JP3221188B2 - Rosin emulsion composition, method for producing the same, sizing agent, sizing method, and sized paper - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION This invention is rosin-based emulsion composition, a method of manufacturing the same, a sizing agent, relates to a sizing method and size papers, especially the dispersant fatty acid and rosin-based material in the emulsion solids Stable in water
In the dispersed rosin emulsion composition,
The powder is a rosin emulsion composition using at least a high molecular weight emulsifying dispersant , especially when the papermaking speed is high and the drying conditions are mild, that is, the papermaking system in which the amount of heat applied to the wet paper is relatively small, For example, the present invention relates to a sizing agent which exerts an excellent sizing effect on paper produced under the drying conditions of a paper machine having a Yankee dryer and also has excellent mechanical stability and storage stability.

[0002]

2. Description of the Related Art In the papermaking industry, there are problems associated with improving paper quality, closing papermaking systems, and using waste paper or broke containing calcium carbonate as a raw material for papermaking.
On the other hand, the speed of a paper machine is further increased in order to improve productivity, and as a result, drying is rapidly performed under relatively low temperature conditions. Regarding the latter, there is a tendency that a conventional sizing agent cannot impart sufficient sizing degree to paper.

[0003]

For example, when an anionic rosin sizing agent, especially a solution type rosin sizing agent which is an alkali neutralized reinforced rosin is used, the sizing effect is superior to that of a solution type rosin sizing agent. In the case of using a dispersion type rosin-based sizing agent having a wide pH range for papermaking, the drying conditions cannot be said to be sufficient during the papermaking by a high-speed paper machine,
In order to obtain a predetermined sizing degree, the amount of the sizing agent added must be increased, which not only increases the cost but also causes a problem that foaming is remarkable in the papermaking process. Under such circumstances, when the paper making speed is high and the drying conditions are relatively gentle, for example, a paper machine having a Yankee dryer (for example, a paper machine for pure white roll paper, etc.)
Alternatively, there is a strong need for a rosin-based emulsion sizing agent that exhibits an excellent sizing effect even on paper made under the drying conditions of an ultrahigh-speed newsprint machine.

[0004] It is an object of the present invention to provide an excellent sizing effect on paper made in a papermaking system in which drying conditions are relatively mild, as in the case of making a paper with a high-speed paper machine, and furthermore, provide mechanical stability and storage. It is an object of the present invention to provide a rosin-based emulsion composition having excellent stability, a method for producing the same, a sizing agent containing the composition, a sizing method, and sized paper.

[0005]

Means for Solving the Problems The present invention, in order to solve the above problems, and at least one belongs to the number 15 or more fatty acids carbon as (A) a main component, and (B) a rosin-based material ( a rosin emulsion composition was stably dispersed in water by C) dispersing agent, less in the above dispersing agent
Rosin-based emulsion using high molecular weight emulsifying dispersant
It provides a composition .

At this time, the fatty acid having 15 or more carbon atoms of the component (A) is at least one selected from the group consisting of synthetic higher fatty acids, natural higher fatty acids, dimers of unsaturated fatty acids and trimers of unsaturated fatty acids. Being a seed, component (A) and component (B)
Having a mixture particle in which the components are premixed in the dispersoid,
Component (A) is 0.5 to 20 parts by weight, component (B) is 60 to
A total of 100 parts by weight of 98.5 parts by weight and 1 to 20 parts by weight of the component (C) was stably dispersed in water, and the solid content was 20 parts by weight.
Preferably, it is a dispersion of about 60% by weight.

The present invention also provides a method for producing these rosin-based emulsion compositions, a sizing agent containing the composition, a sizing method, and a sized paper.

Hereinafter, the present invention will be described in detail. The fatty acids having 15 or more carbon atoms of (A) constituting the present invention are fatty acids having 15 or more carbon atoms, and include synthetic fatty acids, natural fatty acids, and polymers of these unsaturated fatty acids. Examples include synthetic higher fatty acids, natural higher fatty acids, dimers of unsaturated fatty acids, and trimers of unsaturated fatty acids. Specifically, unsaturated fatty acids such as palmitic acid, stearic acid and behenic acid, unsaturated fatty acids such as oleic acid, natural fatty acids such as tallow fatty acid, soybean oil fatty acid and tall oil fatty acid, and polymers of unsaturated fatty acids such as dimer acid And the like. These can be used singly or plurally belonging to each group, or plurally of two or more groups. In addition, at least one kind belonging to fatty acids having 15 or more carbon atoms as a main component
It indicates that fatty acids having less than 15 carbon atoms, for example, coconut oil fatty acids, lauric acid, myristic acid, and the like may be contained in a range that does not impair the performance of the emulsion composition.

The rosin-based substance of the component (B) in the present invention includes gum rosin, tall oil rosin, wood rosin and modified products of these rosins, and these may be used alone or as a mixture of two or more. The modified rosin may be partially or substantially completely hydrogenated, disproportionated, polymerized, or modified with formaldehyde. In addition, fortified rosins obtained by addition reaction of these rosin-based substances with α, β─ unsaturated carboxylic acid are also included in the rosin-based substances. Representative examples of the α, β カ ル ボ ン unsaturated carboxylic acid used herein include unsaturated dibasic acids such as fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid and citraconic anhydride; Monobasic acids such as acrylic acid or methacrylic acid. Further, esters of rosin with polyhydric alcohols such as glycerin and pentaerythritol, and reaction products of rosin with epoxy compounds are also included in the rosin-based substances.

[0010] dispersing agent of the component (C) in the present invention, low
Emulsifying dispersant using at least a polymer emulsifying dispersant and / or
Or made of a protective colloid is not particularly limited, Mochiiruko the polymeric emulsifying dispersant alone
In addition to the polymer emulsifying dispersant, various kinds of low molecular surfactants and protective colloids such as casein, lecithin, polyvinyl alcohol and modified starch can be used together with the polymer emulsifying dispersant. may be used in combination other alone or in combination of two or more. Various low molecular surfactants include rosin alkali metal salts, reinforced rosin alkali metal salts, alkyl benzene sulfonates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, polyoxyethylene monosulfates. And styryl phenyl ether sulfate, alkyl sulfate, alkyl naphthalene sulfonate, naphthalene sulfonate formaldehyde condensate, polyoxyethylene alkyl ether sulfosuccinate monoester salt, polyoxyethylene alkylphenyl ether sulfosuccinate monoester salt And polyoxymono and distyryl phenyl ether sulfosuccinic acid monoester salts, and alkylphenoxypolyoxyethylene propyl sulfonate. Surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene mono- and distyryl phenyl ether, polyoxypropylene polyoxyethylene glycol glycerin fatty acid ester, sorbitan fatty acid ester, polyethylene glycol fatty acid ester, poly Oxyethylene sorbitan fatty acid ester, cane sugar fatty acid ester,
Nonionic surfactants such as pentaerythritol fatty acid ester, propylene glycol fatty acid ester, fatty acid diethanolamide, polyoxypropylene polyethylene glycol, and further, tetraalkylammonium chloride, trialkylbenzylammonium chloride, alkylamine, monooxyethylenealkylamine, Cationic surfactants such as polyoxyethylene alkylamine can be exemplified.

The polymer emulsifying and dispersing agent is not particularly limited, but is basically a hydrophobic group, a nonionic group and / or a nonionic group.
Alternatively, a synthetic polymer having an ionic group or a general natural polymer-based emulsifying dispersant can be used. For example, a partially or completely neutralized product of anionic styrene / (meth) acrylic acid-based copolymer, anionic Alternatively, cationic (meth) acrylic ester copolymers or (meth) acrylamide copolymers, cationic polyaminopolyamide─epichlorohydrin resin, polyalkylenepolyamine─epichlorohydrin resin, poly (diallylamine) ─epichlorohydrin resin, etc. are exemplified. can do. These polymeric emulsifying and dispersing agents may be used alone or in combination of two or more as protective colloids.

The emulsion composition of the present invention comprises the above components (A), (B) and (C), 60 to 98.5 parts by weight of a rosin-based substance of the component (B), and a fatty acid of the component (A). 0.5 to 20 parts by weight, preferably 1 to 20 parts by weight, more preferably 1 to 15 parts by weight, and 1 to 20 parts by weight, more preferably 3 to 10 parts by weight of the dispersant of the component (C). Is preferred. When the amount of the component (A) is less than 0.5 part by weight, the effect on size performance and the like is lower than that in the above range, and when the amount is more than 20 parts by weight, the effect on size performance and the like tends to level off, It is not economically favorable. When the dispersant is less than 1 part by weight, the effect of emulsifying and dispersing the mixture of the rosin-based substance and the fatty acid and the storage stability are lower than those in the above range. Is not particularly improved, and the size performance and foamability are not better than those in the above range.

The method of including the above content of the component (A) in the solid content of the emulsion is not particularly limited.
After melt-mixing 0.5 to 20 parts by weight of the component (A) and 98.5 to 60 parts by weight of the component (B), preferably 98.5 to 60 parts by weight of a rosin-based material reinforced with an α, β unsaturated carboxylic acid, the component (C) Emulsifying and dispersing using 1 to 20 parts by weight, or the component (B),
Preferably, a rosin-based substance reinforced with an α, β─ unsaturated carboxylic acid is emulsified and dispersed with the component (C),
The component (A) may be mixed by emulsifying and dispersing the component (C), or any method may be used. The former is preferred in terms of size performance. The total solid content of the emulsion after emulsification and dispersion is preferably 20 to 60% by weight, more preferably 30 to 60% by weight.
５０50% by weight.

The method for producing the rosin emulsion composition of the present invention is not particularly limited. For example, as described in JP-B-54-36242, the above-mentioned component (A) and the above-mentioned (B) A) a method of preparing an oil-in-water emulsion by mixing a solution obtained by previously dissolving the components in an oil-soluble solvent, the above-mentioned component [C], and water and treating with a homogenizer (solvent method); As described, the component (A) and the component (B) are melt-mixed, and the component (C) and a portion of water are mixed with stirring to form a water-in-oil emulsion. Method of phase transition to oil-in-water emulsion by adding water (phase inversion method), Tokubo Sho5
As described in JP-A-3-32380, the above component (A) and the component (B) are melt-mixed, and the above component (C) is further mixed, and then the oil-in-water emulsion is passed through a homogenizer under high pressure. A manufacturing method (mechanical method) or the like is used.

The rosin emulsion composition thus obtained has a total solid content of 20 to 60% by weight, preferably 30 to 60% by weight.
The emulsion particles have an average particle size (cumulative 50% size in a weight-based particle size distribution) of 1 μm or less, preferably 0.5 μm or less. Average particle size is 1
If the particle size exceeds μm, a precipitate is likely to be formed during storage, and mechanical stability tends to be poor. Cumulative 50%
The diameter was measured with a Master Sizer (Malvern). Further, the pH of the composition liquid is 2.5 to 6.5.

The rosin emulsion composition itself is very stable and excellent in storage stability. The sizing agent comprising this composition can be applied to dry paper under relatively mild drying conditions, particularly in a high-speed paper machine, ie, to wet paper. In the case of a paper machine having a relatively small amount of heat, for example, a paper machine having a Yankee dryer or an ultra-high-speed newsprint paper machine, particularly in an acidic or neutral paper machine (pH 4 to 8), it is applied to paper in comparison with conventional sizing agents. Not only is the sizing performance excellent, but it also has the advantage that adjustment from weak sizing to strong sizing is possible. In addition, the sizing agent of the present invention is characterized in that papermaking tools such as press rolls and dryer canvases are less contaminated.

The sizing method of the present invention is carried out by adding the sizing agent of the present invention to, for example, a wet end portion in a paper or paperboard manufacturing process. Specifically, the sizing agent of the present invention is added to an aqueous dispersion of pulp in an amount of 0.01 to 5% by solid content, preferably 0.05 to 2% by solid content, based on the dry weight. The component (A) emulsified and dispersed by the component (C) and the component (B) emulsified and dispersed by the component (C) can be separately added to the pulp slurry. The use of a sizing agent has a better size effect and is easier to handle.

The sizing method according to the present invention is preferably used for the following papermaking systems. Papermaking systems made with a Yankee machine, such as pure white roll paper. Papermaking systems produced by ultra-high-speed paper machines, such as newsprint. Papermaking systems in which the amount of bansulfate used is limited to small amounts, such as neutral liners, rust-proof liners, and metal interleaving paper. Papermaking systems in which calcium carbonate is mixed from waste paper raw materials, such as gypsum board base paper, white board, coated base paper, medium quality paper, general liners and cores. Papermaking system using a small amount of calcium carbonate as filler,
For example, neutral printing writing paper, neutral coated paper, neutral PPC paper, neutral pressure-sensitive base paper, neutral inkjet paper, and neutral information paper. Papermaking systems in which the amount of the fixing agent used is limited, for example, kraft paper.

The above sizing method and sizing agent can be used as a surface sizing method and a surface sizing agent,
In this case, a conventional method such as spraying, dipping, and coating is applied to the wet paper web.

The sized paper of the present invention contains at least the component (A) and the component (B), and may further contain the component (C). The content varies depending on the type of paper. , 0.01 to 5% by weight of solid content.
Each component is identified by analysis. An example of the analysis method is pyrolysis GC-MS (gas chromatography ク ロ マ ト グ ラ フ ィ mass spectrometry).

In producing paper or paperboard, pulp raw materials include bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp, or thermomechanical pulp. Any of used paper pulp, such as used newspaper, used magazine, used corrugated paper, and used deinked paper, can be used. Further, a mixture of the pulp raw material and synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin, and polyvinyl alcohol can also be used.

Additives such as fillers, dyes, dry strength agents, wet strength agents, retention enhancers, and drainage improvers are also required to develop the physical properties required for each paper type. You may use it according to. Fillers include clay, talc,
Heavy or light calcium carbonate may be used, and these may be used alone or in combination. Examples of the dry paper strength improver include anionic polyacrylamide, cationic polyacrylamide, amphoteric polyacrylamide, and cationized starch, and these may be used alone.
You may use together. Examples of the wet paper strength improver include polyamide / epichlorohydrin resin, melamine / formaldehyde resin, urea / formaldehyde resin and the like, and these may be used alone or in combination with anionic polyacrylamide. Examples of the retention aid include anionic or cationic high molecular weight polyacrylamide, a combination of silica sol and cationized starch, and a combination of bentonite and cationic high molecular weight polyacrylamide. Examples of the drainage improver include polyethyleneimine, cationic or anionic polyacrylamide, and the like. Further, starch, polyvinyl alcohol, dye, coating color, surface sizing agent, anti-slip agent and the like may be applied as required by a size press, a gate roll coater, a bill blade coater, a calender or the like. In addition, bansulfate may be used before, after or simultaneously with the addition of the sizing agent of the present invention.

The paper sized by using the sizing agent of the present invention in a papermaking system having a high bansulfate addition rate or a papermaking system in which the amount of bansulfate used is limited to a small amount is particularly gentle as described above. Demonstrates excellent sizing performance not found in conventional rosin-based sizing agents even under mild drying conditions.

[0024]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to production examples of the above-mentioned components (A), (B) and (C), examples using the components, and comparative examples. However, the present invention is not limited to this example. In addition, in each example, all parts and% are based on weight unless otherwise specified.

Production of rosin-based material (B) Production of fumaric acid-enhanced rosin 90 parts of fumaric acid was gradually added to 440 parts of gum rosin in a molten state at about 200 ° C, and almost all of the fumaric acid was reacted. Thereafter, 470 parts of tall oil rosin treated with formaldehyde (modification ratio: 3%) was further added, and the mixture was melt-stirred and homogenized, and then the reaction product was cooled to room temperature. This reaction product (reinforced rosin) was obtained by adding 9% of fumaric acid to rosin.

Production of Polymeric Emulsifying and Dispersing Agents Polymeric emulsifying and dispersing agents (C─1) and (C─1) for Examples for stabilizing the dispersion of a rosin-based material as follows:
2) was manufactured. # 1 Anionic polymer dispersant for Examples (C # 1)
According to the production method of Reference Example 10 of JP-A-61-108796, a styrene / methacrylic acid-based copolymer neutralized product (C # 1) was produced as follows. Styrene 55
Parts, 30 parts of methacrylic acid, 5 parts of itaconic acid, 10 parts of lauryl acrylate, 50 parts of 10% sodium formaldehyde naphthalenesulfonate, 1 part of ammonium persulfate and 200 parts of water. Heated for minutes. Then cooled to 70 ° C., 48.5
35.5 parts of sodium hydroxide and 7 parts of water were gradually added dropwise, followed by stirring for 30 minutes and cooling to room temperature.
An anionic polymer dispersion (C # 1) having a solid content of 30% was obtained.

# 2 Preparation of Cationic Polymeric Dispersant (C # 2) for Examples Preparation of cationic poly (meth) acrylamide having a hydrophobic group described in Example 1 of JP-A-2-177534 According to the method, a polymer dispersant (C
-2). In a 1-liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, 31.4 parts of dimethylaminoethyl methacrylate,
85.3 parts of a 50% aqueous acrylamide solution, styrene 2
0.8 parts, ion-exchanged water 100.6 parts, isopropyl alcohol 143.3 parts, n-dodecyl mercaptan 0.
6 parts were charged, and the pH was adjusted to 4.5 with a 20% acetic acid aqueous solution. The mixture was heated to 60 ° C. under a nitrogen gas atmosphere while stirring. As a polymerization initiator, 2.3 parts of a 5% aqueous solution of ammonium persulfate was added, the temperature was raised to 80 ° C., and the temperature was maintained for 1.5 hours.
0.7 parts of aqueous solution was added. After maintaining at the same temperature for another hour, 100 parts of ion-exchanged water was added, and then isopropyl alcohol was distilled off. After the distillation was completed, ion-exchanged water was further added to produce a cationic polymer dispersion (C # 2) having a solid concentration of 20.4%.

Production of Rosin Emulsion Composition # 1 Examples 1 to 7 The fumaric acid-enriched rosin obtained in # 1 and the fatty acids shown in Table 1 were mixed at the ratios shown in the same table, and heated and melted at about 150 ° C. ,
While stirring vigorously, the dispersing agent obtained was added and mixed as shown in the same table to obtain a water-in-oil emulsion. Hot water was gradually added to this to invert the phase to obtain an oil-in-water emulsion. Hot water was quickly added to the emulsion to form a stable oil-in-water emulsion, and then cooled to room temperature. The solid content of the thus obtained emulsion is about 45 to 50%, and the cumulative 50% diameter (hereinafter, referred to as “weight”) in the weight-based particle size distribution measured by a Master Sizer (manufactured by Malvern).
(Referred to as an average particle diameter) was about 0.2 to 0.5 μm, which was stable for a long period of time.

# 2 Comparative Examples 1-4 As shown in the corresponding column of Table 1, whether or not fatty acids were used
A rosin emulsion composition was obtained in the same manner as in the above example except that a fatty acid having a carbon number of less than 15 was used. Table 1 shows the compositions and properties of the rosin emulsion compositions of the above Examples and Comparative Examples.

[0030]

[Table 1]

Using the rosin emulsion compositions obtained in the above Examples and Comparative Examples as sizing agents, the results of a size effect test conducted under the following test conditions are shown in Table 2. All the added chemicals were shown by the weight ratio of solid content to the absolute dry weight of the pulp.

Size effect test bleached kraft pulp (pulp ratio of softwood to hardwood is 1: 4
The mixed pulp) was diluted with diluting water having a hardness of 100 ppm so as to have a pulp concentration of 2.5%, and beaten to a Canadian standard freeness of 350 ml using a beater. 1.2 liters of this pulp slurry was weighed into a disintegrator, and the sizing agents of the above Examples and Comparative Examples were added simultaneously with the amounts shown in Table 2 and 1.5% bansulfate, followed by stirring for 30 minutes. Next, this pulp slurry was diluted to a concentration of 0.25% with dilution water of pH 4.5, and then cationic polyacrylamide (Nippon PMC) was used as a fixing agent.
0.05% of Papermaking Co., Ltd. DS410) was added and the paper was made (pH 4.5) with a Noble and Wood paper machine to obtain a test paper having a basis weight of 65 g / m ² . Drying of the wet paper was performed under a predetermined drying condition using a drum dryer. The obtained test paper was subjected to a constant temperature and humidity environment (20 ° C., 65% relative humidity) for 2 hours.
After humidification for 4 hours, the size was measured by the Stechich method. The results are shown in Table 2. In the table, among the drying conditions,
The condition at 80 ° C. for 100 seconds corresponds to “when the drying conditions are relatively mild”.

[0033]

[Table 2]

Stationary stability test [0034] 100 ml of the sizing agent of the above example and comparative example was placed in a test tube having a length of 30 cm and an inner diameter of 2.1 cm, and after standing for 3 months,
The height (cm) of the precipitate that settled at the bottom was measured. Table 3 shows the measurement results.

Mechanical Stability Test A Marlon-type stability test was performed for 5 minutes at a temperature of 25 ° C., a load of 20 Kg, and a rotation speed of 800 rpm, by putting 50 g of each of the sizing agents of the above Examples and Comparative Examples in a cup. The formed aggregate was filtered through a 325 mesh wire net, and the amount of the precipitate relative to the total solid content was measured and expressed as a percentage. Table 3 shows the measurement results.
Shown in

[0036]

[Table 3]

[0037]

According to the present invention, be at least one and, rosin emulsion composition was stably dispersed in water by a dispersing agent and a rosin-based material belonging to the number 15 or more fatty acids carbon, the At least high-molecular milk
Rosin-based emulsion composition using a dispersing agent, a method for producing the same, a sizing agent, a sizing method, and a sized paper can be provided.When sizing is performed using a sizing agent containing the rosin-based emulsion composition, machine speed can provide a paper which exhibits excellent sizing effect not be found in conventional anionic or cationic b di emissions emulsion in the mild conditions drying conditions at high speed. Further, this sizing agent is excellent in storage stability and mechanical stability.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-59-89357 (JP, A) JP-B-37-12702 (JP, B1) JP-B-37-12001 (JP, B1) (58) Field (Int.Cl. ⁷ , DB name) D21H 11/00-27/42

Claims (9)

(57) [Claims] 1. A rosin emulsion composition in which (A) at least one of fatty acids having 15 or more carbon atoms as a main component and (B) a rosin-based substance are stably dispersed in water by a ( C) dispersant. Material , which is rare in the above dispersants.
Rosin-based emulsion using high molecular weight emulsifying dispersant
Composition . 2. The fatty acid of (A) is at least one selected from the group consisting of synthetic higher fatty acids, natural higher fatty acids, dimers of unsaturated fatty acids and trimers of unsaturated fatty acids. A rosin-based emulsion composition. 3. Component (A) is 0.5 to 20 parts by weight, (B)
60 to 98.5 parts by weight of component and 1 to 20 component (C)
The rosin emulsion composition according to claim 1 or 2, wherein a total of 100 parts by weight of the total weight is stably dispersed in water to obtain a dispersion having a solid content of 20 to 60% by weight. 4. The rosin emulsion composition according to claim 1, wherein a mixture particle obtained by previously mixing the component (A) and the component (B) is contained in the dispersoid. 5. Component (A) is 0.5 to 20 parts by weight, (B)
60 to 98.5 parts by weight of component and 1 to 20 component (C)
The rosin emulsion composition according to claim 4, wherein a total of 100 parts by weight of the total weight is stably dispersed in water to obtain a dispersion having a solid content of 20 to 60% by weight. 6. The method for producing a rosin emulsion composition according to claim 4, wherein the component (A) and the component (B) are mixed, and the mixture is dispersed in water using the component (C). 7. A sizing agent containing the rosin emulsion composition according to claim 1. 8. A sizing method using the rosin emulsion composition according to claim 1 as a sizing agent. 9. (A) a fatty acid having 15 or more carbon atoms,
A sized paper containing (B) a rosin-based substance and (C) a polymer-based emulsifying and dispersing agent .