JP3002024B2 - Alkenyl succinic acid emulsion sizing agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel alkenyl succinic acid emulsion sizing agent having a high concentration and excellent storage stability, and provides a high sizing effect to paper.

[0002]

2. Description of the Related Art Saponification type (solution type) rosin sizing agents have long been used as internal sizing agents for papermaking in so-called acidic papermaking using bansulfate in combination. It is known that the sizing effect on the addition rate is low, and that the sizing effect decreases in the recent increase in water temperature due to the closed effluent and near neutral pH range. Emulsion-type rosin-based sizing agents have been found to improve the above-mentioned essential disadvantages of saponified rosin-based sizing agents.However, at a low addition rate, the sizing effect is low, and it is not always satisfactory. It is not at present.

In order to make up for the drawbacks of these rosin-based sizing agents, sizing agents obtained by alkali saponification of alkenyl succinic acid have recently been used as sizing agents having excellent sizing effect at a low addition ratio (Japanese Patent Application Laid-Open (JP-A) No. 2000-150630). Showa 58-21
No. 4598), but in high temperature papermaking and near neutral papermaking pH range, there is a disadvantage that the size effect is reduced as in the case of the saponified rosin-based sizing agent.

As an alkenyl succinic acid emulsion sizing agent, an alkenyl succinic anhydride containing an emulsifier is mixed with a cationized starch solution or water in an amount of 0.5 to 1%.
A method of emulsifying at a low concentration of about 3% and using it as a sizing agent for neutral papermaking is known (US Pat. No. 382106).
No. 9).

The mechanism of action of alkenyl succinic anhydride in neutral papermaking is that the anhydride group of alkenyl succinic anhydride directly reacts with the hydroxyl group of pulp to be fixed on pulp fibers and exhibit a size effect. is there. Therefore, the alkenyl succinic anhydride in conventional neutral papermaking must be added to the pulp slurry as an anhydride. However, since alkenyl succinic anhydride has high reactivity with water, if alkenyl succinic anhydride is emulsified and dispersed in water in advance, it reacts with water within a short time to lose the acid anhydride group, In addition to losing the function as a neutral sizing agent, the emulsification state changes in the process of changing alkenyl succinic anhydride to alkenyl succinic acid, and aggregation, precipitation and separation occur. As described above, the emulsion sizing agent of alkenyl succinic anhydride in neutral papermaking cannot be stored in the form of an emulsion beforehand as a high-concentration product because it can be stored for only a few hours in the state of an aqueous dispersion. In addition to the work problem that the emulsifier must be emulsified and dispersed using an emulsifier immediately before, in the acidic region where bansulfate is used as a fixing agent, the size effect rises slowly, and the size effect immediately after papermaking is poor. There are drawbacks.

As described above, the reason that the conventional emulsion of alkenyl succinic anhydride has a poor size effect immediately after paper making in acidic paper making is that the emulsion sizing agent is fixed on the pulp fiber in the form of an acid anhydride, so that the acid sizing is not effective. Alkenyl succinic anhydride reacts slowly with pulp, and it takes time for alkenyl succinic anhydride to react with water to form alkenyl succinic acid, which further reacts with bansulfate to develop a size effect. It is thought to be. Therefore, if alkenyl succinic anhydride can be converted into alkenyl succinic anhydride in advance and emulsified, the reaction with bansulfate proceeds quickly, and a good size effect can be expected even in an acidic region.

However, alkenyl succinic acid is an extremely hydrophilic substance, so it is extremely difficult to emulsify it. Conventionally, it is difficult to obtain an emulsion which can maintain a high concentration and a stable state for a long period of time by conventional techniques. Was. Further, if alkenyl succinic anhydride is emulsified by a conventional method as described above, the alkenyl succinic anhydride reacts with water in the emulsified solution and changes to alkenyl succinic acid,
Although an emulsion of alkenyl succinic acid is obtained, the emulsified state changes in the process of converting alkenyl succinic anhydride to alkenyl succinic acid, and a stable emulsion of alkenyl succinic acid cannot be obtained. That is, even if it is possible to temporarily prepare an emulsion of alkenyl succinic anhydride at a high concentration,
Alkenyl succinic anhydride reacts with water in the emulsion to change into alkenyl succinic acid, and coagulation, precipitation and separation occur, and a stable emulsion cannot be maintained. An emulsion having good properties could not be obtained.

[0008]

Accordingly, the present invention overcomes the disadvantages of the saponified alkenyl succinic acid-based sizing agent and the alkenyl succinic anhydride-based emulsion sizing agent described above. It is an object of the present invention to provide a novel alkenyl succinic acid emulsion sizing agent which exhibits an excellent sizing effect immediately after papermaking at a low addition ratio even in a pH range, and has a high concentration and excellent storage stability.

[0009]

Means for Solving the Problems The inventors of the present invention have solved the above-mentioned problems and have conducted intensive studies to make use of the excellent properties of alkenyl succinic acid as a raw material for sizing agents in the form of an emulsion. The use of an emulsifier selected in (1) and / or an anionic polymer type emulsifying dispersant having an appropriate monomer composition and / or blending of a hydrocarbon-based resin having no acid group provides excellent storage stability at a high concentration. An alkenyl succinic acid emulsion sizing agent can be produced, and this emulsion is extremely excellent in storage stability, low addition ratio, high temperature papermaking, and even in papermaking in a pH range close to neutrality, the conventional saponified alkenyl succinic acid-based emulsion is used. The present inventors have found that the present invention exerts an excellent sizing effect not found in sizing agents, and has completed the present invention.

That is, according to the present invention, an alkenyl succinic acid obtained from a reaction product of a branched internal olefin having 12 to 18 carbon atoms and maleic anhydride is used in an amount of 25 parts by weight or more per 100 parts by weight of the solid content of the emulsion sizing agent. The present invention relates to an alkenyl succinic acid-based emulsion sizing agent having a solid content of 25% by weight or more, in which a contained composition is dispersed in water by an anionic polymer type emulsifying dispersant or the dispersing agent and the emulsifier.

For producing the sizing agent of the present invention having such a constitution, any conventionally known emulsifying method may be used, but the inversion method can be used most easily. That is, after sufficiently melt-mixing a composition containing 25 parts by weight or more of alkenyl succinic acid, further thoroughly mix an emulsifier or an anionic polymer type emulsifying dispersant or both an emulsifying agent and an anionic polymer type emulsifying dispersant. The sizing agent of the present invention can be easily obtained by gradually adding water while stirring and inverting the phase.

[0012] Further, a part or all of the emulsifier and / or the anionic polymer type emulsifier / dispersant is dissolved in water to be added instead of being previously added to a composition containing 25 parts by weight or more of alkenyl succinic acid, It is also possible to emulsify with.

When a high-pressure emulsifier is used, an emulsion of alkenyl succinic acid which is finer and more excellent in stability can be obtained. In this case, the alkenyl succinic acid is replaced by 2
Heating the composition containing 5 parts by weight or more to a molten state,
Hot water, an emulsifier, and / or an anionic polymer-type emulsifying dispersant are added to the mixture, preliminarily emulsified by a homogenizer, and then emulsified by a high-pressure emulsifier.

Further, a composition containing at least 25 parts by weight of alkenyl succinic acid is dissolved in a water-insoluble organic solvent such as benzene or toluene, and then water, an emulsifier and / or an anionic polymer type emulsifier are added. It is a matter of course that an emulsification method in which an organic solvent is distilled off after emulsification by a homogenizer or a high-pressure emulsifier can be used.

In the present invention, an emulsion sizing agent which is stable and has an excellent size effect even when alkenyl succinic acid alone is emulsified with an anionic polymer type emulsifying dispersant can be obtained. If a resin is blended, an emulsion exhibiting an even more stable and excellent size effect can be obtained. The mixing ratio is alkenyl succinic acid 25 to 95
The hydrocarbon resin is 75 to 5 parts by weight with respect to parts by weight.

As the alkenyl succinic acid used in the present invention, those produced by reacting an alkenyl succinic anhydride with an equimolar amount of water can be used. Alkenyl succinic anhydride can be obtained by a known method.
An addition reaction of an olefin and maleic anhydride can be used.
18 branched internal olefins are desirable because of their excellent size effect. Alkenyl succinic acid obtained from a straight-chain olefin is inferior in size effect, but can be partially used in an alkenyl succinic acid obtained from a branched olefin as long as the effects of the present invention are not impaired.

If alkenyl succinic anhydride is used instead of alkenyl succinic anhydride and emulsification is carried out in the same manner, an aqueous emulsion containing alkenyl succinic anhydride can be obtained. In this case, the alkenyl succinic anhydride reacts with water in the emulsion and changes to alkenyl succinic acid after about 1 to 2 days. However, the alkenyl succinic anhydride is characterized by the coexistence of the hydrocarbon resin which is a feature of the present invention. Unlike the emulsion of the product alone, the emulsified state does not change at all in the process of changing alkenyl succinic anhydride to alkenyl succinic acid, and contains alkenyl succinic acid in a stable form without aggregation, precipitation, separation, etc. The sizing agent of the present invention is obtained.

As described above, when emulsifying alkenyl succinic anhydride as it is, the compounding of a hydrocarbon resin is essential, but when emulsifying alkenyl succinic acid, the compounding of a hydrocarbon resin is not always necessary. .

The hydrocarbon resin used in the present invention includes:
A resin having no acid group and having compatibility with alkenyl succinic acid or alkenyl succinic anhydride can be used.However, in order to improve the emulsifiability of alkenyl succinic acid and the stability of the emulsion, the heat of petroleum is reduced. Aromatic resins, aliphatic petroleum resins, and aromatic resins produced by polymerizing cracked oil fractions having a boiling range of about 20 to 280 ° C. obtained by cracking.
Aliphatic mixed petroleum resins, aromatic methylene resins substantially free of oxygen atoms obtained by reacting aromatic compounds with formaldehyde in the presence of a catalyst, and methylene, ether, acetal, methylol An aromatic formaldehyde resin bonded by, for example, is preferred.

As described above, since the hydrocarbon resin used in the present invention does not contain any acid groups such as rosin substances, it exhibits only a low size effect. However, when it is used in combination with alkenyl succinic acid, This has the effect of significantly improving emulsifying properties and stability of the emulsion. The mixing ratio of alkenyl succinic acid, which is the main component of the sizing agent of the present invention, and the hydrocarbon resin is 25 to 95 parts by weight of alkenyl succinic acid,
The ratio is 75 to 5 parts by weight of the hydrocarbon resin.

If desired, further resinous materials such as rosin, the reaction product of rosin with α, β-unsaturated polybasic acids, disproportionated rosin, polymerized rosin, hydrogenated rosin, rosin and formaldehyde Modified rosin, such as reaction products, fatty acids, tall oil, or paraffin wax,
A composition containing a petroleum hydrocarbon or the like can also be used. In this case, the proportion of the alkenyl succinic acid or the total amount of the alkenyl succinic acid and the hydrocarbon resin having no acid group in the composition is 50% by weight. % Is preferable. That is, if the proportion of the resinous substance other than alkenyl succinic acid or a mixture of alkenyl succinic acid and a hydrocarbon resin having no acid group in the composition exceeds 50% by weight, the size effect is reduced, which is not preferable. .

The emulsifier preferably used in the present invention includes one or a mixture of two or more selected from anionic and nonionic. Examples of such emulsifiers include alkyl benzene sulfonate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene aralkyl phenyl ether sulfate, alkyl ether sulfate, polyoxyethylene. Alkyl ether phosphates and salts thereof,
Anionic surfactants such as polyoxyethylene alkyl phenyl ether phosphate and salts thereof, polyoxyethylene aralkyl phenyl ether phosphate and salts thereof, and polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene aralkyl phenyl Nonionic surfactants such as ether, sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester are included. Among them, polyoxyethylene nonyl phenyl ether phosphate or polyoxyethylene nonyl phenyl ether sulfate is preferred.

The polymer type emulsifying and dispersing agent preferably used in the present invention is a monomer constituting a hydrophilic group (A).
Examples include an anionic component comprising a copolymer of the component and the component (B), which is a monomer constituting a hydrophobic group, or a partially or completely saponified product thereof. Here, as the component (A), acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, and the like can be used.
As the component (B), styrene monomers such as styrene and α-methylstyrene, acrylic esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate and butyl methacrylate, methacryl esters and (meth) One or more of acrylamide, acrylonitrile and the like can be used.

The proportion of the polymer type emulsifying dispersant in the total monomers constituting the polymer or copolymer is such that the component (A) is 5 to 100% by weight, preferably 20 to 95% by weight.
And the component (B) is 95 to 0% by weight, preferably 80 to 5% by weight.
% By weight. If the amount of the component (A) is less than 5% by weight, no dispersing effect is exhibited. The polymerization or copolymerization reaction when synthesizing the dispersion stabilizer may be performed by known emulsion polymerization or solution polymerization.Partial or complete saponification of the copolymer is obtained by using sodium hydroxide, It can be obtained by saponification with an alkali such as potassium hydroxide. The saponification ratio at that time differs depending on the method of use, and is not particularly limited. The number average molecular weight of the anionic polymer type emulsifying dispersant is 1,000,000 or less, preferably 1
10,000 to 300,000.

The mixing ratio of the emulsifier and / or the polymer type emulsifying dispersant is 1 to 20 parts by weight, preferably 3 to 10 parts by weight, per 100 parts by weight of the composition containing 25 parts by weight or more of alkenyl succinic acid. Department.

The obtained emulsion sizing agent is mixed with alkenyl succinic acid or alkenyl succinic acid and 15 parts by weight or less , preferably 5 to 10 parts by weight, of a water-soluble acrylamide-based polymer with respect to 100 parts by weight of the hydrocarbon resin. Then, the mechanical stability of the emulsion is improved.
Here, the acrylamide-based water-soluble polymer is, for example, a completely or partially saponified product of a copolymer of (meth) acrylamide and (meth) acrylic acid or a complete copolymer of (meth) acrylamide and a copolymer of (meth) acrylic acid and acrylonitrile. Or a partially or partially saponified product of a copolymer of (meth) acrylamide and (meth) acrylic acid and styrene and having a molecular weight of 100,000 to 60
I mean everything.

The sizing agent according to the present invention can be added to the papermaking material in any step before the end of the papermaking operation, just like the conventional rosin-based sizing agent. Before or after the addition of the sizing agent according to the present invention to
By adjusting H to about 4.0 to 7.0, the pulp can be fixed. In use, it can be used in an optional ratio with other sizing agents such as a conventional rosin-based sizing agent and a petroleum resin sizing agent.

Usage fee (addition amount) of the sizing agent according to the present invention
Is in the range of 0.01 to 5.0% by weight, preferably 0.05 to 3.0% by weight, based on the weight of the dry pulp in the case of internal sizing.

[0029]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following cases, “parts” means “parts by weight” unless otherwise specified.

<Storage Stability Test> Alkenyl succinic acid emulsion sizing agents prepared by the methods described in Examples 1 to 20, the commercial sizing agent of Comparative Example 1, and the alkenyl succinic acids prepared in Comparative Examples 3, 4, and 6 Add the acid-based emulsion sizing agent to a 50 ml glass bottle
g, leave at room temperature (25 ° C.), and after 1 day, 7 days,
The stability after 60 days was visually observed. For those with poor stability, oily substances separated and precipitated at the bottom of the bottle or at the top of the liquid.
Note that Comparative Examples 2 and 5 were not subjected to storage stability tests because they were saponified types and not emulsion types.

The results are shown in Table 1.

<Size Effect Measurement Test> Bleached kraft pulp (LBKP) was diluted with city water to a pulp concentration of 2.5%, and the Canadian freeness was about 450 using a beater.
Beat to the milliliter. Next, the obtained pulp slurry is made into a 2.0% by weight slurry with city water at 50 ° C., and bansulfate (1.0% by weight based on pulp) is added with stirring.
Thereafter, the mixture was diluted to 0.5% by weight with water at pH 4.5 and 50 ° C., and the sizing agents of Examples 1 to 19 and Comparative Examples 1 to 6 (based on 0.3% by weight of pulp) were added. (Paper basis weight 60 g / m ² ).
The wet paper obtained here is pressed and dried as usual. Immediately after drying, the obtained paper was at a temperature of 20 ° C. and a humidity of 65% R.
After humidifying for one day in a constant temperature and humidity room of H, JIS P8122
And the size effect was measured by the Steckicht method.

Further, for the purpose of a high pH papermaking test, evaluation was also made on the case where 0.7% by weight of pulp was added to pulp and the pH of the dilution water and the pH of the papermaking water were set to 6.0. The sizing agents of Examples 1 to 20 and Comparative Examples 4 and 6 were used after 10 days of emulsification, and the emulsion sizing agent of alkenyl succinic anhydride of Comparative Example 3 had poor storage stability and maintained an emulsified state after 10 days of emulsification. Since it was not, the one immediately after emulsification was used.

<Mechanical Stability Test> Examples 15 and 1
6 and the mechanical stability of Comparative Example 1
It carried out according to the mechanical stability test described in -6387. That is, 50 g of each sizing agent diluted to a concentration of 10% was put into an apparatus (Marlon testing machine) shown in JIS K-6387, and the rotation speed was 1000 rpm under a load of 10 kg.
For 30 minutes, and the generation of sludge was visually observed.
The results are shown in Table 3. As shown in Table 3, Example 15 of the present invention produced less sludge than Comparative Example 1, and Example 16 in which an acrylamide-based water-soluble polymer was added showed no generation of sludge. Did not.

<Synthesis of Polymer Type Dispersion Stabilizer> (Synthesis Example 1) 30 parts of styrene, n-butyl acrylate 3
0 parts, acrylic acid 40 parts, isopropyl alcohol 5
Part, polyoxyethylene (degree of polymerization 13) distyrylphenyl ether sulfate ammonium 4 parts, polyoxyethylene (degree of polymerization 15) octyl phenyl ether 1
Parts, 2 parts of ammonium persulfate and 600 parts of water.
Polymerization was carried out with stirring at 0 ° C for 3 hours. Next, after cooling to 60 ° C., 20 parts of 38.9% potassium hydroxide was gradually added dropwise, followed by stirring at 60 ° C. for 30 minutes and cooling to room temperature. The solid content of the saponified styrene-acrylic acid copolymer is 15% (% by weight, the same applies hereinafter), the saponification rate is 25%,
The number average molecular weight of the copolymer before saponification was about 170,000.

(Synthesis Example 2) 35 parts of styrene, 30 parts of n-butyl acrylate, 35 parts of acrylic acid, 5 parts of isopropyl alcohol, 4 parts of ammonium polyoxyethylene (degree of polymerization 15) oleyl phenyl ether sulfate,
One part of polyoxyethylene (degree of polymerization: 12) dodecylphenyl ether, 2 parts of ammonium persulfate, and 600 parts of water were mixed and polymerized with stirring at 80 ° C. for 3 hours. Next, after cooling to 60 ° C., 40 parts of 48.5% sodium hydroxide was gradually added dropwise, followed by stirring at 60 ° C. for 30 minutes and cooling to room temperature. The solid content of the saponified styrene-acrylic acid copolymer was 15%, the saponification rate was 100%, and the number average molecular weight of the copolymer before saponification was about 160,000.

(Synthesis Example 3) Isopropyl alcohol 10
Dissolve 40 parts of maleic anhydride in 0 parts, heat to reflux temperature under a nitrogen stream, and drop a mixture of 60 parts of n-butyl acrylate, 1 part of azobisisobutyronitrile, and 100 parts of isopropyl alcohol in 2 hours. did. After maintaining at that temperature for another 2 hours, 29 parts of sodium hydroxide, 520 parts of water
Parts of the mixture were added dropwise. Next, the isopropyl alcohol was distilled off while heating to the boiling point, and water was added to add a solid content of 2%.
A light brown transparent aqueous solution having 0%, a saponification rate of 90% and a molecular weight of about 10,000 was obtained.

(Synthesis Example 4) Stearyl methacrylate 10
Parts, n-butyl acrylate 30 parts, acrylic acid 60 parts,
5 parts of isopropyl alcohol, 5 parts of ammonium polyoxyethylene (degree of polymerization 13) distyrylphenyl ether sulfate and 790 parts of water were mixed, and the mixture was heated with stirring. When the temperature reached 70 ° C., 10% ammonium persulfate was added. Milliliter was added, and the mixture was further heated and polymerized at 80 ° C. for 2 hours. Then, after cooling to 60 ° C, 20%
167 parts of sodium hydroxide were gradually added dropwise, stirred for 30 minutes, and cooled to room temperature. The solid content of the saponified acrylic acid-methacrylic acid copolymer was 13%, and the saponification rate was 100%. The number average molecular weight of the copolymer before saponification was about 100,000.

(Synthesis Example 5) Stearyl methacrylate 4
Parts, n-butyl acrylate 7 parts, acrylic acid 89 parts, 1
% 2-mercaptoethanol 5 parts and polyoxyethylene (degree of polymerization 13) distyryl phenyl ether sulfate 5 parts ammonium were mixed, polymerized in the same manner as in Synthesis Example 4, and saponified with 20% sodium hydroxide 148 parts.
A copolymer having a solid content of 12% and a saponification rate of 60% was obtained. The number average molecular weight of the copolymer before saponification was about 50,000.

(Synthesis Example 6) 7 parts of n-butyl acrylate
93 parts of acrylic acid, 1% 2-mercaptoethanol 10
And 25 parts of 20% sodium dodecylbenzenesulfonate were mixed and polymerized in the same manner as in Synthesis Example 4, and saponified with 103 parts of 20% sodium hydroxide to obtain a solid content of 12%.
A copolymer having a saponification rate of 40% was obtained. The number average molecular weight of the copolymer before saponification was about 20,000.

(Synthesis Example 7) Stearyl methacrylate 4
Parts, 7 parts of n-butyl acrylate, 75 parts of acrylic acid, 14 parts of acrylamide, 1% 2-mercaptoethanol 5
Parts, ammonium polyoxyethylene (degree of polymerization 13) distyryl phenyl ether sulfate 5 parts, and
Thereafter, polymerization was carried out in the same manner as in Synthesis Example 4 and saponified with 242 parts of 20% sodium hydroxide to obtain a copolymer having a solid content of 14% and a saponification rate of 100%. The number average molecular weight of the copolymer before saponification was 50,000.

(Synthesis Example 8) Stearyl methacrylate 4
Parts, n-butyl acrylate 15 parts, acrylic acid 81 parts,
5 parts of 1% 2-mercaptoethanol and 5 parts of ammonium polyoxyethylene (degree of polymerization 13) distyrylphenyl ether sulfate were mixed, polymerized in the same manner as in Synthesis Example 4, and saponified with 226 parts of 20% sodium hydroxide. A copolymer having a solid content of 13% and a saponification rate of 100% was obtained. The number average molecular weight of the copolymer before saponification was 60,000.

(Synthesis Example 9) 100 parts of methacrylic acid, 5 parts of isopropyl alcohol, 10 parts of ammonium polyoxyethylene (degree of polymerization 13) distyryl phenyl ether sulfate and 885 parts of water were mixed, and the mixture was heated to 70 with stirring. 10% ammonium persulfate 5
Then, the mixture was further heated and polymerized at 80 ° C. for 2 hours. Next, after cooling to 60 ° C., 47 parts of 20% sodium hydroxide was gradually added dropwise, stirred for 30 minutes, and cooled to room temperature. The saponified methacrylic acid polymer had a solid content of 11%, a saponification ratio of 20%, and a number average molecular weight of the polymer before saponification of about 150,000.

Example 1 An aromatic methylene resin (trade name: Oligotec 1400, Mitsubishi Petroleum) was added to 70 parts of an alkenyl succinic anhydride obtained by an addition reaction of a propylene oligomer (average carbon number: 18) with maleic anhydride. stock),
After mixing 30 parts of an average molecular weight of 900) and adding 4 parts of polyoxyethylene (degree of polymerization 17) nonylphenyl ether phosphate and 3 parts of ammonium polyoxyethylene (degree of polymerization 4) nonylphenyl ether sulfate,
Water is gradually added, phase inversion emulsification is performed, and the total solid content is 40% by weight.
An oil-in-water emulsion was prepared.

Example 2 A commercially available aromatic methylene resin (trade name: Oligotec 1300, Mitsubishi Petroleum) was added to 70 parts of alkenyl succinic anhydride obtained by addition reaction of propylene oligomer (average carbon number: 15) with maleic anhydride. (Average molecular weight 700) 30 parts, and polyoxyethylene (degree of polymerization 17) nonylphenyl ether phosphate 8 parts is added. Next, 10 parts of a 20% aqueous solution obtained by saponifying a commercially available styrene-maleic acid copolymer (trade name: HASMA1100, Misawa Ceramic Chemical Co., Ltd.) at a saponification rate of 60% was added, and water was gradually added. ,
Phase-inversion emulsification was performed to prepare an oil-in-water emulsion having a total solid content of 45% by weight.

Example 3 A commercially available aromatic methylene resin (trade name: Oligotec 1300, Mitsubishi Petroleum) was added to 80 parts of an alkenyl succinic anhydride obtained by an addition reaction of a propylene oligomer (average carbon number: 15) with maleic anhydride. (Average molecular weight: 700) 20 parts, and polyoxyethylene (polymerization degree 17) nonylphenyl ether phosphate 4 parts, polyoxyethylene (polymerization degree 4) nonylphenyl ether sulfate 3 parts ammonium, oleic acid Add 2 parts. After 13 parts of the emulsifying dispersant of Synthesis Example 1 was added, water was gradually added to carry out phase inversion emulsification to prepare an oil-in-water emulsion having a total solid content of 40% by weight.

Example 4 A linear internal olefin (average carbon number 16) and maleic anhydride were added to 60 parts of alkenyl succinic anhydride obtained by addition reaction of propylene oligomer (average carbon number 15) and maleic anhydride. 10 parts of alkenyl succinic anhydride obtained by the addition reaction and 30 parts of a commercially available aromatic methylene resin (trade name: Oligotec 1400, Mitsubishi Petroleum Co., Ltd., average molecular weight 900) were mixed, and polyoxyethylene (polymerization degree: 17 ) Nonylphenyl ether phosphate 4 parts, polyoxyethylene (polymerization degree 1
0) 1 part of distyryl phenyl ether phosphate,
3 parts of ammonium polyoxyethylene (degree of polymerization 4) nonylphenyl ether sulfate are added. Then, water was gradually added to cause phase inversion emulsification to prepare an oil-in-water emulsion having a total solid content of 40% by weight.

Example 5 Commercially available aromatic methylene resin (trade name: Oligotec 1300, Mitsubishi Petroleum) was added to 70 parts of alkenyl succinic anhydride obtained by addition reaction of propylene oligomer (average carbon number: 15) with maleic anhydride. Co., Ltd., 25 parts of an average molecular weight of 700) and 5 parts of fumarated rosin (fumalation ratio: 9%), 4 parts of polyoxyethylene (polymerization degree: 17) nonylphenyl ether phosphate, polyoxyethylene (polymerization degree: 17) 4) Add 3 parts ammonium nonylphenyl ether sulfate. Then, water was gradually added to cause phase inversion emulsification to prepare an oil-in-water emulsion having a total solid content of 40% by weight.

Example 6 30 parts of an aromatic formaldehyde resin (average molecular weight: 770) was mixed with 70 parts of an alkenyl succinic anhydride obtained by an addition reaction of a propylene oligomer (average carbon number: 15) with maleic anhydride. 6 parts of nonylphenyl ether phosphate of polyoxyethylene (degree of polymerization 17) and 12 parts of a 25% aqueous solution of sodium dodecylbenzenesulfonate are added. Then, water was gradually added to cause phase inversion emulsification to prepare an oil-in-water emulsion having a total solid content of 40% by weight.

Example 7 30 parts of an aromatic formaldehyde resin (average molecular weight: 770) was mixed with 70 parts of an alkenyl succinic anhydride obtained by an addition reaction of a propylene oligomer (average carbon number: 15) with maleic anhydride. Polyoxyethylene (degree of polymerization 17) nonylphenyl ether phosphate 5 parts, polyoxyethylene (degree of polymerization 1
5) Add 3 parts of nonylphenyl ether. After adding 8 parts of the emulsifying dispersant of Synthesis Example 3, water was gradually added to carry out phase inversion emulsification to prepare an oil-in-water emulsion having a total solid content of 35% by weight.

Example 8 A commercial aromatic methylene resin (trade name: Oligotec 1400, Mitsubishi Petroleum) was added to 60 parts of an alkenyl succinic anhydride obtained by an addition reaction of a propylene oligomer (average carbon number: 12) and maleic anhydride. (Average molecular weight: 900) and 40 parts of polyoxyethylene (polymerization degree: 17) nonyl phenyl ether phosphate and 3 parts of ammonium polyoxyethylene (polymerization degree: 4) nonyl phenyl ether sulfate. Then, water was gradually added to cause phase inversion emulsification to prepare an oil-in-water emulsion having a total solid content of 40% by weight.

Example 9 An alkenyl succinic anhydride obtained by an addition reaction of a propylene oligomer (average carbon number: 15) and maleic anhydride was added to 80 parts of an aliphatic petroleum resin (trade name: Escolets 1304, Tonex Corporation) ), Average molecular weight 1000) and 20 parts of polyoxyethylene (degree of polymerization 17) nonylphenyl ether phosphate 7 parts. Then slowly add water,
The emulsion was subjected to phase inversion to prepare an oil-in-water emulsion having a total solid content of 40% by weight.

Example 10 Commercially available aromatic methylene resin (trade name: Oligotec 1300, Mitsubishi Petroleum) was added to 40 parts of alkenyl succinic anhydride obtained by addition reaction of propylene oligomer (average carbon number: 15) with maleic anhydride. (Average molecular weight: 700) 60 parts, and polyoxyethylene (weight 17) nonylphenyl ether phosphate 8 parts was added and heated to 60 ° C. Next, a commercially available anionic oligomer emulsifier (trade name: Polywet SN)
-4, Sumitomo Nogatack Co., Ltd.) 6 parts of a 45% aqueous solution was added, and then water was gradually added to cause phase inversion emulsification to obtain a total solid content of 4%.
An oil-in-water emulsion of 0% by weight was prepared.

Example 11 Commercially available aromatic methylene resin (trade name: Oligotec 1040, Mitsubishi Petroleum) was added to 90 parts of alkenyl succinic anhydride obtained by addition reaction of propylene oligomer (average carbon number: 15) with maleic anhydride. Co., Ltd., average molecular weight 300) 10 parts and a 25% strength aqueous solution of sodium dodecylbenzenesulfonate 40
Was added and mixed with 257 parts of warm water at 40 ° C. using a homomixer. Subsequently, the mixture was passed twice through a piston-type high-pressure emulsifier (APV-Gaulin Co., Ltd.) under a pressure of 300 kg / cm ² to prepare an oil-in-water emulsion having a total solid content of 30% by weight.

Example 12 An alkenyl succinic acid was prepared by reacting an alkenyl succinic anhydride obtained by an addition reaction of a propylene oligomer (average carbon number: 15) with maleic anhydride with an equimolar amount of water. 60 parts of this alkenyl succinic acid and a commercially available aromatic methylene resin (trade name: Oligotec 1100, Mitsubishi Oil Co., Ltd., average molecular weight 350)
After adding 40 parts of polyoxyethylene (degree of polymerization: 4) ammonium nonylphenyl ether sulfate and 40 parts of the emulsifying dispersant of Synthesis Example 2, the mixture was mixed with 257 parts of hot water using a homomixer (5000 rpm). did. After cooling, an oil-in-water emulsion having a total solid content of 30% by weight was prepared.

Example 13 A commercially available aromatic methylene resin (trade name: Oligotec 1100, Mitsubishi Petroleum) was added to 90 parts of an alkenyl succinic anhydride obtained by an addition reaction of a propylene oligomer (average carbon number: 15) with maleic anhydride. (Agency Co., Ltd., average molecular weight: 350) 10 parts were mixed, and Synthesis Example 2
Was added and mixed with 315 parts of warm water at 90 ° C. using a homomixer. Subsequently, this emulsified product was subjected to a piston type high-pressure emulsifying machine (APV-Gaulin Co., Ltd.) for 500 hours.
After homogenizing twice under a pressure of kg / cm ^2, the mixture was rapidly cooled to room temperature to prepare an oil-in-water emulsion having a total solid content of 35% by weight.

Example 14 An alkenyl succinic acid was prepared by reacting an alkenyl succinic anhydride obtained by an addition reaction of a propylene oligomer (average carbon number: 15) with maleic anhydride with an equimolar amount of water. 21 parts of the emulsifying and dispersing agent of Synthesis Example 7 was added to 100 parts of the alkenyl succinic acid, and 137 parts of warm water was added.
0000 rpm). Subsequently, the emulsion was homogenized by passing it through a piston-type high-pressure emulsifier (APV-Gaulin Co., Ltd.) four times under a pressure of 700 kg / cm ² , rapidly cooled to room temperature, and cooled to room temperature. An oil-in-water emulsion of 40% by weight was prepared.

Example 15 An alkenyl succinic acid was prepared by reacting an equimolar amount of water with an alkenyl succinic anhydride obtained by an addition reaction of a propylene oligomer (average carbon number: 15) with maleic anhydride. 80 parts of this alkenyl succinic acid and a commercially available aromatic methylene resin (trade name: Oligotec 1100, Mitsubishi Oil Co., Ltd., average molecular weight 350)
After mixing 20 parts and adding 23 parts of the emulsifying dispersant of Synthesis Example 4, 135 parts of hot water and a homomixer (100
00 rpm). Subsequently, the emulsified product was treated with a piston-type high-pressure emulsifier (manufactured by APV-Gaulin) at 700 k.
After homogenizing four times under a pressure of g / cm ^2, the mixture was rapidly cooled to room temperature to prepare an oil-in-water emulsion having a total solid content of 40% by weight.

(Example 16) To 250 parts of the emulsion prepared in Example 15, 20 parts of a commercially available anionic acrylamide polymer (trade name: Polyaclon V, Misawa Ceramic Chemical Co., Ltd.) having a solid content of 15% was mixed. An oil-in-water emulsion having a total solid content of 38% by weight was obtained.

Example 17 An alkenyl succinic acid was prepared by reacting an alkenyl succinic anhydride obtained by an addition reaction of a propylene oligomer (average carbon number: 12) with maleic anhydride with an equimolar amount of water. 33 parts of the emulsifying and dispersing agent of Synthesis Example 5 was added to 100 parts of this alkenyl succinic acid, and the mixture was mixed with 164 parts of warm water and 40 ° C. using a homomixer (100 parts).
00 rpm). Subsequently, the emulsified product was treated with a piston-type high-pressure emulsifier (manufactured by APV-Gaulin) for 700 hours.
After homogenizing four times under a pressure of kg / cm ^2, the mixture was rapidly cooled to room temperature to prepare an oil-in-water emulsion having a total solid content of 35% by weight.

Example 18 An alkenyl succinic acid was prepared by reacting an alkenyl succinic anhydride obtained by an addition reaction of maleic anhydride with a propylene oligomer (average carbon number: 15) with an equimolar amount of water. After adding 23 parts of the emulsifying dispersant of Synthesis Example 8 to 100 parts of this alkenyl succinic acid, 135 parts of warm water and 50 ° C. were mixed with a homomixer (100 parts).
00 rpm). Subsequently, the emulsified product was treated with a piston-type high-pressure emulsifier (manufactured by APV-Gaulin) for 700 hours.
After homogenizing four times under a pressure of kg / cm ^2, the mixture was rapidly cooled to room temperature to prepare an oil-in-water emulsion having a total solid content of 40% by weight.

Example 19 An alkenyl succinic acid was prepared by reacting an alkenyl succinic anhydride obtained by the addition reaction of a propylene oligomer (average carbon number: 15) with maleic anhydride with an equimolar amount of water. 80 parts of this alkenyl succinic acid and 20 parts of cylinder stock were mixed, 17 parts of the emulsifying dispersant of Synthesis Example 6 was added, and then mixed with 174 parts of hot water at 90 ° C. using a homomixer (10000 rpm). Subsequently, this emulsion is subjected to a piston type high-pressure emulsifier (APV).
4 under pressure of 700 kg / cm ^2.
After passing through and homogenizing, the mixture was rapidly cooled to room temperature to prepare an oil-in-water emulsion having a total solid content of 35% by weight.

Example 20 An alkenyl succinic acid was prepared by reacting an alkenyl succinic anhydride obtained by the addition reaction of a propylene oligomer (average carbon number: 15) with maleic anhydride with an equimolar amount of water. 80 parts of this alkenyl succinic acid and 20 parts of tall oil (trade name: SR-30, Harima Chemicals, Inc.) were mixed, and emulsifying dispersant 23 of Synthesis Example 4 was mixed.
After the addition, 171 parts of hot water was mixed at 90 ° C. with a homomixer (10000 rpm). Subsequently, this emulsion was subjected to a piston type high-pressure emulsifier (APV-Gaulin Co., Ltd.) for 7 minutes.
After homogenizing by passing through 4 times under a pressure of 00 Kg / cm ^2, the mixture was rapidly cooled to room temperature to prepare an oil-in-water emulsion having a total solid content of 35% by weight.

Example 21 An alkenyl succinic acid was prepared by reacting an equimolar amount of water with an alkenyl succinic anhydride obtained by an addition reaction of an n-butene oligomer (average carbon number: 16) with maleic anhydride. 21 parts of the emulsifying dispersant of Synthesis Example 7 was added to 100 parts of the alkenyl succinic acid, and 137 parts of warm water was added.
0000 rpm). Subsequently, the emulsion was homogenized by passing it through a piston-type high-pressure emulsifier (APV-Gaulin Co., Ltd.) four times under a pressure of 700 kg / cm ² , rapidly cooled to room temperature, and cooled to room temperature. An oil-in-water emulsion of 40% by weight was prepared.

Example 22 An alkenyl succinic acid was prepared by reacting an alkenyl succinic anhydride obtained by an addition reaction of a propylene oligomer (average carbon number: 15) with maleic anhydride with an equimolar amount of water. 80 parts of this alkenyl succinic acid and a commercially available aromatic methylene resin (trade name: Oligotec 1100, Mitsubishi Oil Co., Ltd., average molecular weight 350)
After mixing 20 parts and adding 27 parts of the emulsifying and dispersing agent of Synthesis Example 9, 134 parts of hot water and a homomixer (100
00 rpm). Subsequently, 700 kg of this emulsified product was obtained using a piston type high-pressure emulsifier (manufactured by APV-Gaulin).
After homogenizing four times under a pressure of / cm ^2, the mixture was rapidly cooled to room temperature to prepare an oil-in-water emulsion having a total solid content of 40% by weight.

Comparative Example 1 A commercially available emulsion-type rosin-based sizing agent (OT-500J, manufactured by Dick Hercules Co., Ltd.) having a solid content of 50% in which a component containing fumarated rosin as a main component was emulsified with a polymer type emulsifying dispersant. ) Was used.

Comparative Example 2 A commercially available saponified rosin-based sizing agent (manufactured by Misawa Ceramic Chemical Co., Ltd., PF size: 800 L) having a solid content of 50% was prepared by saponifying a component containing maleated rosin as a main component with kaseikari. Using.

Comparative Example 3 100 parts of alkenyl succinic anhydride obtained by the addition reaction of a propylene oligomer (average carbon number: 15) and maleic anhydride were mixed with polyoxyethylene (degree of polymerization: 4) nonyl phenyl ether sulfate ammonium 10 After stirring well at 50 ° C,
One part of this mixture is mixed with 99 parts of water, and mixed with a homomixer.
0000 rpm, stirred and emulsified for 1 minute, total solid content 1% by weight
Oil-in-water emulsion was obtained.

Comparative Example 4 A commercially available aromatic methylene resin (trade name: Oligotec 1400, 60 parts) of an alkenyl succinic anhydride obtained by an addition reaction of a linear internal olefin (average carbon number: 16) and maleic anhydride was added. 40 parts of Mitsubishi Petroleum Co., Ltd., average molecular weight 900) were mixed, and polyoxyethylene (degree of polymerization 17) nonylphenyl ether phosphate 8 parts and polyoxyethylene (degree of polymerization 10) distyrylphenyl ether phosphate 2 parts were mixed. And add
The emulsion was subjected to phase inversion to obtain an oil-in-water emulsion having a total solid content of 40% by weight.

Comparative Example 5 Potassium hydroxide 2 was added to 60 parts of an alkenyl succinic anhydride obtained by an addition reaction of a propylene oligomer (average carbon number: 12) and maleic anhydride.
An aqueous solution consisting of 6 parts and 126 parts of water is added and the temperature is adjusted to 90
C. to 100.degree. C. and stir. After 3 hours, the mixture was cooled to room temperature to obtain a saponified alkenyl succinic acid-based sizing agent having a total solid content of 40% by weight.

Comparative Example 6 Forty parts of alkenyl succinic anhydride obtained by addition reaction of a propylene oligomer (average carbon number: 15) with maleic anhydride was mixed with 60 parts of fumarated rosin (fumalation ratio: 9%). Then, 4 parts of polyoxyethylene (polymerization degree 17) nonylphenyl ether phosphate and 3 parts of ammonium polyoxyethylene (polymerization degree 4) nonylphenyl ether sulfate are added. Subsequently, water was gradually added, and phase inversion emulsification was performed to obtain an oil-in-water emulsion having a total solid content of 40% by weight.

[0072]

The alkenyl succinic acid-based emulsion sizing agent according to the present invention has higher storage stability at a higher concentration than the conventional alkenyl succinic anhydride emulsion sizing agent and has an excellent sizing effect immediately after papermaking. Is shown. In addition, compared to a saponified alkenyl succinic acid-based sizing agent, the reduction in size effect is small even in high-temperature papermaking and in a wide pH range.

[0073]

[Table 1]

[0074]

[Table 2]

[0075]

[Table 3]

Continuation of the front page (56) References JP-A-2-47393 (JP, A) JP-A-54-15010 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) D21H 17 / 15 D21H 17/43

Claims (6)

(57) [Claims] An alkenyl succinic acid (alkenyl succinic acid itself) obtained from a reaction product of a branched internal olefin having 12 to 18 carbon atoms and maleic anhydride per 100 parts by weight of a solid content of an emulsion sizing agent . same.) the composition containing more than 25 parts by weight is dispersed in water by an anionic polymer emulsion dispersant or anionic polymer emulsion dispersant and emulsifier, solid concentration 25 wt% or more alkenyl A succinic acid emulsion sizing agent. 2. An alkenyl succinic acid obtained from a reaction product of a branched internal olefin having 12 to 18 carbon atoms and maleic anhydride, and 25 to 95 parts by weight of an alkenyl succinic acid and 75 to 5 parts by weight of a hydrocarbon resin having no acid group. An alkenyl succinic acid-based emulsion sizing agent having a solid content concentration of 25% by weight or more, wherein a composition containing the mixture of the above as a main component is dispersed in water by an emulsifier and / or an anionic polymer type emulsifying dispersant. 3. 50 to 95 parts by weight of alkenyl succinic acid obtained from the reaction product of a branched internal olefin having 12 to 18 carbon atoms with maleic anhydride, rosin, rosin derivative, tall oil, fatty acid, paraffin wax, petroleum oil A composition mainly composed of 50 to 5 parts by weight of a mixture of one or more components selected from hydrocarbons is dispersed in water by an anionic polymer type emulsifying dispersant. An alkenyl succinic acid emulsion sizing agent of not less than% by weight. 4. The sizing agent according to claim 2, wherein the hydrocarbon resin is at least one selected from petroleum resins, aromatic methylene resins, and aromatic-formaldehyde resins. Alkenyl succinic acid emulsion sizing agent. 5. The sizing agent according to claim 1, wherein the anionic polymer type emulsifying dispersant is (A) acrylic acid, methacrylic acid, maleic acid, maleic anhydride,
5 to 100% by weight of one or more anionic unsaturated monomers selected from itaconic acid and fumaric acid and (B) selected from styrenes, acrylic esters, methacrylic esters (meth) acrylamide, and acrylonitrile An alkenyl succinic acid-based emulsion sizing agent, which is a polymer or copolymer comprising 95% to 0% by weight of one or more nonionic unsaturated monomers or a partially or completely saponified product thereof. 6. The sizing agent according to claim 1, 2, 3, 4, or 5, wherein a completely or partially saponified copolymer of (meth) acrylamide and (meth) acrylic acid, or (meth) acrylamide and Completely or partially saponified copolymer of (meth) acrylic acid and acrylonitrile or completely or partially saponified copolymer of (meth) acrylamide and (meth) acrylic acid and styrene having a molecular weight of 100,000 to 600,000 Emulsion solids 10
An alkenyl succinic acid emulsion sizing agent containing not more than 15 parts by weight of solids with respect to 0 parts by weight.