JPH0465101B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a thickener composition for vinyl chloride paste sol (hereinafter simply referred to as a thickener composition unless otherwise required). Conventional technology and its problems Dipping method coating method, slush molding method, etc. are known as processing methods for vinyl chloride paste sol. In order to achieve uniformity, prevention of penetration into the substrate, and increase in coating speed, the vinyl chloride paste sol is required to be a fluid with appropriate thixotropy. Conventional vinyl chloride paste sol is
It was prepared by adding a thixotropic agent to a vinyl chloride paste range, and was given the above properties. Thickeners such as organic bentonite, finely divided silica, aluminum stearate, benzylidene sorbitol, and finely divided calcium carbonate are known as thixotropic agents used for the above purpose. However, all of the thickeners listed above are powders, and in order to give the vinyl chloride paste sol the desired thixotropy, it is necessary to sufficiently disperse or dissolve the thickener. . Therefore, a suitable dispersing machine is required for kneading, dispersing, dissolving, etc., which has the drawback of requiring a great deal of labor. In addition, organic bentonite and benzylidene sorbitol are used as a gel-like thixotropic agent prepared by vigorously mixing or heating-mixing with a plasticizer such as dioctyl phthalate (DOP) for the purpose of facilitating kneading, dispersion, or dissolution. There is also. However, although organic bentonite DOP gels provide some thixotropy, they cause significant discoloration when vinyl chloride paste sol is gelled by heating. That is, there is a drawback that the thermal stability of the vinyl chloride paste sol is inhibited. In addition, benzylidene sorbitol has low solubility in plasticizers, etc., so heating to 180°C or higher is required to prepare the gel.In order to suppress the hydrolysis of benzylidene sorbitol caused by heating, it is thermally stabilized. Further, since the strength of the gel produced is extremely high, it requires a great deal of effort to mix the gel into the vinyl chloride paste sol. Means for Solving the Problems As a result of extensive research in view of the current state of the technology as described above, the present inventor has discovered a method for combining rosin ester and/or fatty acid ester with finely divided silica and/or finely divided calcium carbonate (hereinafter referred to as finely divided carbonate). (called Cal)
When a thickener composition mixed with the above is used as a thixotropic agent, the thickener composition can be easily dispersed into a vinyl chloride paste sol, and the desired desired thixotropy can be achieved. The inventors have found that the vinyl chloride paste sol obtained has very good storage stability and thermal stability, leading to the completion of the present invention. That is, the present invention provides (a) () rosin, hydrogenated rosin, disproportionated rosin,
One or a mixture of two or more selected from polymerized rosin, phenol-modified rosin, and dibasic acid-modified rosin, and one selected from methyl alcohol, glycerin, pentaerythritol, dipentaerythritol, ethylene glycol, diethylene glycol, and triethylene glycol. or rosin ester obtained by reacting a mixture of two or more of them and/or () stearic acid, palmitic acid, oleic acid, linoleic acid, linoleic acid, adipic acid, hydroxy fatty acid, tallow fatty acid, coconut oil fatty acid, toll One or more mixtures selected from oil fatty acids are reacted with one or more mixtures selected from methyl alcohol, ethyl alcohol, butyl alcohol, glycerin, pentaerythritol, ethylene glycol, and triethylene glycol. Fatty acid ester obtained by
The thickener composition for vinyl chloride paste sol contains (b) 5 to 50 parts by weight of finely divided silica and/or 30 to 150 parts by weight of finely divided calcium carbonate per 100 parts by weight. Fine silica (powder) and fine charcoal (powder)
As mentioned above, it is inappropriate to blend the polyvinyl chloride paste sol with the polyvinyl chloride paste sol because it requires a great deal of effort to disperse the polyvinyl chloride paste sol. Furthermore, rosin esters and fatty acid esters are usually viscous liquids or solids, although they vary somewhat depending on the type, and do not themselves have the effect of imparting thixotropy to vinyl chloride paste sol. However, rosin ester and/or
Or, a composition obtained by pre-mixing a fatty acid ester with finely divided silica and/or finely divided charcoal,
The synergistic effect of the constituent material composition makes it an extremely effective thixotropic agent. The rosin ester used in the present invention includes:
One or a mixture of two or more selected from so-called rosins containing abietic acid as a main component, hydrogenated rosins, disproportionated rosins, polymerized rosins, phenol-modified rosins, dibasic acid-modified rosins, and methyl alcohol, glycerin, Examples include those obtained by reacting one type or a mixture of two or more types selected from pentaerythritol, dipentaerythritol, ethylene glycol, diethylene glycol, triethylene glycol, and the like. The fatty acid ester used in the present invention includes:
One or a mixture of two or more selected from stearic acid, palmitic acid, oleic acid, linoleic acid, linoleic acid, adipic acid, hydroxy fatty acid, tallow fatty acid, coconut oil fatty acid, tall oil fatty acid, etc., and methyl alcohol, ethyl Examples include those obtained by reacting one or a mixture of two or more selected from alcohol, butyl alcohol, glycerin, pentaerythritol, ethylene glycol, triethylene glycol, and the like. The fine powder silica used in the present invention is one that is commonly used as a thickener and has a specific surface area of 50 m ² /g or more by the BET method, such as wet synthetic hydrated silica, vapor phase anhydrous silica, aerogel method or hydrogel method. Examples include silica. Among these, vapor phase anhydrous silica, such as “Aerosil”
(manufactured by Nippon Aerosil Co., Ltd.) is suitable. In addition, as fine coal, those obtained by a sedimentation method with an average particle size of about 3 μm or less, preferably an average particle size of 0.2 μm or less, are used, but in particular, those with this particle size are surface-treated with organic or inorganic substances. Preferably. Organic substances used in the above surface treatment include fatty acid soaps, hydroxy fatty acid soaps, rosin soaps, alkylbenzenesulfonic acids, alkylnaphthalenesulfonic acids, anionic surfactants such as their sodium salts, and cationic interfaces of the alkyl ammonium salt type. activator,
Examples include nonionic surfactants such as polyethylene glycol type and polyhydric alcohol type, and nonionic organic compounds such as fatty acid esters, phthalate esters, and rosin esters.
Examples include hydrous oxides such as Al ₂ O ₃ , SiO ₂ , ZnO, and TiO ₂ . The blending ratio of the rosin ester and/or fatty acid ester and the finely divided silica and/or fine carbonaceous powder in the thickener composition of the present invention is 5 to 50 parts by weight of the finely divided silica per 100 parts by weight of the rosin ester and/or fatty acid ester. It is necessary that the amount of fine carbonaceous carbon is 30 to 150 parts by weight. In the above, when the amount of fine silica is less than 5 parts by weight or the amount of fine carbon is less than 30 parts by weight, the effect of imparting thixotropy is extremely small and is not practical. On the other hand, when the amount of fine silica exceeds 50 parts by weight or the amount of fine carbon exceeds 150 parts by weight, it is extremely difficult to prepare the composition, and the dispersibility of the resulting composition is extremely poor. Therefore, when used in a vinyl chloride paste sol formulation, although it imparts thixotropy to some extent, undispersed lumps are present in the vinyl chloride paste sol, and furthermore, a product with poor appearance such as poor transparency is obtained. The method for preparing the composition of the present invention is not particularly limited, and is carried out by kneading a predetermined amount of finely powdered silica and/or fine charcoal into a rosin ester and/or fatty acid ester to obtain a particle size of about 40 μm or less. The above-mentioned kneading can be carried out using a wide variety of known kneading methods, such as a propeller agitator, a disper, a planetary mixer, an agitator and a crusher, and a three-roll mill. Preferably, a propeller agitator or the like is used. After premixing, it is preferable to perform three-roll processing. Further, when the viscosity of the rosin ester, fatty acid ester, etc. to be used is high, it is advantageous in terms of dispersion to lower the viscosity by heating appropriately. The composition of the present invention may optionally contain a plasticizer such as DOP, and further a mineral oil that is compatible with the plasticizer. By using these, the composition of the present invention can be prepared more easily without reducing the effects of the present invention, and the dispersibility in vinyl chloride paste sol can be further improved. The composition of the present invention is mainly used as a thixotropic agent for vinyl chloride paste sol. It can be used in the same manner as conventional thixotropic agents for vinyl chloride paste and sol. For example, in addition to the plasticizer, the composition of the present invention and the vinyl chloride paste resin may optionally contain diluents, heat stabilizers, lubricants, fillers, colorants, etc.
Additives commonly used in the processing of vinyl chloride, such as blowing agents, foam stabilizers, and wetting agents, may be added and kneaded. The kneading method is the same as before, using a pony mixer,
This can be easily carried out using a machine such as a Hobart mixer, kneader, crusher, ball mill, propeller agitator, or disper. The proportion of the composition of the present invention and the vinyl chloride paste resin to be used is not particularly limited and is determined to be an appropriate proportion depending on the processing conditions, but generally the former is 1 to 20% by weight relative to the latter.
That's about it. As the vinyl chloride paste resin, those manufactured by known methods such as emulsion polymerization method and fine suspension polymerization method can be widely used. That is, generally commercially available products can be preferably used, and typical examples include "Zeon 121", "Zeon 25" (manufactured by Nippon Zeon Co., Ltd.), "Kane Vinyl PSH-10", and "Kane Vinyl PSH-20". (manufactured by Kanebuchi Chemical Co., Ltd.), “Vinica P”
-415”, “Vinica P-400” (Mitsubishi Monsanto Chemical
Co., Ltd.). Furthermore, as the plasticizer added to the vinyl chloride paste resin together with the composition of the present invention, those commonly used in this field can be effectively used, such as ester plasticizers such as DOP and dioctyl adipate, Examples include epoxy compounds such as epoxidized soybean oil and epoxidized linseed oil, reactive plasticizers such as diallyl phthalate and glycidyl methacrylate, and secondary plasticizers such as chlorinated paraffin. Effects of the Invention A vinyl chloride paste sol using the composition of the present invention as a thixotropic agent has extremely high thixotropy and is particularly excellent in non-dripability. Moreover, even if it is left standing or stirred for a long time, its viscosity does not change. Further, the above-mentioned sol has good thermal stability and excellent transparency, so that it can be easily colored into any desired color. EXAMPLES The features of the present invention will be made clearer with the following examples. The following products were used as raw material compounds in the Examples and Comparative Examples. ●Rosin ester: “Ester Gum HD” made by Arakawa Chemical Co., Ltd. ●Fatty acid ester: “ME175” made by Nippon Oil & Fats Co., Ltd. ●Fine powder silica: “Aerosil #200” made by Nippon Aerosil Co., Ltd. ●Fine charcoal “Shiroenka O” “Manufactured by Shiraishi Kogyo Co., Ltd. ●Vinyl chloride paste resin: “Geon121” Made by Nippon Zeon Co., Ltd., 1700 Vinyl chloride ●Cd, Ba-based composite stabilizer: “MARK-NL” Manufactured by Adeka Argus Co., Ltd. ●Organic bentonite: "Oluben" manufactured by Shiraishi Kogyo Co., Ltd. Examples 1 to 4, Comparative Examples 1 and 2 Thickener compositions having the compositions shown in Table 1 were prepared as follows. 500 c.c. of rosin ester or fatty acid ester.
The mixture was weighed into a beaker, heated to 60 to 80°C, and the remaining ingredients were added while stirring with a small disper type stirrer (hereinafter referred to as disper stirrer) to prepare a premix. This premix was then applied to three small test rolls (5 inches in diameter x 11 inches long;
Pass it twice through a rotation ratio of 1:2.3:5.8) to uniformly disperse powders such as fine silica and fine coal.
A thickener composition having a particle size of about 20 μm was prepared. still,
The thickener compositions obtained in Examples 1 to 4 and Comparative Example 1 were all paste-like viscous products, whereas the thickener compositions obtained in Comparative Example 2 were bead-like dry mixtures, and were not used for testing. Even when kneaded with three small rolls, it did not become paste-like.

[Table] Next, 6 g of the obtained thickener composition was added to 100 g of vinyl chloride paste resin, 100 g of DOP, and Cd, Ba.
A vinyl chloride paste sol was obtained by stirring and mixing with 2 g of a composite stabilizer for 5 minutes using a disperser. In addition, comparative example 2
The dispersion was very poor. Comparative example 3 Vinyl chloride paste resin 100g, DOP 100g
and 2g of Cd, Ba-based composite stabilizer and 2g of finely divided silica.
g and 4 g of fine charcoal were directly added as powders, and the mixture was stirred and mixed with a disper for 5 minutes to obtain a vinyl chloride paste sol. However, the dispersion of fine powdered silica and fine coal was very poor. Comparative Example 4 Organic bentonite 15g Methanol 3g DOP 82g An organic bentonite pregel having the above composition was prepared in advance, and 6g of the pregel was mixed with 100g of vinyl chloride paste resin, 100g of DOP, and 2g of Cd, Ba-based composite stabilizer with disper stirring for 5 minutes. A vinyl chloride paste sol was obtained. Comparative example 5 Vinyl chloride paste resin 100g, DOP 100g
Then, 6 g of warmed rosin ester was added to 2 g of Cd, Ba-based composite stabilizer, and the mixture was stirred and mixed with a disper for 5 minutes to obtain a vinyl chloride paste sol. Test Example The vinyl chloride paste sols obtained in Examples 1 to 4 and Comparative Examples 1 to 5 were examined for thixotropy, non-dripability, storage stability, transparency, and thermal stability. The results are shown in Table 2. The following symbols and phrases have the following meanings. V ₆ : BM viscosity at 6 rpm (25°C, cps) V ₁₂ : BM viscosity at 12 rpm (25°C, cps) V ₆₀ : BM viscosity at 60 rpm (25°C, cps) Thixotropy index: V ₆ /V ₆₀ Drop-free coefficient: Yield value Y (dyne/cm ² )/Corrected viscosity V ₉ (cps
) Y=12( _V6 - _V12 )/100 _V9 = _2V12 - _V6 Thermal stability: The state after heating at 190°C for 15 minutes was evaluated as follows. ○: Good △: Slightly good ×: Bad XX: Fairly poor Transparency: The transparency after heating at 190° C. for 5 minutes was evaluated in the same manner as above.

[Table] As is clear from Table 2, the vinyl chloride paste sol using the composition of the present invention has high thixotropy and non-dripability, and is also excellent in storage stability, thermal stability, and transparency. .

Claims (1)

[Scope of Claims] 1 (a) () One or a mixture of two or more selected from rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, phenol-modified rosin, and dibasic acid-modified rosin, and methyl alcohol. , glycerin, pentaerythritol, dipentaerythritol, ethylene glycol, diethylene glycol, and triethylene glycol. Rosin ester and/or () stearic acid, palmitic acid, and olein obtained by reacting with one or a mixture of two or more selected from the group consisting of diethylene glycol, diethylene glycol, and triethylene glycol. acid, one or a mixture of two or more selected from linoleic acid, linoleic acid, adipic acid, hydroxy fatty acid, tallow fatty acid, coconut oil fatty acid, tall oil fatty acid, and methyl alcohol, ethyl alcohol, butyl alcohol, glycerin, penta (b) 5 to 50 parts by weight of finely divided silica and/or finely divided calcium carbonate per 100 parts by weight of a fatty acid ester obtained by reacting one or more mixtures selected from erythritol, ethylene glycol, and triethylene glycol; A thickener composition for vinyl chloride paste sol containing 30 to 150 parts by weight.