JPH0657146A - Paper size composition - Google Patents

Abstract

PURPOSE:To obtain a rosinous diester excellent as a size for neutral papermaking by reacting a rosin with a dihydric alcohol and an alpha,beta-unsaturated carbonyl compound successively or simultaneously, CONSTITUTION:A rosin (e.g. gum rosin) is prereacted with a dihydric alcohol (e.g. ethylene glycol) and an alpha,beta-unsaturated carbonyl compound (e.g. maleic acid) successively or simultaneously at a temperature below the boiling point of the dihydric alcohol, usually 150-200 deg.C, and further reacted at 225-280 deg.C to obtain a size for neutral papermaking based on a rosinous diester containing a dicarboxylic acid (anhydride) group and represented by the formula (wherein R1 is a residue of rosin acid or a residue of maleopimaric acid; R2 is a residue of a dihydric alcohol; and R, is a residue of maleopimaric acid). The reaction product has 15-40wt.% of a component of a molecular weight of 290-315, 10-35wt.% of a component of a molecular weight of 390-420, 1-25wt.% of a component of a molecular weight of 580-660 and 20-50wt.% of a component of a molecular weight of 670-880.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sizing agent for papermaking, and more particularly to an internally added sizing agent which is extremely effective in papermaking in a neutral to weakly acidic range and a method for producing the same.

[0002]

2. Description of the Related Art Rosin-based sizing agents have been widely used as paper sizing agents. The size development of this rosin-based sizing agent is due to the fact that the sulfate band used as an auxiliary agent acts as a retention agent and a hydrophobizing agent for the rosin-based sizing agent. Since this sulfuric acid band becomes acidic when dissociated, the rosin-based sizing agent was used in the acidic range. However, in recent years, the durability problem of acidic paper and calcium carbonate as a coating color pigment for printing paper have become widespread, and along with the increase in the content of calcium carbonate in waste paper, there is an increasing trend to manufacture paper with a neutral type. Therefore, it is desired to make paper in a neutral to weakly acidic range, but conventional rosin emulsion sizing agents mainly use so-called fortified rosin modified with α, β-unsaturated dibasic acid using an anionic surfactant. In the system as described above, especially the papermaking pH is 6.5.
As a result, the size effect is significantly reduced. Therefore, in order to obtain a predetermined sizing degree, the amount of sizing agent has to be increased, but if this is done, not only the excess sizing agent is used, but the cost rises, but also foaming in the papermaking system, generation of pitch, etc. Inconvenience in operation occurs, and the paper quality is also adversely affected. Under these circumstances, alkylketene dimer (AKD) -based sizing agents, especially as neutral paper sizing agents,
Alkenyl succinic anhydride (ASA) -based sizing agents are widely used, but both AKD and ASA are reactive sizing agents with cellulose, so there is a problem in stability. That is,
The above AKD and ASA are used as a dispersion in which a cationic starch or the like is used as a protective colloid, but the stability of the dispersion of these reactive sizing agents is poor, and when they are accumulated in a papermaking system, they become tacky due to the destruction of the dispersion. The number of papermaking tools has increased, causing a serious problem in terms of workability such as stains on papermaking tools, and improvement is desired. Above, A
Recently, while the improvement of KD and ASA type sizing agents is being considered,
A rosin-based neutral sizing agent has been proposed. As examples thereof, JP-A-62-250297 and JP-A-63-120
Those described in 198, Japanese Examined Patent Publication No. 2-36629 and the like are known.

[0003]

By the way, JP-A-62-62
No. 250297 and Japanese Patent Publication No. 2-36629 use an aqueous dispersion containing a specific α, β unsaturated dibasic acid-modified rosin ester. In JP-A-62-25029, C.I. H. It is an aqueous dispersion containing an α, β-unsaturated dibasic acid-modified rosin ester of a polyhydric alcohol consisting of O, but the size effect is significantly reduced when sizing at a papermaking pH of 7 or more, and it is a neutral paper. It cannot be said that the sizing agent is a sufficient sizing agent. On the other hand, Special Fairness 2-
The invention described in 36629 is a British Patent No. 859,7.
No. 87 is a mixture of alkanolamine ester of toughened rosin and toughened rosin, the size effect of which only results from the presence of the toughened rosin, ie the alkanolamine ester of rosin does not impart sizing.
It is described that the partial amino alcohol ester of rosin is characterized by sizing near neutral by modifying with α, β-unsaturated dibasic acid. This is α, β-in the rosin part of the rosin ester of amino alcohol.
Unsaturated dibasic acid is introduced, and it is understood that this shows a size developing effect. Furthermore, JP-A-63-120198
The invention described in 1) is a reinforced rosin and (meth) acrylic acid alkyl ester and / or styrene compound and (meth)
A rosin emulsion sizing agent consisting of an acrylic acid alkylaminoalkyl ester or a copolymer with an alkylaminoalkylamide, but this sizing agent has a difficulty in sizing in the neutral range, and is a size for neutral paper. Not enough as a drug. Therefore, in view of such circumstances, it is an object of the present invention to provide a good sizing agent which is excellent in stability and particularly has a quick start-up in a neutral region, and a method for producing the same.

[0004]

The present inventors have found that a) rosins, b) specific dihydric alcohols, and c) α, β-unsaturated carbonyl compounds with respect to b) relative to the carboxyl group equivalent of a). When the reaction product obtained by sequentially or simultaneously reacting is used as a sizing agent at a charging ratio such that the ratio of hydroxyl group equivalent of 0.2 to 1.5, excellent effects for neutral papermaking are obtained. As a result of further finding out that the reaction product contributes to the size effect in neutral papermaking in the reaction product, it was found to be a dileonate of a dihydric alcohol, rosin and maleopimaric acid, and to complete the present invention. I arrived. That is, the present invention has the following formula (1)

Embedded image (R1 represents a rosin acid residue or a maleopimaric acid residue, R2 represents a dihydric alcohol residue, and R3 represents a maleopimaric acid residue.) A neutral papermaking sizing agent containing a diester of a rosin-based substance having a group as a main component. The compound of the above formula 1 is produced by sequentially or simultaneously reacting a) rosins, b) dihydric alcohols and c) α, β-unsaturated carbonyl compounds. In particular, a) rosins, b) dihydric alcohols and c)
When the α, β-unsaturated carbonyl compounds are reacted sequentially or simultaneously, b) relative to the carboxyl group equivalent of a)
The hydroxyl equivalent ratio of COOH / OH = 1 / 0.2
The amount of α, β unsaturated carbonyl compound added is preferably 2 to 20 parts by weight per 100 parts by weight of rosins. The rosin is selected from the group consisting of gum rosin, tall oil rosin and wood rosin 1
One kind or two or more kinds are selected. Examples of the dihydric alcohol include ethylene glycol, propylene glycol,
It is preferable to select one or two selected from the group consisting of neopentyl glycol and hydrogenated bisphenol A, particularly ethylene glycol and propylene glycol, which are dihydric alcohols having a boiling point of 210 ° C. or less. The α, β-unsaturated carbonyl compound is selected from the group consisting of maleic acid and maleic anhydride. By the way, the reaction between the low-boiling dihydric alcohol and the rosin has not been examined by a reaction method which is industrially efficient than the conventional one. The esterification reaction of a rosin with a dihydric alcohol having a boiling point of 220 ° C or lower is 200 to 210 ° C.
You have to react for a long time in the vicinity. Also, 230 ℃
When the reaction is carried out at the above high temperature, the low boiling point dihydric alcohol is removed out of the system together with the reaction distilled water, and the loss increases. When α, β-unsaturated carbonyl compounds are reacted with rosins after the esterification reaction at high temperature, rosins having a levopimaric acid skeleton are decreased, and isomerization occurs in the dehydroabietic acid skeleton. Therefore, the reaction becomes extremely difficult to proceed, which is not preferable. On the other hand, the α, β-unsaturated carbonyl compound and the rosin are reacted in advance,
Even if the reaction is carried out at around 210 ° C., a large amount of polymer condensate having a MW of 1000 or more is produced, which is not preferable in terms of emulsification and size. Therefore, as a result of diligent research, a) rosins, b) dihydric alcohols, and c) α, β-unsaturated carbonyl compounds were sequentially or simultaneously preliminarily maintained at a temperature not higher than the boiling point of the dihydric alcohol, usually at 150 to 200 ° C. After the reaction, the reaction temperature was 225 ° C to 280 ° C to synthesize a reaction product having a molecular weight of 1000 to 500. That is, as shown in FIG. 1, in the first step, a) rosins, b) dihydric alcohols, and c) α, β-unsaturated carbonyl compounds are sequentially or simultaneously preliminarily heated at 150 to 200 ° C. When reacted, the compounds represented by formula 6 to formula 10 shown in FIG. 2 are obtained. This reaction includes maleic anhydride represented by formula 4, a Diels-Alder addition reaction between maleic acid and rosin represented by formula 3, and maleic anhydride represented by formula 4.
It is considered that the half ester formation between maleic acid and the dihydric alcohol represented by the formula 5 is progressing in parallel, which suppresses the distillation of the dihydric alcohol. Next, in the second step shown in FIG. 3, when the reaction is carried out at a reaction temperature of 225 ° C. to 280 ° C., the esterification product of the low boiling point dihydric alcohol and maleic anhydride or maleic acid reacts with rosin at 220 ° C. or higher. In the process, the ester portion with maleic acid is cleaved to form a 5-membered ring anhydride, which is stabilized by the ester formation of rosin with a tertiary carboxylic acid. That is,
In this reaction, the compound produced is maleopimaric acid represented by formula 6, dihydric alcohol of dihydric alcohol represented by formula 9 and rosin, dihydric alcohol of dihydric alcohol represented by formula 11 or 12 and diresinate of maleopimaric acid represented by formula 8 The main product is diresinate of dihydric alcohol and maleopimaric acid represented by
0 or more polyester is produced. This mixed reaction product contains 15 to 40% of components having a molecular weight of 290 to 315,
10-35% of components with molecular weight 390-420, molecular weight 5
80 to 660 component is 1 to 25%, molecular weight 670 to 88
The component of 0 shows a molecular weight distribution of 20 to 50%, but the component particularly contributing to the size effect in neutral papermaking is represented by the above formula 1
A compound represented by formula 2, that is, 2 represented by formula 11 or 12
It is a diresinate of a polyhydric alcohol, rosin and maleopimaric acid, and when produced by the method of the present invention, it has been found that the reaction product contains at least 20% or more effective amount in neutral papermaking in the reaction product (Fig. 4). reference). On the other hand, the conventional method hardly contains the above active ingredient (see FIG. 5). Various sizing agents can be prepared using the above active ingredients. The reaction product may be used as it is to adjust the sizing agent. In that case, the following formula (2) is used based on the weight of the mixture.

Wherein R is a C10-C24 alkylphenol group or a linear or branched alkyl group, n is an integer of 6-20, and X or Y is H or SO ₃ M.
And M is sodium, potassium, or an ammonium group) 1 to 10% by weight of the specific surfactant represented by
When the solid content concentration is 20 to 60% by weight, a papermaking sizing agent having excellent emulsification properties and storage stability can be obtained. In particular, when the surfactant represented by the above formula 2 is used, it is preferable to contain 0.5 to 10% by weight of casein. This is because the emulsion stability is further improved. Specific examples of the surfactant represented by the above formula 2 include Aerosol A-103 manufactured by American Cyanamid (the above formula (2)
In which R is an alkylphenol), and Softanol MES-12 manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd. (corresponding product in which R is a higher secondary alcohol in the above formula (2)). Further, the solid content of the reaction product is 80 to
A styrene- (meth) acrylic acid type monomer copolymer partially saponified or completely saponified product 1 to 20 parts by weight is dispersed in water to 99 parts by weight, and a solid content concentration is 20 to 60% by weight.
In that case, a neutral sizing agent for papermaking which has good emulsifying property and sizing property, has no foaming during papermaking, and has excellent operability can be obtained. Here, the partially saponified or completely saponified copolymer of styrene- (meth) acrylic acid-based monomer means that the content of styrene-based monomer is 15 to 40% by weight and the content of (meth) acrylic acid ester-based monomer is 5 to 40%. Wt%, (meta)
A partial saponification or complete saponification product of a copolymer having an acrylic acid monomer content of 25 to 65% by weight and other monomers content of 0 to 15% by weight, and having a weight average molecular weight of 5,000 to 500,000. Specific examples thereof include styrene, vinyltoluene, α-methylstyrene and the like, and one kind or several kinds can be used.
Specific examples of the (meth) acrylic acid ester-based monomer include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, Stearyl methacrylate and the like can be given as a typical example, and one kind or several kinds can be used. A specific example of the (meth) acrylic acid monomer is acrylic acid or methacrylic acid, and one kind or two kinds can be used. Other monomers include styrene sulfonic acid, sodium styrene sulfonate, polyoxyethylene allyl nonyl phenyl ether sulfate, ammonium salt of polyoxyethylene allyl nonyl phenyl ether sulfate, acrylamide, acrylonitrile, maleic anhydride, maleic acid, fumaric acid. , Itaconic acid, etc. are mentioned as typical examples, and one or several kinds can be used. The styrene- (meth) acrylic acid copolymer partially saponified product or completely saponified product may be produced by a hydrocarbon-based solvent such as toluene or xylene, a ketone such as methyl ethyl ketone, or an alcohol solvent such as isopropyl alcohol or butyl alcohol. Solution polymerization using a peroxide type or azo type polymerization initiator, and saponification with an alkali such as Na, K or ammonia.
A method of performing water solubilization and solvent removal, a method of performing emulsion polymerization using a persulfate or the like as a polymerization initiator, and then saponifying with an alkali such as Na, K or ammonia, and solubilizing water can be used. Further, the solid content of the reaction product is 60 to 95.
Copolymer of a cationic vinyl monomer and an aromatic vinyl monomer, a cationic vinyl monomer and a (meth) acrylic acid ester, or a cationic vinyl monomer, an aromatic vinyl monomer and a (meth) acrylic acid ester, based on parts by weight. When 5 to 95 parts by weight of (emulsifier polymer) is dispersed in water and the solid content concentration is 20 to 60% by weight, a neutral papermaking sizing agent having an excellent sizing effect can be obtained. As the above-mentioned emulsifier polymer, especially for a cationic vinyl monomer and / or (meth) acrylic acid ester,
At least one of rosin acid, α, β unsaturated carbonyl compound addition rosin acid or rosin ester 0.1 to 15
It is preferable to use a copolymerized product in the presence of mol% in terms of emulsifying property and size property. As a specific example thereof, a basic monomer having a tertiary amino group is suitable as the cationic vinyl monomer, and examples thereof include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and dimethylaminopropyl ( (Meth) acrylate, diethylaminopropyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide,
Examples thereof include dimethylaminopropyl (meth) acrylamide and diethylaminopropyl (meth) acrylamide. In addition, salts of these basic monomers with inorganic or organic acids can also be used. Further, a quaternary ammonium salt obtained by reacting the above basic monomer with a quaternizing agent such as methyl chloride, benzyl chloride, dimethylsulfate, epichlorohydrin, or dimethyldiallylammonium chloride can also be used.
Styrene or its derivative can be used as the aromatic vinyl monomer. Specific examples thereof include styrene, α-methylstyrene, vinyltoluene and the like. The (meth) acrylic acid ester is an ester of acrylic acid and / or methacrylic acid, and specific examples thereof include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl acrylate. Examples thereof include ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate. As rosin acid, gum rosin, wood rosin, tall oil rosin, etc. can be used, and as α, β unsaturated carbonyl compound-added rosin,
Maleated rosin, fumarized rosin, acrylated rosin and the like can be used, and as rosin esters, rosin ethylene glycol ester, rosin propylene glycol ester, rosin glycerin ester, maleinized rosin ethylene glycol ester, maleated rosin Rosin propylene glycol ester, maleated rosin glycerin ester and the like can be used. Either one of the aromatic vinyl monomer and the (meth) acrylic acid ester can be used, or both can be used in combination. 0.1 to 15 mol of these cationic vinyl monomer and aromatic vinyl monomer and / or (meth) acrylic acid ester with respect to the cationic vinyl monomer, aromatic vinyl monomer and / or (meth) acrylic acid ester. % Rosin acid or α, β
Unsaturated carbonyl compounds are dissolved in a solvent in the presence of rosin acid and rosin ester, and heated to react in the presence of a catalyst for copolymerization. After the reaction is completed, the solvent is distilled off, water is added to disperse the water, and the water is solubilized to obtain an emulsifier polymer.

[0005]

EXAMPLES Examples of the present invention will be described below. The following examples illustrate the invention but do not limit it in any way. In the following description, “part” means “part by weight” unless otherwise specified.

Synthesis of Rosin Derivative Synthesis Example 1 A 1000 CC four-necked flask equipped with a stirrer, a thermometer, a water divider, a cooling pipe and a nitrogen gas introduction pipe was charged with tall oil rosin (acid value 170 ) 700 parts to 160
Dissolve by heating to ℃. At this temperature, 40.3 parts by weight of propylene glycol are charged. (COOH: OH = 1: 0.9) Maleic anhydride 84 at 160 ° C. after the completion of the charging.
Prepare the department. After the maleic anhydride charge is completed, the temperature is raised to 250 ° C. over 2 hours. The reaction is performed for 8 hours while dehydrating at 250 ° C. The acid value of the obtained resin is 14
It was 1.5.

Synthesis Example 2 700 parts of tall oil rosin (acid value 170) was introduced into a four-neck flask for 1000 CC equipped with a stirrer, a thermometer, a water divider, a cooling pipe and a nitrogen gas introduction pipe under introduction of nitrogen gas. 160
Dissolve by heating to ℃. At this temperature, 24.2 parts by weight of propylene glycol are charged. (COOH: OH = 1: 0.3) Maleic anhydride 84 at 160 ° C. after the completion of the charging.
Prepare the department. After the completion of the maleic anhydride charging, the temperature is raised to 260 ° C. over 2 hours. The reaction is performed for 8 hours while dehydrating at 260 ° C. The acid value of the obtained resin is 168.
Met.

Synthesis Example 3 A 1000 CC four-necked flask equipped with a stirrer, a thermometer, a water separator, a cooling pipe and a nitrogen gas introducing pipe was charged with 700 parts of tall oil rosin (acid value 170) under introduction of nitrogen gas. 160
Dissolve by heating to ℃. At this temperature, 72.5 parts by weight of propylene glycol are charged. (COOH: OH = 1: 0.9) Maleic anhydride 10 at 160 ° C. after completion of charging
Prepare 9.9 copies. After the maleic anhydride is charged, the temperature is raised to 240 ° C. over 2 hours. The reaction is performed for 8 hours while dehydrating at 240 ° C. The acid value of the obtained resin was 100.7.

Synthesis Example 4 700 parts of tall oil rosin (acid value 170) was introduced into a four-neck flask for 1000 CC equipped with a stirrer, a thermometer, a water separator, a cooling pipe and a nitrogen gas introduction pipe under nitrogen gas introduction. 160
Dissolve by heating to ℃. At 160 ° C., 84 parts of maleic anhydride are charged. After completion of the maleic anhydride charging, 200
The temperature is raised to ℃ and the reaction is carried out for 2 hours. After the reaction, cool to 180 ° C. Propylene glycol 56.4 at this temperature
Charge the parts by weight. (COOH: OH = 1: 0.7) After the completion of charging, the temperature is raised to 260 ° C. over 1 hour. Two
The reaction is performed for 8 hours while dehydrating at 60 ° C. The acid value of the obtained resin was 120.

Synthesis Example 5 A 1000 CC four-necked flask equipped with a stirrer, a thermometer, a water divider, a cooling pipe and a nitrogen gas introducing pipe was charged with 700 parts of tall oil rosin (acid value 170) under introduction of nitrogen gas. 160
Dissolve by heating to ℃. At this temperature, 56.4 parts by weight of propylene glycol are charged. (COOH: OH = 1: 0.7) Maleic anhydride 84 at 160 ° C. after the completion of the charging.
Prepare the department. After the maleic anhydride is charged, the temperature is raised to 240 ° C. over 2 hours. The reaction is performed for 8 hours while dehydrating at 240 ° C. The acid value of the obtained resin is 12
It was 3.6.

Synthesis Example 6 700 parts of tall oil rosin (acid value 170) was introduced into a four-neck flask for 1000 CC equipped with a stirrer, a thermometer, a water divider, a cooling pipe and a nitrogen gas introduction pipe under the introduction of nitrogen gas. 160
Dissolve by heating to ℃. Ethylene glycol 4 at this temperature
Charge 0.8 parts by weight. (COOH: OH = 1: 0.62) Maleic anhydride 70 at 160 ° C. after completion of charging
Prepare the department. After the maleic anhydride charge is completed, the temperature is raised to 250 ° C. over 2 hours. The reaction is performed for 8 hours while dehydrating at 250 ° C. The acid value of the obtained resin is 119.
Met.

Synthesis Example 7 700 parts of tall oil rosin (acid value 170) was introduced into a four-neck flask for 1000 CC equipped with a stirrer, a thermometer, a water divider, a cooling pipe and a nitrogen gas introduction pipe under introduction of nitrogen gas. 160
Dissolve by heating to ℃. At this temperature, 56.4 parts by weight of propylene glycol are charged. (COOH: OH = 1: 0.7) Maleic anhydride 84 at 160 ° C. after the completion of the charging.
Prepare the department. After the maleic anhydride charging is completed, the temperature is raised to 230 ° C. over 2 hours. The reaction is performed for 8 hours while dehydrating at 230 ° C. The acid value of the obtained resin is 131
Met.

Synthesis Example 8 A 1000 CC four-necked flask equipped with a stirrer, a thermometer, a water divider, a cooling pipe and a nitrogen gas introducing pipe was charged with 700 parts of tall oil rosin (acid value 170) under introduction of nitrogen gas. 160
Dissolve by heating to ℃. At this temperature, 56.4 parts by weight of propylene glycol are charged. (COOH: OH = 1: 0.7) After completion of the charging, at 160 ° C., maleic anhydride 63
Prepare the department. After the completion of the maleic anhydride charging, the temperature is raised to 260 ° C. over 2 hours. The reaction is performed for 8 hours while dehydrating at 260 ° C. The acid value of the obtained resin is 107.
Met.

Comparative Synthesis Example 1 700 parts of tall oil rosin (acid value 170) was introduced into a four-neck flask for 1000 CC equipped with a stirrer, a thermometer, a water divider, a cooling pipe and a nitrogen gas introduction pipe under introduction of nitrogen gas. 160
Dissolve by heating to ℃. At this temperature, 56.4 parts by weight of propylene glycol are charged. (COOH: OH = 1: 0.7) Maleic anhydride 84 at 160 ° C. after the completion of the charging.
Prepare the department. After the maleic anhydride charging is completed, the temperature is raised to 200 ° C. over 1 hour. The reaction is performed for 8 hours while dehydrating at 200 ° C. The acid value of the obtained resin is 146.
Met.

Comparative Synthesis Example 2 700 parts of tall oil rosin (acid value 170) was introduced into a four-neck flask for 1000 CC equipped with a stirrer, a thermometer, a water divider, a cooling pipe and a nitrogen gas introduction pipe under nitrogen gas introduction. 160
Dissolve by heating to ℃. At this temperature, 56.4 parts by weight of propylene glycol are charged. (COOH: OH = 1: 0.7) Maleic anhydride 84 at 160 ° C. after the completion of the charging.
Prepare the department. After the maleic anhydride charging is completed, the temperature is raised to 210 ° C. over 1 hour. The reaction is carried out for 8 hours while dehydrating at 210 ° C. The acid value of the obtained resin is 146.
Met.

Comparative Synthesis Example 3 (for comparison purposes, rosins according to Example 10 of Japanese Patent Laid-Open No. 60-161472 Showa) Four 1000 CCs equipped with a stirrer, thermometer, water divider, cooling pipe and nitrogen gas introduction pipe To a necked flask, 210 parts of 700 parts of tall oil rosin (acid value 170) was introduced under nitrogen gas.
Dissolve by heating to ℃. At 210 ° C., 49 parts by weight maleic anhydride were added portionwise over 20 minutes.
After 1 hour, 35 parts by weight of propylene glycol were added slowly over 20 minutes and kept at a temperature of 210 ° C. for 3 hours. (COOH: OH = 1: 0.43) The acid value of the obtained resin was 140.

Comparative Synthesis Example 4 700 parts of tall oil rosin (acid value 170) was introduced into a four-neck flask for 1000 CC equipped with a stirrer, a thermometer, a water divider, a cooling pipe and a nitrogen gas introduction pipe under introduction of nitrogen gas. 160
Dissolve by heating to ℃. At this temperature, 56.4 parts by weight of propylene glycol are charged. (COOH: OH = 1: 0.7) After the completion of charging, the temperature is raised to 260 ° C. over 2 hours. Two
The reaction is performed for 8 hours while dehydrating at 60 ° C. The acid value of the obtained resin was 99.

Comparative Synthesis Example 5 700 parts of tall oil rosin (acid value 170) was heated to 160 ° C. in a four-neck flask for 1000 CC equipped with a stirrer, a thermometer, a cooling pipe and a nitrogen gas introduction pipe, while introducing nitrogen gas. Dissolve by heating. At 160 ° C., 84 parts of maleic anhydride are charged. After the completion of the maleic anhydride charging, the temperature is raised to 260 ° C. over 2 hours. The reaction is carried out at 260 ° C for 4 hours. The acid value of the obtained resin was 191.

Comparative Synthesis Example 6 A 1000 CC four-necked flask equipped with a stirrer, a thermometer, a cooling pipe, and a nitrogen gas introduction pipe was introduced with formaldehyde-treated tall oil rosin (acid value 165) under nitrogen gas.
0 part is heated to 200 ° C. and dissolved. At 200 ° C., 60 parts by weight of fumaric acid were divided and charged in 30 minutes.
Hold at 00 ° C for 2 hours. The acid value of the obtained resin was 225.

The reaction products produced in the above-mentioned synthesis examples and comparative synthesis examples were subjected to resin constant and GPC analysis and are shown in Table 1.

[Table 1] In particular, GPC charts of Synthesis Example 4 and Comparative Synthesis Example 2 are shown in FIGS. 4 and 5. Peak A in the figure represents a rosin acid portion and is a peak containing rosin isomers such as abietic acid and dehydroabietic acid. Peak B represents a reinforced rosin portion, and is a peak containing maleopimaric acid and the like. Peak C
Is a peak containing a diester of rosin acid and propylene glycol represented by Formula 4. Peak D is a peak represented by the above formula (1) and containing the compounds represented by formula 11 and formula 12. As is clear from comparison between FIG. 4 and FIG. 5, the generation states of the peaks C, D, and E are different. Particularly, in Synthesis Example 4 (FIG. 4), the peak areas of C and D are large, and the ratio of the rosin acid portion (peak A) is decreasing. This indicates that the esterification reaction for obtaining the target compound proceeds efficiently. On the other hand, in Comparative Synthesis Example 2 (FIG. 5), conversely, the peaks of C and D are small and the detection start time of peak E is before 1.40 × 10 minutes, so that the spread to the high molecular weight side is large. Has become
It can be seen that completely different compounds are produced depending on the reaction conditions. Therefore, in Synthesis Example 4, the dihydric alcohol of the dihydric alcohol represented by the above formula 11 or 12 and rosin and maleopimaric acid was added in an effective amount (about 2
Although it is contained in an amount of 0% by weight or more), it is understood that the effective amount is not reached in Comparative Synthesis Example 2.

Polymerization of Emulsifier Polymer Polymerization Example 1 1 equipped with stirrer, thermometer, reflux condenser and dropping funnel
Allylnonylphenol EO 9 mol adduct ammonium sulfate 10
Parts, methacrylic acid 45 parts, n-butyl methacrylate 1
5 parts, 25 parts of styrene, 5 parts of α-methylstyrene, 2 parts of dodecyl mercaptan, 7 parts of sodium dodecylbenzene sulfonate, 350 parts of ion-exchanged water, 10 parts of 10% ammonium persulfate aqueous solution are mixed and stirred, and kept at 85 ° C. for 5 hours. After cooling to 50 ° C, 20% potassium hydroxide 132
Parts were gradually added and water was added to obtain a pale yellow translucent liquid having a solid content of 20%.

Polymerization Example 2 1 equipped with a stirrer, thermometer, reflux condenser and dropping funnel
A 000 cc four-necked flask was charged with 10 parts by weight of rosin and 100 parts of isopropyl alcohol, thoroughly degassed with nitrogen gas, and then heated to a reflux temperature to dissolve the rosin.
A mixed solution of 60 parts of styrene, 30 parts of dimethylaminoethyl methacrylate and 2 parts of azobisisobutyronitrile was added dropwise thereto over 1 hour, and the mixture was reacted for 6 hours while refluxing. Then, about 70 of isopropyl alcohol was distilled off while continuing heating, and then a solution of 11 parts of acetic acid dissolved in 100 parts of water was added dropwise. The obtained aqueous dispersion was further heated, and the remaining isopropyl alcohol was distilled off. Next, 330 parts of water was added, 18 parts of epichlorohydrin was added thereto, and the mixture was reacted at 85 to 95 ° C. for 1 hour, and water was added to obtain a bluish white translucent liquid having a solid content of 20%.

Preparation of Sizing Agent Example 1 200 parts of the resin of Synthesis Example 1 was dissolved in 200 parts of toluene,
50 parts of polymer emulsifier of Polymerization Example 1 (10 parts of active ingredient),
350 parts of ion-exchanged water was added and mixed with a homomixer at 40 ° C. Subsequently, this dispersion was passed once through a piston type high pressure emulsifying machine (200 kg / cm ² ) to obtain a fine dispersion.
Then, toluene and some water were distilled off by vacuum distillation to obtain an aqueous dispersion. The resulting emulsion contained 37% solids.

Example 2 100 parts of the resin of Synthesis Example 2 was melted at 180 ° C.
Cool to 30 ° C. SOFTANOL ME to this molten resin
S-1212 parts (3 parts active ingredient) was slowly added with stirring, then 10% casein solution (5 parts casein, 2 parts).
5% ammonia water 2.6 parts, diluted to 50 parts with water) 5
0 part was gradually added dropwise. 60 parts of additional hot water (95 ° C.) was gradually added dropwise to invert the emulsion into an O / W type emulsion.
After adding 130 parts of hot water, the internal temperature is rapidly cooled to 30 ° C. The resulting emulsion contained 31% solids.

Example 3 200 parts of the resin of Synthesis Example 3 was dissolved in 200 parts of toluene,
50 parts of polymer emulsifier of Polymerization Example 1 (10 parts of active ingredient),
350 parts of ion-exchanged water was added and mixed with a homomixer at 40 ° C. Subsequently, this dispersion was passed once through a piston type high pressure emulsifying machine (200 kg / cm ² ) to obtain a fine dispersion.
Then, toluene and some water were distilled off by vacuum distillation to obtain an aqueous dispersion. The resulting emulsion contained 37% solids.

Example 4 200 parts of the resin of Synthesis Example 4 was dissolved in 200 parts of toluene,
100 parts of polymer emulsifier of Polymerization Example 2 (active ingredient 20
Parts) and 350 parts of ion-exchanged water were added and mixed with a homomixer at 40 ° C. Subsequently, this dispersion was passed once through a piston type high pressure emulsifying machine (200 kg / cm ² ) to obtain a fine dispersion. Then, toluene and some water were distilled off by vacuum distillation to obtain an aqueous dispersion. The obtained emulsion has a solid content of 3
It contained 5%.

Example 5 200 parts of the resin of Synthesis Example 5 was dissolved in 200 parts of toluene,
50 parts of polymer emulsifier of Polymerization Example 1 (10 parts of active ingredient),
350 parts of ion-exchanged water was added and mixed with a homomixer at 40 ° C. Subsequently, this dispersion was passed once through a piston type high pressure emulsifying machine (200 kg / cm ² ) to obtain a fine dispersion.
Then, toluene and some water were distilled off by vacuum distillation to obtain an aqueous dispersion. The resulting emulsion contained 37% solids.

Example 6 200 parts of the resin of Synthesis Example 6 was dissolved in 200 parts of toluene,
50 parts of polymer emulsifier of Polymerization Example 1 (10 parts of active ingredient),
350 parts of ion-exchanged water was added and mixed with a homomixer at 40 ° C. Subsequently, this dispersion was passed once through a piston type high pressure emulsifying machine (200 kg / cm ² ) to obtain a fine dispersion.
Then, toluene and some water were distilled off by vacuum distillation to obtain an aqueous dispersion. The resulting emulsion contained 37% solids.

Example 7 200 parts of the resin of Synthesis Example 7 was dissolved in 200 parts of toluene,
50 parts of polymer emulsifier of Polymerization Example 1 (10 parts of active ingredient),
350 parts of ion-exchanged water was added and mixed with a homomixer at 40 ° C. Subsequently, this dispersion was passed once through a piston type high pressure emulsifying machine (200 kg / cm ² ) to obtain a fine dispersion.
Then, toluene and some water were distilled off by vacuum distillation to obtain an aqueous dispersion. The resulting emulsion contained 37% solids.

Example 8 100 parts of the resin of Synthesis Example 8 was melted at 180 ° C.
Cool to 0 ° C. Aerosol A-1 is added to this molten resin.
03 8.8 parts (3 parts active ingredient) were added slowly with stirring, then 10% casein solution (4 parts casein, 2 parts)
5% ammonia water 2.0 parts, diluted to 70 parts with water) 70
A portion was gradually dropped. 40 parts of additional hot water (95 ° C.) was gradually added dropwise to invert the emulsion into an O / W type emulsion. After adding 130 parts of hot water, the internal temperature is rapidly cooled to 30 ° C. The resulting emulsion contained 31% solids.

Comparative Example 1 100 parts of the resin of Comparative Synthesis Example 1 is melted at 180 ° C. and cooled to 130 ° C. While stirring this molten resin 1
0% casein solution (5 parts casein, 10% NaOH 1.
9 parts, diluted with water to a total amount of 50 parts) 50 parts were gradually added dropwise. 60 parts of additional hot water (95 ° C.) was gradually added dropwise, and O /
Inverted to W type emulsion. After adding 130 parts of hot water, the internal temperature is rapidly cooled to 30 ° C. The resulting emulsion contained 31% solids.

Comparative Example 2 200 parts of the resin of Comparative Synthesis Example 1 was dissolved in 200 parts of toluene, and 50 parts of the polymer emulsifier of Polymerization Example 1 (active ingredient 10
Parts) and 350 parts of ion-exchanged water were added and mixed with a homomixer at 40 ° C. Subsequently, this dispersion was passed once through a piston type high pressure emulsifying machine (200 kg / cm ² ) to obtain a fine dispersion. Then, toluene and some water were distilled off by vacuum distillation to obtain an aqueous dispersion. The obtained emulsion has a solid content of 3
It contained 7%.

Comparative Example 3 200 parts of the resin of Comparative Synthesis Example 2 was dissolved in 200 parts of toluene and 50 parts of the polymer emulsifier of Polymerization Example 1 (active ingredient 10
Parts) and 350 parts of ion-exchanged water were added and mixed with a homomixer at 40 ° C. Subsequently, this dispersion was passed once through a piston type high pressure emulsifying machine (200 kg / cm ² ) to obtain a fine dispersion. Then, toluene and some water were distilled off by vacuum distillation to obtain an aqueous dispersion.

Comparative Example 4 100 parts of the resin of Comparative Synthesis Example 3 were melted at 150 ° C. and 10 parts by weight of 25% aqueous borax solution were added slowly with stirring. 7 parts by weight of casein and 2
Twenty-five parts by weight of water was slowly added into the resulting water-in-oil emulsion until the oil-in-water emulsion was formed. The internal temperature was cooled to 30 ° C or lower to obtain an aqueous dispersion.

Comparative Example 5 200 parts of the resin of Comparative Synthesis Example 3 was dissolved in 200 parts of toluene to prepare a 10% aqueous casein solution (4 parts casein, 10% Na).
1.5 parts of OH, diluted with water to a total amount of 40 parts), 40 parts, and 340 parts of ion-exchanged water were added and mixed with a homomixer at 40 ° C. Subsequently, this dispersion was passed once through a piston type high pressure emulsifying machine (200 kg / cm ² ) to obtain a dispersion. After that, toluene and some water were distilled off under reduced pressure to obtain an aqueous dispersion. The resulting emulsion contained 35% solids.

Comparative Example 6 200 parts of the resin of Comparative Synthesis Example 4 was dissolved in 200 parts of toluene and 50 parts of the polymer emulsifying agent of Polymerization Example 1 (active ingredient 10
Parts) and 350 parts of ion-exchanged water were added, and mixed with a homomixer at 40 ° C. Subsequently, this dispersion was passed once through a piston type high pressure emulsifying machine (200 kg / cm ² ) to obtain a fine dispersion. Then, toluene and some water were distilled off by vacuum distillation to obtain an aqueous dispersion. The resulting emulsion contained 31% solids.

Comparative Example 7 200 parts of the resin of Comparative Synthesis Example 5 was dissolved in 200 parts of toluene and 50 parts of the polymer emulsifying agent of Polymerization Example 1 (active ingredient 10
Parts) and 350 parts of ion-exchanged water were added and mixed with a homomixer at 40 ° C. Subsequently, this dispersion was passed once through a piston type high pressure emulsifying machine (200 kg / cm ² ) to obtain a fine dispersion. Then, toluene and some water were distilled off by vacuum distillation to obtain an aqueous dispersion. The obtained emulsion has a solid content of 3
It contained 1%.

Comparative Example 8 200 parts of the resin of Comparative Synthesis Example 6 was dissolved in 200 parts of toluene, and 24 parts of S-12 of Softanol (active ingredient 6).
Part) and 380 parts of ion-exchanged water were added and mixed with a homomixer at 40 ° C. Subsequently, this dispersion was passed once through a piston type high pressure emulsifying machine (200 kg / cm ² ) to obtain a fine dispersion. Then, toluene and some water were distilled off by vacuum distillation to obtain an aqueous dispersion. The obtained emulsion has a solid content of 3
It contained 5%.

The sizing agents of Examples 1 to 8 and Comparative Examples 1 to 8 are summarized in Table 2 and the storage stability of each sizing agent was tested. The results are shown in Table 2.

[Table 2] In addition, the Steckigt sizing degree (seconds) at the papermaking pHs of 6.5, 7.0 and 7.5 was measured. The results are shown in Table 3.

[Table 3] Furthermore, the foamability in white water was tested, and the results are shown in Table 4.

[Table 4]

Sizing Evaluation Test Method Pulp: L / NBKP (L / N 8/2) CSF 420 ml Method: A predetermined amount of calcium carbonate is added to 2.5% slurry of the above pulp and stirred. Cationic starch is added with stirring and after 2 minutes the sizing agent is added. 30 seconds later, the liquid sulfuric acid band is added. 30 seconds after that, a polyacrylic amide type retention agent is added. Thirty seconds after that, handmade paper (66 to 70 g / m ² ) was prepared using a handmade tester according to a conventional method. The obtained handmade paper was subjected to a size test after being left for 1 day in a high temperature and humidity chamber at a temperature of 20 ° C. and a humidity of 65%. Adjusting pH pH 6.5 calcium carbonate 2% vs. sulfur, liquid sulfuric acid band 2% pH 7.0 calcium carbonate 10% vs. sulfur, liquid sulfuric acid band 2% pH 7.5 calcium carbonate 10% vs. sulfur, liquid sulfuric acid band 1%

Test Method for Evaluating Foaming Property Synthetic white water: 0.5 g of calcium carbonate was dispersed in 900 ml of ion-exchanged water to prepare liquid aluminum sulfate (Al.
The pH is adjusted to 7.3 by adding 0.7 g (containing 4.2%). Add Na2SO4 to this solution to obtain an electric conductivity of 1000μ.
Adjust to S / cm and use this solution as synthetic white water. Method: Dilute the sizing agent with the above synthetic white water, prepare a test solution with a sizing agent concentration of 0.05% (solid), and test at 40 ° C. A 100 ml test solution is put in a 200 ml graduated cylinder, tightly stoppered, strongly shaken up and down 10 times, and allowed to stand still, and changes in the generated bubbles are observed.

Static stability test method: Each aqueous dispersion 500 in a glass container for 550 ml.
g and store at 25 ° C. for 2 months for storage stability test. The agglomerated precipitate formed was filtered off with a 200-mesh wire net and the amount of precipitation relative to the total resin is shown.

[0042]

As is clear from the above description, the sizing agent according to the present invention has the following formula (1):

Embedded image (R1 represents a rosin acid residue or a maleopimaric acid residue, R2 represents a dihydric alcohol residue, and R3 represents a maleopimaric acid residue.) Since the main component is a diester of a rosin-based substance having a group, it exhibits an excellent size effect in neutral papermaking. Further, by using the emulsifier according to the present invention together, there is an advantage that excellent storage stability, no foaming and excellent operability can be obtained.

[Brief description of drawings]

FIG. 1 is a structural formula showing a first step of a manufacturing method according to the present invention.

FIG. 2 is a structural formula showing a typical compound in a reaction product formed by the production method according to the present invention.

FIG. 3 is a structural formula showing a second step of the manufacturing method according to the present invention.

FIG. 4 shows a GPC chart of a reaction product in Synthesis Example 4.

5 shows a GPC chart of a reaction product in Comparative Synthesis Example 4. FIG.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masao Hamada 4 Harima Kasei Co., Ltd., 671 Mizusui, Noguchi-cho, Kakogawa-shi, Hyogo

Claims (19)

[Claims] 1. The following formula (1): (R1 represents a rosin acid residue or a maleopimaric acid residue,
R2 represents a dihydric alcohol residue, and R3 represents a maleopimaric acid residue. ) A neutral papermaking sizing agent containing a dicarboxylic acid or acid anhydride group-containing rosin-based diester as a main component. 2. A) rosin, b) dihydric alcohol and c)
The following formula (1) is obtained by reacting α, β-unsaturated carbonyl compounds sequentially or simultaneously (R1 represents a rosin acid residue or a maleopimaric acid residue, and R2 represents a dihydric alcohol. A residue, and R3 represents a maleopimaric acid residue.) A neutral papermaking sizing agent composed of a reaction product containing a diester of a rosin-based substance having a dicarboxylic acid or acid anhydride group. 3. The neutral papermaking sizing agent according to claim 2, wherein the rosin is one or more selected from the group consisting of gum rosin, tall oil rosin and wood rosin. 4. The neutral papermaking sizing agent according to claim 2, wherein the dihydric alcohol is one or two dihydric alcohols having a boiling point of 210 ° C. or lower selected from the group consisting of ethylene glycol and propylene glycol. . 5. The α, β-unsaturated carbonyl compound is selected from the group consisting of maleic acid and maleic anhydride.
3. The neutral papermaking sizing agent according to claim 2, which is one or two kinds. 6. A reaction product obtained by reacting a) a rosin, b) a dihydric alcohol having a boiling point of 210 ° C. or less, and c) maleic acid and maleic anhydride, sequentially or simultaneously, has a molecular weight of 290.
~ 315 component 15-40%, molecular weight 390-420
Is 10 to 35%, the component having a molecular weight of 580 to 660 is 1 to 25%, and the component having a molecular weight of 670 to 880 is 20 to 50%.
% Of the reaction product is dispersed in water. Neutral papermaking sizing agent. 7. The sizing agent according to any one of claims 1 to 5 has the following formula (2) based on the weight of the mixture: (In the formula, R is a C10-C24 alkylphenol group or a linear or branched alkyl group, and n is 6-20.
And X or Y is H or SO ₃ M,
(M is sodium, potassium or ammonium group) 1 to 10% by weight of a specific surfactant and 0 to 10% by weight of casein, and a solid content concentration of 20 to 60% by weight Sizing agent for paper making. 8. The papermaking sizing agent according to claim 7, further comprising 0.5 to 10% by weight of casein. 9. The sizing agent solid content 8 according to claim 1 or 2.
0 to 99 parts by weight and 1 to 20 parts by weight of a partially saponified or completely saponified copolymer of styrene- (meth) acrylic acid-based monomer are dispersed in water to give a solid content of 20 to 60% by weight.
The sizing agent for neutral papermaking, characterized in that 10. A copolymer of 60 to 95 parts by weight of a solid content of the sizing agent according to claim 1 to 5 and a cationic vinyl monomer, an aromatic vinyl monomer and / or a (meth) acrylic acid ester (emulsifier). Polymer) 5 to 95 parts by weight are dispersed in water to have a solid content concentration of 20 to 60% by weight, and a sizing agent for neutral papermaking. 11. The emulsifier polymer, wherein at least one of rosin acid, α, β unsaturated carbonyl compound addition rosin acid or rosin ester is added to a cationic vinyl monomer and / or (meth) acrylic acid ester. The neutral papermaking sizing agent according to claim 10, wherein a copolymerized product in the presence of 0.1 to 15 mol% is used. 12. A) rosins, b) dihydric alcohols and c)
The ratio of the hydroxyl equivalent of b) to the carboxyl equivalent of a) of the α, β-unsaturated carbonyl compound is 0.2 to 1.5.
The reaction product containing a diester of a rosin-based substance having a dicarboxylic acid or acid anhydride group represented by the above formula 1 is obtained and dispersed in water. A method for producing a neutral sizing agent for papermaking. 13. A) rosins and b) 2 having a boiling point of 210 ° C. or lower
When the c) α, β-unsaturated carbonyl compound is reacted sequentially or simultaneously with the polyhydric alcohol, the reaction is performed at a temperature not higher than the boiling point of the dihydric alcohol, and then 225 ° C to 280 ° C.
13. The production method according to claim 12, wherein the reaction is carried out by. 14. The obtained reaction product has a molecular weight of 290.
~ 315 component 15-40%, molecular weight 390-420
Ingredients: 10-35%, molecular weight: 580-660
1 to 25%, a component having a molecular weight of 670 to 880, 20 to 50
The manufacturing method according to claim 12, wherein the manufacturing method comprises%. 15. When dispersing the reaction product in water, 1 to 10% by weight of the specific surfactant represented by the above formula 2 is used in terms of solid content, and the solid content concentration is 20 to 60% by weight. The manufacturing method according to claim 12. 16. The production method according to claim 15, which further comprises casein in an amount of 0.5 to 10% by weight. 17. When the reaction product is dispersed in water, styrene is added to 80 to 99 parts by weight of the reaction product.
Copolymer of (meth) acrylic acid-based monomer Partial saponification or complete saponification 1 to 20 parts by weight is used together, and solid content concentration is 20.
The manufacturing method according to claim 12, wherein the content is -60% by weight. 18. When the reaction product is dispersed in water, the copolymerization of 60 to 95 parts by weight of the reaction product with a cationic vinyl monomer, an aromatic vinyl monomer and / or a (meth) acrylic acid ester is carried out. The production method according to claim 13, wherein the combined content (emulsifier polymer) is 5 to 95 parts by weight, and the solid content concentration is 20 to 60% by weight. 19. The emulsifier polymer comprises at least one kind of rosin acid, α, β unsaturated carbonyl compound-added rosin acid or rosin ester to a cationic vinyl monomer and / or (meth) acrylic acid ester. The production method according to claim 18, wherein a copolymerized product in the presence of 0.1 to 15 mol% is used.