JP2005264036A - Vinyl chloride-based resin particle for paste and its composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a vinyl chloride-based resin for paste, giving a sol with very low viscosity, enabling it to use for thin-film coating at a high speed without using any diluent or using it only in a very small amount. <P>SOLUTION: The vinyl chloride-based resin particle for paste is characterized by the followings, When dividing the particle diameters in the range of 0.1-200 μm into a plurality of classes, the dividing is carried out to make 56 classes so that the value of the difference between the maximum and minimum particle diameter common logarithm values in each the class, becomes equal. When setting the particles in the range of 0.10-10.10 μm particle diameter as 100% by volume, the ratio of particles in each the class in the range of 0.34-2.27 μm particle diameter, is at least 3.0% by volume in all individual classes. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a vinyl chloride resin particle for paste and a composition thereof. More specifically, the present invention relates to a vinyl chloride resin particle for paste and a composition thereof having a low sol viscosity when a composition (hereinafter also referred to as sol) is prepared using vinyl chloride resin particles and a plasticizer.

Since the vinyl chloride resin composition for paste has excellent properties such as flame retardancy, it also has excellent workability, so it can be used for wall materials, flooring materials, leather, canvas, vehicle interior parts, steel plate coats, cotton It is used in the manufacture of products such as material coats, yarn coats, work gloves, toys, and sundries, and is extremely useful. For this reason, various methods have been developed for producing a vinyl chloride resin for paste and a composition thereof.
In the production of a vinyl chloride polymer for paste, polymerized particles having a particle size of about 0.1 μm to about 100 μm can be obtained by finely suspending (microsuspension) or emulsion (emulsion) polymerization of the monomer in an aqueous medium. Polymerized particles obtained by normal polymerization have a particle size distribution with one peak in the frequency distribution. When a sol was prepared using these vinyl chloride polymer particles and a plasticizer, it was difficult to perform thin film coating at high speed because the sol viscosity was high in a high shear region.
In order to reduce the viscosity of the sol, polymerization is performed a plurality of times to produce polymer particles having different particle sizes (or particle size distributions), and these are mixed to form polymer particles having a distribution of two or more peaks in the frequency distribution. Has also been done.
However, even if this polymer particle is used, the sol viscosity in a high shear region is not yet sufficiently low. Therefore, in high-speed coating applications such as vinyl wallpaper production that needs to be applied to a thin film, it is necessary to adjust the viscosity. In general, a volatile organic liquid component (also referred to as a diluent or a viscosity adjusting solvent) is added for processing.

For example, polyvinyl chloride resin particles (A) having a particle diameter of 0.01 μm or more and less than 0.45 μm are 30 to 50% by weight, and polyvinyl chloride resin particles having a particle diameter of 0.45 μm or more and less than 4.5 μm. The polyvinyl chloride resin particles (C) having 35 to 55% by weight of (B) and a particle size of 4.5 to 20 μm are composed of 10 to 30% by weight, and the average particle size in the granules is 20 to 130 μm. A polyvinyl chloride resin granule for paste processing (Patent Document 1), characterized in that the particle diameter is distributed in a range of at least 0.2 to 10 μm, and particles (component A) less than 0.5 μm, The distribution of 0.5 to 4 μm particles (component B), 4 μm or more (component C) is 10 to 30% by weight of component A, and the weight ratio of components B and C is (B) / (C) = 30 / It is characterized by being 70-60 / 40 Although there is a polyvinyl chloride resin for paste processing (Patent Document 2), etc., even if these polymers are used, since the sol viscosity is still high, a diluent is actually used. It is a fact.
And as a method of 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, and (A) the particle size distribution is less than 2 μm, 15 to 55% by weight of particles having a peak distribution diameter of 0.2 to 1.5 μm, (B) less than 15% by weight of particles of 2 μm to less than 4 μm, and (C) having a particle size distribution of 4 μm or more. There is a vinyl chloride resin (Patent Document 3) characterized in that the distribution is composed of 40 to 80% by weight of particles having a 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.

JP-A-9-309998 JP 2003-238621 A Japanese Patent Laid-Open No. 10-231322

Thus, even in the case of using a low-viscosity polymer as described above, in high-speed coating applications such as vinyl wallpaper production that needs to be applied to a thin film, the viscosity of the sol is still high. It was common to add a diluent.
However, in recent years, chemical substances from building materials by sick houses have become a problem, and it is desired that the total VOC (volatile organic component) is also low from the viewpoint of human health. That is, it is desired that as little volatile organic components as possible remain in the product. Therefore, it is desirable that the sol as the raw material has as little volatile organic components as possible.
And, when coating thin films at high speed, those with extremely low viscosity are required, but those that do not use any diluent or have extremely low sol viscosity even at very small use amounts have been developed. The current situation is not.
Therefore, the development of a vinyl chloride resin for paste that can produce a sol with a very low viscosity that can be used for a thin film coating at high speed even without using a diluent at all or even in a very small use amount is awaited. .

  It is an object of the present invention to provide a vinyl chloride resin for pastes that can be used for thin film coating at high speed without using any diluent or with a very small amount of use, and that can provide a sol with a very low viscosity. There is to do.

  The inventors of the present invention have made extensive studies in order to solve the above-described problems. As a result, by giving the vinyl chloride resin particles a specific particle size distribution, a diluent is not used or very little. As a result of finding that a sol having a very low viscosity can be obtained even in use and further researching it, the present invention has been completed.

The present invention comprises the following inventions.
1． In dividing the particle diameter of 0.1 to 200 μm into a plurality of sections, the section is divided into 56 sections so that the difference in the common logarithm of the upper and lower particle diameters of each section is equal, and the particle diameter of 0.10 to 10 When the particles contained in the range of 10 μm are defined as 100% on a volume basis, the proportion of particles existing in each section in the section having a particle diameter of 0.34 to 2.27 μm is based on the volume in any section. Vinyl chloride resin particles for paste, characterized by being 3.0% or more.
2. (1) The vinyl chloride resin particles described in 1 above, (2) a plasticizer, (3) an organic liquid having a boiling point of 60 to 300 ° C. at normal pressure, and the total amount of these components is 100% by weight. And the component (1) is 25 to 75% by weight, the component (2) is 25 to 75% by weight, and the component (3) is 0 to 2.0% by weight. Composition.

When the vinyl chloride resin particles for paste of the present invention are divided into a plurality of sections with a particle diameter of 0.1 to 200 μm, the difference in the common logarithm of the upper and lower particle diameters of each section is equal. When the particles contained in the range of particle size 0.10 to 10.10 μm are defined as 100% on the basis of volume, the particles existing in each category in the particle size range 0.34 to 2.27 μm The ratio is 3.0% or more on a volume basis in any of the categories.
The resin composition of the present invention has a very low sol viscosity even when no diluent is used or very little use, and can be used for high-speed thin film coating. Is.

The present invention has been made based on the following findings.
(1) Since the conventional vinyl chloride resin particle composition for paste has a high sol viscosity, the sol viscosity is reduced by using a diluent.
However, in recent years, it has been found that the presence of a diluent is not preferred depending on the application (wallpaper, etc.), and the use of a diluent as little as possible, that is, the development of vinyl chloride resin particles for pastes having a low sol viscosity. Became.
However, what has been developed for the above-mentioned purposes has very little need to use a diluent, and even if so, a very low viscosity sol that can be used for high-speed thin film coating is obtained. There was nothing to be done.
(2) Under such circumstances, when searching for a method of obtaining vinyl chloride resin particles for pastes that can be used for high-speed thin film coating and become a sol with an extremely low viscosity, a specific method for vinyl chloride resin particles It has been found that vinyl chloride-based resin particles for paste that give a very low viscosity sol can be obtained simply by having a particle size distribution without using a diluent.
(3) That is, when the vinyl chloride resin particles divide the particle diameter of 0.1 to 200 μm into a plurality of sections, the difference in the common logarithm of the upper and lower particle diameters of each section is equal. The number of particles existing in each section in the section having a particle diameter of 0.34 to 2.27 μm is divided into 56 sections and the particle size in the range of 0.10 to 10.10 μm is defined as 100% by volume. It has been found that when the ratio is 3.0% or more on a volume basis in any of the categories, vinyl chloride resin particles for paste having extremely low viscosity characteristics can be obtained.
In any case, the vinyl chloride resin particles for paste of the present invention have a very low sol viscosity and can be used for thin film coating at high speed without using a diluent (volatile organic liquid). Therefore, it is most suitable for applications (building materials) where the presence of volatile organic liquid is a problem, and its usefulness is very high.

Hereinafter, the present invention will be described in more detail.
When the vinyl chloride resin particles for paste according to the present invention are divided into a plurality of sections with a particle diameter of 0.1 to 200 μm, the difference between the common logarithm values of the upper and lower particle diameters of each section becomes equal. The number of particles existing in each section in the section having a particle diameter of 0.34 to 2.27 μm is divided into 56 sections and the particle size in the range of 0.10 to 10.10 μm is defined as 100% by volume. The ratio is characterized by being 3.0% or more on a volume basis in any of the categories.
Therefore, the above-described configuration requirements and applications of the present invention will be described below.

(1) Vinyl chloride resin particles The degree of polymerization of the vinyl chloride diameter resin of the present invention is not particularly limited, but is usually 400 or more and may contain a gel component (tetrahydrofuran insoluble component). Preferably it is 600-2000. When a polymer having a degree of polymerization of less than 600 is used, the polymer is poor in thermal stability and easily colored yellow. In addition, product strength may be reduced. When a polymer having a degree of polymerization of more than 2000 is used, the foamability and moldability (gelability) are adversely affected, so that productivity and designability are likely to deteriorate.
For production of the vinyl chloride resin particles of the present invention, a known method carried out in an aqueous medium is employed without any particular limitation. Examples of the copolymerizable monomer include vinyl acetate, ethylene, vinylidene acetate, acrylonitrile, diallyl phthalate, and allyl methacrylate. Usually, the content of these components is preferably 20 mol% or less.
The vinyl chloride resin particles of the present invention require a more trapezoidal distribution in the volume-based frequency distribution. That is, when the particle diameter in the range of 0.10 to 10.10 μm is defined as 100%, the volume reference frequency is 3.0% or more in all the sections in the particle diameter range of 0.34 to 2.27 μm. It is necessary to be. Preferably, the volume reference frequency is 3.0 or more in all sections in the expanded particle size range, that is, the particle size range of 0.34 to 2.60 μm. If the particle size range with a frequency of 3.0% or more is narrower than this, or if there is a segment of less than 3% in the middle, the particle size distribution will be distorted and the sol will not have low viscosity.
In order to obtain a sol having a lower viscosity, the volume reference frequency is 3.0 or more in all sections in the particle diameter range of 0.34 to 2.60 μm, and all in the particle diameter range of 0.10 to 10.10 μm. The volume reference frequency of the section is preferably 8.0% or less, and more preferably 7.0% or less. That is, there is no peak protruding in the range of 0.10 to 10.10 μm (exceeding 8.0%), and the particle size is set so that there is as little deviation as possible in the range of 0.34 to 2.60 μm. It is important to distribute.
More preferably, the volume reference frequency is 3.5% or more and the particle diameter is 0.10 to 10.10 μm in all the sections of the expanded particle diameter range, that is, the particle diameter range of 0.34 to 2.60 μm. The volume reference frequency is 7.0% or less in all sections of the range.
In the present invention, the particles contained in the range of 0.34 to 2.27 μm may be 42% by volume or more with respect to the vinyl chloride resin particles in the range of 0.10 to 10.10 μm. Required (because 14 categories are included). Preferably it is 50 volume% or more, More preferably, it is 60 volume% or more.

Vinyl chloride resin particles having such a particle size distribution can be obtained by various methods. For example, emulsion polymerization with different particle diameters can be carried out a plurality of times and these can be mixed to obtain a seed method. Further, resin particles obtained by fine suspension polymerization or suspension polymerization may be used.
The vinyl chloride resin particles having a particle diameter outside the range of 0.10 to 10.10 μm can be optionally included. The addition amount is not particularly limited, but it is desirable that particles having a particle diameter of less than 0.10 μm are not contained as much as possible. When a large amount of particles of less than 0.10 μm are contained, the sol viscosity in the low shear region tends to increase. Particles having a particle diameter of less than 0.10 μm are preferably less than 10% by volume of particles having a particle diameter in the range of 0.10 to 10.10 μm. On the other hand, particles having a particle diameter of more than 10.10 μm may lower the sol viscosity and may be included to some extent, but if included in a large amount, the design and surface smoothness of the product deteriorate.
Accordingly, the particle size exceeding 10.10 μm is preferably 40% by volume or less, more preferably 20% to 0% by volume, relative to the particles having a particle diameter in the range of 0.10 to 10.10 μm.

(2) Vinyl chloride resin particle composition The vinyl chloride resin particle composition of the present invention is characterized in that the vinyl chloride resin particle component has a specific particle size distribution. It is also included that the vinyl chloride resin particle component has its particle size distribution. That is, even if a plurality of (several types) of vinyl chloride resin particles are mixed to prepare a sol, the viscosity of the sol is lowered if the vinyl chloride resin particle component contained in the sol satisfies the particle size distribution of the present invention. .

1) Organic liquid component In the vinyl chloride resin particle composition of the present invention, the organic liquid component may not be used, but when used, the organic liquid component having a boiling point of 60 to 300 ° C at normal pressure is 2. It is essential that the amount is 0.0% by weight or less. When there are more organic liquid components than this, the volatile component contained in the product after shaping | molding will increase, and it may cause a sick house. The organic liquid component having a boiling point of 60 to 300 ° 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) Other components In the present invention, for example, plasticizers and additives can be used as other components.
(Plasticizer)
The plasticizer is an essential component as a compounding agent for plastisol. The plasticizer is an important component because the sol fluidity, viscosity stability, processability such as gelling and melting properties, and the properties of the molded product are determined depending on the type or amount of use of the plasticizer.
Examples of the plasticizer include, but are not limited to, for example, phthalic acid esters such as dioctyl phthalate (DOP) and diisononyl phthalate (DINP), adipic acid such as dioctyl adipate (DOA) and diisononyl adipate (DINA) Preference is given to esters, citrate esters such as acetyltributyl citrate (ATBC), sulfonate esters such as Bayer brand name mezamol, trioctyl trimellitic acid ester (TOTM), epoxidized soybean oil, etc. Used.
The amount of plasticizer used is preferably 25 to 75% by weight. If it is less than 25% by weight, the product is hard, and if it is more than 75% by weight, it becomes difficult to mold the product. Usually, the boiling point of these plasticizers exceeds 300 ° C. at normal pressure. It is better not to use a boiling point of 300 ° C. or less at normal pressure. Also, a plasticizer that contains as little impurities as possible as volatile components is desirable.

(Additive)
If necessary, this composition can be used as a stabilizer for inorganic powders such as calcium carbonate, titanium oxide, silica, calcium chloride / zinc-based, barium / zinc-based, tin-based and lead-based vinyl chloride polymers, diazo Organic foaming agents such as carbonamide (ADCA), thermally expandable microcapsules, and the like can also be used in combination. Further, a non-vinyl chloride resin may be used in combination.
Although the usage-amount of an additive is not specifically limited, 500 weight% or less is preferable in total with respect to the composition of this invention, More preferably, it is 0-300 weight%. When other components are contained in excess of 500% by weight, the concentration of the vinyl chloride resin particle component is lowered, so that it is difficult to form the sol by heating.
In the present invention, when powdered calcium carbonate is included as a component of the vinyl chloride resin particle composition, when the specific surface area of the calcium carbonate is 200 to 4000 cm ² / g or less, the sol viscosity is markedly increased. I found it to decrease.
This is considered to be because when the vinyl chloride resin particles of the present invention are combined with the above-mentioned specific calcium carbonate, the particle size distribution of the solid particles in the sol works well on the sol viscosity.
When the specific surface area of calcium carbonate is less than 200 cm ² / g, since the particle diameter is large, the surface smoothness becomes poor when a sol is formed into a thin film. On the other hand, when the specific surface area exceeds 4000 cm ² / g, the viscosity of the sol is relatively high.
As for the amount of calcium carbonate added. 10-300 weight% is preferable with respect to the composition of this invention, More preferably, it is 40-200 weight%. Usually, calcium carbonate for wallpaper has a specific surface area of 5000 to 10000 cm ² / g, and the composition of the present invention containing such calcium carbonate can be suitably used particularly for wallpaper. .

(3) Use The manufacture of the product from the vinyl chloride resin composition for the present paste involves first preparing a plastisol, then forming (shaping), gelling, subsequently heating and melting, and then cooling. It is carried out by a method of obtaining a desired molded body. Hereinafter, this point will be described.

1) Preparation of plastisol Preparation of plastisol requires that a vinyl chloride resin composition for paste and a compounding agent such as a plasticizer or an additive are mixed and uniformly dispersed.
This is because, as described above, insufficient dispersion not only causes the problem that the viscosity varies depending on the mixing batch or the dispersion progresses during storage, resulting in large viscosity fluctuations. Physical properties such as deterioration of the surface smoothness of the product will be deteriorated.
As a mixer for preparing plastisol, an ordinary one, for example, a uniaxial dissolver, a biaxial mixer, a butterfly, a pony, a Hobart mixer, or the like is used.

2) Molding method As the molding method for shaping, various methods can be used depending on the product.
For example, a coating molding method, a dipping molding method, a slush molding method, a casting molding method, a rotational molding method and the like can be mentioned.
The molded body shaped by the above method is heated to be gelled and fixed in shape. The heating method is performed by a normal method, for example, an oven, a tunnel type heating furnace or the like. The temperature is about 120 to 150 ° C. according to the resin used.
Subsequently, the gelled molded body is heated and melted to 160 to 250 ° C. and then cooled to obtain a final product.

3) Products Various products can be manufactured by the above molding method. For example, the following are mentioned.
Coating molding (floor materials, wall materials, steel plates, leather, films, etc.), dipping molding (electric parts, industrial parts, gloves, sundries, etc.), slash molding (boots, toys, automotive interior materials, etc.), cast molding (cans) Seals, food samples, etc.), rotational molding (automobile interior materials, toys, etc.).
The vinyl chloride resin composition for paste according to the present invention is optimal for interior materials such as wallpaper, because it does not use any diluent (organic liquid) or only a small amount can be used.

By using the vinyl chloride resin particles of the present invention, the viscosity of the composition containing a plasticizer can be lowered.
Therefore, since it can be easily processed with a very small amount even if it does not use an organic liquid component as a diluent, even if it is used, the amount of total VOC (volatile organic component) generation is small. Products can be provided.
As described above, the sol viscosity of the present invention is extremely low, and it is not particularly necessary to use a diluent (volatile organic liquid). Therefore, the use of the volatile organic liquid is a problem (building materials) or the like. It is optimal and 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.
Measurement of particle size distribution and the like in each of the following examples was performed by the following method.
(Particle size distribution)
The particle size distribution of the present invention was measured using a laser light scattering method, and the measuring instrument was LA-910 (manufactured by Horiba, Ltd.).
(Measurement condition)
Dispersion: Dioctyl adipate (DOA)
Refractive index ratio: 1.03
Ultrasonic irradiation: 5 minutes Data acquisition frequency: 10
(Measuring method)
Particles existing in each category are determined by dividing the range of particle size 0.1 to 200 μm into 56 categories so that the difference in the common logarithm of the boundary particle size of the categories is equal to each other. The volume reference frequency was measured.

〔Particle size〕
The particle size of the vinyl chloride polymer in the latex was measured using a Bl-DCP Particlesizer (manufactured by Brookheaven Industries).

〔Specific surface area〕
The specific surface area of calcium carbonate was measured using a powder specific surface area measuring device SS-100 type (manufactured by Shimadzu Corporation).

1. Production of polymer latex (1) Seed latex In a 30-liter pressure vessel made of stainless steel, 15 kg of ion exchange water, 43 g of sodium dodecylbenzenesulfonate, 35 g of 1-octadecanol, 59 g of lauroyl peroxide, 7.2 k of vinyl chloride monomer g was added and stirred for 30 minutes to mix well at 20 ° C. Then, 10 liters of the contents were transferred to a 15 liter polymerization can through a homogenizer (homogenizer). Then, it superposed | polymerized at 48 degreeC for 13 hours, stirring with a paddle blade 70rpm. The resulting latex had a solid content concentration of 32 wt%, and the polymer particles were monodispersed (single distribution) with a peak particle size of 0.58 μm and a weight average particle size of 0.73 μm.

(2) Vinyl chloride polymer particle latex A
A 15-liter polymerization can was charged with 5.5 kg of ion-exchanged water, 33 g of sodium dodecylbenzenesulfonate, 444 g of seed latex, and 4.6 kg of vinyl chloride monomer. Polymerization was performed at 62 ° C. for 15 hours while stirring with a paddle blade at 70 rpm. The obtained latex had a solid content concentration of 37.5 wt%, and the polymer particles were monodispersed with a peak particle size of 2.95 μm and a polymerization average particle size of 2.84 μm.

(3) Vinyl chloride polymer particle latex B
A 15-liter polymerization can was charged with 5.3 kg of ion-exchanged water, 33 g of sodium dodecylbenzenesulfonate, 800 g of seed latex, and 4.6 kg of vinyl chloride monomer. Polymerization was conducted at 62 ° C. for 13 hours while stirring with a paddle blade at 70 rpm. In the obtained latex, the solid content concentration of the latex was 38.4 wt%, and the polymer particles were monodispersed particles having a peak particle size of 2.22 μm and a weight average particle size of 2.2 μm.

(4) Vinyl chloride polymer particle latex C
Charge 12 kg of ion exchange water, 84 g of sodium dodecylbenzenesulfonate, 50 g of 1-hexadecanol, 8 g of lauroyl peroxide, and 9.6 kg of vinyl chloride monomer into a 30 liter pressure vessel made of stainless steel, and mix well at 20 ° C. For 30 minutes. Then, 10 liters of the contents were transferred to a 15 liter polymerization can through a homogenizer (homogenizer). Thereafter, polymerization was performed at 62 ° C. for 10 hours while stirring with a paddle blade at 70 rpm. The obtained latex had a solid content concentration of 47.6 wt%, and the polymer particles were monodispersed with a peak particle size of 1.02 μm and a weight average particle size of 0.97 μm.

(5) Vinyl chloride polymer particle latex D
In a 15 liter polymerization vessel, 5.2 kg of ion-exchanged water, 0.9 g of sodium lauryl sulfate, 3.2 g of sodium formaldehyde sulfoxylate, 0.05 g of sodium ethylenediaminetetraacetate and 5.0 kg of vinyl chloride monomer were added. Prepared. The mixture was stirred with a paddle blade at 70 rpm, and polymerized at 64 ° C. for 14 hours while continuously charging a total of 660 g of 5 wt% aqueous sodium dodecylbenzenesulfonate. The obtained latex had a solid content concentration of 40.7 wt%, and the polymer particles were monodispersed with a peak particle size of 0.34 μm and a polymerization average particle size of 0.34 μm.
The production results of the above latexes A to D are shown in Table 1.

2. Production of Vinyl Chloride Polymer Particles Latex A, B, C, and D obtained above were mixed at the ratio shown in Table 2, and polyoxyethylene higher alcohol ether (Emulgen 707, manufactured by Kao Corporation) was added to vinyl chloride polymer 100. Latex added to 0.2 parts was spray-dried to obtain vinyl chloride polymer particles (dry powder) PVC-A, B, C, D, E, F, G.
Moreover, 35/25/40 weight parts of vinyl chloride polymer particles (powder) PVC-D, E, and F were mixed to obtain PVC-H.
By the measurement method described above, the particle size distribution of each vinyl chloride polymer particle and the volume frequency of the particles present in each section were measured. The measurement results are shown in Table 3.
Then, the particle size distribution of each vinyl chloride polymer particle was determined according to the following criteria.

<Judgment criteria>
P: The volume frequency is 3% or more in all the sections having a particle diameter of 0.34 to 2.27 μm.
Q: The volume frequency is less than 3% in the vicinity of the beginning of the section having a particle diameter of 0.34 to 2.27 μm (small particle diameter side).
R: The volume frequency is less than 3% near the end of the section having a particle diameter of 0.34 to 2.27 μm (large particle diameter side).
S: Volume frequency is less than 3% in the vicinity of both ends of a section having a particle diameter of 0.34 to 2.27 μm.
T: There is a section in which the volume frequency is less than 3% in the middle of a section having a particle diameter of 0.34 to 2.27 μm.
P ^* : The volume frequency is 3.5% or more in all sections of the particle diameter of 0.34 to 2.60 μm and 7% or less in all sections of the 0.10 to 10.10 μm section.
P ^** : The volume frequency is 3.0% or more in all sections of the particle diameter section of 0.34 to 2.60 μm.
P ^*** : Volume frequency is 3.0% or more in all sections of the particle diameter of 0.34 to 2.60 μm, and 8% or less in all sections of the particle diameter of 0.10 to 10.10 μm. is there.
As described above, the determinations of P, P ^* , P ^** , and P ^*** satisfy the definition of the particle size distribution of the present invention, but the determinations of Q, R, S, and T Therefore, this rule is not satisfied.

  Determination of the component ratio of each vinyl chloride polymer particle and its particle size distribution is shown in Table 2, and the particle size of the polymer particles constituting each category and the volume frequency of each category particle are shown in Table 3.

（注）２００．００μｍのカラムは、１７４．６２〜２００．００μｍの範囲の値である。

(Note) The 200.00 μm column has a value in the range of 174.62 to 200.00 μm.

From the results shown in Table 3, when the ratio of the particle size of 0.34 to 2.27 μm in PVC-A to H was calculated, A69.1%, B76.3%, C78.2%, D68.8%, E77.2%, F97.1%, G51.1%, and H71.1%.
For reference, the measurement results for PVC-A are graphed and shown in FIG.

3. Vinyl chloride polymer composition (Example 1)
A PVC-A was used as the vinyl chloride polymer, and the composition was blended as composition a in Table 4 for 10 minutes using a raikai machine to obtain a sol. When the viscosity of the obtained vinyl chloride polymer composition was measured using a double cylindrical rotary viscometer (manufactured by Haake, RS100), the viscosity at a shear rate of 600 ^s-1 was 3010 mPa · s.

(Examples 2 to 11)
In the same manner as in Example 1, using the vinyl chloride polymer shown in Table 4, the composition was changed to the composition b to f shown in Table 4 to obtain a sol, and the viscosity of the resulting vinyl chloride polymer composition was obtained. Was measured respectively.

(Comparative Examples 1-8)
In the same manner as in Example 1, using the vinyl chloride polymer particles shown in Table 2, using the composition of the composition as the composition of Table 4, a sol was obtained, and the viscosity of the obtained vinyl chloride polymer was measured. did.

＊１ 炭カル−Ａ：ＳＳ＃３０（日東粉化工業（株）製、比表面積；約3000ｃｍ²／ｇ）
＊２ 炭カル−Ｂ：ＳＳ＃８０（日東粉化工業（株）製、比表面積；約8500ｃｍ²／ｇ）
＊３ シリカ：乾式シリカ（レオロシール；（株）トクヤマ製）
＊４ トナー：チタン粒子トナー（ＮＷＳ９１４Ｗ；日本ピグメント（株）製）
＊５ 安定剤：Ｂａ／Ｚｎ系安定剤（ＫＦ６５J２；共同薬品（株）製）
＊６ 発泡剤−Ａ：アゾジカルボンアミド（ＡＺＨ；大塚化学（株）製）
＊７ 発泡剤一Ｂ：熱膨張性マイクロカプセル（Ｆ−８０；松本油脂製薬（株）製）
＊８ アクリル：アクリル樹脂粒子（ゼオンＦ３４５；ゼオン化成（株）製）
＊９ ブレンドレジン：ＰＢＺＸＡ（平均粒子径３５μｍ；新第一塩ビ（株）製）

* 1 Charcoal Cal-A: SS # 30 (manufactured by Nitto Flour Industry Co., Ltd., specific surface area: about 3000 cm ² / g)
* 2 Charcoal Cal-B: SS # 80 (manufactured by Nitto Flour Industry Co., Ltd., specific surface area: about 8500 cm ² / g)
* 3 Silica: Dry silica (Reorosil; manufactured by Tokuyama Corporation)
* 4 Toner: Titanium particle toner (NWS914W; manufactured by Nippon Pigment Co., Ltd.)
* 5 Stabilizer: Ba / Zn-based stabilizer (KF65J2; manufactured by Kyodo Pharmaceutical Co., Ltd.)
* 6 Foaming agent-A: Azodicarbonamide (AZH; manufactured by Otsuka Chemical Co., Ltd.)
* 7 Foaming agent 1B: Thermally expandable microcapsules (F-80; manufactured by Matsumoto Yushi Seiyaku Co., Ltd.)
* 8 Acrylic: Acrylic resin particles (Zeon F345; manufactured by Zeon Kasei Co., Ltd.)
* 9 Blend resin: PBZXA (average particle size 35 μm; manufactured by Shin-Daiichi PVC Co., Ltd.)

  Table 5 shows the viscosity measurement results of Examples and Comparative Examples.

  From the results shown in Table 5, in order to obtain a vinyl chloride resin composition having a very low sol viscosity, it is a requirement of the present invention, that is, the ratio of particles present in each section in the section of 0.34 to 2.27 μm. However, it turns out that it is necessary to satisfy the requirement that it is 3.0% or more on the volume basis in any of the sections.

  The vinyl chloride resin composition for paste according to the present invention is suitable for use as an interior material such as wallpaper because it does not use a diluent (organic liquid) at all or only a small amount can be used. .

It is a graph which shows the particle size distribution of PVC-A of a vinyl chloride polymer particle.

Claims (2)

  When dividing the particle diameter of 0.1 to 200 μm into a plurality of sections, the section is divided into 56 sections so that the difference between the common logarithm values of the upper and lower particle diameters of each section becomes equal, and the particle diameter of 0.10 to 10 When the particles included in the range of 10 μm are defined as 100% on a volume basis, the ratio of particles existing in each section in the section having a particle diameter of 0.34 to 2.27 μm is based on the volume in any section. Vinyl chloride resin particles for paste, characterized by being 3.0% or more. (1) Vinyl chloride resin particles according to claim 1 (2) Plasticizer (3) An organic liquid having a boiling point of 60 to 300 ° C. under normal pressure, and the total amount of these components is 100% by weight Sometimes the component (1) is 25 to 75% by weight, the component (2) is 25 to 75% by weight, and the component (3) is 0 to 2.0% by weight. Stuff.

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