JP2015124316A - Vinyl chloride resin for paste processing and vinyl chloride resin composition for paste processing using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vinyl chloride resin for paste processing which is capable of giving a foam having a high expansion ratio, good surface smoothness, and a dense cell structure, and to provide a vinyl chloride resin composition obtained therefrom.SOLUTION: The vinyl chloride paste resin contains 0.1-3 pts.wt. of a polyoxyalkylene alkyl ether represented by general formula (1) based on 100 pts.wt. of a vinyl chloride resin. The vinyl chloride resin composition is obtained from the vinyl chloride paste resin. (In the formula, R1 represents hydrogen or a 1-20C alkyl, alkenyl, or alkylene group; R2 represents hydrogen or a 1-10C alkyl, alkenyl, or alkylene group; and n represents an integer of 11 or more.)

Description

  The present invention relates to a vinyl chloride resin for paste processing (hereinafter sometimes abbreviated as “paste vinyl chloride”) and a paste vinyl chloride composition obtained therefrom. More specifically, the present invention has a high foaming ratio and good surface smoothness. The present invention relates to a paste PVC that gives a plastisol from which a foam having a dense cell structure can be obtained, and a paste PVC composition obtained therefrom.

  Paste PVC is generally processed as paste PVC sol by kneading with compounding agents such as plasticizers, stabilizers and foaming agents, and various molded products are obtained by various processing methods. Among them, building materials such as wallpaper, flooring and foam sheets are one of the main uses of paste PVC.

  In general, wallpaper, flooring, foamed sheets, etc., are prepared by applying paste vinyl chloride sol to a backing material such as flame retardant paper and heating, printing process for coloring the original fabric by gravure printing, etc. Manufactured by a method comprising a foaming process in which foam is heated and an embossing process in which a pattern is applied to the foam. If a high-magnification foam can be obtained in the foaming process for controlling the thickness of the product, the coating thickness of the raw fabric can be reduced to reduce the amount of paste PVC used. Therefore, a paste vinyl chloride sol capable of obtaining a high-magnification foam from the viewpoint of reducing environmental burden and manufacturing cost is desired.

  Until now, in order to obtain a high-magnification foam, paste PVC with a controlled particle size has been developed (see, for example, Patent Document 1 and Patent Document 2).

  However, when the particle size distribution is restricted for a paste PVC that exhibits various properties by controlling the particle size, the viscosity characteristics and processability deteriorate.

  On the other hand, a high-magnification foam can be obtained by changing the type and amount of the foaming agent and stabilizer added during blending (see, for example, Patent Document 3).

  However, changing the type of foaming agent or stabilizer changes the surface smoothness, and increasing the amount added leads to an increase in cost. Further, the use of a large amount of a stabilizer containing heavy metal is not preferable from the viewpoint of safety, and the desired paste vinyl chloride sol has not been developed yet.

JP 2009-91423 A JP-A-9-309998 Japanese Patent Laid-Open No. 10-53756

  An object of the present invention is to solve the above-mentioned problems and to provide a paste vinyl chloride capable of obtaining a high-magnification foam that cannot be obtained by conventional paste vinyl chloride and a novel paste vinyl chloride composition obtained therefrom. .

  In view of the state of the prior art as described above, the present inventors diligently studied to obtain a paste PVC capable of obtaining a high-magnification foam and a paste PVC composition obtained therefrom, and as a result, specified additives are added. By using it, it discovered that the target paste vinyl chloride and the paste vinyl chloride composition obtained from it were obtained, and came to complete this invention. That is, the present invention contains 0.1 to 3 parts by weight of a polyoxyalkylene alkyl ether represented by a predetermined general formula with respect to 100 parts by weight of a vinyl chloride resin, and the vinyl chloride for paste processing is characterized by Resin and a vinyl chloride resin composition for paste processing using the same.

  Hereinafter, the present invention will be described in detail.

  The paste vinyl chloride of the present invention contains 0.1 to 3 parts by weight of a polyoxyalkylene alkyl ether represented by the following general formula (1) with respect to 100 parts by weight of a vinyl chloride resin. When the content of the polyoxyalkylene alkyl ether is less than 0.1 parts by weight, the effect of improving the expansion ratio is insufficient. On the other hand, when the content exceeds 3 parts by weight, the sol is thickened and the processability is lowered. Furthermore, since it becomes the viscosity range suitable for a process, it is preferable to contain 0.2-1.8 weight part, and it is still more preferable to contain 0.5-1.5 weight part.

(Wherein R1 represents hydrogen or an alkyl group, alkenyl group or alkylene group having 1 to 20 carbon atoms, R2 represents hydrogen or an alkyl group, alkenyl group or alkylene group having 1 to 10 carbon atoms, and n is 11 or more. Represents an integer.)
Here, the polyoxyalkylene alkyl ether represented by the general formula (1) has a propylene addition mole number (n) of 11 or more, for example, polyoxyethylene lauryl ethers, polyoxyethylene myristol ethers, Polyoxyethylene cetyl ethers, polyoxyethylene stearyl ethers, polyoxyethylene oleyl ethers, polyoxypropylene lauryl ether, polyoxypropylene myristel ether, polyoxypropylene cetyl ether, polyoxypropylene stearyl ether, polyoxypropylene oleyl Examples thereof include polyoxypropylene alkyl ethers such as ether. Specific examples of these polyoxyethylene lauryl ethers include, for example, polyoxyethylene (12) lauryl ether (Kao Corporation, trade name: Emulgen 120), polyoxyethylene (21) lauryl ether (Nikko Chemicals Corporation). , Trade name: NIKKOL BL-21), polyoxyethylene (25) lauryl ether (Nikko Chemicals Corporation, trade name: NIKKOL BL-25), polyoxyethylene (47) lauryl ether (Kao Corporation), trade name Specific examples of polyoxyethylene cetyl ethers include, for example, polyoxyethylene (15) cetyl ether (Nikko Chemicals Co., Ltd., trade name: NIKKOL BC-15), polyoxy Ethylene (20) cetyl ether (Nikko Chemicals) Co., Ltd.), trade name: NIKKOL BC-20), polyoxyethylene (23) cetyl ether (Nikko Chemicals Co., Ltd., trade name: NIKKOL BC-23), polyoxyethylene (25) cetyl ether (Nikko Chemicals Co., Ltd.) , Trade name: NIKKOL BC-25), polyoxyethylene (30) cetyl ether (Nikko Chemicals Co., Ltd., trade name: NIKKOL BC-30), polyoxyethylene (40) cetyl ether (Nikko Chemicals Co., Ltd.) Name: NIKKOL BC-40) and the like. Specific examples of the polyoxyethylene stearyl ethers include, for example, polyoxyethylene (20) stearyl ether (Nikko Chemicals Co., Ltd., trade name: NIKKOL BS-20). , Polyoxyethylene (50) stearyl ether ( Wang Co., Ltd., trade name: Emulgen 350) and the like. Specific examples of the polyoxyethylene oleyl ethers include, for example, polyoxyethylene (15) oleyl ether (Nikko Chemicals Co., Ltd., trade name: NIKKOL). BO-15V), polyoxyethylene (30) oleyl ether (Kao Corporation, trade name: Emulgen 430), polyoxyethylene (50) oleyl ether (Nikko Chemicals Corporation, trade name: NIKKOL BO-50V), etc. Is mentioned. If the propylene addition mole number (n) of the polyoxyalkylene alkyl ether represented by the general formula (1) is less than 11, the expansion ratio may be less than 5.0 times, and the embossing becomes shallow, so that the embossing becomes shallow. The embossed pattern may not be supported.

  The paste vinyl chloride of the present invention is a polymerization initiator, an emulsifier, an emulsification aid, a buffer, a higher alcohol, a higher fatty acid, a higher fatty acid ester, a dispersion aid such as chlorinated paraffin, and the like in the polymerization of paste vinyl chloride such as a polymerization degree adjuster. In addition, a generally added substance or the like may be contained.

  The paste vinyl chloride of the present invention is a vinyl chloride resin latex obtained by obtaining a vinyl chloride resin latex by a general emulsion polymerization method, micro suspension polymerization method, seed emulsion polymerization method, seed micro suspension polymerization method, etc. In addition, 0.1 to 3 parts by weight of polyoxyalkylene alkyl ether represented by the following general formula (1) is added to 100 parts by weight of the vinyl chloride resin, and then water is removed for production. it can.

(Wherein R1 represents hydrogen or an alkyl group, alkenyl group or alkylene group having 1 to 20 carbon atoms, R2 represents hydrogen or an alkyl group, alkenyl group or alkylene group having 1 to 10 carbon atoms, and n is 11 or more. Represents an integer.)
Examples of the method for removing moisture from the vinyl chloride resin latex include spray drying, fluidized bed drying, aeration drying, rotary drying, conductive heating drying, and the like. A method by drying is preferred.

  The seed microsuspension polymerization method is shown below as an example of a method for obtaining a vinyl chloride resin latex used in producing the paste vinyl chloride of the present invention.

  The seed micro-suspension polymerization method is 1) the first step of obtaining a vinyl chloride resin seed latex containing a vinyl chloride resin containing an oil-soluble polymerization initiator by the micro suspension polymerization method, and 2) the obtained seed latex. The vinyl chloride monomer, or a monomer copolymerizable with vinyl chloride monomer, is polymerized with gentle stirring in the presence of deionized water, an emulsifier, a buffer, and if necessary, an emulsification aid such as higher alcohol. Is a polymerization method comprising a second stage in which the seed latex is enlarged to obtain a vinyl chloride resin latex.

  Here, examples of the monomer copolymerizable with the vinyl chloride monomer include vinyl esters such as vinyl acetate, vinyl propionate, vinyl myristate, vinyl benzoate, acrylic acid, methacrylic acid, maleic acid, fumaric acid. Unsaturated carboxylic acid or anhydride thereof, acrylic acid esters such as methyl acrylate, ethyl acrylate and butyl acrylate, methacrylic acid esters such as methyl methacrylate, ethyl methacrylate and butyl methacrylate, maleic acid ester , Unsaturated carboxylic acid esters such as fumaric acid esters and cinnamic acid esters, vinyl ethers such as vinyl methyl ether, vinyl amyl ether and vinyl phenyl ether, monoolefins such as ethylene, propylene, butene and pentene, vinylidene chloride, Styrene and its Conductor, acrylonitrile, can be cited methacrylonitrile, etc. These vinyl monomers can be used with one or more.

  Examples of the emulsifier include alkyl sulfates such as sodium lauryl sulfate and myristyl sulfate, alkylaryl sulfonates such as sodium dodecylbenzenesulfonate and potassium dodecylbenzenesulfonate, sodium dioctylsulfosuccinate, dihexylsulfosuccinic acid. Sulfosuccinates such as sodium, fatty acid salts such as ammonium laurate and potassium stearate, anionic emulsifiers such as polyoxyethylene alkyl sulfates, polyoxyethylene alkylaryl sulfates, sorbitan monooleate, polyoxyethylene sorbitan mono Sorbitan esters such as stearate, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters Those conventionally known nonionic emulsifiers such as the like may be employed alone or in combination.

  Examples of the buffer include alkali metal monohydrogen phosphate, alkali metal dihydrogen phosphate, potassium hydrogen phthalate, sodium hydrogen carbonate, boric acid-caustic potassium solution, and the like.

  Examples of the emulsification aid used as necessary include higher alcohols such as cetyl alcohol and lauryl alcohol, higher fatty acids such as lauric acid, palmitic acid and stearic acid, esters thereof, aromatic hydrocarbons, higher fatty acid hydrocarbons, Examples thereof include halogenated hydrocarbons such as chlorinated paraffin.

  The seed latex used in the seed micro suspension polymerization method can be prepared by the following micro suspension polymerization method. First, add vinyl chloride monomer, oil-soluble polymerization initiator, surfactant, buffering agent, higher alcohol, higher fatty acid, higher fatty acid ester, dispersing aid such as chlorinated paraffin, and polymerization degree adjuster if necessary. Premix and homogenize with a homogenizer to adjust the oil droplets. As a homogenizer at this time, for example, a colloid mill, a vibration stirrer, a two-stage high-pressure pump, or the like can be used. Then, the homogenized liquid is sent to the polymerization vessel, the temperature in the polymerization vessel is raised while gently stirring to start the polymerization reaction, and the oil-soluble polymerization initiator is added by carrying out the polymerization until a predetermined conversion rate is reached. It is possible to adjust the contained seed latex.

  As the oil-soluble polymerization initiator, diacyl peroxide having a 10-hour half-life temperature of 30 to 70 ° C. is preferable. Examples of such a polymerization initiator include isobutyryl peroxide, 3,3,5-trimethylhexanoyl peroxide. Examples thereof include oxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, and succinic acid peroxide.

  When the paste vinyl chloride of the present invention is used as a paste vinyl chloride composition by blending a plasticizer, a filler, a foaming agent and the like, a good foam can be obtained. It is preferable to blend ~ 200 parts by weight, filler 300 parts by weight or less, and foaming agent 0.1-30 parts by weight.

  Examples of the plasticizer include bis (2-ethylhexyl) phthalate (hereinafter abbreviated as DOP), diisononyl phthalate, diisodecyl phthalate, dibutyl phthalate and the like, adipic acid (2-ethylhexyl), Adipic acid esters such as diisononyl adipate, trimellitic acid esters such as tri (2-ethylhexyl) trimellitic acid, triisodecyl trimellitic acid and trinormaloctyl trimellitic acid, tri (2-ethylhexyl) phosphate, phosphoric acid Phosphate esters such as tricresyl and trixylenyl phosphate, benzoic acid esters such as diethylene glycol dibenzoate and dipropylene glycol dibenzoate, other polyester plasticizers, sebacic acid esters, mazelineic acid esters, maleic acid esters Epoxidized vegetable oil, it can generally be used those which are used as plasticizers.

  Examples of the filler include calcium carbonate, diatomaceous earth, magnesium carbonate, and titanium oxide.

  Examples of foaming agents include inorganic foaming agents such as sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, ammonium nitrite, amide compounds, sodium borohydride, isocyanate compounds, azodicarbonamide, azobisisobutyronitrile, barium. Azo compounds such as azodicarboxylate, hydrazine derivatives such as p, p′-oxybisbenzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide, semicarbazide compounds, azides, nitroso compounds such as dinitrosopentamethylenetetramine, triazole compounds, etc. An organic foaming agent is mentioned. And it is also possible to use together the said foaming agent and decomposition accelerators, such as zinc white (zinc oxide), as needed.

  In addition, a stabilizer may be used in combination, and examples of the stabilizer include an epoxy stabilizer, a barium stabilizer, a calcium stabilizer, a tin stabilizer, and a zinc stabilizer. Commercially available composite stabilizers such as calcium-zinc and barium-zinc can also be used.

  Furthermore, in addition to paste PVC, plasticizer, filler, and foaming agent, which are essential components for the paste PVC composition of the present invention, it is usually added to the paste PVC composition within a range not exceeding the object of the present invention. Additives such as antioxidants, flame retardants, diluents, lubricants, UV absorbers, colorants such as pigments, surfactants, antistatic agents, etc. may be added, and their blending amounts are also generally used. It does not matter as long as it is done.

  The paste PVC of the present invention has a high foaming ratio, good surface smoothness, and can obtain a foam having a dense cell structure, and its industrial value is very high.

  Next, the content of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these.

  The evaluation method of the paste PVC obtained from the examples is shown below.

<Average particle size>
Using a laser diffraction / scattering particle size distribution measuring apparatus (Horiba, Ltd., trade name LA-700), measurement was performed twice under the condition of a refractive index of 1.3 to obtain an average particle diameter.

<Degree of polymerization>
The degree of polymerization was calculated by a solution viscosity measurement method using a JISK6721 Ubbelohde viscometer.

<Foaming ratio>
The expansion ratio was calculated by the following formula (1).

Foaming ratio = (foam thickness−raw fabric thickness) / raw fabric thickness (1)
<Surface smoothness>
The surface smoothness of the obtained foam was evaluated by visual observation.

  The evaluation criteria of surface smoothness are shown below.

○: Surface is smooth ×: Surface is rough <Cell structure>
The cell structure of the obtained foam was evaluated by visual observation.

○: Cell structure is dense ×: Cell structure is rough Synthesis Example 1
A 1 m ³ stainless steel autoclave was charged with 360 kg of deionized water, 300 kg of vinyl chloride monomer, 5.7 kg of lauroyl peroxide and 30 kg of a 15 wt% sodium dodecylbenzenesulfonate aqueous solution, and circulated for 3 hours using a homogenizer for homogenization. Thereafter, the temperature of the reaction system was raised to 45 ° C. to initiate polymerization. After the pressure of the polymerization system is reduced, the unreacted vinyl chloride monomer is recovered, and the solid content is 35% by weight, the average particle diameter is 0.55 μm, and the seed contains 2% by weight of lauroyl peroxide based on the polymer. Latex a was obtained.

Synthesis example 2
After charging 400 kg of deionized water, 350 kg of vinyl chloride monomer, 2 kg of 16 wt% aqueous potassium laurate and 5 kg of 16 wt% aqueous sodium dodecylbenzenesulfonate in a 1 m ³ stainless steel autoclave, the temperature of the reaction system was raised to 60 ° C. The polymerization was started. After the pressure in the polymerization system dropped, unreacted vinyl chloride monomer was recovered to obtain a seed latex b having a solid content of 40% by weight and an average particle size of 0.15 μm.

Production Example 1
In a 2.5 L stainless steel autoclave, 650 g of deionized water, 550 g of vinyl chloride monomer, 5.5 g of 5 wt% sodium dodecylbenzenesulfonate, 11.0 g of 1 wt% boric acid-caustic potassium solution, obtained by Synthesis Example 1 4 parts by weight of seed latex a having an average particle diameter of 0.55 μm per 100 parts by weight of vinyl chloride monomer, and 2 parts of seed latex b having an average particle diameter of 0.15 μm obtained in Synthesis Example 2 per 100 parts by weight of vinyl chloride monomer. Polymerization was started by charging parts by weight and raising the temperature of the reaction mixture to 66 ° C. From the start of the polymerization to the end of the polymerization, 0.75 parts by weight of 5% sodium dodecylbenzenesulfonate was continuously added to the vinyl chloride monomer. When the polymerization pressure dropped from the saturated vapor pressure of the vinyl chloride monomer at 66 ° C. to 0.539 MPa, the polymerization was stopped, the unreacted vinyl chloride monomer was recovered, the average particle size was 1.4 μm, and the polymerization degree was 700. A vinyl chloride resin latex was obtained.

Production Example 2
In a 2.5 L stainless steel autoclave, 650 g of deionized water, 550 g of vinyl chloride monomer, 5.5 g of 5 wt% sodium dodecylbenzenesulfonate, 11.0 g of 1 wt% boric acid-caustic potassium solution, obtained by Synthesis Example 1 4 parts by weight of seed latex a having an average particle diameter of 0.55 μm with respect to 100 parts by weight of vinyl chloride monomer, and 4 parts by weight of seed latex b having an average particle diameter of 0.15 μm obtained by Synthesis Example 2 with respect to 100 parts by weight of vinyl chloride monomer. Polymerization was started by charging parts by weight and raising the temperature of the reaction mixture to 61 ° C. From the start of the polymerization to the end of the polymerization, 0.75 parts by weight of 5% sodium dodecylbenzenesulfonate was continuously added to the vinyl chloride monomer. When the polymerization pressure dropped from the saturated vapor pressure of the vinyl chloride monomer at 61 ° C. to 0.471 MPa, the polymerization was stopped, the unreacted vinyl chloride monomer was recovered, the average particle size was 1.3 μm, and the polymerization degree was 900 A vinyl chloride resin latex was obtained.

Production Example 3
In a 2.5 L stainless steel autoclave, 650 g of deionized water, 550 g of vinyl chloride monomer, 5.5 g of 5 wt% sodium dodecylbenzenesulfonate, 11.0 g of 1 wt% boric acid-caustic potassium solution, obtained by Synthesis Example 1 4 parts by weight of seed latex a having an average particle diameter of 0.55 μm per 100 parts by weight of vinyl chloride monomer, and 8% of seed latex b having an average particle diameter of 0.15 μm obtained in Synthesis Example 2 per 100 parts by weight of vinyl chloride monomer. Polymerization was started by charging parts by weight and raising the temperature of the reaction mixture to 52 ° C. From the start of the polymerization to the end of the polymerization, 0.75 parts by weight of 5% sodium dodecylbenzenesulfonate was continuously added to the vinyl chloride monomer. When the polymerization pressure dropped from the saturated vapor pressure of the vinyl chloride monomer at 52 ° C. to 0.353 MPa, the polymerization was stopped, the unreacted vinyl chloride monomer was recovered, the average particle size was 1.1 μm, and the polymerization degree was 1300. A vinyl chloride resin latex was obtained.

Production Example 4
In a 2.5 L stainless steel autoclave, 650 g of deionized water, 550 g of vinyl chloride monomer, 5.5 g of 5 wt% sodium dodecylbenzenesulfonate, 11.0 g of 1 wt% boric acid-caustic potassium solution, obtained by Synthesis Example 1 4 parts by weight of seed latex a having an average particle size of 0.55 μm with respect to 100 parts by weight of vinyl chloride monomer, and 5% of seed latex b having an average particle size of 0.15 μm obtained by Synthesis Example 2 with respect to 100 parts by weight of vinyl chloride monomer. Polymerization was started by charging parts by weight and raising the temperature of the reaction mixture to 61 ° C. From the start of the polymerization to the end of the polymerization, 0.75 parts by weight of 5% sodium dodecylbenzenesulfonate was continuously added to the vinyl chloride monomer. When the polymerization pressure dropped from the saturated vapor pressure of the vinyl chloride monomer at 61 ° C. to 0.471 MPa, the polymerization was stopped, the unreacted vinyl chloride monomer was recovered, the average particle size was 1.2 μm, and the polymerization degree was 900 A vinyl chloride resin latex was obtained.

Example 1
Polyoxyethylene (12) lauryl ether (Kao Co., Ltd., trade name: Emulgen 120) is added to 1 kg of the vinyl chloride resin latex (average particle size: 1.4 μm, polymerization degree: 700) obtained in Production Example 1. 2.4 g (0.6 parts by weight with respect to 100 parts by weight of vinyl chloride resin) is added and stirred, and spray-dried at a hot air temperature of 110 ° C. and an outlet temperature of 50 ° C. using a rotary disk type spray dryer. A granular paste PVC was obtained (content of polyoxyalkylene alkyl ether represented by the general formula (1) (based on 100 parts by weight of vinyl chloride resin for paste processing, the same shall apply hereinafter): 0.596 parts by weight) .

  For 100 parts by weight of the obtained paste PVC, 45 parts by weight of DOP (J-Plus, Inc., grade industry) as a plasticizer and 70 parts by weight of calcium carbonate (Sankyo Seimitsu Co., Ltd., trade name first grade) as a filler Parts, 15 parts by weight of titanium oxide (Taika Co., Ltd., trade name: JR600A) as a pigment, 3 parts by weight of foaming agent (Otsuka Chemical Co., Ltd., trade name: AZ Ultra 1050), diluent (JX Nippon Mining Corporation), A paste vinyl chloride composition was obtained using 10 parts by weight of a trade name N10) and 3 parts by weight of a stabilizer (Sakai Chemical Industry Co., Ltd., trade name KF708S) using a dissolver.

  The obtained paste vinyl chloride composition was coated on a flame retardant paper preheated at 180 ° C. for 5 seconds to a thickness of 0.14 mm, and heated at 180 ° C. for 12 seconds to obtain an original fabric.

  After measuring the thickness of the obtained raw fabric, the foam was obtained by heating at 230 ° C. for 35 seconds. Then, the thickness of the obtained foam was measured and foaming magnification, surface smoothness, and cell structure were evaluated. The test results are shown in Table 1. The expansion ratio was 5.1 times and 5.0 times or more, the surface was smooth, and the cells had a dense structure.

Example 2
Except for changing polyoxyethylene (12) lauryl ether to polyoxyethylene (47) lauryl ether (Kao Co., Ltd., trade name: Emulgen 150), a paste PVC and a paste PVC composition were prepared in the same manner as in Example 1. Obtained and produced a foam, and evaluated the expansion ratio, surface smoothness, and cell structure. The test results are shown in Table 1. The expansion ratio was 5.4 times and 5.0 times or more, the surface was smooth, and the cells had a dense structure.

Example 3
Except for changing polyoxyethylene (12) lauryl ether to polyoxyethylene (30) oleyl ether (Kao Co., Ltd., trade name: Emulgen 430), a paste PVC and a paste PVC composition were prepared in the same manner as in Example 1. Obtained and produced a foam, and evaluated the expansion ratio, surface smoothness, and cell structure. The test results are shown in Table 1. The expansion ratio was 5.2 times and 5.0 times or more, the surface was smooth, and the cell had a dense structure.

Example 4
Polyoxyethylene (12) lauryl ether (Kao Co., Ltd., trade name: Emulgen 120) was added to 1 kg of the vinyl chloride resin latex (average particle size: 1.3 μm, polymerization degree: 900) obtained in Production Example 2. 2.4 g (0.6 parts by weight with respect to 100 parts by weight of vinyl chloride resin) is added, spray-dried at a hot air temperature of 110 ° C. and an outlet temperature of 50 ° C. using a rotary disk type spray dryer, and a granular paste Vinyl chloride was obtained (content of polyoxyalkylene alkyl ether represented by general formula (1): 0.596 parts by weight).

  Using the obtained paste PVC, a foam was produced in the same manner as in Example 1, and the foaming ratio, surface smoothness, and cell structure were evaluated. The test results are shown in Table 2. The expansion ratio was 5.1 times and 5.0 times or more, the surface was smooth, and the cells had a dense structure.

Example 5
Except for changing polyoxyethylene (12) lauryl ether to polyoxyethylene (47) lauryl ether (Kao Co., Ltd., trade name: Emulgen 150), a paste PVC and a paste PVC composition were prepared in the same manner as in Example 4. Obtained and produced a foam, and evaluated the expansion ratio, surface smoothness, and cell structure. The test results are shown in Table 2. The expansion ratio was 5.4 times and 5.0 times or more, the surface was smooth, and the cells had a dense structure.

Example 6
Except for changing polyoxyethylene (12) lauryl ether to polyoxyethylene (30) oleyl ether (Kao Co., Ltd., trade name: Emulgen 430), a paste PVC and a paste PVC composition were prepared in the same manner as in Example 4. Obtained and produced a foam, and evaluated the expansion ratio, surface smoothness, and cell structure. The test results are shown in Table 2. The expansion ratio was 5.2 times and 5.0 times or more, the surface was smooth, and the cell had a dense structure.

Example 7
Polyoxyethylene (12) lauryl ether (Kao Co., Ltd., trade name: Emulgen 120) was added to 1 kg of the vinyl chloride resin latex (average particle size: 1.1 μm, polymerization degree: 1300) obtained in Production Example 3. 2.4 g (0.6 parts by weight with respect to 100 parts by weight of vinyl chloride resin) is added and spray-dried at a hot air temperature of 158 ° C. and an outlet temperature of 55 ° C. using a rotary disk type spray dryer to obtain paste vinyl chloride (Content of polyoxyalkylene alkyl ether represented by the general formula (1): 0.596 parts by weight).

  For 100 parts by weight of the obtained paste PVC, 45 parts by weight of DOP (J-Plus, Inc., grade industry) as a plasticizer, and 10 parts by weight of calcium carbonate (Sankyo Seimitsu Co., Ltd., trade name first grade) as a filler Parts, 15 parts by weight of titanium oxide (Taika Co., Ltd., trade name: JR600A) as a pigment, 3 parts by weight of foaming agent (Otsuka Chemical Co., Ltd., trade name: AZ Ultra 1050), diluent (JX Nippon Mining Corporation), A paste vinyl chloride composition was obtained using 10 parts by weight of a trade name N10) and 3 parts by weight of a stabilizer (Sakai Chemical Industry Co., Ltd., trade name KF708S) using a dissolver.

  Using the obtained paste vinyl chloride composition, a foam was produced in the same manner as in Example 1, and the expansion ratio, surface smoothness, and cell structure were evaluated. The test results are shown in Table 3. The expansion ratio was 7.2 times and 5.0 times or more, the surface was smooth, and the cells had a dense structure.

Example 8
Except for changing polyoxyethylene (12) lauryl ether to polyoxyethylene (47) lauryl ether (Kao Co., Ltd., trade name: Emulgen 150), a paste PVC and a paste PVC composition were prepared in the same manner as in Example 7. Obtained and produced a foam, and evaluated the expansion ratio, surface smoothness, and cell structure. The test results are shown in Table 3. The expansion ratio was 7.4 times and 5.0 times or more, the surface was smooth, and the cell had a dense structure.

Example 9
Except for changing polyoxyethylene (12) lauryl ether to polyoxyethylene (30) oleyl ether (Kao Co., Ltd., trade name: Emulgen 430), a paste PVC and a paste PVC composition were prepared in the same manner as in Example 7. Obtained and produced a foam, and evaluated the expansion ratio, surface smoothness, and cell structure. The test results are shown in Table 3. The expansion ratio was 7.3 times and 5.0 times or more, the surface was smooth, and the cells had a dense structure.

Example 10
Polyoxyethylene (47) lauryl ether (Kao Co., Ltd., trade name: Emulgen 150) was added to 1 kg of the vinyl chloride resin latex (average particle size: 1.2 μm, polymerization degree: 900) obtained in Production Example 4. 2g (0.5 parts by weight with respect to 100 parts by weight of vinyl chloride resin) is added and spray-dried at a hot air temperature of 110 ° C and an outlet temperature of 50 ° C using a rotary disk spray dryer. Obtained (content of polyoxyalkylene alkyl ether represented by the general formula (1): 0.498% by weight).

  Using the obtained paste PVC, a foam was produced in the same manner as in Example 1, and the foaming ratio, surface smoothness, and cell structure were evaluated. The test results are shown in Table 4. The expansion ratio was 5.9 times and 5.0 times or more, the surface was smooth, and the cells had a dense structure.

Example 11
Except for changing the amount of polyoxyethylene (47) lauryl ether added to 4 g (1.0 part by weight with respect to 100 parts by weight of vinyl chloride resin), paste PVC and paste PVC composition were the same as in Example 10. To obtain foams, and the foaming magnification, surface smoothness, and cell structure were evaluated. The test results are shown in Table 4. The expansion ratio was 6.0 times and 5.0 times or more, the surface was smooth, and the cells had a dense structure.

Example 12
Paste vinyl chloride and paste vinyl chloride composition in the same manner as in Example 10 except that the amount of polyoxyethylene (47) lauryl ether added was changed to 6 g (1.5 parts by weight with respect to 100 parts by weight of vinyl chloride resin). To obtain foams, and the foaming magnification, surface smoothness, and cell structure were evaluated. The test results are shown in Table 4. The expansion ratio was 6.3 times and 5.0 times or more, the surface was smooth, and the cells had a dense structure.

Example 13
Except for changing the addition amount of the foaming agent to 4 parts by weight, a paste PVC and a paste PVC composition were obtained in the same manner as in Example 1 to produce a foam, and the foaming ratio, surface smoothness, and cell structure were evaluated. did. The test results are shown in Table 1. The expansion ratio was 5.6 times and 5.0 times or more, the surface was smooth, and the cell had a dense structure.

Comparative Example 1
Except for not adding polyoxyethylene (12) lauryl ether, paste vinyl chloride and paste vinyl chloride composition were obtained in the same manner as in Example 1 to produce a foam, and the foaming ratio, surface smoothness, and cell structure were evaluated. The test results are shown in Table 5. Although the surface was smooth and the cell was a dense structure, the expansion ratio was less than 4.6 times and 5.0 times, which was inferior to Example 1.

Comparative Example 2
Except for changing polyoxyethylene (12) lauryl ether to polyoxyethylene (4) lauryl ether (Kao Co., Ltd., trade name: Emulgen 105), a paste PVC and a paste PVC composition were prepared in the same manner as in Example 1. Obtained and produced a foam, and evaluated the expansion ratio, surface smoothness, and cell structure. The test results are shown in Table 5. Although the surface was smooth and the cell was a dense structure, the expansion ratio was less than 4.8 times and 5.0 times, which was inferior to Example 1.

Comparative Example 3
Except for changing polyoxyethylene (12) lauryl ether to polyoxyethylene (9) lauryl ether (Kao Co., Ltd., trade name: Emulgen 109P), a paste PVC and a paste PVC composition were prepared in the same manner as in Example 1. Obtained and produced a foam, and evaluated the expansion ratio, surface smoothness, and cell structure. The test results are shown in Table 5. Although the surface was smooth and the cell was a dense structure, the expansion ratio was less than 4.9 times and 5.0 times, which was inferior to Example 1.

Comparative Example 4
Except not adding polyoxyethylene (12) lauryl ether, paste vinyl chloride and a paste vinyl chloride composition were obtained like Example 4, a foam was produced, and foaming magnification, surface smoothness, and cell structure were evaluated. The test results are shown in Table 6. The surface was smooth and the cells were dense, but the foaming ratio was 4.6 times and below 5.0 times, which was inferior to Example 4.

Comparative Example 5
Except for changing polyoxyethylene (12) lauryl ether to polyoxyethylene (4) lauryl ether (Kao Co., Ltd., trade name: Emulgen 105), a paste PVC and a paste PVC composition were prepared in the same manner as in Example 4. Obtained and produced a foam, and evaluated the expansion ratio, surface smoothness, and cell structure. The test results are shown in Table 6. Although the surface was smooth and the cell was a dense structure, the expansion ratio was less than 4.8 times and 5.0 times, which was inferior to Example 4.

Comparative Example 6
Except for changing polyoxyethylene (12) lauryl ether to polyoxyethylene (9) lauryl ether (Kao Co., Ltd., trade name: Emulgen 109P), a paste PVC and a paste PVC composition were prepared in the same manner as in Example 4. Obtained and produced a foam, and evaluated the expansion ratio, surface smoothness, and cell structure. The test results are shown in Table 6. Although the surface was smooth and the cell was dense, the foaming ratio was less than 4.9 times and 5.0 times, which was inferior to Example 4.

Comparative Example 7
Except not adding polyoxyethylene (12) lauryl ether, paste vinyl chloride and paste vinyl chloride composition were obtained like Example 7, and the foam was produced and foaming magnification, surface smoothness, and cell structure were evaluated. The test results are shown in Table 7. Although the surface was smooth and the cell was a dense structure, the expansion ratio was 6.5 times, which was inferior to Example 7.

Comparative Example 8
Except for changing polyoxyethylene (12) lauryl ether to polyoxyethylene (4) lauryl ether (Kao Corporation, trade name: Emulgen 105), a paste PVC and a paste PVC composition were prepared in the same manner as in Example 7. Obtained and produced a foam, and evaluated the expansion ratio, surface smoothness, and cell structure. The test results are shown in Table 7. The surface was smooth and the cell had a dense structure, but the expansion ratio was 6.7 times, which was inferior to Example 7.

Comparative Example 9
Except for changing polyoxyethylene (12) lauryl ether to polyoxyethylene (9) lauryl ether (Kao Co., Ltd., trade name: Emulgen 109P), a paste PVC and a paste PVC composition were prepared in the same manner as in Example 7. Obtained and produced a foam, and evaluated the expansion ratio, surface smoothness, and cell structure. The test results are shown in Table 7. Although the surface was smooth and the cell was a dense structure, the expansion ratio was 6.8, which was inferior to Example 7.

Comparative Example 10
Except for changing the addition amount of the foaming agent to 4 parts by weight, a paste PVC and a paste PVC composition were obtained in the same manner as in Comparative Example 1, a foam was produced, and the expansion ratio, surface smoothness, and cell structure were evaluated. did. The test results are shown in Table 5. The expansion ratio was 5.0 times, inferior to that of Example 1, and the surface was rough and the cell was also rough.

Comparative Example 11
Except for not adding polyoxyethylene (47) lauryl ether, paste vinyl chloride and paste vinyl chloride composition were obtained in the same manner as in Example 10 to produce foams, and the foaming ratio, surface smoothness, and cell structure were evaluated. The test results are shown in Table 8. The surface was smooth and the cell had a dense structure, but the foaming ratio was 5.6 times, which was inferior to Example 10.

  The paste vinyl chloride of the present invention can obtain a high-magnification foam in the foaming process in which the paste vinyl chloride composition of the present invention obtained from the present invention controls the thickness of the product, The amount of bisol used can be reduced. Therefore, it is expected to be widely used as a paste vinyl chloride sol capable of obtaining a high-magnification foam from the viewpoint of reducing environmental burden and manufacturing cost.

Claims (2)

A vinyl chloride resin for paste processing, comprising 0.1 to 3 parts by weight of a polyoxyalkylene alkyl ether represented by the following general formula (1) with respect to 100 parts by weight of a vinyl chloride resin.

(Wherein R1 represents hydrogen or an alkyl group, alkenyl group or alkylene group having 1 to 20 carbon atoms, R2 represents hydrogen or an alkyl group, alkenyl group or alkylene group having 1 to 10 carbon atoms, and n is 11 or more. Represents an integer.) A plasticizer of 20 to 200 parts by weight, a filler of 300 parts by weight or less, and a foaming agent of 0.1 to 30 parts by weight are blended with 100 parts by weight of the vinyl chloride resin for paste processing according to claim 1. A vinyl chloride resin composition for paste processing.