JP3102958B2 - Papermaking 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 emulsion sizing agent excellent in storage stability, and provides an excellent sizing effect in a wide pH range of papermaking from an acidic range to a pH range close to neutrality. Things.

[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 in which a sulfuric acid band is used in combination. It is known that the size effect on the rate is low, and that the size effect decreases in a pH range close to neutrality due to an increase in water temperature due to the recent closure of wastewater. Emulsion-type rosin-based sizing agents have been found to improve the above-mentioned essential disadvantages of saponified rosin-based sizing agents. At present, it is not always satisfactory because of problems. In addition, the size effect also decreases with an increase in papermaking pH. Therefore, when used in a papermaking pH range close to neutrality, it is necessary to use a cationic polymer or the like in combination.

In order to compensate for the disadvantages of these rosin-based sizing agents, a sizing agent in which an alkali saponified alkenylsuccinic acid is blended with rosin as an emulsifying stabilizer and emulsified by a solvent emulsification method using toluene or the like has been proposed. (Japanese Patent Publication No. 56-22929). However, since the alkali saponified alkenyl succinic acid is not suitable for the inversion emulsification method, not only does a harmful solvent remain in the product, but if it is used in a near neutral pH range of papermaking, Tappi
Journal (February 1991, pages 178-181)
As shown in (d), there is a defect that the scum is left in a state of a very-highly hydrophilic fighting substance, and the size effect is reduced.

[0004] In addition, α-
Examples using an addition reaction product of an olefin with maleic anhydride (JP-A-55-25444) and examples using a hydrate of an addition reaction product of an α-olefin with maleic anhydride -89357) has been proposed,
If used as an anhydride, the emulsion will eventually break down due to the hydration reaction, resulting in poor stability of the sizing agent.Also, even when used as a hydrate, alkenyl succinic acid derived from α-olefin is used as a raw material. However, acid paper making using a sulfuric acid band as a fixing agent has a drawback of poor size performance (Japanese Patent Application No. 3-196962).

As proposed in Japanese Patent Application No. 3-196962, an excellent sizing effect can be obtained by emulsifying a hydrate of an addition reaction product of a branched olefin having 12 to 18 carbon atoms and maleic anhydride. As shown, since the alkenyl succinic acid is more expensive than rosin, it has not been used except for special applications where economics is not an issue. Also, if rosin is blended in an amount of 50% or more with emphasis on economy, there is a disadvantage that emulsion particles become coarse and the size effect is reduced.

[0006]

Accordingly, the present invention overcomes the above-mentioned disadvantages of rosin emulsion sizing agents,
Further, the present invention provides a novel emulsion sizing agent which shows an excellent sizing effect at a low addition ratio in a wide pH range, and has a high concentration and excellent storage stability.

[0007]

Means for Solving the Problems The present inventors have intensively studied to solve the above problems and utilize the excellent properties of branched alkenyl succinic acid as a raw material for sizing agents to rosin emulsion sizing agents. Results: (a) Propylene oligomer having an average carbon number of 12 to 18
And / or 3 to 25% by weight of a hydrate of an addition reaction product of an n-butene oligomer and maleic anhydride. (B) Enhanced rosin and / or a modified product thereof 97 to 75
% By weight of an essential resin component, and (c) an emulsion sizing agent emulsified by adding 3 to 30 parts by weight of an emulsifier and / or a polymer dispersant with respect to 100 parts by weight of the resin component. Outstanding performance not seen with conventional rosin emulsion sizing agents, showing excellent sizing effect over a wide pH range over a range close to that, and excellent storage stability at high concentrations with a solid content of 30% or more. And found that the present invention was completed.

The olefin used as a raw material for the component (a) of the present invention is a propylene oligomer or an n-butene oligomer having an average of 12 to 18 carbon atoms, which is a branched internal olefin in average molecular structure. Further, an olefin having an average carbon number of 14 to 16 is desirable in that it has an excellent size effect. Propylene oligomer and n
Needless to say, -butene oligomers can be mixed and used for the addition reaction, and both maleated compounds can be used as a mixture. Alkenyl succinic acid obtained from a straight-chain olefin is not preferable because the size effect is inferior. Even when a branched internal olefin is used with an isobutene oligomer as a raw material, the foamability of the emulsion becomes remarkable, which is not desirable. The addition reaction between the olefin and the maleic anhydride may be performed by a known method as disclosed in, for example, Japanese Patent Publication No. 4-37199.

The reinforced rosin of the component (b) of the present invention is a reaction product of a rosin raw material and an α, β-unsaturated carboxylic acid such as maleic acid or fumaric acid, and modified products thereof include polymers and hydrogenated products. , Reactants with aldehydes. It goes without saying that a part of the fortified rosin can be replaced by a rosin raw material and / or a modified product thereof.

The mixing ratio of the component (a) and the component (b)
Component (a) is 3 to 25% by weight, and component (b) is 97 to 75.
%, Desirably 5 to 20% by weight of the component (a) and 95 to 80% by weight of the component (b). If the component (a) is blended in an amount of 25 to 50% by weight, the emulsion particles tend to be coarse, and the size effect is reduced.
The sizing effect is restored again as the amount exceeds 50% by weight and approaches 100% by weight. However, since alkenyl succinic acid is more expensive than rosin, it is not practical except for special applications where economics are not a problem. Absent.

As the emulsifier of the component (c) of the present invention, those used in conventional rosin emulsion sizing agents can be used. For example, alkyl benzene sulfonate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene aralkyl phenyl ether sulfate, alkyl ether sulfate, polyoxyethylene alkyl ether phosphate And its salts, polyoxyethylene alkyl phenyl ether phosphates and their salts, polyoxyethylene aralkyl phenyl ether phosphates and their salts and other anionic surfactants and polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ether, Oxyethylene aralkyl phenyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc. Nonionic surface active agents. Further, a cationic surfactant such as an alkylamine salt, an alkyltrimethylammonium chloride, or an alkylbenzyldimethylammonium chloride may be used.

The polymer type emulsifying and dispersing agent may be a copolymer of component (A) which is a monomer constituting a hydrophilic group and component (B) which is a monomer constituting a hydrophobic group, or a copolymer thereof. Anionic ones consisting of partially or completely saponified products are mentioned. Here, component (A) includes acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid and the like, and component (B) includes styrene, α
Styrene monomers such as methylstyrene, methyl acrylate, methyl methacrylate, ethyl acrylate,
Examples include acrylic esters such as ethyl methacrylate, butyl acrylate, and butyl methacrylate, methacryl esters, (meth) acrylamide, and acrylonitrile. If necessary, a cationic monomer may be added as the component (C) and polymerized to use as a cationic polymer type emulsifying dispersant.

For the production of the sizing agent of the present invention, any known emulsifying method including a solvent emulsifying method may be used. Above all, it is preferable to use the inversion emulsification method because no harmful solvent remains. Specifically, the components (a) and (b) are heated and melt-mixed, and the emulsifier and / or the polymer dispersant of the component (c) are gradually added dropwise thereto with stirring, and a predetermined amount of water is further added. The water-in-oil type emulsion is inverted and emulsified by dripping under heating and stirring.

The sizing agent according to the present invention can be added to a papermaking material at any step before the end of the papermaking operation, just like a conventional rosin emulsion sizing agent. Before or after the addition of the sizing agent according to the present invention to the slurry, the slurry can be fixed to the pulp by adding a sulfuric acid band to adjust the pH to 4.0 to 7.0. In use, it can be used in combination with other sizing agents such as a conventional rosin-based sizing agent and petroleum resin sizing agent at an arbitrary ratio.

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.

[0016]

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.

<Measurement of emulsion particle size and storage stability test> The emulsion sizing agents prepared by the methods described in Examples 1 to 5 and the average particle size of the emulsions of Comparative Examples 1 to 6 were measured by Microtrac manufactured by Reeds & Noslap Slap Co., Ltd. It was measured using SPA. In addition, 25 g of the emulsion sizing agents of Examples 1 to 5 and Comparative Examples 1 to 6 were placed in a glass bottle for 50 ml and left at room temperature (25 ° C.), and the stability after 1, 7 and 60 days was visually observed. Observed. For those with poor stability, the resin was separated and precipitated at the bottom of the bottle or at the top of the liquid.

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 Canadian freeness was about 430 using a beater.
Beat to the milliliter. Next, the obtained pulp slurry was made into a 2.0% by weight slurry with 50 ° C city water, and a sulfuric acid band (1.0% by weight with respect to pulp) was 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 5 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 thus obtained was pressed and dried as usual. The obtained paper was conditioned for one day in a constant temperature and humidity room at a temperature of 20 ° C. and a humidity of 65% RH, and then the size effect was measured by the Stechich method in accordance with JIS P8122.

For the purpose of a high pH papermaking test, evaluation was also made of a case where a sulfuric acid band was added at 0.7% by weight based on pulp to make the dilution water pH and the papermaking water pH 6.0.

The results are shown in Table 2.

[0022]

Example 1 Propylene oligomer (average carbon number 15)
An alkenyl succinic anhydride was prepared by reacting an equimolar amount of water with the alkenyl succinic anhydride obtained by the addition reaction between the alkenyl succinic anhydride and maleic anhydride. 10 g of this alkenyl succinic acid and 90 g of fumarated rosin (fumarization ratio: 9% by weight) were equipped with a stirrer, a thermometer, a condenser and a dropping funnel.
The mixture was melt-mixed at 160 ° C., stirred and mixed with an anionic surfactant, Hytenol NF-093 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) as an emulsifier.
16.7 g of the active ingredient (30%) was added dropwise over 20 minutes.
While heating, 94 g of distilled water heated to 90 ° C. was further added dropwise over 1 hour under stirring to prepare an oil-in-water emulsion having a total solid content of 50.1% by weight.

[0023]

Example 2 Propylene oligomer (average carbon number 18)
An alkenyl succinic anhydride was prepared by reacting an equimolar amount of water with an alkenyl succinic anhydride obtained by an addition reaction between the alkenyl succinic anhydride and maleic anhydride. 20 g of this alkenyl succinic acid and 80 g of fumarated rosin (fumarization ratio 9% by weight) were stirred with a stirrer,
Put into a 500 ml separable flask equipped with a thermometer, a condenser and a dropping funnel, melt and mix at 160 ° C., stir, and add thereto an anionic surfactant Neonor N-12 (first 20 g of an active ingredient (manufactured by Kogyo Seiyaku Co., Ltd., 25%) was added dropwise over 20 minutes. While heating, 90 g of distilled water heated to 90 ° C. was further added dropwise over 1 hour under stirring to prepare an oil-in-water emulsion having a total solid content of 50.6% by weight.

[0024]

Embodiment 3 Stirrer, thermometer, condenser, dropper
60 g of styrene, 25 g of acrylic acid, 15 g of butyl acrylate in a 500 ml separable flask equipped with
Hytenol NF-08 as an emulsifier for anionic surfactant
(Manufactured by Daiichi Kogyo Seiyaku Co., Ltd., active ingredient 100%) 5 g, 2
-0.1 g of mercaptoethanol and 400 of distilled water
g was added and the temperature was raised to 70 ° C. Ammonium persulfate 0.
The polymerization reaction was started by adding 5 g, and kept at the same temperature for another 2 hours. After cooling to 50 ° C., saponification was performed by adding 27 g of 50% sodium hydroxide and 70 g of distilled water. The obtained polymer dispersant had a solid content of 20% by weight. An alkenyl succinic anhydride was prepared by reacting an alkenyl succinic anhydride obtained by an addition reaction of a propylene oligomer (average carbon number: 14) with maleic anhydride with an equimolar amount of water.
15 g of this alkenyl succinic acid and 85 g of formaldehyde-treated fumarated rosin (fumarization ratio: 9% by weight) were provided with a stirrer, a thermometer, a condenser and a dropping funnel.
In a 0 ml separable flask, the mixture was melted and mixed at 160 ° C., and 7 g (35 g in a solid state) of the above-mentioned polymer dispersant and solid was dropped into this over 20 minutes with stirring. While heating, distilled water 80 further heated to 90 ° C. under stirring.
g was added dropwise over 1 hour to prepare an oil-in-water emulsion having a total solid content of 49.4% by weight.

[0025]

Example 4 n-butene oligomer (average carbon number 16)
An alkenyl succinic anhydride was prepared by reacting an equimolar amount of water with an alkenyl succinic anhydride obtained by an addition reaction between the alkenyl succinic anhydride and maleic anhydride. 10 g of this alkenyl succinic acid and fumarated rosin treated with formaldehyde (fumarization ratio 9
90% by weight) into a 500 ml separable flask equipped with a stirrer, a thermometer, a condenser and a dropping funnel.
The mixture was melt-mixed at 160 ° C., stirred, and mixed with 10 g of anionic surfactant Neonor N-12 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., active ingredient 25%) as an emulsifier and the high-molecular weight prepared in Example 3. Molecular dispersant, 5 g solid (25 g
g) was added dropwise over 30 minutes. While heating, 80 g of distilled water heated to 90 ° C. was further added dropwise with stirring over 1 hour to prepare an oil-in-water emulsion having a total solid content of 49.6% by weight.

[0026]

Embodiment 5: Stirrer, thermometer, condenser, dropper
40 g of acrylic acid, 10 g of butyl acrylate, 10 g of stearyl methacrylate, 40 g of 2-ethylhexyl methacrylate
g, Hytenol NF-08 as an anionic surfactant
(Manufactured by Daiichi Kogyo Seiyaku Co., Ltd., active ingredient 100%) 5 g, 2
-0.1 g of mercaptoethanol and 450 of distilled water
g was added and the temperature was raised to 70 ° C. Ammonium persulfate 0.
The polymerization reaction was started by adding 5 g, and kept at the same temperature for another 2 hours. After cooling to 50 ° C., saponification was performed by adding 44 g of 50% sodium hydroxide and 38 g of distilled water. The obtained polymer dispersant had a solid content of 20% by weight. An alkenyl succinic acid was prepared by reacting an alkenyl succinic anhydride obtained by an addition reaction of a propylene oligomer (average carbon number: 14) with maleic anhydride with an equimolar amount of water.
15 g of this alkenyl succinic acid and 85 g of fumarated rosin treated with formaldehyde (fumarization ratio: 9% by weight) were provided with a stirrer, a thermometer, a condenser and a dropping funnel.
The mixture was melt-mixed at 160 ° C. in a 0 ml separable flask, and 7 g (35 g in a solid state) of the above-mentioned polymer dispersant and solid was dropped into the mixture with stirring over 20 minutes. While heating, distilled water 80 further heated to 90 ° C. under stirring.
g was added dropwise over 1 hour to prepare an oil-in-water emulsion having a total solid content of 49.8% by weight.

[0027]

Comparative Example 1 A commercially available emulsion-type rosin-based sizing agent (Dick Hercules Co., Ltd.) having a solid content of 50% in which a component mainly composed of fumarated rosin is emulsified with a polymer type emulsifying dispersant.
OT-500J).

[0028]

Comparative Example 2 In Example 1, 100 g of fumarated rosin (fumarization ratio 9% by weight) was used without using alkenyl succinic acid.
The emulsification operation was performed in the same manner as in Example 1 to prepare an oil-in-water emulsion having a total solid content of 50.1% by weight.

[0029]

Comparative Example 3 An emulsification operation was carried out in the same manner as in Example 3 except that alkenyl succinic acid was not used and 100 g of formaldehyde-treated fumarated rosin (fumarization ratio: 9%) was used. A 3% by weight oil-in-water emulsion was prepared.

[0030]

Comparative Example 4 An emulsification operation was carried out in the same manner as in Example 5 except that alkenyl succinic acid was not used and 100 g of formaldehyde-treated fumarated rosin (fumarization ratio: 9%) was used. A 5% by weight oil-in-water emulsion was prepared.

[0031]

Comparative Example 5 Alkenyl succinic anhydride was prepared by reacting an alkenyl succinic anhydride obtained by the addition reaction of 1-tetradecene (reagent) with maleic anhydride with an equimolar amount of water. 10 g of this alkenyl succinic acid and 90 g of fumarated rosin (9% by weight of fumarate) are put into a 500 ml separable flask equipped with a stirrer, a thermometer, a condenser, and a dropping funnel. Anionic surfactant as an emulsifier, Hytenol NF-093 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., active ingredient 30)
%) Was added dropwise over 20 minutes. While heating, 94 g of distilled water heated to 90 ° C. was further added dropwise with stirring over 1 hour to prepare an oil-in-water emulsion having a total solid content of 50.1% by weight.

[0032]

Comparative Example 6 Propylene oligomer (average carbon number: 14)
An alkenyl succinic anhydride obtained by the addition reaction of alkenyl succinic anhydride and maleic anhydride is reacted with an equimolar amount of potassium hydroxide to form an alkenyl succinic acid potassium salt solution (solid content 40% by weight).
Was adjusted. This potassium alkenyl succinate solution 2
5 g and fumarated rosin (fumarization ratio 9% by weight) 90 g,
Anionic surfactant as an emulsifier, Neonol N-12
(Daiichi Kogyo Seiyaku Co., Ltd., active ingredient 25%), 20 g,
Distilled water (350 g) and toluene (100 g) were added and mixed, and the mixture was emulsified twice with a piston-type high-pressure emulsifier (APV-Gaulin Co., Ltd.) under a pressure of 300 kg / cm ² , and toluene was distilled off under reduced pressure. Then, an oil-in-water emulsion having a total solid content of 31.3% by weight was prepared.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

The emulsion sizing agent according to the present invention comprises:
Overcoming the drawback of the conventional rosin emulsion sizing agent, in which the sizing effect is remarkably reduced in the pH range close to neutrality, shows excellent sizing effect at a low addition rate in a wide pH range, and has excellent storage stability at a high concentration. And a novel emulsion sizing agent.

────────────────────────────────────────────────── (5) References JP-A-3-199487 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) D21H 17/00-27/42

Claims (2)

(57) [Claims] 1. A hydrate of an addition reaction product of a propylene oligomer and / or an n-butene oligomer having an average number of carbon atoms of 12 to 18 with maleic anhydride. / Or its modified products 97 to 75
(C) an emulsion sizing agent having a solid content of 30% or more by adding 3 to 30 parts by weight of an emulsifier and / or a polymer dispersant to 100 parts by weight of the resin component. 2. The emulsion sizing agent according to claim 1, which is produced by an inverse emulsification method.