JPS6024876B2 - Internal sizing agent composition for paper manufacturing - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides the following method by incorporating a water-soluble salt of an alkenyl- or alkylsuccinic acid and an anion-modified acrylic- or methacrylic amide polymer or copolymer.
The present invention relates to an internal sizing agent composition for paper manufacturing that dramatically improves the size effect of a water-soluble salt of alkenyl or -alkyl succinic acid.

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 domestic product and has problems such as price fluctuations and unstable supply. , petroleum resin-based sizing agents, and many other proposals have been made as alternative synthetic internal sizing agents. However, from the viewpoint of performance or cost, synthetic internal sizing agents other than petroleum resin sizing agents are hardly put to practical use. Moreover, the use of petroleum resin-based sizing agents currently in practical use is limited due to their performance, so there is a demand for the development of internally added sizing agents that are superior to rosin-based sizing agents in terms of performance and price. ing. On the other hand, in order to further improve the size effect of rosin-based sizing agents, attempts have also been made to use hydrophilic and relatively high-molecular substances such as carboxymethyl cellulose, urea-formaldehyde resin, starch, and gum arabic. It is being
Additionally, the anion-modified acrylamide polymer used as a paper reinforcing agent does not exhibit any size effect by itself, but when used in combination with a rosin-based sizing agent, the size effect is slightly increased. It is known to improve However, this paper strength enhancer is more expensive than the sizing agent, and the degree of improvement in the size effect thereof is small, so it has not been used solely for the purpose of improving the sizing effect of the sizing agent. Furthermore, this type of paper strength agent aqueous solution is not compatible with commonly used aqueous solutions of rosin-based sizing agents and petroleum resin-based sizing agents at practical concentrations, and separates into two phases. For this reason, when producing sized paper that requires paper strength, both are added to the valve slurry separately, and an internally added sizing agent containing both an anion-modified acrylamide polymer and a sizing agent has never been proposed. There was no. On the other hand, a water-soluble I salt of alkenyl- or alkylsuccinic acid has already been proposed as an internal sizing agent for paper manufacturing (Samurai Kosho 40-565), but according to the study of the present inventor, this internal sizing agent The effectiveness of the sizing agent varies greatly depending on its molecular structure, and when water-soluble salts of alkenyl or alkyl succinic acids obtained from Q-olefins are used as internal sizing agents, their effects are unsatisfactory and cannot be used in rosin. It could not be used as a substitute for other sizing agents.

For this reason, a paper processing method has recently been proposed in which a water-soluble salt of alkenylsuccinic acid or a mixed aqueous solution of it and a polyacrylamide-based treatment agent is used as a surface sizing agent (Tokukan Sho 52-46111). The present inventors also investigated the use of water-soluble salts of alkenyl or alkyl succinic acids made from highly branched olefins as internal sizing agents. As a result, this internally added sizing agent showed a better sizing effect than the rosin sizing agent in a low addition amount range, as shown in the attached Figure 1. However, this internally added sizing agent had approximately the same sizing effect as the rosin sizing agent when added in an amount of around 1% (based on pulp solid weight %), and had a rather inferior sizing effect when added in an even higher amount. A particular problem is that when the amount added exceeds about 1%, there is a phenomenon that the sizing of the paper does not increase even if the amount added is further increased. Therefore, the present inventors solved the above-mentioned drawbacks without impairing the superiority of the internal sizing agent made of a water-dropping salt of an alkenyl or alkyl succinic acid derived from a branched olefin over a rosin sizing agent in the area of low addition amount. We have conducted repeated research to improve the phenomenon of the size effect reaching a plateau in the region of high addition amounts.

As a result, an anion-modified acrylic or monomethacrylic amide polymer or copolymer B was added internally to a water-soluble salt A of alkenyl or alkyl succinic acid derived from a branched olefin using a sizing agent containing an appropriate proportion of an anion-modified acrylic or monomethacrylic amide polymer or copolymer B. It has been discovered that when sizing is performed, the synergistic effect of the two dramatically improves the size effect over a wide range of addition amounts, as shown in the attached Figure 1, and the phenomenon of the size effect reaching a plateau is completely eliminated. reached. Such a remarkable improvement was completely unexpected and surprising. The internal sizing agent composition of the present invention is an alkenyl or alkyl succinic acid derived from a branched olefin.
Since this sizing agent contains both an anion-modified acrylic or methacrylamide polymer or copolymer in a homogeneous and compatible form, there is no need to add them separately to the pulp slurry, It can be used by simply replacing the sizing agent with the sizing agent composition of the present invention,
This has the advantage of simplifying the process.

The alkenyl- or alkylsuccinic acid water-dropping salt used in the present invention must be produced from highly branched C6-C,3 olefins, and the branched olefins include propylene, butylene and One type of olefin selected from isobutylene, or a mixture of two or more types, is treated with an acid catalyst such as sulfuric acid, solid phosphoric acid, or liquid phosphoric acid, or with a fluoride catalyst such as aluminum chloride.
- Obtained by polymerization or copolymerization in the presence of a Delphrafluorocarbon catalyst.

The polymerization or copolymerization product thus obtained is a mixture of a large number of branched olefin isomers, and is predominantly internal olefins. For example, in nonene obtained by polymerizing propylene, the main components are 2,3-, 2,4-,
It is known that about 90% of 2,5- and 3,4-dimethylheptene are internal olefins (Brenne et al.
stoff-Chemie, Vol. 11, pp. 331-33)
. The C6-C,6 branched olefin from propylene, butylene and/or isobutylene thus obtained and the Q,8 monounsaturated dicarboxylic acid or its acid anhydride are mixed without a catalyst, preferably in an inert atmosphere such as nitrogen. Heated at 1800 to 2500C, preferably 200 to 230C, under normal pressure or increased pressure in a tank, and at that temperature 0.5
After reacting for ~30 hours, preferably 1 to 2 hours, unreacted olefin and Q,8-unsaturated dicarboxylic acid or its acid anhydride are removed by distillation to obtain alkenylsuccinic acid or its acid anhydride. . Note that some by-products may be produced depending on the reaction conditions. In that case, the alkenylsuccinic acid or its acid anhydride can be further distilled under reduced pressure to remove the by-products, but since the amount is small, in the case of the present invention, the by-products can be removed. is not necessarily required. By saponifying the alkenylsuccinic acid or its acid anhydride thus obtained with an alkali, a water-soluble salt of alkenylsuccinic acid can be obtained. If alkenylsuccinic acid or its acid anhydride is hydrogenated to convert the alkenyl group into an alkyl group and then saponified, or after saponification and then hydrogenated to convert the alkenyl group to an alkyl group, a hydrolyzed salt of alkylsuccinic acid can be obtained. is obtained. Since the double bond of an alkenyl group is easily hydrogenated, hydrogenation is carried out under usual conditions, for example, using a nickel catalyst or other catalyst in an organic solvent or an aqueous solution, and heating under normal pressure or increased pressure. Olefins used in the production of alkenyl- or alkylsuccinic acids or their acid anhydrides by reaction of olefins with Q,P-unsaturated dicarboxylic acids or their acid anhydrides include size-effect and anion-modified -acrylic- or -methacrylic acids. In terms of compatibility with amide polymers or English polymers, C8-C obtained by homopolymerization or copolymerization of C3-C4 monoolefins
,8 branched olefins are preferred, and C,2 propylene tetramers and triisobutylene are particularly preferred.

In addition, as the Q,8-unsaturated dicarboxylic acid, maleic acid,
Fumaric acid, citraconic acid, itaconic acid, or acid anhydrides thereof are used, and maleic anhydride is particularly preferred from the viewpoint of economy and reactivity. Examples of the alkali used for saponification include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, ammonia, amines such as trimethylamine and dimethylamine, and alkanolamines such as diethanolamine and triethanolamine. It will be done. The anionically modified acrylic- or monomethacrylic amide polymers or copolymers used in the present invention contain monomer units in the form of Q,6-unsaturated mono- or dicarboxylic acids or their alkali metal or ammonium salts [with the proviso that , R is hydrogen or a methyl group, R' is hydrogen or a COOM group, M is hydrogen,
alkali metal or ammonium group] and monomer units in the form of acrylamide or methacrylamide [
However, R represents hydrogen or a methyl group], by a known method, for example, partially hydrolyzing polyacrylamide with ammonia or an alkali metal hydroxide, such as an alkali such as sodium hydroxide or potassium hydroxide, or Acrylamide or methacrylamide Q
, 8-unsaturated monocarboxylic acid or Q, 8-unsaturated dicarboxylic acid, or their salts such as ammonia, amines, alkali metals, etc. are copolymerized.

From the viewpoint of compatibility with alkenyl- or alkylsuccinic acid, the anion-modified acrylic- or -methacrylic amide polymer or copolymer used in the present invention preferably has as many monomer units as the above formula '1}. However, considering the size effect, 1 to 30 mol%, preferably 3 to 20 mol% is appropriate, and the remaining 70 to 99 mol%, preferably 80 to 98 mol%, is composed of monomer units of the above formula (1). It is appropriate to become. Examples of the Q,8-unsaturated monocarboxylic acid or its salts giving the formula '1-' include acrylic acid or methacrylic acid or their salts with ammonia, amines, alkali metals, etc., Q,8-unsaturated dicarboxylic acid or its salts. The salts are selected from maleic acid, fumaric acid, itaconic acid, their acid anhydrides, and their salts with ammonia, amines, alkali metals, and the like. Furthermore, if necessary, 30 mol% or less of the total monomer units of the monomer units of formula [2' may be replaced with monomer units of a copolymerizable vinyl compound. Examples of copolymerizable vinyl compound monomers include diacetone acrylamide, acrylonitrile, vinyl acetate, styrene, acrolein, acrylic acid or methacrylic acid ester, hydroxyacrylic acid ester, glycidyl methacrylate, and the like. Further, the molecular weight of the anion-modified acrylic- or -methacrylamide polymer or copolymer in the present invention is preferably 50,000 to 2,000,000 in terms of polyacrylamide, more preferably 100,000 to 1,000,000 from the viewpoint of compatibility and size effect. is appropriate.

The sizing composition of the present invention is produced by mixing the aqueous solution of component A and the aqueous solution of component B described above, and may contain a small amount of free alkenyl or alkyl succinic acid.

The ratio of A component to B component (A:B weight ratio) is 95:5 to 30:7u, preferably 85:15 to 5 in terms of size effect.
0:50 force is appropriate. The internal sizing agent composition of the present invention, like a normal internal sizing agent, can be added to papermaking materials at any step before the end of the papermaking operation, for example, in the beating process or in pulp slurry after the beating process. After adding the internal sizing agent of the present invention to the sizing agent, sulfuric acid bandate is added to reduce the spots to about 4.0 to 5. It is possible to fix the mackerel to the pulp by adjusting it to 4.2 to 5.0.

The internal sizing agent composition for paper manufacturing of the present invention can be used in the form of a solution containing component A and component B in advance, but if desired, the solution containing component A and the solution containing component B may be mixed together immediately before use. may be used in combination. Don't worry, it can also be used in combination with conventionally used rosin-based sizing agents, petroleum resin-based sizing agents, paper strength enhancers, etc. in any proportion. The paper-making internal sizing agent composition of the present invention contains the above-described components A and B, and its surprising additive size effect is completely unique.

An example of these effects will be explained with reference to the accompanying drawings. Attached Figure 1 shows the added amount (solid weight %) of reinforced rosin or component A.
) is a plot of the size effect (Stekicht method).

In this figure, 1 shows the relationship between the amount added and the size effect when dodecenyl succinic acid sodium salt obtained from propylene tetramer mono and maleic anhydride is used as the component A, and 2 shows the relationship between the addition amount and the size effect of the maleic acid-modified reinforced rosin size agent. Shows a similar relationship. In addition, 3 is an acrylamide-acrylic acid copolymer (monomer weight ratio 95:5, molecular weight approximately 700,000) as the B component for the reinforced rosin size agent.
are added separately at a solid content ratio of 70:30, and 4 is a similar relationship in the case of the internal sizing agent composition of the present invention in which component A and B are mixed at a solid content ratio of 70:30. shows. From the attached Figure 1, component B shows no substantial size effect and is superior to the reinforced rosin sizing agent when the weight percentage of the pulp is less than about 1%, but is inferior to the reinforced rosin sizing agent when it is about 1% or more. It is said that the internal sizing agent composition of the present invention containing component A shown in 4 shows a much larger additive effect than 3 when the reinforced rosin sizing agent and component B are added separately, as seen in 4. The results showed completely unexpected results. In addition, attached Figure 2 compares the relationship between the size effect and the amount of solid content added, including component B, for 3 and 4 shown in attached Figure 1, with the case where component A or the reinforced rosin sizing agent is used alone. It is. When component B is used in combination, even if the amount of solid content added is the same, the amount of reinforced rosin or component A in the solid content is reduced compared to when used alone. For this reason, when a reinforced rosin size agent is used in combination with component B, as seen in 3, the sizing effect is lower than when the reinforced rosin size agent is used alone when the solid content addition amount is the same. However, when the internal sizing agent composition of the present invention containing the A component and the B component is used, even when compared with the amount of solid content added, as seen in 4, when the A component is used alone, the internal sizing agent composition of the present invention is It shows a much better size effect than 2 when used alone. Furthermore, attached 3rd
The figure shows the size effect when the total amount of component A and component B is kept constant and the blending ratio of both is changed. As seen in this figure, the ratio of the B component to the A component (A/
Although the absolute amount of A component decreases as B) increases, the size effect increases rapidly at first, and B/A = 3.
It reaches its maximum at around /7, and thereafter the size effect decreases as the A component decreases. That is, it can be seen that an optimal range exists for the ratio of the A component and the B component. In addition to component A and component B, the internal sizing agent composition of the present invention includes other additives, such as alcohols such as methanol, ethanol, and ethylene glycol, low-temperature stabilizers or thinners such as urea, and starch. , polyvinyl alcohol, casein, protective colloids such as glue, and the like.

EXAMPLES Hereinafter, the internal sizing agent composition of the present invention and its usage will be specifically explained with reference to Examples. In the examples, "parts" mean parts by weight unless otherwise specified, and the size effect was measured by the JISP8122 Steckcht sizing test method. Example 1 504% propylene tetramer and 294% maleic anhydride
The mixture was heated to 215q0 in an autoclave under a nitrogen atmosphere and reacted without catalyst for 5 hours.

After the reaction, the reaction mixture was taken out and unreacted propylene tetramer and maleic anhydride were distilled off under reduced pressure to obtain 518 parts of dodecenyl succinic anhydride as a pale yellow oil. A total of 3 parts of a 20% aqueous sodium hydroxide solution and 7 parts of distilled water milk were added to 250 parts of the obtained dodecenyl succinic anhydride.
The mixture was saponified for 2 hours at a temperature of 9 psi to obtain an aqueous solution (aqueous solution A-1) containing 30% of the sodium salt of dodecenylsuccinic acid (component A). The spots of this aqueous solution are 8.2
Met. Next, 95 parts of acrylamide, 5 parts of acrylic acid
Distilled water was added to the mixture to dissolve it, and 4 parts of inpropyl alcohol and 0.5 parts of ammonium persulfate were added and polymerized for 4 hours at 60° C. in a nitrogen stream. After the polymerization reaction is complete, add 20% sodium hydroxide aqueous solution 1
An aqueous solution of an acrylamide-acrylic acid copolymer (component B) containing 38 parts and a solid content of 10% (aqueous solution B-1)
I got it. The viscosity of this aqueous solution is 20,000 centipoise (
(25°C), the molecular weight of the copolymer was approximately 700,000. Aqueous solution A-1, 7 base parts obtained in this way, aqueous solution B-1, 9 parts of water and 4 parts of distilled water were mixed at 4 and 0, and A/B=70 no 3 or more solid content 15%. A transparent internal sizing agent composition was obtained.

The internal sizing agent composition of the present invention had a viscosity of 450 centipoise (25° C.) and a pH of 7.2. Next, the freeness C. F. = Softwood/hardwood adjusted to 345cc: 2
A 3% slurry of 0/8q bleached kraft pulp is prepared, and the inventor's internal sizing agent composition is added to this slurry at a solid content of 0.6% or 1.0% per dry pulp. % added,
While stirring, add sulfuric acid as a fixing agent and make a slurry.
The pH of the solution was adjusted to 4.5.

This valve slurry was further diluted to a pulp concentration of approximately 0.2% with water adjusted to 4.5 with sulfuric acid band, and T
After paper was made using an APPI standard sheet machine and dehydrated under pressure (4k9/〆x1 minute), the wet paper was heat-treated using a rotary dryer at 105 to 110 qo for 3 minutes. This handmade paper has a basis weight of 60 yen/paper. As comparative sizing agents, the reinforced rosin sizing agent and the aqueous solution A-1 and aqueous solution B-1 used in the preparation of the internal sizing agent composition of the present invention were each used alone. The tied paper was left in a room at a temperature of 2 psi and a humidity of 60% for 24 hours, and then the size effect was measured.

The results are shown in Table 1. Table 1 Example 2 5 parts of Raney nickel was added to 1250 parts of the aqueous solution A-obtained in Example 1, and the mixture was heated to 100°C under a hydrogen pressure of 10k9/m in an autoclave, and a decrease in pressure was observed. Hydrogenation is carried out until the hydrogen is completely dissolved, and after cooling, the catalyst is removed by heating in a furnace.
A 0% aqueous solution (aqueous solution A-2) was obtained.

When this aqueous solution was made acidic by adding hydrochloric acid and the separated organic layer was collected and its bromine number was measured, the bromination was almost 0, indicating that the double bond of the dodecenyl group was almost completely hydrogenated. This was confirmed. This aqueous solution A-2,1
00 parts, 75 parts of the aqueous solution B-1 obtained in Example 1 and 75 parts of distilled water were mixed at 30:00, A/B=80/2.
A transparent internal sizing agent composition containing 15% solid content was obtained.

The internal sizing agent composition of the present invention had a viscosity of 110 centipoise (at 25° C.) and a pH of 7.5. Freeness degree ℃
．． F. A 3% slurry of softwood unbleached kraft bulb adjusted to 400 cc was prepared, and the internal sizing agent composition of the present invention was added to this slurry at a solid content of 0.1 per dry pulp.
%, 0.3%, or 0.5%, add sulfuric acid as a fixing agent while stirring, and adjust the pH of the slurry to 5.
I set it to 0.

This slurry was further diluted to a pulp concentration of about 0.2% with water adjusted to 5.0% with sulfuric acid solution to obtain handmade paper according to Example 1. The size effect was measured using a reinforced rosin sizing agent and aqueous solution A-2 used in the preparation of the internal sizing agent composition of the present invention as a comparative sizing agent. The results are shown in Table 2. Table 2 Example 3 Dodecenylsuccinic anhydride 3 obtained in the same manner as Example 1
To 35 parts, 48 parts of 30% potassium hydroxide and 27 parts of distilled water were added, and the mixture was stirred at a temperature of 90 qo for 3 hours to form a rennan. A-3) was obtained.

The pH of this aqueous solution was 8.4. Next, 885 parts of distilled water were added to 85 parts of acrylamide and 15 parts of acrylic acid to dissolve them.Further, 5 parts of inpropyl alcohol and 1 part of potassium persulfate were added, and the mixture was polymerized for 4 hours at a temperature of 60°C in a nitrogen stream. After the polymerization reaction was completed, 4 parts of a 20% aqueous sodium hydroxide solution were added to obtain an aqueous solution (aqueous solution B-2) of an anion-modified acrylamide-acrylic acid copolymer (component B) containing 10% solids. The viscosity of this aqueous solution was 16,000 centipoise (25o0), and the molecular weight of the copolymer was about 500,000. The thus obtained aqueous solution A-3, 7 foundations, aqueous solution B-1, h2 anchor and 1 part of distilled water were mixed at 40q0, A/B=70
/30 A transparent internal sizing agent composition containing 20% solid content was obtained.

The internal sizing agent composition of the present invention had a viscosity of 1900 centipoise and a pH of 7.4. Takufudo C. F. =4
A 3% slurry of bleached kraft pulp with a softwood/hardwood ratio of 20/8 adjusted to 0.00 cc was prepared, and the internal sizing agent composition of the present invention was added to this slurry at a solid content of 0.3% and 0.00 cc as solid content per dry pulp. By adding 6% or 1.0%, hand-made paper was obtained according to Example 1, and the size effect was measured.

As comparative sizing agents, a reinforced rosin sizing agent, aqueous solution A-3 used for preparing the internal sizing agent composition of the present invention, and a rosin emulsion sizing agent (commercially available sizing agent) were used. The results are shown in Table 3. Table 3 Example 4 In the same manner as the reaction of propylene tetramer and maleic anhydride in Example 1, diisobutylene, propylene trimer, triisoptylene, and propylene betamer were reacted with maleic anhydride to obtain octenyl succinic acid. Anhydride, nonenylsuccinic anhydride, dodecenylsuccinic anhydride, and pentadecenylsuccinic anhydride are saponified with a saponification equivalent of potassium hydroxide to produce an aqueous solution containing 40% of the corresponding alkenylsuccinate (component A). adjusted.

Aqueous solution B-2 of Example 3 and distilled water were added to these alkenyl succinic acid potassium salt aqueous solutions, and the ratio of A component to B component (A/B) was 70/30. Internal sizing agent compositions were prepared respectively. The size effect of the obtained internal sizing agent composition of the present invention was compared with that of an aqueous solution of potassium alkenylsuccinate salt used in preparing the internal sizing agent composition of the present invention. The test was conducted under the same conditions as in Example 3, except that the amount of the sizing agent or sizing agent composition added was 0.5% based on the dry pulp as a solid content. The results are shown in Table 4. Table 4

[Brief explanation of the drawing]

Attached FIG. 1, attached FIG. 2, and attached FIG. 3 are graphs showing an example of the size effect test results for the internal sizing agent composition of the present invention and a comparative sizing agent. Figure 2 Figure 3

Claims (1)

[Claims] 1 a C_6 to C_1_3 obtained by polymerizing one type of olefin selected from propylene, butylene and isobutylene or copolymerizing two or more types of olefins
at least one type of alkenylsuccinic acid or a water-soluble salt of alkylsuccinic acid derived from a branched olefin, A; and b
An internal additive size for paper manufacturing characterized by containing at least one type B of an anion-modified acrylic-methacryl-amide polymer or copolymer in a weight ratio of A/B of 95/5 to 30/70. agent composition.