JP2001073293A - Paper sized by combined use of rosin bond type cationic polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a paper having an excellent sizing effect by sizing using a cationic copolymer-based sizing agent containing a styrene, a (meth)acrylic acid aminoalkyl ester, or the like., as constituent monomer components together with a well-known sizing agent such as a reactive sizing agent or a rosin-based sizing agent. SOLUTION: This paper is obtained by subjecting a pulp slurry to wet papermaking in the presence of both a water-dispersible or water-soluble cationic polymer, which is obtained by copolymerizing (B) a styrene with (C) an acrylic acid or an methacrylic acid aminoalkyl ester in the presence of (A) at least one kind of a rosin-based resin selected from the group consisting of rosins, fortified rosins, rosin esters and fortified rosin esters, subjecting the copolymer to a cationization treatment and a reactive sizing agent or a rosin-based sizing agent. Since the polymer is a cationic polymer in which the bulky hydrophobic bulk of a rosin ring is integrally bonded, in sizing in a combination of the polymer and the wall-known reactive sizing agent, or the like, a paper having excellent sizing effect is obtained in comparison with a polymer free from the bond.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a rosin-bonded cationic polymer, which is an alkyl ketene dimer (hereinafter referred to as AK).
D), a known reactive sizing agent such as alkenyl succinic anhydride (hereinafter, referred to as ASA), or a rosin-based sizing agent, in combination with a known sizing agent, for sizing electrophotographic paper, paper such as newsprint, Provided is a paper exhibiting an excellent sizing effect not only by acidic papermaking but also by neutral papermaking without using a sulfate band or alkali papermaking using calcium carbonate as a filler.

[0002]

BACKGROUND OF THE INVENTION Neutral papermaking has better paper strength retention than acid papermaking, and can extend the use time of felts and wires in papermaking, improving drainage of the web and improving formation. There is an advantage that the formation is improved and the paper quality is improved. Also, unlike the case of acidic papermaking, there are few problems of paper deterioration and drainage regulation, and it is advantageous in terms of water recycling.

As sizing agents for neutral papermaking, AKD,
Reactive sizing agents such as ASA are commonly used,
These materials alone have no fixing ability to pulp fibers and need to be used in combination with cationic polymers such as cationic starch and cationic polyacrylamide. Usually, the sizing of the reactive sizing agent is difficult to control in sizing and causes slippage of the paper, so there is a problem in operability and the like, and there is room for improvement in sizing.

[0004]

2. Description of the Related Art On the other hand, US Pat. No. 2,964,445 discloses a conventional sizing agent effective for neutral papermaking.
In (Prior Art 1), a copolymer of a styrene homolog and an aminoalkyl ester of acrylic acid or methacrylic acid (hereinafter the superordinate term of acrylic acid and methacrylic acid is referred to as (meth) acrylic acid) is quaternized with an alkyl halide. Disclosed are cationic cationic sizing agents. Also, JP-A-48-11
No. 407 (prior art 2) discloses a copolymer obtained by quaternizing the above copolymer with epihalohydrin instead of alkyl halide. Further, JP-A-3-16797 (Prior Art 3) discloses that, in an electrophotographic transfer paper containing a sizing agent and a calcium carbonate-based filler, the sizing agent is composed of styrenes and aminoalkyl (meth) acrylic acid. Ester (or a quaternary salt thereof) as a constituent monomer, or water-dispersible or styrenes and aminoacrylamide of (meth) acrylic acid (or a quaternary salt thereof) as a constituent monomer Disclosed are water-soluble copolymers.

[0005]

Since the sizing agents of the above prior arts 1 to 3 are both cationic polymers, the AK
It is conceivable that sizing is performed in combination with a reactive sizing agent such as D or ASA. However, as will be seen from the test examples described later, in practice, alkali paper or filler made of calcium carbonate as a filler is used. Does not provide a sufficient size effect.

The present invention relates to a neutral paper-making method using a cationic copolymer-based sizing agent containing styrenes and aminoalkyl esters of (meth) acrylic acid as constituent monomer components in combination with the reactive sizing agent and the like. Another object of the present invention is to obtain paper excellent in size effect even by alkali papermaking.

[0007]

Means for Solving the Problems In copolymerizing styrenes and aminoalkyl esters of (meth) acrylic acid, the present inventors have proposed that rosins, reinforced rosins, or rosins are added to both monomers. It has been found that when a rosin-based resin such as an ester coexists and these three components are copolymerized and quaternized, a very stable water-soluble copolymer can be obtained. Therefore, when a known reactive sizing agent such as AKD or ASA, or a known rosin sizing agent such as a strengthened rosin sizing agent is used in combination with the above water-soluble polymer to which a rosin resin is bonded, Sizing agent alone or, compared to the case of sizing using a known sizing agent in combination with the cationic polymers of the above-mentioned conventional techniques 1 to 3, excellent sizing effect by neutral papermaking or alkali papermaking. The inventors have found that paper can be obtained and completed the present invention.

[0008] That is, the present invention 1 comprises (A) rosins, reinforced rosins obtained by reacting rosins with α, β-unsaturated carboxylic acids, rosin esters obtained by reacting rosins with polyhydric alcohols, And rosins to polyhydric alcohols and α,
In the presence of at least one rosin-based resin selected from the group consisting of reinforced rosin esters obtained by reacting β-unsaturated carboxylic acids, (B) styrenes, and (C) aminoalkyl of acrylic acid or methacrylic acid A copolymerization reaction of an ester and a water-dispersible or water-soluble rosin-bonded cationic polymer cationized with a quaternizing agent or acid, and an alkyl ketene dimer, a reactive sizing agent such as alkenyl succinic anhydride, Is a paper obtained by wet-making a pulp slurry using the above method.

The present invention 2 is a rosin which is obtained by reacting the water-dispersible or water-soluble rosin-bonded cationic polymer of the above-mentioned present invention 1 with rosins and rosins with α, β-unsaturated carboxylic acids. Rosin esters selected from the group consisting of rosin esters obtained by reacting rosins with polyhydric alcohols, and reinforced rosin esters obtained by reacting rosins with polyhydric alcohols and α, β-unsaturated carboxylic acids It is a paper obtained by wet-making a pulp slurry in combination with a rosin-based sizing agent containing at least one resin as an active ingredient.

[0010] The present invention 3 is a paper characterized in that aminoacrylamide of acrylic acid or methacrylic acid is used in place of the aminoalkyl ester of acrylic acid or methacrylic acid of (C) of the present invention 1 or 2 above. is there.

A fourth aspect of the present invention is a paper obtained by wet-making the pulp slurry according to any one of the first to third aspects of the invention, wherein calcium carbonate is contained as a filler.

A fifth aspect of the present invention is a paper obtained by wet-making the pulp slurry according to any of the first to third aspects in the absence of a sulfate band.

According to a sixth aspect of the present invention, the paper of any one of the first to fifth aspects of the present invention is used as an electrophotographic paper, an ink jet paper, a newsprint,
It is a paperboard or the like.

[0014]

DETAILED DESCRIPTION OF THE INVENTION First, the present invention relates to a sizing method in which a special cationic polymer consisting of a polymer having a bulky rosin ring bonded thereto is used in combination with a known reactive sizing agent such as AKD or ASA. Secondly, in place of the reactive sizing agent, this rosin-bonded special cationic polymer was sized in combination with a known rosin-based sizing agent such as a reinforced rosin sizing agent. Papermaking.

The above-mentioned rosin-bonded cationic polymer is prepared by reacting styrenes with (a) styrene in the presence of at least one rosin-based resin selected from the group consisting of rosins, reinforced rosins, rosin esters, and reinforced rosin esters. It is produced by copolymerizing a reactive monomer of an aminoalkyl ester of (meth) acrylic acid. Therefore, the rosin-based resin may be a rosin, a reinforced rosin, a rosin ester, or a reinforced rosin ester, or may be used in combination. The rosin is a concept including tall oil rosin, gum rosin, and wood rosin, which can be used alone or in combination, and includes disproportionated rosin, polymerized rosin, hydrogenated rosin, or other chemically modified rosin. The above-mentioned reinforced rosins are obtained by reacting rosins with α, β-unsaturated carboxylic acids by a known method. In this case, the reaction temperature is about 150 to 300 ° C., and the reaction time is about 1 to 24 hours. The amount of the α, β-unsaturated carboxylic acid charged is about 20 parts by weight or less based on 100 parts by weight of the rosin. Examples of the α, β-unsaturated carboxylic acids include α, β-unsaturated carboxylic acids or acid anhydrides thereof, fumaric acid, (anhydride) maleic acid, itaconic acid, (anhydride) citraconic acid, acrylic acid, Methacrylic acid and the like can be mentioned.

The above-mentioned rosin esters are those obtained by producing a rosin and a polyhydric alcohol by a known esterification method. As the conditions for the esterification reaction, the charged ratio of rosin to polyhydric alcohol is COOH / O in terms of the hydroxyl equivalent of alcohol relative to the carboxyl equivalent of rosin.
H = 1 / 0.2-1.2, reaction temperature 150-300
C. and a reaction time of about 2 to 30 hours are appropriate. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, neopentyl glycol,
Trimethylene glycol, tetramethylene glycol,
Dihydric alcohols such as 1,3-butanediol and 1,6-hexanediol, trihydric alcohols such as glycerin, trimethylolpropane, trimethylolethane, and triethylolethane; tetrahydric alcohols such as pentaerythritol and dipentaerythritol; Alternatively, amino alcohols such as triethanolamine, tripropanolamine, triisopropanolamine, N-isobutyldiethanolamine, and N-n-butyldiethanolamine can be used alone or in combination.

The fortified rosin esters are obtained by reacting rosins with polyhydric alcohols and α, β-unsaturated carboxylic acids sequentially or simultaneously. The esterification reaction with a polyhydric alcohol and the reinforcing reaction with an α, β-unsaturated carboxylic acid are as described above. When rosins are esterified at a high temperature and then reacted with α, β-unsaturated carboxylic acids, rosins having a levopimare skeleton are reduced, isomerized into a dehydroabietic acid skeleton, and the reaction proceeds. Care must be taken because it may be difficult to do so. Conversely, after pre-reacting rosins and α, β-unsaturated carboxylic acids and then performing an esterification reaction at a high temperature, a high molecular weight polymer condensate is likely to be generated,
Care must be taken as well.

As the styrenes, styrene, α-
Methylstyrene, vinyltoluene, p-chlorostyrene and the like can be mentioned. Examples of the aminoalkyl ester of (meth) acrylic acid include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, 3-dimethylamino-2-hydroxypropyl acrylate, and 3-dimethylamino-2-hydroxy. Propyl methacrylate and the like.

The method for producing the rosin-bonded polymer is not particularly limited. Generally, a styrene as a hydrophobic monomer and an aminoalkyl ester of (meth) acrylic acid as a hydrophilic monomer are mixed with the rosin. Radical copolymerization using an initiator such as azoisobutyronitrile in an organic solvent such as benzene and isopropyl alcohol in the presence of a system resin, and after removing the solvent, adding water and having the copolymer The tertiary amino group is cationized by a conventional method to produce an aqueous solution or aqueous dispersion of the rosin-bonded cationic polymer. The mixing ratio of the rosin-based resin to both the styrenes and the aminoalkyl ester of (meth) acrylic acid is preferably 0.1 to 15.0% by weight. When the amount is less than 0.1% by weight, the function of the bulky hydrophobic component caused by the rosin-based resin is reduced, and the size effect is reduced. Conversely, when the amount exceeds 15.0% by weight, the bulky hydrophobic portion is strengthened. The chemical stability of the aqueous solution or dispersion of the rosin-bound polymer may be slightly affected. In the production of the rosin-bonded polymer, an aminoacrylamide of (meth) acrylic acid can be used instead of the aminoalkyl ester of (meth) acrylic acid.
The production method in this case is basically the same as that of the aminoalkyl ester. Examples of the aminoacrylamide of (meth) acrylic acid include dimethylaminoethyl acrylamide, dimethylaminoethyl methacrylamide, dimethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide and the like. In the polymerization reaction for obtaining the rosin-bonded polymer, an alkyl acrylate, an alkyl methacrylate, or the like may be added as a monomer component other than the constituent monomers. As the alkyl ester of (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and the like. The rosin-bound polymer is cationized with a quaternizing agent. Examples of the quaternizing agent include epihalohydrin such as epichlorohydrin, dihalohydrin, alkyl halides such as methyl chloride, ethyl chloride, ethyl bromide and butyl bromide, aromatic halides such as benzyl chloride, dihaloethylene, propylene oxide, dimethyl sulfate, and diethyl sulfate. And the like. Also, in place of the quaternizing agent, hydrochloric acid,
It can also be cationized with an inorganic acid such as sulfuric acid, a carboxylic acid such as acetic acid or propionic acid, or an organic acid such as sulfonic acid.

The rosin-bonded cationic polymer is excellent in chemical stability and has no foaming property. For this reason, when this rosin-bonded cationic polymer is used in combination with a known reactive sizing agent such as AKD or ASA, neutral papermaking in the absence of a sulfate band or alkali papermaking using calcium carbonate as a filler is used. In a very effective size effect. Further, even when used in combination with a known rosin-based sizing agent, a very effective sizing effect is exhibited not only in acidic papermaking in the presence of a sulfate band but also in neutral papermaking or alkali papermaking.
The known rosin-based sizing agent means a sizing agent containing at least one rosin-based resin selected from the group consisting of rosins, reinforced rosins, rosin esters, and reinforced rosin esters as an active ingredient, and There is no limitation on the form, such as a conversion type or an emulsion type. Incidentally, the paper of the present invention 1 is a paper obtained by adding a rosin-bonded polymer to the pulp slurry in combination with the above-mentioned known reactive sizing agent and wet-making the pulp slurry. The paper of the present invention 2 is paper wet-processed in combination with the above-mentioned known rosin-based sizing agent. The pulp fibers constituting the pulp slurry include N, which is usually used for papermaking.
Wood pulp such as BKP and LBKP, deinked pulp (DIP)
In addition, non-wood pulp such as linter pulp, hemp, bagasse, kenaf, esparto grass and straw, semi-synthetic fiber such as rayon and acetate, or synthetic fiber such as polyolefin, polyamide and polyester can be used. Needless to say, fillers, dyes, paper strength agents, retention agents, defoamers, and the like can be added to the pulp slurry as needed. Paper obtained by wet papermaking is a broad concept including printing / writing / drawing paper such as electrophotographic paper and ink jet paper, newsprint, packaging paper, tissue paper, hybrid paper, paperboard, and cardboard.

The rosin-bonded cationic polymer is not only used as an internal sizing agent, but also has a good compatibility with coating agents such as polyvinyl alcohol and oxidized starch. It is. When used as a surface sizing agent, the sizing agent is mixed with an aqueous solution of the oxidized starch or polyvinyl alcohol,
The obtained coating solution may be applied using a bar coater or the like at a basis weight suitable for the type of paper, and dried. In addition, the rosin-bonded cationic polymer of the present invention can be used in combination with known cationic polymers such as cationic starch and cationic polyacrylamide.

[0022]

[Function] When styrenes and aminoalkyl (meth) acrylate are copolymerized, if rosin-based resins such as rosins, reinforced rosins, and rosin esters are coexisted, the termination reaction of the polymerization will be rosin-based resin. It is presumed that the radical addition reaction to the rosin-based resin proceeds, including the case where a radical addition reaction to the rosin resin occurs. Therefore, the reaction product is a polymer in which bulky rosin rings are organically integrally bonded, and is a copolymer in which styrenes and aminoalkyl (meth) acrylate are merely used as constituent monomer components. It is chemically and physically different from the aforementioned prior arts 1 to 3. That is, the bonding of the rosin ring gives the polymer an appropriate molecular weight as a sizing agent and improves the water dispersibility or water solubility of the polymer. Since this rosin-bonded polymer is a cationic polymer, it functions to self-fix to anion-chargeable fiber pulp,
It also functions as a fixing aid for reactive sizing agents such as AKD and ASA that do not have self-fixing ability, and after fixing to pulp fiber, exhibits a good size effect due to the bulky hydrophobic property of the rosin ring. Conceivable.

When the rosin-bonded cationic polymer is actually used in combination with a known reactive sizing agent and a known rosin-based sizing agent as shown in the test examples described below, Provides a much better size effect than sizing alone. Secondly, an excellent sizing effect is exhibited even when sizing is performed using a known sizing agent and the sizing agents of the above-mentioned conventional techniques 1 to 3 in combination. For example, in alkaline papermaking containing calcium carbonate as a filler, the sizing agents of the prior arts 1 to 3 have no chemical relationship with calcium carbonate, but as described above, the cationic polymer used in the present invention is Since the rosin ring is organically bonded to the polymer, a reaction occurs between the carboxyl group of the rosin ring and calcium carbonate, and as water insolubilizes, the N cations in the molecule cause the fiber pulp to form a fiber. It is believed that fusing is further accelerated and this is one factor that makes a difference in effectiveness from the prior art cationic polymers. Note that such a function is the same even when aminoacrylamide of (meth) acrylic acid is used instead of aminoalkyl ester of (meth) acrylic acid.

[0024]

As shown in the test examples described below, rosins,
A rosin-bonded type in which styrenes and aminoalkyl esters of (meth) acrylic acid are reacted as constituent monomer components in the presence of reinforced rosins, rosin esters, or a rosin-based resin composed of reinforced rosin esters. When the cationic polymer is sized in combination with a known reactive sizing agent such as AKD and ASA, the size of the reactive sizing agent is much better than that of the sizing alone, in neutral papermaking or alkali papermaking. The effect and inkjet suitability can be imparted to various types of paper such as electrophotographic paper, inkjet paper, newsprint, and paperboard. This rosin-bonded cationic polymer is expected to function as a fixing aid for the reactive sizing agent, as well as self-fixing to the pulp fiber. In other words, the sizing effect is synergistically enhanced between the two sizing agents. There is a function to do. In addition, the combined use of this rosin-bonded polymer and a known reactive sizing agent,
Prior art 1 which is a copolymer having only an aminoalkyl ester of (meth) acrylic acid as a constituent monomer component
The sizing effect and ink jet suitability are superior to the case where the cationic polymer No. 3 is used in combination with a sizing agent.
That is, the rosin-bonded cationic polymer of the present invention is more effective than the cationic polymers of the above-described prior arts 1 to 3 in the effect of enhancing the sizing property for the reactive sizing agent (or a function as a fixing aid). The advantage is also remarkable. On the other hand, such a function of enhancing the size of the rosin-bonded cationic polymer is basically achieved even when a known rosin-based sizing agent such as an enhanced rosin sizing agent is used in place of the reactive sizing agent. The same is true. Therefore, a paper having an excellent size effect can be obtained not only by acidic papermaking but also by neutral papermaking or alkali papermaking.

[0025]

EXAMPLES The following are examples of the production of rosin-bonded cationic polymers, examples of the sizing test of electrophotographic paper made by using the rosin-bonded polymer of the production example in combination with AKD in the presence of calcium carbonate, and Examples of sizing tests of hand-made paper made by using the rosin-bonded polymer in combination with a known rosin-based size will be sequentially described. Further, “parts” and “%” in the following examples and test examples refer to “parts by weight” and “% by weight” unless otherwise specified. In addition, the present invention is described in the following examples,
It is needless to say that the present invention is not restricted to the test examples and the like, and can be arbitrarily modified within the technical idea of the present invention.

First, in Production Examples 1 to 9 of the following rosin-bonded cationic polymer, Production Example 1 is an example in which rosin was reacted with an aminoalkyl ester of methacrylic acid and styrene, and Production Example 2 was a production example 1. Example in which rosin was replaced with reinforced rosin as a basis, Production Example 3 was an example in which rosin ester was substituted based on Production Example 1, Production Example 4 was an example in which rosin ester was substituted based on Production Example 1, and Production Example 5 was An alternative example of the quaternizing agent based on Production Example 1, Production Example 6 is an example in which a reinforced rosin ester, an aminoalkyl ester of acrylic acid, and styrene were reacted, and Production Example 7 was based on Production Example 6 with methacrylic acid. An example using an aminoalkyl ester, Production Example 8 is an example using aminoacrylamide of acrylic acid based on Production Example 6, and Production Example 9 is Production Example 6.
This is an example in which an acrylic ester is added based on the above. Comparative Production Examples 1 and 2 are blank examples of rosin-based resin, and are based on the above-mentioned prior arts 1 to 3.

<< Production Example 1 >> Rosin 20 was placed in a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel.
g, styrene 70 g, N, N-dimethylaminoethyl methacrylate 24 g, and isopropyl alcohol 70 g were charged and heated to the reflux temperature to dissolve. Next, a solution of 2 g of azoisobutyronitrile in 30 g of isopropyl alcohol was dropped into the reaction system over 1 hour from the dropping funnel, and further kept at the same temperature for 5 hours to complete the reaction.
Next, 70 g of isopropyl alcohol was distilled off from the obtained reaction solution, and 9 g of acetic acid and 100 g of water were dropped and dissolved. Then, 380 g of water and epichlorohydrin 1
By adding 4 g and performing a reaction at 80 to 85 ° C. for 3 hours, a rosin-bonded cationic polymer was obtained.

<< Production Example 2 >> A rosin-bonded cationic polymer was reacted in the same manner as in Production Example 1 except that 20 g of maleated rosin (maleization ratio: 8%) was used instead of rosin. Obtained.

<< Production Example 3 >> Instead of rosin, rosin ester (glycerin esterification rate: OH / COOH = 0.
5) The reaction was carried out in the same manner as in Production Example 1 except that 20 g was used to obtain a rosin-bonded cationic polymer.

Production Example 4 The same procedure as in Production Example 1 was carried out except that 20 g of maleated rosin ester (maleization ratio: 8%, glycerin esterification ratio: OH / COOH = 0.5) was used as the rosin ester. The reaction was carried out to obtain a rosin-bonded cationic polymer.

<< Production Example 5 >> A rosin-bonded cationic polymer was obtained in the same manner as in Production Example 1, except that 19 g of benzyl chloride was used instead of epichlorohydrin as a quaternizing agent.

<< Production Example 6 >> In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel, 100 g of isopropyl alcohol and maleated rosin ester (maleation ratio: 8%, glycerin esterification ratio: OH) / CO
(OH = 0.5) 20 g was charged and heated to the reflux temperature to dissolve. Next, from the dropping funnel, 70 g of styrene,
A mixed solution comprising 22 g of N, N-dimethylaminoethyl acrylate and 2 g of azoisobutyronitrile was dropped into the reaction system over 2 hours, and further kept at the same temperature for 5 hours,
The reaction was completed. Next, 70 g of isopropyl alcohol was distilled off from the obtained reaction solution, and 9 g of acetic acid and 100 g of water were further added to dissolve. Then, 380 g of water
And 14 g of epichlorohydrin, and reacted at 80 to 85 ° C. for 3 hours to obtain a rosin-bonded cationic polymer.

<< Production Example 7 >> 28 g of N, N-diethylaminoethyl methacrylate as an aminoalkyl ester
A rosin-bonded cationic polymer was obtained by the same reaction as in Production Example 6 except that was used.

<< Production Example 8 >> Instead of aminoalkyl ester, N, N-dimethylaminopropylacrylamide 2
A rosin-bonded cationic polymer was obtained by reacting in the same manner as in Production Example 6 except that 2 g was used.

Production Example 9 A rosin-bonded cationic polymer was reacted in the same manner as in Production Example 6 except that the amount of styrene was 56 g, and 11 g of butyl acrylate was newly added as the third component of the monomer. A coalescence was obtained.

Comparative Production Example 1 100 g of isopropyl alcohol was charged into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel. After heating to the reflux temperature, 78 g of styrene was added from the dropping funnel. A mixed solution consisting of 24 g of N, N-dimethylaminoethyl methacrylate and 2 g of azoisobutyronitrile was dropped into the reaction system over 2 hours, and further kept at the same temperature for 5 hours to complete the reaction. Next, 75 g of isopropyl alcohol was distilled off from the obtained reaction solution, and 9 g of acetic acid and 420 g of water were further removed.
g was added and dissolved to obtain a cationic polymer.

<< Comparative Production Example 2 >> 14 g of epichlorohydrin was further added to the sizing agent obtained in Comparative Production Example 1, and the reaction was carried out at 80 to 85 ° C. for 3 hours to obtain a cationic polymer.

Therefore, the cationic polymer of each of Production Examples 1 to 9 and Comparative Production Examples 1 and 2 was used in combination with AKD, and subjected to alkali paper making using calcium carbonate as a filler.
To 9 and Comparative Examples 1 to 3, and a sizing test was performed. << Examples of Size and Inkjet Suitability Tests of Electrophotographic Paper Sized Together with Rosin-Binding Cationic Polymer and AKD >> Bulled Pulp Slurry (LBKP: NBKP
= 8: 2, freeness: 400 mL), and 5% (based on the absolute dry pulp weight) of calcium carbonate (TP-121; manufactured by Okutama Kogyo Co., Ltd.) was added as a filler, and then the above Production Examples 1 to 9 and Comparative Production Example 1 were added. 2 were added in the amounts shown in FIG. 1 and the cationic starch (Neotack 40) was added.
T; Japan Food Processing Co., Ltd.) and 0.5% of an AKD-based sizing agent (Harsize AK-720H; Harima Chemicals, Inc.). Further, 0.02% of colloidal silica (BMA-780; manufactured by Nissan Eka Chemicals) was added as an inorganic retention agent. Next, a handmade paper having a basis weight of 60 g / m ² was prepared using a handmade tester (TAPPI standard sheet machine) according to a conventional method, and then 0.8 g of oxidized starch (MS-3800; manufactured by Japan Food Processing Co., Ltd.). / M ² and sodium chloride in 0.1
Each of the electrophotographic papers of Examples 1 to 9 and Comparative Examples 1 and 2 was manufactured as shown in FIG. 1 by applying each under the condition of 5 g / m ² . Further, based on Example 1 described above, Comparative Example 3 was made using a sheet sized only with the AKD sizing agent alone without using the rosin-bonded cationic polymer.
The pH at the time of adding various additives and at the time of papermaking was 7.3.

Each of the obtained papers was left in a constant temperature / humidity room at a temperature of 20 ° C. and a humidity of 65% for one day immediately after the paper was made, and was conditioned by the Steckigt method (JIS P8122). The sizing degree (second) was measured for each addition amount. Since the electrophotographic paper also serves as an inkjet paper, an inkjet suitability test was performed in the following manner.
That is, using an ink jet printer (BJC-400J; manufactured by Canon Inc.), a pattern of horizontal ruled lines was printed on each sheet after humidity control, and the degree of bleeding was evaluated on a five-point scale. According to this evaluation criterion, the better the degree of bleeding approaches 5 and the worse the degree of bleeding approaches 1, the practical level is generally 3.5 or more, and the practicality is poor if it is lower than 3. means.

FIG. 1 shows the test results. Under the same addition amount of the sizing agent, it was confirmed that the degree of Stekigt sizing of Examples 1 to 9 was larger than that of Comparative Examples 1 to 3 both immediately after papermaking and after moisture conditioning. In particular, the size effect of Examples 1 to 9 is remarkable as compared with Comparative Example 3 sized only with an AKD-based sizing agent, and compared with Comparative Examples 1 and 2 in which both a cationic polymer of the prior art and AKD were sized together. Even showed excellent size effect. In all of Examples 1 to 9, the degree of Stigecht sizing was greater after humidity conditioning than immediately after papermaking. This is probably because the rosin-bonded cationic polymer acts as a fixing aid to promote the fixing reaction of AKD to pulp fibers. On the other hand, with respect to inkjet suitability, Examples 1 to 9 were confirmed to be superior to Comparative Examples 1 to 3 under the same addition amount of the sizing agent.
In particular, even when the addition amount of the cationic polymer used in combination with AKD is as small as 0.2%, Examples 1 to 9 are evaluated as 3.5 or more, while Comparative Examples 1 and 2 are evaluated as 2. 5 or less, and when the addition amount is 0.4%, Examples 1 to 9
In comparison with Comparative Examples 1-2, the evaluation was 3.5.
It was below. Incidentally, the inkjet suitability evaluation of Comparative Example 3 was 1.5.

From this, paper sized together with a rosin-bonded cationic polymer and an AKD sizing agent is
In alkaline paper making using calcium carbonate as a filler, A
Demonstrates superior sizing effect and ink jet suitability as compared to paper sized solely with KD-based sizing agent and paper sized together with the cationic polymers of Prior Art 1 to 3 and AKD-based sizing agent. Was revealed. It was also confirmed that the rosin-based resin to be bound exhibited the same level of size and ink jet suitability regardless of the type of rosin, reinforced rosin, rosin ester, or reinforced rosin ester. In particular, when sizing a combination of a cationic polymer of a system having a styrene and an aminoalkyl ester of (meth) acrylic acid or aminoacrylamide as a constituent monomer together with an AKD sizing agent, Examples 1 to 9 and Comparative Examples 1 to From the comparison with 2, the presence or absence of a bulky rosin ring in the polymer greatly affects the sizing properties of paper and inkjet suitability. It turned out to be a significant advantage.

In the above test examples, the sizing properties of paper obtained by sizing a rosin-bonded cationic polymer in combination with an AKD sizing agent were examined. In the following test examples, a known rosin-based cationic polymer was used in place of the AKD sizing agent. A sizing test was performed on the paper obtained by the combined sizing using a sizing agent. << Example of sizing test of hand-made paper sized together with rosin-bonded cationic polymer and rosin-based sizing agent >> 2.0% sulfuric acid band in pulp slurry (freeness: 380 mL) of beaten cardboard and used magazine paper , A polyacrylamide-based paper strength agent (Harmide EX-310H;
0.3% rosin-based sizing agent (Harima NES)
-745; manufactured by Harima Kasei Co., Ltd.), and each cationic polymer of Production Examples 2 to 3, 6 and 9 and Comparative Production Examples 1 and 2 was added to 0.7% as shown in FIG. 1% was added. Further, a polyacrylamide-based retention agent (DR-
After adding 0.02% of 7300 (manufactured by Hymo Co.), a hand-made paper (for corrugated cardboard liner) having a basis weight of 40 g / m ² was manufactured using a hand-made tester (TAPPI standard sheet machine) according to a conventional method. As shown in FIG.
13 and Comparative Examples 4 and 5. In addition, the tenth embodiment
Comparative Example 6 was based on the above, but using only the rosin-based sizing agent alone without using the rosin-bonded cationic polymer. The pH at the time of addition of various additives and at the time of papermaking was 6.5. For each of the obtained liner papers, the sizing degree (second) after humidity control was measured under the same conditions as in the above Test Example.

FIG. 2 shows the test results. Example 10
It was confirmed that the degree of Stekigt of No. 13 was larger than Comparative Examples 4 to 6. From this, the rosin-bonded cationic polymer is not only used in combination with the AKD sizing agent, but also in combination with the known rosin sizing agent.
(Sizing in the presence of a sulfate band) can also give an excellent size effect to the paper, and the rosin-based resin to be bound can be reinforced rosins, rosin esters, reinforced rosin esters, etc. It was revealed that they exhibited the same level of size.

[Brief description of the drawings]

FIG. 1 is a chart showing the results of sizing and ink jet suitability tests on electrophotographic paper sized together with each cationic polymer and an AKD sizing agent of Production Examples and Comparative Production Examples.

FIG. 2 is a table showing the results of a sizing test on liner paper sized together with each cationic polymer and a rosin-based sizing agent of Production Examples and Comparative Production Examples.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4L055 AG11 AG12 AG40 AG41 AG50 AG63 AG71 AG73 AG92 AH01 AH12 AH13 AH50 FA17 GA06 GA09 GA11 GA16 GA34

Claims (6)

[Claims] (A) Rosins, fortified rosins obtained by reacting α, β-unsaturated carboxylic acids with rosins, rosin esters obtained by reacting polyhydric alcohols with rosins, and rosins (B) styrenes and (C) acrylic in the presence of at least one rosin-based resin selected from the group consisting of reinforced rosin esters obtained by reacting polyhydric alcohols with α, β-unsaturated carboxylic acids. A water-dispersible or water-soluble rosin-bonded cationic polymer obtained by a copolymerization reaction of an acid or an aminoalkyl ester of methacrylic acid with a quaternizing agent or an acid, and an alkyl ketene dimer, alkenyl succinic anhydride Paper made by wet-making pulp slurry in combination with a reactive sizing agent such as 2. A water-dispersible or water-soluble rosin-bonded cationic polymer according to claim 1, wherein the rosin is a rosin, and the rosin is reacted with an α, β-unsaturated carboxylic acid. Rosin esters obtained by reacting polyhydric alcohols, and at least one rosin resin selected from the group consisting of rosin esters obtained by reacting rosins with polyhydric alcohols and α, β-unsaturated carboxylic acids. Paper obtained by wet-making a pulp slurry in combination with a rosin-based sizing agent containing as an active ingredient. 3. A paper characterized in that an aminoacrylamide of acrylic acid or methacrylic acid is used in place of the aminoalkyl ester of acrylic acid or methacrylic acid according to claim 1 or 2 (C). 4. A paper made by wet-making the pulp slurry according to claim 1, wherein the pulp slurry contains calcium carbonate as a filler. 5. A paper obtained by wet-making the pulp slurry according to claim 1 in the absence of a sulfuric acid band. 6. The paper according to claim 1, wherein the paper is electrophotographic paper, ink-jet paper, newsprint, paperboard, or the like.