JPH0138155B2 - - Google Patents

Description

[Detailed description of the invention]

Industrial Application Field: The present invention relates to a method for producing an aqueous emulsion suitable as a waterproofing agent for paper, textiles, and plaster products, and in particular to a method for producing an aqueous emulsion suitable as a waterproofing agent for paper, textiles, and plaster products. This invention relates to a method for producing an aqueous emulsion in which the emulsion is forced into water in the presence of a protective colloid of an alkali salt of a styrene-maleic acid copolymer. BACKGROUND OF THE INVENTION Traditionally, aqueous emulsions of synthetic hydrocarbon resins, waxes and fatty acids have been widely used as water-repellent and waterproofing agents for paper and textiles or for water-proofing and waterproofing of building materials. However, this aqueous emulsion required the use of a large amount of surfactant during its production. The presence of surfactants has a negative effect on the water repellency and waterproofing properties of aqueous emulsions due to their inherent hydrophilic properties, and prevents the hydrocarbon resin, which is the main waterproofing agent, from fully demonstrating its performance. I couldn't do it. When a conventional water-based emulsion is used to coat corrugated paperboard, high temperatures of approximately 160 to 180°C are encountered during the lamination process of corrugated board manufacturing, so this conventional water-based emulsion waterproofing agent is susceptible to thermal deterioration caused by surfactants. This often caused a decrease in water repellency. Generally, for waterproofing gypsum products, alkylbenzene sulfonate surfactants are used in combination as foaming agents. Conventional waterproofing agents have not been able to provide sufficient waterproofing properties. The waterproofness of this gypsum board can be measured by the increase in weight of a test piece after immersing the gypsum board in water. Problem to be Solved by the Invention: When the aqueous emulsion of the present invention is used as a coating agent for corrugated paperboard and a waterproofing agent for plasterboard, the conventional drawbacks are overcome. Means for Solving the Problems: The present invention solves the problem in the boiling point range -20 to
Selected from the group consisting of unsaturated carboxylic acid adducts of synthetic hydrocarbon resins obtained by polymerizing _C5 to _C9 fractions at 250°C by Friedel-Crafts reaction, or monohydric or polyhydric alcohol esters of such adducts. at least one substance; at least one wax; then melted, and the resulting melt and an aqueous protective colloid solution of an alkali salt of a styrene-maleic acid copolymer are mixed together under mechanical stirring. A process for producing aqueous emulsions suitable as waterproofing agents for paper, textile or plaster products, which comprises emulsification and subsequent forced emulsification under high pressure in a piston-type high-pressure emulsifier. In addition, in the method of the present invention, higher fatty acids or metal soaps of higher fatty acids can be added together with wax. When the aqueous emulsion of the present invention was used as a coating agent for corrugated board, no decrease in water repellency due to thermal deterioration was observed. Similarly, when using the aqueous emulsion of the present invention as a waterproofing agent for gypsum board, almost no decrease in waterproofness was observed. Traditionally, these drawbacks have been attributed to the presence of surfactants in significant amounts in aqueous emulsions. In the present invention, various components are dispersed using a protective colloid aqueous solution of an alkali salt of a styrene-maleic acid copolymer. In the present invention, higher fatty acids or higher fatty acid metal soaps are used as optional ingredients. When the aqueous emulsion produced according to the present invention is mixed with a gypsum component and cured, the curing may be carried out at a high temperature of about 120° C. and under pressure. Since gypsum products manufactured under high temperature and pressure in this manner have poor water repellency, higher fatty acids or higher fatty acid metal soaps are further added in the present invention. Further, higher fatty acids or higher fatty acid metal soaps can also be added to paper products. The reason for forced emulsification under high pressure using a piston-type high-pressure emulsifier is that the water-soluble polymer of the present invention cannot be sufficiently emulsified by ordinary emulsification methods. The synthetic hydrocarbon resin used in the present invention has a boiling point range of -20 to 250°C produced during naphtha decomposition.
The softening point obtained by polymerizing the C ₅ - C ₉ fraction of
There are some solids. As a synthetic hydrocarbon resin derivative, 1 to 10wt
% adducts of unsaturated carboxylic acids, monohydric or polyhydric alcohol esters of this adducts are used. Examples of unsaturated carboxylic acids used for modifying hydrocarbon resins include maleic acid, maleic anhydride,
There are α,β-unsaturated polybasic acids such as fumaric acid and itaconic acid, and unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid, which are added by mixing with hydrocarbon resin and heating reaction at 180 to 220°C. get something Alcohols used for esterification include monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, octyl alcohol, cetyl alcohol and stearyl alcohol, dihydric alcohols such as ethylene glycol, propylene glycol and butylene glycol, and others. There are polyhydric alcohols such as glycerin and pentaerythritol, and the esterification reaction is carried out by heating the unsaturated acid adduct and alcohol to 180-220°C, and the degree of esterification is up to half ester. As waxes, paraffin wax, oxidized paraffin, polyethylene wax, montan wax, carnauba wax, microcrystalline wax, etc. are used. Fatty acids include higher fatty acids such as stearic acid and oleic acid, and metal soaps thereof include calcium, magnesium, zinc, aluminum and zirconium salts. The alkali salt of styrene-maleic acid copolymer used as a protective colloid has a molecular weight of 1000 or more.
Preferably, it is an alkali metal salt of a copolymer of 5000. Potassium and sodium are used as alkali metals. Ammonia, morpholine, dimethylamine, etc. are used as other alkali salts. The proportion of the above raw materials used is 3 to 80 parts, preferably 5 to 50 parts of the synthetic hydrocarbon resin or its derivative;
Wax or fatty acids 95-20 parts, preferably 90
~60 parts and 2 to 20 parts, preferably 5 to 15 parts of the alkali salt of the styrene-maleic acid copolymer. Synthetic hydrocarbon resin, wax, and if necessary higher fatty acids or higher fatty acid metal soaps are mixed and melted in a predetermined ratio, and added to an aqueous solution of an alkali salt of a styrene-maleic acid copolymer for protective colloid. Pre-emulsify at 200°C using a powerful stirrer with high shear and under pressure if necessary. In this case, when an unsaturated carboxylic acid derivative of a hydrocarbon resin is used, it is preferable to saponify the resin derivative at the same time by adding an alkali, preferably an organic alkali such as dimethylamine, to the aqueous protective colloid solution. The pre-emulsion is then passed through a piston-type high-pressure emulsifier or colloid mill at least once under a pressure of 100 to 500 Kg/cm ² , preferably 200 to 300 Kg/cm ² for forced emulsification and quenching to form the desired fine particles. Obtain an emulsion of particles. The emulsion is obtained at a high concentration of approximately 40%, can be diluted with water to any concentration, and has excellent storage stability. In addition, if preliminary emulsification is performed without using an alkaline salt aqueous solution of styrene-maleic acid copolymer, which is a protective colloid, phase separation will occur immediately after discharge from the emulsifier, and forced emulsification will no longer be possible. Can not. The aqueous emulsion produced according to the present invention can be applied to paper and fibers, particularly corrugated board liners, to improve their waterproof properties, and any known coating method can be used such as roll coating, brush coating, dipping, etc. . Furthermore, when manufacturing gypsum products, especially gypsum board boards, an aqueous emulsion can be added to the water used to knead the gypsum to improve the waterproofness of the product. Therefore, the obtained gypsum board board can also be used in places where water is used, such as bathrooms, washrooms, and kitchens. This invention will be explained in more detail by the following examples. In addition, in this specification, the description "part" represents a part by weight, and the description "%" represents weight %. Example 1 Hi-Resin #120 (C ₉ produced during naphtha decomposition)
Synthetic hydrocarbon resin manufactured by Federal Petroleum Resin Co., Ltd. obtained by polymerizing fraction 85-100% by Friedel-Crafts reaction, softening point 120°C, bromine number 30) 71 parts, melting point
259 parts of paraffin wax (145〓 (63℃)) and 40 parts of aluminum stearate were mixed and melted at a temperature of 120℃ under a pressure of 1.5Kg/cm ² in an autoclave, and styrene maleic anhydride copolymer was added to this mixture. Potassium salt (molar ratio of styrene to maleic acid is 2:
1. 600 parts of warm water containing 30 parts of molecular weight 1000-3000) was added and mixed, and pre-emulsified at the same pressure. The obtained emulsion is processed using a piston-type high-pressure emulsifier.
A stable aqueous emulsion with a concentration of 40% was obtained by passing it twice under a pressure of 300 Kg/cm ² . Example 2 Hi-Resin #90 (synthetic hydrocarbon manufactured by Toho Oil Resin Co., Ltd. obtained by polymerizing 20-40% of _C5 fraction and 80-60% of _C9 fraction produced during naphtha decomposition by Friedel-Crafts reaction) Resin, softening point 90℃, bromine number
45) 950 parts of maleic anhydride and 50 parts of maleic anhydride were heated and stirred in a reaction vessel at 210°C for 4 hours to obtain 1000 parts of a maleated hydrocarbon resin having a saponification value of 105 and a softening point of 99°C. 130 parts of this maleic hydrocarbon resin and a melting point of 125
〓 (52℃) 200 parts of paraffin wax and 40 parts of calcium stearate are mixed and mixed with dimethylamine.
20 parts, styrene-maleic acid copolymer ammonium salt (molar ratio of styrene to maleic acid is 1.4:1,
Add 30 parts (molecular weight 4000-5000) and 600 parts of warm water,
Pre-emulsified. The obtained emulsion was heated under a pressure of 350 kg/cm ² using a piston-type high-pressure emulsifier.
A stable aqueous emulsion with a concentration of 40% was obtained. Example 3 Hi-Resin #60 (synthetic hydrocarbon manufactured by Toho Oil Resin Co., Ltd. obtained by polymerizing 40-60% of _C5 fraction and 60-40% of _C9 fraction produced during naphtha decomposition by Friedel-Crafts reaction) Resin, softening point 60℃, bromine number
55) 100 parts, 240 parts of paraffin wax with a melting point of 125〓 (52℃) and 30 parts of aluminum stearate were heated and melted, and styrene-maleic acid copolymer potassium salt (the molar ratio of styrene to maleic acid
1.2:1, molecular weight 2000-3000) 600% warm water containing 30 parts
of the mixture was added, and pre-emulsification was carried out at a liquid temperature of 90°C. The obtained emulsion was passed twice under a pressure of 300 Kg/cm ² using a piston-type high-pressure emulsifier to obtain a stable aqueous emulsion with a concentration of 40%. Example 4 Hi-Resin #60 (synthetic hydrocarbon manufactured by Toho Oil Resin Co., Ltd. obtained by polymerizing 40-60% _C5 fraction and 60-40% _C9 fraction generated during naphtha decomposition by Friedel-Crafts reaction) Resin, softening point 60℃, bromine number
55) 100 parts, 200 parts of paraffin wax with a melting point of 125〓 (52 °C), 50 parts of polyethylene wax with an acid value of 20 and a softening point of 103 °C, and 20 parts of zirconium stearate.
30 parts of styrene-maleic acid copolymer ammonium salt (mole ratio of styrene to maleic acid 1.8:1, molecular weight 3000-4000) and 600 parts of warm water containing 1.6 parts of dimethylamine were added for pre-emulsification. I did it. The obtained emulsion was passed once under a pressure of 250 kg/cm ² using a piston-type high-pressure emulsifier to obtain a stable aqueous emulsion with a concentration of 40%. Example 5 879 parts of the maleated petroleum resin obtained in Example 2 and 121 parts of stearyl alcohol were heated at 210°C in a reaction vessel.
Heat and stir for 4 hours to obtain an acid value of 25 and a softening point of 72°C.
1000 parts of an esterified product of maleated hydrocarbon resin was obtained. 100 parts of this esterified product, melting point 145〓(63
Heat and melt 270 parts of paraffin wax at
Styrene-maleic acid copolymer potassium salt (molar ratio of styrene to maleic acid is 1.6:1, molecular weight 1
~20,000) Add 600 parts of warm water containing 30 parts, and bring the liquid temperature to 90℃.
Preliminary emulsification was performed at The obtained emulsion was passed twice under a pressure of 300 kg/cm ² using a piston-type high-pressure emulsifier to obtain a 40% stable aqueous emulsion. The aqueous emulsions obtained in Examples 1 to 5 were used as waterproofing agents for paper and gypsum board, and their performances were compared. Example 1 Waterproofing agent base for paperboard Paper Kraft liner 220 g/cm ² Coating method Roll coating on the surface (using Radikku Pie processor) Coating amount 0.2 g/cm ² (solid content) Drying method 1 80°C for 3 minutes ( Drum dryer) 2 Dry at 80℃ for 3 minutes, then dry at 170℃ for 60 minutes (hot air drying) Test item 1 Water repellency JIS P-8137 2 Sliding angle test JTAPPI Weight pressure 15.5Kg/
cm ² result

[Table] Example 2 Gypsum board waterproofing agent Raw materials: β-type hemihydrate gypsum Water-toning ratio 75% Waterproofing agent addition amount vs. plaster 2% 3% 4% (solid content) Test piece Dimensions 20mm x 20mm x 80mm Weight 40g Curing Conditions 2 hours at room temperature and 24 hours at constant temperature at 50°C Water absorption rate (%) = (B-A)/A x 100 A Weight of test piece after drying at 50°C for 24 hours B Immersed in water at 25°C and then surfaced with paper Weight of test piece after wiping off moisture

【table】

[Table] Commercial product A used in Comparative Examples 1 and 2
and B is a commercially available synthetic hydrocarbon resin,
This product consists of paraffin wax and surfactant.

Claims (1)

[Claims] 1 Boiling point range produced during naphtha decomposition -20 to 250
Selected from the group consisting of unsaturated carboxylic acid adducts of synthetic hydrocarbon resins obtained by polymerizing C ₅ - C ₉ fractions of °C by Friedel-Crafts reaction, or monohydric or polyhydric alcohol esters of such adducts. At least one substance and at least one wax are mixed, then melted, and the resulting melt is mixed with an aqueous protective colloid solution using a salt of a styrene-maleic acid copolymer and an alkali under mechanical stirring. A method for producing an aqueous emulsion for use as a waterproofing agent for paper, textile or plaster products, which comprises pre-emulsifying the emulsion in a piston-type high-pressure emulsifying machine under high pressure.