JP2010013768A - Dispersing agent for rosin emulsion sizing agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new rosin emulsion sizing agent having excellent sizing effect, hardly causing problems such as foaming and contamination in paper-making process and having excellent runnability: and to provide a dispersing agent to realize the sizing agent. <P>SOLUTION: The dispersing agent for rosin emulsion sizing agents is produced using a vinyl monomer comprising (a) at least one of hydrophobic vinyl monomer, (b) at least one of anionic water-soluble vinyl monomer and (c) at least one of nonionic water-soluble vinyl monomer; and (d) at least one of polyvalent mercapto compound as essential components and polymerizing the components. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention has an excellent sizing effect, a novel rosin emulsion sizing agent having excellent operability and less prone to problems such as foaming and dirt in the papermaking process, and a rosin emulsion sizing agent used to produce the sizing agent It relates to a dispersant. In particular, the present invention relates to a rosin emulsion sizing agent dispersant and / or a sizing agent using the dispersing agent, which uses a copolymer obtained by using a polyvalent mercapto compound as a constituent component as a sizing agent dispersing agent. .

  The Japanese paper industry has long used rosin emulsion sizing agents for paper sizing, but in the 1980s, the use of calcium carbonate, an inexpensive pigment, as a coating color for coated paper and coated paperboard The amount increased. Then, coated paper and coated paperboard containing a large amount of calcium carbonate have been recycled, and have begun to be used as waste paper or used paper. Since calcium carbonate is basic, it has the effect of increasing the pH of the papermaking system when mixed in the papermaking system. For this reason, in the conventional acidic papermaking system, when waste paper or waste paper containing calcium carbonate is used, the papermaking pH rises and the size effect of the sizing agent for acidic papermaking is not sufficiently exhibited. If the amount of sulfuric acid band added is increased in order to lower the papermaking pH, the problem of contamination such as scales will occur in the papermaking process. In order to solve this problem, a rosin emulsion sizing agent for weakly acidic to neutral papermaking was developed in the 1990s, and a rosin emulsion sizing agent suitable for acidic to neutral papermaking and each papermaking condition seems to be used. And today.

  Rosin emulsion sizing agent is used for acidic papermaking, with rosin and modified rosin with maleic acid or fumaric acid added to rosin to be emulsified, and copolymerization of styrene and / or (meth) acrylic monomer and anionic vinyl monomer. A rosin emulsion sizing agent using a product as a dispersant is used (see, for example, Patent Documents 1 and 2). For weakly acidic and neutral papermaking, styrene and / or (meth) acrylic monomers and anions are prepared by mixing rosin and a mixture of modified rosin with maleic acid or fumaric acid added to rosin and polyhydric alcohol rosin ester. A rosin emulsion sizing agent in which a copolymer of a non-ionic vinyl monomer such as a reactive vinyl monomer and / or (meth) acrylamide is used as a dispersant is mainly used. Various types of rosin emulsion sizing agents have been proposed to date, but in the papermaking industry, rosin emulsion sizing agents that give a better sizing effect and foaming and dirt in the papermaking process to further reduce costs. Rosin emulsion sizing agent with better sizing effect and more. Development of a rosin emulsion sizing agent that is free from problems such as foaming and dirt is desired (see, for example, Patent Documents 3 to 8).

In order to increase the size effect of the rosin emulsion sizing agent, it is effective to increase the molecular weight of the dispersant. This is because, when the molecular weight of the dispersant is increased, the coating property and protective colloid property for the emulsified product are improved, and the emulsified state is stabilized. However, if the molecular weight of the dispersant is increased too much, there arises a problem that the foaming property against foaming of the emulsion is deteriorated. In addition, since the foam surface is easy to dry, the “skinning phenomenon” that forms a film on the surface of the product is likely to occur, and if the film enters the papermaking system, the strainer becomes clogged or dirty, causing operational problems. It becomes. For this reason, when trying to increase the molecular weight of the dispersant in order to increase the size effect, the rosin emulsion sizing agent using the dispersant is poor in foaming and easily foams, and the purpose can be achieved. It was difficult.
JP 56-169898 A JP 7-258994 A JP-A-62-2223393 Japanese Patent Laid-Open No. 1-203031 JP-A-8-337997 Japanese Patent Laid-Open No. 10-245795 JP 2003-55891 A JP 2007-56416 A

  An object of the present invention is to provide a novel rosin emulsion sizing agent that has an even better sizing effect than conventional rosin emulsion sizing agents, is less likely to cause problems such as foaming and dirt in the papermaking process, and has excellent operability. It is to provide a dispersant for the sizing agent that makes it possible.

  As a result of intensive studies to solve the above problems, the present inventor has found that rosin-based emulsion sizing agents are a) at least one hydrophobic vinyl monomer; b) at least one anionic water-soluble substance. A vinyl monomer; and c) a vinyl monomer composed of at least one nonionic water-soluble vinyl monomer, and d) a polyvalent mercapto compound as an essential component. The new rosin emulsion sizing agent obtained in this way has a better sizing effect than conventional rosin emulsion sizing agents, and is less likely to cause problems such as foaming and dirt in the papermaking process, and has excellent operability. The present invention has been completed.

  That is, the present invention is a rosin-based emulsion sizing agent dispersant comprising: a) at least one hydrophobic vinyl monomer; b) at least one anionic water-soluble vinyl monomer; and c) at least It is a dispersant for a rosin emulsion sizing agent obtained by polymerizing, as essential components, a vinyl monomer composed of one nonionic water-soluble vinyl monomer and d) at least one polyvalent mercapto compound.

  In the rosin emulsion sizing agent dispersant, the present invention provides a total of 100 parts by weight of a monomer comprising a) component 6 to 40 parts by weight, b) component 6 to 40 parts by weight, and c) component 6 to 70 parts by weight. The d) component is used in an amount of 0.01 to 3 parts by weight, based on the rosin-based emulsion sizing agent dispersant.

  Furthermore, the present invention disperses a rosin-based material containing at least one of rosins and reinforced rosins and / or at least one of rosin esters and reinforced rosin esters in the rosin emulsion sizing agent dispersion described above. Rosin emulsion sizing agent.

  The rosin emulsion sizing agent produced using the rosin emulsion sizing agent dispersant of the present invention has a further superior size effect than conventional rosin emulsion sizing agents, such as foaming and dirt in the papermaking process. It is difficult to cause problems and has excellent operability.

Examples of the hydrophobic vinyl monomers a) which can be used in the present invention include (meth) acrylic acid alkyl esters having an alkyl group having 1 to 30 carbon atoms and cycloalkyl (meth) acrylates having 5 to 20 carbon atoms. There are at least one monomer selected from esters, aromatic olefins and aliphatic olefins. Specifically, there are butyl (meth) acrylate, cyclohexyl (meth) acrylate, ethylhexyl (meth) acrylate, etc., styrenes, monomers of styrene compounds, and the like. Cyclohexyl methacrylate is preferred.
The component a) can be used in an amount of 6 to 40 parts by weight of the total of the monomers a) to c), that is, 100 parts by weight. More preferably, it is 6-30 weight part. When the amount is less than 6 parts by weight, the affinity between the rosin-based material and the dispersant is reduced. When the amount is 40 parts by weight or more, the affinity with the rosin-based material is improved, but the affinity for the aqueous dispersion medium is decreased. Thus, a good emulsifying dispersant cannot be obtained.

  Examples of the anionic water-soluble vinyl monomers that can be used in the present invention include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinyl sulfonic acid, (meta And) at least one monomer selected from allyl sulfonic acid, styrene sulfonic acid, (meth) acrylic alkyl sulfonic acid and salts thereof. Of these, methacrylic acid and itaconic acid are preferred. Component b) can be used in an amount of 6 to 40 parts by weight out of a total of 100 parts by weight of monomers a) to c). The amount is preferably 7 to 30 parts by weight. When the amount is less than 6 parts by weight, the hydrophilicity of the dispersant is lowered and good emulsifiability cannot be obtained. When it exceeds 40 parts by weight, the mechanical stability of the rosin emulsion sizing agent containing an emulsion obtained by the dispersant tends to be deteriorated.

  Nonionic water-soluble vinyl monomers as component c) that can be used in the present invention include, for example, (meth) acrylamide, N, N-alkyl (C1-2) (meth) acrylamide, (meth) acrylonitrile, vinyl acetate , (Meth) allyl alcohol, 2-hydroxyethyl (meth) acrylic ester, polyoxyethylene (meth) acrylic ester, polyoxypropylene (meth) acrylic ester, and the like. Of these, acrylamide is preferred. The component c) is 6 to 70 parts by weight, preferably 7 to 60 parts by weight, out of a total of 100 parts by weight of the monomers a) to c). When the amount is less than 6 parts by weight, the stability of the rosin emulsion sizing agent containing the emulsion obtained by the dispersant to calcium carbonate is not good, and when it exceeds 70 parts by weight, good emulsifying properties cannot be obtained.

  The polyvalent mercapto compound as component d) that can be used in the present invention includes ethylene glycol bisthioglycolate, butanediol bisthioglycolate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthioglycolate, and other thioglycols. There are at least one compound selected from acid derivatives, mercaptopropionic acid derivatives such as trimethylolpropane tristhiopropionate and pentaerythritol tetrakisthiopropionate. Of these, pentaerythritol tetrakisthioglycolate and pentaerythritol tetrakisthiopropionate are preferred. The component d) can be used in an amount of 0.01 to 3 parts by weight, preferably 0.1 to 2 parts by weight, based on a total of 100 parts by weight of the components a) to c). When the amount is less than 0.01 part by weight, the effect obtained by adding the polyvalent mercapto compound is very small, so that the effect cannot be expected. On the other hand, if it exceeds 3 parts by weight, the chain transfer effect becomes strong, the molecular weight of the dispersant tends to decrease, and this tends to cause a decrease in emulsification and performance, which is not preferable.

  In addition to the components a) to d), the dispersant of the present invention includes n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, stearyl mercaptan, thiophenol, thiobenzoic acid, thiol as mercaptans. Salicylic acid, naphthalenethiol, toluenethiol, mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoglycol, thioglycerin, cysteamine hydrochloride (salt), mercaptopropionic acid (salt), thioglycolic acid (salt), thioacetic acid (salt) thiomalic acid (Salt), methyl, ethyl, propyl, butyl, methoxybutyl, n-octyl, 2-ethylhexyl and the like thioglycolic acid ester and mercaptopropionic acid ester, terpinolene, α-methyl Rusuchiren, the α- methylstyrene dimer or the like can be used in a range that does not inhibit the performance of dispersants. These additives may make it easier to adjust the molecular weight of the dispersant.

  The dispersant of the present invention can be produced by a conventionally known polymerization method such as solution polymerization, emulsion polymerization or suspension polymerization. In the case of solution polymerization, polymerization is performed using water, lower alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and tertiary butyl alcohol, and solvents such as acetone, methyl ethyl ketone, and dioxane. Two or more of these solvents can be used in combination. In the case of emulsion polymerization or suspension polymerization, a known anionic and / or nonionic surfactant is used and polymerization is carried out in the solvent.

  A well-known thing can be used for a polymerization initiator. For example, persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate, redox polymerization catalysts based on combinations of these persulfates and reducing agents, or azo catalysts such as 2'2-azobisisobutyronitrile, Or organic peroxides, such as hydrogen peroxide, t-butyl peroxide, and benzoyl peroxide, can be mentioned.

  The obtained polymer can be used by neutralizing the carboxylic acid in the copolymer of the dispersant of the present invention with an inorganic and / or organic alkali as necessary. Examples of the inorganic alkali used for neutralization include sodium hydroxide and potassium hydroxide, and examples of the organic alkali include organic amines such as ammonium, monoethanolamine, diethanolamine, and triethanolamine. The neutralization of the copolymer with the alkali may be either complete neutralization or partial neutralization as necessary.

  The weight average molecular weight (Mw) of the obtained copolymer is about Mw 1000 to 700,000, preferably 1000 to 500,000. When the weight average molecular weight is less than 1000, the emulsifying ability with respect to the rosin-based substance is inferior, and when it exceeds 700,000, the viscosity of the sizing agent obtained by the dispersant tends to increase, which is not preferable.

Using the rosin emulsion sizing agent dispersant of the present invention, a rosin emulsion sizing agent can be produced by emulsifying and dispersing a rosin substance.
Examples of rosin-based substances that can be used in the present invention include rosins, reinforced rosins, rosin esters, and reinforced rosin esters, which can be used alone or in combination. The blending ratio and blending component of the rosin substance can be appropriately changed depending on the conditions of the papermaking process in which the rosin emulsion sizing agent is used. For example, when the pH of the papermaking process is about 4.5 to 5.0, the blending amount of reinforced rosins is 50% to 100% by weight, and rosin esters and / or reinforced rosin esters are 0 to 50% by weight. When the pH of the papermaking process is about 5.5 to 7.0, 10 to 60% by weight of reinforced rosins and 10 of rosin esters and / or reinforced rosin esters are used. It is preferable to mix and use -60% by polymerization.

  Examples of rosins that can be used in the present invention include gum rosin, tall oil rosin, wood rosin, and the like, and these modified products such as hydrogenated rosin, disproportionated rosin, polymerized rosin, and aldehyde-modified rosin. One or more kinds selected from the rosins can be used in combination.

  The reinforced rosins that can be used in the present invention are those obtained by adding 1 to 20% by weight, preferably 3 to 18% by weight, of α, β-unsaturated carboxylic acid and / or its anhydride to the aforementioned rosins. . Examples of the α, β-unsaturated carboxylic acid and / or anhydride thereof include α, such as fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, and citraconic anhydride. β-unsaturated dibasic carboxylic acid and its anhydride, α, β-unsaturated monobasic carboxylic acid such as acrylic acid and methacrylic acid, and the like, one or more selected from these Can be used in combination.

  The rosin esters that can be used in the present invention are obtained by an esterification reaction of the above rosins with alcohols, phenols, epoxy compounds and the like. It may contain fully and / or partially esterified products and may contain unreacted rosins. Alcohols include glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, diglycerin, sorbitol and the like. Phenols include hydroquinone, pyrogallol, bisphenol A and the like. Epoxy compounds include glycidyl ether type epoxy resins. The esterification reaction can be carried out using one or more of the alcohols, phenols, and epoxy compounds. The reaction method can be carried out by a known method.

  The reinforced rosin esters that can be used in the present invention are those obtained by adding an α, β-unsaturated carboxylic acid and / or an anhydride thereof to the rosin esters. The addition reaction may be any stage before the esterification reaction, simultaneously with the esterification reaction, or after the esterification reaction.

  The rosin emulsion sizing agent according to the present invention is obtained by emulsifying and dispersing a rosin-based substance using the dispersant of the present invention. The amount of the dispersant used is 1 to 15% by weight based on the total solid content, Preferably, it is 3 to 10% by weight. If the amount is less than 1% by weight, the dispersibility is not sufficient and it is difficult to emulsify the rosin-based material. If the amount exceeds 15% by weight, foaming in the paper-making system increases, resulting in an increase in cost.

  The method for emulsifying rosins using the dispersant of the present invention is not particularly limited, and is a known method (for example, the methods described in US Pat. No. 2,393,179, US Pat. No. 3,565,755, and US Pat. No. 4,157,982). ).

  For example, it can be emulsified by any method such as phase inversion emulsification, solvent emulsification, and mechanical emulsification. By optimizing emulsification conditions such as shear force and pressure, a rosin emulsion having a desired particle size and particle size distribution can be obtained.

  In emulsification, a known surfactant or polymer copolymer can be used in combination as long as the effect of the dispersant of the present invention is not impaired. Examples of surfactants that can be used in combination include alkylamine salts and quaternized products thereof, and alkylamidoamines as cationic surfactants. Nonionic surfactants include polyoxyalkylene phenyl ether and polyoxyalkylene alkyl ether. Sorbitan alkyl esters, polyoxyalkylene sorbitan alkyl esters, polyoxyalkylene rosin esters, and the like, and anionic surfactants include alkali neutralized salts of rosins and reinforced rosins, alkylbenzene sulfonates, alkyl sulfates, Naphthalene sulfonates, ASA alkali salts, polyoxyalkylene alkyl ether sulfates, and the like. Examples of the polymer copolymer include a styrene-methacrylic acid copolymer and a (meth) acrylamide copolymer.

  The rosin emulsion has a small particle size and is uniformly fixed on the paper sheet at the wet end and is easily distributed uniformly. Since it is large, it becomes easy to receive chemical modification, which causes a decrease in the imparted size, which is not preferable. On the other hand, if the particle size of the rosin emulsion is large, fixing at the wet end becomes non-uniform, and physical stability deteriorates, causing problems such as storage stability and contamination in the papermaking process. Neutral papermaking may be preferable because the specific surface area is small, so that it is difficult to undergo chemical modification, and the size property is hardly lowered. The rosin emulsion obtained by the production method of the present invention is adjusted to the desired particle size by adjusting the structure or blending amount of the rosin-based emulsion sizing agent, the blending ratio of the rosin-based material, the emulsification conditions, and the like. A rosin emulsion suitable for the papermaking pH requirement can be produced, which is preferable.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to these examples. In the following, the weight average molecular weight was measured under the following conditions.

Measuring instrument: GPC-8020 mode III manufactured by Tosoh Corporation
Column: Tosoh GPWXL
Measurement temperature: 40 ° C
Detector: differential refractometer A B-type viscometer (manufactured by Tokyo Keiki Co., Ltd .: BM) was used for measuring the viscosity.

<Manufacture of dispersant>
(Production Example 1)
In a five-necked flask equipped with a thermometer, cooler, stirrer, and nitrogen inlet tube, 120 parts of styrene as a hydrophobic vinyl monomer, 28.6 parts of n-butyl methacrylate, as an anionic water-soluble vinyl monomer 114.3 parts of methacrylic acid, 50 parts of 40% acrylamide aqueous solution as a nonionic water-soluble vinyl monomer, 5.7 parts of terpinolene, 2.9 parts of normal dodecyl mercaptan, pentaerythritol tetrakis as a polyvalent mercapto compound 2.9 parts of thioglycolate was charged. Thereafter, 390.0 parts of water and 280.0 parts of isopropyl alcohol were added and heated to 80 ° C. As a polymerization initiator, 5.7 parts of ammonium persulfate was added, and polymerization was performed for 4 hours. Then, isopropyl alcohol was distilled off and water was added to obtain Dispersant 1 having a concentration of 30%, a weight average molecular weight (Mw) of 87000, and a viscosity of 800 mPa · s.

(Production Example 2)
In the same apparatus as in Production Example 1, 76.0 parts of styrene, 76.0 parts of normal butyl methacrylate, 23.4 parts of 2-ethylhexyl acrylate, 87.8 parts of acrylic acid, 58% 40% acrylamide aqueous solution .5 parts, 5.8 parts of α-methylstyrene dimer, and 1.5 parts of ethylene glycol bisthioglycolate as a polyvalent mercapto compound were charged. Thereafter, 385 parts of water, 280 parts of isopropyl alcohol and 5.8 parts of azoisobutyronitrile as a polymerization initiator were added and dissolved, heated to 80 ° C., and kept at the same temperature for 4 hours. Thereafter, isopropyl alcohol was distilled off in the same manner as in Example 1, and water was added to obtain Dispersant 2 having a concentration of 30%, Mw of 85000, and a viscosity of 920 mPa · s.

(Production Example 3)
In the same reactor as in Production Example 1, 58.3 parts of styrene, 58.3 parts of cyclohexyl methacrylate, 58.3 parts of normal butyl methacrylate, 99.1 parts of methacrylic acid, 15 parts of 40% acrylamide aqueous solution, 5.8 parts of terpinolene, 5.8 parts of α-methylstyrene dimer, and 2.9 parts of pentaerythritol tetrakisthioglycolate as a polyvalent mercapto compound were charged. 411 parts of water and 280 parts of isopropyl alcohol were added and dissolved at 80 ° C. As a polymerization initiator, 5.8 parts of ammonium persulfate was added, and polymerization was performed for 4 hours. Thereafter, isopropyl alcohol was distilled off and water was added to obtain Dispersant 3 having a concentration of 30%, Mw 96000, and viscosity 750 mPa · s.

(Production Example 4)
In the same reactor as in Production Example 1, 41.3 parts of styrene, 41.3 parts of cyclohexyl methacrylate, 41.3 parts of n-butyl acrylate, 82.6 parts of methacrylic acid, and 172. 3 parts, 13.8 parts of terpinolene, 2.7 parts of n-dodecyl mercaptan, and 2.5 parts of butanediol bisthioglycolate as a polyvalent mercapto compound were charged. Thereafter, 316.7 parts of water, 280 parts of isopropyl alcohol, and 5.8 parts of azobisisobutyronitrile were added and dissolved at 40 ° C. After confirmation of dissolution, the mixture was heated to 80 ° C. and maintained at the temperature for 4 hours, and then isopropyl alcohol was distilled off, and water was added to obtain Dispersant 4 having a concentration of 30%, Mw 88000, and viscosity of 1050 mPa · s.

(Production Example 5)
In the same reactor as in Production Example 1, 100.5 parts of cyclohexyl methacrylate, 28.7 parts of 2-ethylhexyl acrylate, 71.7 parts of methacrylic acid, 215.3 parts of 40% acrylamide aqueous solution, and 1 part of terpinolene Then, 0.5 parts of 2-ethylhexyl mercaptopropionate and 1.5 parts of pentaerythritol tetrakisthioglycolate as a polyvalent mercapto compound were charged. Furthermore, 290.9 parts of water and 280 parts of isopropyl alcohol were added, 5.8 parts of azobisisobutyronitrile was added as a polymerization initiator, and the concentration was 30%, Mw 101000, viscosity 960 mPa · s in the same manner as in Example 4. Dispersant 5 of s was obtained.

(Production Example 6)
In the same reactor as in Production Example 1, 57.2 parts of cyclohexyl methacrylate, 57.2 parts of n-butyl acrylate, 85.8 parts of methacrylic acid, 214.5 parts of 40% acrylamide aqueous solution and 2.2. 9 parts, 2.9 parts of α-methylstyrene dimer, and 2.6 parts of trimethylolpropane tristhioglycolate as a polyvalent mercapto compound were charged. Furthermore, 291.3 parts of water and 280 parts of isopropanol were charged and heated to 80 ° C. Thereafter, 5.7 parts of ammonium persulfate was added as a polymerization initiator and reacted for 4 hours. Thereafter, isopropanol was distilled off, and the concentration was adjusted with water to obtain Dispersant 6 having a concentration of 30%, Mw of 89000, and a viscosity of 860 mPa · s.

(Production Example 7)
In the same reactor as in Production Example 1, 56.7 parts of cyclohexyl methacrylate, 28.4 parts of n-butyl methacrylate, 28.4 parts of 2-ethylhexyl acrylate, 248 parts of 40% aqueous acrylamide solution, and 56 of itaconic acid 0.7 parts, sodium p-styrenesulfonate 8.5 parts, sodium vinylsulfonate 5.7 parts, terpinolene 2.8 parts, α-methylstyrene dimer 2.8 parts, 2-mercaptoethanol 2 .8 parts, 1.2 parts of pentaerythritol tetrakisthioglycolate as a polyvalent mercapto compound, 271.2 parts of water, and 280 parts of isopropyl alcohol were added. The mixture was heated to 80 ° C., 5.7 parts of ammonium persulfate was added as a polymerization initiator, and the reaction was performed at the same temperature for 4 hours. Thereafter, isopropyl alcohol was distilled off, and the concentration was adjusted with water, whereby Dispersant 7 having a solid content of 30%, Mw of 120,000, and a viscosity of 800 mPa · S was obtained.

(Production Example 8)
In the same reactor as in Production Example 1, 34.2 parts of cyclohexyl methacrylate, 22.8 parts of 2-ethylhexyl acrylate, 320.3 parts of 40% aqueous acrylamide solution, 71.2 parts of itaconic acid, methallylsulfonic acid 14.2 parts of sodium, 14.2 parts of sodium vinyl sulfonate, 0.6 parts of terpinolene, 5.7 parts of 2-mercaptoethanol, 1.0 of pentaerythritol tetrakisthiopropionate as a polyvalent mercapto compound 227.9 parts of water and 280 parts of isopropyl alcohol were added, and 5.7 parts of azoisobutyronitrile was added as a polymerization initiator and dissolved at 40 ° C. Then, after heating to 80 ° C. and carrying out polymerization for 4 hours, isopropyl alcohol was distilled off and the concentration was adjusted with water to obtain Dispersant 8 having a solid content of 30%, Mw of 140000, and a viscosity of 700 mPa · s.

(Production Examples 9-15)
Comparative dispersants 1 to 7 were obtained in the same manner as in Production Examples 1 to 7 except that the polyvalent mercapto compound was not used.

(Production Example 16)
Comparative dispersant 8 was obtained in the same manner as in Production Example 8, except that pentaerythritol tetrakisthiopropionate was not used and terpinolene was changed to 1.6 parts.

  Table 1 shows the weight average molecular weights (Mw) of the dispersants 1-8 and the comparative dispersants 1-8.

<Manufacture of reinforced rosin>
(Production Example 17: Rosin fumaric acid-reinforced product)
920 parts of gum rosin are charged into a 1 L four-necked flask, heated and melted at 200 ° C., and then 80 parts of fumaric acid is added and held at the same temperature for 3 hours to obtain a reaction product R1 of SV (saponification number) 233 It was.

(Production Example 18: Rosin maleic anhydride fortified product)
920 parts of gum rosin are charged into a 1 L four-necked flask and heated and melted at 200 ° C. Thereafter, 80 parts of maleic anhydride was added and held at the same temperature for 3 hours to obtain a reaction product R2 of SV246.

(Production Example 19: Glycerin ester of rosin)
600 parts of gum rosin and 55 parts of glycerin were charged into a 1 L four-necked flask and heated to 200 ° C. under a nitrogen stream to conduct a dehydration reaction. Thereafter, a dehydration reaction was further performed at 270 ° C. for 14 hours to obtain a reaction product R3 of AV30.

(Production Example 20: anhydrous maleic oxide of rosin ester)
950 parts of the reaction product obtained in Example 19 is charged into a 1 L four-necked flask and heated and melted at 200 ° C. Thereafter, 50 parts of maleic anhydride was added and held at the same temperature for 3 hours to obtain a reaction product R4 of SV85.

(Example 1: Production of rosin emulsion sizing agent)
Add 100 parts of fumarated rosin obtained in Production Example 17 to a 1 L autoclave, heat and melt to 150 ° C., and add 3.3 parts of 48% sodium hydroxide to 30 parts of the dispersant obtained in Production Example 1 The resulting mixture was further phase-inverted while adding 85 parts of hot water to obtain a rosin emulsion sizing agent having a solid content of 50%.

(Examples 2-8, Comparative Examples 1-8)
In the same manner as in Example 1, the dispersants 2 to 8 and comparative dispersants 1 to 8 were used, and the rosin substances obtained in Production Examples 17 to 20 were used at the composition ratios shown in Table 2, respectively. Rosin emulsion sizing agents each having a solid content of 50% were obtained.

<Measurement of particle size>
It was measured with a Shimadzu laser diffraction / scattering particle size distribution analyzer SALD-2100. The measured particle diameter is the median diameter.

<Mechanical stability test>
The sizing agent of Example or Comparative Example (50 g) was put into a cup, and a Marlon stability test was performed at 25 ° C., a load of 20 kg, and a rotation speed of 1000 rpm for 10 minutes. The produced agglomerate was filtered through 200 mesh, and the agglomeration amount relative to the total solid content was shown as a percentage.

<Redispersibility in water>
1 g of air-dried sizing agent and 50 g of tap water were placed in a test tube and stirred gently to observe the redispersibility of the dry matter. Evaluation was performed in a three-step evaluation with 3 being easily dispersed, 2 being dispersed by stirring about 10 times, and 1 being not dispersed at all.

<Standing stability test>
500 cc of the sizing agent of Example or Comparative Example was put in a test tube having a length of 100 cm and an inner diameter of 3 cm, and left standing at room temperature in a cool and dark place for 2 months. The height (mm) of the sediment that settled to the bottom was measured.

<Bubbling test>
Pulp (LBKP / NBKP = 8/2) beaten to 400 cc of Canadian Standard Freeness was used as a 2.0% pulp slurry, and calcium carbonate (TP-121 manufactured by Okutama Kogyo Co., Ltd.) having a pulp solid content of 15%, 1% sulfuric acid band, 0.5% cationized starch (Nato Nippon Cat. 3210) and 2% of each sizing agent obtained in Examples and Comparative Examples were added, and the calcium chloride aqueous solution was adjusted to 100 German hardness. The pulp concentration was diluted to 0.2% and placed in a box-type container. The pulp slurry was circulated with a pump and dropped into a container from a height of 30 cm. The area of bubbles accumulated on the liquid level after 10 minutes was shown as a percentage of the total liquid surface area.

<Evaluation of size effect by hand-drawing test>
Corrugated waste paper pulp beaten up to 400 cc of Canadian Standard Freeness containing 15% ash and 15% ash is used as a pulp slurry with a dry dry solid content of 2%. The pulp slurry after addition of chemicals for all paper has a pH of 6.5. An amount of sodium hydroxide was added. This pulp slurry was obtained in the above examples and comparative examples of 1.5% sulfuric acid band, 0.5% cationized starch Cato 3210, 0.4% or 0.5% from NSC Japan, based on the absolutely dry pulp. Each sizing agent was added and diluted to a pulp concentration of 0.2%, and the water hardness of the pulp slurry was adjusted to 100 German hardness with calcium chloride. Paper was made with a JIS round paper machine so that the basis weight was 80 g / m ² in accordance with JIS P8222. The wet paper was dried at 90 ° C. for 2 minutes using a drum dryer. The obtained sizing paper was conditioned in accordance with JIS P8111, and the sizing degree of the test paper was measured in accordance with JIS P8122.

  The evaluation results of the above tests are shown in Table 3 and Table 4.

  As can be seen from Table 3 and Table 4, it can be confirmed that the rosin emulsion sizing agent of the present invention has an excellent sizing effect and lower foamability than the sizing agent obtained in the comparative example.

  The rosin emulsion sizing agent of the present invention can be used as a rosin emulsion sizing agent for papermaking because it has an excellent sizing effect and less foamability than conventional rosin emulsion sizing agents.

Claims (4)

a) at least one hydrophobic vinylic monomer;
b) at least one anionic water-soluble vinyl monomer; and c) a vinyl monomer comprising at least one nonionic water-soluble vinyl monomer;
d) A rosin emulsion sizing agent dispersant obtained by polymerizing at least one polyvalent mercapto compound as an essential component.   a) Component 6 to 40 parts by weight, b) Component 6 to 40 parts by weight, and c) Component 6 to 70 parts by weight. The rosin emulsion sizing agent dispersant according to claim 1, wherein the rosin emulsion sizing agent is used in an amount.   The rosin-based emulsion sizing agent dispersion according to claim 1 or 2, wherein the polymer of claim 1 is further completely and / or partially neutralized with an inorganic and / or organic alkali.   A rosin obtained by dispersing a rosin-based material containing at least one of rosins and reinforced rosins and / or at least one of rosin esters and reinforced rosin esters with the dispersant according to claim 1. Emulsion sizing agent.