JPS60133053A - Manufacture of rosin-based emulsion sizing agent - Google Patents

Abstract

PURPOSE:To obtain titled agent of great sizing effect and high stability through an inversion process, by incorporating a combination of specific surfactant with water-soluble acid in a modified rosin material consisting of three-component reaction product from rosin, alpha,beta-unsaturated polybasic acid and resol. CONSTITUTION:(A) 100pts.wt. of a modified rosin material with an acid value 180-210 and softening point 85-110 deg.C prepared by the reaction of heating between (i) 100pts.wt. of rosin, (ii) 5-12pts.wt. of alpha,beta-unsaturated polybasic acid or its anhydride, and (iii) 1-15pts.wt. of resol-type phenol-formaldehyde initial condensate (resol) is incorporated with (B) 15-35pts.wt. of a dispersant aq. solution with a pH 2.5-3.5 containing (i) a surfactant of formula (R is 8-24C hydrophobic hydrocarbon; M is monovalent cation, n is 5-25) (3-7wt% based on the component (A)) and (ii) a water-soluble acid (5-10wt% based on said surfactant) followed by adding warm water to effect emulsification, thus obtaining the objective agent. As the component (B), combination of an alkylbenzene sulfonic acid-based surfactant in a range 10-30wt% would be more effective.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a rosin-based emulsion sizing agent mainly used in the paper manufacturing process, and more specifically, it uses a special modified rosin material as a raw material, and When this product is dispersed in water to form a rosin emulsion 1-nizing agent, a specific dispersant and a water-soluble acid (Jl) are added to this product as a dispersion aid to form a new rosin emulsion. Relates to a method for producing sizing agents.

[Prior Art] Conventionally known rosin-based emulsion sizing agents are more susceptible to deterioration of the sizing effect due to deterioration of the quality of water used in the paper manufacturing process and rise in temperature, compared to similarly known saponified aqueous solution type reinforced rosin sizing agents. Recently, it has attracted particular attention because of its resistance to

However, even with this sizing agent, there are still problems in terms of the stability of the emulsion, and improvements are desired.

The manufacturing method of rosin-based emulsion sizing agents is mainly a high-pressure emulsification method using a high-pressure homogenizer, and an aqueous dispersant solution is added to a molten rosin-based material, and the rosin-based material is inverted from a continuous phase to a dispersed phase. It is broadly divided into the inversion method. Although the former method can produce a rosin-based emulsion with extremely fine particle diameters, it requires a large-scale emulsification device, and the latter method is considerably difficult to efficiently produce a fine-particle emulsion. Emulsification of rosin-based substances by the inversion method has traditionally been carried out in the Bevoid method, in which rosin-based substances are placed in an aqueous medium by using a small amount of alkali, such as caustic soda, in combination with a protective colloid such as casein. Recently, the use of various synthetic surfactants as dispersants in water for rosin-based substances has been studied in this inversion method. For example, JP-A-52-77206J+ discloses an aqueous dispersion of a reinforced rosin produced by an inversion method using a salt of a sulfuric acid half ester of polyoxyethylene alkyl ether or polyoxyethylene alkylaryl ether as a dispersant. The fortified rosin obtained by this method is an addition reaction product of 1) gin or formaldehyde treatment [1] gin and an acidic compound containing a c=c-c=o group, and this is an addition reaction product of 1) gin or formaldehyde treatment [1] gin and an acidic compound containing a c=c-c=o group, and this is added with a non-reinforced rosin and/or a filler. A suitable mixture of these is disclosed as a rosin-based material. Also, JP-A-5
No. 5-106534 describes the use of polyoxyethylene disdylylphenyl ether as a dispersant in water using the same rosin-based material inversion method as described above. iii! There is a description that salts of acid half esters are suitable, and that they require only a small amount of use, and that an aqueous emulsion with excellent mechanical stability can be obtained.

By the way, the present inventors have conducted research on various rosin-based substances, their dispersants, and their emulsification methods, particularly by the inversion method, in order to produce a rosin-based emulsion suitable as a sizing agent for paper manufacturing.

As a result, the starting material rosin-based material is a three-component reaction of rosin, αβ/unsaturated polybasic acid or its anhydride, and a resol-type phenol/formaldehyde initial condensate (hereinafter sometimes simply referred to as [resol]). After selecting a modified rosin material (hereinafter simply referred to as "modified rosin material"), a dispersant having the general formula: R-0+CH2Cl-120)nS03M is selected.

(However, R: hydrophobic hydrocarbon group having 8 to 24 carbon atoms, M
: monovalent cation, n: an integer of 5 to 25), and a water-soluble acid as a dispersion aid is used in combination, regardless of the type of rosin used as the raw material. It was found that the modified rosin material can be emulsified homogeneously, and that it is possible to form an emulsion with fine emulsion particles, excellent mechanical stability, and a high size effect. Contains a reactant with a high melting point and a low acid value, which is a reactant between rosin and resol, compared to a reinforced rosin material (a two-component reactant of rosin and an αβ/unsaturated polybasic acid or its anhydride), In addition, since the crystallinity of the modified rosin material is effectively prevented, the rosin-based emulsion sizing agent that disperses it in water not only has an excellent size effect, but also prevents the reagglomeration and hydration crystallization of dispersed particles. It has the characteristics that the generation of coarse particles is extremely reduced, and the stability is also extremely good.

However, even though the modified rosin material has the above-mentioned excellent properties, it has the disadvantage that it is not easy to operate when emulsifying it, making it impossible to obtain the desired product.

As a result of intensive research on this point, we found that instead of the general reinforced rosin mentioned above, we used a specific modified rosin material made by reacting this material with resol, and added it to the above-mentioned dispersant and dispersion. For the first time, it has been discovered that an emulsion sizing agent with good operability and excellent quality can also be produced by an inversion method when used in combination with an auxiliary agent.

Incidentally, the present inventors have previously developed a method for producing a rosin-based emulsion sizing agent by a high-pressure emulsification method using or in combination with various surfactants as an emulsification method in water of a modified rosin material, which is the three-component reactant. proposed (patent application 1984-1983)
(No. 992, Japanese Patent Application No. 54-38419) Unlike the previous invention, the present invention has confirmed that it is possible to produce a stable rosin-based emulsion sizing agent with good dispersibility even by the inversion method. It is.

In addition, even if any of the various conventionally known surfactants are used, a modified rosin material consisting of a three-component reactant of rosin-dβ, unsaturated polybasic acid and resol can be stably dispersed in water by the inversion method. However, if a surfactant having a specific chemical structure as described above is used in combination with a water-soluble acid as a dispersion aid, a modified rosin material can be dispersed in water by an inversion method. Surprisingly, an aqueous emulsion of a modified rosin material having a fine particle size can be obtained very easily and reliably. It was found that it exhibits stability.

[Purpose of the Invention] The present invention selects as a raw material a modified rosin material consisting of a three-component reaction product of rosin, αβ, unsaturated polybasic acid, and resol, which was conventionally employed only by high-pressure emulsification method, and adds a specific By combining a dispersing agent and a dispersing aid, the modified substance can be dispersed in water under the inversion method, and in general use, it can exhibit excellent size effect as well as good stability. This emulsion amount-enhancing agent can be easily produced industrially.

[Structure of the Invention] The present invention provides a compound obtained by reacting the above-mentioned at, a2, and b1 General formula R
-0(CH2CH2-O+nS○IM, where R: hydrophobic hydrocarbon group having 8 to 24 carbon atoms M: monovalent cation n: surfactant represented by an integer from 5 to 25 b2: water-soluble acid and b3 : This is a method for producing a rosin-based emulsion size, which is characterized in that an aqueous dispersant solution [B] consisting of water is added, mixed uniformly, and then water is added while stirring to emulsify.

[Disclosure of the Invention] According to conventional knowledge, [1] When preparing an aqueous emulsion of a gin-based substance, it is common practice to use a small amount of an alkaline substance together with various surfactant substances and protective colloid substances. . The reason for this is thought to be that some of the carboxyl groups contained in rosin-based substances are saponified by alkaline substances, producing water-soluble soaps of rosin-based substances, which exhibit excellent surface-active properties. Ta.

However, when the modified rosin substance is emulsified in water by the inversion method using the surfactant represented by the general formula as a dispersant, the presence of an alkaline substance only has the opposite effect and makes emulsification impossible. That's what happens. The details of the reason are not clear at present, but the water-soluble soap generated from the alkaline substance and the modified rosin material works together with the surfactant to promote the penetration of water into the modified rosin material, attracting It is thought that this is because the modified rosin substance accelerates crystallization and hydrolysis, impairing its emulsifying property in water.

On the other hand, various types of surfactants represented by the above general formula are commercially available, but since M in all of them is an ammonium group or an alkali metal, they are suitable for use with the modified rosin material of the present invention by the inversion method. It is considered that it cannot be used as a dispersant. However, when this is used in combination with a water-soluble acid, the action of ammonium groups and alkali metals, which are alkaline substances, is suppressed, and it is thought that a very good dispersion action is achieved.

The modified rosin material [A] used in the present invention includes various rosins, such as gum rosin, wood rosin, tall oil rosin, or mixtures thereof, and αβ-unsaturated polybasic acids or their anhydrides, such as maleic acid and fumaric acid. Acid, maleic anhydride, itaconic acid, etc., and a resol type phenol/formaldehyde initial condensate obtained by heating and reacting them with a softening point of 85 to 110°C and an acid value of 180 to 210.
Modified rosin materials such as In order to obtain such a modified rosin material, it is necessary to add αβ to 10011 parts of rosin.
・Unsaturated polybasic acid or its anhydride 5-12 G parts and resol type phenol/form\aldehyde initial synthesis product 1-
15 parts by weight and heated at a temperature of 150 to 220°C.
Heat reaction for 8 hours. Resol 311 phenol
The formaldehyde precondensate is produced by reacting a phenol, preferably an alkylphenol, with formaldehyde in the presence of an alkali catalyst according to a conventional method.

In the present invention, the dispersing agent for the modified rosin substance () has the general formula R-0+CH2Cl-12-0), SO3M, but R
: Hydrophobic hydrocarbon group having 8 to 24 carbon atoms M: Monovalent cation n: Uses a surfactant represented by an integer of 5 to 25, and various commercially available products with the corresponding chemical structure are available. Available for use.

Specifically, R is an octyl 151 nonyl group, a lauryl group,
An alkyl group such as a stearyl group, an alkylphenyl group such as a tertiary-butylphenyl group, a octylphenyl group, a nonylphenyl group, a hydrocarbon group such as a styrenated or distyrenated phenyl group, and M is an alkali such as Na or Metals, ammonia, various alkyl amines, and alkanol amines can be used, and any of them can be used in combination.

Water-soluble acids as dispersion aids used in combination with the above surfactants include water-soluble inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; water-soluble acids such as formic acid, acetic propionic acid, and P-toluenesulfonic acid. Examples include organic carboxylic acids and water-soluble organic sulfonic acids.

In carrying out the present invention, an acidic dispersant aqueous solution containing a surfactant represented by the general formula and a water-soluble acid is added dropwise to the melt of the modified rosin substance [A], while sufficient stirring is carried out. After forming a homogeneous transparent or translucent solution, water is added while stirring vigorously to form a milky white emulsion containing the modified rosin material as a dispersed phase. In this case, the dispersant aqueous solution contains 3 to 7% of a surfactant and 5 to 10% of a water-soluble acid based on the amount of modified rosin material used, and has a pH of 5 or less. , preferably PH2, 5-3.
The total amount thereof is preferably 15 to 35 parts by weight based on 100 parts by weight of the molten modified rosin material. Within this range, the mixture of the melt-modified rosin υ1 and the dispersant aqueous solution becomes a uniform transparent to translucent solution. Of course, the amount of water used in the dispersant aqueous solution may be adjusted as appropriate within a range where the mixture shown in L has a uniform appearance or so that the mixture exhibits a uniform appearance. In addition, the dispersant aqueous solution is added dropwise to the melted modified rosin material at a melting temperature that is usually 20°C or more higher than the melting point of the modified rosin material, so that the temperature of the homogeneous mixture after the dispersant aqueous solution is dropped is approximately 100°C. Adjust to η.

Thereafter, water at 80 to 95° C. is added dropwise under stirring to cause phase inversion, thereby obtaining a finely divided rosin-based emulsion sizing agent in which the modified rosin substance is a dispersed phase.

[Effect of the invention] When producing the rosin-based emulsion sizing agent according to the present invention, in addition to the above-mentioned specific surfactant, it is also possible to use a small amount of a surfactant having another chemical structure. Be careful when using highly alkaline surfactants, as this may interfere with the emulsification state.
When this is used as an aqueous dispersant solution, one that is stable even in the coexistence with a water-soluble acid should be selected and used. Particularly preferably (J1) A specific example of a surfactant that can be used is a known alkylbenzenesulfonic acid surfactant.In this case, the weight of the surfactant of the general formula is 10 When used together in the range of ~30%, emulsification of the modified rosin substance in water becomes easier, and a finer emulsion can be obtained.
When this is used as a sizing agent, the reactivity with sulfuric acid band is increased, and as a result, an excellent sizing effect can be exhibited. The structure of the present invention is as described above, and according to the present method, 1. an aqueous emulsion of a specific modified rosin material containing a resol-type phenol formaldehyde initial synthesis product, which was conventionally produced only by high-pressure emulsification method; Or a rosin-based emulsion sizing agent with better performance using the inversion method! In addition, the rosin-based emulsion sizing agent obtained by the present invention exhibits excellent effects such as excellent stability and a high lees effect. .

[Embodiments] The present invention will be specifically described below based on Examples and Comparative Examples.

[Production Example] 206 parts of roseoctylphenol and 65 parts of parabomaldehyde (IIIi content 92%) were dissolved in 1 to luene,
65 parts of dehyde (92% pure product) were dissolved in toluene, 2 parts of caustic soda was added thereto, and the mixture was reacted at 65° C. for 10 hours to obtain a toluene solution of resol of rosewood phenol.

Add the above resol toluene solution in an amount equivalent to 24 parts including solid content to 800 parts of gum rosin and melt by heating,
Heating was continued while distilling off toluene, and at a temperature of 180°C, 16 parts of maleic anhydride and 32 parts of fumaric acid were added.
By reacting at 0 to 200°C for 2 hours and further at 200 to 205°C for 4 hours, a modified rosin material, which is a reaction product of rosin, αβ/unsaturated polyethyl acid, and resol, was obtained.

This -modified rosin material had an acid value of 185 and a softening point (ring and ball method) of 88°C.

[Example 1] Modified rosin substance 100Q obtained in the production example is charged into a flask equipped with a stirrer, and the temperature is raised to 130 to 140°C on an oil bath to melt it. In a separate container, 5 q of a general formula surfactant and 150 ml of dry water at 40° C. are weighed out and completely dissolved to obtain an aqueous dispersant solution. The pH of this dispersant aqueous solution was 8.0. This was mixed with 90% acetic acid 04q. At this time, the pH of the dispersant aqueous solution decreased to 3.1.

This acidic dispersant aqueous solution is dropped into a flask loaded with molten rosin over a period of 10 to 20 minutes. At this time, the contents are sufficiently stirred to mix as uniformly as possible. At the end of dropping the dispersant aqueous solution, the temperature of the contents was 95 to 100°C, resulting in a completely transparent homogeneous mixture.

Next, while maintaining the internal temperature at 90°C or higher, the temperature was heated to 85°C while stirring.
90g of dry water at ~90°C was added over 20-30 minutes. During this time, the contents turn from a milky white creamy state to II.
This results in an emulsion having a particle size of III. After that, the inner temperature was lowered to 30° C. or less by cooling. The obtained rosin-based emulsion sizing agent had a solid content of 5o and 5% p)44
．． 0 (10 times diluted solution), viscosity 120 cps/20'
It was C.

[Example 2 and Example 3] The same procedure as in Example 1 was carried out except that the amount of surfactant used in the dispersant aqueous solution in Example 1 was changed to 30 and 7Q, and modified autologous resin was prepared. Emulsification of the substance was extremely easy, and the resulting rosin-based emulsion sizing agent was as described in Example 1.
It was a fine particulate emulsion almost identical to that obtained in Shino.

[Comparative Example 1] Everything was the same as in Example 1 except that acetic acid was not added to the dispersant aqueous solution in Example 1, and the weakly alkaline dispersant aqueous solution of P l-18 was used as is. The operation was carried out to emulsify the modified rosin material. Emulsification was somewhat difficult when hot water was added, but phase inversion was completed by increasing the stirring speed. (Compared to the emulsion of Example 1, the aqueous emulsion of the modified rosin material obtained was more cloudy and appeared to be an unstable emulsion containing coarse particles.)

[Example 4] Instead of using the aqueous dispersant solution in Example 1, P containing 1,2 q of sodium dodecylbenzenesulfonate was used.
A rosin-based emulsion leasing agent of the present invention was obtained in the same manner as in Example except that the aqueous dispersant solution of I-f3.2 was used. Emulsification was carried out very easily, and the resulting rosin-based emulsion sizing agent was a fine particulate emulsion with an appearance as good as or better than that obtained in Example 1.

[Example 5] The modified rosin material 100Q obtained in the production example was mixed with a stirrer.
Pour into a flask and heat to 130-140℃ on an oil bath.
melt. In a separate container, weigh out 5Ω of a surfactant with the general formula (%) and 15Q of warm water at 40°C, and after completely melting, add 4g of 90% citric acid to make a homogeneous and transparent aqueous dispersant solution (PI -13,2) to 1!1k.

This aqueous dispersant solution was added dropwise to the flask over 10 to 20 minutes while stirring to mix uniformly. The contents of the flask attained a completely clear appearance at a temperature of 95-100°C.

Next, while keeping the internal temperature above 90°C, the
90 CJ of warm water at 5-90°C was added for 20-30 minutes.

During this time, phase inversion occurred and an aqueous emulsion of the modified gin substance was easily obtained, which was directly cooled to 15 ml to obtain the rosin-based emulsifying agent of the present invention. This was a stable aqueous emulsion with very good dispersion, solids content 50.71%, 114.1 (10x dilution), viscosity 130 cps/20°C.

[Example 6] In place of the aqueous dispersant solution in Example 5, an aqueous dispersant solution (PI-13,2) further containing 0.5 () of sodium dodecylbenzenesulfonate was used. A rosin-based emulsion sizing agent of the present invention was obtained by operating in the same manner as in Example 5. This product showed a good dispersion state in the non-woven fabric.

[Comparative Examples 2 and 3] In Example 5, [instead of using a dispersant aqueous solution, an acetic acid-free dispersant aqueous solution (PH 8,1) and acetic acid-free sodium dodecylbenzenesulfonate O,5C were used. ] The modified rosin material was emulsified in the same manner as in Example 5, except that each of the dispersant aqueous solutions (PI-48, 2) containing the following were used. In either case, emulsification is somewhat difficult [
Then, as in the comparative example, the stirring speed was increased to complete the phase inversion.
Two aqueous emulsions of modified rosin materials were obtained. These emulsions appeared to be unstable emulsions containing coarse particles.

[Example 7] Modified rosin material 100Q obtained in Production Example is charged into a flask equipped with a stirrer, and heated to 130 to 140°C on an oil bath to melt. Weigh out 7q of a general formula surfactant and 15g of dry water at 40°C in a separate container, and after completely dissolving them, add 0.5j of 90% acetic acid to make a homogeneous transparent dispersant aqueous solution (PI-12, 8) was obtained.This aqueous dispersant solution was added dropwise to the flask and stirred to mix uniformly.The contents of the flask were slightly cloudy at a temperature of 95 to 100°C, but were almost transparent. .

Next, while maintaining the internal temperature at 90°C or higher, 85-90°C Dry Water 90C1 was added dropwise under stirring 111'. While maintaining a homogeneous state, the contents became creamy and then underwent phase inversion to reduce the viscosity and become an emulsion with a good appearance and having finely dispersed particles.

This was cooled down to 30° C. or lower to obtain 1] a resin-based industrial marsupilizing agent of the present invention. The obtained [ ] gin emulsion sizing agent had a solid content of 50.6% and a P 1-43.
9 (10-fold dilution).

[Comparative Example 4] All operations were performed in the same manner as in Example 7, except that instead of using the dispersant aqueous solution in Example 7, a dispersant aqueous solution (Pl-18, 3) was used without adding acetic acid. 19 to emulsify the modified rosin material to form a rosin emulsion. The appearance of this emulsion was somewhat heterogeneous containing coarse particles.

[Test Example 1] Each of the emulsions obtained in the above Examples and Comparative Examples was tested for stability and size effect using the following test method. The results will be posted.

(Test method) Product stability: 500 ml of rosin emulsion is placed in a 60 cc glass cup, and the product is released in a 40°C dry-water environment to observe oral stability.

Those with poor stability should be analyzed together with the oral route. The waste settles to the bottom of the bottle and accumulates 11.

Mechanical stability...Test diluted to 1% solids 50
Add 0g to a household mixer (2 volumes) and repeat continuous stirring 3 times for 3 minutes each. After that, it was filtered through a 200-mesh filter bag, and the remaining residue was weighed and expressed as a precipitation rate using the following formula.

Size effect measurement...Valve l BKPcs f 40
0m of 2.4% pulp slurry was mixed by adding 20% of talc to the pulp as filler 1, adding and mixing the activity nizing agent at 0.2% to the pulp, and further adding and mixing 2% of sulfuric acid to the pulp. to fix the sizing agent.

Paper tsubo made with TAPPI standard hand paper machine Hand-cut the paper so that the hanging is 65Q/Td.

After that, press dry as usual, Humidity control size degree (Sutekihi [- method) was measured.

(Leaving space below) Procedure No. 111 (Method) Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office, Showa, 1997. 1. Indication of the case. 1982 Patent Application No. 241728. 2. Name of the invention. Rosin-based emulsion sizing agent. Manufacturing method 3 Relationship with the case of the person making the amendment Patent applicant: Seiko Kagaku Kogyo Co., Ltd. 4 Agent: Nobukazu Kosato Kaikan, 1-18-14 Nishi-Shinbashi, Minato-ku, Tokyo
Law and Patent Office 5 Date of amendment order: March 27, 1982

Claims (4)

[Claims] (1) aI: Rosin a2: αβ/unsaturated polybasic acid or its anhydride a3 Niresol-type phenol/formaldehyde initial condensate Melt of modified rosin material [A] obtained by reacting the above a1, a2, and a3 For, b1 d general formula R-0
(CH2Cl-12-〇)n803 M, however, R:
A dispersant aqueous solution [B] consisting of a hydrophobic hydrocarbon group having 8 to 24 carbon atoms, M: a monovalent cation, n: a surfactant represented by an integer of 5 to 25, b2: a water-soluble acid, and b3: water. A method for producing a rosin-based emulsion sizing agent, which is characterized in that the rosin-based emulsion sizing agent is added and mixed uniformly, and then emulsified by adding warm water while stirring. (2) Modified rosin substance [A] is aI 20 gin 100 heavy dark part a2: αβ unsaturated polybasic acid or its anhydride 5 to 12
Weight part a3 is a heated reaction product of 1 to 15 parts by weight of Niresol type phenol formaldehyde initial condensate, acid value 180 to 210, softening point 85
Claim 1 which is a modified rosin material at ~110°C
A method for producing a zero gin emulsion sizing agent as described in Section 1. (3) The method for producing a rosin emulsion sizing agent according to claim 1, wherein the aqueous dispersant solution [B] further contains an alkylbenzene sulfonic acid surfactant. (4) The dispersant aqueous solution [B] is p+-i2. The method for producing a rosin-based emulsion sizing agent according to claim 1 or 3, which is an acidic aqueous solution of s to 35.