formula H ₂
N—R ⁴ (NR ⁵ —R ⁴ ) n—NH ₂ , R ⁴ is a chain or cyclic alkylene group having 2 to 13 carbon atoms, R ⁵ is hydrogen or a methyl group, and n is 0 to 5 The compound represented by the integer value of is preferable. For example, ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, methyliminobispropylamine, trimethylhexamethylenediamine, isophoronediamine, cyclopentadienediamine, bis (paraaminocyclohexyl) methane, bis Aminomethylcyclohexane, N-aminopropylcyclohexylamine, xylenediamine, diaminodiethyldiphenylmethane, o-
Trizine, toluylenediamine, phenylenediamine,
Examples thereof include bisaminopropylpiperazine, diaminodiphenyl ether, diaminobenzanilide, and dianisidine. Examples of amino alcohols include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine and the like.

When at least one of alkenylsuccinic anhydride and alkenylsuccinic acid is reacted with the above amines, one unreacted carboxyl group, hydroxyl group or amino group is selected depending on the type of amines used and the charging ratio. The alkenyl succinic acid derivative having the above is synthesized. Therefore, further monohydric alcohols, polyhydric alcohols, primary carboxylic acids may be used alone or in combination with these reaction products to synthesize an alkenylsuccinic acid derivative that has undergone an esterification reaction or an amidation reaction, The present invention can also use these. Such alcohols and primary carboxylic acids are preferably obtained by reacting at least one of alkenyl succinic anhydride and alkenyl succinic acid with amines, and then adding and reacting them. Alternatively, alkenyl succinic anhydride and alkenyl succinic acid are used. At least one kind of succinic acid may be mixed and reacted with alcohols and primary carboxylic acids, and then amines may be added and further reacted, or all of them may be simultaneously mixed and reacted.

The above-mentioned monohydric alcohols have the general formula R
A compound represented by ⁶ OH, wherein R ⁶ represents a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms is preferable. For example, methyl alcohol, ethyl alcohol, butyl alcohol, octyl alcohol, lauryl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol,
Typical examples are aliphatic alcohols such as eicosyl alcohol, and cyclic alcohols such as cyclopentanol, cyclohexanol, benzyl alcohol and rosin alcohol, and these can be used alone or in combination of two or more kinds. The polyhydric alcohol is composed of a compound having 2 to 10 OH groups, and typical examples thereof include ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, glycerin,
Examples thereof include diglycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and bisphenol. These can be used alone or in combination of two or more.

The primary carboxylic acids are represented by the general formula R ⁷ C
A compound represented by OOH and R ⁷ is a chain or cyclic hydrocarbon group having 4 to 24 carbon atoms is preferable. Examples thereof include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and behenic acid, and these can be used alone or in combination of two or more kinds. Incidentally, corresponding primary carboxylic acid anhydrides can be used instead of these primary carboxylic acids, and the primary carboxylic acids of the present invention also include these.

In the present invention, the reaction product of at least one of alkenyl succinic anhydride and alkenyl succinic acid with a monohydric alcohol is a monoester or diester produced by an addition reaction and / or a dehydration reaction of these substances. Derivatives and mixtures thereof. The monohydric alcohols may be used singly or in combination of two or more, but after mixing with at least one of alkenylsuccinic anhydride and alkenylsuccinic acid, or while dropping the other component into one component, the temperature may range from room temperature to 250. Any method in which the reaction is carried out at about C for about 30 minutes to 24 hours may be used. As the monohydric alcohols, those represented by the above general formula R ⁶ OH, and specific examples thereof can be applied as they are. When the reaction product of at least one of the above alkenyl succinic anhydride and alkenyl succinic acid and a monohydric alcohol contains a monoester and an unreacted carboxyl group, a polyhydric alcohol is further added to carry out an esterification reaction. Alkenyl succinic acid derivatives can be synthesized. The reaction temperature at this time is 120 to 25.
The reaction time is preferably 0 ° C. and 2 to 24 hours. As the polyhydric alcohol, those described above for the polyhydric alcohol can be applied.

In the present invention, the reaction product of at least one of alkenylsuccinic anhydride and alkenylsuccinic acid with a polyhydric alcohol is an ester derivative produced by an addition reaction and / or a dehydration reaction of these substances. Is. The polyhydric alcohols may be used alone or in combination of two or more kinds, but after mixing with at least one of alkenylsuccinic anhydride and alkenylsuccinic acid, or while dropping the other component into one component, the temperature may range from room temperature to 250 ° C. Any method in which the reaction is carried out at about C for about 30 minutes to 24 hours may be used. As the polyhydric alcohol, those described above for the polyhydric alcohol can be applied. When carrying out the reaction of at least one of the above-mentioned alkenyl succinic anhydride and alkenyl succinic acid with polyhydric alcohols, unreacted carboxyl group, hydroxyl group and these functional groups are changed depending on the type of polyhydric alcohol used and the charging ratio. A plurality of alkenyl succinic acid derivatives are synthesized. Therefore, these reaction products can be used alone or in combination of two or more kinds of monohydric alcohols and primary carboxylic acids to synthesize an alkenylsuccinic acid derivative which has been subjected to an esterification reaction, which can also be used in the present invention. . As the monohydric alcohols, those represented by the above general formula R ⁶ OH, and specific examples thereof can be applied as they are. As the primary carboxylic acids, those represented by the above general formula R ⁷ COOH, and the exemplified products can be used as they are.

The rosin-based substance as the component (B) in the present invention is gum rosin, tall oil rosin, wood rosin and modified products of these rosins, which may be used alone or in combination with 2
Used as a mixture of two or more species. Examples of the modified rosin include a partially or substantially completely hydrogenated product, a disproportionated product, a polymerized product, and a formaldehyde-modified product. Further, the rosin-based substance also includes a reinforced rosin obtained by addition-reacting an α, β-unsaturated carboxylic acid with these rosin-based substances.
Typical examples of the α, β-unsaturated carboxylic acid used here are unsaturated dibasic acids such as fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, and citraconic anhydride. Examples thereof include unsaturated monobasic acids such as acrylic acid and methacrylic acid, and these may be used alone or in combination of two or more. Furthermore, rosin and glycerin,
Esters of polyhydric alcohols such as pentaerythritol and reaction products of rosin and epoxy compounds are also included in the rosin-based substance.

The dispersant of the component (C) in the present invention comprises an emulsifying dispersant and / or a protective colloid,
Although not particularly limited, various low-molecular-weight surfactants, at least one emulsifying dispersant of a polymeric emulsifying dispersant, protective colloids such as casein, lecithin, polyvinyl alcohol, and modified starch can be used. You may use it individually or in combination of 2 or more types. As various low-molecular-weight surfactants, alkali metal salts of rosin, alkali metal salts of reinforced rosin, alkylbenzene sulfonates,
Polyoxyethylene alkyl ether sulfate ester salt,
Polyoxyethylene alkyl phenyl ether sulfate ester salt, polyoxyethylene mono- and distyryl phenyl ether sulfate ester salt, alkyl sulfate ester salt,
Alkyl naphthalene sulfonate, naphthalene sulfonate formaldehyde condensate, polyoxyethylene alkyl ether sulfosuccinic acid monoester salt, polyoxyethylene alkylphenyl ether sulfosuccinic acid monoester salt, polyoxyethylene mono and distyryl phenyl ether sulfosuccinic acid monoester Salts, anionic surfactants such as alkylphenoxy polyoxyethylene propyl sulfonate, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene mono- and distyryl phenyl ethers, polyoxypropylene polyoxyethylene glycol glycerin Fatty acid ester, sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethyl ester Non-ionic surfactants such as sorbitan fatty acid ester, sucrose fatty acid ester, pentaerythritol fatty acid ester, propylene glycol fatty acid ester, fatty acid diethanolamide, polyoxypropylene polyoxyethylene glycol, and tetraalkylammonium chloride, trialkyl Benzyl ammonium chloride, alkylamine,
Examples include cationic surfactants such as mono- and polyoxyethylene alkylamines.

The polymeric emulsifying dispersant is not particularly limited, but basically, a hydrophobic group, a nonionic group and / or
Alternatively, a synthetic polymer having an ionic group or a general natural polymer-based emulsifying dispersant can be used. For example, a partially or completely neutralized product of anionic styrene- (meth) acrylic acid-based copolymer, anionic Alternatively, cationic (meth) acrylic acid ester-based copolymer or (meth) acrylamide-based copolymer, cationic polyaminopolyamide-epichlorohydrin resin, alkylenepolyamine-epichlorohydrin resin, poly (diallylamine)
—Epichlorohydrin resin and the like can be exemplified.
These polymeric emulsifying dispersants may be used alone or in combination of two or more as a protective colloid.

The emulsion composition of the present invention comprises the above-mentioned components (A), (B) and (C), 50 to 98 parts by weight of the rosin substance as the component (B), and alkenylsuccinic acid as the component (A). 1 to 49 parts by weight of the derivative, more preferably 2
˜20 parts by weight and 1 to 20 parts by weight, more preferably 3 to 10 parts by weight of the component (C) dispersant. When the amount of the component (A) is less than 1 part by weight, the effect on the size performance and the like is lower than that in the above range, and 50
When the amount is more than the weight part, the influence on the size performance tends to reach a peak, which is economically unfavorable. Also, (C)
If the amount of the component is less than 1 part by weight, the action of emulsifying and dispersing the mixture of the rosin-based substance of the component (B) and the alkenylsuccinic acid derivative of the component (A) and the storage stability are lower than those in the above range, and 20 parts by weight Even if the amount is larger than the above range, the emulsifying and dispersing action is not particularly improved, and the size performance and foamability are not better than those in the above range.

There are no particular restrictions on the method of incorporating the above-mentioned content of the component (A) into the emulsion solids,
After 1 to 49 parts by weight of the component (A) and 98 to 50 parts by weight of the rosin-based substance fortified with the component (B), preferably α, β-unsaturated carboxylic acid, are melt-mixed, and then the dispersant of the component (C) is used. A dispersion obtained by emulsifying and dispersing in water or a component (B), preferably a rosin-based substance fortified with an α, β-unsaturated carboxylic acid, which is dispersed in the component (C), and a component (A) in the component (C). It is also possible to mix or emulsify and disperse the mixture, or to carry out by any method. The former is preferable in terms of size performance. The total solid content of the emulsion after emulsification and dispersion is 20 to
60% by weight is preferred, more preferably 30-50% by weight
Is.

The method for producing the rosin emulsion composition of the present invention is not particularly limited, but, for example, according to the method described in JP-B-54-36242, (B) and (A). A method of dissolving the components in a solvent, adding the component (C), and then producing an oil-in-water emulsion through a homogenizer (solvent method), JP-A-54-7720.
According to the method described in Japanese Patent Publication No. 9, the component (A) is mixed with the melted component (B), and the mixture (C) is added to the mixture.
A method of mixing the components to form a water-in-oil emulsion and adding inversion water to cause a phase transition to an oil-in-water emulsion (phase inversion method) according to the method described in JP-B-53-32380. , (A) and (B) are melt-mixed, and further (C) is mixed, and then an oil-in-water emulsion is produced through a homogenizer under high pressure (mechanical method).

The rosin emulsion composition thus obtained, when used as a sizing agent, has excellent storage stability and mechanical stability, and is applied to a wet paper under relatively mild drying conditions on a high-speed paper machine. Relatively less heat
For example, in the case of a paper machine having a Yankee dryer or a paper machine for ultra-high speed newsprint, especially in an acidic or neutral paper making system (pH 4 to 8), the size performance imparted to paper is superior to that of the conventional size. In addition, it has an advantage that it can be adjusted from weak size to strong size. Further, the sizing agent of the present invention is characterized in that a papermaking tool such as a press roll or a dryer canvas is less contaminated.

The sizing method of the present invention is carried out by adding a sizing agent containing the rosin diameter emulsion composition of the present invention to, for example, the wet end portion in the process of producing paper or paperboard. Specifically, the sizing agent of the present invention is added to an aqueous dispersion of pulp in an amount of 0.01 to 5% by solid weight, preferably 0.05 to 2% by solid weight, based on its dry weight. Further, it is also possible to separately add a component obtained by emulsifying and dispersing the component (A) with the component (C) and a component obtained by emulsifying and dispersing the component (B) with the component (C) to the pulp slurry. The use of a sizing agent has a better sizing effect and is easier to handle.

The sized paper of the present invention exhibits excellent sizing effect in sizing paper obtained by using the sizing agent of the present invention in a papermaking system rich in sulphate sulphate, and further sulphate of sulphate cannot be used. Or papermaking system whose usage is limited to a small amount, such as neutral pure white roll paper, neutral liner,
Anticorrosion liner and metal interleaving paper, papermaking system in which calcium carbonate is mixed from used paper materials, such as gypsum board base paper, white board, coated base paper, neutral paper, general liner and core,
Paper-making systems that use calcium carbonate as a filler, such as neutral printing writing paper, neutral coated base paper, neutral PPC paper, neutral thermosensitive base paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, and fixing agent It is obtained by using the sizing agent of the present invention in a paper-making system whose amount used is limited, for example, kraft paper, and exhibits excellent sizing performance not found in conventional rosin-based sizing agents.

The above sizing method and sizing agent can also be used as a surface sizing method and surface sizing agent.
In this case, a conventional method such as spraying, dipping, coating or the like is applied to the wet paper thus made.

The sized paper of the present invention contains at least the component (A), the component (B), and may further contain the component (C), but the content varies depending on the type of paper. , And a range of 0.01 to 5% by solid weight. Each component is identified by analysis. Examples of the analysis method include thermal decomposition GC-MS (gas chromatography mass spectrometry).

In the production of paper or paperboard, pulp raw materials are bleached or unbleached pulp such as bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, groundwood pulp, mechanical pulp or thermomechanical pulp. Any of used pulp such as used newspaper, used magazine, used corrugated cardboard or deinked used paper can be used. Further, the pulp material and inorganic fibers such as asbestos, or polyamide, polyimide,
Mixtures with synthetic fibers such as polyesters, polyolefins, polyvinyl alcohol and the like can also be used.

Additives such as a filler, a dye, a dry paper strength improver, a wet paper strength improver, a retention improver, and a drainage improver may be used as necessary in order to express the physical properties required for each paper type. You may use it. Examples of the filler include clay, talc, heavy or light calcium carbonate, etc. 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, which may be used alone or in combination. Wet paper strength improvers include polyamide
Examples thereof include epichlorohydrin resin, melamine / formaldehyde resin, urea / formaldehyde resin, which may be used alone or in combination with anionic polyacrylamide. Examples of the yield improver include anionic or cationic high molecular weight polyacrylamide, a combination of silica sol and cationized starch, a combination of bentonite and cationic high molecular weight polyacrylamide, and the like.
Examples of the drainage improving agent include polyethyleneimine, cationic or anionic polyacrylamide, and the like.
If necessary, starch, polyvinyl alcohol, dye, coating color, surface sizing agent, anti-slip agent, etc. may be applied with a size press, gate roll coater, bill blade coater, calender or the like. Also,
Bansulfate may be used before, after, or simultaneously with the addition of the sizing agent of the present invention.

[0032]

EXAMPLES The present invention will be described in more detail below with reference to production examples of the above components (A), (B) and (C), and examples and comparative examples using the same. It is not limited to the example of. In the examples, parts and% are based on weight unless otherwise specified.

Production of Alkenyl Succinic Acid Derivative -1 Dodecenyl succinic anhydride-stearyl amine reaction product (A-1) 51.4 parts of dodecenyl succinic anhydride (trade name DDSA manufactured by Sanyo Kasei Co., Ltd.) at about 100 ° C 52.1 parts of stearylamine was added dropwise, and after the addition, the temperature was gradually raised to 150 ° C. The reaction is carried out at 150 ° C. for 5 hours to produce water (3.
(5 parts) was distilled off to obtain 100 parts of a dodecenylsuccinic anhydride-stearylamine reaction product (A-1) of an imide compound which is an alkenylsuccinic acid derivative. -2 Dodecenyl succinic anhydride-diethylamine reaction product (A-2) 21.6 parts of diethylamine was added dropwise to 78.4 parts of dodecenyl succinic anhydride (trade name DDSA manufactured by Sanyo Chemical Industry Co., Ltd.) at about 100 ° C. After that, the temperature was gradually raised to 150 ° C. The reaction was carried out at 150 ° C for 1 hour to obtain 100 parts of a dodecenylsuccinic anhydride-diethylamine reaction product (A-2) which was an alkenylsuccinic acid monoamide compound.

-3 Pentadecenylsuccinic anhydride-
Diethylenetriamine reaction product (A-3) 93.5 parts of pentadecenylsuccinic anhydride (trade name PDSA-DA manufactured by Sanyo Kasei Co., Ltd.) and 10 parts of diethylenetriamine were used in place of dodecenylsuccinic anhydride and ethylenediamine. Then, the reaction was carried out in the same manner as in the production example of -1 above. The distilled water was 3.5 parts, and 100 parts of pentadecenyl succinic anhydride-diethylenetriamine reaction product (A-3) of the alkenyl succinic acid derivative was obtained, which has an acid value of 55. It was a monoamide and imide derivative of the acid. -4 Dodecenyl succinic anhydride-ethylenediamine reaction product (A-4) 10.8 parts of ethylenediamine was added dropwise to 95.7 parts of dodecenyl succinic anhydride (trade name DDSA manufactured by Sanyo Chemical Industry Co., Ltd.) at about 100 ° C. After that, the temperature was gradually raised to 150 ° C. The reaction is carried out at 150 ° C. for 5 hours to produce water (6.
5 parts) was distilled off to obtain 100 parts of a dodecenylsuccinic anhydride-ethylenediamine reaction product (A-4) of an imide compound which is an alkenylsuccinic acid derivative. -5 Dodecenyl succinic anhydride-monoisopropanolamine reaction product (A-5) Dodecenyl succinic anhydride (Sanyo Kasei Kogyo KK, trade name DDSA) 90.3 parts at about 100 ° C. and 12.7 parts monoisopropanolamine. Drop, and gradually after dropping 150
The temperature was raised to ° C. The reaction was carried out at 150 ° C. for 5 hours, and the produced water (3 parts) was distilled off to obtain 100 parts of a dodecenylsuccinic anhydride-monoisopropanolamine reaction product (A-5) which is an alkenylsuccinic acid derivative.

-6 Dodecenyl succinic anhydride-diethylamine-oleyl alcohol reaction product (A-6) Dodecenyl succinic anhydride obtained by the above-mentioned -2
Oleyl alcohol (45.5 parts) was added to diethylamine reaction product (A-2) (57.5 parts), and dehydration reaction was performed at 180 ° C. for 6 hours (distilled water was 3 parts).
Dodecenyl succinic anhydride which is an esterified product of 2)-
Diethylamine-oleyl alcohol reaction product (A-6)
100 parts were obtained.

-7 Pentadecenylsuccinic anhydride-
Diethylenetriamine-bisphenol A reaction product (A-
7) 10 parts of bisphenol A was added to 91.6 parts of the pentadecenylsuccinic anhydride-diethylenetriamine reaction product (A-3) obtained in -3 above, and dehydration reaction was carried out at 200 ° C for 12 hours (distillation). Water was 1.6 parts), and pentadecenylsuccinic anhydride-diethylenetriamine-bisphenol A which is an esterified product of (A-3).
100 parts of the reaction product (A-7) was obtained. -8 Pentadecenylsuccinic anhydride-diethylenetriamine-glycerin reaction product (A-8) In 98.8 parts of pentadecenylsuccinic anhydride-diethylenetriamine reaction product (A-3) obtained in -3 above. Glycerin (3 parts) was added, and dehydration reaction was performed at 200 ° C. for 12 hours (the amount of distilled water was 1.8 parts).
Pentadecenyl succinic anhydride-diethylenetriamine-glycerin reaction product (A-
8) 100 parts were obtained.

-9 Octadecenyl succinic anhydride-
Rosin alcohol reaction product (A-9) Octadecenyl succinic anhydride (Dixi) at about 150 ° C.
e Chem. Rosin alcohol (product name: Abitol, manufactured by Rika Hercules Co., Ltd.) in 50 parts of product name: ODSA manufactured by the company
0 part was added and the reaction was carried out at 150 ° C. for 6 hours to obtain an alkenylsuccinic acid monoester product (A-9) 100. -10 Octenyl succinic anhydride-ethylhexyl alcohol reaction product (A-10) Octenyl succinic anhydride (Dixie) at about 150 ° C.
Chem. 38 parts of ethylhexyl alcohol was added to 62 parts of trade name ODSA manufactured by the company, and the reaction was carried out at 150 ° C. for 6 hours to obtain 100 parts of octenylsuccinic anhydride-ethylhexyl alcohol reaction product (A-10) which was an alkenylsuccinic acid monoester compound. Obtained. -11 Octadecenyl succinic anhydride-Ethylhexyl alcohol-Bisphenol A reaction product (A-11) According to the above-mentioned -10, octadecenyl succinic anhydride 6
From 0.7 parts and 22.6 parts of ethylhexyl alcohol,
83.3 parts of alkenyl succinic acid monoester derivative were obtained. To this product, 19.8 parts of bisphenol A was further added, and dehydration reaction was carried out at 200 ° C. for 8 hours (distilled water was 3.1 parts) to obtain octadecenyl succinic anhydride-
100 parts of an ethylhexyl alcohol-bisphenol A reaction product (A-11) was obtained.

-12 Pentadecenylsuccinic anhydride-Ethylene glycol reaction product (A-12) Pentadecenylsuccinic anhydride at about 150 ° C (trade name PDSA-DA manufactured by Sanyo Kasei Co., Ltd.) 92 Ethylene glycol 8.8 parts was added to 0.1 part and reacted at 150 ° C. for 6 hours to obtain 100 parts of pentadecenylsuccinic anhydride-ethylene glycol reaction product (A-12). -13 Pentadecenyl succinic anhydride-ethylene glycol-stearic acid reaction product (A-13) Pentadecenyl succinic anhydride-ethylene glycol reaction product (A-12) 57. 0
45.9 parts of stearic acid was added to 10 parts, and dehydration reaction was carried out at 200 ° C. for 8 hours (the distilled water was 2.9 parts), and pentadecenyl which was an esterified product of (A-12). 100 parts of a succinic anhydride-ethylene glycol-stearic acid reaction product (A-13) was obtained.

Production of rosin-based substance (B) -1 Production of fumaric acid fortified rosin 80 parts of fumaric acid was gradually added to 450 parts of gum rosin in a molten state at about 200 ° C., and almost all fumaric acid reacted. After the completion, 470 parts of tall oil rosin treated with formaldehyde (modification rate 3%) was added, and the mixture was melted and stirred for homogenization, after which the reaction product was cooled to room temperature. The reaction product (toughened rosin) was 8% fumaric acid added to rosin.

Production of Polymer Emulsified Dispersant Polymer emulsified dispersants (C-1) and (C- for Examples for dispersing and stabilizing a rosin-based substance are prepared as follows.
2) was produced. -1 Anionic Polymer Dispersant for Examples (C-1)
Manufacture of a styrene-methacrylic acid copolymer neutralized product (C-1) was manufactured in the following manner according to the manufacturing method of Reference Example 10 of JP-A No. 61-108796. Styrene 55
Parts, methacrylic acid 30 parts, itaconic acid 5 parts, lauryl acrylate 10 parts, 10% sodium naphthalene sulphonate formaldehyde condensate 50 parts, ammonium persulfate 1 part and water 200 parts by mixing and stirring, and at 30 ° C. under pressure at 30 ° C. Heated for minutes. Then it was cooled to 70 ° C. and 48.5.
By gradually adding 35.5 parts of sodium hydroxide and 7 parts of water, stirring for 30 minutes, and then cooling to room temperature,
An anionic polymer dispersion liquid (C-1) having a solid content of 30% was obtained.

-2 Production of Cationic Polymer Dispersant (C-2) for Examples Production of cationic poly (meth) acrylamide having a hydrophobic group described in Example 1 of JP-A-2-177534. According to the method, the polymeric dispersant (C
-2) was produced. A 1 liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube was charged with 31.4 parts of dimethylaminoethyl methacrylate.
85.3 parts of 50% acrylamide aqueous solution, styrene 2
0.8 parts, ion-exchanged water 100.6 parts, isopropyl alcohol 143.3 parts, n-dodecyl mercaptan 0.
6 parts were charged and the pH was adjusted to 4.5 with a 20% aqueous acetic acid solution. The temperature of this mixed solution was raised to 60 ° C. under a nitrogen gas atmosphere while stirring. 2.3 parts of 5% ammonium persulfate aqueous solution was added as a polymerization initiator, and the temperature was raised to 80 ° C. and kept for 1.5 hours.
0.7 part of the aqueous solution was added. After holding at the same temperature for 1 hour, 100 parts of ion-exchanged water was added, isopropyl alcohol was then distilled off, and ion-exchanged water was further added to the cationic polymer dispersion liquid having a solid content concentration of 20.4% (C
-2) was manufactured.

Production of Rosin-Based Emulsion Composition -1 The fumaric acid-enhanced rosin obtained in Examples 1 to 15 and the alkenylsuccinic acid derivative obtained in Example 1 were mixed in the proportions shown in Table 1, and heated and melted at about 150 ° C. While stirring vigorously, the dispersant obtained in (4) was added and mixed as shown in the same table to give a water-in-oil emulsion. Hot water was gradually added to this to invert the phase to form an oil-in-water emulsion, and hot water was further quickly added to this to form a stable oil-in-water emulsion, which was then cooled to room temperature. The emulsion thus obtained has a solid content of about 45-
50%, cumulative 50% in weight-based particle size distribution measured by Master Sizer (Malvern)
The diameter (hereinafter referred to as the average particle diameter) was 0.2 to 0.4 μm, which was stable for a long period of time.

-2-Comparative Examples 1 and 2 A rosin emulsion composition (size) was obtained in the same manner as in the above Examples except that the alkenylsuccinic acid derivative was not used and the composition shown in Table 1 was used. Table 1 shows the composition and properties of the rosin emulsion compositions of the above Examples and Comparative Examples.
Shown in.

[0044]

[Table 1]

Table 2 shows the results of a size effect test conducted under the following test conditions using the rosin emulsion compositions obtained in the above Examples and Comparative Examples as a sizing agent. All the added chemicals are shown by the weight ratio of solid content to absolute dry weight of pulp.

-1 Size effect test 1 Bleached kraft pulp (pulp ratio of softwood to hardwood is 1: 4
Was mixed with water for dilution having a hardness of 100 ppm so as to have a pulp concentration of 2.5%, and beaten up to 350 ml of Canadian standard freeness using a beater. 1.2 liters of this pulp slurry was weighed in a disintegrator, and the sizing agents of the above Examples and Comparative Examples were added in the amounts shown in Table 2 (0.3% or 0.4%) and 1.5% vanadium sulfate. Were added simultaneously and then stirred for 30 minutes. The pulp slurry is then diluted to a concentration of 0.
Dilute to 25% and then use cationic polyacrylamide as a fixing agent (Paper Strength Agent DS41 manufactured by Nippon PMC Co., Ltd.)
0) was added in an amount of 0.05%, and the paper was made at a paper making pH of 4.5 with a Noble and Wood paper making machine to obtain a test paper having a basis weight of 65 g / m ² . The wet paper web was dried under a predetermined drying condition using a drum dryer. The obtained test paper was conditioned under a constant temperature and constant humidity environment (20 ° C., 65% relative humidity) for 24 hours, and then the sizing degree was measured by the Steckit method. The results are shown in Table 2. In the table, among the drying conditions, the conditions of 80 ° C. and 100 seconds correspond to “when the drying conditions are relatively gentle”.

[0047]

[Table 2]

-2 Size effect test 2 1.2 liters of pulp slurry beaten under the same conditions as in the test of -1 in the preceding paragraph were weighed in a disintegrator, and the sizing agents of the above Examples and Comparative Examples were used in the amounts shown in Table 2. (0.4% or 0.8
%) And 1.0% vanadium sulfate and the above DS as a fixing agent
0.2% of 410 was added and then stirred for 10 minutes. The pulp slurry is then diluted to a concentration of 0.2 with diluted water of pH 8.
Diluted to 5%, 2% of light calcium carbonate (Tamapearl 121S manufactured by Okutama Industry Co., Ltd.), and high molecular weight cationic polyacrylamide as a retention agent (Japan PM
0.01% of retention agent RD814) of C Co., Ltd. was added, paper was made at a paper making pH of 8 with a Noble and Wood paper machine, and the basis weight was 6
A test paper of 5 g / m ² was obtained. The wet paper web was dried under a predetermined drying condition using a drum dryer. The obtained test paper is placed in a constant temperature and humidity environment (20 ° C, 65% relative humidity) for 24 hours.
After conditioned for time, the sizing degree was measured by the Steckit method.
The results are shown in Table 3.

[0049]

[Table 3]

Stationary Stability Test 100 ml of the sizing agents 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 6 months.
The height (cm) of the precipitate deposited on the bottom was measured. The measurement results are shown in Table 4.

Mechanical Stability Test 50 g of each sizing agent of the above Examples and Comparative Examples was put in a cup, and a Marlon type stability test was conducted at a temperature of 25 ° C., a load of 20 Kg and a rotation speed of 800 rpm for 5 minutes. The generated agglomerates were filtered through a wire mesh of 325 mesh, and the amount of precipitation with respect to the total solid content was measured and expressed as a percentage. The measurement results are shown in Table 4.
Shown in.

[0052]

[Table 4]

[0053]

According to the present invention, since a rosin emulsion composition containing an alkenylsuccinic acid derivative, a method for producing the same, a sizing agent and a sizing method can be provided, a sizing agent containing this rosin emulsion composition can be provided. When used for sizing, it is possible to provide a paper exhibiting an excellent sizing effect not found in conventional anionic or cationic rosin emulsions even under conditions of high papermaking speed and mild drying conditions. Further, this sizing agent has excellent storage stability and mechanical stability.

Claims (21)

[Claims] 1. An (A) alkenyl succinic acid derivative,
A rosin-based emulsion composition in which a dispersoid containing (B) a rosin-based substance and (C) a dispersant is stably dispersed in water. 2. An alkenyl succinic anhydride and an alkenyl, wherein the alkenyl succinic acid derivative (A) is at least one selected from the group consisting of primary amines, secondary amines, polyvalent amines and amino alcohols. The rosin-based emulsion composition according to claim 1, which is a reaction product with at least one succinic acid. 3. The rosin according to claim 2, wherein the primary amine is a compound represented by the general formula R ¹ NH ₂ (wherein R ¹ represents a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms). System emulsion composition. 4. An alkenyl succinic acid derivative of (A) at least one selected from the group consisting of secondary amines, polyamines and amino alcohols, and at least alkenyl succinic anhydride and alkenyl succinic acid. The rosin according to claim 1, which is a reaction product obtained by reacting a reaction product with one kind with at least one kind selected from the group consisting of monohydric alcohols, polyhydric alcohols and primary carboxylic acids. System emulsion composition. 5. The secondary amines are R ² R ³ NH (provided that R ² R ³ NH
² and R ³ are the same or different and each represents a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms).
The rosin-based emulsion composition according to any one of 1 to 4. 6. A polyvalent amine is represented by the general formula H ₂ N--R ⁴ (N
R ⁵ --R ⁴ ) n--NH ₂ (provided that R ⁴ has _{2 to} 13 carbon atoms
A chain or cyclic alkylene group, R ⁵ is hydrogen or a methyl group, and n is represented by an integer value of 0 to 5). . 7. The amino alcohol is at least one selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine. A rosin-based emulsion composition as described in 1. 8. The rosin emulsion composition according to claim 1, wherein the alkenylsuccinic acid derivative (A) is a reaction product of a monohydric alcohol and at least one of alkenylsuccinic anhydride and alkenylsuccinic acid. 9. An alkenyl succinic acid derivative of (A) is obtained by further reacting a reaction product of a monohydric alcohol with at least one of alkenyl succinic anhydride and alkenyl succinic acid with a polyhydric alcohol. The rosin-based emulsion composition according to claim 1, which is a reaction product. 10. The rosin emulsion composition according to claim 1, wherein the alkenylsuccinic acid derivative (A) is a reaction product of a polyhydric alcohol and at least one of alkenylsuccinic anhydride and alkenylsuccinic acid. . 11. A reaction product of the alkenylsuccinic acid derivative of (A) with a polyhydric alcohol and at least one of an alkenylsuccinic anhydride and an alkenylsuccinic acid, and at least one of a monohydric alcohol and a primary carboxylic acid. The rosin-based emulsion composition according to claim 1, which is a reaction product obtained by reacting seeds. 12. The monohydric alcohol is R ⁶ OH (provided that
R ⁶ is rosin emulsion composition according to any one of claims 4 is a compound represented by showing a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms) 11. 13. The polyhydric alcohol has an OH group of 2 to 10.
The rosin-based emulsion composition according to any one of claims 4 to 7 or 9 to 11, which is a compound having an individual group. 14. The primary carboxylic acid has the general formula R ⁷ COO.
The rosin-based emulsion composition according to any one of claims 4 to 7 or 11, which is represented by H (however, R ⁷ represents a chain or cyclic hydrocarbon group having 4 to 24 carbon atoms). 15. The rosin emulsion composition according to claim 1, wherein the alkenylsuccinic acid derivative (A) is at least two kinds of the alkenylsuccinic acid derivatives described in any one of claims 2 to 14. 16. An alkenyl succinic anhydride in (A),
The rosin-based emulsion composition according to any one of claims 2 to 15, wherein the alkenylsuccinic acid is a reaction product of an olefin having 6 to 30 carbon atoms and maleic anhydride, or an olefin having 6 to 30 carbon atoms and maleic acid. . 17. The rosin-based emulsion composition according to claim 1, wherein the component (A) and the component (B) are dispersed by forming a mixture particle. 18. A total of 100 parts by weight of 1 to 49 parts by weight of component (A), 50 to 98 parts by weight of component (B) and 1 to 20 parts by weight of component (C) are stably dispersed in water, 19. A dispersion having a solid content concentration of 20 to 60% by weight.
The rosin-based emulsion composition according to any one of 1. 19. A rosin emulsion composition according to claim 1, wherein the components (A) and (B) are mixed and the mixture is dispersed in water using the component (C). Method. 20. A sizing agent containing the rosin-based emulsion composition according to any one of claims 1 to 18. 21. A sizing method using the rosin-based emulsion composition according to any one of claims 1 to 18 as a sizing agent.