KR101190661B1 - Vinyl chloride plastisol composition and foam product - Google Patents

Abstract

It does not use organic solvents as a diluent, or at least the amount used is low viscosity, high-speed molding, troubles such as thickness imbalance during the molding of the coat or plastisol leak to the back of knife It is possible to obtain a vinyl chloride plastisol composition for paste, which can be avoided.

(A) Vinyl chloride type composed of vinyl chloride polymer, plasticizer and inorganic filler

In the plastisol composition, (1) the inorganic filler contains calcium carbonate having a particle size distribution in which the cumulative frequency (volume basis) of particles larger than 150 μm is 5% or less, and (2) the mode diameter is 30 μm or more and 100 μm or less. Vinyl chloride-based plastisol composition,

(B) The vinyl chloride plastisol composition as described in (A) which contains 30-100 weight part of plasticizers, and 30-200 weight part of calcium carbonates of (A) description with respect to 100 weight part of vinyl chloride-type polymers.

Description

Vinyl chloride plastisol composition and foamed product

The present invention relates to a vinyl chloride plastisol composition for paste and a foamed molded article.

The vinyl chloride-based plastisol composition for pastes is excellent in workability and excellent in appearance, and at the same time, the molded body has excellent properties such as flame retardancy and excellent workability. It is widely used for the manufacture of leather, canvas, vehicle interiors, steel sheet coats, face coats, seal coats, work gloves, toys, and general merchandise.

In particular, the foamed molded article made of a vinyl chloride-based plastisol composition for paste as a housing interior material has been widely used for its flame retardancy, workability, and designability in fields such as wall materials, floor materials, and general merchandise.

Vinyl chloride-based foams are generally produced by applying a vinyl chloride-based plastisol composition for paste onto a substrate such as paper, followed by heat drying and a heating foaming step.

The vinyl chloride plastisol composition for paste is mainly composed of inorganic fillers such as vinyl chloride paste resin, plasticizer, and calcium carbonate, and furthermore, in forming and coating on a substrate, a hydrocarbon solvent called a diluent as a viscosity modifier. Bulk addition is common.

Recently, consumers' interest in sick house syndrome is high. Among them, a hydrocarbon solvent used as a viscosity modifier is mentioned as one of the causative agents of sick house syndrome. There is a demand for a foam product in which the amount of the hydrocarbon solvent is reduced in an amount that can not be ignored.

As a method of obtaining a low viscosity pastesol without using a diluent, for example, the specific surface area is 1.0-3.5 m ² / g, (A) has a particle size distribution of less than 2 μm, and the peak diameter of the distribution is 0.2 15 to 55% by weight of at least one particle in ˜1.5 μm, (B) less than 15% by weight of particles of 2 μm or more and less than 4 μm, and (C) 4 μm or more, with a peak diameter of 7 to 15 μm. There is a vinyl chloride-based resin (Patent Document 1) characterized by consisting of at least one particle 40 to 80% by weight.

However, the low viscosity method described above aims to obtain a low viscosity paste sol over a wide shear rate range from the low shear region to the high shear region, even when the amount of plasticizer is reduced. It may be said that such low viscosity is aimed at within the range of. However, when a thin film is coated at high speed, extremely high low viscosity is required, and thus, the above is not sufficient.

In addition, in the vinyl chloride plastisol composition, the viscosity behavior is improved. For example, in the vinyl chloride plastisol composition mainly containing particulate vinyl chloride resin, particulate inorganic filler, and plasticizer, In the case where the total weight of the vinyl chloride resin and the inorganic filler is 100, the particle size distribution of the particles of the precursor made of the vinyl chloride resin and the inorganic filler is 20 to 35 wt% of fine particles of less than 2 μm, and more than 2 μm and less than 10 μm. Ultrafine filler having a particle size of less than 0.2 μm when the weight of the inorganic filler is 100 and the particle size of the inorganic filler is set to 100 to 25 to 40 wt% of the neutral particles and 30 to 50 wt% of the coarse particles of 10 μm or more. Vinyl chloride, characterized in that it is composed of 25 to 35% by weight, 0.2 to 15% by weight of the neutral filler less than 15μm, 25 to 40% by weight of the granulated filler of 15μm or more Plastisol composition (Patent Document 2).

However, the above-mentioned vinyl chloride plastisol composition is intended for air spraying aptitude for anti-chipping paint, floor undercoat, spray sealer, etc. of automobiles, and in view of using an organic solvent, It is not different from the conventional one.

[Patent Document 1] Japanese Patent Laid-Open No. 10-231322

[Patent Document 2] Japanese Patent Application Laid-Open No. 2-208347

In particular, when foaming a vinyl chloride-based plastisol composition for a paste to obtain a foamed molded product, the viscosity of the plastisol is increased when the amount of the diluent is not used or the amount is small even when used. Uneven thickness during high-speed molding, problems such as leakage after the blade of plastisol, irregularities on the surface of the foam, and problems such as cell puncturing may occur when embossing. There was a problem that significantly damaged the appearance of the product.

Therefore, the organic solvent is not used as a diluent, or the amount used is at least low viscosity, high-speed molding, uneven thickness during coat molding, or plastisol leak to the back of Development of a vinyl chloride-based plastisol composition for pastes, which can avoid troubles such as a knife, and a technique for obtaining a vinyl chloride-based foamed molded article having excellent surface smoothness, fewer troubles such as cell puncture during embossing, and a good appearance. I am waiting for this.

An object of the present invention is to use an organic solvent as a diluent, or to use at least a low viscosity, high-speed molding, uneven thickness during coat molding, and troubles such as leakage after the blade of plastisol. The present invention provides a vinyl chloride-based plastisol composition for paste, and excellent surface smoothness, few troubles such as cell puncture during embossing, and a foamed molded article having good appearance.

Means for solving the problem

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, the present inventors studied closely, and when using the calcium carbonate which has distribution of specific particle diameter as an inorganic filler for vinyl chloride type plastic sol, the vinyl chloride type plastisol obtained is a diluent. In order to complete the present invention, the present inventors found that an organic solvent is not used or the amount used is at least low in viscosity, high-speed molding is possible, and foamed molded articles having excellent characteristics can be obtained. Reached.

This invention consists of the following inventions.

1.A vinyl chloride-based plastisol composition composed of a vinyl chloride polymer, a plasticizer, and an inorganic filler, wherein the inorganic filler has (1) cumulative frequency (volume basis) of particles larger than 150 µm of 5% or less, and (2 A vinyl chloride plastisol composition comprising a calcium carbonate having a particle size distribution having a mode diameter of 30 μm or more and 100 μm or less.

2. The vinyl chloride plastisol composition according to the above 1, which contains 30 to 100 parts by weight of a plasticizer and 30 to 200 parts by weight of calcium carbonate based on phase 1 with respect to 100 parts by weight of the vinyl chloride polymer.

3. The vinyl chloride plastisol composition according to the above 1 or 2, wherein the vinyl chloride plastisol composition contains a blowing agent.

4.The foamed molded article formed by foam-molding the plastisol composition of said 3 description.

5. The molded foam according to the above 4, wherein the molded foam is embossed.

6. The foamed molded article according to 4 or 5 above, wherein the foamed molded article is a wallpaper or a cushion floor.

The biggest feature of this invention is the calcium carbonate having a specific particle size distribution as an inorganic filler, that is, (1) the cumulative frequency (volume basis) of particles larger than 150 μm is 5% or less, and (2) the mode diameter is 30 μm or more and 100 μm. It is for obtaining the vinyl chloride type resin composition for paste which solved the said subject by using calcium carbonate which has the following particle size distribution.

Background Art Conventionally, calcium carbonate having a particle size of 1 to 20 µm is used as an inorganic filler in the production of wallpaper and cushion floor.

Therefore, the calcium carbonate having a specific particle size distribution of the present invention has a large particle diameter as compared to calcium carbonate used in the production of conventional foams, but is characterized by a remarkably large particle size, that is, a small amount of granulation. have.

As described above, the calcium carbonate used as the inorganic filler in the present invention has a large particle size in a specific range, does not contain granules, and the viscosity of the plastisol is lower than that of the conventional plastisol, and is thick even at high speed molding. There is no irregularity, and there are few troubles such as the trailing edge leakage of the plastisol when the base material is applied to the substrate by a comma coater or the like, and the molded article exhibits surface smoothness and becomes slightly roughened in the foam cell, so that the embossing process is performed. It is estimated that trouble such as cell puncture of the city can be avoided and a product excellent in appearance can be obtained.

Hereinafter, the present invention will be described in detail.

The present invention relates to a vinyl chloride-based plastisol composition composed of a vinyl chloride polymer, a plasticizer, and an inorganic filler, wherein, as an inorganic filler, (1) the cumulative frequency (volume basis) of particles larger than 150 μm is 5% or less, And (2) a calcium carbonate having a particle size distribution having a mode diameter of 30 μm or more and 100 μm or less, but the present composition may further contain a blowing agent, an additive, or the like as a component.

Here, the component of the vinyl chloride plastisol composition of this invention, its preparation method, etc. are demonstrated below.

(1) Components of Vinyl Chloride Plastisol Composition

1) Inorganic Filler

In the present invention, the inorganic filler has a particle size distribution measured by the light scattering method, (1) a cumulative frequency (volume basis) of particles larger than 150 μm is 5% or less, and (2) calcium carbonate having a mode diameter of 30 μm or more and 100 μm or less. It is essential to use.

Although the particle size distribution of calcium carbonate can be measured by the light scattering method, it is preferable to use the laser diffraction scattering type particle size distribution measuring device.

By the said measurement, the particle size and the frequency in the particle diameter are measured, and the particle size distribution comprised by a particle size and a frequency is measured.

The cumulative frequency here is a value obtained by integrating the frequency of the particle size range, and the mode diameter is the particle size showing the highest frequency in the particle size distribution curve.

In the present invention, the particle size distribution needs to satisfy the above requirements (1) and (2) at the same time, and if any of the requirements is omitted, the object of the present invention cannot be achieved.

That is, the requirement (1) is that the cumulative frequency of the particles larger than 150 µm of calcium carbonate is 5% or less, preferably 3% or less, and more preferably 1% or less.

In this case, if the cumulative frequency exceeds 5%, troubles such as leakage after the blade of the plastisol are likely to occur at the time of coating molding, particularly at high speed, and the foam cells of the foam become rough or surface smoothness deteriorates. Not desirable

Moreover, although the mode diameter of calcium carbonate used by this invention is 30 micrometers or more and 100 micrometers or less, Preferably it is 35 micrometers or more and 90 micrometers or less, More preferably, they are 40 micrometers or more and 80 micrometers or less.

In this case, when it is smaller than 30 µm, the viscosity of the plastisol rises remarkably, troubles such as thickness imbalance and leakage behind the plastisol blade occur, and at the same time, cell puncture easily occurs during embossing. On the other hand, if it is larger than 100 µm, leakage is likely to occur after the blade, and at the same time, the foam cell becomes rough or surface smoothness is deteriorated, which is not preferable.

The content of calcium carbonate is 30 to 200 parts by weight, preferably 40 to 150 parts by weight, more preferably 50 to 130 parts by weight, based on 100 parts by weight of the vinyl chloride resin. It is preferable at the point of view.

In this case, when less than 30 weight part, troubles, such as a cell puncture, may arise or become too flexible. On the other hand, when it is more than 200 parts by weight, the strength of the foam decreases, and there is a possibility that it is easily broken.

Since calcium carbonate used affects the color of a product, it is good to use B * value measured with a color difference meter of 2 or less, Preferably it is 1 or less, More preferably, it is 0.5 or less.

2) vinyl chloride polymer

The vinyl chloride polymer may be a homopolymer having a content derived from a vinyl chloride monomer of 50 mono% or more, or a copolymer of a vinyl chloride monomer with another monomer.

Examples of the monomer copolymerized with a vinyl chloride monomer include vinyl esters of 2 to 18 carbon atoms such as vinyl acetate and vinyl caproate, acrylic esters such as methyl acrylate and methyl methacrylate, ethylene, and 1-pentene. Epoxy-containing substances, such as olefins, arylglycidyl ether, and glycidyl methacrylate, vinyl ethers, such as isobutyl vinyl ether and an octyl vinyl ether, acrylnitrate maleic anhydride, etc. are mentioned.

The vinyl chloride polymer can be obtained by a conventional method, for example, by a polymerization method such as emulsion polymerization, seed emulsion polymerization, fine suspension polymerization or seed fine suspension polymerization.

(Emulsion polymerization)

In emulsion polymerization, pure water, an emulsifier, a water-soluble polymerization initiator, and the like are put into a polymerization reactor, degassing in the polymerization reactor or substitution by an inert gas such as nitrogen is carried out as necessary, and vinyl chloride alone or vinyl chloride is mainly used. A mixture with a comonomer obtained by copolymerization with a polymer is added and stirred to form an emulsifier micelle layer in which the monomer is solubilized, while the polymerization is carried out by raising the temperature in the polymerization reactor. In order to control the reaction rate and the particle size, it is also possible to add an emulsifier, an initiator, a reducing agent and the like during the polymerization reaction. The polymerization temperature is preferably in the range of 30 to 80 ° C. By this emulsion polymerization, the aqueous acidic solution of the polymer which has a single mode and narrow particle size distribution of average particle diameter about 0.2-0.7 micrometer, and a distribution range of average particle diameter ± 0.2-0.4 micrometer is obtained.

(Seed emulsion polymerization method)

Seed emulsion polymerization method is to seed the polymer obtained by emulsion polymerization as a seed, and to encapsulate it in the water medium by polymerization of monomers, and to cover the surface of the polymer particles with an emulsifier composed of an anionic surfactant for stabilizing the polymer particles. It superposes | polymerizes using a water-soluble polymerization initiator, adding in harmony with advancing of a polymerization reaction so that it may not exceed a required amount. As for polymerization temperature, the range of 30-80 degreeC is preferable.

By this seed emulsion polymerization, the allele which has one sharp particle diameter distribution of the average particle diameter which enlarged the seed about 0.9-2.0 micrometers and the distribution range of the average particle diameter ± 0.3-0.5 micrometer is produced. In addition to this allelic visa, it often has a bimodal particle size distribution incorporating by-product small particles having an average particle diameter of about 0.2 to 0.4 µm in a ratio of 20% by weight or less.

(Micro suspension polymerization)

In microsuspension polymerization, first of all, a mixture with a comonomer obtained by copolymerizing with vinyl chloride alone or vinyl chloride in an aqueous medium, an oil-soluble polymerization initiator, an emulsifier, higher alcohols, higher fatty acids and esters thereof, Dispersion aids, such as chlorinated paraffin, and other additives are added, premixed, homogenized by a homogenizer, and the grain size is controlled. As the homogenizer, for example, a colloid mill, a vibration stirrer, a two-stage high pressure pump, or the like can be used.

It is possible to send the homogenized liquid to the polymerization vessel, raise the temperature in the polymerization vessel with gentle stirring to start the polymerization reaction, and then polymerize it until it reaches a predetermined conversion rate. It is preferable that superposition | polymerization temperature is 30-80 degreeC.

By this microsuspension polymerization, it is possible to obtain an aqueous dispersion of vinyl chloride-based polymers of spherical polymer particles having a particle size of primary particles continuously distributed over a wide range of about 0.05 to 5 μm and having an acid frequency distribution.

(Seed fine suspension polymerization)

In seed microsuspension polymerization, a seed polymer in which pure water and a polymerization initiator remain in a particle is placed in a polymerizer, and degassing in the polymerizer or, if necessary, substituted with an inert gas such as nitrogen, and then vinyl chloride alone or vinyl chloride. It is possible to add a mixture with the comonomer obtained by copolymerizing with this as a main agent, and to advance polymerization by raising the temperature in the polymerization reactor with gentle stirring. It is preferable that superposition | polymerization temperature is 30-80 degreeC. In the case of seed fine suspension polymerization, a polymerization initiator does not need to be added newly.

By seed microsuspension polymerization, an aqueous dispersion of vinyl chloride-based aggregates of spherical polymer particles having an acid-shaped particle diameter distribution continuously in a wide range of primary particles having a particle size of about 0.3 to 10 µm can be obtained.

(After treatment)

Solid content concentration of the aqueous dispersion of the vinyl chloride type polymer obtained by said emulsion polymerization, seed emulsion polymerization, microsuspension polymerization, or seed microsuspension polymerization is about 35-55 weight% normally. Such an aqueous dispersion can be concentrated to about 40 to 65% by weight by ultrafiltration or evaporation, but if it is concentrated to 60% by weight or more, the fluidity of the aqueous dispersion tends to change, and therefore an aqueous dispersion having a concentration lower than 60% by weight is usually used. To the spray drying treatment.

First, the concentration method of the aqueous dispersion liquid of a vinyl chloride type polymer includes, for example, concentration using a dialysis membrane or an ultrafiltration membrane, concentration by a vacuum evaporator, concentration by a thin film evaporator, and the like. Among these, in the case of membrane concentration, the membrane to be used is not particularly limited, and examples thereof include cellulose acetate membrane, polysulfone membrane, polyamide membrane, polyacrylonitrile membrane, and fluororesin membrane. have.

Next, in the spray drying process, there is no restriction | limiting in particular in the spray dryer used, For example, a rotary disk type atomizer, an air atomizer type atomizer, a pressurized nozzle type atomizer, etc. are mentioned as a spray type. Since the rotating disk type atomizer can respond widely to fluctuation | variation, such as the flow volume, density, and a viscosity of an aqueous acid solution, it can be used suitably.

Although there is no restriction | limiting in particular also in the contact system of hot air and a droplet group, It is preferable that a cocurrent system reduces the heat history distribution of resin granules. The drying air can be collected from the air, and it is not necessary to adjust the humidity on purpose, but the humidity is not limited. The higher the inlet temperature of the drying air, the higher the drying efficiency can be hoped for, but if it exceeds 200 ° C, the sol dispersibility of the resin granules deteriorates. However, as in the prior art, a low temperature of 100 ° C. or less is not essential, higher than 100 ° C. and 200 ° C. or less are preferable, and a range of 110 to 170 ° C. is particularly preferable.

Moreover, the range of 40-70 degreeC is preferable, and, as for the outlet temperature of drying air, the range of 45-55 degreeC is more preferable. As for the degree of drying, the moisture contained in the dried granules is 0.05-1. It is preferable that it is 5 weight%, and it is more preferable that it is 0.1-1.0 weight%. The outlet temperature of the drying air and the moisture content of the dried granules can be adjusted by controlling the supply rate of the aqueous dispersion liquid of the vinyl chloride polymer and the temperature and air volume of the drying hot air.

The diameter of the spray droplets is determined by the feed rate and the solid content concentration of the aqueous dispersion of the vinyl chloride-based polymer, the disk rotation speed in the rotary disk atomizer, the atomizer air pressure and the air volume in the two-fluid nozzle atomizer, and the pressurized nozzle. In the type atomizer, it is possible to control the pressure as a main factor.

By spray-drying the aqueous dispersion liquid of a vinyl chloride type polymer, granules with an average particle diameter of 20-150 micrometers can be obtained normally.

Although the vinyl chloride polymer of this invention can be obtained by the said method, it is preferable to use the low viscosity plastisol under high shear rate.

For example, the particle size by the laser lime method is continuously distributed widely in the range of at least 0.2-6 μm, has two maximum values in frequency, and has a particle size of 0.2-0.5 μm, which gives the maximum value of the small particle group, of the large particle group. It has a particle size distribution of 1.5 to 4.0 µm giving a maximum value, an average particle diameter of 1.3 to 4.0 µm, and a particle size distribution of 5 to 40% by weight of particles having an average particle diameter of 0.5 µm or less. -The sabers outflow amount of the paste obtained by mixing 45 parts by weight of ethyl hexyl phthalate is 3 g / 100 sec or more, and the vinyl chloride resin for paste processing (Patent Literature 3), having a particle diameter of 0.1 to 200 μm, is divided into a plurality of divisions. When the difference between the upper and lower limits of each division is the same as the difference between the common logarithms, the division is divided into 56 divisions, and the particles included in the particle size range of 0.10 to 10.27 μm are 100% by volume. Vinyl chloride-based resin particles for pastes (Patent Document 4) and the like, wherein the proportion of particles present in each section in a section having a particle diameter of 0.34 to 2.27 μm is 3.0% or more on a volume basis in any section. .

[Patent Document 3] WO98 / 46654 Publication

[Patent Document 4] Japanese Patent Application No. 2004-80315

3) plasticizer

The plasticizer used in the present invention may be any plasticizer used in the vinyl chloride plastisol, and is used without particular limitation.

Specifically, dibutyl phthalate, di- (2-ethylhexyl) phthalate, di-n-octyl phthalate, diisobutyl phthalate, diheptyl phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, di Phthalic acid derivatives such as phenyl phthalate and butyl benzyl phthalate; isophthalic acid derivatives such as di- (2-ethylhexyl) isophthalate and diisooctyl isophthalate; di-n-butyl adipate and di- (2-ethylhexyl) adi Adipic acid derivatives such as pate, diisodecyl adipate and diisononyl adipate; azaline acid derivatives such as di- (2-ethylhexyl) azelate, diisooctyl azelate and di- (n-hexyl azelate); Sebacic acid derivatives such as di-n-butyl sebacate and di- (2-ethylhexyl) sebacate; di-n-butyl maleate, dimethyl maleate, diethyl maleate, di- (2-ethylhexyl) Maleic acid such as latex Derivatives; fumaric acid derivatives such as di-n-butyl fumarate and di- (2-ethylhexyl) fumarate; tri- (2-ethylhexyl) trimerate, tri-n-octyltrimerate, triisooctyl Trimellitic acid derivatives such as remerate and tri-n-hexyl trimellitate; pyromellitic acid derivatives such as tetra- (2-ethylhexyl) pyromellitate and tetra-n-octyl pyromellitate; triethyl citrate, Citric acid derivatives, such as acetyl triethyl citrate and acetyl tri (2-ethylhexyl) citrate; monomethyl itaconate, monobutyl itacorate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc. Itaconic acid derivatives; oleic acid derivatives such as butyl oleate, glyceryl monooleate, diethylene glycol monooleate; licer such as glyceryl monoricinoleate, diethylene glycol monoricinoleate Cynolic acid derivatives; stearic acid derivatives such as glyceryl monostearate and diethylene glycol distearate; other fatty acid derivatives such as diethylene glycol monolaurate, diethylene glycol diferonate, pentaerythritol fatty acid ester; tributyl phosphate, Phosphoric acid derivatives such as tri- (2-ethylhexyl) phosphate, triphenylphosphate, and tricrezyl phosphate; glycol derivatives such as diethylene glycol dibenzoate, dipropylene glycol dibenzoate and dibutylmethylenebisthioglycolate; Glycerin derivatives such as glycerol monoacetate, glycerol triacetate, and glycerol tributylate; Polyester plasticizers such as adipic acid polyesters, sebacic acid polyesters, and phthalic acid polyesters; polymerizable plasticizers such as diaryl phthalates, acrylic monomers and oligomers, and the like. Very suitable are ester-based and citric acid-based esters. These plasticizers may be used by one type, and may be used in combination of 2 or more type. The content of the plasticizer is 30 parts by weight to 100 parts by weight, preferably 35 parts by weight to 80 parts by weight, and more preferably 40 parts by weight to 70 parts by weight per 100 parts by weight of the vinyl chloride resin. If the amount of the plasticizer is less than 30 parts by weight, the viscosity may increase, and workability may become difficult. If the amount of the plasticizer is more than 100 parts by weight, the product may become sticky or soft, resulting in unstable shape.

4) Foaming agent

As the blowing agent for forming a foamed molded article using vinyl chloride-based plastisol, known foaming agents are used without limitation, and specific examples thereof include azo dicarbonamide, azobisisobutyronitrile, diazoaminobenzene and the like. Nitroso compounds, such as a compound, dinitrosopentamethylenetetramine, N, N- dinitroso-N, and N-dimethyl phthalamide, a paratorenesulfonyl hydride, 4, 4-oxy bis (benzenesulfonylhydra Sulfonylhydride compounds such as died), and expandable balloons such as microcapsules. The usage-amount is 0.1-10 weight part per 100 weight part of vinyl chloride resins, and 0.5-5 weight part is preferable. If it is less than 0.1 part by weight, the foam may not be obtained. On the other hand, if it is more than 10 parts by weight, a uniform foam cell may not be obtained, and the foam surface may not be smooth.

5) additive

Various additives can be used in the range which does not impair the effect of this invention.

Examples of the inorganic compound include aluminum hydroxide, magnesium hydroxide, silica, tark, clay, diatomaceous earth, mica, alumina, and the like. Further, titanium cadmium oxide (cadmium sulfide), chromium yellow (lead chromate) and timothy Inorganic pigments such as Knox (antimony trioxide), White lead (alkaline lead carbonate) and Bengara (iron trioxide); Inorganic flame retardants such as antimony trioxide; Inorganic gelling agents such as calcium silicate and silica aerosil; Inorganic fillers such as inorganic kickers such as zinc; and the like.

You may add the said inorganic compound combining 1 type (s) or 2 or more types as needed.

In addition, heat and light stabilizers such as zinc octanoate, calcium stearate, zinc salts, cadmium octanoate, barium ricinoleate, or the like may be added. It is also possible to use the thing disperse | distributed to the plasticizer and the high boiling point liquid component.

In addition, in the range which does not impair the effect of this invention, you may add additives, such as a ultraviolet absorber, antioxidant, and mold inhibitor.

6) thinner

In this invention, although the organic solvent does not need to be used as a diluent, when using, it is good that the organic solvent component of the boiling point of 60-290 degreeC in normal pressure is 2.0 weight% or less. If there are more organic solvent components than this, the volatile components contained in the molded product may increase, which may cause sick house syndrome. The organic solvent component of boiling point 60-290 degreeC becomes like this. Preferably it is 1.0 weight% or less, More preferably, it is 0.1 weight% or less. It is preferable that there are few organic liquid components other than a plasticizer in a composition as much as possible.

(2) Preparation of plastisol

Preparation of the plastisol is carried out by mixing, stirring and mixing the plastisol constituents. As the plastisol mixer, a conventional one, for example, a Henschel mixer, a biaxial mixer, a butterfly mixer, a uniaxial dissolver, a pony mixer, a hobert mixer, or the like is used.

(3) products

As a manufacturing method of a product, various methods are used according to a product, For example, a coating molding method, the dipping molding method, the slash molding method, the mold molding method, the rotation molding method, etc. are mentioned, The vinyl chloride-type plastisol of this invention is mentioned. The composition is most suitable for foams.

As a method for producing a foam, a method of molding a known foam is adopted. For example, after the plastisol is applied to a substrate such as paper using a knife coater, a comma coater, a die coater, and the like, the resin is heated and solidified. And, if necessary, a method of heating and foaming by printing or surface treatment.

And a foam is embossed in order to improve designability as needed. Since the vinyl chloride plastisol composition of the present invention is excellent in embossing, in particular, mechanical embossing processability, the vinyl chloride plastisol composition is particularly suitable for producing a product having mechanical embossing.

The use of the vinyl chloride-based foamed molded article of the present invention is not particularly limited and can be suitably used as long as it is a foamed molded article such as wallpaper, cushion floor, tile carpet, toys, daily necessities, and the like. It is preferable to be used and supplied in the field of wallpaper use or cushion floor which considers physical properties such as cell puncture property of the city.

(1) The vinyl chloride-based plastisol composition of the present invention is low in viscosity, capable of high-speed molding, and troubles such as irregularities in thickness at the time of coat molding and leakage after the blade of the plastisol can be avoided.

Moreover, the product obtained is excellent in surface smoothness, few troubles, such as cell puncture at the time of embossing, and are favorable in external appearance.

(2) Since the present plastisol composition does not use a volatile organic solvent as a diluent and is very small in use, and can be easily used for processing, a product having a low total VOC (volatile organic component) generation amount is provided. You can do it.

Therefore, in the present invention, the sol viscosity is extremely low, and in particular, since the diluent (volatile organic liquid) can be extremely reduced, it is optimal for applications in which the presence of volatile organic liquids is a problem (building material, cushion floor) and the like. Is very high.

Carrying out the invention  Form for

Hereinafter, although an Example etc. are given and this invention is demonstrated in more detail, this invention is not limited to this. And "part" means a "weight part" unless there is particular notice.

Physical property measurement and physical property evaluation of an Example etc. were made with the following method.

<Particle diameter distribution>

Using a laser diffraction scattering particle size distribution analyzer (La910W: manufactured by Horiba, Ltd.), the samples were measured in a di-2-ethylhexyl azate after stirring and ultrasonic irradiation for 5 minutes, followed by stirring and a refractive index of 1.15.

<Surface smoothness>

It carried out by visual observation and set it as the following five steps of evaluation.

◎ ： Very smooth surface

(Circle): There is a little irregularities.

(Triangle | delta): There exists a small unevenness | corrugation as a whole.

×: There are small irregularities and some large irregularities.

X x: There is a big unevenness | corrugation as a whole.

<Cell punk castle>

Using an embossing machine (infrared: Sankei Co., Ltd., Matsus Co., Ltd., Furnace lentgh 2m), A3 size foam is heated at 220 ° C and 4m / min. The boss worked and observed the number of cellpunks.

<Viscosity>

Low shear viscosity (1.25 sec ^-1 )

The paste sol was prepared in an atmosphere of 23 ° C. and 50% RH, and left in the same atmosphere for 1 hour. Then, the BL viscometer No. was used using a BL-type viscometer (VISCOMETER TV-30: manufactured by Tokyo Instruments Co., Ltd.). Using 4 rotors, the rotation speed was measured at 6 rpm.

High shear viscosity (1500 sec ^-1 )

After making paste sol in atmosphere of 23 degreeC, 50% RH, and leaving it to stand for one hour in the same atmosphere, die length 1.0mm, die using caprograph (CAPIROGRAPH 1C: Toyo Tokai Co., Ltd. product) It measured with the nozzle of 10.01 mm in length.

And low low shear viscosity indicates that the transferability of the plastisol to the molding machine is appropriate, and low high shear viscosity indicates that the coating ability is excellent.

<Thickness irregularity>

On the paper, 100 points of thickness were measured for every 1 cm in the application | coating direction and the dried semigel disk which apply | coated plastisol was made thickness irregularity in the difference between the maximum value and the minimum value.

<B * value>

It measured using VG2000 made in Japan.

In addition, a B * value shows that a smaller thing is excellent in whiteness.

<Leak test after plastisol blade>

A stainless steel cylindrical roll having a diameter of 200 mm and a height of 150 mm was placed sideways in a high direction, and the plastisol was formed on the cylindrical roll at 159 rpm using a tester provided with a comma coater so that the gap with the roll was 150 μm thereon. 50 ml of saline were dripped and the time until plastisol squeezed out after the comma coater day was measured.

<State of cell>

The cross section of the foam was observed using a CCD camera, and visual evaluation was made into the following five stages of evaluation.

(Double-circle): A cell is very dense.

(Circle): A little small coarse cell is seen.

△ ： There are small coarse cells as a whole

Δ˜ ×: There are small coarse cells and some large coarse cells.

X: There are large coarse cells as a whole.

<Flexibility>

The touch when a foam was touched by hand was made into the following five stages of evaluation.

1: It is hard.

2: We feel slightly hard

3: Appropriate flexibility.

4: It feels a little soft.

5: It is soft.

(Example 1)

1. Preparation of calcium carbonate

2 kg of calcium carbonate (cold water 70: manufactured by Nitto Powder Co., Ltd.) was placed in a ball mill pot (5 L) with a steel ball, and pulverized with a ball mill (manufactured by a centralized air company) for 24 hours. Thereafter, 200 mesh and 500 mesh sieves were repeated, and the pulverized calcium carbonate was placed on the 200 mesh, subjected to classification treatment for 30 minutes while vibrating, and granulated and finely divided calcium carbonate was obtained on the 500 mesh sieve.

Next, the molecular diameter of the obtained calcium carbonate was stirred in a di-2-ethylhexyl adipate using a laser diffraction scattering particle size distribution analyzer (La910W: manufactured by Horiba, Ltd.) and irradiated with ultrasonic waves for 5 minutes. When measured by stirring and refractive index 1.15, the cumulative frequency of the particle | grains larger than 150 micrometers was 0.1%, and the mode diameter was 45 micrometers. Moreover, when B * value was measured with the color difference meter, it was +0.3.

2. Preparation of Vinyl Chloride Resin

<Polymerization>

100 L of glass lining autoclave was degassed, 40 kg of deionized water, 16 kg of vinyl chloride monomer, 140 g of sodium lauryl sulfate, 240 g of stearyl alcohol, 7.5 g of lauryl peroxide were added, and homogenized with a homogenizer until 63 ° C. The temperature was raised to initiate polymerization. The polymerization was stopped when the pressure in the reactor dropped to 0.05 MPa, and the unreacted monomer was recovered to obtain an aqueous dispersion of vinyl chloride resin.

<Drying>

To the above aqueous dispersion, 0.4 part of sodium lauryl sulfate, 0.4 part of polyoxyethylene alkyl ether and 1.0 part of zinc chloride were added to 100 parts of the polymer, and stirred and homogenized, followed by spray drying with a spray dryer (a rotary atomizer manufactured by Nirosa). To obtain a powder of vinyl chloride resin.

3. Preparation of Plastisol

80 g of said calcium carbonate of 1, 100 g of said 2 vinyl chloride resins, 60 g of diisononyl phthalates (CG: Esta Co., Ltd. product) as a plasticizer, 12 g of titanium oxides (R900: manufactured by Dupont) as an inorganic pigment, Ba / Zn type 4 g of stabilizer (KF705E: Co., Ltd. product), 3 g of azodicarbonamide (AZH-25: Ozuka Chemical Co., Ltd.) and 5 g of a deductant (BKY20386: BICKEMY Co., Ltd.) as a blowing agent The mixture was kneaded using a solver to obtain a plastisol.

4. Preparation of Semigel Sheet

Using a coating machine equipped with a comma coater (multi coater: manufactured by Nishimura Machinery Co., Ltd.), the above-mentioned plastisols of 150 μm in thickness were applied on a 100 cm wide and 110 μm thick paper, and were immediately irradiated with infrared rays. The semigel sheet | seat was obtained by passing through (2m long length).

5. Preparation of Foam

The semigel sheet of 4 was cut into an A3 size and foamed in a hot air oven (manufactured by Matisse Co., Ltd.) at 215 ° C for 50 seconds to obtain a foam.

The surface was very smooth.

6. Embossing processing

The foam of 5 above was heated at 220 ° C. and 4 m / min (30 second stay time) using a remote embossing machine (infrared: Sankei Co., Ltd. product, Emboss part: Matisse Co., Ltd., length 2m). The foam was sandwiched with emboss roll and rubber roll and embossed.

The emboss was clean, and observed the number of cellpunks, but it was not noticeable at all.

The obtained product is optimal as a wallpaper.

(Example 2)

In preparation of the calcium carbonate of Example 1, it carried out similarly to Example 1 except having used the sieve of 170 mesh and 500 mesh instead of the 200 mesh and 500 mesh sieve used for classification.

(Example 3)

In preparation of the calcium carbonate of Example 1, it shifted similarly to Example 1 except having used the sieve of 250 mesh and 500 mesh instead of the 200 mesh and 500 mesh sieve used for classification.

(Example 4)

In preparation of the calcium carbonate of Example 1, it shifted similarly to Example 1 except having used the 115 mesh and 500 mesh sieve instead of the 200 mesh and 500 mesh sieve used for classification.

(Example 5)

In preparation of the calcium carbonate of Example 1, it shifted similarly to Example 1 except having used the sieve of 325 mesh and 500 mesh instead of the 200 mesh and 500 mesh sieve used for classification.

(Example 6)

In preparation of the calcium carbonate of Example 1, the sieve used for classification was implemented similarly to Example 1 except having used the 115 mesh and the 500 mesh sieve instead of the 200 mesh and 500 mesh sieve.

(Example 7)

In the preparation of the calcium carbonate of Example 1, the grinding was carried out for 36 hours instead of 24 hours, and in the classification, except that 100 and 500 mesh sieves were used instead of 200 and 500 mesh sieves. Was implemented in the same manner as in Example 1.

(Example 8)

In Example 7, it carried out similarly to Example 7 except having carried out for 1 hour instead of performing classification by a sieve for 30 minutes.

(Example 9)

1. Preparation of vinyl chloride resin

120 parts by weight of water was added to the premixer, and 0.5 parts by weight of a mixed alcohol having 10 to 18 carbon atoms (melting point of 25 ° C) mainly containing lauryl alcohol was added while stirring at 28 ° C, followed by 0.8 weight of sodium dodecyl benzene sulfonate. Part was added to prepare an emulsion. Next, 0.07 weight part of 50 weight% n-hexane solutions of diisopropyl peroxydicarbonate were added here, and nitrogen substitution and vacuum degassing were repeated twice each. Subsequently, 100 weight part of vinyl chlorides were added, it stirred for 30 minutes by the 0.95 kW / m < ³ > stirring net stirring forces, and pre-mixed, and it homogenized by the two-stage high pressure homogenizer.

Subsequently, the resultant was transferred to another degassed 10 liter pressure reactor, the temperature was increased while stirring under mild conditions for the purpose of heat transfer, and microsuspension polymerization was carried out at 62 占 폚. When the polymerization conversion ratio reached 90% by weight, the polymer was cooled and the unreacted monomer was removed, thereby obtaining a safe polymer particle aqueous dispersion in a state where there was almost no scale. Then, the polymer particle aqueous acid solution was dried with a spray dryer, and then ground with a hammer mill to obtain a vinyl chloride resin.

2. Preparation of Plastisol

It carried out similarly to Example 1 except having used the vinyl chloride resin of said 1 instead of the vinyl chloride resin of Example 1.

3. Preparation of Semigel Sheet

It carried out similarly to Example 1.

4. Preparation of foam

It carried out similarly to Example 1.

5. Embossing Machining

It carried out similarly to Example 1.

(Example 10)

1. Foam layer plastisol

The plastisol of Example 1 was used.

2. Preparation of Top Layer Plastisol

100 g of vinyl chloride resin (PQHH: Shinil vinyl chloride Co., Ltd. product), 60 g of diisononyl phthalates (CG: Ester Co., Ltd. product), 4 g of Ba / Zn system stabilizers (KF705E: Co., Ltd. product), And 5 g of a deducting agent (BKY20386: manufactured by BIC Chemie Co., Ltd.) were kneaded using a resolver to prepare a plastisol.

3. Preparation of Semigel Sheet

By using the coater equipped with a knife coater (Matis Corporation oven), the above-mentioned foamed layer plastisol was cut into 300 μm grains using a knife coater on A3 sized glass paper.

Subsequently, the obtained coating was heated in an oven for 30 seconds to obtain a semigel sheet of a foam layer.

Next, on the obtained semigel sheet, the top layer was coated with the plastisol of 2 to a thickness of 200 μm, and heated in an oven for 30 seconds to obtain a semigel sheet.

4. Preparation of foam

The semigel sheet obtained by the above 3 was foamed in a hot air oven (manufactured by Matisse Co., Ltd.) at 215 ° C for 50 seconds to obtain a foam.

The surface of the foam was very smooth.

5. Embossing Machining

The foam obtained in the above 4 was heated at 220 ° C. and 4 m / min (stay time 30 seconds) using a remote embossing machine (infrared: manufactured by Sankei Co., Ltd., embossed by Matisse Co., Ltd., 2 m long). Thereafter, the foam was sandwiched with an emboss roll and a rubber roll, and embossed.

Embossed neatly and observed number of Sherpanks, but was not recognized at all.

The obtained product is optimal as a cushion floor.

(Comparative Example 1)

In the preparation of the calcium carbonate of Example 1, the grinding was carried out for 36 hours instead of 24 hours, and the classification was performed using a sieve of 200 mesh and 500 mesh to remove granulated and fine particles on a 500 mesh sieve. Instead of obtaining calcium carbonate, only 500 mesh sieves were classified and calcium carbonate passed through a 500 mesh sieve was used in the same manner as in Example 1.

(Comparative Example 2)

In Example 7, it carried out similarly to Example 7 except having performed classification by a sieve for 2 hours instead of 30 minutes.

(Comparative Example 3)

In preparation of the calcium carbonate of Example 1, it carried out similarly to Example 1 except having used the 100 mesh and 500 mesh sieve instead of the 200 mesh and 500 mesh sieve.

(Examples 11-15)

In the preparation of the plastisol of Example 1, it carried out similarly to Example 1 except having replaced the diisononyl phthalate compounding quantity of calcium carbonate and a plasticizer with the compounding quantity shown in Table 2.

The result of Examples 1-10 and Comparative Examples 1-3 is shown in Table 1, and the result of Examples 11-15 is shown in Table 2.

From the results of Tables 1 and 2, (1) the cumulative frequency (volume basis) of particles larger than 150 μm was 5% or less, and (2) the mode diameter was 30 μm or more and 100 μm or less for the particle size distribution of calcium carbonate of the inorganic filler. If the two requirements are satisfied at the same time, the desired object of the present invention can be achieved. If any one of the two requirements is lacking, the desired object of the present invention cannot be achieved, and thus the calcium carbonate of the present invention It can be seen that the definition of the particle size distribution has significant significance.

Industrial availability

The vinyl chloride-based plastisol composition of the present invention has a low viscosity, is capable of high-speed molding, and troubles such as irregularities in thickness at the time of coat molding and poor plaque sol (leak leakage) can be avoided. Moreover, the obtained product is excellent in surface smoothness, few troubles, such as cell puncture at the time of embossing, and the external appearance is favorable, and it is applicable to various products. In particular, it can use suitably for uses, such as a wallpaper and a cushion floor.

Claims (7)

In a vinyl chloride plastisol composition composed of a vinyl chloride polymer, a plasticizer, and an inorganic filler, The inorganic filler contains (1) calcium carbonate having a particle size distribution with a cumulative frequency (volume basis) of particles larger than 150 µm of 5% or less, (2) a mode diameter of 30 µm or more and 100 µm or less, 30-100 weight part of said plasticizers, and 30-200 weight part of said calcium carbonates are contained with respect to 100 weight part of said vinyl chloride-type polymers, The vinyl chloride type plastisol composition characterized by the above-mentioned. delete The vinyl chloride plastisol composition according to claim 1, wherein the vinyl chloride plastisol composition contains a blowing agent. A foamed molded product obtained by foaming the plastisol composition according to claim 3. The molded foam according to claim 4, wherein the molded foam is embossed. 5. The molded foam according to claim 4, wherein the molded foam is a wallpaper or a cushion floor. 6. The molded foam according to claim 5, wherein the molded foam is a wallpaper or a cushion floor.