JP2005306905A - Vinyl chloride plastisol composition and expansion formed product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a vinyl chloride plastisol composition for a paste, having a low viscosity, formable at a high speed and avoiding troubles such as thickness unevenness or leakage to the blade back during coat forming even when an organic solvent is not used as a diluent or the amount thereof used is small. <P>SOLUTION: (a) The vinyl chloride plastisol composition is composed of a vinyl chloride polymer, a plasticizer and an inorganic filler and the vinyl chloride plastisol composition is characterized in that calcium carbonate having (1) ≤5% cumulative frequency (based on the volume) of particles larger than 150 μm and (2) a particle diameter distribution of ≥30 to ≤100 μm mode diameter is contained as the inorganic filler. (b) The vinyl chloride plastisol composition described in (a) comprises 30-100 pts.wt. of the plasticizer and the calcium carbonate described in (a) in an amount of 30-200 pts.wt. based on 100 pts.wt. of the vinyl chloride polymer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

The vinyl chloride plastisol composition for paste has excellent processability and can easily obtain a product with good appearance, and the molded product has excellent properties such as flame retardancy, and is excellent in workability. Therefore, it is widely used in the manufacture of wall materials, floor materials, leather, canvas, vehicle interior products, steel plate coats, cotton material coats, yarn coats, work gloves, toys, daily goods.
In particular, as a housing interior material, a foam molded article made of a vinyl chloride plastisol composition for paste is excellent in flame retardancy, workability, and design in the fields of wall materials, flooring materials, daily necessities, etc. Widely used.
The vinyl chloride foam is generally produced by applying a vinyl chloride plastisol composition for paste on a substrate such as paper, followed by heat drying and a heat foaming process.
The vinyl chloride plastisol composition for paste is mainly composed of a vinyl chloride paste resin, a plasticizer, and an inorganic filler such as calcium carbonate, and is further referred to as a diluent as a viscosity modifier in coating and molding on a substrate. It is common to add a large amount of a hydrocarbon-based solvent.

In recent years, consumer interest in sick house syndrome is high. Among them, hydrocarbon solvents used as viscosity modifiers are listed as one of the inducers of sick house syndrome. Moreover, since a non-negligible amount of hydrocarbon solvent remains in the final product, a foam product in which the amount is reduced as much as possible is demanded.
As a method for obtaining a low-viscosity paste sol without using a diluent, for example, the specific surface area is 1.0 to 3.5 m ² / g, (A) the particle size distribution is less than 2 μm, 15 to 55% by weight of particles having a peak diameter of 0.2 to 1.5 μm, (B) less than 15% by weight of particles of 2 μm or more and less than 4 μm, and (C) having a particle size distribution of 4 μm or more, There is a vinyl chloride resin (Patent Document 1) characterized in that it is composed of 40 to 80% by weight of particles having a distribution peak diameter of 7 to 15 μm.
However, the above-mentioned low viscosity method aims to obtain a low-viscosity paste sol over a wide shear rate region from a low shear region to a high shear region even when the amount of plasticizer is reduced. Although it may be said that the viscosity is reduced to some extent within the range of the objective, when the thin film coating is performed at a high speed, an extremely high viscosity is required, so the above is still sufficient. That's not true.

Further, in the vinyl chloride plastisol composition, the viscosity behavior is improved, for example, a vinyl chloride plastisol composition mainly composed of a particulate vinyl chloride resin, a particulate inorganic filler, and a plasticizer. In the product, when the total weight of the vinyl chloride resin and the inorganic filler is 100, fine particles 20 to 35 having a particle size distribution of less than 2 μm of the total particle composed of the vinyl chloride resin and the inorganic filler. The inorganic filler is configured so that the medium particle is 25 to 40% by weight, and the coarse particle is 30 to 50% by weight of 10 μm or more, and the weight of the inorganic filler is 100%. The distribution of particle size of the material is 25 to 35% by weight of an ultrafine filler having a particle size of less than 0.2 μm, 30 to 45% by weight of a medium particle filler having a particle size of 0.2 μm or more and less than 15 μm, and a coarse particle filler of 15 μm or more. There exists a vinyl chloride plastisol composition (patent document 2) characterized by being comprised so that it may become 25-40 weight% of fillers.
However, the above-mentioned vinyl chloride plastisol composition is intended for air spraying for use in automotive chipping-resistant paints, underfloor undercoats, spray sealers, etc., and in the use of organic solvents, It is not different from things.

Japanese Patent Laid-Open No. 10-231322 JP-A-2-208347

In particular, when foaming a vinyl chloride plastisol composition for paste to obtain a foamed molded product, if the diluent is not used in the composition or the amount used is small even if used, the plastisol Due to the high viscosity of the product, troubles such as uneven thickness at high speed molding and leakage from the back of the blade occur. If the foam surface is uneven or embossed, trouble such as cell puncture occurs. There was a problem that the appearance was remarkably impaired.
Therefore, even if an organic solvent is not used as a diluent or the amount used is small, the viscosity is low, high-speed molding is possible, and troubles such as thickness unevenness and blade back leakage during coating molding can be avoided. Development of a technique for obtaining a vinyl chloride foam molded article having excellent plastisol composition and surface smoothness, less troubles such as cell puncture during embossing, and good appearance is awaited.

  The problem of the present invention is that the paste has a low viscosity and can be molded at high speed without using an organic solvent as a diluent or a small amount of use, and can avoid troubles such as uneven thickness and blade back leakage during coating molding An object of the present invention is to obtain a vinyl chloride-based foamed molded article having excellent appearance and a vinyl chloride-based plastisol composition for use, and having excellent surface smoothness, less problems such as cell puncture during embossing.

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, when using calcium carbonate having a specific particle size distribution as an inorganic filler for vinyl chloride plastisol, the resulting vinyl chloride resin can be obtained. As for plastisol, even if no organic solvent is used as a diluent or the amount used is small, the viscosity is low, high-speed molding is possible, and foamed molded products with excellent characteristics can be obtained. As a result, the present invention has been completed.

The present invention comprises the following inventions.
1. In a vinyl chloride plastisol composition comprising a vinyl chloride polymer, a plasticizer, and an inorganic filler, as an inorganic filler, (1) the cumulative frequency (volume basis) of particles larger than 150 μm is 5% or less, and (2 ) A vinyl chloride plastisol composition comprising calcium carbonate having a particle size distribution with a mode diameter of 30 μm to 100 μm.
2. 2. The vinyl chloride plastisol composition according to 1 above, comprising 30 to 100 parts by weight of a plasticizer and 30 to 200 parts by weight of calcium carbonate as described in 1 above with respect to 100 parts by weight of the vinyl chloride polymer.
3. 3. The vinyl chloride plastisol composition according to 1 or 2 above, wherein the vinyl chloride plastisol composition contains a foaming agent.
4). A foam-molded product obtained by foam-molding the plastisol composition described in the above item 3.
5). 5. The foam molded article according to 4 above, wherein the foam molded article is embossed.
6). 6. The foam molded article according to 4 or 5 above, wherein the foam molded article is wallpaper or a cushion floor.

The greatest feature of the present invention is that 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) mode diameter By using calcium carbonate having a particle size distribution of 30 μm or more and 100 μm or less, a vinyl chloride resin composition for paste that solved the above problems was obtained.
Conventionally, calcium carbonate having a particle size of 1 to 20 μm has been used as an inorganic filler in the manufacture of wallpaper, cushion floors, and the like.
Therefore, the calcium carbonate having a specific particle size distribution of the present invention has a particle size larger than that of calcium carbonate used in the production of conventional foams, but has a significantly larger particle size, that is, the amount of coarse particles. It is characterized by a few points.
Thus, the calcium carbonate used as the inorganic filler in the present invention has a large particle size in a specific range and does not contain coarse particles. Therefore, the viscosity of the plastisol is lower than that of the conventional plastisol, and at the time of high speed molding. However, there is no unevenness in thickness and there are few troubles such as leakage of the blade back when applying to a substrate with a comma coater, etc., so that the molded product exhibits surface smoothness and the foamed cells become slightly rough. It is presumed that troubles such as cell puncture at the time of embossing can be avoided and a product having an excellent appearance can be obtained.

Hereinafter, the present invention will be described in detail.
The present invention relates to a vinyl chloride plastisol composition comprising a vinyl chloride polymer, a plasticizer, and an inorganic filler. As an inorganic filler, (1) the cumulative frequency (volume basis) of particles larger than 150 μm is 5% or less. (2) The composition is characterized in that it contains calcium carbonate having a particle size distribution with a mode diameter of 30 μm or more and 100 μm or less. The composition further comprises a foaming agent, an additive, and the like as constituent components It can be.

Therefore, the components of the vinyl chloride plastisol composition of the present invention and the preparation method thereof will be described below.
(1) Components of vinyl chloride-based plastisol composition 1) Inorganic filler The present invention provides an inorganic filler having a particle size distribution measured by a light scattering method of (1) cumulative frequency of particles larger than 150 μm (volume basis). Is 5% or less, and (2) it is essential to use calcium carbonate having a mode diameter of 30 μm or more and 100 μm or less.
Although the particle size distribution of calcium carbonate can be measured by a light scattering method, the measurement is preferably performed using a laser diffraction scattering type particle size distribution measuring apparatus.
By measuring the particle size and the frequency at the particle size by the above measurement, the particle size distribution including the particle size and the frequency is measured.
The cumulative frequency here is a value obtained by integrating the frequencies in the particle diameter range, and the mode diameter is the particle diameter showing the highest frequency in the particle diameter distribution curve.
In the present invention, the particle size distribution needs to satisfy the above requirements (1) and (2) at the same time, and the object of the present invention cannot be achieved without any requirement.
That is, requirement (1) is that the cumulative frequency of particles larger than 150 μm of calcium carbonate is 5% or less, preferably 3% or less, more preferably 1% or less.
In this case, if the cumulative frequency exceeds 5%, troubles such as blade back leakage are likely to occur at the time of coating molding, particularly at high speed molding, and foam cells of the foam are roughened or surface smoothness is deteriorated. Is not preferable.
The requirement (2) is that the mode diameter of calcium carbonate used in the present invention is 30 μm or more and 100 μm or less, preferably 35 μm or more and 90 μm or less, and more preferably 40 μm or more and 80 μm or less.
In this case, if it becomes smaller than 30 μm, the viscosity of the plastisol is remarkably increased, and troubles such as uneven thickness and leakage from the blade back occur, and cell puncture easily occurs during embossing. On the other hand, if it is larger than 100 μm, leakage from the blade back is likely to occur, and the foamed cells are roughened or the surface smoothness is deteriorated.
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 from the viewpoint of texture and strength.
In this case, if the amount is less than 30 parts by weight, there is a possibility that problems such as cell puncture may occur or the film becomes too soft. On the other hand, when the amount is more than 200 parts by weight, the strength of the foam may be lowered and easily damaged.
Since the calcium carbonate used affects the color of the product, the B * value measured with a color difference meter should be 2 or less, preferably 1 or less, more preferably 0.5 or less. .

2) Vinyl chloride polymer The vinyl chloride polymer may be a homopolymer having a vinyl chloride monomer-derived content of 50 mol% or more, or a copolymer of a vinyl chloride monomer and another monomer.
Examples of monomers copolymerized with vinyl chloride monomer include vinyl esters having 2 to 18 carbon atoms such as vinyl acetate and vinyl caproate, acrylic esters such as methyl acrylate and methyl methacrylate, ethylene, 1 -Olefins such as pentene, epoxy-containing materials such as allyl glycidyl ether and glycidyl methacrylate, vinyl ethers such as isobutyl vinyl ether and octyl vinyl ether, and acrylonitrile maleic anhydride.
The vinyl chloride polymer can be obtained by a usual method, for example, a polymerization method such as emulsion polymerization, seeding emulsion polymerization, fine suspension polymerization or seeding fine suspension polymerization.

(Emulsion polymerization)
In emulsion polymerization, pure water, an emulsifier, a water-soluble polymerization initiator, etc. are charged into a polymerization vessel, and the inside of the polymerization vessel is degassed or replaced with an inert gas such as nitrogen as required, and vinyl chloride alone or vinyl chloride The mixture is mixed with a comonomer that can be copolymerized therewith and stirred to form an emulsifier micelle layer in which the monomer is solubilized, and the polymerization proceeds by raising the temperature in the polymerization vessel. In order to control the reaction rate and particle size, an emulsifier, an initiator, a reducing agent and the like can be added during the polymerization reaction. The polymerization temperature is preferably in the range of 30 to 80 ° C. By this emulsion polymerization, an aqueous dispersion of a polymer having a narrow particle size distribution in a single mode having an average particle size of about 0.2 to 0.7 μm and a distribution range of an average particle size ± 0.2 to 0.4 μm. Obtain a liquid.

(Seeding emulsion polymerization method)
The seeded emulsion polymerization method comprises an anionic surfactant for stabilizing the polymer particles by using the polymer obtained by emulsion polymerization as a seed and enlarging the polymer particles by polymerization of the monomer in an aqueous medium. Polymerization is performed using a water-soluble polymerization initiator while adding an emulsifier in accordance with the progress of the polymerization reaction so as not to exceed the amount necessary to cover the surface of the polymer particles. The polymerization temperature is preferably in the range of 30 to 80 ° C.
By this sowing emulsion polymerization, the seeds are enlarged with an average particle size of about 0.9 to 2.0 μm and a distribution range of one sharp particle size frequency distribution with an average particle size of ± 0.3 to 0.5 μm. Large particles are produced. In addition to the large particles, by-product small particles having an average particle size of about 0.2 to 0.4 μm are often included in a proportion of 20% by weight or less, and the particles often have a bimodal particle size distribution.

(Fine suspension polymerization)
For fine suspension polymerization, first, in an aqueous medium, vinyl chloride alone or a mixture of vinyl chloride as a main component and a copolymerizable monomer, an oil-soluble polymerization initiator, an emulsifier, and a higher grade if necessary Dispersing aids such as alcohol, higher fatty acids and esters thereof, chlorinated paraffin, and other additives are added and premixed, and homogenized by a homogenizer to adjust the particle size of the oil droplets. As the homogenizer, for example, a colloid mill, a vibration stirrer, a two-stage high pressure pump, or the like can be used.
The homogenized liquid is sent to the polymerization vessel, the temperature in the polymerization vessel is raised while gently stirring to start the polymerization reaction, and then the polymerization can be carried out until a predetermined conversion rate is reached. The polymerization temperature is preferably 30 to 80 ° C.
By this fine suspension polymerization, an aqueous dispersion of a vinyl chloride polymer of spherical polymer particles in which the primary particle diameter is continuously distributed over a wide range of about 0.05 to 5 μm and has a mountain-shaped frequency distribution. Can be obtained.

(Seeding fine suspension polymerization)
In seeding fine suspension polymerization, pure water and seed polymer in which the polymerization initiator remains in the particles are charged into the polymerization vessel, and deaeration in the polymerization vessel or replacement with an inert gas such as nitrogen as necessary. After the polymerization, the polymerization can be advanced by charging vinyl chloride alone or a mixture of vinyl chloride as a main component and a comonomer that can be copolymerized therewith, and gradually increasing the temperature in the polymerization vessel while stirring gently. The polymerization temperature is preferably 30 to 80 ° C. In the case of seeding fine suspension polymerization, a polymerization initiator may not be newly added.
Aqueous dispersion of vinyl chloride polymer of spherical polymer particles having a mountain-shaped particle size distribution continuously in a wide range of primary particle size of about 0.3 to 10 μm by seeding fine suspension polymerization A liquid can be obtained.

(Post-processing)
The solid content concentration of the aqueous dispersion of the vinyl chloride polymer obtained by the above emulsion polymerization, seeding emulsion polymerization, fine suspension polymerization or seeding fine suspension polymerization is usually about 35 to 55% by weight. Such an aqueous dispersion can be concentrated to about 40 to 65% by weight by ultrafiltration or evaporation, but if concentrated to 60% by weight or more, the fluidity of the aqueous dispersion is likely to change. An aqueous dispersion having a concentration lower than% by weight is subjected to a spray drying treatment.
First, examples of a method for concentrating an aqueous dispersion of a vinyl chloride polymer include concentration using a dialysis membrane or an ultrafiltration membrane, concentration using a vacuum evaporator, and concentration using a thin film evaporator. Among these, in the case of membrane concentration, the membrane to be used is not particularly limited, and examples thereof include cellulose acetate membranes, polysulfone membranes, polyamide membranes, polyacrylonitrile membranes, and fluororesin membranes. .
Next, with respect to the spray drying treatment, there is no particular limitation on the spray dryer to be used. For example, examples of the spray format include a rotating disk atomizer, a two-fluid nozzle atomizer, and a pressure nozzle atomizer. Among these, the rotating disk atomizer can be preferably used because it can widely cope with fluctuations in the flow rate, density, viscosity and the like of the aqueous dispersion.
There is no particular limitation on the contact method between the hot air and the droplet group, but the combined flow method is preferable for reducing the thermal history distribution of the resin granules. The drying air can be collected from the atmosphere, and it is not necessary to adjust the humidity. However, humidity adjustment is not limited. The higher the inlet temperature of the drying air, the higher the drying efficiency can be expected. However, when the temperature exceeds 200 ° C., the sol dispersibility of the resin granules deteriorates. However, a low temperature of 100 ° C. or lower as in the prior art is not essential, and may be higher than 100 ° C. and 200 ° C. or lower, particularly preferably in the range of 110 to 170 ° C.
Moreover, the range of 40-70 degreeC is preferable and, as for the exit temperature of drying air, the range of 45-55 degreeC is more preferable. The degree of drying is preferably 0.05 to 1.5% by weight, more preferably 0.1 to 1.0% by weight, of water contained in the dried granule. 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 of the vinyl chloride polymer and the temperature and air volume of the drying hot air.
The spray droplet diameter depends on the supply rate and solid content of the aqueous dispersion of the vinyl chloride polymer, the rotational speed of the disk for the rotary disk atomizer, the atomizing air pressure and air volume for the two-fluid nozzle atomizer, and the pressure nozzle. In a type atomizer, pressure can be controlled as a main factor.
By spray-drying an aqueous dispersion of a vinyl chloride polymer, granules having an average particle diameter of 20 to 150 μm can be usually obtained.

The vinyl chloride polymer of the present invention can be obtained by the above-mentioned method, but is preferably one that gives a low-viscosity plastisol under a high shear rate.
For example, the particle size obtained by laser diffraction method is widely distributed continuously in a range of at least 0.2 to 6 μm, has two maximum values in frequency, and gives the maximum value of a group of small particles. Is 0.2 to 0.5 μm, the particle size giving the maximum value of the group of large particles is 1.5 to 4.0 μm, and the average particle size is 1.3 to 4.0 μm. The particle size distribution is 5 to 40% by weight of particles having a particle size of 0.5 μm or less, and the saver spillage of the paste obtained by mixing 100 parts by weight of the resin and 45 parts by weight of di-2-ethylhexyl phthalate is 3 g. / Vinyl chloride-based resin for paste processing (Patent Document 3), characterized in that it is 100 seconds or longer, when dividing a particle size of 0.1 to 200 μm into a plurality of sections, the upper and lower particle diameters of each section Is divided into 56 categories so that the difference in common logarithm values is equal. When the particles included in the range of 0.10 to 10.27 μm are defined as 100% on the volume basis, the proportion of particles present in each section in the section of the particle size of 0.34 to 2.27 μm Also in this section, it is possible to use vinyl chloride resin particles for paste (Patent Document 4) and the like characterized by being 3.0% or more on a volume basis.

WO 98/46654 Japanese Patent Application No. 2004-80315

3) Plasticizer The plasticizer used in the present invention may be any plasticizer used for vinyl chloride plastisol, and is used without particular limitation.
Specifically, phthalic acid derivatives such as dibutyl phthalate, di (2-ethylhexyl) phthalate, di-n-octyl phthalate, diisobutyl phthalate, diheptyl phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, diphenyl phthalate, butyl benzyl phthalate Isophthalic acid derivatives such as di (2-ethylhexyl) isophthalate and diisooctylisophthalate; adipic acid derivatives such as di-n-butyl adipate, di (2-ethylhexyl) adipate, diisodecyl adipate and diisononyl adipate; Ethylhexyl) azelate, diisooctylazelate, azelaic acid derivatives such as G (n-hexylazelate; g-n-butyl sebacate, di- (2 Sebacic acid derivatives such as ethyl hexyl) sebacate; maleic acid derivatives such as di-n-butyl maleate, dimethyl maleate, diethyl maleate, di (2-ethylhexyl) maleate; di-n-butyl fumarate, di (2- Fumaric acid derivatives such as ethylhexyl) fumarate; trimellitic acid derivatives such as tree (2-ethylhexyl) trimellitate, tree n-octyl trimellitate, triisooctyl trimellitate, tree n-hexyl trimellitate; Ethyl hexyl) pyromellitic acid, pyromellitic acid derivatives such as tetra-n-octyl pyromellitate; citric acid derivatives such as triethyl citrate, acetyl triethyl citrate, acetyl tri- (2-ethylhexyl) citrate; Itaconic acid derivatives such as louitaconate, monobutyl itacolate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate; oleic acid derivatives such as butyl oleate, glyceryl monooleate, diethylene glycol monooleate; glyceryl monoricinoleate, diethylene glycol monolith Ricinoleic acid derivatives such as sinolate; stearic acid derivatives such as glycerin monostearate and diethylene glycol distearate; other fatty acid derivatives such as diethylene glycol monolaurate, diethylene glycol dipelargonate and pentaerythritol fatty acid esters; tributyl phosphate, tree (2 -Ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, etc. Phosphoric acid derivatives; glycol derivatives such as diethylene glycol dibenzoate, dipropylene glycol dibenzoate, and dibutylmethylene bisthioglycolate; glycerin derivatives such as glycerol monoacetate, glycerol triacetate, and glycerol tributyrate; adipic acid-based polyester, sebacic acid-based polyester And polyester plasticizers such as phthalic acid polyesters; diallyl phthalates, polymerizable plasticizers such as acrylic monomers and oligomers, etc., among which phthalic acid ester-based, adipic acid ester-based and citric acid-based esters The system type is preferred. These plasticizers may be used alone or in combination of two or more. The content of the plasticizer is 30 to 100 parts by weight, preferably 35 to 80 parts by weight, and more preferably 40 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 becomes high and the processability may become difficult. If the amount is more than 100 parts by weight, the product may become sticky or soft, and the shape may not be stable.

4) Foaming agent A known foaming agent for forming a foamed molded article using vinyl chloride plastisol can be used without any limitation. Specific examples thereof include azodicarbonamide, azobisisobutyro Azo compounds such as nitrile and diazoaminobenzene, nitroso compounds such as dinitrosopentamethylenetetramine, N, N-dinitroso-N, N-dimethylphthalamide, p-toluenesulfonyl hydrazide, 4,4-oxybis (benzenesulfonyl hydrazide), etc. Sulfonyl hydrazide compounds, and foamable balloons such as microcapsules. The amount used is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight per 100 parts by weight of the vinyl chloride resin. If the amount is less than 0.1 parts by weight, the foam may not be obtained. On the other hand, if the amount is more than 10 parts by weight, uniform foam cells may not be obtained, and the surface of the foam may not be smooth.

5) Additives Various additives can be used as long as the effects of the present invention are not impaired.
Examples of inorganic compounds include aluminum hydroxide, magnesium hydroxide, silica, talc, clay, diatomaceous earth, mica, and alumina. Further, titanium white (titanium oxide) cadmium yellow (cadmium sulfide), chrome yellow (chromic acid). Lead), thiomonox (antimony trioxide), white lead (basic lead carbonate), bengara (iron sesquioxide), inorganic flame retardants such as antimony trioxide, inorganic gels such as calcium silicate and silica aerosil An inorganic filler such as an inorganic kicker such as zinc oxide.
Said inorganic compound may be added combining 1 type (s) or 2 or more types as needed.
Further, heat and light stabilizers such as zinc octoate, calcium stearate, or zinc salts, cadmium octoate, barium ricinoleate and the like may be added. What was disperse | distributed to the plasticizer and the high boiling point liquid component can also be used.
In addition, additives such as an ultraviolet absorber, an antioxidant, and an antifungal agent may be added as long as the effects of the present invention are not impaired.

6) Diluent In the present invention, an organic solvent may not be used as a diluent. However, when used, the organic solvent component having a boiling point of 60 to 290 ° C. at normal pressure is 2.0% by weight or less. It is good. When there are more organic solvent components than this, the volatile component contained in the product after shaping | molding will increase, and it may cause a sick house. The organic solvent component having a boiling point of 60 to 290 ° C. is preferably 1.0% by weight or less, more preferably 0.1% by weight or less. It is desirable that the organic liquid component other than the plasticizer is as small as possible in the composition.

(2) Preparation of plastisol The plastisol is prepared by mixing, stirring and mixing the above-described plastisol components. As a mixer for plastisol, a normal one, for example, a Henschel mixer, a twin screw mixer, a butterfly mixer, a single screw dissolver, a pony mixer, a Hobart mixer, or the like is used.

(3) Product As a manufacturing method of the product, various methods can be used depending on the product, and examples thereof include a coating molding method, a dipping molding method, a slush molding method, a casting molding method, a rotational molding method and the like. However, the vinyl chloride plastisol composition of the present invention is optimal for foams.
As a method for producing a foam, a known method for forming a foam is adopted. For example, plastisol is applied to a substrate such as paper using a knife coater, comma coater, die coater, and the like, and is heated and solidified. After that, if necessary, a method of performing printing or surface treatment and heating and foaming can be mentioned.
Furthermore, the foam is embossed as necessary to improve the design. Since the vinyl chloride plastisol composition of the present invention is excellent in embossing, particularly mechanical embossing, it is particularly suitable for the production of products with mechanical embossing.
The use of the vinyl chloride foam-molded article of the present invention is not particularly limited, and can be suitably used as long as it is a foam-molded article such as wallpaper, cushion floor, tile carpet, toy, daily goods, etc. It is preferable to be used in wallpaper applications and cushion floor fields where physical properties such as surface smoothness and embossing are important.

(1) The vinyl chloride plastisol composition of the present invention has a low viscosity and can be molded at high speed, and can avoid troubles such as uneven thickness and blade back leakage during coating molding.
Moreover, the product obtained is excellent in surface smoothness, has few troubles such as cell puncture during embossing, and has a good appearance.
(2) Since the present plastisol composition can be easily processed with a very small amount even if it does not use or uses a volatile organic solvent as a diluent, the total VOC ( Volatile organic components) A product with a small amount of generation can be provided.
Therefore, in the present invention, the sol viscosity is extremely low, and particularly the diluent (volatile organic liquid) can be reduced as much as possible. Therefore, the present invention is optimal for applications where the presence of the volatile organic liquid is a problem (building materials, cushion floors). , Its usefulness is very high.

  Hereinafter, although an example etc. are given and the present invention is explained still in detail, the present invention is not limited to these. “Parts” means “parts by weight” unless otherwise specified.

Measurement of physical properties and evaluation of physical properties in Examples and the like were performed by the following methods.
<Particle size distribution>
Using a laser diffraction / scattering particle size distribution analyzer (La910W: manufactured by HORIBA, Ltd.), the sample was stirred in di-2-ethylhexyl adipate, irradiated with ultrasonic waves for 5 minutes, and then measured with a refractive index of 1.15 under stirring.

<Surface smoothness>
The following five-step evaluation was performed by visual inspection.
A: Very smooth surface B: Slightly small unevenness
Δ: Small unevenness as a whole.
X: In addition to small irregularities, there are slightly large irregularities.
XX: There are large unevenness as a whole.
<Serpunk properties>
Using a far-red embossing machine (infrared furnace: manufactured by Sankei Co., Ltd., embossed part: manufactured by Matisse Co., Ltd., furnace length: 2 m), a foam having a size of A3 was heated at 220 ° C. at 4 m / min. The foam was embossed and the number of cell punctures was observed.

<Viscosity>
・ Low shear viscosity (1.25 sec ^-1 )
A paste sol was prepared in an atmosphere of 23 ° C. and 50% RH and allowed to stand in the same atmosphere for 1 hour. Then, using a BL type viscometer (VISCOMETER TV-30: manufactured by Tokyo Keiki Co., Ltd.), a BL viscometer No. Measurement was carried out at 6 rpm using a 4-rotor.
・ High shear viscosity (1500 sec ^-1 )
A paste sol was prepared in an atmosphere of 23 ° C. and 50% RH, and left for 1 hour in the same atmosphere. Then, using a capilograph (CAPIROGRAPH 1C: manufactured by Toyo Seiki Co., Ltd.), a die diameter of 1.0 mm and a die length Measurement was performed with a nozzle of 10.1 mm.
A low shear viscosity is suitable for transporting plastisol to a molding machine, and a low high shear viscosity indicates excellent coating suitability.

<Thickness unevenness>
The thickness of the semi-gel original fabric coated with plastisol and dried on paper was measured at 100 points for each 1 cm in the coating direction, and the difference between the maximum value and the minimum value was defined as uneven thickness.

<B ^* value>
The measurement was performed using Nippon Denshoku VG2000.
Note that the smaller the B ^* value, the better the whiteness.

<Edge leakage test>
A cylindrical roll made of stainless steel having a diameter of 200 mm and a height of 150 mm is installed at a distance of 159 rpm on a test machine in which a comma coater is installed so that the distance between the roll and the roll is 150 μm. 50 ml of plastisol was dropped on it, and the time until the plastisol flew from the back of the comma coater was measured.

<Cell status>
Using a CCD camera, the cross section of the foam was observed and visually evaluated as the following five-step evaluation.
A: The cell is very dense.
○: Slightly small cell roughness is observed.
Δ: Small cell roughness as a whole Δ-X: In addition to small cell roughness, there is some large cell roughness.
X: There is large cell roughness overall.

<Flexibility>
The touch when the foam was touched by hand was evaluated according to the following five grades.
1: Hard.
2: Feels slightly hard 3: Appropriate flexibility.
4: Feels slightly soft.
5: Soft.

(Example 1)
1. Preparation of calcium carbonate 2 kg of calcium carbonate (Cold Water 70: manufactured by Nitto Flour Chemical Co., Ltd.) is placed in a ball mill pot (5 L) containing steel ball balls, and pulverized for 24 hours with a ball mill (manufactured by Chuo Kako Trading Co., Ltd.). It was. Thereafter, the sieves of 200 mesh and 500 mesh were overlapped, and the pulverized calcium carbonate was put on the 200 mesh, and the classification process was performed for 30 minutes while vibrating to obtain calcium carbonate from which coarse particles and fine particles were removed on the 500 mesh sieve. .
Next, the particle size of the obtained calcium carbonate was stirred in a di-2-ethylhexyl adipate using a laser diffraction / scattering particle size distribution measuring device (La910W: manufactured by HORIBA, Ltd.), irradiated with ultrasonic waves for 5 minutes, When measured with a refractive index of 1.15 under stirring, the cumulative frequency of particles larger than 150 μm was 0.1%, and the mode diameter was 45 μm. Further, when the B ^* value was measured with a color difference meter, it was +0.3.

2. Manufacture of vinyl chloride resin <Polymerization>
A 100 L glass-lined autoclave was degassed, charged with 40 kg of deionized water, 16 kg of vinyl chloride monomer, 140 g of sodium lauryl sulfate, 240 g of stearyl alcohol, and 7.5 g of lauryl peroxide, and homogenized with a homogenizer, 63 ° C. The temperature was raised to 0 and polymerization was started. When the pressure in the reactor dropped by 0.05 MPa, the polymerization was stopped and the unreacted monomer was recovered to obtain an aqueous dispersion of vinyl chloride resin.

<Dry>
To the aqueous dispersion, 0.4 parts of sodium lauryl sulfate, 0.4 parts of polyoxyethylene alkyl ether and 1.0 part of zinc chloride are added per 100 parts of the polymer, and the mixture is stirred and homogenized. By spray drying with a rotary atomizer type manufactured by Niro Co., Ltd., a vinyl chloride resin powder was obtained.

3. Preparation of plastisol 80 g of calcium carbonate of 1 above, 100 g of vinyl chloride resin of 2 above, 60 g of diisononyl phthalate (CG: manufactured by Esther Co.) as a plasticizer, 12 g of titanium oxide (R900: manufactured by DuPont) as an inorganic pigment, Ba / 4 g of Zn-based stabilizer (KF705E: manufactured by Kyodo Yakuhin Co., Ltd.), 3 g of azodicarbonamide (AZH-25: manufactured by Otsuka Chemical Co., Ltd.) as a foaming agent, and 5 g of a viscosity reducing agent (BKY20386: manufactured by Big Chemie) Was kneaded using a dissolver to obtain a plastisol.

4). Manufacture of semi-gel sheet Using a coating machine equipped with a comma coater (multi-coater: manufactured by Nishimura Machinery Co., Ltd.), the above 3 plastisol with a thickness of 150 μm is coated on a paper with a width of 100 cm and a thickness of 110 μm. A semi-gel sheet was obtained by passing through (manufactured by Sankei Co., Ltd., furnace length 2 m) (stay time 25 seconds).

5). Production of Foam The semi-gel sheet of 4 above was cut into A3 size and foamed in a hot air oven (made by Matisse Co., Ltd.) at 215 ° C. for 50 seconds to obtain a foam.
The surface was very smooth.

6). Embossing Using the above 5 foam, using a far-infrared embossing machine (infrared furnace: manufactured by Sankei Co., Ltd., embossed part: manufactured by Mathis Co., Ltd., furnace length: 2 m), 220 ° C., 4 m / min (stay time) 30 seconds), the foam was sandwiched between an embossing roll and a rubber roll and embossed.
The emboss was clean and observed the number of serpunks, but was not recognized at all.
The resulting product is optimal as wallpaper.

(Example 2)
In preparation of the calcium carbonate of Example 1, it replaced with the sieve of 200 mesh and 500 mesh used for classification, and performed similarly to Example 1 except having used the sieve of 170 mesh and 500 mesh.

(Example 3)
In preparation of the calcium carbonate of Example 1, it replaced with the sieve of 200 mesh and 500 mesh used for classification, and performed similarly to Example 1 except having used the sieve of 250 mesh and 500 mesh.

Example 4
In preparation of the calcium carbonate of Example 1, it replaced with the sieve of 200 mesh and 500 mesh used for classification, and performed similarly to Example 1 except having used the sieve of 115 mesh and 500 mesh.

(Example 5)
In preparation of the calcium carbonate of Example 1, it replaced with the sieve of 200 mesh and 500 mesh used for classification, and performed similarly to Example 1 except having used the sieve of 325 mesh and 500 mesh.

(Example 6)
In the preparation of calcium carbonate in Example 1, the same procedure as in Example 1 was performed, except that the sieves used for classification were replaced with the sieves of 200 mesh and 500 mesh, and the sieves of 115 mesh and 500 mesh were used.

(Example 7)
In the preparation of calcium carbonate of Example 1, grinding was performed for 36 hours instead of 24 hours, and classification was performed except that 100 mesh and 500 mesh sieves were used instead of 200 mesh and 500 mesh sieves. The same procedure as in Example 1 was performed.

(Example 8)
In Example 7, classification was performed in the same manner as in Example 7 except that classification with a sieve was performed for 1 hour instead of 30 minutes.

Example 9
1. Manufacture of vinyl chloride resin Add 120 parts by weight of water to a premixer and add 0.5 parts by weight of a mixed alcohol having 10 to 18 carbon atoms (melting point: 25 ° C.) mainly composed of lauryl alcohol while stirring at 28 ° C. Then, 0.8 part by weight of sodium dodecylbenzenesulfonate was added to prepare an emulsion. Next, 0.07 part by weight of 50% by weight n-hexane solution of diisopropylperoxydicarbonate was added thereto, and nitrogen substitution and vacuum degassing were repeated twice. Subsequently, 100 parts by weight of vinyl chloride was charged, premixed by stirring for 30 minutes at a power required for net stirring of 0.95 kW / m ³ , and then homogenized with a two-stage high-pressure homogenizer.
Next, it is transferred to another deaerated 10 liter pressure-resistant reactor similar to the above, and the temperature is increased while stirring under mild conditions for heat transfer, and fine suspension polymerization is performed at 62 ° C. It was. When the polymerization conversion rate reached 90% by weight, the mixture was cooled and the unreacted monomer was removed to obtain a safe aqueous dispersion of polymer particles with almost no scale. Next, the polymer particle aqueous dispersion was dried with a spray dryer and pulverized with a hammer mill to obtain a vinyl chloride resin.

2. Preparation of plastisol The same procedure as in Example 1 was conducted except that the vinyl chloride resin of 1 was used instead of the vinyl chloride resin of Example 1.

3. Production of semigel sheet The same procedure as in Example 1 was performed.

4). Production of foam The same procedure as in Example 1 was performed.

5). Embossing The same as in Example 1.

(Example 10)
1. Foamed layer plastisol The plastisol of Example 1 was used.

2. Preparation of top layer plastisol 100 g of vinyl chloride resin (PQHH: manufactured by Shin Daiichi Vinyl Co., Ltd.), 60 g of diisononyl phthalate (CG: manufactured by Esther Co., Ltd.) as a plasticizer, Ba / Zn-based stabilizer (KF705E: joint chemical ( 4 g) and 5 g of a viscosity reducing agent (BKY20386: manufactured by Big Chemie) were kneaded using a dissolver to prepare a plastisol.

3. Preparation of a semi-gel sheet By using a coating machine (Matis oven) equipped with a knife coater, the foamed layer plastisol 1 was coated on a large A3 glass paper with a thickness of 300 μm using a knife coater. .
The resulting coating was then heated in a microwave for 30 seconds to obtain a foamed semi-gel sheet.
Next, on the obtained semigel sheet, the above plastisol 2 was coated with a top layer having a thickness of 200 μm, and heated in a microwave oven for 30 seconds to obtain a semigel sheet.

4). Production of Foam The semigel sheet obtained in 3 above was foamed at 215 ° C. for 50 seconds in a hot air oven (manufactured by Matisse) to obtain a foam.
The surface of the foam was very smooth.

5). Embossing Using the far-red embossing machine (infrared furnace: manufactured by Sankei Co., Ltd., embossed part: manufactured by Matisse Co., Ltd., furnace length: 2 m), the foam obtained in 4 above is 220 ° C., 4 m / min. After heating at (stay time 30 seconds), the foam was sandwiched between an embossing roll and a rubber roll and embossed.
The emboss was clean and observed the number of serpunks, but was not recognized at all.
The resulting product is optimal as a cushion floor.

(Comparative Example 1)
In the preparation of the calcium carbonate of Example 1, grinding is performed for 36 hours instead of 24 hours, classification is performed using 200 mesh and 500 mesh sieves, and coarse particles are placed on a 500 mesh sieve. Instead of obtaining calcium carbonate from which fine particles had been removed, classification was carried out using only a 500 mesh sieve, and the same procedure as in Example 1 was carried out except that calcium carbonate passed through a 500 mesh sieve was used.

(Comparative Example 2)
In Example 7, classification was performed in the same manner as in Example 7 except that classification with a sieve was performed for 2 hours instead of 30 minutes.

(Comparative Example 3)
In the preparation of the calcium carbonate of Example 1, it carried out similarly to Example 1 except having used the sieve of 100 mesh and 500 mesh instead of the sieve of 200 mesh and 500 mesh.

(Examples 11 to 15)
In the preparation of the plastisol of Example 1, the same procedure as in Example 1 was performed except that the blending amounts of calcium carbonate and the plasticizer diisononyl phthalate were changed to the blending amounts shown in Table 2.
The results of Examples 1 to 10 and Comparative Examples 1 to 3 are shown in Table 1, and the results of Examples 11 to 15 are shown in Table 2.

  From the results of Tables 1 and 2, regarding the particle size distribution of calcium carbonate as the inorganic filler, (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 or less. When the two requirements are satisfied at the same time, the intended purpose of the present invention can be achieved. However, if either of the two requirements is absent, the intended purpose of the present invention cannot be achieved. From this, it can be seen that the definition of the particle size distribution of the calcium carbonate of the present invention has a particular significance.

The vinyl chloride plastisol composition of the present invention has a low viscosity and can be molded at high speed, and can avoid troubles such as thickness unevenness and blade back leakage during coating molding. In addition, the product obtained is excellent in surface smoothness, has few troubles such as cell puncture during embossing, and has a good appearance, and thus can be applied to various products. It can be optimally used especially for applications such as wallpaper and cushion floors.

Claims (6)

  In a vinyl chloride plastisol composition comprising a vinyl chloride polymer, a plasticizer, and an inorganic filler, as an inorganic filler, (1) the cumulative frequency (volume basis) of particles larger than 150 μm is 5% or less, and (2 ) A vinyl chloride plastisol composition comprising calcium carbonate having a particle size distribution with a mode diameter of 30 μm to 100 μm.   The vinyl chloride plastisol composition according to claim 1, which comprises 30 to 100 parts by weight of a plasticizer and 30 to 200 parts by weight of calcium carbonate according to claim 1 with respect to 100 parts by weight of the vinyl chloride polymer.   The vinyl chloride plastisol composition according to claim 1 or 2, wherein the vinyl chloride plastisol composition contains a foaming agent.   A foam-molded product obtained by foam-molding the plastisol composition according to claim 3.   The foamed molded product according to claim 4, wherein the foamed molded product is embossed. The foamed molded product according to claim 4 or 5, wherein the foamed molded product is a wallpaper or a cushion floor.