JPH08283515A - Vinyl chloride resin composition for paste and its production - Google Patents

Abstract

PURPOSE: To produce a vinyl chloride resin powder composition which can develop a sufficient thixotropy even in a common method of preparing a paste sol. CONSTITUTION: This composition comprises 100 pts.wt. vinyl chloride polymer and 0.5-2 pts.wt. polyurea-urethane-based compound. In a process for producing the above polymer in finely powdered form by spray-drying a vinyl chloride polymer obtained by subjecting a monomer mixture based on vinyl chloride to emulsion polymerization or microsuspension polymerization, 0.5-2 pts.wt. polyurea-urethane compound and 0.5-10 pts.wt. liquid surfactant, based on 100 pts.wt. vinyl chloride polymer, are added to the aqueous dispersion before spray drying.

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition for paste and a method for producing the same. More particularly, it relates to a vinyl chloride resin composition that gives a paste sol having high thixotropy and a method for producing the same. [0002] Conventionally, a dipping method has been generally used for molding a vinyl chloride resin paste sol as a raw material into gloves, caps for electric appliances, coatings for hoses and tools, and the like. In this method, a glove mold is dipped in the paste sol or a metal mold or a fiber hose is dipped in the paste sol to attach the sol to the periphery of the mold or fiber, and then this is heated with a gel. It is made into a product. In this case, the amount of sol deposited depends on the fluidity of the sol itself, and since the dripping of the sol and the amount deposited are contradictory, the sol is adjusted to have thixotropy in order to obtain a desired thickness. A well-known use of the paste sol is vinyl wallpaper. As the processing method, the paste sol is adhered to the original fabric in a desired amount and a desired pattern, and then heated and gelled. In that case, it is often foamed. To attach the paste sol to the original fabric, a rotary screen method has recently been adopted in which the colored paste sol is transferred to a pattern through a cylindrical screen. In the rotary screen method, it is required that the paste sol quickly exits the screen corresponding to the pattern of the pattern and does not drip after adhering to the original fabric. It is desired that the sol have the appropriate thixotropy. As a method of imparting thixotropy to such a paste sol, as disclosed in JP-A-6-3408
Japanese Patent Publication No. 36 proposes to use a plurality of vinyl chloride resin powders having different particle sizes for the paste sol. Further, in JP-A-6-228396, when a vinyl chloride resin powder and a plasticizer and various additives are mixed to form a paste sol, silicic anhydride and a thixotropic agent are mixed together. Paste gel compositions have been proposed. However, JP-A-6-
In the paste sol in which a plurality of vinyl chloride resin powders having different particle sizes are mixed as proposed in No. 340836, physical properties other than thixotropy, for example, the surface smoothness of the processed product becomes low. Further, the one using silicic acid anhydride as the thixotropic agent described in JP-A-6-228396 has a negative effect on the physical properties such as a decrease in the surface smoothness of the processed product during the processing accompanied by foaming, and therefore it is used as a wallpaper. Is inappropriate. Further, with other thixotropic agents, it is difficult to mix uniformly when forming a paste sol, and complicated operations such as adding small amounts and mixing are required. Therefore, the present invention provides a composition of a vinyl chloride resin powder which exhibits sufficient thixotropy even by a usual method for preparing the paste sol, and a method for producing the same. That is, the present invention provides a vinyl chloride resin composition for a paste, which comprises 0.5 to 2 parts by weight of a polyurea-urethane compound per 100 parts by weight of a vinyl chloride polymer. Further, a method for producing a finely powdered resin by spray-drying an aqueous dispersion of a vinyl chloride polymer obtained by emulsion polymerization or microsuspension polymerization of a vinyl chloride-based monomer. In the aqueous dispersion before spray drying, a mixture of 0.5 to 2 parts by weight of a polyurea-urethane compound and 0.5 to 10 parts by weight of a liquid surfactant per 100 parts by weight of the vinyl chloride polymer. The present invention provides a method for producing a vinyl chloride resin composition for paste, which comprises adding and mixing. The vinyl chloride polymer in the present invention means
It is a monomer mainly composed of a vinyl chloride monomer, that is, a vinyl chloride monomer alone or a polymer of a vinyl chloride monomer and a monomer copolymerizable therewith. Examples of the copolymerizable monomer include alkyl vinyl esters such as vinyl acetate, and (meth) acrylic acid alkyl esters such as methyl acrylate and methyl methacrylate. The vinyl chloride polymer can be formed from the monomer by a well-known polymerization method which is usually used for producing a vinyl chloride resin for paste. For example, an emulsion polymerization method and a micro suspension polymerization method using an aqueous medium containing an emulsifier can be mentioned. The emulsifiers used in these polymerization methods are ordinary anionic emulsifiers and nonionic emulsifiers, and the amount thereof is about 0.1 to 3 parts by weight per 100 parts by weight of all monomers. An aqueous dispersion of a vinyl chloride polymer is obtained by the above-mentioned polymerization method. To obtain a vinyl chloride resin for paste, the aqueous dispersion is spray-dried and the vinyl chloride polymer is taken out as a powder. . The spray drying method may be a known method and is not particularly limited. The polyurea-urethane compound is a compound represented by the following [Chemical formula 7]. Embedded image (R—O—CO—NH—R ¹ —NH—CO—NH
-) ₂ R ^{2 In the} formula, R is a group represented by the following [Chemical formula 8] or [Chemical formula 7]. Embedded image C _n H _{2n + 1} (where n is an integer of 4 to 22) embedded image C _m H _{2m + 1} (C _p H _2p O) _r (where m is an integer of 1 to 18) , P is an integer of 2 to 4, r is 1
It is an integer of -10. In the formula, R ¹ is any of the groups represented by the following [External 5]. [Outer 5] In the formula, R ² is any of the groups represented by the following [Extra 6]. [External 6] The polyurea-urethane compound is specifically described in JP-B-58-29978, and is generally used in a form diluted with an aprotic polar solvent containing a lithium salt. In the present invention, polyurea is added to the aqueous dispersion of vinyl chloride polymer before spray drying the aqueous dispersion.
The urethane compound is mixed uniformly. In the aqueous dispersion,
In order to add and uniformly mix the polyurea-urethane compound, the polyurea-urethane compound and the liquid surfactant are mixed in advance, and the mixed solution is added and mixed with the aqueous dispersion. By using a liquid surfactant, the polyurea-urethane compound can be easily mixed with the aqueous dispersion. The liquid surfactant is a liquid when it is mixed with the polyurea-urethane compound, and when it is heated and mixed, it may be a liquid at that temperature. . The surfactant preferably has an HLB value of 9.5 to 19. For example, nonionic surfactants such as glycerin fatty acid ester, sorbitol fatty acid ester, sorbitan fatty acid ester, polyoxyethylene alkyl ether and alkyl allyl ether are preferable. More specifically, there are polyoxyethylene sorbitan trioleate and polyoxyethylene nonylphenyl ether. The amount used is 1 to 5 parts by weight with respect to 1 part by weight of the polyurea-urethane compound,
It is preferably 2 to 5 parts by weight. If the amount of the surfactant is less than 1 part by weight, it is difficult to mix the both uniformly, and if the amount exceeds 5 parts by weight, the corresponding effect is not exhibited. To mix the polyurea-urethane compound and the liquid surfactant, it is sufficient to simply put them in a container and stir. The method of adding the mixture of the polyurea-urethane compound-liquid surfactant to the aqueous dispersion of the vinyl chloride polymer and mixing them uniformly is not particularly specified as long as they can be mixed. . The amount of the polyurea-urethane compound-liquid surfactant mixture added to the aqueous dispersion of the vinyl chloride polymer is 100% of the vinyl chloride polymer in the aqueous dispersion.
0.5 to 2 parts by weight of the polyurea-urethane compound
The amount is parts by weight. If it is less than 0.5 part by weight, the paste sol of the vinyl chloride resin composition does not exhibit sufficient thixotropy. When the amount is more than 2 parts by weight, the paste sol is not preferable because the viscosity at a high shear rate is too high. A mixture of the polyurea-urethane compound-liquid surfactant was added to an aqueous dispersion of a vinyl chloride polymer and uniformly mixed, and the mixture was dried by a known spray drying method to obtain a fine powder. A vinyl chloride resin composition for paste is obtained. The finely powdered vinyl chloride resin composition for paste can be made into a pacesol by a known method. That is, a paste sol having high thixotropy can be obtained by adding a plasticizer, a filler, and various additives to the resin composition in an appropriate amount and type according to the intended use. INDUSTRIAL APPLICABILITY The vinyl chloride resin composition for a paste of the present invention is a paste having a high thixotropy when it is made into a paste sol without any complicated operation, that is, by a method of preparing an ordinary paste sol. It can be a sol. Further, the method for producing a vinyl chloride resin composition for a paste of the present invention is a vinyl chloride resin that can uniformly disperse a thixotropic agent without the need for a special operation and sufficiently develop the performance of the agent. A composition can be obtained. The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Parts and% in the examples and comparative examples are by weight unless otherwise specified. The physical properties were measured by the following methods.・ Viscosity (poise) of paste sol; 23 ° C, relative humidity 6
With a Brookfield BL type viscometer in a constant temperature and humidity room of 0%, No. The measurement was carried out using a 4 rotor at 6 rpm and 12 rpm. · Thixotropy; the viscosity of the 6 rpm V _6, 12 rpm
Let V ₁₂ be the viscosity of the corrected viscosity V ₉ (poise) and the yield value Y _V (dyne / dyne /
cm ² ) and calculate thixotropic index (T
I) was calculated. [Number 1] V ₉ = 2V ₁₂ -V ₆ Equation 2] _{Y V = 12 (V 6 -V} 12) Equation 3] _{TI = Y V / (V 9} × 100) [0025] Example 1 100L of Degas the glass-lined autoclave, deionized water 40 kg, vinyl chloride monomer 16 kg, sodium lauryl sulfate 140 g, stearyl alcohol 2
40 g and 7.5 g of di-2-ethylhexyl peroxydicarbonate were charged, homogenized with a homogenizer and then heated to 64 ° C. to start polymerization. When the pressure in the reactor dropped by 0.5 kg / cm ² , 18 kg of vinyl chloride monomer was added to continue the polymerization, and the pressure in the reactor became 0.5
The polymerization was stopped at the point where the pressure decreased by kg / cm 2, and the unreacted monomer was recovered to obtain an aqueous dispersion of a vinyl chloride polymer. In a 1 L stainless steel container equipped with a stirrer, a polyurea-urethane compound (R6237 manufactured by BYK-Chemie GmbH manufactured by BYK-Chemie) and polyoxyethylene nonylphenyl ether (Emulgen manufactured by Kao Co., Ltd.) are represented by the formulas [7] below. PI20T HLB 13.23 liquid) was stirred and mixed at a ratio of 1: 2 for 30 seconds to prepare a mixed solution. [Outer 7] While stirring the aqueous dispersion of the vinyl chloride polymer, the above-mentioned mixed solution is added in an amount such that 1 part of the polyurea-urethane compound is added to 100 parts of the vinyl chloride polymer in the aqueous dispersion. After stirring and mixing for 30 seconds, spray drying was performed to obtain a vinyl chloride resin. To 100 parts of this vinyl chloride resin, as a plasticizer, 55 parts of dioctyl phthalate (DOP), 50 parts of calcium carbonate (Shiroishi Industry Co., Ltd., Whiten H), titanium oxide (Ishihara Sangyo Co., Ltd., R820) ) 15 parts, foaming agent (AZH, Otsuka Chemical Co., Ltd.) 3 parts, stabilizer (manufactured by Kyodo Yakuhin Co., Ltd., KF65J2) 3 parts and diluent (manufactured by Sankei Sangyo Co., Ltd., mineral terpene) 7 parts And mixed for 15 minutes with a stirring mixer to obtain plastisol. The flow characteristics of the obtained paste sol were evaluated. The results are shown in Table 1.
Shown in Example 2 Example 2 was repeated except that the polyurea-urethane compound and the polyoxyethylene nonylphenyl ether were mixed at a ratio of 1: 5. The results are shown in Table 1. Comparative Example 1 Similar to Example 1 except that the polyurea-urethane compound was not used and only 5 parts of polyoxyethylene nonylphenyl ether was added to the aqueous dispersion of the vinyl chloride polymer. Went to. The results are shown in Table 1. Comparative Example 2 The procedure of Example 1 was repeated except that the polyurea-urethane compound and the polyoxyethylene nonylphenyl ether were used in a ratio of 1: 0.5. The results are shown in Table 1.
Shown in Comparative Example 3 In the same manner as in Example 1 except that polyoxyethylene nonylphenyl ether was not used and only 1 part of the polypolyurea-urethane compound was added to the aqueous dispersion of the vinyl chloride polymer. went. The results are shown in Table 1. The polyurea-urethane compound was not sufficiently dispersed in the aqueous dispersion. [Table 1]

Claims (1)

Claims: 1. A vinyl chloride resin composition for a paste, which comprises 0.5 to 2 parts by weight of a polyurea-urethane compound per 100 parts by weight of a vinyl chloride polymer. 2. The vinyl chloride resin composition for paste according to claim 1, wherein the polyurea-urethane compound is a compound represented by the following [Chemical formula 1]. Embedded image (R—O—CO—NH—R ¹ —NH—CO—NH
-) ₂ R ^{2 In the} formula, R is a group represented by the following [Chemical formula 2] or [Chemical formula 3]. Embedded image C _n H _{2n + 1} (where n is an integer of 4 to 22) embedded image C _m H _{2m + 1} (C _p H _2p O) _r (where m is an integer of 1 to 18) , P is an integer of 2 to 4, r is 1
It is an integer of -10. In the formula, R ¹ is any of the groups represented by the following [External 1]. [Outside 1] In the formula, R ² is any of the groups represented by the following [External 2]. [Outside 2] 3. A method for producing a fine powdery polymer by spray-drying an aqueous dispersion of a vinyl chloride polymer obtained by emulsion polymerization or microsuspension polymerization of a vinyl chloride-based monomer. In 0.5 to 2 parts by weight of a polyurea-urethane compound and 0.5 to 100 parts by weight of a liquid surfactant per 100 parts by weight of the vinyl chloride polymer in the aqueous dispersion before spray drying.
The method for producing a vinyl chloride resin composition for a paste according to claim 1, wherein a mixture with 10 parts by weight is added and mixed. 4. The method for producing a vinyl chloride resin composition for a paste according to claim 3, wherein the polyurea-urethane compound is a compound represented by the following [Chemical formula 4]. Embedded image (R—O—CO—NH—R ¹ —NH—CO—NH
-) ₂ R ^{2 In the} formula, R is a group represented by the following [Chemical formula 5] or [Chemical formula 6]. Embedded image C _n H _{2n + 1} − (where n is an integer of 4 to 22) embedded image C _m H _{2m + 1} (C _p H _2p O) _r − (where m is 1 to 18) Is an integer, p is an integer of 2 to 4, r is 1
It is an integer of -10. In the formula, R ¹ is any of the groups represented by the following [External 3]. [Outside 3] In the formula, R ² is any of the groups represented by the following [External 4]. [Outside 4] 5. A liquid surfactant having an HLB value of 9.5.
It is -19, The manufacturing method of the vinyl chloride resin composition for pastes of Claim 3 characterized by the above-mentioned.