JP2002212896A - Method for fixing neutral rosin sizing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for fixing, neutral rosin sizing agent with which in a neutral paper making, the sizing effect of the neutral rosin sizing agent can be economically improved without negatively affecting the function of a yield improver and reducing a yield at a wire part. SOLUTION: This method for fixing the neutral rosin sizing agent is both a neutral rosin sizing agent and a crosslinking type diallyldimethylammonium halide polymer are present in raw material slurry for paper making.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for fixing a neutral rosin sizing agent. More specifically, the present invention relates to a method for fixing a neutral rosin sizing agent capable of improving the sizing effect of a neutral rosin sizing agent in a neutral papermaking without reducing a yield rate in a wire part.

[0002]

2. Description of the Related Art Sizing agents are used to impart water resistance to paper and resistance to penetration of ink and water.
In conventional acidic papermaking, so-called reinforced rosin, which is obtained by adding maleic anhydride to rosin, is used as a sizing agent.
The treatment was carried out using a sulfuric acid band as a fixing agent to give a desired size. However, when a sulfuric acid band is used, the paper is yellowed or the strength is reduced. Therefore, neutral papermaking has been performed to prevent the paper from being deteriorated. In neutral papermaking, alkenyl succinic anhydride as a sizing agent,
Alkyl ketene dimers and the like are widely used. However, the alkyl ketene dimer has a slow reaction rate, does not exhibit the size effect immediately after drying even if it is adsorbed by the papermaking raw material and remains in the papermaking, and cannot be used as a base paper for coating on-machine. In addition, there is a problem that the friction coefficient of the paper decreases and the paper surface becomes slippery. Alkenyl succinic anhydride reacts with water and is easily decomposed, so it is emulsified with the cationic polymer and added to the raw material slurry, but the emulsified particles not adsorbed by the papermaking raw material decompose and flow out into white water However, the recovered emulsified particles in the white water gradually aggregate to cause pitch trouble, or do not contribute to the size effect even if adsorbed by the raw material. For this reason, a so-called neutral rosin sizing agent has been developed which can be used for neutral papermaking at pH 5 to 8.5. However, a neutral rosin sizing agent reduces the cohesive ability of a later added retention aid because the surface charge is anionic. To cope with this point, a method of adding a large amount of cationically modified starch to neutralize the surface charge of the neutral rosin sizing agent is generally performed, but the cationically modified starch has a low cationic charge density. Therefore, it must be added in a large amount, which also reduces the effect of the retention aid. If the yield rate is not improved, the yield rate of the sizing particles adsorbed on the pulp or the fine fibers is not improved, and the size effect is not improved. Neutral rosin sizing agents are generally anionic, but in acidic papermaking, a large amount of sulfate band is added, and as a result, the papermaking system becomes acidic, thereby impairing the function of the retention aid. Relatively few factors. However, in the neutral or alkaline papermaking, in addition to the neutral rosin sizing agent, the influence of various anionic substances produced in the process of producing pulp and waste paper is much greater than in the case of acidic papermaking. Fixing agents such as dimethylamine-epichlorohydrin polymer and polyethyleneimine are used to control the surface charge, but the degree of polymerization is not sufficiently high, and the contained low molecular components adversely affect the papermaking system. There is a problem that becomes high.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a neutral rosin sizing agent for neutral papermaking which does not adversely affect the function of the retention aid and does not reduce the yield in the wire part. The purpose of the present invention is to provide a method for fixing a neutral rosin sizing agent that can improve the size effect.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, a neutral rosin sizing agent and a crosslinked diallyldimethylammonium halide polymer have been incorporated into a papermaking raw material slurry. By coexisting,
Found that a neutral rosin sizing agent can be efficiently fixed and a paper having a good sizing effect can be economically produced;
Based on this finding, the present invention has been completed. That is, the present invention provides (1) a method for fixing a neutral rosin sizing agent, wherein a neutral rosin sizing agent and a cross-linked diallyldimethylammonium halide polymer coexist in a papermaking raw material slurry; The raw material slurry according to claim 1, wherein the neutral rosin sizing agent and the crosslinked diallyldimethylammonium halide polymer are added simultaneously, or the crosslinked diallyldimethylammonium halide polymer is added after the neutral rosin sizing agent is added. 3. The fixing method of the neutral rosin sizing agent according to item 1 or 2, wherein (3) the neutral rosin sizing agent is an emulsion emulsified by an anionic protective colloid.
(4) The method according to the above item 1, 2 or 3, wherein the amount of the crosslinked diallyldimethylammonium halide polymer to be added is 0.0018 to 0.2 parts by weight per 100 parts by weight of the pulp in the papermaking raw material slurry. A method for fixing a neutral rosin sizing agent, and (5) a method for fixing a neutral rosin sizing agent fixing paper, wherein a neutral rosin sizing agent and a cross-linked diallyldimethylammonium halide polymer are coexistent in a papermaking raw material slurry. Manufacturing method.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the fixing method of a neutral rosin sizing agent of the present invention, a neutral rosin sizing agent and a crosslinked diallyldimethylammonium halide polymer coexist in a papermaking raw material slurry. Neutral rosin sizing agent used in the present invention, by weakly acidic to alkaline, by modifying a part or all of the rosin that is difficult to exhibit the size effect, without impairing the size effect originally possessed by rosins, its application area It is expanded from weakly acidic to alkaline. The neutral rosin sizing agent used in the present invention is not particularly limited. For example, a neutral rosin sizing agent which can be produced by an esterification reaction of a rosin with a trihydric or tetrahydric alcohol, or a commercially available neutral rosin sizing agent is used You can also. The crosslinked diallyldimethylammonium halide polymer used in the present invention is not particularly limited, and examples thereof include a crosslinked diallyldimethylammonium chloride polymer and a crosslinked diallyldimethylammonium bromide polymer. Among these, a crosslinked diallyldimethylammonium chloride polymer can be particularly preferably used. The method for producing the crosslinked diallyldimethylammonium halide polymer used in the present invention is not particularly limited.For example, a diallyldimethylammonium halide monomer and a polyfunctional crosslinkable monomer are dissolved in water to form a water-soluble polymer. By adding an initiator, replacing the atmosphere with an inert gas and heating, a crosslinked diallyldimethylammonium halide polymer can be obtained.

There is no particular limitation on the polyfunctional crosslinkable monomer to be used. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate Acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, N, N'-methylenebis (meth)
Acrylamide, glycerin tri (meth) acrylate,
Divinylbenzene, diallyl phthalate, diallyl maleate, triallyl trimellitate, ethylene glycol diallyl ether, diallylamine, triallylamine, triallyl isocyanurate, triallyl phosphate, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, aliphatic Examples thereof include polyhydric alcohol di- or polyglycidyl ether, N-methylolacrylamide, and glycidyl methacrylate. These crosslinkable monomers are
It is preferable to use 0.005 to 0.5 part by weight based on 100 parts by weight of diallyldimethylammonium halide. If the amount of the crosslinkable monomer is less than 0.005 parts by weight based on 100 parts by weight of diallyldimethylammonium halide, the degree of crosslinking may be low and the performance as a fixing agent may be insufficient. If the amount of the crosslinkable monomer exceeds 0.5 parts by weight with respect to 100 parts by weight of diallyldimethylammonium halide, the degree of crosslinking may be too high and the performance as a fixing agent may be insufficient.

There is no particular limitation on the polymerization initiator used. For example, 2,2′-azobis (2-amidinopropane) dihydrochloride, 4,4′-azobis (4-cyanovaleric acid), 2,2 ′ -Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobisisobutylamide dihydrate,
Azobisisobutyronitrile, 2,2'-azobis (2,4
Azo-based initiators such as -dimethylvaleronitrile), persulfates, redox initiator systems in which peroxides such as alkyl peroxides and sulfites, ferrous salts, amine compounds and the like are combined. it can. In addition, polymerization can be performed by irradiating light in the presence of a photosensitizer such as benzophenone or benzoin ethyl ether. Among these, a water-soluble azo initiator can be suitably used. The structural unit of the crosslinked diallyldimethylammonium halide polymer used in the present invention is not particularly limited,
For example, any structure of a 6-membered piperidinium ring and a 5-membered pyrrolidinium ring may be used, or a polymer in which these two types of structures coexist may be used. In the method of the present invention, the crosslinked diallyldimethylammonium halide polymer is preferably added simultaneously with the neutral rosin sizing agent, or after the neutral rosin sizing agent is added. By adding a neutral rosin sizing agent and a cross-linked diallyldimethylammonium halide polymer simultaneously, or by adding a neutral rosin sizing agent after addition, anions other than the neutral rosin sizing agent such as pulp fiber and foreign matter can be obtained. The consumption of the cation site of the crosslinked diallyldimethylammonium halide polymer due to the reaction with the component can be prevented, and the reaction between the crosslinked diallyldimethylammonium halide polymer and the neutral rosin sizing agent can be efficiently promoted.

In the method of the present invention, the neutral rosin sizing agent is preferably an emulsion emulsified by an anionic protective colloid. Examples of the anionic protective colloid include a styrene- (meth) acrylic acid copolymer and casein. The emulsion emulsified by the anionic protective colloid is effectively fixed to the pulp fiber by the crosslinked diallyldimethylammonium halide polymer. In the method of the present invention, the amount of the crosslinked diallyldimethylammonium halide polymer to be added depends on the amount of pulp in the papermaking raw material slurry.
It is preferably 0.0018 to 0.2 part by weight, more preferably 0.003 to 0.02 part by weight, per 100 parts by weight. The amount of the crosslinked diallyldimethylammonium halide polymer added was 0.0 per 100 parts by weight of pulp.
If the amount is less than 018 parts by weight, a remarkable size effect may not be exhibited. If the amount of the crosslinked diallyldimethylammonium halide polymer exceeds 0.2 parts by weight per 100 parts by weight of the pulp, the surface charge of the pulp or the filler tends to be too positively charged, or the weight of the unadsorbed crosslinked diallyldimethylammonium halide polymer is increased. The coalescence may be released to the papermaking system, and the one-pass retention at the wire part may be reduced.

At present, in neutral papermaking at around pH 7, a sulfuric acid band of 1.5 per 100 parts by weight of pulp in a papermaking raw material slurry is used.
However, since the size effect is improved by applying the method of the present invention, the amount of the sulfate band can be reduced to 0.5 to 1 part by weight per 100 parts by weight of the pulp. it can. Further, cationized starch is usually added to the papermaking raw material slurry for the purpose of fixing the sizing agent, yield of the filler, improving drainage, etc.
By applying the method of the present invention, a sufficient sizing effect can be obtained without reducing the addition amount of the cationized starch or without impairing the fixation of the neutral rosin sizing agent without adding the cationized starch. be able to. According to the method of the present invention, it is possible to reduce the amount of the neutral rosin sizing agent to improve the size effect. For example, a neutral rosin sizing agent per 100 parts by weight of pulp may be used.
In a papermaking system containing 5 parts by weight, the amount of the neutral rosin sizing agent can be reduced to 0.3 parts by weight. Even when the addition amount of the crosslinked diallyldimethylammonium halide polymer is 0.02 parts by weight per 100 parts by weight of pulp, the amount of the neutral rosin sizing agent is increased due to an increase in raw material costs due to the addition of the crosslinked diallyldimethylammonium halide polymer. The decrease in raw material costs due to the decrease in the cost is much more economical.

[0010]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. Table 1 shows the structure and molecular weight of the fixing agent used in Examples and Comparative Examples, and the solid content and viscosity of the fixing agent dispersion.

[0011]

[Table 1]

Example 1 A hardwood kraft pulp (LBKP) was subjected to a Canadian standard freeness test (Canadian standard free).
(essence, CSF) was adjusted to 450 mL, and the pulp slurry concentration was adjusted to 1% by weight. 400 mL of this pulp slurry was collected in a 500 mL polybeaker, and a stirrer with a turbine blade was attached. 600rpm
Light calcium carbonate [Okutama Kogyo Co., Ltd., Tamapearl 121] 5 with respect to 100 parts by weight of pulp while stirring.
Parts by weight and stirred for 30 seconds, 1 part by weight of sulfuric acid band is added and stirred for 20 seconds, and 0.3 parts by weight of cationized starch [Oji Constarch Co., Ltd., Ace K100] is added and stirred for 10 seconds. And 0.5 parts by weight of a neutral rosin sizing agent [Arakawa Chemical Industries, Ltd., SPNT-87]
After stirring for 0 second, the fixing agent A-1 [crosslinked diallyldimethylammonium chloride polymer having a molecular weight of 680,000 (DAD
MAC)], and stirred for 20 seconds. Next, the sheet was put into a sheet machine filled with 8 L of tap water, and paper was made according to JIS P8209. The wet paper was sandwiched between three filter papers and pressed at a pressure of 490 kPa for the first time for 5 minutes and for the second time for 2 minutes. Next, it was dried at 115 ° C. for 1 minute using a rotary drum dryer. 23 ° C, 50% R
After adjusting the humidity for 24 hours in a constant temperature and humidity chamber of H, JIS P8
The Stechig sizing degree was measured according to 122. The Stöckicht sizing degree was 30 seconds. Example 2 A paper was made in the same manner as in Example 1 except that the amount of the fixing agent A-1 added was 0.005 parts by weight per 100 parts by weight of pulp, and the degree of Stigcht sizing was measured. The Steckigt sizing degree was 28 seconds. Example 3 Instead of fixing agent A-1, fixing agent A-2 [molecular weight 140
The paper was made in the same manner as in Example 1 except that 10,000 cross-linked DADMACs were used, and the degree of Stigecht sizing was measured. The Stöckicht sizing degree was 30 seconds. Example 4 A paper was made in the same manner as in Example 3 except that the amount of the fixing agent A-2 added was 0.005 parts by weight per 100 parts by weight of the pulp, and the degree of Stigcht sizing was measured. The Stekigt sizing degree was 27 seconds. Comparative Example 1 A paper was made in the same manner as in Example 1 except that the fixing agent B-1 [linear DADMAC having a molecular weight of 680,000] was used instead of the fixing agent A-1, and the Stöckigt sizing degree was measured. The Stöckicht sizing degree was 21 seconds. Comparative Example 2 A paper was made in the same manner as in Comparative Example 1 except that the amount of the fixing agent B-1 was 0.005 parts by weight per 100 parts by weight of pulp, and the degree of Stigcht sizing was measured. The Stekigt sizing degree was 17 seconds. Comparative Example 3 Fixing agent B-2 [molecular weight 140] instead of fixing agent A-1
Papermaking was performed in the same manner as in Example 1 except that 10,000 linear DADMACs were used, and the degree of Stigecht sizing was measured. The Stöckicht sizing degree was 20 seconds. Comparative Example 4 A paper was made in the same manner as in Comparative Example 3 except that the amount of the fixing agent B-2 added was 0.005 parts by weight per 100 parts by weight of the pulp, and the degree of Stigcht sizing was measured. The Steckigt sizing degree was 17 seconds. Comparative Example 5 Papermaking was performed in the same manner as in Example 1 except that fixing agent B-3 [linear dimethylamine-epichlorohydrin polymer having a molecular weight of 200,000 (DMA-Epi)] was used instead of fixing agent A-1. Then, the degree of Stekigt sizing was measured. The Stekigt sizing degree was 15 seconds. Comparative Example 6 A paper was made in the same manner as in Comparative Example 5 except that the amount of the fixing agent B-3 added was 0.005 parts by weight per 100 parts by weight of the pulp, and the degree of Stigcht sizing was measured. The Stekigt sizing degree was 16 seconds. Comparative Example 7 Papermaking was performed in the same manner as in Example 1 except that fixing agent B-4 [cross-linked DMA-Epi having a molecular weight of 50,000] was used instead of fixing agent A-1, and the degree of Stekigt sizing was measured. . The Stekigt sizing degree was 17 seconds. Comparative Example 8 A paper was made in the same manner as in Comparative Example 7 except that the amount of the fixing agent B-4 added was 0.005 parts by weight per 100 parts by weight of the pulp, and the degree of Stigcht sizing was measured. The Stekigt sizing degree was 15 seconds. Comparative Example 9 Instead of the fixing agent A-1, fixing agent B-5 [molecular weight: 200
Of polyethyleneimine (PEI)], and the papermaking was carried out in the same manner as in Example 1 to measure the degree of Stigecht sizing. The Stöckicht sizing degree was 20 seconds. Comparative Example 10 Papermaking was carried out in the same manner as in Comparative Example 9 except that the amount of the fixing agent B-5 added was 0.005 parts by weight per 100 parts by weight of pulp, and the degree of Stigcht sizing was measured. The Stekigt sizing degree was 15 seconds. Comparative Example 11 A paper was made in the same manner as in Example 1 except that the fixing agent was not added, and the degree of Stigecht sizing was measured. The Stekigt sizing degree was 15 seconds. Examples 1 to 4 and Comparative Example 1
Table 2 shows the results of Nos. To 11.

[0013]

[Table 2]

As can be seen from Table 2, some of the fixing agents used in the comparative examples show a slight size effect. However, according to the method of the present invention, 100% by weight of a crosslinked diallyldimethylammonium chloride polymer is used. It can be seen that the addition of 0.005 to 0.01 parts by weight with respect to 0.1% improves the sizing degree by about 15 seconds. Example 5 Papermaking was carried out in the same manner as in Example 1 except that the amount of the neutral rosin sizing agent added was changed to 0.4 part by weight per 100 parts by weight of pulp, and the degree of Stigcht sizing was measured. The Stöckicht sizing degree was 29 seconds. Example 6 Papermaking was carried out in the same manner as in Example 1 except that the amount of the neutral rosin sizing agent added was changed to 0.3 part by weight per 100 parts by weight of pulp, and the degree of Stekigt sizing was measured. The Stöckicht sizing degree was 10 seconds. Comparative Examples 12 and 13 Except that fixing agent B-1 was used instead of fixing agent A-1,
Papermaking was performed in the same manner as in Examples 5 to 6, and the degree of Stigecht sizing was measured. Comparative Examples 14 and 15 Except that fixing agent B-3 was used instead of fixing agent A-1,
Papermaking was performed in the same manner as in Examples 5 to 6, and the degree of Stigecht sizing was measured. Comparative Examples 16 to 17 Papermaking was carried out in the same manner as in Examples 5 to 6 except that the fixing agent was not added, and the degree of Stigecht sizing was measured. Example 5
Table 3 shows the results of Comparative Examples 1 to 6, Comparative Examples 12 to 17, Example 1, Comparative Example 1, Comparative Example 5, and Comparative Example 11.

[0015]

[Table 3]

As can be seen from Table 3, according to the method of the present invention, even if the amount of the neutral rosin sizing agent is reduced from 0.5 parts by weight to 0.3 parts by weight per 100 parts by weight of pulp, Good size effect is obtained. Example 7 The amount of the sulfuric acid band added was set at 0.
Except for using 7 parts by weight, papermaking was performed in the same manner as in Example 1,
The Stöckicht sizing degree was measured. The Stöckicht sizing degree was 30 seconds. Example 8 The amount of the sulfuric acid band added was set at 0.
Except that it was 5 parts by weight, paper was made in the same manner as in Example 1,
The Stöckicht sizing degree was measured. The Stekigt sizing degree was 15 seconds. Comparative Examples 18 to 19 Papermaking was conducted in the same manner as in Examples 7 and 8 except that the fixing agent B-1 was used instead of the fixing agent A-1, and the degree of Stigecht sizing was measured. Comparative Examples 20 to 21 Papermaking was performed in the same manner as in Examples 7 and 8 except that the fixing agent B-3 was used instead of the fixing agent A-1, and the degree of Stigecht sizing was measured. Comparative Examples 22 to 23 Except that the fixing agent was not added, papermaking was carried out in the same manner as in Examples 7 and 8, and the degree of Stigecht sizing was measured. Example 7
Table 4 shows the results of Comparative Examples 1 to 8, Comparative Examples 18 to 23, Example 1, Comparative Example 1, Comparative Example 5 and Comparative Example 11.

[0017]

[Table 4]

As can be seen from Table 4, according to the method of the present invention, even if the amount of the sulfuric acid band is reduced from 1 part by weight to 0.5 part by weight per 100 parts by weight of pulp, good sizing effect can be obtained. can get. Example 9 A paper was made in the same manner as in Example 1 except that the amount of the cationized starch added was 0.15 parts by weight per 100 parts by weight of the pulp, and the degree of Stigcht sizing was measured. The Stöckicht sizing degree was 30 seconds. Example 10 Example 1 except that no cationized starch was added.
The paper was made in the same manner as described above, and the degree of Stigecht sizing was measured.
The Steckigt sizing degree was 28 seconds. Comparative Examples 24 to 25 Papermaking was performed in the same manner as in Examples 9 to 10 except that the fixing agent B-1 was used instead of the fixing agent A-1, and the degree of Stigecht sizing was measured. Comparative Examples 26 to 27 Papermaking was performed in the same manner as in Examples 9 to 10 except that the fixing agent B-3 was used instead of the fixing agent A-1, and the degree of Stigecht sizing was measured. Comparative Examples 26 to 27 Papermaking was conducted in the same manner as in Examples 9 to 10 except that the fixing agent was not added, and the degree of stickiness was measured. Examples 9 to 10, Comparative Example 24
To 29, Example 1, Comparative Example 1, Comparative Example 5, and Comparative Example 11
Table 5 shows the results.

[0019]

[Table 5]

As can be seen from Table 5, according to the method of the present invention, a good sizing effect can be obtained even if the amount of cationized starch is reduced or not added.

[0021]

According to the method of fixing a neutral rosin sizing agent of the present invention, the sizing effect is improved because the fixing ratio of the sizing agent is increased. Therefore, not only can the amount of the sizing agent be reduced, but also the amount of the sulfuric acid band having a fixing effect of the sizing agent and the amount of the cationized starch can be reduced. And a significant contribution to the papermaking industry can be made.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hiroyuki Suzuki 3-4-7 Nishi-Shinjuku, Shinjuku-ku, Tokyo F-term (reference) in Kurita Kogyo Co., Ltd. 4L055 AA03 AC06 AG12 AG48 AG50 AG65 AG93 AG97 AG98 AH09 AH12 AH50 EA32 FA17 GA34

Claims (5)

[Claims] 1. A method for fixing a neutral rosin sizing agent, wherein a neutral rosin sizing agent and a crosslinked diallyldimethylammonium halide polymer coexist in a papermaking raw material slurry. 2. A neutral rosin sizing agent and a crosslinked diallyldimethylammonium halide polymer are simultaneously added to a papermaking raw material slurry, or a crosslinked diallyldimethylammonium halide polymer is added after the neutral rosin sizing agent is added. The method for fixing a neutral rosin sizing agent according to claim 1. 3. The method for fixing a neutral rosin sizing agent according to claim 1, wherein the neutral rosin sizing agent is an emulsion emulsified by an anionic protective colloid. 4. The amount of the crosslinked diallyldimethylammonium halide polymer added to the pulp 1 in the papermaking raw material slurry.
4. The method for fixing a neutral rosin sizing agent according to claim 1, wherein the amount is 0.0018 to 0.2 part by weight per 100 parts by weight. 5. A process for producing a neutral rosin sizing agent fixing paper, wherein a neutral rosin sizing agent and a cross-linked diallyldimethylammonium halide polymer are coexistent in a papermaking raw material slurry.