JPS5891896A - Papermaking size agent - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] Specifically, the present invention relates to a sizing agent for paper manufacturing that can impart excellent sizing effects to paper, especially when papermaking water is hard water or when papermaking is performed at high temperatures. .

So-called synthetic sizing agents have been known as sizing agents for rosin-based sizing agents.

One such synthetic sizing agent is known as a papermaking sizing agent containing succinic acid having a hydrocarbon substituent as an active ingredient.

For example, in Japanese Patent Publication No. 565-1977, carbon number 8 to 1 is
A method is disclosed in which a water-soluble salt of succinic acid having 5 hydrocarbon substituents is used in conjunction with an internal paper sizing agent. However, these sizing agents are not necessarily satisfactory in terms of size effect, hard water dispersibility, etc. compared to rosin-type sizing agents. Alternatively, a paper sizing agent comprising an aqueous emulsion of a substituted succinic acid having an alkyl group is disclosed. The sizing agent was published in Japanese Patent Publication No. 40-5.
Unlike the soap-type sizing agent disclosed in No. 65, it becomes an emulsion when diluted with water.

However, this emulsion has a problem of poor storage stability. In order to eliminate this problem, a substituted succinic acid having a constant carbon number for glaze (especially one having an IW substituent carbon number of 4 to 8) or a surfactant may be used in combination.
The use of a substituted succinic acid having a specific number of carbon atoms or a surfactant in combination significantly reduces its original size effect. Therefore, such
The sizing agent disclosed in No. 59 cannot be said to be a synthetic sizing agent that simultaneously satisfies size performance and storage stability.

In addition, a sizing agent made only of substituted succinic acid that does not contain any substituted succinic acid having the specified number of carbon atoms usually becomes an emulsion when diluted with water to a low concentration, but it has poor storage stability, and therefore, it is difficult to make paper. When used in a factory or the like, such an emulsion-type sizing agent must be mechanically sheared just before use to force redispersion and homogenization, which is not convenient in terms of handling.

Furthermore, such an aqueous emulsion has a sizing agent at a concentration that is generally commercialized (usually a non-volatile content concentration of 30 to 80% by weight).
) will result in an unstable emulsion or opaque aqueous solution, and in even worse cases, the active ingredient and water will be mixed together.
It may separate into layers. Therefore, it is quite difficult to commercialize it as a sizing agent.

The present inventors conducted various studies on partially neutralized substituted succinic acids and their viscosity and behavior, and as a result, they obtained the following new knowledge. In other words, when the degree of neutralization of substituted succinic acid is gradually increased with a specific neutralizing agent, the phase separation of water and the active ingredient when unneutralized becomes an emulsion → a clear aqueous solution (
There is an interesting series of phase change processes in which A) changes from a translucent or transparent aqueous solution to an aqueous gel (gelatinous material) to a slightly cloudy liquid, and finally reaches a transparent aqueous solution (B) through complete neutralization. I found out that it can be observed.

As mentioned above, only unneutralized and completely saponified (neutralized) types of substituted succinic acid type synthetic sizing agents are known in the technical field. Therefore, what is conventionally referred to as an aqueous solution regarding substituted succinic acid refers to the transparent aqueous solution (B) shown in the series of phase change processes described above, and the extremely unexpected phenomenon of the formation of the transparent aqueous solution (A) occurs. That was not expected at all.

The present inventors have discovered that this unique transparent aqueous solution (A) has a product concentration of a sizing agent (usually an active ingredient concentration of 30 to aott%).
Therefore, within this range, it can be handled in exactly the same way as the conventionally known aqueous solution of completely saponified substituted succinic acid, and it also has size effects (especially effects in hard water paper making and high temperature paper making) and It was discovered that it can be used as a paper sizing agent with excellent hard water dispersibility, and the present invention was completed.

That is, the present invention provides substituted succinic acid represented by the general formula (1): (wherein R represents an alkyl group or an alkenyl group having 9 to 16 carbon atoms) to a substituted succinic acid represented by the general formula (
(2): A basic compound represented by 1 (wherein, R, R2 and R3 are different but the same and represent a hydrogen atom, a methyl group, an ethyl group or a hydroxyethyl group) with a degree of neutralization of 1 The present invention relates to a paper sizing agent characterized in that it contains as an active ingredient a partially neutralized substituted succinic acid obtained by partial neutralization to a concentration of 30% to 30%.

In the present invention, it is essential to use a specific substituted succinic acid represented by the general formula (1).

That is, in the general formula (1), the substituent represented by R is a linear or branched alkyl group or alkenyl group having 9 to 16 carbon atoms.

Preferred examples of such substituted iR include nonenyl group, decenyl group, dodecenyl group, dodecyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, and the like.

If the number of carbon atoms in the substituent H is less than 9, the hard water dispersibility is good, but the size effect is insufficient, while if the number of carbon atoms in the substituent H is more than 16, the size effect and hard water dispersibility are poor. This is not preferable since both of them are insufficient.

Among the compounds represented by the general formula <1), alkenyl-substituted succinic acid can be obtained by addition reacting an olefin having 9 to 16 carbon atoms with maleic anhydride. That is, in the presence of the olefin and anhydrous maleic St-catalyst or in the absence of a catalyst, preferably in an atmosphere of an inert gas such as nitrogen, under normal pressure or increased pressure, 180 to 25
0°0, preferably 190-220°0, 1-
It can be obtained by reacting for 50 hours, preferably 10 to 36 hours. The molar ratio of olefins to maleic anhydride is not particularly limited, but it is usually appropriate to use 0.4 to 2 mol, preferably 0.8 to 163 mol, of maleic anhydride per mol of olefin. Further, after the reaction is completed, alkenyl-substituted succinic acid can be obtained by distilling and removing unreacted olefins and maleic anhydride.

Among the compounds represented by the general formula (I), alkyl-substituted succinic acid can be easily obtained by hydrogenating the alkenyl-substituted succinic acid.

In order to obtain the sizing agent of the present invention, it is necessary to further partially neutralize the specific substituted succinic acid represented by the general formula (I) with the specific basic compound. That is, the specific basic compound is limited to those represented by the general formula (n). Specific examples of the compound represented by general formula (II) include ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, monoethanolamine, jetanolamine, triethanolamine, and the like. Furthermore, according to the present invention, the general formula (
The substituted succinic acid represented by I) must be adjusted to a degree of neutralization within a very limited specific range with the specific basic compound represented by the general formula (II), and if both of these conditions are met, Only if you are satisfied at the same time,
It can be used as an excellent paper sizing agent.

When normally substituted succinic acid is partially neutralized, the hydrophilicity of the resulting partially neutralized substituted succinic acid differs depending on the type of substituent of the substituted succinic acid used, especially the number of carbon atoms. Therefore, although it is not necessarily possible to uniquely determine the optimal degree of neutralization, according to the present invention, the degree of neutralization of the carboxyl group contained in the substituted succinic acid by the basic compound of the general formula (...) is usually 1. ~30%, preferably 2
It is preferable to adjust it to a range of 20%.

If the degree of neutralization is less than 1%, the desired aqueous solution will not be obtained at the sizing agent product concentration (active ingredient concentration is 30-80% by weight), resulting in an unstable emulsion or two layers of active ingredient and water. Unfavorable because it forms a liquid. Also, the degree of neutralization is 31-8
In the 0% range, the sizing agent product concentration becomes an aqueous gel-like substance (gelatin-like substance) with extremely high viscosity, making it extremely difficult to handle and causing various troubles in the process from production to use. Therefore, the value of the product decreases.

Further, in a range where the degree of neutralization exceeds 80%, the properties of the resulting sizing agent are close to those of a conventionally known fully saponified sizing agent, and the sizing performance and hard water dispersibility become insufficient, which is not preferable.

The method of using the sizing agent of the present invention is similar to that of known sizing agents. For example, the sizing agent of the present invention may be used before, after, or simultaneously with the addition of a fixing agent such as sulfuric acid to an aqueous slurry of pulp. The paper may be made in a pH range of about 4 to 6.

At this time, fillers such as clay and talc and various filler retention agents associated with their use are also used in combination as in the past. The sizing agent of the present invention is usually 0.05 to 3% (
(based on dry weight), especially about 0.0
Its outstanding performance is exhibited in the range of use of 5 to 0.5%. Furthermore, the sizing agent of the present invention exhibits the desired excellent performance even under hard water papermaking conditions and high temperature papermaking conditions. It can also be suitably used under conditions where the papermaking water is hard water, such as when waste paper such as, for example, is used as a pulp source.

Next, the present invention will be explained in more detail by reference examples, working examples, and comparative examples, but the present invention is not limited to these examples. In addition, below, % is weight%,
MS is parts by weight.

Reference Example 1 α- Containing 46% of butylene oligomers (those with 12 carbon atoms), 15% of those with 15 carbon atoms, and 15% of those with 16 carbon atoms
Alkenylsuccinic anhydride was obtained by adding maleic anhydride to the mixture of olefins). Water was added to the selected alkenyl-substituted succinic acid, a hydrolysis reaction was carried out under reflux (100°a) for about 1 hour, and then the water was evaporated to obtain the alkenyl-substituted succinic acid.

Reference Example 2 Propylene oligomer (a mixture of α-olefins containing 76% of those with 12 carbon atoms and 17% of those with 11 carbon atoms) dimaleic anhydride was added to obtain an alkenyl-substituted succinic anhydride. This is a reference example. Hydrolysis reaction and water evaporation were carried out in the same manner as in Example 1 to obtain alkenyl-substituted succinic acid.

Reference Example 3 Maleic anhydride was added to n-decene-5 to obtain an alkenyl-substituted succinic anhydride. Next, a hydrogenation reaction is carried out in a hydrogen gas atmosphere using a palladium-activated carbon catalyst,
An alkyl-substituted succinic anhydride was obtained. A hydrolysis reaction was carried out in the same manner as in Reference Example 1 to obtain alkyl-substituted succinic acid.

Reference Example 4 An alkenyl-substituted succinic acid was obtained by conducting an experiment in the same manner as in Reference Example 1 except that n-dodecene-O was used as the butylene oligomer.

Example 1 1180 parts of alkenyl succinate rj obtained in Reference Example 1, 118.6 parts of deionized water and 3.7 parts of 25% ammonia water
202.3 parts of a sizing agent with a degree of neutralization of 10% and a non-volatile content of 40% were prepared by mixing the following parts: This sizing agent was a clear aqueous solution.

The size performance and hard water dispersibility of the obtained sizing agent were examined according to the test method described below.

(Size performance test) The pulp (L-BKp) was
Freeness, 450 ml was dissolved in IIIJ, and this was made into a 1% aqueous slurry. The sizing agent obtained in this example' was added to the slurry at a concentration of 0.2% (in terms of solid content) based on the pulp, and then sulfuric acid was added at a concentration of 2% based on the pulp.
After adding it at 5% (in terms of solid content), it was uniformly dispersed. This slurry was made into paper using a Tappi Standard Sheet Machine so that the paper size was 1i6o±19/m2. The obtained wet paper was compressed and dehydrated, then dried at 100°0 for 1 minute, and further dried for 20QO1 at a relative humidity of 65%.
After conditioning the humidity for 4 hours, the size degree (seconds) of each was measured by the Stekicht method.

The sizing degree is the sizing degree (hereinafter referred to as high size) when 50° O soft water (hardness 30 I H) is used as papermaking water, and the sizing degree when 350° hard water (hardness 20' DH) is used as papermaking water. We investigated both the hard water size performance (hereinafter referred to as hard water size).

(Hard water dispersibility test) Hard water (hardness 30°DH) was applied to the sizing agent obtained in this example.
was added to dilute the sizing agent so that the nonvolatile content concentration was 1100 pp, and the sizing agent was allowed to stand at room temperature and the state of the internal liquid was visually observed.

The results of each test are shown in Table 1.

Examples 2 to 16 Two experiments were conducted in the same manner as in Example 1 except that the type and degree of neutralization of the substituted succinic acid and the basic compound (neutralizing agent) were changed to those shown in Table 1. was prepared.

, The properties of the obtained sizing agent at a concentration of 40%, the results of the size performance test, and the results of the hard water dispersibility test were
Shown in the table.

Comparative Examples 1 to 4 Example 1 except that at least one of the type of neutralizing agent and the degree of neutralization used was changed to those shown in Table 1, or no neutralizing agent was used (Comparative Example 1) Experiments were conducted in the same manner as above, and sizing agents were prepared for each.

Table 1 shows the properties of the obtained sizing agent at a concentration of 40%, the results of the size performance test, and the results of the hard water dispersibility test.

The sizing agents obtained in Comparative Examples 1 and 4 did not form an aqueous solution at a nonvolatile content concentration of 40%, and the active ingredient and water separated into layers (see Table 1).

Therefore, when making paper, the purity of the obtained sizing agent (
(non-volatile content: 100%) was forcibly dispersed as it was in pulp slurry, and its size performance was measured.

Comparative Examples 5 to 7 Substituted succinic acid was replaced with that obtained in Reference Example 1, and no neutralizing agent was used (Comparative Example 5), or the type of neutralizing agent and the degree of neutralization were as shown in Table 1. An experiment was carried out in the same manner as in Example 1 except that the substances shown were used, and sizing agents were prepared.

Table 1 shows the properties of the obtained sizing agent at a concentration of 40%, the results of the size performance test, and the results of the hard water dispersibility test.

Note that the sizing agent obtained in Comparative Example 5 did not become an aqueous solution at a nonvolatile content concentration of 40%, and the active ingredient and water separated into layers (see Table 1). Therefore, during paper making, the pure content (non-volatile content: 100%) of the obtained sizing agent was forcibly dispersed as it was in the pulp slurry IJ-, and its sizing performance was measured.

Moreover, the sizing agent obtained in Comparative Example 7 had a nonvolatile content of 40
%, it was a gelatinous aqueous gel.

Reference Example 5 An experiment was conducted in the same manner as in Reference Example 1 except that n-octene-1 was used as the butylene oligomer to obtain alkenyl-substituted succinic acid.

Comparative Examples 8 to 11 Substituted succinic acid was replaced with that obtained in Reference Example 5, and no neutralizing agent was used (Comparative Example 8). An experiment was conducted in the same manner as in Example 1 except that the sizing agents were replaced with those shown in , and sizing agents were prepared for each.

Table 1 shows the properties of the obtained sizing agent at a concentration of 40%, the results of the size performance test, and the results of the hard water dispersibility test.

Note that the sizing agent obtained in Comparative Example 8 did not become an aqueous solution at a nonvolatile content concentration of 40%, and the active ingredient and water separated into layers (see Table 1). Therefore, when making paper, the pure content (non-volatile content 100%) of the obtained sizing agent was directly used as a sizing agent within the range of bulp slurry light (Examples 1 to 16).
) are all transparent aqueous solutions at a concentration of 40%, and have excellent size performance and hard water dispersibility.

On the other hand, the sizing agents (Comparative Examples 1 to 11) in which the type of neutralizing agent and the degree of neutralization are outside the scope of the present invention have insufficient sizing performance and hard dispersibility, and the concentration when commercialized is Within this range, it may separate into two layers or form an aqueous gel, which is undesirable.

As described above, according to the present invention, the sizing agent is generally transparent at the concentration used as a product, has excellent sizing performance, especially when using hard water or high-temperature water, and has good hard water dispersibility. An excellent sizing agent is provided.

Claims (1)

[Scope of Claims] 1. Substituted succinic acid represented by the general formula (I);
■): 1 -N -R3(n) (In the formula, R□, R2 and R3 are different from each other or the same and represent a water purple atom, a methyl group, an ethyl group or a hydroxyethyl group) Substitution obtained by partial neutralization with a basic compound such that the degree of neutralization is 1 to 50%. A paper sizing agent characterized by containing a partially neutralized product of succinic acid as an active ingredient.