JPH06248596A - Papermaking sizing agent - Google Patents

Abstract

(57) [Summary] [Purpose] The present invention relates to an alkenylsuccinic anhydride type paper sizing agent which suppresses the occurrence of stains on the paper because of little generation of stains on the dryer part, and exhibits an excellent sizing effect. [Structure] A carbon number distribution is characterized by containing an addition reaction product of a maleic anhydride and a linear internal olefin having 17 or less carbon atoms of less than 5% by weight and 18 or more carbon atoms of 95% by weight or more. Sizing agent for paper making.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alkenyl succinic anhydride type paper sizing agent used by emulsification, which is less likely to cause stains on the dryer part, so that stains on paper can be suppressed. Moreover, the present invention relates to a sizing agent exhibiting an excellent sizing effect.

[0002]

2. Description of the Related Art Generally, in the production of paper, a large amount of fillers such as talc and clay is used for improving printability and whiteness and imparting opacity. There is an increasing trend to use calcium carbonate, which exists in large quantities and is inexpensively available.

However, so-called anionic sizing agents, such as rosin-based sizing agents that have been commonly used as paper-making sizing agents, are used in the acidic sizing method of fixing to pulp with a sulfuric acid band, and therefore calcium carbonate is used as a filler. When used, it has the drawback that calcium carbonate is decomposed by the acidity of the papermaking system.

Therefore, in order to solve this problem, various so-called neutral sizing agents have been proposed which can be sized in a neutral region or an alkaline region without using a sulfuric acid band.

For example, in Japanese Patent Publication No. 39-2305,
General formula

[Chemical 1] A neutral sizing agent represented by the formula (R is a dimethyl group and trimethylene group, and R'is a group selected from an alkyl group having 5 or more carbon atoms, an alkenyl group, an aralkyl group, and an aralkenyl group) has been proposed. 53-2852
The 6 discloses, (wherein, R _x and R _y is an alkyl group containing from 4 to 10 carbon atoms, respectively.) In formula _{R x -CH 2 -CH = CH-} CH 2 -R y in Sizing agents have been proposed which consist of the reaction product of the represented internal olefin and maleic anhydride.

Further, in JP-A-57-154495, maleic anhydride is added to a linear internal olefin mixture in which double bonds are almost evenly distributed at each position except the α-position having 8 to 10 carbon atoms. A sizing agent composed of the mixed alkenyl succinic anhydride obtained in this way has been proposed, and is disclosed in Japanese Patent Application Laid-Open No. Sho 5 (1993) -58.
In 9-179898, the proportion of olefins having 14 to 36 carbon atoms and having double bonds at the 2-, 3- and 4-positions is 10 to 65 mol%, respectively, and their total is 70. A sizing agent has been proposed which comprises a reaction product obtained by the addition reaction of a linear olefin mixture having a molar ratio of not less than or equal to maleic anhydride and / or a hydrogenated product of the reaction product. In addition, JP-A-60-990
Studies on emulsifiers have also been conducted as described in 99.

These alkenyl succinic anhydride type papermaking sizing agents are usually emulsified with a homomixer, a homogenizer or the like using a water-soluble polymer compound such as cationized starch or a surfactant such as polyoxyalkylene aryl ether. , Added to the paper stock in the form of an aqueous emulsion,
Since neither emulsifying property nor stability after emulsifying was sufficient, there was a problem that a satisfactory size effect could not be obtained, or a chest called a wet end generated stains on the papermaking system of the press part. . This problem is by-produced when an alkenyl succinic anhydride (one-to-one adduct) is produced by reacting an olefin with maleic anhydride as described in Japanese Patent Application No. 3-194980. There is a method of using the 1: 2 adduct and the decarbonated product of the 1: 2 adduct to control the emulsion particle size to reduce the stain.

[0008]

As described above, these alkenylsuccinic anhydride type sizing agents have been improved in terms of size effect and reduction of stains on the wet end. However, the occurrence of stains on the dryer part was still not reduced, and the problem of spots on the paper called "eyeballs and lees" caused by stains on the paper was never solved. Previous studies have not clarified the mechanism of occurrence of spots on paper, and if spots on paper occur, it is necessary to commercialize the spots on the paper during winding, and it is not possible to reduce spots on paper from the viewpoint of productivity. It was a very important issue. However, it is difficult to solve this problem within the range of conventional techniques such as improvement of the structure of the raw material olefin, the type of emulsifier, the emulsification method, etc., and a sizing agent based on a completely new idea has been desired.

An object of the present invention is to provide a sizing agent which suppresses the generation of spots on a paper because it causes less stain on the dryer portion and exhibits an excellent sizing effect.

[0010]

As a result of earnest research to achieve this object, the present inventor found out the cause of stains on the dryer portion, and found that stains on the dryer portion are the cause of spots on the paper. This led to the present invention. That is, the present inventor paid attention to the stain on the dryer part and examined it.

As a result, the stain is an alkenyl succinic acid calcium salt produced by the reaction of alkenyl succinic anhydride with water and alkenyl succinic acid and calcium carbonate. It meant that the succinic anhydride was volatilized. The boiling point of this alkenylsuccinic anhydride was 400 ° C. or higher in terms of atmospheric pressure, and it was unexpected that it would volatilize in the dryer section at a temperature of about 150 ° C. Probably, it is considered that the water vaporized from the wet paper causes a steam distillation state and is distilled under reduced pressure to volatilize. It is considered that the volatilized alkenyl succinic anhydride adhered to various parts of the dryer and the dryer canvas, and eventually reacted with water and calcium carbonate used as a filler to form alkenyl succinic acid and a calcium salt to form stains. It is presumed that this stain was peeled off on the surface of the paper, causing spots on the paper called "eyeballs, lees".

Even more surprisingly, the carbon number distribution of the raw material olefin of the sizing agent used was such that C16 was 57.
Although the content of C18 was 43% by weight, the content of alkenylsuccinic acid and its calcium salt collected as a stain in the dryer part was found to be much more concentrated in the raw material olefin analysis result. . The analysis results are shown in Table 1.

[0013]

[Table 1]

Based on this, the present inventors have conducted diligent research, paying attention to the volatility of alkenylsuccinic anhydride. As a result, it has been found that by increasing the raw material olefin carbon number of the alkenyl succinic anhydride, it is possible to reduce the volatilization amount of the alkenyl succinic anhydride and prevent stains and spots on the paper from the dryer part. Invented the invention. Thus, controlling the raw material olefin carbon number of the alkenyl succinic anhydride type sizing agent in order to prevent stains on the dryer part and spots on the paper has never been noticed in the past, and the present invention is completely new. It is an alkenyl succinic anhydride type sizing agent found from a viewpoint. In fact, most of the alkenylsuccinic anhydride type sizing agents currently on the market are produced from olefins containing a large amount of carbon atoms of 17 or less.

The present invention will be described in more detail. In the present invention, the carbon number distribution is such that a carbon number of 17 or less is less than 5% by weight and a carbon number of 1 is used.
8 or more is a sizing agent for papermaking containing an addition reaction product of a linear internal olefin and 95% by weight or more with maleic anhydride as an active ingredient, and more preferably has a carbon number distribution of 17 or less. Less than wt%, carbon number 18-20 is 69
It is a papermaking sizing agent characterized by containing an addition reaction product of a linear internal olefin having 100 to 100% by weight and 21 or more carbon atoms and less than 30% by weight with maleic anhydride. As the linear internal olefin used as a raw material, a linear α-olefin having the above carbon number distribution, which is isomerized by using a catalyst, or one obtained by dehydrogenating n-paraffin can be used. In order to carry out distillation separation accurately in the order of several numbers, it is desirable to isomerize and use an ethylene oligomer α-olefin produced by polymerization of ethylene and having a carbon number of 2 in increments. Further, the isomerization of α-olefin can be carried out by the method described in JP-A-61-119797.

Further, in order to maximize the performance of the present invention, it is desirable that the proportion of the olefin having 18 to 20 carbon atoms is large. When the content of olefins having 17 or less carbon atoms increases, the occurrence of dryer stains increases, so it is desirable that the content is substantially less than 1% by weight. However, if less than 5% by weight, it is compared with conventional sizing agents. Therefore, dirt on the dryer can be reduced. An olefin having 21 or more carbon atoms may be contained, but if the content increases, the pour point rises and handling becomes difficult, and the temperature during emulsification must be raised, and the emulsified particle size Since it also becomes rough, the size effect also decreases, so it is preferable to suppress it to less than 30% by weight. Moreover, even if it contains a small amount of branched olefin, α-olefin, paraffin and the like, it can be used as a raw material olefin.

The addition reaction between the linear internal olefin and maleic anhydride may be carried out by any ordinary method, with or without a catalyst. As an example, heating to 180 to 250 ° C. under a non-catalyst, preferably in an inert atmosphere such as nitrogen gas under normal pressure or under pressure, and at that temperature, 1
~ 30 hours. The molar ratio of the two charged is not particularly limited, but it is desirable to use maleic anhydride in an amount of 0.5 to 3 mol per 1 mol of the olefin. Unreacted olefin and maleic anhydride are taken out of the system by distillation.

In order to perform pulp sizing using the papermaking sizing agent of the present invention containing the addition reaction product of the linear internal olefin and maleic anhydride obtained as described above, this sizing agent is usually used. Is added to the stock as an emulsion uniformly dispersed in water. In order to improve the dispersion in water, various emulsifiers such as polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene sorbitol fatty acid ester, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl aryl ether, and fatty acid ester of polyhydric alcohol. , Polyoxyalkylene alkyl ether sulfate ester salt, polyoxyalkylene alkyl ether phosphate ester, polyoxyalkylene alkyl aryl ether phosphate ester, polyoxyalkylene aralkyl aryl ether phosphate ester, and various cations as suspending agents. Compounds such as cationized starch,
Cationic polyacrylamide and the like can be used alone or in combination.

The amount of the emulsifier to be used in combination with the maleic anhydride addition reaction product of the present invention is determined in consideration of the type and dispersibility of the emulsifying device, but it is usually a linear internal olefin and maleic anhydride. 0.5 for the addition reaction product with
-20% by weight is preferable, and 1-10% by weight is more preferable.

When the cationic compound is used as the suspending agent, the amount thereof is usually preferably 30 to 600% by weight, more preferably 50% by weight, based on the addition reaction product of the linear internal olefin and maleic anhydride. 100-300% by weight
Is.

As the emulsifying device, a homomixer, a homogenizer, a nozzle type emulsifying device, an orifice type emulsifying device,
An apparatus used for emulsifying a conventional alkenylsuccinic acid type sizing agent such as a turbine type emulsifying apparatus can be used as it is.

After emulsification, the sizing agent of the present invention can be added to the pulp slurry at any step of the paper making step. The amount of the sizing agent of the present invention to be used varies depending on the type of pulp used, the papermaking conditions, the use of the paper, etc., but normally it is preferable to use 0.05 to 3.0% by weight based on the dry weight of pulp.

In order to fix the sizing agent of the present invention to pulp, a cationic compound such as cationic starch, cationic polyacrylamide, polyamine polyamide-epichlorohydrin resin is usually used as a fixing agent. 0.01 to dry weight of pulp
It is preferably 5.0% by weight, more preferably 0.03 to
It is 3.0% by weight. Any of these fixing agents can be added at the same time as, before or after the addition of the sizing agent. However, in order to obtain the optimum fixing effect, it is preferable to add it after the sizing agent.

If desired, the sizing agent of the present invention can be used in combination with various sizing agents other than the present invention in an arbitrary ratio. When sizing, talc,
Of course, it is possible to use all kinds of fillers such as clay, titanium oxide, calcium carbonate, calcium sulfate and aluminum hydroxide.

[0025]

EXAMPLES Next, examples will be shown in order to specifically describe the present invention. Example 1 C ₁₈ (C ₁₆ : 0.1% by weight, C ₁₈ : 99.9% by weight) as a main component, ethylene oligomer-α-olefin was isomerized using a nickel octanoate catalyst and an alkylaluminum catalyst. Obtained linear internal olefin (double bond position distribution; 1-position: 0 mol%, 2-position: 13 mol%, 3-position: 12
Mol%, 4th position: 15 mol%, ⁵⁺ position: 60 mol%) 10
583 g of maleic anhydride (molar ratio to olefin of 1.5) was added to 00 g, and 215 g without catalyst in an autoclave.
The reaction was carried out at ℃ for 8 hours. Unreacted olefin and maleic anhydride were removed from the reaction solution by distillation under reduced pressure to obtain 1320 g of an olefin-maleic anhydride addition reaction product.

Example 2 C ₂₀ (C ₁₈ : 0.4% by weight, C ₂₀ : 98.2% by weight, C
₂₂ : 1.4% by weight) The main component ethylene oligomer-α-olefin was isomerized in the same manner as in Example 1 to obtain a linear internal olefin (double bond position distribution; 1-position: 0 mol%, 2nd: 12 mol%, 3rd: 11 mol%, 4th: 14
525 g of maleic anhydride (molar ratio to olefin of 1.5) was added to 1000 g of (mol%, 5 ⁺ position: 63 mol%), and 1250 g of an olefin-maleic anhydride addition reaction product was obtained according to the operation method of Example 1. .

Example 3 Carbon number distribution (C ₁₈ : 0.5% by weight, C ₂₀ : 28.0% by weight, C ₂₂ : 25.0% by weight, C ₂₄ : 19.0% by weight, C
₂₆ : 15.0% by weight, C ₂₈ : 9.0% by weight, C ₃₀ or more:
3.5 wt% of ethylene oligomer α-olefin was isomerized in the same manner as in Example 1 to obtain a linear internal olefin (positional distribution of double bonds; 1-position: 0 mol%, 2-position:
9 mol%, 3rd position: 9 mol%, 4th position: 12 mol%, 5
⁺ Position: 70 mol%) Maleic anhydride 470 to 1000 g
g (to olefin molar ratio of 1.5) was added, and 1185 g of an olefin-maleic anhydride addition reaction product was obtained according to the operation method of Example 1. The product has a melting point of 30 ° C.,
It was a solid at room temperature.

Comparative Example 1 A linear chain obtained by isomerizing an ethylene oligomer α-olefin having a carbon number distribution (C ₁₆ : 99.8% by weight, C ₁₈ : 0.2% by weight) in the same manner as in Example 1 Internal olefin (double bond position distribution; 1-position: 0 mol%, 2-position: 13 mol%, 3-position: 12 mol%, 4-position: 17 mol%, 5 ⁺ position: 5
8 mol%) and 655 g of maleic anhydride (molar ratio to olefin of 1.5) are added to 1000 g of olefin and maleic anhydride addition reaction product 139 according to the operation method of Example 1.
0 g was obtained.

Comparative Example 2 An ethylene oligomer α-olefin having a carbon number distribution (C ₁₆ : 56.8% by weight, C ₁₈ : 43.2% by weight) was used in Example 1.
The linear internal olefin obtained by isomerization in the same manner as above (positional distribution of double bonds; 1-position: 0 mol%, 2-position: 12 mol%, 3-position: 12 mol%, 4-position: 15 mol%, 5 ⁺ Position: 6
623 g of maleic anhydride (molar ratio to olefin of 1.5) to 1000 g of 1 mol%), and the olefin-maleic anhydride addition reaction product 136 according to the operating method of Example 1.
0 g was obtained.

With respect to the olefin / maleic anhydride addition reaction products of Examples 1 to 3 and Comparative Examples 1 and 2, the heat loss measurement and the size effect measurement test were conducted.

(Measurement of Heat Loss) 5 mg of the olefin-maleic anhydride addition reaction products of Examples 1 to 3 and Comparative Examples 1 and 2 were placed on a thermobalance (TGA-50 manufactured by Shimadzu Corporation), and the flow rate was 25 ml / min. 10 up to 200 ℃ in nitrogen stream
The temperature was raised at ° C / min, and the weight loss rate at 200 ° C was measured.
The results are shown in Figure 1, the C ₁₇ or less in the raw material olefin 5
Sizing according to the invention containing less than wt% Examples 1-3
Is a comparative example 1 containing a large amount of C ₁₇ or less olefin.
It can be seen that the volatilization loss is extremely small compared with 2. In addition, when a papermaking test was performed on the samples of Example 1 and Comparative Example 1 using an actual machine, Example 1 was particularly excellent in the degree of stains on the dryer and spots on the paper.

(Size effect measurement test) 10 g of an olefin-maleic anhydride addition reaction product was added as an emulsifier to polyoxyethylene nonylphenyl ether (HLB13) 0.
5 g was added and mixed well. 1.5% to 1 g of this mixture
99 g of the cationized starch solution was added, and the mixture was emulsified for 2 minutes at 7,000 rpm using a TK homomixer M type manufactured by Tokushu Kika Kogyo Co., Ltd.

The emulsion was mixed with a 1% pulp slurry (LBK).
P, CSF = 430 ml) and 0.1, 0.15 or 0.2% by weight of the reaction product of the olefin / maleic anhydride addition reaction product.
(To the pulp solid content), and then, with stirring, 0.8% by weight of cationized starch (to the pulp solid content) and 0.03% of cationic polyacrylamide (to the pulp solid content). In addition, papermaking was performed by a TAPPI standard sheet machine by a conventional method. The filler used is light calcium carbonate, and the amount used is 20% by weight (based on pulp solids content).

Then, the obtained wet paper was compressed and dehydrated, dried by heating with a rotary dryer at 105 ° C. for 1 minute, and conditioned in a room at 20 ° C. and a relative humidity of 65% for 24 hours. The grammage of the obtained hand-made paper after humidity conditioning corresponds to 60 g / m ² . The sizing degree of this hand-made paper was measured by the Steckigt sizing degree test method of JIS P8122. The results are shown in Table 2. Although Example 3 containing a large amount of C ₂₁ or more in the raw material olefin exhibited a slightly lower size effect, the other size agents had substantially the same effect.

[0035]

[Table 2]

[0036]

EFFECT OF THE INVENTION The sizing agent of the present invention is extremely excellent in terms of suppressing the generation of stains on paper, because it hardly causes stains at the dryer portion, and has the same or better size effect than conventional products. Indicates.

[0037]

[Brief description of drawings]

FIG. 1 shows the results of heat loss measurement of the olefin / maleic anhydride addition reaction products of Examples 1 to 3 and Comparative Examples 1 and 2 by a thermobalance.

Claims (2)

[Claims] 1. An addition reaction product of a linear internal olefin having a carbon number distribution of 17 or less and less than 5 wt% and a carbon number of 18 or more and 95 wt% or more and maleic anhydride is contained. A sizing agent for paper making characterized by 2. A straight chain internal olefin having a carbon number distribution of less than 1% by weight of 17 or less carbon atoms, 69 to 100% by weight of 18 to 20 carbon atoms and less than 30% by weight of C21 or more and anhydrous. The sizing agent for papermaking according to claim 1, which contains an addition reaction product with maleic acid.