Paste vinyl chloride resin composition

Abstract

To provide a paste vinyl chloride-based resin composition which has high surface strength and foaming property, and has excellent characteristics, in particular, for foam wall paper, and a foam molding of the same.SOLUTION: A paste vinyl chloride-based resin composition contains, with respect to 100 pts.wt. of a vinyl chloride-based resin having a degree of polymerization of 1,200 or more and 2,200 or less, more than 0.1 pt.wt. and 5 pts.wt. or less of an acrylic resin, and with respect to 100 pts.wt. of a paste vinyl chloride-based resin containing 0.05 pt.wt. or more and 2.5 pts.wt. or less of alkyl benzene sulfonate, 20 pts.wt. or more and 70 pts.wt. or less of a plasticizer, 50 pts.wt. or less of a filler, 10 pts.wt. or more and 30 pts.wt. or less of a pigment, 1 pt.wt. or more and 4.5 pts.wt. or less of a stabilizer, 1 pt.wt. or more and 4.5 pts.wt. or less of a foaming agent, and 1 pt.wt. or more and 30 pts.wt. or less of a viscosity-reducing agent.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a paste vinyl chloride resin composition having excellent surface strength, elongation, foaming properties, and surface smoothness, and particularly excellent properties for use as foamed wallpaper.

Background Art

[0002] A paste vinyl chloride resin for paste processing (hereinafter sometimes abbreviated as paste vinyl chloride) is generally kneaded together with a plasticizer, a filler, a stabilizer, or other compounding agents to prepare a paste vinyl chloride composition sol, and the paste vinyl chloride composition sol is used in various molding processes to be used for various molded products such as wallpaper, tile carpets, and gloves.

[0003] In the field of wallpaper applications, the shortage of wallpaper installation workers and the aging of the population have become problems, and wall covering materials that are easy to install are in demand. For this reason, for example, in a wall covering material having a backing paper for wallpaper and a resin layer, generally, a product having a light weight and easy to handle is preferred. In addition, in order to conceal the unevenness of the base to be constructed, there are many that are thickened using a foaming agent.

[0004] However, when thickening the wallpaper using a foaming agent, the surface strength of the wallpaper may decrease, and the risk of damage during construction or in daily life after construction may increase.

[0005] In order to solve this problem, for example, a foamed wallpaper having high surface strength and sufficient thickness while being lightweight and a method for manufacturing the same have been proposed (see, for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] However, in the foamed wallpaper proposed in Patent Document 1, no consideration has been given to the vinyl chloride resin composition for foamed wallpaper.

[0008] Therefore, an object of the present invention is to provide a paste vinyl chloride composition and a foam thereof which have high surface strength, surface smoothness and foamability, and are particularly suitable for foamed wallpaper.

Means for Solving the Problems

[0009] As a result of intensive studies on the above problems, the present inventor has found that a paste vinyl chloride composition containing a specific amount of a plasticizer, filler, pigment, stabilizer, foaming agent, and viscosity reducer with respect to a paste vinyl chloride containing a specific amount of an acrylic resin and an alkylbenzenesulfonate in a vinyl chloride resin has extremely high surface strength and good foamability, and has thus completed the present invention.

[0010] That is, the present invention relates to a paste vinyl chloride resin composition characterized in that, with respect to 100 parts by weight of a vinyl chloride resin having a polymerization degree of 1200 or more and 2200 or less, 100 parts by weight of a paste vinyl chloride resin containing more than 0.1 part by weight and 5 parts by weight or less of an acrylic resin and 0.05 part by weight or more and 2.5 parts by weight or less of an alkylbenzenesulfonate contains 20 parts by weight or more and 70 parts by weight or less of a plasticizer, 50 parts by weight or less of a filler, 10 parts by weight or more and 30 parts by weight or less of a pigment, 1 part by weight or more and 4.5 parts by weight or less of a stabilizer, 1 part by weight or more and 4.5 parts by weight or less of a foaming agent, and 1 part by weight or more and 30 parts by weight or less of a viscosity reducer.

[0011] Hereinafter, the present invention will be described in detail.

[0012] The paste vinyl chloride that constitutes the paste vinyl chloride composition of the present invention contains, based on 100 parts by weight of the vinyl chloride resin, more than 0.1 part by weight and 5 parts by weight or less of an acrylic resin, and 0.05 part by weight or more and 2.5 parts by weight or less of an alkylbenzene sulfonate. And the vinyl chloride resin has a degree of polymerization of 1200 or more and 2200 or less, and particularly preferably has a degree of polymerization of 1200 or more and 1800 or less, and more preferably 1300 or more and 1700 or less, since it can provide a paste vinyl chloride composition excellent in surface strength and surface smoothness. Here, when the degree of polymerization is less than 1200, the surface strength is inferior. On the other hand, when the degree of polymerization exceeds 2200, the surface smoothness is inferior. As a method for measuring the degree of polymerization of the vinyl chloride resin, for example, a method of calculating the degree of polymerization by a solution viscosity measurement method using an Ubbelohde viscometer of JIS K6721 can be mentioned.

[0013] As the vinyl chloride resin, not only a vinyl chloride homopolymer but also a copolymer may be used. Examples of the copolymerizable monomers in that case include vinyl esters such as vinyl acetate, vinyl propionate, vinyl myristate, and vinyl benzoate; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and fumaric acid or their anhydrides; acrylic acid esters such as methyl acrylate, ethyl acrylate, and butyl acrylate; methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; unsaturated carboxylic acid esters such as maleic acid ester, fumaric acid ester, and cinnamic acid ester; 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 derivatives, acrylonitrile, methacrylonitrile, and the like.

[0014] The vinyl chloride resin may be a vinyl chloride resin obtained by an emulsion polymerization method, a micro-suspension polymerization method, a seed emulsion polymerization method, a seed micro-suspension polymerization method, etc., which are generally known polymerization methods for paste vinyl chloride. A vinyl chloride resin latex can be obtained by these polymerization methods, and it can be obtained by removing the water content of the obtained latex. At that time, examples of the method for removing water from the vinyl chloride resin latex include methods such as spray drying, fluidized bed drying, through-air drying, rotary drying, and conduction heating drying. Among them, the method by spray drying is preferred because water can be removed efficiently.

[0015] The following shows an example of a method by the seed micro-suspension polymerization method for producing the vinyl chloride resin and the vinyl chloride resin latex.

[0016] The seed micro-suspension polymerization method consists of: 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; 2) the second step of polymerizing the obtained seed latex with vinyl chloride monomer or a vinyl chloride monomer and a monomer copolymerizable therewith in the presence of deionized water, an emulsifier, a buffer, and an emulsification aid such as a higher alcohol as necessary with gentle stirring to enlarge the seed latex and obtain a vinyl chloride resin latex.

[0017] Here, examples of the monomer copolymerizable with vinyl chloride monomer include the monomers described above. In addition to the alkylbenzene sulfonates described later, examples of the emulsifier include alkyl sulfate salts such as sodium lauryl sulfate and myristyl sulfate; sulfosuccinate salts such as sodium dioctyl sulfosuccinate and sodium dihexyl sulfosuccinate; fatty acid salts such as ammonium laurate and potassium stearate; anionic emulsifiers such as polyoxyethylene alkyl sulfate salts and polyoxyethylene alkyl aryl sulfate salts; sorbitan esters such as sorbitan monooleate and polyoxyethylene sorbitan monostearate; and nonionic emulsifiers such as polyoxyethylene alkyl phenyl ethers and polyoxyethylene alkyl esters. One or more of the conventionally known ones can be used. Examples of the buffer include alkali metal monohydrogen phosphates, alkali metal dihydrogen phosphates, potassium hydrogen phthalate, sodium hydrogen carbonate, boric acid - potassium hydroxide solution, and the like.

[0018] Furthermore, examples of the emulsification aid used as needed include higher alcohols such as cetyl alcohol and lauryl alcohol; higher fatty acids such as lauric acid, palmitic acid, and stearic acid, and their esters; aromatic hydrocarbons, higher fatty acid hydrocarbons, and halogenated hydrocarbons such as chlorinated paraffin.

[0019] In addition, the vinyl chloride-based resin seed latex used in the seed micro-suspension polymerization method can be prepared by the following micro-suspension polymerization method. First, a premix is prepared by adding a vinyl chloride monomer, an oil-soluble polymerization initiator, a surfactant, a buffer, a higher alcohol, a higher fatty acid, a higher fatty acid ester, a dispersion aid such as chlorinated paraffin, and, if necessary, a polymerization degree regulator, and then homogenized by a homogenizer to adjust the oil droplets. As the homogenizer at this time, for example, a colloid mill, a vibration stirrer, a two-stage high-pressure pump, etc. can be used. Then, the homogenized liquid is sent to a polymerization vessel, and the polymerization reaction is started by raising the temperature in the polymerization vessel while gently stirring, and the vinyl chloride-based resin seed latex containing the oil-soluble polymerization initiator is adjusted by performing polymerization until a predetermined conversion rate is reached.

[0020] As the oil-soluble polymerization initiator at that time, a diacyl peroxide having a half-life temperature of 30 to 70 °C for 10 hours is preferable. Examples of such an oil-soluble polymerization initiator include isobutyryl peroxide, 3,3,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic peroxide, and the like.

[0021] As the acrylic resin constituting the paste vinyl chloride, any resin belonging to the category of acrylic resins may be used. For example, polymethyl methacrylate, poly(methyl methacrylate-butyl acrylate) copolymer, poly(methyl methacrylate-ethyl acrylate) copolymer, poly(methyl methacrylate-octyl acrylate) copolymer, etc. can be mentioned. Among them, since it becomes a paste vinyl chloride excellent in the balance between high surface strength and foamability, it is preferably an acrylic resin having a glass transition temperature (Tg) of -40°C to 50°C, and particularly preferably an acrylic resin having a weight average molecular weight of 50,000 to 200,000. The weight average molecular weight at this time can be determined as a standard polystyrene conversion value by, for example, gel permeation chromatography. The acrylic resin may be an acrylic resin constituting the aqueous acrylic resin emulsion described later. Further, it is preferably an acrylic resin constituting a thickening type aqueous acrylic resin emulsion.

[0022] Since the acrylic resin is particularly excellent in foamability and surface strength, it preferably has an average particle size of 50 nm or more and 1000 nm or less, and more preferably 100 nm or more and 400 nm or less. Examples of the method for measuring the average particle size at this time include a method calculated from the results of laser diffraction particle size distribution measurement and electron microscope observation.

[0023] The paste vinyl chloride contains more than 0.1 part by weight and 5 parts by weight or less of the acrylic resin. Since it is particularly excellent in foamability and surface smoothness, it is preferably 0.3 part by weight or more and 3 parts by weight or less, and more preferably 0.8 part by weight or more and 1.5 parts by weight or less. Here, when it is 0.1 part by weight or less, the surface smoothness is poor. On the other hand, when it exceeds 5 parts by weight, the viscosity when made into a sol becomes high, and problems may occur in handleability.

[0024] As the alkylbenzene sulfonate constituting the paste vinyl chloride, any substance belonging to the category of alkylbenzene sulfonates may be used. For example, sodium dodecylbenzene sulfonate, potassium dodecylbenzene sulfonate, ammonium dodecylbenzene sulfonate, triethanolammonium dodecylbenzene sulfonate, etc. can be mentioned. Among them, sodium dodecylbenzene sulfonate is preferred because it is possible to provide a paste vinyl chloride with excellent surface smoothness.

[0025] The paste vinyl chloride contains 0.05 to 2.5 parts by weight of an alkylbenzene sulfonate. In particular, since it has excellent surface smoothness and surface strength, it is preferably 0.5 to 2.0 parts by weight, and more preferably contains 0.8 to 1.5 parts by weight. The alkylbenzene sulfonate may be an emulsifier when obtaining a vinyl chloride resin, and the amount may be adjusted by using the emulsifier used in the preparation of the vinyl chloride resin as it is, or by adding or reducing it separately. Here, when the amount of the alkylbenzene sulfonate is less than 0.05 parts by weight, the surface smoothness is poor. On the other hand, when it exceeds 2.5 parts by weight, the surface strength is poor.

[0026] The paste vinyl chloride may contain other substances generally added during the preparation of vinyl chloride resins, such as polymerization initiators, emulsifiers, emulsification aids, buffers, higher alcohols, higher fatty acids, higher fatty acid esters, dispersion aids such as chlorinated paraffins, and polymerization degree regulators, as long as the object and effect of the present invention are not deviated.

[0027] As a method for manufacturing the paste vinyl chloride, any manufacturing method may be used. For example, a method of mixing a vinyl chloride resin, an acrylic resin, and an alkylbenzene sulfonate, a method of mixing an acrylic resin with the above-mentioned vinyl chloride resin latex and drying it, and as a more efficient method, a method of mixing an aqueous acrylic resin emulsion as the acrylic resin and drying it can be mentioned. As the aqueous acrylic resin emulsion at this time, a commercially available product may be used. For example, (trade name) Polytoron E418 (manufactured by Asahi Kasei Corporation), (trade name) LX874 (manufactured by Nippon Zeon Co., Ltd.), (trade name) Polytoron A655 (manufactured by Asahi Kasei Corporation), (trade name) Polytoron Z332 (manufactured by Asahi Kasei Corporation), (trade name) Polytoron E5300 (manufactured by Asahi Kasei Corporation), (trade name) Polytoron A655 (manufactured by Asahi Kasei Corporation), (trade name) LX851C (manufactured by Nippon Zeon Co., Ltd.), (trade name) LX851F2 (manufactured by Nippon Zeon Co., Ltd.), (trade name) LX814 (manufactured by Nippon Zeon Co., Ltd.), (trade name) LX855E1 (manufactured by Nippon Zeon Co., Ltd.), (trade name) Aron A-7055 (manufactured by Toagosei Co., Ltd.), (trade name) Aron B-300K (manufactured by Toagosei Co., Ltd.), (trade name) Aron B-500 (manufactured by Toagosei Co., Ltd.), (trade name) Primal TT-615 (manufactured by Rohm and Haas Company), (trade name) Primal TT-935 (manufactured by Rohm and Haas Company), (trade name) Primal ASE-60 (manufactured by Rohm and Haas Company), (trade name) Primal ASE-75 (manufactured by Rohm and Haas Company), (trade name) Primal ASE-95 (manufactured by Rohm and Haas Company), (trade name) Primal RM-5 (manufactured by Rohm and Haas Company), (trade name) SN Thickener A-818 (manufactured by San Nopco Ltd.), (trade name) SN Thickener A-850 (manufactured by San Nopco Ltd.), (trade name) Osticker V-500 (manufactured by Nichika Chemical Co., Ltd.), (trade name) Reodic 250H (manufactured by Nippon Junyaku Co., Ltd.), (trade name) Reodic 835H (manufactured by Nippon Junyaku Co., Ltd.), etc. can be mentioned.Among them, those with particularly excellent foaming properties include (trade name) Aron A-7055 (manufactured by Toagosei Co., Ltd.), (trade name) Aron B-300K (manufactured by Toagosei Co., Ltd.), (trade name) Aron B-500 (manufactured by Toagosei Co., Ltd.), (trade name) Primal TT-615 (manufactured by Rohm and Haas), (trade name) Primal TT-935 (manufactured by Rohm and Haas), (trade name) Primal ASE-60 (manufactured by Rohm and Haas), (trade name) Primal ASE-75 (manufactured by Rohm and Haas), (trade name) Primal ASE-95 (manufactured by Rohm and Haas), (trade name) Primal RM-5 (manufactured by Rohm and Haas), (trade name) SN Thickener A-818 (manufactured by San Nopco Ltd.), (trade name) SN Thickener A-850 (manufactured by San Nopco Ltd.), (trade name) Osticker V-500 (manufactured by Nihon Kayaku Co., Ltd.), (trade name) Reodic 250H (manufactured by Nippon Pure Chemical Co., Ltd.), (trade name) Reodic 835H (manufactured by Nippon Pure Chemical Co., Ltd.) and other thickening type aqueous acrylic resin emulsions, further alkali thickening type aqueous acrylic resin emulsions, and preferably an alkali thickening type aqueous acrylic resin emulsion with a weight average molecular weight of 50,000 to 200,000 and a pH of 2 to 4 containing an acrylic resin. Also, as the drying method of the latex, the same methods as those for removing moisture from the above-mentioned vinyl chloride resin latex can be mentioned. Among them, the method by spray drying is preferred because moisture can be removed efficiently. And the paste vinyl chloride can be manufactured as a granular material with excellent handleability by spray drying.

[0028] The paste vinyl chloride is a paste vinyl chloride containing an alkylbenzene sulfonate and an acrylic resin, and in some cases, a particulate acrylic resin. Its shape can be any, for example, paste vinyl chloride particles containing an alkylbenzene sulfonate and a particulate acrylic resin can be mentioned.

[0029] The paste PVC composition of the present invention has extremely high surface strength and good foamability. Therefore, based on 100 parts by weight of the paste PVC, it contains 20 parts by weight or more and 70 parts by weight or less of a plasticizer, 50 parts by weight or less of a filler, 10 parts by weight or more and 30 parts by weight or less of a pigment, 1 part by weight or more and 4.5 parts by weight or less of a stabilizer, 1 part by weight or more and 4.5 parts by weight or less of a foaming agent, and 1 part by weight or more and 30 parts by weight or less of a viscosity reducer.

[0030] Examples of the plasticizer include phthalic acid esters such as bis(2-ethylhexyl) phthalate (which may be abbreviated as DOP), diisononyl phthalate, diisodecyl phthalate, and dibutyl phthalate; adipic acid esters such as (2-ethylhexyl) adipate and diisononyl adipate; trimellitic acid esters such as tri(2-ethylhexyl) trimellitate, triisodecyl trimellitate, and trinormal octyl trimellitate; phosphoric acid esters such as tri(2-ethylhexyl) phosphate, tricresyl phosphate, and trixylenyl phosphate; benzoic acid esters such as diethylene glycol dibenzoate and dipropylene glycol dibenzoate; and other polyester-based plasticizers, sebacic acid esters, myristic acid esters, maleic acid esters, epoxidized vegetable oils, etc., which are generally used as plasticizers. The amount of the plasticizer at that time is 20 parts by weight or more and 70 parts by weight or less based on 100 parts by weight of the paste PVC. Here, when the amount of the plasticizer is less than 20 parts by weight, the viscosity becomes high and the handleability of the sol deteriorates. On the other hand, when it exceeds 70 parts by weight, the foaming ratio decreases.

[0031] Examples of the filler include calcium carbonate, diatomaceous earth, magnesium carbonate, etc. The amount of the filler at that time is 50 parts by weight or less based on 100 parts by weight of the paste PVC, and preferably 15 parts by weight or more and 50 parts by weight or less. Here, when the amount of the filler exceeds 50 parts by weight, the surface smoothness deteriorates.

[0032] The pigments are not particularly limited, and examples include titanium oxide, zinc white, lithopone, lead white, etc. These may be used alone or in combination of two or more. The amount of the pigment at that time is 10 parts by weight or more and 30 parts by weight or less, preferably 15 parts by weight or more and 25 parts by weight or less, based on 100 parts by weight of the paste PVC. Here, when the pigment is less than 10 parts by weight, the hiding power decreases. When it exceeds 30 parts by weight, the viscosity becomes high and the handleability of the sol deteriorates.

[0033] Examples of the foaming agent include inorganic foaming agents such as sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, ammonium nitrite, amide compounds, sodium borohydride; isocyanate compounds; azo compounds such as azodicarbonamide, azobisisobutyronitrile, barium azodicarboxylate; hydrazine derivatives such as p,p'-oxybisbenzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide; semicarbazide compounds; azo compounds; nitroso compounds such as dinitrosopentamethylenetetramine; organic foaming agents such as triazole compounds. The foaming agent may be a commercially available product. For example, as azodicarbonamide, (trade name) AZ Ultra 1050 (manufactured by Otsuka Chemical Co., Ltd.) can be mentioned. And, if necessary, it is also possible to use the above foaming agent in combination with a decomposition accelerator such as zinc white (zinc oxide). The amount of the foaming agent at that time is 1 part by weight or more and 4.5 parts by weight or less, based on 100 parts by weight of the paste PVC. Here, when the foaming agent is less than 1 part by weight, the foaming ratio decreases. On the other hand, when it exceeds 4.5 parts by weight, the surface smoothness deteriorates.

[0034] In addition, examples of the stabilizer include epoxy stabilizers, barium stabilizers, calcium stabilizers, tin stabilizers, zinc stabilizers, etc. Moreover, commercially available composite stabilizers such as calcium-zinc-based and barium-zinc-based stabilizers can also be used. Among them, calcium-zinc-based stabilizers, for example, (trade name) LFX88 (manufactured by Dainichi Kasei Kogyo Co., Ltd.), are preferred because they particularly improve the foamability. The amount of the stabilizer at that time is 1 part by weight or more and 4.5 parts by weight or less with respect to 100 parts by weight of the paste PVC. Here, when the amount of the stabilizer is less than 1 part by weight, the foaming ratio and thermal stability decrease. On the other hand, when it exceeds 4.5 parts by weight, the foaming ratio decreases.

[0035] The viscosity reducer reduces the viscosity of the plastisol and improves the processability by blending aliphatic hydrocarbons, aromatic hydrocarbons, etc. Examples of commercially available products include (trade name) N10 (manufactured by JX Nippon Mining & Metals Co., Ltd.), (trade name) EXXSOL TM D40 (manufactured by Ando Parachem Co., Ltd.), etc. The amount of the viscosity reducer at that time is 1 part by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the paste PVC. Here, when the amount of the viscosity reducer is less than 1 part by weight, the viscosity becomes high and the handling property of the sol deteriorates. On the other hand, when it exceeds 30 parts by weight, the surface smoothness deteriorates.

[0036] Furthermore, when making the paste PVC composition, additives that are usually added to the paste PVC composition within a range not exceeding the object of the present invention, such as antioxidants, flame retardants, lubricants, ultraviolet absorbers, colorants such as pigments, surfactants, antistatic agents, etc., may be added, and their blending amounts may also be within the generally used range.

[0037] The paste PVC composition of the present invention can be made into a paste PVC sol excellent in molding processability by blending a plasticizer, a filler, a pigment, a foaming agent, a diluent, and a stabilizer. And it is applicable to various uses such as films, sheets, wallpapers, floor materials, foamed sheets, etc., and is particularly suitable for foams that require surface smoothness, surface strength, foamability, etc., and further for cushion floors and foamed wallpapers.

Advantages of the Invention

[0038] The paste vinyl chloride composition of the present invention can provide a foam excellent in surface strength, surface smoothness, and foamability, and its industrial value is very high.

Examples

[0039] The evaluation method of the paste vinyl chloride resin composition obtained from the examples is shown below.

[0040] <Degree of polymerization of vinyl chloride resin> Using an Ubbelohde viscometer of JIS K6721, the degree of polymerization was calculated by the solution viscosity measurement method.

[0041] <Expansion ratio> The obtained paste vinyl chloride resin composition sol was calculated as a foam by the following formula (1). Expansion ratio = (thickness of foam - thickness of original fabric) / thickness of original fabric (1) <Surface smoothness> The obtained paste vinyl chloride resin composition was used as a foam, and its surface smoothness was visually observed and evaluated. The evaluation criteria for surface smoothness are shown below. ○: The surface is smooth. ×: The surface is rough.

[0042] <Surface strength> Based on the test in accordance with the standard "Surface Reinforced Wallpaper Performance Regulations" established by the Wallpaper Industry Association, the damage state of the surface during scratching was visually judged. The evaluation criteria are shown below. ○: Tearing of the surface layer can be seen, but the backing material such as paper cannot be seen. ×: The surface is torn and the backing material such as paper can be clearly seen.

[0043] <Sol viscosity> 150 mL of the paste vinyl chloride resin composition sol was placed in a 150 mL polypropylene cup, and the viscosity was evaluated using a B8H type viscometer (manufactured by Tokyo Keiki Co., Ltd.) rotor No. 5 under the condition of a rotation speed of 20 rpm. The lower the sol viscosity value, the better the sol viscosity characteristics.

[0044] <Hidden property> It was evaluated using a hidden gray scale conforming to JIS A 6921, and those of grade 4 or higher were considered to have passed. Judgment criteria Grade 1: Clearly visible. Grade 2: Visible. Grade 3: Barely visible. Grade 4: Not visible.

[0045] Synthesis Example 1 1 m 3 360 kg of deionized water, 300 kg of vinyl chloride monomer, 5.7 kg of lauroyl peroxide, and 30 kg of a 15 wt% aqueous solution of sodium dodecylbenzenesulfonate were charged into a stainless steel autoclave, and the mixture was circulated for 3 hours using a homogenizer for homogenization treatment. Then, the temperature of the reaction system was raised to 45 °C to initiate polymerization. After the pressure of the polymerization system decreased, the unreacted vinyl chloride monomer was recovered to obtain a vinyl chloride-based resin seed latex (a) having a solid content of 35 wt%, an average particle diameter of 0.55 μm, and containing 2 wt% of lauroyl peroxide based on the vinyl chloride-based resin.

[0046] Synthesis Example 2 1 m 3 400 kg of deionized water, 350 kg of vinyl chloride monomer, 2 kg of a 16 wt% aqueous solution of potassium laurate, and 5 kg of a 16 wt% aqueous solution of sodium dodecylbenzenesulfonate were charged into a stainless steel autoclave, and the temperature of the reaction system was raised to 60 °C to initiate polymerization. After the pressure of the polymerization system decreased, the unreacted vinyl chloride monomer was recovered to obtain a vinyl chloride-based resin seed latex (b) having a solid content of 40 wt% and an average particle diameter of 0.15 μm.

[0047] Production Example 1 610 g of deionized water, 730 g of vinyl chloride monomer, 15 g of a 5 wt% aqueous sodium dodecylbenzenesulfonate solution, 4 parts by weight of a vinyl chloride resin seed latex (a) with an average particle diameter of 0.55 μm obtained according to Synthesis Example 1, and 7 parts by weight of a vinyl chloride resin seed latex (b) with an average particle diameter of 0.15 μm obtained according to Synthesis Example 2 were charged into a 2.5 L stainless steel autoclave. The temperature of this reaction mixture was raised to 45 °C to initiate polymerization. During the period from the start to the end of polymerization, 0.7 part by weight of a 5 wt% aqueous sodium dodecylbenzenesulfonate solution was continuously added with respect to the vinyl chloride monomer. Polymerization was stopped when the polymerization pressure dropped from the saturated vapor pressure of the vinyl chloride monomer at 45 °C to 0.28 MPa, and the unreacted vinyl chloride monomer was recovered to obtain a vinyl chloride resin latex with an average particle diameter of 1.4 μm. The degree of polymerization of the vinyl chloride resin at that time was 1650.

[0048] 4 g (equivalent to 1 part by weight with respect to 100 parts by weight of the vinyl chloride resin) of a thickening type aqueous acrylic resin emulsion (manufactured by Toagosei Co., Ltd., trade name: Aron B-300K, average particle diameter 0.15 μm) was added to 1 kg of the obtained vinyl chloride resin latex (average particle diameter: 1.4 μm, degree of polymerization: 1650), and then stirred. Spray drying was carried out using a rotary disk type spray dryer at a hot air temperature of 160 °C and an outlet temperature of 55 °C to obtain a paste vinyl chloride resin.

[0049] The obtained paste vinyl chloride resin contained 1 part by weight of an acrylic resin with an average particle diameter of 150 nm and 0.9 part by weight of sodium dodecylbenzenesulfonate with respect to 100 parts by weight of the vinyl chloride resin.

[0050] Production Example 2 Into a 2.5 L stainless steel autoclave, 610 g of deionized water, 730 g of vinyl chloride monomer, 15 g of a 5 wt% aqueous solution of sodium dodecylbenzenesulfonate, 4 parts by weight of a vinyl chloride-based resin seed latex (a) with an average particle size of 0.55 μm obtained according to Synthesis Example 1, and 7 parts by weight of a vinyl chloride-based resin seed latex (b) with an average particle size of 0.15 μm obtained according to Synthesis Example 2 were charged per 100 parts by weight of the vinyl chloride monomer. The temperature of this reaction mixture was raised to 45 °C to initiate polymerization. During the period from the start of polymerization to the end of polymerization, 0.7 part by weight of a 5 wt% aqueous solution of sodium dodecylbenzenesulfonate was continuously added to the vinyl chloride monomer. Polymerization was stopped when the polymerization pressure dropped from the saturated vapor pressure of the vinyl chloride monomer at 51 °C to 0.40 MPa, and the unreacted vinyl chloride monomer was recovered to obtain a vinyl chloride-based resin latex with an average particle size of 1.4 μm. The degree of polymerization of the vinyl chloride-based resin at that time was 1300.

[0051] To 1 kg of the obtained vinyl chloride-based resin latex (average particle size: 1.4 μm, degree of polymerization: 1300), 4 g of a thickening type aqueous acrylic resin emulsion (manufactured by Toagosei Co., Ltd., trade name: Aron B-300K, average particle size 0.15 μm) (equivalent to 1 part by weight per 100 parts by weight of the vinyl chloride-based resin) was added and then stirred, and spray-dried using a rotary disk type spray dryer at a hot air temperature of 160 °C and an outlet temperature of 55 °C to obtain a paste vinyl chloride-based resin.

[0052] The obtained paste vinyl chloride-based resin contained 1 part by weight of an acrylic resin with an average particle size of 150 nm and 0.9 part by weight of sodium dodecylbenzenesulfonate per 100 parts by weight of the vinyl chloride-based resin.

[0053] Production Example 3 610 g of deionized water, 730 g of vinyl chloride monomer, 15 g of a 5 wt% aqueous solution of sodium dodecylbenzenesulfonate, 4 parts by weight of a vinyl chloride-based resin seed latex (a) with an average particle size of 0.55 μm obtained according to Synthesis Example 1, and 7 parts by weight of a vinyl chloride-based resin seed latex (b) with an average particle size of 0.15 μm obtained according to Synthesis Example 2 were charged into a 2.5 L stainless steel autoclave. The temperature of this reaction mixture was raised to 45 °C to initiate polymerization. During the period from the start of polymerization to the end of polymerization, 0.7 part by weight of a 5 wt% aqueous solution of sodium dodecylbenzenesulfonate was continuously added to the vinyl chloride monomer. Polymerization was stopped when the polymerization pressure dropped from the saturated vapor pressure of the vinyl chloride monomer at 45 °C to 0.28 MPa, and the unreacted vinyl chloride monomer was recovered to obtain a vinyl chloride-based resin latex with an average particle size of 1.4 μm. The degree of polymerization of the vinyl chloride-based resin at that time was 1650.

[0054] 6 g (equivalent to 1.5 parts by weight based on 100 parts by weight of the vinyl chloride-based resin) of a thickening-type aqueous acrylic resin emulsion (manufactured by Toagosei Co., Ltd., trade name: Aron B-300K, average particle size 0.15 μm) was added to 1 kg of the obtained vinyl chloride-based resin latex (average particle size: 1.4 μm, degree of polymerization: 1650), and then stirred. Spray drying was performed using a rotary disk type spray dryer at a hot air temperature of 160 °C and an outlet temperature of 55 °C to obtain a paste vinyl chloride-based resin.

[0055] The obtained paste vinyl chloride-based resin contained 1.5 parts by weight of an acrylic resin with an average particle size of 150 nm and 0.9 part by weight of sodium dodecylbenzenesulfonate based on 100 parts by weight of the vinyl chloride-based resin.

[0056] Example 1 To 100 parts by weight of the paste vinyl chloride resin obtained in Production Example 1, 30 parts by weight of diisononyl phthalate (manufactured by J Plus Co., Ltd., grade for industrial use) as a plasticizer, 20 parts by weight of calcium carbonate (manufactured by Sankyo Seifun Co., Ltd., grade first-class) as a filler, 15 parts by weight of titanium oxide (manufactured by Teika Co., Ltd., (trade name) JR600A) as a pigment, 3 parts by weight of azodicarbonamide (manufactured by Otsuka Chemical Co., Ltd., (trade name) AZ Ultra 1050) as a foaming agent, and 10 parts by weight of a viscosity-reducing agent which is a de-aromatized hydrocarbon (manufactured by Ando Parachem Co., Ltd., (trade name) EXXSOL TM D40), and 3 parts by weight of a Ca / Zn-based stabilizer (manufactured by Dai-Kyowa Kasei Kogyo Co., Ltd., (trade name) LFX88) as a stabilizer were blended to obtain a paste vinyl chloride resin composition, which was kneaded using a dissolver to obtain a paste vinyl chloride resin composition sol.

[0057] The viscosity of the obtained paste vinyl chloride resin composition sol was 11000 mPa·s.

[0058] Also, the obtained paste vinyl chloride resin composition sol was coated on a flame-retardant paper pre-heated at 190°C for 10 seconds to a thickness of 0.12 mm, and heated at 190°C for 8 seconds to obtain a base fabric. After measuring the thickness of the obtained base fabric, it was heated at 225°C for 25 seconds to obtain a foam. Then, the thickness of the obtained foam was measured, and the expansion ratio, surface smoothness, and hiding property were evaluated. The test results are shown in Table 1. The expansion ratio was 6.9 times, and it was excellent in surface smoothness and surface strength.

[0059] Example 2 A paste vinyl chloride resin composition and a paste vinyl chloride resin composition sol were prepared in the same manner as in Example 1, except that 40 parts by weight of a plasticizer and 15 parts by weight of a viscosity-reducing agent were used, and evaluation as a foam was performed. The results of evaluating the expansion ratio, surface smoothness, and cell structure are shown in Table 1. The expansion ratio was 5.6 times, and it was excellent in surface smoothness and surface strength.

[0060] Example 3 A paste vinyl chloride resin composition and a paste vinyl chloride resin composition sol were prepared in the same manner as in Example 1, except that 40 parts by weight of a plasticizer and 20 parts by weight of a viscosity reducer were used, and evaluation as a foam was carried out. The results of evaluating the expansion ratio, surface smoothness, and cell structure are shown in Table 1. The expansion ratio was 5.8 times, and it was excellent in surface smoothness and surface strength.

[0061] Example 4 A paste vinyl chloride resin composition and a paste vinyl chloride resin composition sol were prepared in the same manner as in Example 1, except that 50 parts by weight of a plasticizer, 4 parts by weight of a foaming agent, and 4 parts by weight of a stabilizer were used, and evaluation as a foam was carried out. The results of evaluating the expansion ratio, surface smoothness, and cell structure are shown in Table 1. The expansion ratio was 6.7 times, and it was excellent in surface smoothness and surface strength.

[0062] Example 5 A paste vinyl chloride resin composition and a paste vinyl chloride resin composition sol were prepared in the same manner as in Example 1, except that 40 parts by weight of a plasticizer and 0 parts by weight of a filler were used, and evaluation as a foam was carried out. The results of evaluating the expansion ratio, surface smoothness, and cell structure are shown in Table 1. The expansion ratio was 7.1 times, and it was excellent in surface smoothness and surface strength.

[0063] Example 6 To 100 parts by weight of the paste vinyl chloride resin obtained by Production Example 2, 40 parts by weight of diisononyl phthalate (manufactured by J Plus Co., Ltd., grade for industrial use) as a plasticizer, 20 parts by weight of calcium carbonate (manufactured by Sankyo Seifun Co., Ltd., grade first class) as a filler, 15 parts by weight of titanium oxide (manufactured by Teika Co., Ltd., (trade name) JR600A) as a pigment, 3 parts by weight of azodicarbonamide (manufactured by Otsuka Chemical Co., Ltd., (trade name) AZ Ultra 1050) as a foaming agent, 10 parts by weight of a viscosity reducer which is a de-aromatized hydrocarbon (manufactured by Ando Parachem Co., Ltd., (trade name) EXSSOL TM D40) and 3 parts by weight of a Ca / Zn-based stabilizer (manufactured by Dai Kyowa Kasei Kogyo Co., Ltd., (trade name) LFX88) were blended to form a paste vinyl chloride resin composition, and kneaded using a dissolver to obtain a paste vinyl chloride resin composition sol.

[0064] The viscosity of the obtained paste vinyl chloride resin composition visol was 3700 mPa·s.

[0065] Also, the obtained paste cyclic vinyl chloride resin composition sol was coated on a flame-retardant paper preheated at 190°C for 10 seconds with a thickness of 0.12 mm, and heated at 190°C for 8 seconds to obtain a base fabric. After measuring the thickness of the obtained base fabric, it was heated at 225°C for 25 seconds to obtain a foam. Then, the thickness of the obtained foam was measured, and the expansion ratio, surface smoothness, and hiding property were evaluated. The test results are shown in Table 1. The expansion ratio was 6.3 times, and it was excellent in surface smoothness and surface strength.

[0066] Example 7 To 100 parts by weight of the paste vinyl chloride resin obtained according to Production Example 3, 40 parts by weight of diisononyl phthalate (manufactured by J Plus Co., Ltd., grade for industrial use) as a plasticizer, 20 parts by weight of calcium carbonate (manufactured by Sankyo Seifun Co., Ltd., grade first-class) as a filler, 15 parts by weight of titanium oxide (manufactured by Teika Co., Ltd., (trade name) JR600A) as a pigment, 3 parts by weight of azodicarbonamide (manufactured by Otsuka Chemical Co., Ltd., (trade name) AZ Ultra 1050) as a foaming agent, 10 parts by weight of a viscosity reducer which is a de-aromatized hydrocarbon (manufactured by Ando Parachem Co., Ltd., (trade name) EXSSOL TM D40), and 3 parts by weight of a Ca / Zn-based stabilizer (manufactured by Dai Kyowa Kasei Kogyo Co., Ltd., (trade name) LFX88) as a stabilizer were blended to form a paste vinyl chloride resin composition, and kneaded using a dissolver to obtain a paste vinyl chloride resin composition sol.

[0067] The viscosity of the obtained paste vinyl chloride resin composition visol was 4750 mPa·s.

[0068] Also, the obtained paste annular vinyl resin composition sol was coated on a flame-retardant paper preheated at 190°C for 10 seconds with a thickness of 0.12 mm, and then heated at 190°C for 8 seconds to obtain a base fabric. After measuring the thickness of the obtained base fabric, a foam was obtained by heating at 225°C for 25 seconds. Then, the thickness of the obtained foam was measured, and the expansion ratio, surface smoothness, and hiding property were evaluated. The test results are shown in Table 1. The expansion ratio was 5.6 times, and it was excellent in surface smoothness and surface strength.

[0069]

Table 1

[0070] Comparative Example 1 A paste vinyl chloride resin composition and a paste vinyl chloride resin composition sol were prepared in the same manner as in Example 1 except that 80 parts by weight of a plasticizer was used, and evaluation as a foam was carried out. The results of evaluating the expansion ratio, surface smoothness, and cell structure are shown in Table 2. The expansion ratio was 4.2 times, and it was inferior in foamability.

[0071] Comparative Example 2 A paste vinyl chloride resin composition and a paste vinyl chloride resin composition sol were prepared in the same manner as in Example 1 except that 40 parts by weight of a plasticizer and 0 part of a pigment were used, and evaluation as a foam was carried out. The results of evaluating the expansion ratio, surface smoothness, and cell structure are shown in Table 2. It was inferior in hiding property and surface smoothness.

[0072] Comparative Example 3 A paste vinyl chloride resin composition and a paste vinyl chloride resin composition sol were prepared in the same manner as in Example 1 except that 40 parts by weight of a plasticizer and 100 parts by weight of a filler were used, and evaluation as a foam was carried out. The results of evaluating the expansion ratio, surface smoothness, and cell structure are shown in Table 2. It was inferior in viscosity, surface strength, and surface smoothness.

[0073] Comparative Example 4 A paste vinyl chloride resin composition and a paste vinyl chloride resin composition sol were prepared in the same manner as in Example 1, except that 40 parts by weight of a plasticizer and 7 parts by weight of a foaming agent were used, and evaluation as a foam was carried out. The results of evaluating the expansion ratio, surface smoothness, and cell structure are shown in Table 2. The expansion ratio was 4.6 times, and it was inferior in surface strength and surface smoothness.

[0074]

Table 2

Industrial Applicability

[0075] The paste vinyl chloride resin composition of the present invention has foamability and provides high surface strength and surface smoothness, and particularly has excellent properties as a foamed wallpaper, so its industrial value is extremely high.

Claims

1. Based on 100 parts by weight of a vinyl chloride resin with a degree of polymerization of 1200 or more and 2200 or less, it contains more than 0.1 part by weight and 5 parts by weight or less of an acrylic resin, and 0.8 part by weight or more and 1.5 parts by weight or less of an alkylbenzene sulfonate. The acrylic resin is an acrylic resin that constitutes a thickening type aqueous acrylic resin emulsion. For 100 parts by weight of the paste vinyl chloride resin, it contains 20 parts by weight or more and 70 parts by weight or less of a plasticizer, 50 parts by weight or less of a filler, 10 parts by weight or more and 30 parts by weight or less of a pigment, 1 part by weight or more and 4.5 parts by weight or less of a stabilizer, 1 part by weight or more and 4.5 parts by weight or less of a foaming agent, and 1 part by weight or more and 30 parts by weight or less of a viscosity reducing agent. A paste vinyl chloride resin composition characterized by this.

2. The paste vinyl chloride resin composition according to Claim 1, wherein the acrylic resin is an acrylic resin with an average particle size of 50 nm or more and 1000 nm or less.

3. The paste vinyl chloride resin composition for processing according to Claim 1 or 2, wherein the foaming agent is azodicarbonamide and the stabilizer is a Ca / Zn based stabilizer.

4. Based on 100 parts by weight of a vinyl chloride resin with a degree of polymerization of 1200 or more and 2200 or less, it contains more than 0.1 part by weight and 5 parts by weight or less of an acrylic resin, and 0.8 part by weight or more and 1.5 parts by weight or less of an alkylbenzene sulfonate. The acrylic resin is an acrylic resin that constitutes a thickening type aqueous acrylic resin emulsion. For 100 parts by weight of the paste vinyl chloride resin, it contains 20 parts by weight or more and 70 parts by weight or less of a plasticizer, 50 parts by weight or less of a filler, 10 parts by weight or more and 30 parts by weight or less of a pigment, 1 part by weight or more and 4.5 parts by weight or less of a stabilizer, 1 part by weight or more and 4.5 parts by weight or less of a foaming agent, and 1 part by weight or more and 30 parts by weight or less of a viscosity reducing agent. A paste processed foamed molded body characterized by having a foaming ratio of 5 times or more and 10 times or less.

5. The paste processed foamed molded body according to Claim 4, characterized by having an embossing process on the surface.

6. The paste processed foamed molded body according to Claim 4 or 5, characterized by being wallpaper or a cushion floor.

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