JPS59144695A - 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 The present invention relates to a sizing agent for paper manufacturing, and more particularly to a sizing agent for paper manufacturing that exhibits a sizing effect superior to that of rosin-based sizing agents and that causes extremely little foaming during use.

Conventionally, so-called rosin-based sizing agents made from rosin have been commonly used as internal sizing agents for paper manufacturing, but rosin is a natural product and has problems such as price fluctuations and unstable supply. As an alternative synthetic sizing agent, a so-called petroleum resin sizing agent made from a petroleum resin obtained from a mixture of C5 and C9 fractions obtained from cracked naphtha oil, and many other synthetic sizing agents have been proposed.

However, until a few years ago, synthetic sizing agents other than petroleum resin sizing agents were hardly put into practical use due to performance or price considerations, and even the petroleum resin sizing agents that were in practical use were not used due to their performance. The reality is that it is limited.

However, in recent years, reaction products of highly branched olefins and maleic anhydride, i.e., water-soluble salts of alkenylcono-phosphate, have been widely used as synthetic sizing agents that are superior to rosin-based sizing agents in terms of performance and price. It's starting to look like this. A paper sizing method using this water-soluble salt of alkenyl succinic acid as an internal sizing agent was published in Japanese Patent Publication No. 40-5.
Although it is already known from Publication No. 65,
It is stated that the water-soluble salt of alkenylsuccinic acid described in Japanese Patent No. 565 must have an alkenyl group having 8 to 15 carbon atoms; if it has an alkenyl group having 16 or more carbon atoms, a satisfactory size effect cannot be obtained. In fact, to date, no water-soluble salt of alkenylsuccinic acid having an alkenyl group having 16 or more carbon atoms, or a sizing agent containing the same, has been known to exhibit a sizing effect superior to that of a rosin-based sizing agent. .

Furthermore, this water-soluble salt of alkenylsuccinic acid has a drawback in foaming properties and is considered to be a practical problem (see Japanese Patent Application Laid-Open No. 54-27003), but according to the research of the present inventors, Foaming occurs when the fixation of the sizing agent to the pulp is inhibited during sizing, and unfixed water-soluble salts of alkenylsuccinic acid or reaction products of alkenylsuccinic acid and sulfuric acid remain in the pulp slurry. It has been found that if the fixing is limited and normal, foaming is hardly observed and there is no problem in practical use.

However, even though inhibition of the fixation of the sizing agent in the papermaking process is an extremely rare phenomenon, the problem of foaming in such cases is that the sizing agent, which is made of a water-soluble salt of alkenylcono-phosphate, This is a drawback.

In this way, conventionally when using the water-soluble salt of the reaction product of L1 monoolefin 8 and maleic anhydride as a sizing agent,
As a result of focusing only on the size effect, attention was focused only on the number of carbon atoms in the monoolefin used as a raw material, and the relationship between the structure, size effect, and foaming properties was not studied, so it was difficult to put it into practical use as a sizing agent. However, there were problems with foaming, and when a monoolefin having 16 or more carbon atoms was used as a raw material, a satisfactory size effect could not be obtained.

Therefore, in order to develop a synthetic sizing agent that exhibits a size effect superior to that of rosin-based sizing agents and that produces less foaming even when inhibited by fixation during use, the present inventors investigated the molecular structure and size effect of the monoolefin used as a raw material, and As a result of intensive research on foaming properties, we have found that the size effect and foaming properties of water-soluble alkenylsuccinic acid salts are expressed by the molecular structure of the olefin used as a raw material, especially the value of the ratio of the number of methylene groups to the number of methyl groups. It varies significantly depending on the state of branching, and when the value of the number of methylene groups relative to the number of methyl groups in the monoolefin that is the raw material is 0.9 or more, the reaction obtained by heating and addition reacting these olefins with maleic anhydride. It has been found that a sizing agent prepared by saponifying a product with an alkali produces very little foaming when inhibited by fixation.

Furthermore, surprisingly, even with monoolefins having 16 or more carbon atoms, which were conventionally considered to be unsuitable as raw materials for sizing agents because a satisfactory sizing effect could not be obtained, the number of methylene groups relative to the number of methyl groups When the value of the ratio of It has been found that not only does it have extremely low foaming, but it also exhibits a sizing effect superior to that of rosin-based sizing agents over a wide range of addition amounts.

Furthermore, based on the knowledge obtained from these results,
As a result of repeated studies, a reaction obtained by reacting a monoolefin or a monoolefin mixture having 16 to 24 carbon atoms and a ratio of methylene groups to methyl groups of 0.9 or more with maleic anhydride. The water-soluble salt [A] obtained by alkali saponification of the product suppresses foaming without impairing the sizing effect when added to conventional paper sizing agents that tend to cause foaming problems when inhibited by fixation. The present invention was discovered based on the discovery that the method has an effect.

As described above, the sizing agent containing the water-soluble salt [A] according to the present invention has a relationship between the foaming property and size effect when the sizing agent is used and the molecular structure of the raw olefin, which has not been clarified in the past. Among monoolefins with carbon atoms of 16 or more, which had not been considered as raw materials for paper sizing agents made of water-soluble salts of alkenylsuccinic acids, A reaction product obtained by a heated addition reaction between a monoolefin or a monoolefin mixture having a number of 16 to 24 and a ratio of the number of methylene groups to the number of methyl groups of 0.9 or more and maleic anhydride. A papermaking sizing agent containing a water-soluble salt [A] obtained by alkali saponification, which not only exhibits a sizing effect superior to rosin-based sizing agents over a wide range of addition amounts, but also foams when inhibited by fixation. It also has very few characteristics.

Polyolefins having 16 or more carbon atoms obtained by polymerizing monoolefins such as general olefins, propylene, butylene, or mixtures thereof in the presence of an acid catalyst such as solid phosphoric acid, liquid phosphoric acid, or a Riederg catalyst such as aluminum chloride. The oligomer has a highly branched structure, with a ratio of the number of methylene groups to the number of methyl groups of less than 0.9. The sizing agent obtained from the maleic anhydride adduct of a highly branched oligomer having 16 or more carbon atoms has a high foaming property and an insufficient sizing effect, so it is not suitable for the purpose of the present invention. Undesirable.

On the other hand, oligomers having 16 or more carbon atoms obtained by polymerizing monoolefins such as propylene, butylene, hexene, and octene or mixtures thereof in the presence of an organoaluminum catalyst, for example, can be obtained by the acid catalyst described above. It has a structure with fewer branches than an oligomer, and the ratio of the number of methylene groups to methyl groups is 0.9 or more.

As already mentioned, monomers with less branching, a ratio of the number of methylene groups to the number of methyl groups of 0.9 or more, and a carbon number of 16 to 24, preferably 16 to 20 Olefins or monoolefin mixtures can be suitably used for the purpose of the present invention because the paper-making sizing agents obtained therefrom are characterized by less foaming when inhibited by fixation.

10,000. Monoolefins or monoolefin mixtures having 25 or more carbon atoms cannot be made into a homogeneous aqueous solution even if the reaction product obtained from them with maleic anhydride is alkaline saponified.
It is not preferable because it is difficult to peel and a satisfactory size effect cannot be obtained even if the foaming property is low.

As the monoolefin or monoolefin mixture having 16 to 24 carbon atoms and having a ratio of the number of methylene groups to the number of methyl groups of 0.9 or more, propylene is used in the present invention. In addition to oligomers obtained by polymerization of butylene, hexene, octene, etc., linear internal olefins obtained by dehydrogenation of n-paraffins, linear α-olefins obtained by polymerization of ethylene, etc. The sizing agents obtained from these monoolefins or monoolefin mixtures are characterized by extremely low foaming when inhibited by fixation, but n- Butylene oligomers and linear internal olefins are preferred.

If desired, a monoolefin having a carbon number of 16 to 24 and a ratio of the number of methylene groups to the number of methyl groups of less than 0.9 may be mixed with a monoolefin having a ratio of 0.9 or more,
The value of the ratio of the number of methylene groups to the number of methyl groups is 0.9
A monoolefin mixture prepared as above can also be used.

Monoolefins or monoolefin mixtures in which the ratio of the number of methylene groups to the number of methyl groups is 22 or more are not suitable for the purpose of the present invention because they have a carbon number of 25 or more.

The reaction product of a monoolefin and maleic anhydride used in the present invention is obtained by reacting the monoolefin and freanic anhydride without a catalyst or in the presence of a reaction promoter such as a peroxide, preferably in an inert atmosphere such as nitrogen at normal pressure. or under pressure,
180-250C.

Preferably, it is heated to 200-230C, and at that temperature 1-
It is obtained by reacting for 30 hours, preferably 3 to 20 hours. The molar ratio of monoolefin and maleic anhydride does not need to be particularly limited, but is 0.5 to 1 mole of monoolefin.
It is desirable to use ~3 mol. After the reaction is complete, the monoolefin and maleic anhydride are removed by distillation to obtain a relatively low viscosity liquid reaction product. Its saponification value (JIS
K 5902) is approximately 250-350. In addition,
Depending on the reaction conditions, some by-products may be produced. In that case, the by-product can be removed as a distillation residue by further distillation under reduced pressure, but since the amount is small, removal of the by-product is not necessarily necessary in the present invention.

The sizing agent of the present invention can be obtained by saponifying the reaction product thus obtained with an alkali to form a transparent aqueous solution.

The alkali used for saponification in the present invention includes:
Examples include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, ammonia, and water-soluble amines such as trimethylamine and diethylamine, but it is preferable to use sodium hydroxide or potassium hydroxide. The amount of alkali used for saponification is 0.8 to 1.2 times, preferably 0.9 to 1.1 times, the required amount predicted from the saponification value of the reaction product of monoolefin and maleic anhydride. use As the amount of alkali decreases, the foamability of the resulting sizing agent increases, and if the amount is less than 0.8 times the required amount predicted from the saponification value, the foamability increases significantly although the size effect is not affected. Undesirable.

The sizing agent according to the present invention has a prime number of 16 to 24,
A monoolefin or monoolefin mixture in which the ratio of the number of methylene groups to the number of methyl groups is 0.9 or more is reacted with maleic anhydride, and the resulting reaction product is used alone or as a monoolefin with a carbon number of 15 or less. or a reaction product of a monoolefin mixture and maleic anhydride;
Alternatively, the olefin or olefin mixture used in the present invention may be mixed with rosin or the like in any proportion and then saponified or saponified and then mixed. It can also be obtained by mixing with a monoolefin mixture in an arbitrary ratio, reacting with maleic anhydride, and saponifying the resulting reaction product.

The water-soluble salt [A] of the maleic anhydride adduct of a monoolefin having 16 to 24 carbon atoms or a mixture of monoolefins in the present invention increases in proportion to the active ingredient of the sizing agent. Since the foam-inhibiting effect becomes stronger, it is desirable that it be present in the active ingredient of the sizing agent in an amount of 10% by weight or more, but even if it is less than 10% by weight, the foam-inhibiting effect will be exerted depending on the amount present. In this case, the other active ingredient may be any sizing agent. In addition, the sizing agent according to the present invention may consist entirely of the water-soluble salt [A].

Just like conventional rosin-based sizing agents, the sizing agent according to the present invention can be added to the paper manufacturing process at any step before the end of the papermaking operation, for example, in the beating process or in the pulp slurry after the beating process. After adding the sizing agent according to the present invention, sulfate is added to adjust the pH to about 4.0-5.5.
Preferably, it can be fixed to pulp by adjusting it to 4.2 to 5.0. Further, in use, it can be used in combination with other sizing agents such as conventional rosin-based sizing agent 2 petroleum resin sizing agent in any proportion, and it can also be used for surface sizing.

In the case of internal addition sizing, the amount of the sizing agent according to the present invention is 0.01 to 5.0% by weight, preferably 0.05 to 5.0% by weight of the pulp, based on the weight of the dry pulp.
3. In the case of surface sizing, it ranges from 0.005 to 0.5 g/lr on a dry weight basis. Apply sizing agent.

As explained above, it was conventionally believed that a satisfactory sizing agent could not be obtained when reacted alone with maleic anhydride, even if monoolefins or monoolefin mixtures with a carbon number of 6 or more, By selecting a monoolefin or a monoolefin mixture having a ratio of the number of methylene groups to the number of methyl groups of 0.9 or more and alkali saponification of the reaction product of this and maleic anhydride, the conventional Contrary to knowledge, Yuno'1. A sizing agent for paper manufacturing that exhibits a good size effect and low foaming properties can be obtained.

The sizing agent of the present invention is a paper-making sizing agent containing a sizing composition having excellent sizing effects and low foaming properties obtained from such frozen monoolefins or monoolefin mixtures having 16 or more carbon atoms. Not only is it superior to rosin-based sizing agents over a wide range of addition amounts, but it also has the characteristic of significantly suppressing foaming when inhibited by fixation.

The characteristics of the sizing agent according to the present invention have been explained above,
The present invention will now be explained in more detail with reference to Comparative Examples and Examples. Note that the ratio of the number of methylene groups to the number of methyl groups in Comparative Examples and Examples is a value measured by nuclear magnetic resonance spectroscopy.

Comparative Example 1 The ratio of the number of methylene groups to the number of methyl groups is 0.8
250 parts by weight of a propylene oligomer mixture having 8 to 10 carbon atoms and 200 parts by weight of maleic anhydride were heated to 215°C under a nitrogen atmosphere in an autoclave, and the mixture was heated to 215°C without a catalyst.
Allowed time to react. After the reaction, the reaction product was taken out and unreacted oligomer and maleic anhydride were distilled off under reduced pressure F to obtain 294 M parts of a yellowish brown oily reaction product. The saponification value of this reaction product was 502. Potassium hydroxide and water in an amount equivalent to the saponification value were added to the obtained reaction product, and the mixture was stirred at 90°C for 2 hours to saponify it, resulting in a solid content of 40
A transparent sizing agent (sizing agent A) containing the following was obtained. The pH of this sizing agent is 10.1.

Comparative Example 2 The ratio of the number of methylene groups to the number of methyl groups is 0.8
7, a mixture of propylene oligomers having 16 to 21 carbon atoms, and 166 parts by weight of maleic anhydride were reacted in the same manner as in Comparative Example 1, and unreacted substances were removed to obtain a yellowish brown oily reaction product 194. Parts by weight were obtained. The saponification value of this reaction product was 320. Comparative example 1
Although the solid content was adjusted to 400 parts by weight by saponification in the same manner as above, the sizing agent became emulsified and a uniformly transparent sizing agent could not be obtained. The pH of this emulsified sizing agent (sizing agent B) is 10.
．． It was 1.

Example 1 The ratio of the number of methylene groups to the number of methyl groups is 0.9
3] 230 parts by weight of a mixture of n-butylene oligomers having a carbon number of 6 to 2o and maleic anhydride 159 parts by weight were obtained. The saponification value of this reaction product was 350. This was saponified in the same manner as in Comparative Example 1 to obtain a transparent sizing agent (sizing agent c) according to the present invention containing 400 parts by weight of solids. The pH of this sizing agent was 10.1.

Example 2 The ratio of the number of methylene groups to the number of methyl groups is 6.1
225 parts of a linear internal olefin having 16 carbon atoms and 100 parts by weight of maleic anhydride were reacted in the same manner as in Comparative Example 1, and unreacted substances were removed to produce 156 parts by weight of a yellow-brown wavy reaction product. I got the department. The saponification value of this reaction product was 352. This was saponified in the same manner as in Comparative Example 1 to obtain a transparent sizing agent (sizing agent D) containing 200 parts by weight of solids. This sizing agent has a pH of 10.0 and is hot.

Example 3 20 parts by weight of the reaction product obtained in Example 1 and 80 parts by weight of the reaction product obtained in Comparative Example 1 were mixed. The saponification value of this mixture was 472. This was saponified in the same manner as the comparative crab to obtain a transparent sizing agent (sizing agent E) according to the present invention containing 400 parts by weight of solids. The pH of this sizing agent is 1
It was 0.1.

Example 4 Part of sizing agent C511:ii obtained in Example 1 and Comparative Example 1
Mix 50 parts by weight of the sizing agent A obtained in
Sizing agent (sizing agent F
) was obtained. The pH of this sizing agent was 10.1.

Example 5 40 parts by weight of the sizing agent D obtained in Example 2 and 80 parts by weight of the sizing agent A obtained in Comparative Example 1 were mixed, and water was added to reduce the solid content to 30 parts by weight.
Transparent sizing agent according to the present invention containing 0 parts by weight (sizing agent G
) was obtained. The pH of this sizing agent was 10.1.

Example 6 A sizing test was conducted on the sizing agents A and B obtained in Comparative Examples 1 to 2 above and the sizing agents (:', D, E, F, and G obtained in Comparative Examples 1 to 5. A commercially available reinforced rosin sizing agent was used as the agent.The test method was as follows.

Beating degree C, F, = 400 CCK: Prepare a three-layer slurry of the prepared hardwood bleached kraft pulp, and add sizing agent A, sizing agent B, and sizing agent C to this slurry.

Sizing agent, sizing agent E, sizing agent F, sizing agent G or reinforced rosin sizing agent as solid content per dry pulp 0
．． 2 wt%, 0.5 wt% or 1 wt% was added and sulfuric acid was added with stirring to bring the pH of the slurry to 4.5. This pulp slurry is further adjusted to pH using sulfuric acid band.
Dilute the pulp to a pulp concentration of approximately 0.2% by weight with water adjusted to 5.0%, make paper using a TAPPI standard sheet machine, dehydrate under pressure (4Kg/cj x 1 minute), and then dry the wet paper in a rotary dryer. Heat treatment was performed at 105° C. for 3 minutes. The basis weight of this handmade paper is equivalent to 60 g/-.

The resulting paper was left in a room at a temperature of 20° C. and a humidity of 65 or above for 24 hours, and then its sizing was measured by the Steckcht sipe test method of JIS-P-8112. The results are shown in Table 1.

Next, in order to examine foaming under conditions where the pulp slurry concentration is low and the sizing agent is susceptible to fixation inhibition, we
F, = 0.8% by weight slurry of bleached hardwood kraft pulp adjusted to 4000H, sizing agent A, sizing agent B
, Sizing agent C, Sizing agent.

Sizing agent E, sizing agent F, sizing agent G, and reinforced rosin sizing agent were added in an amount of 0.5% by weight based on the solid content of the dry pulp, and after adding sulfate to pH 4.5, this pulp slurry 500- Seal the sample in an Erlenmeyer flask and use a horizontal reciprocating shaker (shaking frequency 156 times/min, amplitude 7).
The air bubble content in the pulp slurry when attached to a pulp slurry (0 cod) and shaken for 1 minute was measured using a boardway seaside measuring device (Paper Valve Technology Times Vol. 2, No. 11, 22).
Page). The results are shown in Table 1.

Table 1 In this example, the sizing agent A obtained from a propylene oligomer mixture having 8 to 10 carbon atoms in which the ratio of the number of methylene groups to the number of methyl groups is 0.80 is more effective than the reinforced rosin sizing agent. However, the amount of foaming when inhibited by fixation is greater than that of the reinforced rosin sizing agent. Further, in this example, the emulsion-state sizing agent B obtained from the propylene oligomer mixture having 16 to 21 carbon atoms, in which the ratio of the number of methylene groups to the number of methyl groups is 0.87, has an increased foaming amount. Although smaller than the rosin size, it is clear that the size effect is significantly inferior to the reinforced rosin size.

In contrast, the sizing agent C1 obtained from the oligomer mixture of n-butylene in which the ratio of the number of methylene groups to the number of methyl groups according to the present invention is 0.93 and the number of methylene groups to the number of methyl groups The sizing agent obtained from the linear internal olefin having 16 carbon atoms with a ratio of 6.1 has a superior sizing effect over a wide range of addition amounts to a reinforced rosin sizing agent, and has a high foaming rate. It is also significantly smaller than the enhanced mouth sizing agent.

Also, the sizing agent E1 according to the present invention obtained by mixing the reaction product obtained in the present invention with the reaction product obtained in Comparative Example 1 and then saponifying it, and the sizing agent F obtained by mixing after saponifying the reaction product obtained in Comparative Example 1.
It can be seen that the foaming properties are significantly improved because G and G are also contained over a wide range of addition amounts and have an effect superior to that of the reinforced rosin sizing agent.

Patent applicant: Mitsubishi Oil Corporation Representative Patent Attorney Nobuaki Sakaguchi (1 other person)

Claims (4)

[Claims] (1) A reaction product obtained by heating and addition reacting maleic anhydride with a monoolefin having a leg prime number of 16 to 24 and a ratio of the number of methylene groups to the number of methyl groups of 0.9 or more and a mixture thereof with an alkali Water-soluble salt obtained by saponification [Al-containing papermaking sizing agent. (2) The paper-making sizing agent according to claim 1, wherein the content of the water-soluble salt [A,] is 10% by weight or more of the active ingredient of the sizing agent. (3) The paper sizing agent according to claim 1, wherein the monoolefin or the mixture thereof is an oligomer obtained from a monoolefin having 3 to 8 carbon atoms or a mixture of monoolefins. (4) The paper sizing agent according to claim 1, wherein the monoolefin or a mixture thereof is a linear internal olefin.