JP3968390B2 - Wax dispersion composition - Google Patents

Description

【００３５】
【表２】

【００３６】
【表３】

【００３７】
【表４】

【００３８】
【試験例】
上記本発明で作製したワックス分散液組成物（実施例７〜１０）について、テスター産業（株）製摩擦係数測定装置を用いてワックス分散液組成物の入った塗工紙の摩擦係数を測定した。塗被組成物は次の方法により作製した。固形分換算でカオリン（エンゲルハード，ＵＷ−９０）３０重量部、軽質炭酸カルシウム（奥多摩工業、タマパールＴＰ−２２２−Ｈ）４０重量部、重質炭酸カルシウム（三共製粉、エスカロン＃２０００）３０重量部の合計１００重量部を、水酸化ナトリウム０．１重量部、ポリアクリル酸ソーダ（サンノプコ、ＳＮディスパーサント５０４０）０．１５重量部を溶解させた水にホモミキサーを用いて分散させ固形分濃度、７２％の顔料スラリーを得た。これに接着剤として酸化デンプン（日本食品加工、ＭＳ−３６００）４重量部、スチレン−ブタジエンラテックス（日本合成ゴム、ＪＳＲ０６９６）１２重量部を加え、更に実施例７〜１０のワックス分散液組成物２．５重量部加え、固形分濃度を６４％に調製した塗被組成物を作製した。この塗被組成物を坪量６４ｇ／ｍ^２の市販上質紙に塗被量が１６ｇ／ｍ^２になるようにブレードコーターを用いて塗布後、１３０℃にて１５秒乾燥して顔料塗被紙を作製した。比較のため、ワックス成分として平均粒子径２．３μｍの酸化ポリエチレンワックスの入った顔料塗被紙（比較例１１）、ワックス成分を含まない顔料塗被紙（比較例１２）も作製し、摩擦係数を測定した。またＲ１−Ｉ型印刷試験機を用い、大日本インキオフセット用インキ（グラフ−Ｇ 墨）０．５ｃｃを使用して顔料塗被紙の塗被面に印刷を行い、一昼夜放置した。テスター産業（株）製摩擦係数測定装置を用い、印刷した試験紙と白紙とを接触させて荷重１０００ｇ、速度２００ｍ／分で５回擦り合わせ、印刷した紙から白紙に転移したインキの濃度を目視で判定し、擦れ汚れ防止効果を評価した。その結果を表５に示す。
◎ インキの転移がほとんど無いもの
○ わずかにインキが転移するもの
△ インキの転移が多いもの
× インキの転移が非常に多いもの
【００３９】
【表５】

【００４０】
【発明の効果】
表４から明らかなように本発明のワックス分散液組成物は、分散後の経時安定性が良く短時間で分離してしまうという問題を防止する効果の高いものであり、また表５から明らかなように、潤滑剤、離型剤、摩擦係数低減剤、磨耗防止剤、艶消し剤、擦れ汚れ防止剤、ブロッキング防止剤、撥水剤、耐水化剤などの目的で使用することができ実用上極めて有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a coarse particle wax dispersion composition. More specifically, the present invention relates to a wax dispersion composition having good temporal stability of the wax dispersion composition and hardly separating in a short time.
[0002]
[Prior art]
Conventionally, wax of coarse particles having a particle diameter of 5 to 100 μm is difficult to be stably dispersed, and is often used as it is in a powder state. However, there is an increasing need for a dispersion previously dispersed in water due to problems such as improved mixing of aqueous media, prevention of powder scattering during handling, and prevention of static electricity generation. Thus, a dispersion is proposed in which coarse particle wax is simply dispersed in water using only a dispersant.
[0003]
[Problems to be solved by the invention]
However, conventional dispersions in which coarse particle wax is simply dispersed in water using only a dispersant have poor stability over time and the wax separates during long-term storage. There was a problem that had to be. In addition, the agglomerates after the dispersion cannot be re-dispersed and are difficult to handle.
[0004]
[Means for Solving the Problems]
The present inventor has solved the conventional problems and has aimed to provide a dispersion composition of coarse particle wax having long-term dispersion stability. As a result of intensive studies, the present inventor has completed the present invention. That is, the present invention relates to 100 parts by weight of a wax dispersion composition obtained by dispersing a wax component having an average particle size of 5 to 100 μm in water, and (A) 10 to 60 parts by weight of the wax component, and (B) high fermentability. A lubricating / releasing agent for coated paper , comprising 0.02 to 1 part by weight of a molecular polysaccharide and 0.1 to 5 parts by weight of a dispersant component (C).
[0005]
DETAILED DESCRIPTION OF THE INVENTION
Waxes with an average particle size of 5-100 μm are lubricants, mold release agents, friction coefficient reducers, antiwear agents, matting agents, rubs, especially in applications such as paper coating, paint, ink, concrete, and cement board. It is used for purposes such as antifouling agents, antiblocking agents, water repellents, and water resistance agents. In these applications, the effect is often exerted on the surface of the substance to which the wax is added, but in order to exert the effect on the surface, it is important that the particles protrude from the surface. Large particles are required because they are difficult to exist on the surface.
[0006]
Examples of the wax component that can be used in the wax dispersion composition of the present invention include polyethylene wax, polypropylene wax, ethylene-propylene copolymer wax, Fischer-Tropsch wax, and their partial oxides or ethylenically unsaturated carboxylic acids. Synthetic hydrocarbon waxes such as polymers, montan wax derivatives, paraffin wax derivatives, modified waxes such as microcrystalline wax derivatives, hydrogenated waxes such as hardened castor oil and hardened castor oil derivatives, cetyl alcohol, stearic acid, 12-hydroxystearic acid Higher fatty acids such as alcohol, ester waxes such as glyceryl stearate, polyethylene glycol stearate, stearamide, fatty acid metal salt, phthalic anhydride, chlorinated carbonization Arsenide, and the like.
Of these, preferred are synthetic hydrocarbon waxes such as polyethylene wax, polypropylene wax, ethylene-propylene copolymer wax, Fischer-Tropsch wax and copolymers thereof with partial oxides or ethylenically unsaturated carboxylic acids, Modified waxes such as montan wax derivatives, paraffin wax derivatives, microstarin wax derivatives, higher fatty acids and alcohols such as cetyl alcohol, stearic acid, 12-hydroxystearic acid, stearamide, fatty acid metal salts, more preferably polyethylene wax , Polypropylene wax, ethylene-propylene copolymer wax, Fischer-Tropsch wax and their partial oxides or copolymers with ethylenically unsaturated carboxylic acids Synthetic hydrocarbon waxes such as stearamide, fatty acid metal salts, particularly preferred are polyethylene wax, polypropylene wax, ethylene-propylene copolymer wax, Fischer-Tropsch wax and their partial oxides or ethylenically unsaturated carboxylic acids Synthetic hydrocarbon waxes such as copolymers with acids, higher fatty acids such as cetyl alcohol, stearic acid and 12-hydroxystearic acid, alcohols, stearamides, and fatty acid metal salts.
[0007]
The particle diameter of the wax is 5 to 100 μm, preferably 10 to 50 μm, and more preferably 15 to 30 μm. When the particle diameter exceeds 100 μm, it becomes difficult to exert effects such as lubricity, releasability, and wear resistance, and further, the coating color, the smoothness of the paint surface, and the tactile sensation are deteriorated.
When it is smaller than 5 μm, effects such as rubbing dirt prevention and anti-blocking performance deteriorate.
[0008]
The amount of the wax used is 10 to 60 parts by weight, preferably 20 to 60 parts by weight, and more preferably 20 to 40 parts by weight with respect to 100 parts by weight of the wax dispersion composition. When the amount used exceeds 60 parts by weight, the fluidity is extremely deteriorated and handling becomes difficult. When the amount used is 10 parts by weight or less, the concentration becomes too low, which is not preferable in practice.
[0009]
The fermentable polymer polysaccharide of the present invention is produced by inoculating and fermenting a microorganism containing Xanthomonas campestris, etc., as a strain in a medium containing carbohydrates, nitrogen compounds, appropriate nutrients, etc. For example, what is called by the names and trademarks of dextran, xanthan gum, rhamsan gum, welan gum, gellan gum, leozan, kelzan, curdlan, pullulan and the like can be mentioned. Of these, preferred are xanthan gum, rhamzan gum, welan gum, leozan, and kelzan, more preferred are xanthan gum, rhamzan gum, leozan, and kelzan, and particularly preferred are rhamzan gum and kelzan.
[0010]
Dispersion stability of coarse particle wax is obtained for the first time by using fermentable polymer polysaccharide, and water-soluble polymers such as carboxymethylcellulose, hydroxyethylcellulose, polyacrylic acid soda, and starch can exert such effects. Can not.
[0011]
The addition amount of the fermentable polymer polysaccharide is 0.02 to 1 part by weight, preferably 0.05 to 0.5 part by weight, more preferably 0.05 to 0.3 part by weight with respect to 100 parts by weight of the dispersion. Part. When the addition amount is less than 0.02 parts by weight, sufficient dispersion stability cannot be obtained, and when it exceeds 1 part by weight, the viscosity of the wax dispersion composition is high, which makes it difficult to handle.
[0012]
The dispersant is not particularly limited as long as it can disperse the wax in water, and nonionic surfactants, anionic surfactants, amphoteric surfactants and the like can be used. Specifically, nonionic surfactants include polyoxyethylene alkyl phenyl ethers (polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, etc.), polyoxyethylene alkyl ethers (polyoxyethylene stearyl ether, polyoxyethylene). Ethylene secondary tridecyl ether, etc.), fatty acid polyethylene glycol esters (such as lauric acid polyethylene glycol ester, oleic acid polyethylene glycol ester), fatty acid alkanolamides (such as lauric acid diethanolamide, stearic acid monoethanolamide), fatty acid sorbitan esters ( Oleic acid sorbitan ester, polyoxyethylene lauric acid sorbitan ester, etc.).
[0013]
Anionic surfactants include sulfonates (sodium dodecylbenzene sulfonate, dioctyl sulfosuccinate sodium salt, sodium alpha olefin sulfonate, sodium secondary alkane sulfonate, sodium polystyrene sulfonate, naphthalene sulfonate formalin condensate, Ammonium salt, etc.), sulfate ester salt (lauryl alcohol sulfate sodium salt, polyoxyethylene lauryl ether sulfate sodium salt, polyoxyethylene nonylphenyl ether sulfate sodium salt, etc.), phosphate ester salt (polyoxyethylene nonylphenyl ether) Phosphate ester sodium salt), fatty acid ester alkali metal salt, (sodium stearate, potassium oleate, etc.), etc.
[0014]
Examples of amphoteric surfactants include amino acid types (such as sodium laurylaminopropionate) and betaine types (such as stearyl dimethyl betaine and lauryl dihydroxyethyl betaine).
[0015]
The above dispersant may be used in combination with a high molecular weight surfactant such as polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, polyethylene glycol, polyacrylamide, or sodium polyacrylate.
[0016]
The amount of the dispersant added is usually 0.1 to 5 parts by weight, preferably 0.1 to 3 parts by weight, and more preferably 0.3 to 2 parts by weight with respect to 100 parts by weight of the dispersion. When the amount of the dispersant is less than 0.1 parts by weight, the wax is not sufficiently dispersed in water, and addition exceeding 3 parts by weight is unnecessary, and problems such as intense foaming during dispersion occur.
[0017]
The viscosity of the wax dispersion composition of the present invention is 1000 to 50000 mPa · s (B-type viscometer, 0.6 rpm), preferably 5000 to 30000 mPa · s, and more preferably 7000 to 20000 mPa · s. When the viscosity is less than 1000 mPa · s, sufficient dispersion stability cannot be obtained, and when it exceeds 50000 mPa · s, the viscosity is too high, which makes it difficult to handle.
[0018]
In the wax dispersion composition of the present invention, (1) water, wax, water-soluble polymer, and dispersing agent are placed in a reaction vessel, heated to the melting point of the wax or higher, dispersed by stirring and then cooled, or (2) dispersed. It can be obtained by dispersing pre-particulated wax in water in the presence of an agent. The water-soluble polymer to be used may be added to the above-mentioned water or may be added at the same time as the wax, but it is desirable to add little by little with stirring so as not to cause undissolved residue.
[0019]
To the composition of the present invention, auxiliary agents such as a buffer and a fluidity improver can be added. In particular, since the fermentable polymer polysaccharide used in the present invention is susceptible to spoilage, it is desirable to add a preservative and an antifungal agent such as sorbic acid, dehydroacetic acid, methylnaphthoquinone and p-oxybenzoic acid ester.
[0020]
The temperature for stirring and mixing is not particularly limited, but is usually preferably 20 to 95 ° C. The stirring time is not particularly limited as long as the compound can be uniformly dispersed, but is usually 10 minutes to 10 hours.
[0021]
As a stirring mixer, a propeller type stirrer, a dissolver, a homomixer, a ball mill, a sand mill, an ultrasonic disperser, a kneader, a line mixer, and the like can be usually used.
[0022]
Dispersers include propeller-type stirrers, piston-type high-pressure emulsifiers, homomixers, ultrasonic emulsifier-dispersers, pressure-nozzle emulsifiers, high-speed rotary high-shear stirrers, colloid mills, glass beads, steel balls, etc. A media type disperser that pulverizes and disperses using various media, such as a sand grinder, an agitator mill, a ball mill, and an attritor, can be used, and these two or more types of equipment can be used in combination.
[0023]
The wax dispersion composition of the present invention is widely used for processing processes in the paper pulp industry, the paint industry, the building materials industry, the chemical industry, and the like. Especially in applications such as paper coating, paint, ink, concrete and cement board, lubricants, mold release agents, friction coefficient reducing agents, antiwear agents, matting agents, antifouling agents, antiblocking agents, and water repellents. It can be used for purposes such as water resistance. For example, in paper coating applications, kaolin clay, delaminated clay, calcium carbonate, satin white, titanium oxide, aluminum hydroxide, talc, silica, calcium sulfate, one or more pigments such as pigment, latex, One or more adhesives such as starch, carboxymethyl cellulose, polyvinyl alcohol, and other auxiliary agents such as antifoaming agents, dispersants, coloring agents, preservatives, water retention agents, water resistance agents, fluidity improvers, etc. The wax dispersion composition of the present invention is added to each application in the coating liquid dispersed in the composition. For example, normal coated paper is used as a lubricant and mold release agent in the calendaring process, matte coated paper such as dull coated paper, cast coated paper, etc. As a rubbing anti-smudge agent that prevents the ink from transferring to the white paper area and smearing the white paper area, and for ink jet paper, etc., the paper can be smoothly fed by sliding the stacked paper, and multiple paper feeds can be performed. As a friction coefficient reducing agent for the purpose of preventing, 0.1 to 5 parts by weight of the solid content of the dispersion is added to 100 parts by weight of the pigment.
[0024]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In addition, each component is a weight part with respect to 100 weight part of wax dispersion liquid, The viscosity and dispersion stability immediately after manufacture of the wax dispersion composition obtained by the Example and the comparative example were described in Table 4.
[0025]
The viscosity was measured using a B-type viscosity type, and the scale after rotation for 2 minutes at 0.6 rpm at 25 ° C. was read.
[0026]
The wax dispersion compositions obtained in the examples and comparative examples were allowed to stand at room temperature for 6 months, and the dispersion stability was evaluated by the number of days required until the wax components were separated.
[0027]
Examples 1 and 2 and Comparative Examples 1 and 2
The wax component 20 described in Table 1 was dissolved in 78.73 parts by weight of water in which 1 part by weight of the dispersant described in Table 2 and 0.27 parts by weight of the fermentable polymer polysaccharide described in Table 3 were dissolved. Part by weight was added and dispersed with a propeller-type stirrer. For comparison, a wax dispersion composition containing no fermentable polymer polysaccharide (Comparative Example 1), and 0.27 parts by weight of carboxymethylcellulose (Daiichi Kogyo Seiyaku, Cellogen PR) instead of the fermentable polymer polysaccharide What was used (Comparative Example 2) was prepared.
[0028]
Examples 3 and 4
The wax component 20 described in Table 1 was dissolved in 77.8 parts by weight of water in which 2 parts by weight of the dispersant described in Table 2 and 0.2 parts by weight of the fermentable polymer polysaccharide described in Table 3 were dissolved. Part by weight was added and dispersed with a propeller-type stirrer.
[0029]
Examples 5-7, Comparative Examples 3, 4
The wax component 30 described in Table 1 was dissolved in 67.8 parts by weight of water in which 2 parts by weight of the dispersant described in Table 2 and 0.2 parts by weight of the fermentable polymer polysaccharide described in Table 3 were dissolved. Part by weight was added and dispersed with a propeller-type stirrer. For comparison, a wax dispersion composition not containing fermentable polymer polysaccharide (Comparative Example 3), 0.2 parts by weight of polyacrylic acid soda (San Nopco, Modicol VD-S) instead of fermentable polymer polysaccharide The one used (Comparative Example 4) was also produced.
[0030]
Examples 8 and 9, Comparative Example 5
The wax component 30 described in Table 1 was obtained by dissolving 2 parts by weight of the dispersant described in Table 2 and 0.15 part by weight of the fermentable polymer polysaccharide described in Table 3 in 67.85 parts by weight of water. Part by weight was added and dispersed with a propeller-type stirrer. For comparison, a sample (Comparative Example 5) using 0.15 parts by weight of polyethylene glycol (Sanyo Chemical Industries, PEG 20000) instead of the fermentable polymer polysaccharide was also prepared.
[0031]
Examples 10 and 11, Comparative Examples 6 and 7
The wax component 40 described in Table 1 was dissolved in 57.85 parts by weight of water in which 2 parts by weight of the dispersant described in Table 2 and 0.15 parts by weight of the fermentable polymer polysaccharide described in Table 3 were dissolved. Part by weight was added and dispersed with a propeller-type stirrer. For comparison, a wax dispersion composition containing no fermentable polymer polysaccharide (Comparative Example 6), and using 0.15 parts by weight of hydroxyethyl cellulose (Daicel Chemical Industries, HEC Daicel SP600) instead of the fermentable polymer polysaccharide (Comparative Example 7) was also produced.
[0032]
Examples 12 and 13, Comparative Example 8
The wax component 40 described in Table 1 was dissolved in 57.9 parts by weight of water in which 2 parts by weight of the dispersant described in Table 2 and 0.1 part by weight of the fermentable polymer polysaccharide described in Table 3 were dissolved. Part by weight was added and dispersed with a propeller-type stirrer. For comparison, a sample (Comparative Example 8) using 0.1 part by weight of polyacrylamide (Kurita Industry, High Holder 101) instead of the fermentable polymer polysaccharide was also prepared.
[0033]
Examples 14 and 15 and Comparative Example 9
The wax component 40 described in Table 1 was dissolved in 57.94 parts by weight of water in which 2 parts by weight of the dispersant described in Table 2 and 0.06 part by weight of the fermentable polymer polysaccharide described in Table 3 were dissolved. Part by weight was added and dispersed with a propeller-type stirrer. For comparison, a product (Comparative Example 9) in which 0.06 parts by weight of oxidized starch (Japanese food processing, MS-3600) was used instead of the fermentable polymer polysaccharide was also prepared.
[0034]
[Table 1]

[0035]
[Table 2]

[0036]
[Table 3]

[0037]
[Table 4]

[0038]
[Test example]
About the wax dispersion composition (Examples 7-10) produced by the said invention, the friction coefficient of the coated paper containing a wax dispersion composition was measured using the tester industry Co., Ltd. friction coefficient measuring apparatus. . The coating composition was produced by the following method. 30 parts by weight of kaolin (Engelhard, UW-90) in terms of solid content, 40 parts by weight of light calcium carbonate (Okutama Kogyo, Tamapearl TP-222-H), 30 parts by weight of heavy calcium carbonate (Sankyo Flour Milling, Escalon # 2000) 100 parts by weight of a total of 100 parts by weight of sodium hydroxide and 0.15 parts by weight of sodium polyacrylate (San Nopco, SN Dispersant 5040) were dispersed using a homomixer to obtain a solid content concentration. A 72% pigment slurry was obtained. To this, 4 parts by weight of oxidized starch (Nippon Food Processing, MS-3600) and 12 parts by weight of styrene-butadiene latex (Nippon Synthetic Rubber, JSR0696) were added as an adhesive, and the wax dispersion composition 2 of Examples 7 to 10 was further added. A coating composition having a solid content concentration of 64% was prepared by adding 0.5 part by weight. After coating the coated amount commercial fine paper of coated composition basis weight 64 g / m ² by using a blade coater so as to 16g / m ^2, the pigment coated paper was dried for 15 seconds at 130 ° C. Was made. For comparison, a pigment coated paper (Comparative Example 11) containing an oxidized polyethylene wax having an average particle size of 2.3 μm as a wax component and a pigment coated paper (Comparative Example 12) containing no wax component were also prepared. Was measured. Further, using a R1-I type printing tester, printing was performed on the coated surface of the pigment coated paper using 0.5 cc of Dainippon Ink Offset ink (Graph-G black), and left for a whole day and night. Using a friction coefficient measuring device manufactured by Tester Sangyo Co., Ltd., contact the printed test paper and white paper and rub them 5 times at a load of 1000 g and a speed of 200 m / min, and visually check the density of the ink transferred from the printed paper to the white paper. And the effect of preventing rubbing dirt was evaluated. The results are shown in Table 5.
◎ No ink transfer ○ Slight ink transfer △ Ink transfer a lot × Ink transfer a lot [0039]
[Table 5]

[0040]
【The invention's effect】
As is clear from Table 4, the wax dispersion composition of the present invention has a high effect of preventing the problem of good stability over time after dispersion and separation in a short time. Can be used for purposes such as lubricants, mold release agents, friction coefficient reducing agents, anti-wear agents, matting agents, anti-scrubbing agents, anti-blocking agents, water repellents, water resistance agents, etc. Very useful.

Claims (3)

In 100 parts by weight of a wax dispersion composition obtained by dispersing a wax component having an average particle size of 5 to 100 μm in water, (A) 10 to 60 parts by weight of the wax component, and (B) 0% of the fermentable polymer polysaccharide. 0.02 to 1 part by weight, and (C) 0.1 to 5 parts by weight of a dispersant component, a lubricating / releasing agent for coated papers . 2. The coating according to claim 1, wherein the wax component is at least one selected from the group consisting of polyethylene wax, polypropylene wax, ethylene-propylene copolymer wax, Fischer-Tropsch wax or a modified product thereof, fatty acid amide, and fatty acid metal salt. Lubrication / release agent for paper . The lubricant / release agent for coated paper according to claim 1 or 2 , wherein the fermentable polymer polysaccharide is dextran, xanthan gum, rhamzan gum, welan gum, gellan gum, leozan, kelzan, curdlan, pullulan or a mixture thereof.