JP2607636B2 - Cationic sizing agent for papermaking and sizing method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a cationic sizing agent for papermaking and a sizing method. More specifically, the present invention uses a cationic ketene dimer compound, a polyamine compound, and an amide group-containing cationic product obtained from epihalohydrin as an active ingredient and a cationic sizing agent for papermaking, and uses the sizing agent. The present invention relates to a sizing method for papermaking.

[Problems to be solved by conventional technology and invention]

As a method for sizing cellulose fiber products such as paper, paperboard, and wood fiber board, there are generally an internal addition method in which a sizing agent is added to an aqueous dispersion (slurry) of cellulose pulp, and an internal addition method in which a paper is made in advance. There is a surface method to apply a sizing agent. As the sizing agent, various anionic sizing agents and cationic sizing agents are known.

The anionic sizing agent usually needs to be used in an acidic pH region in combination with a fixing agent and a sulfate band as a size effect developing agent, and therefore, there is a problem that the papermaking machine is worn and the drainage load is increased. .

On the other hand, the cationic sizing agent has a self-fixing property, so that it can be used in a wide pH range from acidic to alkaline, and has an advantage that it can be used particularly for neutral paper making using calcium carbonate which is useful as an inexpensive filler. is there.

However, conventional cationic sizing agents, for example, cationic polymer sizing agents described in JP-B-42-12292 and JP-A-48-11407, both have insufficient sizing effects, and Is disadvantageous in that the re-disintegration of waste paper is deteriorated. Further, a cationic sizing agent described in JP-A-50-116705 and JP-A-55-36390, that is, a condensate of a fatty acid and / or rosin with a polyalkylene polyamine is modified with epihalohydrin. The cationic sizing agent obtained by the above method has a disadvantage that the sizing effect is not satisfactory, and furthermore, the use thereof greatly reduces the paper strength of the obtained paper.

Therefore, the present invention solves the above problems of the conventional cationic sizing agent and the sizing method, has an excellent size effect in a wide pH range from acidic to alkaline, and facilitates the re-dissociation of broke or waste paper. An object of the present invention is to provide a cationic sizing agent and a sizing method which do not cause a reduction in paper strength.

[Means for solving the problem]

The cationic sizing agent for papermaking of the present invention has the following general formula (I): [However, in the above formula, R ¹ and R ² each independently represent a saturated or unsaturated aliphatic hydrocarbon group having 8 to 30 carbon atoms. A reaction component comprising at least one kind of an aliphatic hydrocarbon-substituted ketene dimer compound represented by the formula: and at least one kind of a polyamine compound having from 1 to 10 primary and secondary amino groups in one molecule. An amide group-containing cationic substance consisting of a modified reaction product of an intermediate substance obtained by reacting a reaction component with an epihalohydrin in an amount of 0.3 to 2 equivalents to the remaining amino group of the intermediate substance. It is the main component.

Further, the sizing method for papermaking of the present invention includes adding the cationic sizing agent of the present invention to a pulp slurry to make paper, or applying the paper to the surface of papermaking base paper.

The sizing agent of the present invention is mainly composed of an amide group-containing cationic substance composed of a modified reaction product of the intermediate substance (A) and epihalohydrin (B), and the intermediate substance (A) has at least It comprises a reaction product of a reaction component (a) consisting of one kind of ketene dimer compound of the general formula (I) and a reaction component (b) consisting of at least one kind of polyamine compound.

The ketene dimer compound used as the constituent reaction component (a) of the sizing agent of the present invention is represented by the aforementioned general formula (I), and the aliphatic hydrocarbon group represented by R ¹ and R ² in the formula Has 8 to 30 carbon base papers. When the number of carbon base papers of the hydrocarbon groups R ¹ and R ² is less than 8, the hydrophobicity of the obtained sizing agent becomes insufficient, and the sizing effect becomes unsatisfactory. In addition, hydrocarbon groups R ¹ and R ²
Even if a ketene dimer compound having more than 30 carbon atoms is used, the sizing effect of the obtained sizing agent is not further improved, but it is rather difficult to obtain such a ketene dimer compound.

As the ketene dimer compound used in the present invention,
There are alkyl (saturated aliphatic hydrocarbon group substituted) ketene dimer compounds and unsaturated aliphatic hydrocarbon group substituted ketene dimer compounds. As the alkyl ketene dimer compound, R ¹ and R ² in the general formula (I) are each independently a member selected from the group consisting of octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl and tetracosyl groups And includes, for example, ketene dimer compounds prepared from natural fats and oils mainly containing saturated fatty acids such as coconut oil, palm oil, olive oil, peanut oil, rapeseed oil, beef oil, and lard. The unsaturated aliphatic hydrocarbon group-substituted ketene dimer compound includes, for example, ketene dimer compounds prepared from unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, eleostearic acid, and arachidonic acid. The ketene dimer compound may be used alone or as a mixture of two or more.

The polyamine compound used as the constituent reaction component (b) of the sizing agent of the present invention needs to have 1 to 10 primary and secondary amino groups in one molecule. The amino group having at least one active hydrogen of such a polyamine compound undergoes an addition reaction with the β-propiolactone group of the ketene dimer compound to produce a reaction product. Therefore, a polyamine compound having only a tertiary amino group having no active hydrogen cannot be used in the present invention. In addition, when a polyamine compound having more than 10 amino groups is used, the resulting sizing agent has a cross-linking property, so that there is a disadvantage that the re-disintegration property of the formed paper is reduced.

Examples of polyamine compounds useful in the present invention include dimethylaminoethylamine, dimethylaminopropylamine, diethylaminoethylamine, diethylaminopropylamine, dibutylaminopropylamine, ethylaminoethylamine, 1,2-diaminopropane, and 1,3-diamino. Propane, 1,4-diaminobutane, methylaminopropylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, 2-hydroxyaminopropylamine, bis- (3-amino Propyl) -ether,
Dimethylaminoethoxypropylamine, 1,2-bis-
(3-aminopropoxy) -ethane, 1,3-bis- (3
-Aminopropoxy) -2,2-dimethylpropane, α,
ω-bis- (3-aminopropoxy) -polyethylene glycol ether, iminobispropylamine, methyliminobispropylamine, laurylaminopropylamine, diethanolaminopropylamine, N-aminoethylpiperidine, N-aminoethylpi-4-pecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecholine, N
-Aminopropyl-4-pipecholine and N-aminopropylmorpholine. These polyamine compounds may be used alone or in a combination of two or more.

In order to obtain the intermediate substance (A) as a constituent reaction component of the sizing agent of the present invention, the ketene dimer compound described above is used:
The reaction with the polyamine compound must be carried out in such a mixing ratio that at least one amino group remains in the molecule of the obtained reaction product.

That is, the number of β-propiolactone groups contained in the ketene dimer compound is 1 to the total number X of amino groups contained in one molecule of the polyamine compound to be reacted.
(X-1) and must not exceed the total number of primary and secondary amino groups.

The reaction temperature between the ketene dimer compound and the polyamine compound is preferably 30 to 150 ° C, more preferably 50 to 120 ° C. The reaction time is preferably about 1 to 7 hours, more preferably 2 to 5 hours.

In the reaction between the ketene dimer compound and the polyamine compound, it is not always necessary to use a reaction solvent. Generally, it is sufficient to mix both reaction components and directly heat them. Although there is no particular limitation on the method of mixing the two components, it is usually preferable to gradually add the ketene dimer compound to the polyamine compound so that the reaction proceeds smoothly.

The intermediate substance (A) comprising an addition reaction product of the ketene dimer compound and the polyamine compound and having one or more unreacted amino groups in the molecule is modified by epihalohydrin (B). .

As epihalohydrin, epichlorohydrin, epibromohydrin and the like can be used,
In view of its availability and price, epichlorohydrin is generally used.

In the modification reaction of the intermediate substance, the amount of epihalohydrin used is usually 0.
It is 3 to 2 equivalents, preferably 0.5 to 1.7 equivalents. When the amount of epihalohydrin used is less than 0.3 equivalent, the sizing agent obtained lacks cationicity and the sizing effect becomes insufficient. When the amount of epihalohydrin used is more than twice equivalent, the amount of epichlorohydrin remaining in the reaction product increases, which is unsatisfactory in terms of economy and odor. The type of the residual amino group contained in the intermediate substance is not particularly limited, and may be any of primary, secondary and tertiary amino groups.

The denaturation reaction temperature is usually preferably about 50 to 110 ° C, more preferably 70 to 100 ° C. The denaturation reaction time is preferably about 0.5 to 7 hours, more preferably 1 to 4 hours. In the denaturation reaction, it is preferable that water is usually used as a reaction solvent, and the reaction mixture is made into an aqueous emulsion state to advance the reaction. If necessary, an organic solvent such as methanol, ethanol, or isopropyl alcohol may be used in combination with water, whereby an increase in the viscosity of the reaction system can be appropriately suppressed.

The amide group-containing cationic product, which is an active ingredient of the sizing agent of the present invention, can be easily obtained by the above method. Since the sizing agent active ingredient is obtained as an aqueous dispersion as described above, it can be easily used as a sizing agent without performing any special operation. If necessary, the denaturation reaction product may be diluted with an appropriate amount of water.

The sizing method for papermaking of the present invention is carried out by adding the above-mentioned sizing agent of the present invention to a pulp slurry to make a paper, or applying the sizing agent to the surface of the base paper thus made.

In the sizing method of the present invention, the amount of the sizing agent added or applied is converted into the weight of the solid content of the amide group-containing cationic product, based on the weight of the solid content of the pulp slurry.
It is preferably in the range of 01 to 5%.

The sizing agent of the present invention is self-fixing to pulp due to its appropriate cationicity, does not require the use of a fixing agent such as a sulfate band, and therefore uses a conventional anionic sizing agent. There are no problems with papermaking in the acidic pH range that occur when the papermaking process is performed.

In addition, the cationic sizing agent of the present invention exerts a sufficient sizing effect on pulp in a weakly acidic, neutral to weakly alkaline pH range, and effectively utilizes an inexpensive and useful filler such as calcium carbonate. To be able to

Further, the paper sized by the method of the present invention has a good re-dissociation property, and therefore, it is possible to reuse waste paper and waste paper in the paper making process, thereby streamlining the paper making process and saving resources. .

The sizing agent of the present invention is not only papermaking of cellulose fibers such as pulp, but also papermaking a mixture of the fibers with mineral fibers such as asbestos and rock wool, and synthetic fibers such as polyamide, polyester and polyolefin. It can also be used advantageously when producing paperboard, fiberboard and the like.

In the sizing method of the present invention, the sizing agent of the present invention and a conventionally known sizing agent, such as a rosin-based soap-type sizing agent, a rosin-based emulsion sizing agent, an alkenyl succinate-based sizing agent, and alkenyl succinic anhydride It may be used in combination with at least one kind of system sizing agent and the like, added to the pulp slurry and paper-made, or applied to the surface of the paper-made base paper.

The amount of the sizing agent used in combination is not particularly limited, and may be an appropriate amount in consideration of the purpose of use.
However, in general, the sizing agent of the present invention is preferably used in a range of less than 9 times the weight of the solid content in terms of the solid content weight.

〔Example〕

 The present invention is further described by the following examples.

Example 1 146.2 g of triethylenetetramine was placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet, and a dropping funnel.
(1 mol) and heated to 60 ° C. with stirring. To the solution, 1020 g (2 mol) of ketene dimer dissolved at 70 ° C. was added from a dropping funnel over 1.5 hours. After completion of the dropwise addition, the mixture was kept at 75 ° C for 1 hour, and further kept at 95 ° C for 30 minutes to complete the reaction. The resulting intermediate material is then
After adding 9.8 g and stirring, epichlorohydrin 185.0 g
(2 moles, 1 equivalent relative to the remaining amino groups) at a time, and the mixture was kept at 95 ° C. for 3 hours. After completion of the denaturation reaction, 2653.0 g of 90 ° C warm water was slowly added dropwise to the reaction product solution while stirring was continued. By further adding 4504.0 g of water at 25 ° C., a white emulsion of the sizing agent of the present invention containing a modified reaction product having a solid content of 15% by weight was obtained.

Example 2 The same operation as in Example 1 was performed. However, triethylenetetramine is replaced with tetraethylenepentamine 189.3 g (1 mol)
Replaced with 277.6g epichlorohydrin
(3 moles, 1 equivalent to the remaining amino groups).
A white emulsion of the sizing agent of the present invention was obtained.

Example 3 The same operation as in Example 1 was performed. However, triethylenetetramine is replaced with pentaethylenehexamine 232.4 g (1 mol)
370.8g epichlorohydrin
(4 moles, 1 equivalent to the remaining amino groups).
The same white emulsion as in Example 1 was obtained.

Example 4 The same operation as in Example 1 was performed. However, the amount of epichlorohydrin used was 92.5 g (1.0 mol, 0.
5 equivalents). The same white emulsion as in Example 1 was obtained.

Example 5 The same operation as in Example 1 was performed. However, the amount of epichlorohydrin used was changed to 277.5 g (3.0 mol, 1.5 equivalents to the remaining amino groups). The same white emulsion as in Example 1 was obtained.

Example 6 The same operation as in Example 1 was performed. However, the amount of epichlorohydrin used was changed to 3700 g (4 mol, 2 equivalents based on the remaining amino groups). The same white emulsion as in Example 1 was obtained.

Example 7 In a reaction vessel similar to that of Example 1, 1020 g of ketene dimer was added.
(2 mol), stirred at 65 ° C., dissolved and kept warm. To this, 204.4 g (2 mol) of dimethylaminopropylamine was slowly added from a dropping funnel over 30 minutes. After the completion of the dropwise addition, the temperature was maintained at 80 ° C. for 1 hour to complete the reaction. After adding 5574.6 g of warm water at 85 ° C. to the intermediate substance and stirring, 185.0 g (2 mol) of epichlorohydrin was added at a time, and 90 ml of
Incubated at 2 ° C. for 2 hours. After completion of the denaturation reaction, 4820.0 g of water at 25 ° C. was slowly added to the denaturation reaction product while stirring to obtain a white emulsion having a nonvolatile solid content of 15%.

Example 8 The same operation as in Example 7 was performed. However, dimethylaminopropylamine is converted to N-aminopropylmorpholine 288.4 g
(2 mol). A white emulsion similar to that of Example 7 was obtained.

Comparative Example 1 146.2 g (1 mol) of triethylenetetramine and 546.5 g (2 mol) of hardened tallow fatty acid were placed in the same reaction vessel as in Example 1, and the temperature was raised to 180 ° C. with good stirring. A time dehydration condensation reaction was performed. 90 ° C reaction product
The mixture was cooled to 2525.1 g of hot water at 85 ° C., stirred well, and then 185.0 g of epichlorohydrin was added at once. Then, the reaction system was kept at 90 ° C. for 3 hours. Then 25
841.7 g of water at 50 ° C is added to the reaction system, whereby the nonvolatile content is 20%
Was obtained as a white emulsion.

Comparative Example 2 The same reaction vessel as in Example 1 was charged with 232.4 g (1 mol) of pentaethylenehexamine and heated to 60 ° C. with stirring. 1020 g of ketene dimer dissolved in this at 70 ° C
(2 mol) was added from the dropping funnel over 1.5 hours.
After completion of the dropwise addition, the reaction system was kept at 75 ° C. for 1 hour,
The reaction was completed by heating to 85 ° C. for 30 minutes. Then, 240.2 g (4 mol) of acetic acid at 80 ° C. was added to the reaction product while stirring, and 1492.6 g of warm water at 80 ° C. was slowly added with sufficient stirring. Further, 6965.4 g of water at 25 ° C. was added to the reaction system to obtain a pale yellow emulsion having a nonvolatile content of 15%.

Comparative Example 3 A styrene-based cationic polymer sizing agent (trade name “Polymaron 360” manufactured by Arakawa Chemical Industry Co., Ltd.) was used as it was.

Comparative Example 4 Alkyl ketene dimer emulsion sizing agent (trade name “Size Pine K-903” manufactured by Arakawa Chemical Industry Co., Ltd.)
Was used as it was.

Comparative Example 5 1 g of an alkenyl succinic anhydride sizing agent (trade name “Size Pine SA-860” manufactured by Arakawa Chemical Industry Co., Ltd.) was taken in a sample bottle, and 99 g of water was added thereto. I got

Example 9-16, Comparative Example 6-8 In each Example and Comparative Example, 1% L beated until Canadian Standard Freeness reached 450 ml.
-Calcium carbonate (manufactured by Sankyo Seiko Co., Ltd., trade name "Escalon # 100") as a filler is added to BKP pulp slurry at a solid content of 20%, aluminum sulfate 1%, cationized starch (Oji) National Co., Ltd., trade name "Cato 15") was added at a ratio of 1%. Next, 0.3% of the sizing agent obtained in each of Examples 1 to 8 and Comparative Examples 1 to 3 was added to pulp, and a filler retention agent (trade name “KW-504” manufactured by Arakawa Chemical Industries, Ltd.) ") Was added and dispersed uniformly. At this time, the pulp slurry
pH was 8.0. Paper is made from this pulp slurry using a Tappi Standard Sheet Machine, and the obtained wet paper is dewatered under compression, dried at 100 ° C for 1 minute, and has a relative humidity of 65%.
For 24 hours to obtain a paper having a basis weight of 70 g / m ² . The performance evaluation of the obtained various types of formed paper was performed as follows.

Size effect: The size degree (second) was measured by the Stequich method (JIS P8122).

Paper strength: Breaking length (k) by tensile strength test (JIS P8113)
m) was measured.

Re-disintegration: The time until the completion of dissociation was measured based on JIS P8209 using a standard disintegrator.

 Table 1 shows the evaluation results.

Example 17-24, Comparative Example 9-10 In each Example and Comparative Example, to the same pulp slurry described in Example 9, 1.5% of aluminum sulfate was added to pulp in terms of solid content. Example 1
Each of the sizing agents of No. 8 and Comparative Examples 1 and 3 was added to the pulp at 0.4% and uniformly dispersed. The pH of the pulp slurry at this time was 5.1. Then, drying and humidity control were performed under the same conditions as in Example 9 to obtain a paper having a basis weight of 60 g / m ² . The performance of these laminated papers was evaluated in the same manner as described above.

 Table 2 shows the evaluation results.

Examples 25 to 26, Comparative examples 11 to 14 In each of the examples and comparative examples, the same operation as in Example 9 was performed. However, the composition and amount of the sizing agent are third.
As shown in the table.

 Table 3 shows the evaluation results.

Comparative Example 15 The same operation as in Example 9 was performed. However, the sizing agent described in Comparative Example 5 was used, and the sizing agent addition rate was 0.06.
%. The basis weight of the obtained paper was 70 g / m ² , and the Steckigt sizing degree was 0.5 seconds.

Example 27, Comparative Example 16 In Example 27 or Comparative Example 16, the size of the sizing agent obtained in Example 1 or Comparative Example 1 was changed to 2.5% on the paper obtained in Comparative Example 15 above. 35m by
/ min, 10kg / cm surface application. This at 100 ℃
After drying for 25 minutes, the humidity was controlled for 24 hours under the condition of a relative humidity of 65%, and then the size effect was evaluated by the Stechich method.

 Table 4 shows the evaluation results.

[Effects of the Invention] By the sizing agent and the sizing method of the present invention, paper having a high sizing effect in a wide pH range from weakly acidic to neutral to weakly alkaline can be produced. Also, the sizing and sizing method of the present invention enables the use of inexpensive and effective fillers such as calcium carbonate,
It is extremely useful for the paper industry, such as enabling efficient reuse of waste paper and waste paper.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Jun Ikeda 3-4-133 Imafukuminami, Joto-ku, Osaka-shi, Osaka Arakawa Chemical Industry Co., Ltd. (56) References JP-A-2-139493 (JP, A )

Claims (4)

(57) [Claims] 1. The following general formula (I): [However, in the above formula, R ¹ and R ² each independently represent a saturated or unsaturated aliphatic hydrocarbon group having 8 to 30 carbon atoms. A reaction component comprising at least one kind of an aliphatic hydrocarbon-substituted ketene dimer compound represented by the formula: and at least one kind of a polyamine compound having from 1 to 10 primary and secondary amino groups in one molecule. An amide group-containing cationic substance consisting of a modified reaction product of an intermediate substance obtained by reacting a reaction component with an epihalohydrin in an amount of 0.3 to 2 equivalents to the remaining amino group of the intermediate substance. Cationic sizing agent for paper making, which is a main component. 2. The intermediate substance, wherein the number of β-propiolactone groups contained in the ketene dimer compound is from 1 to (X-) with respect to the total number X of amino groups contained in one molecule of the polyamine compound. 2. The sizing agent according to claim 1, wherein the sizing agent is an intermediate substance which is 1) and is reacted at a charge ratio not exceeding the total number of primary and secondary amino groups. 3. A sizing method for papermaking, comprising adding the cationic sizing agent according to claim 1 to a pulp slurry and applying the sizing agent to the surface of papermaking base paper. 4. The cationic sizing agent according to claim 1, and at least one selected from a rosin-based soap type sizing agent, a rosin-based emulsion sizing agent, an alkenyl succinate-based sizing agent, and an alkenyl succinic anhydride-based sizing agent. One kind is added to the pulp slurry to make paper, or
A sizing method for papermaking, which comprises applying it to the surface of papermaking base paper.