KR930000983B1 - Sizing agent - Google Patents

Abstract

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Description

[Name of invention]

Sizing agent

Detailed description of the invention

The present invention relates to a sizing agent used in the production of cellulose paper.

To date, a wide variety of sizing agents have been proposed for paper making, such as rosin-based, wax-based, alkylketene dimers, polymers, alkenyl succinic anhydrides, and all of which have been used in practice. Since many of these conventional sizing agents are inherently water insoluble, they cannot be used alone and usually have to be dispersed and / or emulsified in water with the aid of an emulsifier. However, there is a drawback that the emulsification is difficult and the additional cost is required.

For example, Japanese Patent Application Publication Nos. 59-144696 (Kawatani) and 59-192798 (Satoo) use reaction products of maleic anhydride and branched internal olefins having 14 to 36 carbon atoms as sizing agents. It is started.

However, alkenylsuccinic anhydride-based sizing agents lose their sizing effect over time due to their inherent properties, especially if they are brought into contact with water for a short time.

Ilkenylsuccinic anhydride-based sizing agents exhibit an appropriate sizing effect at lower concentrations, thus providing greater economic advantages compared to rosin-based, alkenyl-ketene dimers, wax-based sizing agents and the like. However, since the alkenylsuccinic anhydride-based sizing agents have poor water stability, they are severely limited to finish sizing in a short time, which is the biggest disadvantage of commercial applications.

Alkenylsuccinic anhydrides are readily absorbed into the paper itself and exhibit a sizing effect by making the resulting paper water repellent. However, once the acid anhydride is hydrolyzed to the corresponding dicarboxylic acid, the resulting dicarboxylic acid is not readily absorbed and loses the sizing effect. In this way the alkenylsuccinic anhydrides are severely changed in water over time and therefore require appropriate care.

The present inventors have extensively investigated the sizing effects of alkenylsuccinic acids having various structures and derivatives thereof, and as a result, unsaturated hydrocarbyl partial esters of alkenylsuccinic acids and their salts are at least self-emulsifiable in water. And to provide excellent sizing effect (Japanese Patent Application No. 59-241260).

For example, unsaturated hydrocarbyl diesters of alkenylsuccinic acids are not only very difficult to synthesize but also require troublesome processes to emulsify similarly to conventional sizing agents and also require additional auxiliaries such as activators. In addition, they are inferior to unsaturated monohydrocarbyl esters in sizing effect and thus become commercially useless.

On the other hand, saturated moieties (mono)-and di-hydrocarbyl esters of alkenylsuccinic acids are substantially ineffective in sizing and therefore cannot be used as sizing agents. This is because saturated hydrocarbyl mono- and di-esters of alkenylsuccinic acid are substantially not absorbed by the paper and can impart only poor water repellency to the paper.

Thus, in contrast to saturated esters of alkenylsuccinic acid which are only poorly absorbed into the paper and thus have no sizing effect, the unsaturated hydrocarbyl partial esters of alkenylsuccinic acid are strongly absorbed by water and thus make the paper highly water repellent, thereby Along with the advantage of not being hydrolyzed by water, it provides an excellent sizing effect to maintain identity as a stable solution or dispersion for a long time in water. Unsaturated hydrocarbyl partial esters of alkenylsuccinic acid not only exhibit strong water absorption to the paper, but also discoloration and can exhibit a stable sizing effect over a long period of time. In addition, the unsaturated hydrocarbyl partial esters of the present invention provide a consistently stable sized paper sheet.

However, even with this sizing agent, a considerable amount of sizing agent is required to obtain the desired sizing effect, and the cost thereof cannot be ignored.

The present inventors conducted various investigations to improve the sizing effect of the unsaturated hydrocarbyl partial ester of alkenylsuccinic acid, and further improved by using the unsaturated hydrocarbyl partial ester of alkenylsuccinic acid or its water-soluble salt in combination with an acid catalyst. It has been found that a sizing effect can be obtained. The use of acid catalysts with unsaturated partial esters of alkenylsuccinic acids as sizing agents can dramatically reduce the amount of partial esters required.

Unsaturated hydrocarbyl partial esters of alkenylsuccinic acid of the present invention can be brought into a stable emulsified state with cationic starch or the like, which has conventionally been used as a spreader. Various compounds can be considered as alkenylsuccinic acid derivatives having various structures. Among them, unsaturated hydrocarbyl partial esters have excellent sizing effects and are superior to conventional sizing agents in handling.

It is an object of the present invention to provide a novel sizing agent consisting of an unsaturated hydrocarbyl partial ester of an alkenylsuccinic anhydride and an acid catalyst.

More particularly, the present invention provides a paper comprising as partial active ester of one or more alkenylsuccinic acids and / or one or more salts thereof represented by the following formulas (I) and / or (II): As a sizing agent for manufacture;

[Wherein R represents an unsaturated hydrocarbyl group having 6 or more carbon atoms, R 'represents an unsaturated hydrocarbyl group having 3 to 18 carbon atoms], and the sizing agent further contains an acid catalyst. It is about.

It is a further object of the present invention to provide a sizing agent which is at least self-emulsifying, stable for a long time in water and effective at lower concentrations. Another object of the present invention is to provide a sizing agent which can be prepared without difficulty. Still other objects of the present invention will become apparent from the following description.

The most important feature of the present invention is that the sizing effect is greatly improved when sulfonic acid, inorganic acid or Lewis acid are added to the unsaturated hydrocarbyl partial ester of alkenylsuccinic acid by 1 / 100,000 to 1/10 parts by weight of the ester as a catalyst. .

The reasons for the increase in sizing effect achievable with the use of these acid catalysts are not fully understood at present, but can be inferred as follows, although not consistent with a particular theory. Acid catalysts such as sulfonic acid, organophosphoric acid, inorganic acid or Lewis acid excite the unsaturated bonds in the unsaturated hydrocarbyl partial esters, thus creating a state in which the double or triple unsaturated bonds can be easily broken and contained in the cellulose. The etherification reaction with hydroxyl groups or the esterification reaction by dehydration is promoted, so that the sizing agent adheres to the paper more completely in a short time.

The catalyst can be used to greatly reduce the amount of unsaturated hydrocarbyl partial esters and thus provide great economic advantages.

Unsaturated hydrocarbyl partial esters of alkenylsuccinic acids can be readily synthesized by conventional esterification techniques. Thus, in the presence or absence of a catalyst, alkenylsuccinic anhydride or the corresponding acid and unsaturated alcohol are heated together to cause a reaction between them via ring-opening reaction in case of acid anhydride and dehydration in case of acid, while unsaturated partial ester To form. The ratio of acid starting material to unsaturated alcohol is such that the amount of alcohol is sufficient to esterify only one of the carboxyl groups of the acid.

The alkenylsuccinic anhydrides or corresponding acids used are alkenylsuccinic acids or acid anhydrides in which the alkenyl side chains contain 6 or more carbon atoms, for example hexenyl-, octenyl-, decenyl-, octadecenyl- , Docosenyl-, triacontenyl-, isocenyl-succinic acid and the like. Unsaturated alcohols have 3 to 18 carbon atoms such as allyl-, propargyl-, butenyl-, butyne-, pentenyl-, hexenyl-, octenyl-, desenyl-, laurenyl-, oleyl- alcohol and the like. There are all unsaturated alcohols.

Acid catalysts include inorganic acids such as sulfonic acid, organophosphoric acid, phosphoric acid, phosphorous acid, hypophosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, and Lewis acids such as boron fluoride, zinc chloride, aluminum chloride, ferric chloride and the like. These acid catalysts may be used alone or in combination of two or more.

Sulfonate catalysts include benzenesulfonic acid, toluenesulfonic acid, dimethylbenzenesulfonic acid, ethylbenzenesulfonic acid, diethylbenzenesulfonic acid, triethylbenzenesulfonic acid, styrenesulfonic acid, dichlorobenzenesulfonic acid, dichlorotoluenesulfonic acid, aniline sulfonic acid, aminotoluenesulfonic acid, dimethylaniline sulfonic acid Minobenzenesulfonic acid, diaminotoluenesulfonic acid, aniline disulfonic acid, aniline-trisulfonic acid, diaminobenzenedisulfonic acid, ethyl toluidine sulfonic acid, diethylaniline sulfonic acid, chloroaniline sulfonic acid, aminochlorotoluene sulfonic acid, dichloroaniline sulfonic acid, nitrobenzene sulfonic acid, Nitrotoluenesulfonic acid, dinitrobenzenesulfonic acid, dinitrostyrenesulfonic acid, nitrochlorobenzenesulfonic acid, chloronitrotoluenesulfonic acid, dinitrochlorobenzenesulfonic acid, nitroaniline sulfonic acid, phenylhydrazine sulfonic acid, methylphenylhydrazinesulfonic acid, phenolsulfonic acid, cresolsulfonic acid, dihydride Roxybenzene Sulfonic acid, methacrylicoxybenzenesulfonic acid, aminophenolsulfonic acid, aminomethoxybenzenesulfonic acid, dimethoxyanilinesulfonic acid, chloroaminohydroxybenzenesulfonic acid, nitroaminohydroxybenzenesulfonic acid, butylbenzenesulfonic acid, naphthalenesulfonic acid, naphthalene dissulfonic acid, methylnaph Tyl sulfonic acid, ethyl naphthyl sulfonic acid, propyl naphthyl sulfonic acid, butyl naphthyl sulfonic acid, lignin sulfonic acid, naphthalene disulfonic acid, naphthalene trisulfonic acid, naphthylamine sulfonic acid, naphthylamine disulfonic acid, naphthylamine trisulfonic acid, nitronaphthalene sulfonic acid, Nitronaphthalene disulfonic acid, nitronaphthalene trisulfonic acid, naphthol sulfonic acid, dihydroxynaphthalene sulfonic acid, nattitol disulfonic acid, aminotaphthol sulfonic acid, aminonaphthol disulfonic acid, 1- (4'-amino-2'-chlorobenzoylamino) -8 -Naphthol-3,6-disulfonic acid, 1- (4'-nitrobenzene) amino-8-naphthol-3,6-disulfone and nitronaphtholsulfonic acid, anthra Sulfonic acid, anthraquinonesulfonic acid, anthraquinonedisulfonic acid, aminoanthraquinonesulfonic acid, diaminoanthraquinonesulfonic acid, nitroanthraquinonesulfonic acid, dihydroanthraquinonesulfonic acid, diaminodioxyanthraquinonesulfonic acid, diaminoanthraquinonedisulfonic acid, bromine Moethane sulfonic acid, 3-fluoromethanesulfonic acid, perchlorooctane sulfonic acid, aminoethanesulfonic acid, hydroxyheptanesulfonic acid, dodecyloxybutanesulfonic acid, propargyloxypropylsulfonic acid, acetone disulfonic acid, bis [octylsulfonic acid substituted]- Sulfonic acid, dihydroxyethanesulfonic acid, mercaptopropanesulfonic acid, methanesulfonic acid and α-olefinsulfonic acid.

Organophosphoric acid or other esters include nitrilotrimethylphosphoric acid, aminodimethylphosphono monoethylphosphoric acid, ethylenediaminetetramethylphosphoric acid, diethylenetriaminepentamethylphosphoric acid, triethylenetetraamine hexamethylphosphoric acid, hydroxyethylidene diphosphate, Hydroxypropylidenediphosphate, 1,2,4-tricarboxybutane-2-phosphate, 1,2-dicarboxybutane-2-phosphate, 1,2,4-tricarboxyhexane-1-phosphate, β-chloro Ethyl phosphate, Bis [2-hydroxyethyl) methacrylate] acid phosphate, 2-ethylhexyl- phosphate, methyl phosphate, ethyl phosphate, propyl phosphate, butyl phosphate, octylic phosphate, decyl phosphate , Lauryl phosphate, stearyl phosphate, dibutyl phosphate, di (β-chloroethyl) phosphate, di (2-ethylhexyl) phosphate, dimethyl phosphate, diethyl phosphate, diprop Acid phosphate, dioctyl acid phosphate, didecyl acid phosphate, dilauryl acid phosphate, distearyl phosphate, tributyl phosphite, tris- (2-ethylhexyl) phosphite, tridecyl phosphite, tristearyl phosphite, tris Nonyl phenyl) phosphite, trisphenyl phosphite, trislauryl trithio phosphite, tris (2,3-dichloropropyl) phosphite, diphenyldecyl phosphite, diphenyl tridecyl phosphite, trimethyl phosphite, triethyl Phosphite, trioctyl phosphite, trilauryl phosphite, dilauryl hydrogen phosphite, diphenyl hydrogen phosphite, dimethyl hydrogen phosphite, diethyl hydrogen phosphite, dipropyl hydrogen phosphite, dibutyl hydrogen phosphite, di Octyl hydrogen phosphite, didecyl hydrogen phosphite, distearyl hydrogen phosphite. These acid groups listed are only a part of the present invention, but are not limited thereto.

The use of such a catalyst can significantly reduce the amount of unsaturated hydrocarbyl partial esters and thus provides a great economic benefit. The amount of acid catalyst to be used in the sizing agent is 0.0001 to 10.0 parts by weight, preferably 0.001 to 1 part by weight of the acid catalyst per 100 parts by weight of the sizing agent.

Unsaturated partial esters of the present invention can be converted into water-soluble or at least self-emulsifiable products by converting residual free carboxyl groups into salts with alkali metals or water-soluble amines, which can be added to water to obtain a stable aqueous solution or dispersion. In use, it is preferable to use cationic starch, an activator-based alkylene oxide adduct, and the like, which are conventionally used in the art, to sufficiently ensure the advantages of the sizing agent.

The unsaturated hydrocarbyl partial ester of alkenylsuccinic acid of the present invention is added to the paper material by 0.0001 to 10 parts by weight per 100 parts by weight of paper material (dry basis), and preferably by 0.01 to 2.0 parts by weight per 100 parts by weight of paper material. .

The invention is illustrated by the following examples, but the scope of the invention is not limited thereto.

Preparation of Sizing Agents Used in Examples and Comparative Examples

[Comparative Examples 1-15]

In a four-necked flask, 1 mole of dodecenyl succinic anhydride and 1 mole of allyl alcohol were reacted at 110 ± 5 ° C. for 2 hours to form an aminoallyl ester of dodecenyl succinic acid. The product thus obtained was converted to triethanolamine salt, a viscous, tan liquid with good self emulsification in water.

In the same manner, the monoesters described below were prepared and these monoesters were tested for sizing in the form of amine salts, sodium salts or potassium salts.

[Comparative Examples 16 ~ 24]

5 g of the unsaturated monoester of alkenylsuccinic acid shown in Table 1 was added, and cationic starch (10 g) was cut out with 90 ml of water at 95-97 ° C for 15 minutes.

[Comparative Example 25]

A sizing agent was prepared by adjusting the pH of a commercial rosin sizing agent to 4.5 with alum.

Comparative Example 26

A sizing agent was prepared by adding 25% by weight of cationized cellulose to a commercially available alkyl ketene dimer system sizing agent.

Comparative Example 27

10 g of cationic starch was mixed with 90 ml of water, and the resulting mixture was boiled at 95-97 ° C. for 15 minutes and dodecenyl succinic anhydride was added thereto to prepare a sizing agent.

Comparative Example 28

A sizing agent was prepared in the same manner as in Comparative Example 1 except that octadecenyl succinic anhydride was used instead of dodecenyl succinic anhydride.

[Comparative Examples 29-30]

Alkenylsuccinic anhydride was mixed with the amounts of phosphoric acid shown in the table.

[Examples 1-70]

In a three-necked flask, 1 mol of hexenyl succinic anhydride and 1 mol of allyl alcohol were reacted at 110 ± 5 ° C. for 2 hours to synthesize monoallyl ester of hexenyl succinic acid. Benzene sulfonic acid was added to the resulting monoallyl ester of hexenyl succinic acid by 0.1% by weight relative to the weight of monoallyl ester. The product thus obtained was modified with cationic starch to form a homogeneous slurry.

Additional sizing agents were prepared in the same manner as shown in Table 2.

[Test method of sizing degree]

The sizing degree of the sizing agent mentioned above was measured on condition of the following. Each sizing agent was added to the 0.5% aqueous pulp slurry by 0.05, 0.1 and 0.15% by weight (based on solids) and mixed for 15 minutes.

Test conditions are as follows:

Pulp Concentration 0.5%

Paper Making Process Tariff Standard Machine

(TAPPI STANDARD MACHINE)

Reference weight 70g / ㎡

Filler Calcium Bicarbonate

5 minutes at 100 ° C drying

Sizing Test JIS P8122 Stock Kit

(stockigt) sizing test

The results thus obtained were reproduced in the following tables, Table 1 shows comparative examples and Table 2 shows examples of the present invention. Succinic acid is abbreviated as s.a. in each symbol.

TABLE 1

Note: TEA: triethanolamine; DEA: diethanolamine; MEA: monoethanolamine; TEtA: triethylamine; MMtA: Monomethylamine

TABLE 2

A sizing test was conducted to see the change of sizing degree over time. The product obtained by making a sizing agent by the method mentioned above was left to stand at room temperature, and sampled at regular intervals, and sizing test was carried out. The test method is as above. The test results are shown in Table 3.

TABLE 3

The experimental results show that the product of the present invention is stable and has good resistance to hydrolysis. In fact, even after application for several hours, the reduction in sizing effect is small because of the good resistance to hydrolysis of the monoester. You get a lot of advantages from this:

a) no need to hasten the sizing process after the manufacture of the sizing agent;

b) the loss of the sizing agent can be minimized even if the operation is resumed after the prepared sizing agent is left overnight;

c) can not be hydrolyzed and can be mixed for longer periods of time, which allows for a more homogeneous emulsion formation of the sizing agent;

d) The sizing quality of the paper is still stable during several hours of continuous sizing.

Claims (5)

As an active ingredient, a sizing agent useful for making paper containing one or more partial esters of alkenylsuccinic acids represented by the following formula (I) or (II) or one or more salts thereof, further comprising an acid catalyst. A sizing agent characterized by the above-mentioned.

Wherein R represents an unsaturated hydrocarbyl group having 6 or more carbon atoms, and R 'represents an unsaturated hydrocarbyl group having 3 to 18 carbon atoms. The sizing agent according to claim 1, wherein the catalyst is selected from sulfonic acid, organophosphoric acid, inorganic acid or Lewis acid. The sizing agent according to claim 2, wherein the inorganic acid is selected from phosphoric acid, phosphorous acid, hypophosphorous acid, sulfuric acid, hydrochloric acid or nitric acid. The sizing agent according to claim 2, wherein the Lewis acid is selected from boron fluoride, zinc chloride, aluminum chloride or ferric chloride. The sizing agent according to claim 1, wherein the salt is selected from water-soluble amine salts or alkali metal salts.