JPH0453995B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to paper internal sizes. In the industry, sizing agents manufactured from natural rosin or modified rosin, particularly reinforced rosin sizing agents obtained by saponifying maleic acid adducts of rosin, are most used. These sizing agents are fixed onto paper fibers in the acidic range of PH4.0 to 5.0 of the paper stock in combination with sulfuric acid. Due to its acidic nature, it is difficult to use because it causes high corrosion wear and tear on paper-making equipment, reduces the strength and durability of the paper, and decomposes cheap alkaline fillers such as calcium carbonate. There are drawbacks such as. For this purpose, a neutral sizing agent has been proposed that can be fixed to pulp without using sulfuric acid. For example, it is known that an alkyl ketene dimer is dispersed in water in the presence of cationized starch, but this has the drawbacks of being expensive and taking time to develop the size effect. In addition to these, several alkenylsuccinic anhydride type neutral sizing agents have been proposed. For example, in Special Publication No. 39-2305, (R is a dimethylene group and a trimethylene group,
R' is an alkyl group having 5 or more carbon atoms, an alkenyl group,
aralkyl groups and aralkenyl groups), but the only concretely disclosed compounds are examples of branched olefins or linear α-olefins such as propylene oligomers and butene oligomers. , these all have insufficient size effects and cannot be put to practical use. As a solution to this drawback,
No. 28526 describes internal olefins of the general formula Rx- _CH2 -CH=CH- _CH2 -Ry, in which Rx and Ry are each an alkyl group containing 4 to 10 carbon atoms, and anhydrous A sizing agent made of a reaction product with maleic acid is disclosed, and JP-A-57-154495 discloses a sizing agent with double bonds almost evenly distributed at each position except for the α-position with 8 to 18 carbon atoms. A sizing agent comprising a mixed alkenylsuccinic anhydride obtained by adding maleic anhydride to a linear internal olefin mixture has been proposed. However, none of these sizing agents can be said to have sufficient sizing effects. In addition, the internal olefin disclosed in the above-mentioned Japanese Patent Publication No. 53-28526 is
It is obtained by a disproportionation reaction of α-olefin, and has the drawbacks of being accompanied by various difficulties in its production and being expensive. On the other hand, JP-A-57-154495
The internal olefin disclosed in this issue is obtained by dehydrogenating linear paraffin at 400 to 600°C to obtain linear internal olefin, and then adsorbing and separating unreacted paraffin using a molecular sieve. Alternatively, it is obtained by isomerizing α-olefin, which is a low molecular weight polymer of ethylene, and subsequently disproportionating it, which has the disadvantage of requiring a complicated and expensive process and being expensive. The present inventors completed the present invention by diligently developing a neutral sizing agent that overcomes the above-mentioned drawbacks when sizing is performed in a neutral or alkaline region without using a fixing agent such as sulfuric acid. This is what we have reached. That is, the present invention focuses on linear α-
obtained by treating olefin with an acid catalyst,
having the same number of carbon atoms as the linear α-olefin,
A linear olefin mixture in which the proportion of olefins having double bonds at the 2nd, 3rd and 4th positions is 10 to 65 mol%, and the total is 70 mol% or more; The present invention relates to a paper sizing agent containing a reaction product obtained by an addition reaction between an alpha-olefin oligomer-free substance and maleic anhydride and/or a hydrogenated product of the reaction product. The linear olefin, which is a raw material for the neutral sizing agent in the present invention, is characterized by the position of its double bond and the number of carbon atoms as described above. When the number of carbon atoms in the olefin is less than 14, the sizing effect as a neutral sizing agent is poor and the sizing agent lacks storage stability. On the other hand, when the number of carbon atoms exceeds 36, the resulting reaction product has a size effect, but the viscosity is too high, making it difficult to handle and lacking in practicality. A more preferable carbon number range is 15-24. Olefins having carbon numbers within these ranges are used as olefins having a single carbon number or mixed olefins having two or more carbon numbers, and from an economic standpoint, mixed olefins are preferably used. The ratio of double bond positions in the linear olefin mixture in the present invention is such that the 2nd, 3rd, and 4th positions are each 10 to 65 mol%, preferably 15 to 60 mol%, and the total is 70 mol%. % or more, preferably
It is 80 mol% or more. This linear olefin can be clearly distinguished from both the branched olefin and α-olefin disclosed in Japanese Patent Publication No. 39-2305. Furthermore, as is clear from the above formula, the olefin disclosed in Japanese Patent Publication No. 53-28526 is from the 6th position (in the case of 12 to 18 carbon atoms) to the 12th position (in the case of 24 carbon atoms).
Since it has a double bond at almost the center of the molecular chain, there are double bonds at the 2nd, 3rd and 4th positions.
It can be clearly distinguished from the olefin of the present invention which has a content of 70% or more. Furthermore, the olefin disclosed in JP-A-57-154495 has double bonds distributed almost evenly at each position except for the α-position, but in the olefin of the present invention, the number of carbon atoms is In the case of the lower limit of 14, the possible position of the double bond is the 1st position (α position)
to the 7th position (center of the molecular chain), and the total of the 2nd to 4th positions is 70 mol% or more, so the average proportion of each position of the 2nd to 4th positions is about 23% or more, and the 1st and 5th to Since the total of the 7th position is 30 mol% or less, the average proportion of the 1st and 5th to 7th positions is 7.5% or less (even assuming that the 1st position does not exist, the average of the 5th to 7th positions is (the ratio is less than 10%), and it cannot be said that the double bond positions are almost evenly distributed. Furthermore, as the number of carbon atoms increases, the proportion of each position above the fifth position further decreases, which further deviates from the definition of uniform distribution.
Therefore, the linear olefin of the present invention is disclosed in Japanese Unexamined Patent Application Publication No. 1986-
It is clearly different from Olefin in No. 154495. As described above, due to the linear olefin mixture having a double bond distribution that is clearly different from the various olefins proposed so far, it has excellent sizing effects compared to conventional olefin-based sizing agents. It would be unexpected from the prior art to obtain a paper sizing agent that is Note that the distribution of double bonds in the linear olefin mixture can be determined by ¹³ C-NMR. In other words, in ¹³ C-NMR, the chemical shift of the carbon atom at the 3-position of α-olefin is 34.0 ppm, and the 2-
The chemical shift of the carbon atom at position 1 of olefin is
17.9ppm (trans form) and 12.7ppm (cis form)
The chemical shifts of the carbon atom at position 1 of 3-olefin are 14.1 ppm (trans form) and 14.4 ppm (cis form), and the chemical shifts of the carbon atom at position 1 of 4-olefin are 13.7 ppm (trans form) and 13.8ppm
(cis form), chemical shifts of other terminal carbons are
Appears at 14.2ppm. The composition of the olefin having double bonds at the 1st, 2nd, 3rd, 4th, and 5th or higher positions can be determined from the intensity ratio of these chemical shifts. The linear olefin in the present invention can be easily obtained by treating a linear α-olefin having the same number of carbon atoms as the olefin with an acid catalyst under appropriate conditions. As acid catalysts, acidic minerals such as synthetic silica alumina, synthetic silica magnesia, solid phosphoric acid, acid clay, activated clay, H ₃ PW ₁₂ O ₄₀ ,
heteropolyacids such as H ₄ SiW ₁₂ O ₄₀ , H ₃ PMo ₁₂ O ₄₀ ;
Examples include heterogeneous or homogeneous catalysts such as AlCl ₃ -electron donor and BF ₃ -electron donor. Processing conditions are processing temperature 30~250℃, pressure normal pressure~
The reaction time can be appropriately selected from a range of 20 Kg/cm ² and a reaction time of 30 minutes to 10 hours depending on the type of each catalyst and each raw material α-olefin. Further, the processing type may be a batch type, a semi-batch type, or a continuous type. LHSV for continuous type is 0.5~20
A range of is preferred. Furthermore, when treating the linear α-olefin with the above catalyst, the raw material olefin can be treated alone or together with an inert solvent. The unreacted α-olefin content of the linear olefin of the present invention produced by treating the linear α-olefin with an acid catalyst as described above is 20%.
Hereinafter, it is necessary to limit the amount preferably to 10% or less. Further, during the acid catalyst treatment, a small amount of heavy olefin, which is a dimer or more of linear α-olefin, is produced as a by-product, but this is removed by distillation to a substantially non-existent amount and used as a paper sizing agent raw material. The addition reaction between the linear olefin mixture thus obtained and maleic anhydride is carried out according to a conventional method. That is, both are heated to 180 to 180°C under normal pressure or pressurization in an inert gas atmosphere such as nitrogen.
The reaction proceeds easily by heating to 250°C. Although the molar ratio of the two to be charged is not particularly limited, it is usually used in a ratio of 0.4 to 2 moles of maleic anhydride per 1 mole of the linear olefin mixture. After the reaction is completed, unreacted maleic anhydride and the linear olefin mixture are removed by vacuum distillation to obtain the reaction product of the present invention, that is, the maleic anhydride addition reaction product. In this addition reaction, linear olefin 1
The product is mainly produced in which 1 mole of maleic anhydride is added to each mole, but the so-called 1:2 product in which 2 moles of maleic anhydride is added to 1 mole of linear olefin is produced.
Small amounts of adducts, maleic anhydride polymer, etc. are produced as by-products. These by-products may or may not be removed. From an economic standpoint, it is preferable to use the by-product as a sizing agent without removing it. Hydrogenated products obtained by subjecting these reaction products to a conventional hydrogenation reaction using a solid catalyst such as palladium or Raney nickel also belong to the scope of the present invention. To size the pulp using the reaction product obtained as described above, that is, the paper sizing agent, use a strong stirring device such as a homomixer, a homogenizer, or a high-pressure emulsifier to mix the sizing agent in water. This is done by uniformly dispersing the pulp and adding it to the pulp slurry. When dispersing in water, the sizing agent is usually combined with a protective colloid, which is a suspending agent such as cationized starch, gelatin, polyvinyl alcohol, cationic polyacrylamide, or polyethyleneimide, or a nonionic emulsifier. Either method can be used, including combinations of methods. Incidentally, among the above-mentioned suspending agents, cationized starch, cationic polyacrylamide, and polyethyleneimine have an effect as a fixing agent for pulp. Examples of nonionic emulsifiers include polyoxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan trioleate; Alkylene sorbitol fatty acid ester; polyoxyalkylene alkyl ether such as polyoxyethylene alkyl ether; polyoxyalkylene alkylaryl ether such as polyoxyethylene alkyl phenol; polyoxyalkylene monoester or polyoxyalkylene diester such as polyoxyethylene alkyl ester; Examples include polyoxyalkylene alkylamines such as polyoxyethylene alkylamines; polyoxyalkylene alkylamides such as polyoxyethylene alkylamides; esters of polyhydric alcohols and fatty acids; and higher alcohols. In the present invention, the amount of the protective colloid used in combination with the paper sizing agent is determined by taking into consideration the dispersibility of the paper sizing agent in water and the fixing ability of the paper sizing agent to the pulp, and is usually 50 to 500%, preferably is 100~200
%. The amount of nonionic emulsifier to be used is determined taking into account the dispersibility of the paper sizing agent in water, and is usually 3 to 3.
30%, preferably 5-20%. In addition, when the nonionic emulsifier is mixed in advance with the paper sizing agent of the present invention and the mixture is dispersed in water, use a strong stirring device such as when dispersing using the protective colloid described above. It can be easily dispersed by simply passing it through a mixing pulp aspirator or orifice (hereinafter, this method is referred to as the self-emulsification method).
In many cases, the papermaking process can be expected to be simplified. The amount of sizing agent used in the present invention varies somewhat depending on the type of paper and its use, but is generally 0.05 to 5.0% by weight based on the dry pulp. Although it is possible to add 5.0% by weight or more, the size effect does not improve much and it is not economical. As mentioned above, when the sizing agent of the present invention is used in a neutral or alkaline region with a cationic protective colloid or a nonionic emulsifier,
It has good dispersibility in water and, unlike the prior art, exhibits excellent size effects (i.e. exhibits the desired size effect with a lower loading than the prior art) due to the use of a specific olefin. Needless to say, even after long-term storage, it shows almost the same good size effect as immediately after preparation, and is also superior in long-term storage stability compared to conventional techniques. Note that the sizing agent in the present invention can of course be used alone, and if necessary, it can also be used in combination with a conventionally known sizing agent in any proportion. It goes without saying that pigments and fillers such as clay, talc, titanium oxide, calcium carbonate, calcium sulfate, and diatomaceous earth, which are usually added to the paper sized with the sizing agent of the present invention, can also be used. Next, the production and use of the sizing agent of the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples unless the gist thereof is exceeded. Example 1 A flow-through stainless steel reaction tube was filled with 100 ml of synthetic silica alumina and maintained at 130°C. n-hexadecene-1 was added to this reaction tube at a flow rate of 300 ml/hour.
flowed. According to gas chromatography analysis, the reaction liquid at the outlet of the reaction tube had a heavy content of 7% by weight. n obtained by removing heavy components by distillation
According to ¹³ C-NMR, the composition of -hexadecene was as follows.

[Table] 450g of this n-hexadecene and maleic anhydride
195 g was charged into a stainless steel reaction vessel equipped with a stirrer and a thermometer, and after the reaction system was sufficiently purged with dry nitrogen, the reaction was carried out at a reaction temperature of 210° C. for 20 hours.
Unreacted olefin and maleic anhydride were removed from the reaction solution by distillation to obtain 450 g of a maleic anhydride addition reaction product. Example 2 A flowing stainless steel reaction tube was filled with 100 ml of 12-tungstosilicic acid supported on silica gel,
It was maintained at 100°C. n-octadecene-1 was flowed into this reaction tube at a flow rate of 300 ml/hour. The heavy content in the reaction solution at the outlet of the reaction tube is 0%, and its composition is
According to ¹³ C-NMR, the results were as shown in Table 2.

[Table] 500g of this olefin and 190g of maleic anhydride
was charged into a stainless steel reaction vessel equipped with a stirrer and a thermometer, and after the reaction system was sufficiently purged with dry nitrogen, the reaction was carried out at a reaction temperature of 190°C for 30 hours.
Unreacted olefin and maleic anhydride are removed from the reaction solution to form a maleic anhydride addition reaction product.
Obtained 450g. Example 3 In Example 2, instead of n-octadecene-1, α- of C ₁₈ to C ₂₀ obtained by wax decomposition was used.
Olefin (C ₁₈ : 24% by weight, C ₁₉ : 39% by weight,
C ₂₀ :37% by weight) was used to carry out the isomerization reaction. The heavy content in the obtained reaction solution was 0%, and its composition was as shown in Table 3 according to ¹³ C-NMR.

[Table] 600g of this olefin and 190g of maleic anhydride
g was reacted under the same conditions as in Example 2 to obtain 474 g of a maleic anhydride addition reaction product. Comparative Example 1 300 g of n-octadecene-9 and 115 g of maleic anhydride were subjected to an addition reaction in the same manner as in Example 1 to obtain 248 g of a maleic anhydride addition reaction product. Comparative Example 2 Mixed n-paraffin having 15 to 18 carbon atoms and hydrogen were placed in a stainless steel reactor filled with 30 ml of Pt.Li ₂ O. Al ₂ O ₃ catalyst at a reaction temperature of 470°C and a flow rate of 15 ml/min.
The dehydrogenation reaction was carried out by supplying H ₂ /n-paraffin=8.0 (molar ratio). The olefin content in the oil effluent at the reactor outlet was 12% by weight.
This reaction solution was passed through a molecular sieve to recover n-olefin. The carbon number distribution of n-olefin is C ₁₅ : 5% by weight, C ₁₆ : 37% by weight, C ₁₇ : 38
% by weight, C ₁₈ :20% by weight, and the olefin composition according to ¹³ C-NMR analysis was as shown in Table 4.

[Sizing agent evaluation test]

The performance of the maleic anhydride addition reaction products obtained in Examples 1 to 3 and Comparative Examples 1 to 6 was evaluated by the following usage method. Usage Example 1 To 1 g of the maleic anhydride addition reaction product, 20 g of 10% cationized starch and 79 g of water were added and emulsified using a homogenizer. The obtained emulsion was added to a 1% pulp slurry (L-BKP450mlc.sf) so that the maleic anhydride addition reaction product was 0.2 and 0.5% by weight (relative to pulp solid content), and the Tatsupi Standard Machine was added. Paper was made to have a basis weight of 60±1 g/m ² using the following methods. 20% by weight (based on pulp solid content) of CaCO ₃ is added as a filler. Next, the obtained wet paper was compressed and dehydrated, dried at 100° C. for 1 minute, and then conditioned for 24 hours at a relative humidity of 65%, and its physical properties were measured by the Stekicht method.
The results are shown in Table 5. As can be seen from the results shown in Table 6, the sizing agent of the present invention exhibited a higher sizing degree than the sizing agent of the comparative example.

[Table] Usage example 2 Add 1 g of polyethylene glycol nonyl phenyl ether (trade name: Nonypol 160, manufactured by Sanyo Chemical Industries, Ltd.) as an emulsifier to 10 g of the maleic anhydride addition reaction product, mix well, and then add 1 g of this mixture. Add 99g of water and use a stirrer with propeller blades.
It was emulsified by stirring for 10 seconds to obtain a size liquid. Polyamide polyamine resin (AF- manufactured by Arakawa Chemical Co., Ltd.) was added as a fixing agent to 1% pulp slurry.
100) was added in an amount of 0.3% by weight (based on pulp solid content), and the above size solution was mixed with maleic anhydride addition reaction product.
It was added at a concentration of 0.5% by weight (based on pulp solid content). The degree of sizing was then measured in the same manner as in Use Example 1. Further, the degree of sizing was measured after the prepared diluted sizing solution was left to stand for 5 hours. These results are shown in Table 6.
Shown below.

[Table] As can be seen from the results shown in Table 6, the self-emulsifying sizing agent of the present invention has a better sizing effect immediately after emulsification than that of the comparative example, and also has less decrease in sizing after being left for 5 hours. .

Claims (1)

[Claims] 1. Obtained by treating a linear α-olefin having 14 to 36 carbon atoms with an acid catalyst. The proportion of olefins having the same number of carbon atoms as the linear α-olefin and having double bonds at the 2nd, 3rd and 4th positions is 10 to 65 mol%, and the total is 70%.
A reaction product obtained by an addition reaction of a linear olefin mixture containing substantially no oligomer of the linear α-olefin in an amount of mol % or more with maleic anhydride, and/or the reaction Paper sizing agent containing hydrogenated product. 2. The paper sizing agent according to claim 1, wherein the paper sizing agent contains a suspending agent. 3. The paper sizing agent according to claim 2, wherein the suspending agent is selected from the group consisting of cationized starch, gelatin, polyvinyl alcohol, cationic polyacrylic, amide, and polyethyleneimine. 4. The paper sizing agent according to claim 1, wherein the paper sizing agent contains an emulsifier. 5. The emulsifier is selected from the group consisting of polyoxyalkylene sorbitol fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene alkyl ether, polyoxyalkylene alkylaryl ether, polyoxyalkylene monoester, and polyoxyalkylene diester. The paper sizing agent according to claim 4.