JP2023138913A - Vinyl chloride-based resin for paste processing, and vinyl chloride-based resin composition for paste processing containing the same - Google Patents

Abstract

To provide a vinyl chloride-based resin for paste processing which suppresses formation of a crater when a sheet is prepared by coating onto a base material, can obtain a foam excellent in surface smoothness in foaming, is also excellent in leakage suppression characteristics from the rear of a coating blade, and is excellent, especially, for wallpaper, and a vinyl chloride-based resin composition for paste processing containing the same.SOLUTION: A vinyl chloride-based resin for paste processing that contains a vinyl chloride-based resin of a large-particle group of a particle diameter of more than 0.5 μm and 5 μm or less, and a vinyl chloride-based resin of a small-particle group of a particle diameter of 0.5 μm or less satisfies (1) an average degree of polymerization of 700-1,000, (2) cumulative weight frequency of the large-particle group of 60-90 wt.% and cumulative weight frequency of the small-particle group of 10-40 wt.% in particle diameter distribution measurement, and (3) a most frequent diameter of the distribution of the large-particle group of 1.55-1.80 μm, and a most frequent diameter of the distribution of the small-particle group of 0.15-0.45 μm.SELECTED DRAWING: None

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 containing the same. A paste PVC composition sol that suppresses the formation of craters and can produce a foam with excellent surface smoothness when foamed, and a paste that suppresses the formation of craters and has excellent leakage prevention properties from the back of the coating blade. The present invention relates to a paste vinyl chloride that provides a vinyl chloride composition sol and a paste vinyl chloride composition containing the same.

Paste PVC is generally processed into a paste PVC composition sol by kneading it with compounding agents such as plasticizers, stabilizers, and blowing agents, and various molded products can be obtained by various processing methods. Among them, construction materials such as wallpaper, flooring, and foam sheets are one of the main uses of paste PVC.

For example, wallpaper is manufactured by coating a base material with a sol, heating and drying it to produce a raw fabric, and then foaming and embossing the resulting raw fabric. This manufacturing method has a problem in that craters are generated on the original fabric during the process of producing the original fabric, making it impossible to obtain wallpaper with satisfactory quality.

For this reason, there is a need for paste PVC and paste PVC composition sol containing the paste that suppresses the generation of craters, and for example, a method for producing a PVC resin film with fewer surface craters using a calendaring method has been proposed (for example, the patent (See Reference 1).

Japanese Patent Application Publication No. 1-244827

However, the method for manufacturing a vinyl chloride resin film with few surface craters proposed in Patent Document 1 uses a calendaring method, which requires complicated manufacturing equipment and working methods, and there is nothing about a manufacturing method using a simpler coating method. This has not been considered, and it has been desired to create a paste vinyl chloride and a paste vinyl chloride composition that can be applied to a coating method, which is a simpler manufacturing method.

Therefore, the present invention solves these problems and suppresses the formation of craters when coating a base material to create a sheet, which was considered difficult with conventional paste PVC, and provides foaming with excellent surface smoothness during foaming. The object of the present invention is to provide a paste PVC and a paste PVC composition containing the same.

In view of the above-mentioned problems, as a result of intensive studies, the present inventors created a sheet by coating a base material with a paste PVC having a specific degree of polymerization and a specific particle size distribution, and a paste PVC composition containing the same. The inventors have discovered that it is possible to suppress the formation of craters during the process and provide a foam with excellent surface smoothness, and have completed the present invention.

That is, the present invention provides a paste vinyl chloride resin containing a vinyl chloride resin having a large particle group with a particle size exceeding 0.5 μm and 5 μm or less and a vinyl chloride resin having a small particle group having a particle size of 0.5 μm or less, The present invention relates to a vinyl chloride resin for paste processing, which is characterized by satisfying the following characteristics (1) to (3).
(1) Average degree of polymerization is 700 to 1000.
(2) The cumulative weight frequency of the large particle group in particle size distribution measurement is 60 to 90 wt%, and the cumulative weight frequency of the small particle group is 10 to 40 wt%.
(3) The mode diameter of the distribution of the large particle group is 1.55 to 1.80 μm, and the mode diameter of the distribution of the small particle group is 0.15 to 0.45 μm.

The present invention will be explained in detail below.

The paste PVC of the present invention contains a large particle group of vinyl chloride resin with a particle size of more than 0.5 μm and 5 μm or less and a vinyl chloride resin of a small particle group of 0.5 μm or less, and (1) average It is a paste PVC with a degree of polymerization of 700 to 1000. In particular, the average degree of polymerization is preferably from 700 to 900, since this results in excellent surface smoothness during foaming. Here, if the average degree of polymerization exceeds 1000, the surface smoothness during foaming will be poor. On the other hand, if it is less than 700, the mechanical properties and foamability will be poor. Here, the average degree of polymerization may be measured by any method as long as it can be measured; for example, a method of calculating the degree of polymerization by a solution viscosity measurement method using a JIS K6721 Ubbelohde viscometer may be mentioned. can.

The paste PVC of the present invention is a paste PVC in which (2) the cumulative weight frequency of large particle groups in particle size distribution measurement is 60 to 90 wt% and the cumulative weight frequency of small particle groups is 10 to 40 wt%; (2') It is preferable that the cumulative weight frequency of the large particle group is 60 to 80 wt% and the cumulative weight frequency of the small particle group is 20 to 40 wt%, since craters are difficult to form. If the cumulative weight frequency of the large particle group is less than 60 wt% or the small particle group exceeds 40 wt%, the viscosity will increase sharply when the paste PVC composition is made into a sol, making handling difficult. It will be inferior in points. On the other hand, if the cumulative weight frequency of the large particle group exceeds 90 wt% or if the cumulative weight frequency of the small particle group is less than 10 wt%, craters are likely to form during coating. In addition, as a method for measuring the particle size distribution in the present invention, any method can be used as long as it is possible to measure the particle size distribution. For example, paste PVC is dispersed in water to form primary particles, and then the Examples include a method in which primary particles are measured using a disk centrifugal particle size distribution analyzer, a method in which the vinyl chloride resin latex after polymerization is measured using a disk centrifugal particle size distribution analyzer, and the like.

In addition, it is difficult to form craters during coating, is excellent in preventing leakage from the back of the coating blade, and has excellent processability (2''), so the large particle group in particle size distribution measurement is Preferably, the cumulative weight frequency is 80 to 90 wt% and the cumulative weight frequency of the small particle group is 10 to 20 wt%.

The paste PVC of the present invention has (3) a paste PVC in which the mode diameter of the distribution of large particle groups is 1.55 to 1.80 μm, and the mode diameter of the distribution of small particle groups is 0.15 to 0.45 μm. It is. If the most frequent diameter of the large particle group exceeds 1.80 μm or the most frequent diameter of the small particle group exceeds 0.45 μm, craters are likely to form during coating. becomes. On the other hand, when the most frequent diameter of the large particle group is less than 1.55 μm, or when the most frequent diameter of the small particle group is less than 0.15 μm, the viscosity of the paste PVC composition sol increases. Due to the steep climb, handling is inferior. Note that the most frequent diameter means the particle diameter at the top of the peak in the distribution.

Since the paste PVC of the present invention is a paste PVC or paste PVC composition that particularly suppresses the generation of craters, it further contains (4) 60 parts by weight of diisononyl phthalate and 3 parts by weight of a liquid stabilizer per 100 parts by weight of paste PVC. 0 parts by weight to form a paste PVC composition sol, which has a complex viscosity of 10,000 Pa·s or more at 98°C when heated at a rate of 10°C/min using a viscoelasticity measuring device. preferable. Examples of liquid stabilizers used in this case include barium-based stabilizers, calcium-based stabilizers, zinc-based stabilizers, and composite stabilizers such as calcium-zinc-based and barium-zinc-based stabilizers. A commercially available device can be used as the device.

In addition, the paste PVC of the present invention has excellent handling properties when preparing the paste PVC itself, a paste PVC composition sol, or a paste PVC composition. cc, is preferable. Incidentally, the bulk specific gravity can be measured, for example, by a powder property comprehensive measuring device (manufactured by Hosokawa Micron Co., Ltd., (trade name) Powder Tester PT-X).

In addition, the paste PVC of the present invention is a paste PVC or a paste PVC composition that further suppresses the generation of craters, is excellent in preventing leakage on the back of the blade, and has excellent workability. 98 when the paste PVC composition sol was prepared by adding 60 parts by weight of diisononyl phthalate and 3.0 parts by weight of a liquid stabilizer to the parts by weight, and the temperature was raised at a heating rate of 10°C/min using a viscoelasticity measuring device. It is preferable that the complex viscosity at °C is 5000 Pa·s or more, and (6) 53 parts by weight of diisononyl phthalate, 100 parts by weight of calcium carbonate, 10 parts by weight of titanium oxide, and a blowing agent per 100 parts by weight of paste vinyl chloride. 3 parts by weight, 10 parts by weight of diluent, and 3 parts by weight of liquid stabilizer to make a paste PVC composition sol, and the first normal stress difference at a shear rate of 4000 sec ^-1 when measured with a viscoelasticity measuring device was 20000 Pa. It is preferable that the following is true.

Examples of the vinyl chloride resin constituting the paste vinyl chloride of the present invention include vinyl chloride homopolymer resins and vinyl chloride copolymer resins, and examples of monomers copolymerizable with vinyl chloride monomers include vinyl acetate and propion. Vinyl esters such as vinyl acid, vinyl myristate, and vinyl benzoate; Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and fumaric acid, or their anhydrides; Methyl acrylate, ethyl acrylate, butyl acrylate, etc. Acrylic acid esters; 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 methyl ether, vinyl Examples include vinyl ethers such as amyl ether and vinyl phenyl ether; monoolefins such as ethylene, propylene, butene, and pentene; vinylidene chloride, styrene, and their derivatives; acrylonitrile, methacrylonitrile, etc., and one or more of these monomers may be used. Copolymerization may also be performed.

The paste PVC of the present invention is a paste containing polymerization initiators, emulsifiers, emulsification aids, buffers, chain transfer agents, higher alcohols, higher fatty acids, higher fatty acid esters, dispersion aids such as chlorinated paraffin, and polymerization degree regulators. It may contain substances that are generally added when producing vinyl chloride. In addition, methods for producing paste PVC include general emulsion polymerization, micro-suspension polymerization, seeded emulsion polymerization, and seeded micro-suspension polymerization. It can be manufactured as a paste PVC by removing water from vinyl resin latex.

Examples of methods for removing moisture from vinyl chloride resin latex include spray drying, fluidized bed drying, ventilation drying, rotary drying, and conduction heating drying. A method by drying is preferred.

Below, a seed microsuspension polymerization method will be shown as an example of a method for obtaining the vinyl chloride resin latex used to form the paste PVC of the present invention.

The seed micro-suspension polymerization method consists of: i) the first step of obtaining a vinyl chloride resin seed latex containing a vinyl chloride resin containing an oil-soluble polymerization initiator by a micro-suspension polymerization method, and ii) the obtained seed latex. Polymerize vinyl chloride monomer, or vinyl chloride monomer and a monomer copolymerizable with it, with gentle stirring in the presence of deionized water, an emulsifier, a buffer, and if necessary an emulsification aid such as a higher alcohol. This is a polymerization method consisting of a second step in which a vinyl chloride resin latex is obtained by enlarging the seed latex.

Here, examples of the monomer copolymerizable with the vinyl chloride monomer include those mentioned above.

Examples of emulsifiers include alkyl sulfate salts such as sodium lauryl sulfate and potassium myristyl sulfate; alkylaryl sulfonates such as sodium dodecylbenzenesulfonate and potassium dodecylbenzenesulfonate; sodium dioctylsulfosuccinate and dihexylsulfosuccinate. Sulfosuccinates such as sodium acid; fatty acid salts such as ammonium laurate and potassium stearate; anionic emulsifiers such as polyoxyethylene alkyl sulfate ester salts and polyoxyethylene alkylaryl sulfate ester salts: sorbitan monooleate, polyoxyethylene sorbitan One or more conventionally known emulsifiers such as sorbitan esters such as monostearate; polyoxyethylene alkyl phenyl ethers; and nonionic emulsifiers such as polyoxyethylene alkyl esters can be used.

Examples of emulsifying aids 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 include halogenated hydrocarbons such as chlorinated paraffin.

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 chain transfer agents include halogen hydrocarbons such as trichlorethylene and carbon tetrachloride, mercaptans such as 2-mercaptoethanol, octyl 3-mercaptopropionate, and dodecyl mercaptan, and aldehydes such as acetone and n-butyraldehyde. etc., and any material may be used as long as the degree of polymerization can be adjusted.

The vinyl chloride resin seed latex containing an oil-soluble polymerization initiator used in the seed microsuspension polymerization method can be prepared by the following microsuspension polymerization method. First, a dispersion aid such as 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 chlorinated paraffin, and a polymerization degree regulator are added as necessary. Premix and homogenize using a homogenizer to prepare 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 temperature inside the polymerization vessel is raised while stirring gently to initiate a polymerization reaction. By polymerizing until a predetermined conversion rate is reached, an oil-soluble polymerization initiator is added. It is possible to prepare a seed latex containing:

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

Then, in step ii), the obtained vinyl chloride resin seed latex containing an oil-soluble polymerization initiator is enlarged in the presence of a vinyl chloride monomer, etc., and polymerized to form a vinyl chloride resin. It can be latex.

The paste vinyl chloride of the present invention can be used for various purposes as a paste vinyl chloride composition or a paste vinyl chloride composition sol by adding a plasticizer, optionally a filler, a blowing agent, etc. In this case, it is preferable that the composition contains 20 to 200 parts by weight of plasticizer per 100 parts by weight of the paste PVC, since this results in a composition having excellent properties. In addition, when making a foam, for 100 parts by weight of paste PVC, 20 to 200 parts by weight of plasticizer, 1 to 300 parts by weight of filler, 0.1 to 30 parts by weight of blowing agent, and 0.1 part by weight of stabilizer. It is preferable to prepare a paste PVC composition sol containing up to 30 parts by weight.

Examples of plasticizers include phthalate esters such as bis(2-ethylhexyl) phthalate (sometimes abbreviated as DOP), diisononyl phthalate, diisodecyl phthalate, and dibutyl phthalate; adipic acid (2-ethylhexyl) , adipate esters such as diisononyl adipate; trimellitic acid esters such as tri(2-ethylhexyl) trimellitate, triisodecyl trimellitate, trin-octyl trimellitate; tri(2-ethylhexyl) phosphate, phosphorus Phosphoric acid esters such as tricresyl acid and tricylenyl phosphate; Benzoic acid esters such as diethylene glycol dibenzoate and dipropylene glycol dibenzoate; Other polyester plasticizers, sebacic acid ester, mazelaic acid ester, maleic acid ester, epoxidized vegetable oil, etc. , those commonly used as plasticizers can be used.

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

Examples of blowing agents include inorganic blowing agents such as sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, ammonium nitrite, amide compounds, and sodium borohydride; isocyanate compounds, azodicarbonamide, azobisisobutyronitrile, and barium. Azo compounds such as azodicarboxylate; hydrazine derivatives such as p,p'-oxybisbenzenesulfonylhydrazide and p-toluenesulfonylhydrazide; nitroso compounds such as semicarbazide compounds, azide compounds, and dinitrosopentamethylenetetramine; triazole compounds, etc. Examples include organic blowing agents. It is also possible to use the above-mentioned foaming agent together with a decomposition accelerator such as zinc white (zinc oxide), if necessary.

Examples of the stabilizer include epoxy stabilizers, barium stabilizers, calcium stabilizers, tin stabilizers, and zinc stabilizers. Furthermore, commercially available composite stabilizers such as calcium-zinc type, barium-zinc type, etc. can also be used.

Furthermore, when preparing a paste PVC composition, additives that are normally added to paste PVC compositions, such as antioxidants, flame retardants, diluents, lubricants, and ultraviolet absorbers, may be added to the extent that does not exceed the purpose of the present invention. , coloring agents such as pigments, surfactants, antistatic agents, etc. may be added, and the amounts thereof may be within the generally used ranges.

The paste PVC of the present invention can be applied as a paste PVC composition to wallpaper, flooring, construction materials such as foam sheets, etc., because the paste PVC composition sol during molding is excellent in handling properties, and is particularly applicable to foamed sheets. Since the formation of craters on the coated sheet due to the paste PVC composition sol containing the agent is suppressed, it is suitable for foamed wallpaper and foamed sheets with excellent surface smoothness and design.

The paste PVC of the present invention suppresses the formation of craters when it is coated on a base material to create a sheet, and when foamed, it is possible to obtain a foam with excellent surface smoothness, and its industrial value is extremely high. It's expensive.

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Below, methods for evaluating the paste PVC and compositions obtained in Examples will be shown.

<Average degree of polymerization>
The average degree of polymerization was calculated by solution viscosity measurement using a JIS K6721 Ubbelohde viscometer.

<Particle size distribution>
Particle size distribution was measured using a disk centrifugal particle size distribution analyzer (manufactured by Nippon Luft Co., Ltd., (trade name) DC24000UHR).

<Bulk specific gravity>
The measurement was performed using a powder property comprehensive measuring device (manufactured by Hosokawa Micron Co., Ltd., (trade name) Powder Tester PT-X). It correlates with the flow characteristics of the powder, and the higher the value, the better the flow characteristics of the powder.

<Complex viscosity>
A paste PVC composition sol consisting of 100 parts by weight of paste PVC, 60 parts by weight of diisononyl phthalate (manufactured by J-Plus Co., Ltd.), and 3.0 parts by weight of a liquid stabilizer (manufactured by ADEKA Co., Ltd., (trade name) SC-320) was prepared. Using a viscoelasticity measuring device (manufactured by Anton Paar, (trade name) MCR302), the complex viscosity was measured at a measurement temperature of 98° C. when the temperature was raised at a heating rate of 10° C./min.

<Crater evaluation method>
100 parts by weight of paste PVC, 53 parts by weight of diisononyl phthalate (manufactured by J-Plus Co., Ltd.), 100 parts by weight of calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd. (trade name) Whiten H), titanium oxide (manufactured by Teika Co., Ltd.) (Product name) JR600A) 10 parts by weight, blowing agent (Otsuka Chemical Co., Ltd., (Product name) AZ Ultra 1050) 3 parts by weight, diluent (TonenGeneral Sekiyu Co., Ltd., (Product name) Exxsol D40) 20 parts by weight and 3 parts by weight of a stabilizer (manufactured by ADEKA Co., Ltd., (trade name) FL-230) were kneaded using a dissolver to obtain a paste PVC composition sol. The resulting paste PVC composition sol was cooled to 3°C in a low-temperature incubator, then coated with a thickness of 0.12 mm on flame-retardant paper that had been previously heated at 195°C for 5 seconds, and heated at 195°C for 10 seconds. By doing this, an original fabric was prepared, and the number of craters on the original fabric at that time was counted.

<Evaluation method of surface smoothness>
A foam was obtained by heating the obtained original fabric at 230° C. for 35 seconds. The surface smoothness of the obtained foam was evaluated by visual observation.

The evaluation criteria for surface smoothness are shown below.

〇: Surface is smooth ×: Surface is rough <Low shear viscosity evaluation method>
A paste PVC composition sol was prepared with the same formulation as described in <Crater evaluation method>, and a B8H type viscometer (manufactured by Tokyo Keiki Co., Ltd.) rotor No. Low shear viscosity was evaluated using No. 3 at a rotation speed of 20 rpm. Here, those with low shear viscosity in the range of 700 to 2,500 mPa·s were judged to have excellent handling properties.

<Evaluation method of first normal stress>
100 parts by weight of paste PVC, 53 parts by weight of diisononyl phthalate (manufactured by J-Plus Co., Ltd.), 100 parts by weight of calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd. (trade name) Whiten H), titanium oxide (manufactured by Teika Co., Ltd.) Product name) JR600A) 10 parts by weight, blowing agent (manufactured by Otsuka Chemical Co., Ltd., (product name) AZ Ultra 1050) 3 parts by weight, diluent (manufactured by TonenGeneral Sekiyu Co., Ltd., (product name) Exxsol D40) 10 parts by weight and 3 parts by weight of a stabilizer (manufactured by ADEKA Co., Ltd., (trade name) FL-230) were kneaded using a dissolver to obtain a paste PVC composition sol. After the obtained paste PVC composition sol was allowed to stand at 23° C. for 24 hours, the first normal stress difference was measured using a viscoelasticity measuring device (manufactured by Anton Paar, (trade name) MCR302).

Synthesis example 1
360 kg of deionized water, 300 kg of vinyl chloride monomer, 5.7 kg of lauroyl peroxide, and 30 kg of a 15% by weight sodium dodecylbenzenesulfonate aqueous solution were placed in a 1 m ³ stainless steel autoclave, and the polymerization solution was circulated for 3 hours using a homogenizer for homogenization treatment. After this, the temperature of the reaction system was raised to 45°C to start polymerization. After the pressure of the polymerization system was reduced, the unreacted vinyl chloride monomer was recovered to obtain an oil-soluble polymerization initiator-containing vinyl chloride resin seed latex (a) with a solid content of 35% by weight and an average particle size of 0.55 μm. .

Synthesis example 2
360 kg of deionized water, 300 kg of vinyl chloride monomer, 10 kg of lauroyl peroxide, 30 kg of 15% by weight sodium dodecylbenzenesulfonate aqueous solution, and 1.5 kg of dodecyl mercaptan were placed in a 1 m ³ stainless steel autoclave, and the polymerization solution was circulated for 3 hours using a homogenizer. After homogenization, the temperature of the reaction system was raised to 45° C. to initiate polymerization. After the pressure of the polymerization system was reduced, the unreacted vinyl chloride monomer was recovered to obtain an oil-soluble polymerization initiator-containing vinyl chloride resin seed latex (b) with a solid content of 35% by weight and an average particle size of 0.60 μm. .

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

Example 1
In a 2.5 L stainless steel autoclave, 610 g of deionized water, 730 g of vinyl chloride monomer, 15.3 g of 5% by weight sodium dodecylbenzenesulfonate, 10 g of sodium hydrogen phosphate/potassium hydroxide mixture, 3-mercaptopropionic acid-2- 0.5 g of ethylhexyl, 4.4 parts by weight of seed latex (a) with an average particle diameter of 0.55 μm obtained in Synthesis Example 1 per 100 parts by weight of vinyl chloride monomer, and the average particle diameter obtained in Synthesis Example 3. 10.0 parts by weight of 0.15 μm seed latex (c) was added to 100 parts by weight of vinyl chloride monomer, and the temperature of the reaction mixture was raised to 66° C. to initiate polymerization. From the start of the polymerization until the end of the polymerization, 0.7 parts by weight of 5% by weight sodium dodecylbenzenesulfonate was continuously added to the vinyl chloride monomer. When the polymerization pressure decreased from the saturated vapor pressure of the vinyl chloride monomer at 66° C. to 0.402 MPa, the polymerization was stopped, and the unreacted vinyl chloride monomer was recovered to obtain a vinyl chloride resin latex. The vinyl chloride resin in the obtained vinyl chloride resin latex has a cumulative weight frequency of 70.3 wt% of large particles with a particle size of more than 0.5 μm and 5 μm or less, and a mode diameter of 1.73 μm, and a diameter of 0.5 μm. The cumulative weight frequency of the following small particle group was 29.7 wt%, and the mode diameter was 0.22 μm.

The obtained vinyl chloride resin latex was spray-dried using a rotating disc type spray dryer at a hot air temperature of 110°C and an outlet temperature of 50°C to obtain granular paste PVC. The obtained paste PVC had an average degree of polymerization of 790 and a bulk specific gravity of 0.49 g/cc. In addition, a paste PVC composition sol and foam were prepared using the obtained paste PVC, and the complex viscosity, number of craters, surface smoothness, and low shear viscosity were evaluated. The complex viscosity was 16,000 Pa·s, no craters were generated, the surface of the foam was smooth, and the low shear viscosity was a good value of 1,050 mPa·s. The evaluation results are shown in Table 1.

Example 2
In a 2.5 L stainless steel autoclave, 610 g of deionized water, 730 g of vinyl chloride monomer, 15.3 g of 5% by weight sodium dodecylbenzenesulfonate, 10 g of sodium hydrogen phosphate/potassium hydroxide mixture, the average obtained from Synthesis Example 1 4.4 parts by weight of seed latex (a) with a particle size of 0.55 μm per 100 parts by weight of vinyl chloride monomer, and 4.4 parts by weight of seed latex (c) with an average particle size of 0.15 μm obtained in Synthesis Example 3 with 100 parts by weight of vinyl chloride monomer. 10.0 parts by weight was added, and the temperature of this reaction mixture was raised to 63.5°C to initiate polymerization. From the start of the polymerization until the end of the polymerization, 0.7 parts by weight of 5% by weight sodium dodecylbenzenesulfonate was continuously added to the vinyl chloride monomer. When the polymerization pressure decreased from the saturated vapor pressure of the vinyl chloride monomer at 63.5° C. to 0.373 MPa, the polymerization was stopped, and the unreacted vinyl chloride monomer was recovered to obtain a vinyl chloride resin latex. The vinyl chloride resin in the obtained vinyl chloride resin latex has a cumulative weight frequency of 72.1 wt% of large particles with particle diameters exceeding 0.5 μm and 5 μm or less, and a mode diameter of 1.70 μm, and a particle size of 0.5 μm. The following small particle groups had a cumulative weight frequency of 27.9 wt% and a mode diameter of 0.20 μm.

The obtained vinyl chloride resin latex was spray-dried using a rotating disc type spray dryer at a hot air temperature of 110°C and an outlet temperature of 50°C to obtain granular paste PVC. The obtained paste PVC had an average degree of polymerization of 850 and a bulk specific gravity of 0.49 g/cc. In addition, a paste PVC composition sol and foam were prepared using the obtained paste PVC, and the complex viscosity, number of craters, surface smoothness, and low shear viscosity were evaluated. The complex viscosity was 18,500 Pa·s, no craters were generated, the surface of the foam was smooth, and the low shear viscosity was a good value of 1,260 mPa·s. The evaluation results are shown in Table 1.

Example 3
Except that the amount of seed latex (a) added was 5.3 parts by weight per 100 parts by weight of vinyl chloride monomer, and the amount of seed latex (c) added was 12.0 parts by weight per 100 parts by weight of vinyl chloride monomer. By the same method as in Example 1, vinyl chloride resin latex and paste vinyl chloride were obtained.

The vinyl chloride resin in the obtained vinyl chloride resin latex has a cumulative weight frequency of 62.4 wt% of large particles with a particle diameter of more than 0.5 μm and 5 μm or less, and a mode diameter of 1.60 μm, and a diameter of 0.5 μm. The cumulative weight frequency of the following small particle groups was 37.6 wt%, and the mode diameter was 0.21 μm. The obtained paste PVC had an average degree of polymerization of 720 and a bulk specific gravity of 0.53 g/cc. In addition, a paste PVC composition sol and foam were prepared using the obtained paste PVC, and the complex viscosity, number of craters, surface smoothness, and low shear viscosity were evaluated. The complex viscosity was 25,200 Pa·s, no craters were generated, the surface of the foam was smooth, and the low shear viscosity was a good value of 1,800 mPa·s. The evaluation results are shown in Table 1.

Example 4
Except that the amount of seed latex (a) added was 5.0 parts by weight per 100 parts by weight of vinyl chloride monomer, and the amount of seed latex (c) added was 10.0 parts by weight per 100 parts by weight of vinyl chloride monomer. By the same method as in Example 1, vinyl chloride resin latex and paste vinyl chloride were obtained.

The vinyl chloride resin in the obtained vinyl chloride resin latex has a cumulative weight frequency of 65.2 wt% of large particles with a particle size of more than 0.5 μm and 5 μm or less, and a mode diameter of 1.64 μm, and a diameter of 0.5 μm. The cumulative weight frequency of the following small particle groups was 34.8 wt%, and the mode diameter was 0.21 μm. The obtained paste PVC had an average degree of polymerization of 740 and a bulk specific gravity of 0.52 g/cc. In addition, a paste PVC composition sol and foam were prepared using the obtained paste PVC, and the complex viscosity, number of craters, surface smoothness, and low shear viscosity were evaluated. The complex viscosity was 24,000 Pa·s, no craters were generated, the surface of the foam was smooth, and the low shear viscosity was a good value of 1,170 mPa·s. The evaluation results are shown in Table 1.

Comparative example 1
In a 2.5 L stainless steel autoclave, 610 g of deionized water, 730 g of vinyl chloride monomer, 15.3 g of 5% by weight sodium dodecylbenzenesulfonate, 10 g of sodium hydrogen phosphate/potassium hydroxide mixture, the average obtained from Synthesis Example 1 4.4 parts by weight of seed latex (a) with a particle size of 0.55 μm per 100 parts by weight of vinyl chloride monomer, and 4.4 parts by weight of seed latex (c) with an average particle size of 0.15 μm obtained in Synthesis Example 3 with 100 parts by weight of vinyl chloride monomer. 10.0 parts by weight and 0.7 g of 0.1% by weight copper sulfate were added, and the temperature of the reaction mixture was raised to 55° C. to initiate polymerization. During the polymerization, a 0.05% by weight aqueous ascorbic acid solution was continuously added to maintain the polymerization temperature, and the polymerization was stopped when the polymerization pressure decreased from the saturated vapor pressure of vinyl chloride monomer at 55°C to 0.471 MPa. It stopped. Note that from the start of the polymerization until the end of the polymerization, 0.7 parts by weight of 5% by weight sodium dodecylbenzenesulfonate was continuously added to the vinyl chloride monomer. After the polymerization was completed, unreacted vinyl chloride monomer was collected to obtain vinyl chloride resin latex. The vinyl chloride resin in the obtained vinyl chloride resin latex has a cumulative weight frequency of 69.3 wt% of large particles with a particle diameter of more than 0.5 μm and 5 μm or less, and a mode diameter of 1.73 μm, which is 0.5 μm. The cumulative weight frequency of the following small particle groups was 30.7 wt%, and the mode diameter was 0.22 μm.

The obtained vinyl chloride resin latex was spray-dried using a rotating disc type spray dryer at a hot air temperature of 110°C and an outlet temperature of 50°C to obtain granular paste PVC. The obtained paste PVC had an average degree of polymerization of 1200 and a bulk specific gravity of 0.49 g/cc. In addition, a paste PVC composition sol and foam were prepared using the obtained paste PVC, and the complex viscosity, number of craters, surface smoothness, and low shear viscosity were evaluated. The complex viscosity was 14,000 Pa·s, no craters were generated, and the low shear viscosity was a good value of 1,140 mPa·s, but the surface of the foam was rough and its smoothness was poor. The evaluation results are shown in Table 2.

Comparative example 2
A vinyl chloride resin latex and paste vinyl chloride were obtained in the same manner as in Example 1, except that the amount of seed latex (c) added was 15.0 parts by weight per 100 parts by weight of vinyl chloride monomer.

The vinyl chloride resin in the obtained vinyl chloride resin latex has a cumulative weight frequency of 57.5 wt% of large particles with a particle diameter of more than 0.5 μm and 5 μm or less, and a mode diameter of 1.72 μm, which is 0.5 μm. The cumulative weight frequency of the following small particle groups was 42.5 wt%, and the mode diameter was 0.21 μm. The obtained paste PVC had an average degree of polymerization of 720 and a bulk specific gravity of 0.54 g/cc. In addition, a paste PVC composition sol and foam were prepared using the obtained paste PVC, and the complex viscosity, number of craters, surface smoothness, and low shear viscosity were evaluated. The complex viscosity was 25,900 Pa·s, no craters were generated, and the surface of the foam was smooth; however, the low shear viscosity was 3,500 mPa·s, indicating a high viscosity and poor handling properties. The evaluation results are shown in Table 2.

Comparative example 3
A vinyl chloride resin latex and paste vinyl chloride were obtained in the same manner as in Example 1, except that the amount of seed latex (c) added was 2.5 parts by weight per 100 parts by weight of vinyl chloride monomer.

The vinyl chloride resin in the obtained vinyl chloride resin latex has a cumulative weight frequency of 90.9 wt% of large particles with particle diameters exceeding 0.5 μm and 5 μm or less, and a mode diameter of 1.70 μm, and a particle size of 0.5 μm. The following small particle groups had a cumulative weight frequency of 9.1 wt% and a mode diameter of 0.22 μm. The obtained paste PVC had an average degree of polymerization of 700 and a bulk specific gravity of 0.48 g/cc. In addition, a paste PVC composition sol and foam were prepared using the obtained paste PVC, and the complex viscosity, number of craters, surface smoothness, and low shear viscosity were evaluated. The complex viscosity was 8,500 Pa·s, and the number of craters was 100/m ² or more, indicating that craters were likely to occur. The surface of the foam was rough due to craters and had poor smoothness. The evaluation results are shown in Table 2.

Comparative example 4
Instead of adding 4.4 parts by weight of seed latex (a) to 100 parts by weight of vinyl chloride monomer, 2.9 parts by weight of seed latex (b) was added to 100 parts by weight of vinyl chloride monomer. ) was added in an amount of 7.5 parts by weight per 100 parts by weight of vinyl chloride monomer, to obtain vinyl chloride resin latex and paste PVC in the same manner as in Example 1.

The vinyl chloride resin in the obtained vinyl chloride resin latex has a cumulative weight frequency of 77.0 wt% of large particles with a particle size of more than 0.5 μm and 5 μm or less, and a mode diameter of 1.84 μm, and a diameter of 0.5 μm. The cumulative weight frequency of the following small particle groups was 23.0 wt%, and the mode diameter was 0.21 μm. The obtained paste PVC had an average degree of polymerization of 720 and a bulk specific gravity of 0.5 g/cc. In addition, a paste PVC composition sol and foam were prepared using the obtained paste PVC, and the complex viscosity, number of craters, surface smoothness, and low shear viscosity were evaluated. The complex viscosity was 8800 Pa·s, the number of craters was 100/m ² or more, and craters were likely to occur. The surface of the foam was rough due to craters and had poor smoothness. The evaluation results are shown in Table 2.

Comparative example 5
Except that the amount of seed latex (a) added was 6.1 parts by weight per 100 parts by weight of vinyl chloride monomer, and the amount of seed latex (c) added was 15.0 parts by weight per 100 parts by weight of vinyl chloride monomer. By the same method as in Example 1, vinyl chloride resin latex and paste vinyl chloride were obtained.

The vinyl chloride resin in the obtained vinyl chloride resin latex has a cumulative weight frequency of 57.2 wt% of large particles with a particle size of more than 0.5 μm and 5 μm or less, a mode diameter of 1.54 μm, and a diameter of 0.5 μm. The cumulative weight frequency of the following small particle groups was 42.8 wt%, and the mode diameter was 0.21 μm. The obtained paste PVC had an average degree of polymerization of 720 and a bulk specific gravity of 0.53 g/cc. In addition, a paste PVC composition sol and foam were prepared using the obtained paste PVC, and the complex viscosity, number of craters, surface smoothness, and low shear viscosity were evaluated. The low shear viscosity was 3200 mPa·s, and the viscosity was high and the handling property was poor. The evaluation results are shown in Table 2.

Example 5
A vinyl chloride resin latex and paste vinyl chloride were obtained in the same manner as in Example 2, except that the amount of seed latex (c) added was 7.5 parts by weight per 100 parts by weight of vinyl chloride monomer.

The vinyl chloride resin in the obtained vinyl chloride resin latex has a cumulative weight frequency of 88.2 wt% of large particles with a particle diameter of more than 0.5 μm and 5 μm or less, and a mode diameter of 1.70 μm, and a particle size of 0.5 μm. The cumulative weight frequency of the following small particle groups was 11.8 wt%, and the mode diameter was 0.22 μm. The obtained paste PVC had an average degree of polymerization of 850 and a bulk specific gravity of 0.50 g/cc. In addition, a paste PVC composition sol and foam were prepared using the obtained paste PVC, and complex viscosity, number of craters, surface smoothness, low shear viscosity, and first normal stress difference were evaluated. The complex viscosity was 5,600 Pa·s, no craters were generated, the surface of the foam was smooth, the low shear viscosity was 810 mPa·s, and the first normal stress difference was 15,000 Pa, which were good values. Furthermore, no leakage of the paste PVC composition sol from the back of the blade was observed during coating. The evaluation results are shown in Table 3.

Example 6
Except that the amount of seed latex (a) added was 3.9 parts by weight per 100 parts by weight of vinyl chloride monomer, and the amount of seed latex (c) added was 7.5 parts by weight per 100 parts by weight of vinyl chloride monomer. By the same method as in Example 1, vinyl chloride resin latex and paste vinyl chloride were obtained.

The vinyl chloride resin in the obtained vinyl chloride resin latex has a cumulative weight frequency of 85.4 wt% of large particles with a particle diameter of more than 0.5 μm and 5 μm or less, and a mode diameter of 1.73 μm, and a diameter of 0.5 μm. The cumulative weight frequency of the following small particle groups was 14.6 wt%, and the mode diameter was 0.22 μm. The obtained paste PVC had an average degree of polymerization of 719 and a bulk specific gravity of 0.49 g/cc. In addition, a paste PVC composition sol and foam were prepared using the obtained paste PVC, and complex viscosity, number of craters, surface smoothness, low shear viscosity, and first normal stress difference were evaluated. The complex viscosity was 10,600 Pa·s, no craters were generated, the surface of the foam was smooth, the low shear viscosity was 950 mPa·s, and the first normal stress difference was 14,300 Pa, which were good values. Furthermore, no leakage of the paste PVC composition sol from the back of the blade was observed during coating. The evaluation results are shown in Table 3.

Example 7
Except that the amount of seed latex (a) added was 5.0 parts by weight per 100 parts by weight of vinyl chloride monomer, and the amount of seed latex (c) added was 9.0 parts by weight per 100 parts by weight of vinyl chloride monomer. By the same method as in Example 1, vinyl chloride resin latex and paste vinyl chloride were obtained.

The vinyl chloride resin in the obtained vinyl chloride resin latex has a cumulative weight frequency of 81.6 wt% of large particles with a particle size of more than 0.5 μm and 5 μm or less, and a mode diameter of 1.65 μm, which is 0.5 μm. The cumulative weight frequency of the following small particle groups was 18.4 wt%, and the mode diameter was 0.20 μm. The obtained paste PVC had an average degree of polymerization of 759 and a bulk specific gravity of 0.51 g/cc. In addition, a paste PVC composition sol and foam were prepared using the obtained paste PVC, and complex viscosity, number of craters, surface smoothness, low shear viscosity, and first normal stress difference were evaluated. The complex viscosity was 13,000 Pa·s, no craters were generated, the surface of the foam was smooth, the low shear viscosity was 1,140 mPa·s, and the first normal stress difference was 12,300 Pa, which were good values. Furthermore, no leakage of the paste PVC composition sol from the back of the blade was observed during coating. The evaluation results are shown in Table 3.

Example 8
Except that the amount of seed latex (a) added was 5.3 parts by weight per 100 parts by weight of vinyl chloride monomer, and the amount of seed latex (c) added was 9.0 parts by weight per 100 parts by weight of vinyl chloride monomer. By the same method as in Example 1, vinyl chloride resin latex and paste vinyl chloride were obtained.

The vinyl chloride resin in the obtained vinyl chloride resin latex has a cumulative weight frequency of 83.7 wt% of large particles with a particle size of more than 0.5 μm and 5 μm or less, and a mode diameter of 1.58 μm, and a particle size of 0.5 μm. The cumulative weight frequency of the following small particle groups was 16.3 wt%, and the mode diameter was 0.21 μm. The obtained paste PVC had an average degree of polymerization of 730 and a bulk specific gravity of 0.50 g/cc. In addition, a paste PVC composition sol and foam were prepared using the obtained paste PVC, and complex viscosity, number of craters, surface smoothness, low shear viscosity, and first normal stress difference were evaluated. The complex viscosity was 12,800 Pa·s, no craters were generated, the surface of the foam was smooth, the low shear viscosity was 1,100 mPa·s, and the first normal stress difference was 11,200 Pa, which were good values. Furthermore, no leakage of the paste PVC composition sol from the back of the blade was observed during coating. The evaluation results are shown in Table 3.

Comparative example 6
A paste PVC composition sol was prepared using the paste PVC obtained in Comparative Example 1, and the first normal stress difference was evaluated. The first normal stress difference was 22,100 Pa, and leakage of the paste PVC composition sol from the back of the blade was observed during coating. The evaluation results are shown in Table 4.

Comparative example 7
A paste PVC composition sol was prepared using the paste PVC obtained in Comparative Example 2, and the first normal stress difference was evaluated. The first normal stress difference was 25,400 Pa, and leakage of the paste PVC composition sol from the back of the blade was observed during coating. The evaluation results are shown in Table 4.

Comparative example 8
A paste PVC composition sol was prepared using the paste PVC obtained in Comparative Example 4, and the first normal stress difference was evaluated. The first normal stress difference was 20,200 Pa, and leakage of the paste PVC composition sol from the back of the blade was observed during coating. The evaluation results are shown in Table 4.

The paste PVC of the present invention does not form craters when it is coated on a base material to create a sheet, and when foamed, it is possible to obtain a foam with excellent surface smoothness, making it particularly suitable as a building material such as foamed wallpaper. It has such characteristics that its industrial utility value is high.

Claims (12)

A paste vinyl chloride resin containing a vinyl chloride resin with a large particle group with a particle size of more than 0.5 μm and 5 μm or less, and a vinyl chloride resin with a small particle group with a particle size of 0.5 μm or less, comprising the following (1) to ( A vinyl chloride resin for paste processing, characterized by satisfying the characteristics of 3).
(1) Average degree of polymerization is 700 to 1000.
(2) The cumulative weight frequency of the large particle group in particle size distribution measurement is 60 to 90 wt%, and the cumulative weight frequency of the small particle group is 10 to 40 wt%.
(3) The mode diameter of the distribution of the large particle group is 1.55 to 1.80 μm, and the mode diameter of the distribution of the small particle group is 0.15 to 0.45 μm. The above (2) is characterized in that the cumulative weight frequency of the large particle group in (2') particle size distribution measurement is 60 to 80 wt% and the cumulative weight frequency of the small particle group is 20 to 40 wt%. The vinyl chloride resin for paste processing according to claim 1. Furthermore, (4) 60 parts by weight of diisononyl phthalate and 3.0 parts by weight of a liquid stabilizer are blended with 100 parts by weight of the vinyl chloride resin for paste processing to form a sol of the vinyl chloride resin composition for paste processing, and a viscous The paste according to claim 1 or 2, characterized in that the paste also satisfies a complex viscosity of 10,000 Pa·s or more at 98°C when heated at a temperature increase rate of 10°C/min using an elasticity measuring device. Vinyl chloride resin for processing. The vinyl chloride resin for paste processing according to claim 1 or 2, further satisfying (5) a bulk specific gravity of 0.40 to 0.60 g/cc. The above (2) is characterized in that (2'') the cumulative weight frequency of the large particle group in the particle size distribution measurement is 80 to 90 wt% and the cumulative weight frequency of the small particle group is 10 to 20 wt%. The vinyl chloride resin for paste processing according to claim 1. Furthermore, (4') 60 parts by weight of diisononyl phthalate and 3.0 parts by weight of a liquid stabilizer are blended with 100 parts by weight of the vinyl chloride resin for paste processing to prepare a vinyl chloride resin composition sol for paste processing, The paste processing according to claim 5, characterized in that the paste processing also satisfies that the complex viscosity at 98° C. is 5000 Pa·s or more when the temperature is raised at a heating rate of 10° C./min using a viscoelasticity measuring device. Vinyl chloride resin for use. Furthermore, (6) 53 parts by weight of diisononyl phthalate, 100 parts by weight of calcium carbonate, 10 parts by weight of titanium oxide, 3 parts by weight of a blowing agent, 10 parts by weight of a diluent, per 100 parts by weight of the vinyl chloride resin for paste processing. A vinyl chloride resin composition sol for paste processing is prepared by blending 3 parts by weight of a liquid stabilizer, and the first normal stress difference at a shear rate of 4000 sec ^-1 when measured with a viscoelasticity measuring device is 20000 Pa or less. The vinyl chloride resin for paste processing according to claim 5 or 6, which satisfies the following. A vinyl chloride resin composition for paste processing, comprising 20 to 200 parts by weight of a plasticizer based on 100 parts by weight of the vinyl chloride resin for paste processing according to claim 1 or 2. Contains 20 to 200 parts by weight of plasticizer, 1 to 300 parts by weight of filler, 0.1 to 30 parts by weight of blowing agent, and 0.1 to 30 parts by weight of stabilizer for 100 parts by weight of vinyl chloride resin for paste processing. The vinyl chloride resin composition for paste processing according to claim 8, which is a vinyl chloride resin composition sol for paste processing. A vinyl chloride resin composition for paste processing, which contains 20 to 200 parts by weight of a plasticizer based on 100 parts by weight of the vinyl chloride resin for paste processing according to claim 5. The vinyl chloride resin composition for paste processing according to claim 8, which is used for foam wallpaper. The vinyl chloride resin composition for paste processing according to claim 10, which is used for foam wallpaper.