JPH05156184A - Production of vinyl chloride resin power composition - Google Patents

Abstract

PURPOSE:To provide the subject composition excellent in powder properties such as meltability, powder clearance from mold and powder flow and easily moldable. CONSTITUTION:The objective composition is obtained by mixing a vinyl chloride resin of a mean particle diameter of 100-150mum with a plasticizer and a vinyl chloride resin of a mean particle diameter of 0.5-3mum, and agitating the mixture under heating.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is applied to the molding of automobile interior materials such as instrument panels, console boxes and headrests, and the skin materials of interior furnishings such as furniture, and other powder-coated products. The present invention relates to a method for producing a vinyl chloride resin powder composition used in a powder molding method for melting a powder by heat treatment to form a uniform coating film.

[0002]

2. Description of the Related Art The powder molding method used for the above purposes is
This is a general term for molding methods in which a powder of a resin as a raw material is powder-coated on a mold or an object to be coated and then melted to obtain a molded article, and a typical molding method is a fluidized dipping method,
There are electrostatic coating method, thermal spraying method, rotational molding method and slush molding method. Among them, the slush molding method and the rotational molding method are
This is a powder molding method suitable for molding automobile interior materials and interior furnishing materials for dealing with complex designs and weight reductions, or for satisfying high-class feeling such as leather patterns and stitch patterns.

The rotational molding method and slush molding method using such powder generally use a vinyl chloride resin powder composition as a raw material, and a large amount of vinyl chloride resin powder is added to a mold heated to a temperature of 200 ° C. or higher. This is a method in which the body composition is supplied and the powder is welded to the inner surface of the mold, the excess powder is removed and recovered, and the powder adhered to the surface of the mold is completely melted. As can be seen from the characteristics of the molding method, the vinyl chloride resin-based powder composition (hereinafter referred to as the vinyl chloride-based powder composition) used in such a powder molding method has excellent fluidity and moldability of the powder. In addition, the molded product is required to have physical properties suitable for the intended use.

This vinyl chloride powder composition uses a high-speed agitating mixer equipped with a heating jacket and containing a blending agent such as a vinyl chloride resin, a plasticizer, a stabilizer and a pigment at a temperature of 100 to 100 ° C.
It is obtained by dry blending at 150 ° C. Since the vinyl chloride resin that constitutes the resin powder composition absorbs the plasticizer, it satisfies basic powder coating characteristics such as meltability. However, there was a drawback that it was easy to block during storage and during use due to the leaching of the absorbed plasticizer from the vinyl chloride resin, so that it is usually used as an antiblocking agent by emulsion polymerization with low plasticizer absorbability. Fine powder such as vinyl chloride resin is mixed.

However, the fine powder for exhibiting the anti-blocking property is the powder obtained by mixing the plasticizer, the stabilizer and the like with the vinyl chloride resin under heating and then cooling the mixture to room temperature. The fine powder is merely sprinkled on the main vinyl chloride resin.

[0006]

The conventional PVC-based powder composition sprinkled with fine powder for exhibiting the above-mentioned anti-blocking property has practically almost no anti-blocking property and powder breaking property from a mold or the like. No problem. However, since a fine powder of vinyl chloride having a poor meltability and a low plasticizer absorbability is compounded by a method of post-addition, there is a problem in meltability of the vinyl chloride powder composition as a whole.

In view of the above circumstances, the present invention provides a vinyl chloride resin powder composition which has good anti-blocking property and powder breaking property and is easy to mold when molding a skin material. It is intended to provide a method.

[0008]

In order to achieve the above object, a method for producing a vinyl chloride resin-based powder composition according to the present invention comprises the steps of mixing a vinyl chloride resin and a plasticizer under heating. As vinyl chloride resin, average particle size is 1
Vinyl chloride resin having an average particle diameter of 0.5 to 3 μm is added,
It is characterized by being mixed under heating.

Further, in another method for producing a vinyl chloride resin-based powder composition of the present invention, the average particle size is 100 to 150 μm.
In the step of mixing the vinyl chloride resin and the plasticizer under heating, the vinyl chloride resin having an average particle diameter of 0.5 to 3 μm is added and mixed under heating, and after cooling, the average particle diameter is further 0. A vinyl chloride resin of 0.5 to 3 μm is added and mixed at room temperature.

In the present invention, the average particle size is 100 to 15
The vinyl chloride resin having a thickness of 0 μm means a vinyl chloride homopolymer obtained by polymerization of vinyl chloride and a copolymer mainly composed of vinyl chloride and another monomer copolymerizable therewith. Examples of the other monomer include vinyl halide monomers such as vinylidene chloride, acrylic acid esters such as butyl acrylate, ethyl acrylate, and methyl acrylate, methacrylic acid esters such as methyl methacrylate and glycidyl methacrylate, and vinyl acetate alone. A quantity,
Examples thereof include carboxylic acid vinyl esters such as vinyl propionate and vinyl ethers such as cetyl vinyl ether and isobutyl vinyl ether.

The vinyl chloride resin having an average particle size of 100 to 150 μm preferably has a degree of polymerization of 700 to 1300. If the degree of polymerization is less than 700, the strength of the obtained molded article will be weak, and it will be easily broken when used as a skin material, and if the degree of polymerization is more than 1300, the meltability at the time of molding will be poor, such being undesirable.

The average particle size is 100 to 150 μm,
Vinyl chloride resin having a preferred degree of polymerization of 700 to 1300 is
For example, it can be obtained by the following method. To the autoclave, ion-exchanged water is added as a polymerization medium, partially saponified polyvinyl alcohol or methyl cellulose is added as a suspending agent, and the mixture is stirred, and then a radical polymerization initiator such as di-2-ethylhexyl peroxydicarbonate is added. The inside of the autoclave is depressurized, and the polymerization is carried out at a temperature of about 50 to 70 ° C. under stirring until the internal pressure rises to ⁵ to 10 Kg / cm ² . After reacting for 10 to 20 hours, the polymerization is stopped, the obtained slurry is dehydrated with a decanter, and dried with a fluid dryer to obtain a powder. This polymerization is no different from normal suspension polymerization, and the monomers used here such as vinyl chloride, suspension agents,
As the polymerization initiator, a general-purpose one can be used, and commercially available products of such vinyl chloride resin include Aron PVC-TS700, TS800 and TS manufactured by Toagosei Chemical Industry Co., Ltd.
There are 1300 etc.

On the other hand, a vinyl chloride resin having an average particle size of 0.5 to 3 μm means a vinyl chloride single resin obtained by polymerization of vinyl chloride, as in the case of the vinyl chloride resin having an average particle size of 100 to 150 μm. It means a copolymer mainly composed of coalesce and vinyl chloride and another monomer copolymerizable therewith, and the preferred degree of polymerization is 700 to 1700, and more preferably 700 to 1100.

Such vinyl chloride resin having an average particle size of 0.5 to 3 μm is 1 part with respect to 100 parts by weight of vinyl chloride resin having an average particle size of 100 to 150 μm (hereinafter simply referred to as “part”).
Addition of 10 parts is preferred. If the addition amount is less than 1 part, the effect of the addition is not sufficiently exhibited, and if it exceeds 10 parts, the meltability of the obtained powder composition tends to decrease, and the particle size of the powder composition becomes coarse. Too much.

As the vinyl chloride resin having an average particle diameter of 0.5 to 3 μm, vinyl chloride resin powder obtained by emulsion polymerization is suitable, but vinyl chloride particles obtained by suspension polymerization may be pulverized. Those obtained by emulsion polymerization can be obtained, for example, by the method described below. That is, a vinyl chloride monomer and, if necessary, another monomer copolymerizable with the vinyl chloride monomer are charged in ion-exchanged water to which an emulsifier such as sodium dodecylbenzenesulfonate is added, and the persulfate is added. A fine powder of vinyl chloride resin can be obtained by polymerizing while stirring at a temperature of 40 to 65 ° C. in the presence of a water-soluble radical polymerization initiator such as potassium. This method is no different from ordinary emulsion polymerization, and as a finely powdered vinyl chloride resin of an emulsion polymerized product, Tohso Corporation's Ryuron Paste 77
2, or commercially available products such as Zeon 121 manufactured by Nippon Zeon Co., Ltd. can be used.

The vinyl chloride resin powder composition obtained by the present invention basically has an average particle size of 100 to 150 μm.
m vinyl chloride resin is mixed with a vinyl chloride resin having an average particle diameter of 0.5 to 3 μm and a plasticizer under heating. In addition to the plasticizer, a heat stabilizer and a pigment are used. A compounding agent such as the above can be appropriately mixed. As the plasticizer, heat stabilizer and pigment, those generally used as a compounding agent for vinyl chloride resin powder coatings can be widely used.

The above-mentioned plasticizer is generally used for adjusting the mechanical strength and hardness of the resin film, and it is usually preferable to add 50 to 100 parts to 100 parts of vinyl chloride resin. If the amount of the plasticizer added is less than 50 parts, the coating film becomes hard and the impact resistance and flex resistance tend to decrease. If the added amount of the plasticizer exceeds 100 parts, the obtained coating becomes softer than necessary, and the strength, stain resistance, and
It is not preferable because the light resistance is deteriorated.

Specific examples of the plasticizer include, for example, di-n-butyl phthalate, -n-octyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, octyldecyl phthalate, diisodecyl phthalate. ,
Butylbenzyl phthalate, di-2-ethylhexyl isophthalate, or phthalic acid plasticizers such as phthalic acid esters of higher alcohols having about 11 to 13 carbon atoms, n-octyl-n-decyl trimellitate, trimellitic acid trimellitate Trimellitic acid plasticizers such as 2-ethylhexyl, triisodecyl trimellitate, tri-n-octyl trimellitate, di-2-ethylhexyl adipate, di-n-decyl adipate, dibutyl sebacate, dibutyl sebacate Fatty acid ester-based plasticizer such as 2-ethylhexyl, tributyl phosphate, tri-2-ethylhexyl phosphate, 2-ethylhexyl diphenyl phosphate, tricresyl phosphate-based ester plasticizer, epoxidized soybean oil, epoxy Flaxseed oil, epoxidized tall oil fatty acid-2-ethylhexyl Mention may be made of epoxy-based plasticizer and the like, these plasticizers are used alone or in combination.

Further, in the present invention, for the purpose of improving the anti-blocking property of the obtained vinyl chloride resin powder composition, vinyl chloride having a fine particle diameter is used as in the conventionally known vinyl chloride resin powder composition. The system resin may be added at the final stage of the manufacturing process.

As a vinyl chloride resin having a fine particle size (hereinafter referred to as a fine powder PVC added later) used for such a purpose,
Usually, the average particle size is 3 μm or less, and the degree of polymerization is 1300 to 17
A vinyl chloride resin of about 00 is used, and the amount thereof is limited because it is a vinyl chloride resin by emulsion polymerization which is inferior in meltability, and is generally used for 100 parts of the vinyl chloride resin having an average particle diameter of 100 to 150 μm. It was about 10 to 15 parts. As described above, since the amount of the post-added fine-powder PVC used was limited, the meltability was conventionally difficult, but in order to obtain a practically sufficient antiblocking property, the polymerization degree was 1300 to 1700. It was necessary to use such a vinyl chloride resin having a relatively high degree of polymerization. On the other hand, in the present invention, since the vinyl chloride resin having the above-mentioned fine particle diameter, which is blended at the time of heating and mixing the respective components, also acts as an anti-blocking agent, the degree of polymerization of the finely divided PVC added later is 700 to 1100. It is possible to use a vinyl chloride resin having a good melting property. As a result, it is possible to obtain a powder composition excellent in both heat melting property and antiblocking property. In addition, as a matter of course, in the present invention, the finely divided PVC added later has a degree of polymerization of 1300.
Vinyl chloride resins of up to 1700 can also be used.

The heat stabilizer is preferably added in an amount of 0.5 to 10 parts based on 100 parts of the total amount of vinyl chloride resin. If the addition amount of the heat stabilizer is less than 0.5 part, the effect of addition is not sufficiently exerted, and there arises a problem that melting due to heating, discoloration becomes remarkable during film formation, and work control range becomes narrow.

As the pigment, an extender pigment such as calcium carbonate, barium sulfate, zinc white, silica, and silica sand powder can be used, if necessary, in addition to the usual coloring pigment. The amount of the pigment added is preferably 0.5 to 20 parts with respect to 100 parts of the total amount of the vinyl chloride resin. When the amount of the pigment added is less than 0.5 part, the hiding power tends to be insufficient, and when it exceeds 20 parts, the melt viscosity is poor and it is difficult to obtain a good coating film.

The vinyl chloride resin powder composition of the present invention can be produced, for example, by the following method.
A vinyl chloride resin having an average particle diameter of 100 to 150 μm, a vinyl chloride resin having an average particle diameter of 0.5 to 3 μm, a plasticizer,
And a heat stabilizer, a compounding agent such as a pigment, and agitating and mixing at a temperature of 100 to 150 ° C. for 20 to 40 minutes while heating with a high speed mixer equipped with a heating jacket such as a Henschel mixer to obtain a target powder composition. Can be obtained. Further, a vinyl chloride resin having an average particle size of 100 to 150 μm, a plasticizer, and a compounding agent such as a heat stabilizer and a pigment are stirred and mixed while being heated in the high speed mixer, and the high speed mixer is temporarily stopped during the process. The average particle size is 0.5-3
It can also be obtained by adding a vinyl chloride resin having a thickness of μm and heating and mixing again.

A vinyl chloride resin having an average particle diameter of 100 to 150 μm, a vinyl chloride resin having an average particle diameter of 0.5 to 3 μm, and a compounding agent such as a plasticizer, a heat stabilizer and a pigment are mixed in a Henschel mixer. While stirring with a high-speed mixer equipped with such a heating jacket, the mixture is stirred and mixed at a temperature of 100 to 150 ° C. for 20 to 40 minutes, and then cooled to a temperature of 50 to 70.
When the temperature reaches ℃, by adding finely powdered PVC which is added later, mixing and sieving, another vinyl chloride resin powder composition of the present invention can be obtained.

[0025]

The method for producing a vinyl chloride resin powder composition according to the present invention comprises a main vinyl chloride resin powder having an average particle size of 100 to 150 μm and a secondary vinyl chloride resin powder having an average particle size of 0.5 to 3 μm. By mixing the resin fine powder with the plasticizer under heating, it is possible to obtain a vinyl chloride resin powder composition having good meltability, antiblocking property, and fluidity (cutting property).

The reason for this is that, by mixing under heating, the main vinyl chloride resin powder having an average particle size of 100 to 150 μm and the average particle size of 0.5 to 3 μm having poor meltability and low plasticizer absorbability. The plasticizer is also absorbed in the secondary vinyl chloride resin fine powder, and the secondary vinyl chloride resin fine powder covers the surface of the main vinyl chloride resin powder to form a sol, and the main vinyl chloride resin powder It is considered that the surface of the vinyl chloride resin powder composition is uniformly coated with an appropriate degree of denseness, whereby the powder characteristics, particularly the meltability, of the vinyl chloride resin powder composition are remarkably improved.

This means that the vinyl chloride resin powder obtained by the conventional dry blending method in which the vinyl chloride resin powder, the plasticizer and the like are mixed under heating and cooled, and then the surface thereof is sprinkled with fine powder of the vinyl chloride resin. It is also clear from the fact that each of the examples of the present invention exhibits significantly superior powder characteristics as compared with the comparative examples of the resin powder composition shown in Table 1 below.

After cooling the vinyl chloride resin powder composition obtained by the above-mentioned method, fine powder PVC added later is added.
It is possible to further improve the anti-blocking property of the powder while maintaining the above-mentioned excellent powder property by adding and mixing with stirring.

[0029]

EXAMPLES Hereinafter, the method for producing the vinyl chloride resin powder composition of the present invention will be described in detail with reference to Examples.

Example 1 Dioctyl phthalate (D) was added to 100 parts of a vinyl chloride resin having an average particle size of 100 to 150 μm (Aron PVC-TS800 manufactured by Toagosei Chemical Industry Co., Ltd .; polymerization degree: 800).
OP) 70 parts, epoxy resin 3 parts, barium zinc-based composite metal soap 0.5 part, organotin maleate stabilizer 2 parts and titanium oxide 5 parts as a pigment, and an average particle size of 0.
All 3 parts of a vinyl chloride resin (emulsion polymerized product) having a degree of polymerization of 900 at 5 to 3 μm were simultaneously charged into a Henschel mixer which is a high-speed stirring mixer with a heating jacket, and the temperature was adjusted to 10
The mixture was stirred and mixed at 0 to 110 ° C for about 20 to 40 minutes. Then, stirring and mixing are stopped, and after cooling, fine powder PV added later is added.
C has an average particle size of 0.5 to 3 μm and a degree of polymerization of 900.
10 parts of vinyl chloride resin (emulsion polymerized product) was added and stirred,
A powder composition was manufactured by classifying with a 40-mesh sieve.

Example 2 Instead of 3 parts of vinyl chloride resin (emulsion polymerized product) having an average particle size of 0.5 to 3 μm and a degree of polymerization of 900, the average particle size was 0.5 to
Vinyl chloride resin with 3 μm and a degree of polymerization of 900 (emulsion polymerization product)
A powder composition was produced by the same formulation and operation method as in Example 1 except that the amount was 8 parts.

Example 3 Instead of 3 parts of vinyl chloride resin (emulsion polymerized product) having an average particle size of 0.5 to 3 μm and a polymerization degree of 900, the average particle size was 0.5 to
A powder composition was produced by the same formulation and operation method as in Example 1 except that 3 parts of a 3 μm vinyl chloride / vinyl acetate copolymer was used.

Comparative Example 1 70 parts of dioctyl phthalate (DOP), 3 parts of epoxy resin, and 0.5 part of barium-zinc-based composite metal soap per 100 parts of vinyl chloride resin having an average particle size of 100 to 150 μm.
Part, 2 parts of organotin maleate-based stabilizer, and 5 parts of titanium oxide as a pigment are all charged into a Henschel mixer at the same time, heated to a temperature of 100 to 110 ° C., and mixed by stirring.
Then, the mixture was cooled, 10 parts of vinyl chloride resin having an average particle size of 0.5 to 3 μm was added, and the mixture was classified with a 40-mesh sieve to produce a powder composition.

The performance evaluations of the powder compositions of Examples and Comparative Examples are shown in Table 1 below. The evaluations were performed as follows.

Powder cutting property, meltability A nickel plate having a thickness of 3 mm and a length and width of 150 mm is used at a temperature of 220.
Heat to ℃, sprinkle the powder composition and stand for 5 seconds. The powder composition not melted is blown off and heated in an atmosphere at a temperature of 220 ° C. for 20 seconds. The powder composition is sprinkled again, and the powder composition which has not melted is sprayed for 5 seconds, and the temperature is set to 220.
Heat for 20 seconds in ° C. This operation is repeated 4 times to cool the nickel plate with water. The weight of the film thus prepared was measured, and the powder cutting property was evaluated by the amount of powder adhering and melting on a nickel plate having a certain area. The smaller the weight, the better the powder cutting property. An optical micrograph was taken of the obtained film cross section, and the ratio of the completely melted layer in the film cross section consisting of the completely melted layer facing the nickel plate side and the incompletely melted outer layer was measured. From this measurement result, the thickness of the completely melted layer was taken as a percentage of the total thickness and used as a measure of the meltability.

The powder flowable powder compound is left to stand at a temperature of 60 ° C. for 24 hours, and then placed in a funnel for measuring the bulk specific gravity according to JIS K6721. Scrape off the powder compound on the top of the funnel and measure the time it takes for all the powder composition to run off the funnel.

[0038]

[Table 1]

As is clear from Table 1 showing the data of Examples and Comparative Examples in which the powder cutting property, the melting property and the powder fluidity were tested, the Birni chloride-based resin powder composition of the present invention was meltable. It can be seen that the powder has excellent powder cutting property and powder fluidity.

[0040]

Industrial Applicability According to the method for producing a vinyl chloride resin powder composition of the present invention, a vinyl chloride resin having an average particle size of 100 to 150 μm is mixed with a vinyl chloride resin having an average particle size of 0.5 to 3 μm. By mixing the agent with the agent under heating, a high-quality vinyl chloride resin-based powder composition can be produced very simply, easily, and economically.

Particularly, the vinyl chloride resin-based powder composition produced by the method of the present invention has a plasticizer added to the vinyl chloride-based resin as in the known vinyl chloride resin-based powder composition for powder molding. After mixing under heating, the mixture is cooled once, and then vinyl chloride resin fine powder having a small particle size is added to the mixture so that the vinyl chloride resin fine powder is merely sprinkled with the vinyl chloride resin powder. On the other hand, powder characteristics such as meltability and powder breakability of powder during powder molding can be greatly improved.

Further, according to another method for producing a vinyl chloride resin powder composition of the present invention, a vinyl chloride resin composition of good quality can be produced very simply and easily and economically. The obtained vinyl chloride-based resin powder composition is characterized in that it has excellent anti-blocking properties while maintaining the excellent powder characteristics of the powder composition obtained by the above method.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Naonori Asada 1-1 Funami-cho, Minato-ku, Nagoya, Aichi Toagosei Chemical Industry Co., Ltd. Nagoya Research Institute (72) Inventor Yoshito Fujiki, Minato-ku, Aichi 1-1, Funamicho Toagosei Chemical Industry Co., Ltd. Nagoya Research Institute

Claims (2)

[Claims] 1. In the step of mixing a vinyl chloride resin and a plasticizer under heating, a vinyl chloride resin having an average particle size of 100 to 150 μm is used as the vinyl chloride resin, and the average particle size is 0.1. A method for producing a vinyl chloride resin powder composition, which comprises adding a vinyl chloride resin having a thickness of 5 to 3 μm and mixing the resin under heating. 2. In the step of mixing a vinyl chloride resin having an average particle diameter of 100 to 150 μm and a plasticizer with heating, a vinyl chloride resin having an average particle diameter of 0.5 to 3 μm is added and heated. A method for producing a vinyl chloride resin powder composition, which comprises mixing and cooling, and further adding a vinyl chloride resin having an average particle diameter of 0.5 to 3 μm and mixing at room temperature.