JPH07189173A - Rosin emulsion composition, its production, sizing agent sizing method and sized paper - Google Patents

Abstract

PURPOSE:To obtain a sizing agent applicable both to an acidic paper making process and a neutral paper making process, capable of exhibiting excellent sizing effect even under relatively mild conditions of drying as in a high-speed paper making machine and having excellent mechanical and preservative stabilities. CONSTITUTION:This rosin emulsion composition is composed of an alkenylsuccinic acid obtained by reacting an internal olefin having olefinic group at or inner than beta-position with maleic anhydride and/or maleic acid as a main component, a rosin ester and a dispersant.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rosin-based emulsion composition, a method for producing the same, a sizing agent, a sizing method, and sized paper, and more particularly to a special alkenyl succinic acid and rosin ester in the emulsion solid content. A rosin-based emulsion composition containing a dispersant, which exhibits an excellent size effect particularly in a papermaking system in an acidic region as well as in a neutral region, particularly when the papermaking speed is high and the drying condition is mild, that is, wet. The present invention relates to a sizing agent that exerts an excellent sizing effect on paper produced in a papermaking system in which the amount of heat applied to the paper is relatively low, and that also has excellent mechanical stability and storage stability.

[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.
As a countermeasure against this, there is an increasing tendency to make paper in the neutral region where the addition rate of van sulphate is reduced. 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. For these problems, alkenyl succinic acid, alkyl ketene dimer, etc. have been conventionally used as a neutral papermaking sizing agent, but all of them are apt to generate stains in papermaking systems such as press rolls, and have good workability and paper quality. In addition to that, the alkyl ketene dimer has a problem that the onset of the size effect is slow.

Among rosin-based sizing agents, a rosin emulsion sizing agent which is superior in size effect to a solution-type rosin sizing agent and has a wide applicable pH range (a reinforced rosin is finely dispersed in water using an anionic emulsifying dispersant). Although it is dispersed as particles), even if the addition rate of vanadium sulfate is reduced compared to the solution type rosin sizing agent, similar size effect can be exhibited, but size effect in the neutral pH range The decline of is inevitable. Further, as a method for improving the sizing effect in the neutral papermaking system of the above rosin emulsion sizing agent, a sizing agent containing an ester of a trihydric or tetrahydric alcohol and a rosin (Japanese Patent Laid-Open No. 62-2233).
No. 93 and JP-A No. 62-250297) are already known, but the size effect in the neutral papermaking system is still insufficient, and improvement is required.

[0004]

When the above rosin ester emulsion sizing agent is used, it is superior to the rosin emulsion sizing agent in the sizing effect in the neutral region. However, the recent paper machines have improved productivity. Therefore, the speed has been increased, and the satisfactory size effect has not been achieved due to insufficient drying conditions. Therefore, it is necessary to increase the amount of the sizing agent to obtain a predetermined sizing degree, which not only results in cost increase, but also
There is a problem that excessive foaming occurs during the papermaking process, and the preroll of the papermaking machine is contaminated. Under such circumstances, a rosin-based sizing agent corresponding to an increase in the papermaking speed, that is, an excellent sizing effect can be exhibited even on paper manufactured under dry conditions in which the amount of heat applied to wet paper is relatively small. There is a strong demand for the emergence of a rosin ester-based emulsion sizing agent.

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.
Region papermaking system, particularly rosin emulsion composition exhibiting excellent size effect even on paper produced in a neutral papermaking system containing calcium carbonate, and having excellent mechanical stability and storage stability, and production thereof A method, a sizing agent containing this composition, a sizing method and a sized paper are provided.

[0006]

In order to solve the above-mentioned problems, the present invention provides (A) an alkenylsuccinic acid compound obtained by the reaction of an internal olefin whose main component is β or later with maleic acid and / or maleic anhydride. , (B) rosin ester and (C) a dispersant-containing dispersoid are stably dispersed in water to provide a rosin-based emulsion composition.

At this time, the internal olefin has 6 to 30 carbon atoms.
Is an internal olefin, and the rosin ester is an ester of a part or all of at least one carboxyl group selected from the group consisting of rosins, modified rosins and their respective α, β unsaturated carboxylic acid adducts. A compound esterified with an agent or an α, β unsaturated carboxylic acid adduct of an esterified product of rosins and / or modified rosins, and the esterifying agent comprises a monohydric alcohol, a dihydric alcohol and a polyhydric alcohol At least one of the group
Being a seed, the esterifying agent is an epoxy resin having a molecular weight of 10,000 or less having two or more oxirane rings in one molecule, the component (A) is 1 to 49 parts by weight, and the component (B) is 5
A total of 100 parts by weight of 0 to 98 parts by weight and 1 to 20 parts by weight of the component (C) are stably dispersed in water to give a solid content concentration of 20.
It is preferable to prepare a dispersion liquid of about 60% by weight.

The present invention also provides a method for producing a rosin-based emulsion composition in which mixture particles obtained by previously mixing the components (A) and (B) are dispersed in water using the component (C).
The present invention provides a method for producing a rosin-based emulsion composition in which component (B) is dispersed in water with a mixture of component (A) and component (C).

The present invention also provides a sizing agent, a sizing method and a sized paper containing the above rosin emulsion composition.

The present invention will be described in detail below. The alkenyl succinic acid (A) which constitutes the present invention refers to a compound obtained by the reaction of an internal olefin after β with maleic acid and / or maleic anhydride, and a compound having an anhydrous ring (alkenyl succinic anhydride). The compound may be an acid (alkenyl succinic acid) obtained by ring opening, a water-soluble metal salt of this acid (for example, an alkali metal salt), or a mixture thereof. In the present invention, "as a main component"
Means that an alkenyl succinic acid using an α-olefin as an olefin may be additionally contained. Here, the internal olefins after β are β, γ ...
An olefin compound having one or two or more unsaturated bonds in addition to the α-position is represented by an olefin having 6 to 30, preferably 8 to 20, and more preferably 12 to 18 carbon atoms. Either a branched or branched form can be used, or a mixture thereof may be used. In order to produce alkenyl succinic acids, for example, maleic acid and / or maleic anhydride is added to the above internal olefin to give 100 to
It is obtained by reacting at 250 ° C. for 1 to 6 hours. Examples of the alkenyl succinic anhydride include compounds represented by the following structural formulas, and the alkenyl succinic acid is a ring-opened compound thereof.

[0011]

[Chemical 1]

In the formula, R ₁ to R ₅ represent a hydrogen atom or an alkyl group (provided that when R ₄ is hydrogen, R ₅ is an alkyl group), and they may be the same or different.

The rosin ester as the component (B) in the present invention is at least one carboxyl group selected from the group consisting of rosins, modified rosins and their respective α, β unsaturated carboxylic acid adducts. It is an α, β unsaturated carboxylic acid adduct of a compound or an esterified product of rosins and / or modified rosins, which is partially or wholly esterified with an esterifying agent. The esterification agent is preferably used in an equivalent ratio of 0.2 to 1 with respect to a carboxyl group such as rosins. The rosins are gum rosin, tall oil rosin, and wood rosin, and these are used alone or as a mixture of two or more kinds. The modified rosins include those partially or substantially completely hydrogenated, disproportionated, polymerized, and formaldehyde-modified. Further, these rosins and modified rosins also include reinforced rosins obtained by addition reaction of α, β-unsaturated carboxylic acid. Used here α,
Typical β-unsaturated carboxylic acids are fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, unsaturated dibasic acids such as citraconic acid, acrylic acid, methacrylic acid, etc. And unsaturated monobasic acids.

The esterifying agent used in the present invention is at least one selected from the group consisting of monohydric alcohols, dihydric alcohols and polyhydric alcohols, or 2 in one molecule.
It is an epoxy resin having one or more oxirane rings and a molecular weight of 10,000 or less. The polyhydric alcohol has an OH group of 2 to 10
Examples of compounds having individual compounds include, as typical ones, ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, glycerin,
Examples thereof include diglycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and bisphenols, and these may be used alone or in combination of two or more. Epoxy resin is 1
It refers to a compound having two or more oxirane rings in the molecule, and examples thereof include those having a molecular weight of 10,000 or less, and those in the oligomer region are generally preferable. Industrially, for example, it is produced by ring closure by addition of epichlorohydrin to phenols and dehydrochlorination, or oxidation of a double bond, and in terms of classification based on chemical structure, glycidyl ether type, glycidyl ester type, glycidyl amine type. Examples thereof include alicyclic epoxide type resins and linear aliphatic epoxide type resins. Examples of commercially available products include bisphenol A type for glycidyl ether type, hydrogenated bisphenol A type, brominated bisphenol A type, and bisphenol. There are F type, orthocresol novolac type, phenol novolac type, polyhydric alcohol type, polyglycol type, etc., and other polyglycidyl amine type, epoxy modified polyol type, glyoxal type, dimer acid glycidyl ester type, dimer acid modified type, rubber Strange Type, acrylic acid-denatured, an epoxy resin such as tertiary fatty glycidyl ester type are available, it can be used in combination or alone or in combination.

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, emulsifying dispersants of polymeric emulsifying dispersants, protective colloids such as casein, lecithin, polyvinyl alcohol, and modified starch can be used, and these can be used alone or in combination of two or more. You may use it in combination. As various low-molecular-weight surfactants, alkali metal salts of rosin, alkali metal salts of reinforced rosin,
Aliphatic metal salt, alkyl ether fatty acid salt, polyoxyethylene alkyl ether fatty acid salt, acylated amino acid salt such as alkanoyl sarcosinate, alkylbenzene sulfonate, alkane sulfonate, α-olefin sulfonate, α-sulfo fatty acid Ester salt, alkanoylmethyl taurine salt, polyoxyethylene alkyl ether sulfate ester salt, polyoxyethylene alkylphenyl ether sulfate ester salt, polyoxyethylene mono- and distyryl phenyl ether sulfate ester salt, polyoxyethylene fatty acid amide ether sulfate salt, alkyl Sulfate ester, alkylnaphthalene sulfonate,
Naphthalene sulfonate formaldehyde condensate, dialkyl sulfosuccinate, polyoxyethylene alkyl ether sulfosuccinic acid mono (di) ester salt, polyoxyethylene alkylphenyl ether sulfosuccinic acid mono (di) ester salt, polyoxyethylene mono and distyrylphenyl Ether sulfosuccinic acid mono (di) ester salt, alkylphenoxy polyoxyethylene propyl sulfonate, polyoxyethylene sulfophenyl ether salt, alkyl phosphate ester salt, polyoxyethylene alkyl ether phosphate ester salt, polyoxyethylene alkylphenyl ether Anionic surfactant such as phosphate ester salt, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxy Tylene mono and distyryl phenyl ether, polyoxyethylene castor oil, polyoxyethylene lanolin alcohol, polyoxyethylene lanolin, polyoxypropylene polyoxyethylene glycol glycerin fatty acid ester, sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester Nonionic interface such as sucrose fatty acid ester, polyoxyethylene sucrose fatty acid ester, pentaerythritol fatty acid ester, propylene glycol fatty acid ester, fatty acid diethanolamide, alkyl glucoside, alkyl polyglycoside, polyoxypropylene polyethylene glycol, alkyl amine oxide Activator, tetraalkyl ammonium chloride, trialkyl And cationic surfactants such as polyoxyethylene alkyl amine, alkyl imidazolium salt, alkyl picolinium salt, alkyl isoquinolinium salt, and alkyl carboxy betaine, alkyl amino carboxylic acid, alkyl imidazoline type, etc. And the amphoteric surfactant of

The polymeric emulsifying dispersant is not particularly limited, but basically it is 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 of the component (B), and the alkenyl succinic acid of the component (A). 1 to 49 parts by weight, more preferably 2 to 2
It is preferable to contain 0 part by weight and 1 to 20 parts by weight of the dispersant of the component (C). 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 when it is 49 parts by weight or more, the effect on the size performance and the like tends to reach a peak, which is economical. Not good for When the amount of the component (C) is less than 1 part by weight, the action of emulsifying and dispersing the mixture of rosin ester and alkenyl acid and the storage stability are lower than those in the above range, and
When the amount is more than 0 parts by weight, 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 solid content of the emulsion.
After melt-mixing the components (A) and (B), they are emulsified and dispersed with a dispersant of the component (C), or the melted component (B) is emulsified and dispersed with a mixture of the components (A) and (C). Or,
It is possible to carry out either method by mixing a mixture obtained by emulsifying and dispersing the component (A) with the component (C) and a mixture obtained by emulsifying and dispersing the component (B) with the component (C). Is preferable in terms of size performance. The total solid content of the emulsion after emulsified and dispersed is preferably 20 to 60% by weight, more preferably 30.
~ 50% by weight.

The method for producing the rosin-based emulsion composition of the present invention is not particularly limited. For example, the molten component (B) can be prepared according to the method described in JP-B-54-77209. A method of mixing the component (A), the component (C) and the mixture to form a water-in-oil emulsion, and then adding reversal water to produce an oil-in-water emulsion (phase inversion method). According to the method described in JP-A-53-32380, components (A) and (B) are melt-mixed, and further component (C) is mixed, and then an oil-in-water emulsion is produced under a high pressure through a homogenizer. Method (mechanical method) and the like.

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. When the amount of heat applied is relatively small, it has the advantage that it is possible to adjust from a weak size to a strong size in a neutral papermaking region, particularly in a papermaking system in which calcium carbonate is mixed or used as a filler. 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 the sizing agent 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 10% 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 an 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. As the analysis method, for example, GC (gas chromatography),
Examples thereof include GPC (liquid phase chromatography).

In the production of paper or paperboard, pulp raw materials are bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, groundwood pulp, bleached or unbleached high yield pulp such as 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, a mixture of the above pulp raw material and inorganic fibers such as asbestos, or synthetic fibers such as polyamide, polyimide, polyester, polyolefin and polyvinyl alcohol 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 are also necessary in order to exhibit the physical properties required for each paper type. You may use according to it. As a filler, clay, talc,
Examples include heavy or light calcium carbonate, which 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,
You may use together. Examples of the wet paper strength improver include polyamide / epichlorohydrin resin, melamine / formaldehyde resin, urea / formaldehyde resin, etc. These 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. Further, the bansulfate may be used before, after, or simultaneously with the addition of the sizing agent of the present invention.

[0027]

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 Alkenylsuccinic Acids-1 Production of Alkenylsuccinic Acids (A-1) 202 parts of n-dodecene-3 and 98 parts of maleic anhydride were charged into an autoclave of 500 cc, and the atmosphere was replaced with nitrogen, and under nitrogen pressure (5 Kg / It was reacted for 6 hours at 220 ° C. in cm ^2). By separating by distillation, 210 parts of dodecenylsuccinic anhydride (A-1) having an acid value of 421 was obtained. -2 Production of alkenyl succinic acids (A-2 to A-4) n-hexadecene-4, octadecene-4, octene-2 were respectively used instead of n-dodecene-3-1
In the same manner as in hexadecenylsuccinic anhydride (A-
2), octadecenyl succinic anhydride (A-3) and octenyl succinic anhydride (A-4) were obtained. The acid values of the obtained reaction products A-2, A-3, and A-4 are 35, respectively.
It was 3,325,529. -3 Production of Alkenyl Succinic Acids (A-5) Hexadecenylsuccinic Anhydride 100 Obtained in 2
Part is neutralized with 25 parts of caustic soda and 160 parts of water to 40%.
Sodium hexadecenyl succinate solution (A-5)
Got -4 Production of Alkenyl Succinic Acids (A-6) (For Comparative Example) n-Dodecene-3 Instead of α-Olefin n-
Hexadecene-1 was used in the same manner as-1 to obtain an acid value of 3
48 hexadecenyl succinic anhydrides (A-6) were obtained.

Production of Reinforced Rosin Ester -1 Production of Reinforced Rosin Ester (B-1) Gum rosin 1000 having an acid value of 170 was placed in a 2 liter flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, a water divider and a condenser.
Part and 80 parts of glycerin (charge equivalent ratio is OH
/−COOH=0.87) and reacted at 250 ° C. for 12 hours to obtain a reaction product. Next, the temperature was maintained at 200 ° C., 91 parts of maleic acid was added, and the mixture was heated and kept at 200 ° C. for 3 hours to obtain a maleated rosin ester (B-1). -2 Production of fortified rosin ester (B-2) A tall oil rosin 60 having an acid value of 170 was placed in a 1-liter flask equipped with a stirrer, a thermometer, a nitrogen introducing tube, a water diverter and a cooler.
0 parts and epoxy resin (Dainippon Ink and Chemicals Co., Ltd. product name "720", epoxy equivalent 150 g / eq) 160
Part (Equipment ratio is epoxy group / -COOH = 0.5
9) was charged, heated to 250 ° C. under a nitrogen stream, and kept at the same temperature for 10 hours to obtain a reaction product. Then 200
The temperature was maintained at 0 ° C, 57 parts of maleic acid was added, and the mixture was heated and kept at 200 ° C for 3 hours to obtain a maleated rosin ester (B-2). -3. Manufacture of toughened rosin ester (B-3) 30 parts of fumaric acid was gradually added to 485 parts of gum rosin in a molten state at about 200 ° C, and after almost all fumaric acid had reacted, formaldehyde treatment was further performed. (Modification rate: 3%) 485 parts of tall oil rosin were added and homogenized by melting and stirring, and then the reaction product was cooled to room temperature. Next, 91 parts of glycerin was charged (the charge equivalent ratio was --OH /-COOH = 0.87) and reacted at 250 ° C. for 12 hours to obtain a reaction product (B-3).

Production of Polymeric Emulsifying Dispersant Polymeric emulsifying dispersants (C-1) and (C-) for working examples for dispersion-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 Preparation of Cationic Polymer Dispersant (C-2) for Examples The cationic poly (meth) acrylamide having a hydrophobic group described in Example 1 of JP-A-2-177534 was used. A polymeric dispersant (C-2) was produced as follows according to the production method. A 1 liter 4-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube was charged with 31.4% of dimethylaminoethyl methacrylate.
Parts, 50% acrylamide aqueous solution 85.3 parts, styrene 20.8 parts, ion-exchanged water 100.6 parts, isopropyl alcohol 143.3 parts, n-dodecyl mercaptan 0.6 parts, and 20% acetic acid aqueous solution pH. To 4.5
Adjusted to. The temperature of this mixed solution was raised to 60 ° C. under a nitrogen gas atmosphere while stirring. 2.3 parts of a 5% ammonium persulfate aqueous solution was added as a polymerization initiator, the temperature was raised to 80 ° C., and the temperature was maintained for 1.5 hours.
% Aqueous solution 0.7 parts was added. After maintaining at the same temperature for 1 hour, 100 parts of ion-exchanged water was added, then isopropyl alcohol was distilled off, and ion-exchanged water was further added to the dispersion of cationic polymer having a solid content concentration of 20.4% (C-2. ) Was manufactured.

Production of Rosin Ester Emulsion Composition (Sizing Agent) -1 The reinforced rosin ester obtained in Examples 1 to 4 and the alkenyl succinic acid were mixed in the ratio shown in Table 1 and heated to about 150 ° C. for melting. ,
While vigorously stirring, 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 solid content of the emulsion thus obtained is about 45 to 50%, and the cumulative 50% diameter in the weight-based particle size distribution measured by Master Sizer (manufactured by Malvern Instruments Ltd.) (hereinafter,
The average particle size) is 0.28 to 0.38 μm,
It was stable for a long time.

-2 The rosin ester and alkenyl succinic acids obtained in Examples 5 to 6 are shown in Table 1.
Mix in the proportions shown in Table 1, heat and melt to about 150 ° C, and mix vigorously under high temperature and high pressure with the dispersant obtained in the same proportions as shown in the table so that the solid content is 50% with water. Then
The mixture was passed through an industrial homogenizer at a pressure of about 1000 Kg / cm ² and then cooled to room temperature. Each has a solid content of about 50% and an average particle size of 0.32 to 0.3.
It was 8 μm and was stable for a long time. -3 The toughened rosin ester (B-1) obtained in Example 7 was melted by heating at about 150 ° C., and with vigorous stirring, the proportions of dispersant (C-1) and alkenyl succinic acids (A) shown in Table 1 were obtained. The mixture with -5) was added and mixed 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 had a solid content of 50.1% and an average particle size of 0.25 μm, and was stable for a long period of time. -4 Comparative Example 1 An emulsion composition (size) was obtained in the same manner as in Example 1 except that alkenylsuccinic acid was not used. -5 Comparative Example 2 An emulsion composition (size) was obtained in the same manner as in Example 2 except that the alkenylsuccinic anhydride (-4) produced from α-olefin was used. Example above,
Table 1 shows the composition and properties of the rosin emulsion composition of Comparative Example.

[0034]

[Table 1]

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

Size effect test Bleached kraft pulp (pulp ratio of softwood to hardwood is 1: 4
The mixed pulp) was diluted with water for dilution having a hardness of 500 ppm so as to have a pulp concentration of 2.5%, and beaten 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 (0.4% or 0.8%) and 1.0% of vanadium sulfate. Cationic polyacrylamide (DS410, a paper-making agent of Nippon PMC Co., Ltd.) 0.2 is used as a fixing agent.
% And then stirred for 10 minutes. Next, this pulp slurry was diluted to a concentration of 0.25% with diluted water of pH 8, 15% of light calcium carbonate (Tamapearl 121S manufactured by Okutama Kogyo Co., Ltd.), and a high molecular weight cationic polyacrylamide (Nippon P. 0.01% of a retention agent RD814 manufactured by MC Co., Ltd. was added, and paper was made with a Noble and Wood paper machine at a paper making pH of 8 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 test paper thus obtained is subjected to 2 in a constant temperature and constant humidity environment (20 ° C., 65% relative humidity).
After conditioning the humidity for 4 hours, the sizing degree was measured by the Steckit method. The results are shown in Table 2. Of the drying conditions in the table,
The conditions of 80 ° C. and 100 seconds correspond to “when the drying conditions are relatively mild”.

[0037]

[Table 2]

Static stability test 100 ml of the sizing agents of the above-mentioned 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 the static size was 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 3.

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 performed 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. Table 3 shows the measurement results.
Shown in.

[0040]

[Table 3]

[0041]

EFFECTS OF THE INVENTION According to the present invention, alkenyl succinic acids composed of a reaction product of an internal olefin having a β or higher as a main component and at least one of maleic acid and maleic anhydride, and a rosin system containing rosin esters. Since an emulsion composition, a method for producing the same, a sizing agent, a sizing method, and sized paper can be provided, when sizing is performed using a sizing agent containing this rosin-based emulsion composition, the papermaking speed is particularly high and drying conditions are high. It is possible to provide a paper exhibiting an excellent sizing effect not found in conventional anionic or cationic rosin emulsions even under mild conditions. Further, this sizing agent has excellent storage stability and mechanical stability.

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Claims (12)

[Claims] 1. An alkenyl succinic acid obtained by the reaction of (A) an internal olefin whose main component is β or more with maleic acid and / or maleic anhydride, (B) a rosin ester, and (C) a dispersant. A rosin-based emulsion composition in which the dispersoid is stably dispersed in water. 2. The internal olefin of (A) has 6 to 30 carbon atoms.
The rosin-based emulsion composition according to claim 1. 3. The rosin ester of component (B) is at least one selected from the group consisting of rosins, modified rosins and their respective α, β unsaturated carboxylic acid adducts.
The rosin emulsion composition according to claim 1 or 2, which is a compound obtained by esterifying a part or all of the carboxyl groups of the species with an esterifying agent. 4. The rosin ester is an α, β unsaturated carboxylic acid adduct of a compound obtained by esterifying a part or all of the carboxyl groups of rosin and / or modified rosin with an esterifying agent. The rosin-based emulsion composition according to 2. 5. The rosin emulsion composition according to claim 3, wherein the esterifying agent is at least one selected from the group consisting of monohydric alcohols, dihydric alcohols and polyhydric alcohols. 6. The rosin emulsion composition according to claim 3 or 4, wherein the esterifying agent is an epoxy resin having two or more oxirane rings in one molecule and having a molecular weight of 10,000 or less. 7. 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, The rosin-based emulsion composition according to any one of claims 1 to 6, which is a dispersion having a solid content concentration of 20 to 60% by weight. 8. A method for producing 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. 9. A mixture of the component (A) and the component (C),
8. Dispersing the ingredients using the mixture.
A method for producing the rosin-based emulsion composition according to any one of 1. 10. A sizing agent containing the rosin emulsion composition according to any one of claims 1 to 7. 11. A sizing method using the rosin-based emulsion composition according to claim 1 as a sizing agent. 12. A sized paper containing (A) an alkenyl succinic acid obtained from the reaction of an internal olefin having β or more with maleic acid and / or maleic anhydride, and (B) a rosin ester.