JP2513461B2 - Bituminous vinyl chloride resin composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a vinyl chloride resin composition containing bituminous vinyl, which can be used for vinyl chloride resin sheets, plates and various other products, and a method for producing the same.

Bituminous vinyl chloride resin products made by mixing bitumen such as coal tar and coal tar pitch in vinyl chloride resin or coal powder are used for corrosion-resistant tapes such as steel pipes and waterproof sheets for buildings and structures. These have excellent characteristics such as being chemically stable, resistant to acids and alkalis, excellent in oil resistance, electric insulation, and waterproof. However, because coal tar contains carcinogens and has a tar odor, it has become difficult to use tar-based bituminous substances. Asphalt may be used as a bitumen, but asphalt has fewer problems with carcinogenic substances than tar, and has a weaker odor than tar, but has a drawback that it is not compatible with vinyl chloride resin.

Incorporation of bitumen into vinyl chloride resin products, such as sheets and plates, can reduce the price of the product, enhance the thermoplastic properties, and improve the vibration and soundproofing effect. Also, when bonding with an adhesive etc., a wide variety of adhesives can be used, and it has excellent advantages such as excellent workability, so instead of tar type, there is no odor, there is no concern about carcinogenicity There is a need for a bituminous resin that does not exist and is compatible with or has a good affinity with vinyl chloride resin, and the development of such a vinyl chloride resin product containing bitumen is desired. The present invention meets these needs.

An object of the present invention is to provide a vinyl chloride resin composition containing bituminous chloride, which has no odor or asphalt odor like tar-based bituminous matter, has stable physical properties, is inexpensive in price, and a manufacturing method thereof. It is a thing.

And the present invention is characterized in that a petroleum pitch having a softening point of 130 ° C. or higher and a fixed carbon of 40% by weight or more is kneaded in a vinyl chloride resin together with a plasticizer and a process oil to be uniformly mixed. A vinyl chloride resin composition containing bitumen and a softening point of 130 ° C or higher and a fixed carbon content of 4
0% by weight or more of petroleum pitch is dissolved in a plasticizer or process oil or dispersed in fine particles, or a plasticizer,
A method for producing a vinyl chloride resin composition containing bitumen, characterized in that the petroleum pitch is kneaded into a vinyl chloride resin together with a plasticizer and a process oil after being moistened with the process oil and uniformly mixed. It is what

The petroleum pitch referred to in the present invention is a petroleum pitch produced by a process of heat treating a vacuum residue of crude oil at a high temperature, and has a softening point (ring and ball method) of 130 ° C or higher, usually 130 to 25
At 0 ° C., the fixed carbon content is 40% by weight or more, usually 40 to 80% by weight. If the softening point is 130 ° C or lower, the heat resistance of the bituminous vinyl chloride resin composition to be molded may be impaired, and if the fixed carbon is 40% by weight or less,
Small reinforcement effect. That is, strength such as tensile strength in the vinyl chloride resin composition containing bituminous cannot be expected. The petroleum pitch referred to in the present invention is richer in aromaticity than asphalt and has an aromaticity close to that of coal tar pitch. Shows good compatibility with coal tar, creosote, anthracene oil, etc. Also, it has good compatibility with process oils rich in aromatic or naphthenic hydrocarbons. Usually, it is supplied in powder form, but it can be further pulverized into fine particles by a grinder, a mill or the like. Fine-grained petroleum pitch is also porous. It is hydrophobic and has good affinity with plasticizers and process oils.

Furthermore, petroleum pitch is chemically stable, stable to microorganisms, tasteless, odorless, and nontoxic, has an excellent reinforcing effect, can be obtained in a large amount, and is stable at a low price.
Further, if necessary, other bitumen, a thermoplastic resin or the like may be used together with the petroleum pitch. For example, bituminous materials include gilsonite, asphaltene, propane deasphalted asphalt, tar, and coal tar pitch.

Examples of the thermoplastic resin include petroleum resin and its modified resin, coumarone indene resin and its modified resin, rosin and its derivative, terpene resin, synthetic terpene resin, and alkylbenzene resin. These combined use is used in the range which does not impair the characteristic of petroleum pitch.

The plasticizers and process oils referred to in the present invention are those that can be used as plasticizers and additives for vinyl chloride resins, process oils for rubber, and the like. For example, dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DO
P), dioctyl phthalate (D _n OP), dioctyl adipate (DOA), other well-known ester plasticizers, epoxidized vegetable oil, nitrile synthetic rubber, chlorinated polyethylene, ethylene / hineyl acetate copolymer, chlorinated paraffin, There are anthracene oil, tar, aromatic-based oils of petroleum-based auxiliary plasticizers, naphthene-based oils, petroleum-based aromatic and naphthene-based process oils used for rubber softeners, compounding agents and the like. These can be used alone or in combination.

Among the above plasticizers, nitrile synthetic rubber, chlorinated polyethylene, ethylene / vinyl acetate copolymer, etc. are useful for plasticizing vinyl chloride resin, but are not used for dispersing or moistening petroleum pitch. Plasticizer for dispersing and wetting petroleum pitch, process oil,
A liquid at room temperature is used. To dissolve or disperse petroleum pitch alone in a plasticizer or process oil, add and mix petroleum pitch powder to the liquid material of the plastic residue and process oil, and thoroughly pulverize it with a grinder or mill to obtain fine particles. Can be dispersed in. A considerable amount of heat is generated in this grinding and mixing process. By this wet grinding step, petroleum pitch can be dispersed in a plasticizer, process oil, etc. in high concentration in the form of fine particles. Further, depending on the types and blending of the plasticizer and the process oil, some of the components of petroleum pitch are dissolved in the plasticizer and the process oil. It also expands and disperses.

The petroleum pitch dispersion thus obtained is uniform and smooth, and there is no sedimentation of petroleum pitch. Good mixability, dispersibility, and affinity with vinyl chloride resin. Normal,
When petroleum pitch is used alone and no other bituminous material or thermoplastic resin is used, it shows a viscous liquid with 50% by weight of petroleum pitch, plasticizer and 50% by weight of process oil, 60% by weight of petroleum pitch, plasticizer , If the process oil is 40% by weight, it becomes a paste.

When it is desired to reduce the amount of the plasticizer and the process oil with respect to the petroleum pitch powder, it is advisable to add a suitable amount of the plasticizer and the process oil to the fine powder of the petroleum pitch, mix them, and wet them.
The powder does not fly and is convenient to handle. It also has good mixability and dispersibility in vinyl chloride resin. Further, if it is granulated rather than simply moistened, it becomes easier to handle.

The vinyl chloride resin referred to in the present invention is a homopolymer of vinyl chloride. Examples of the copolymer include a copolymer of vinyl chloride and vinyl acetate, a copolymer of vinyl chloride and vinylidene chloride, a copolymer of vinyl chloride and a small amount of ethylene or propylene, and a copolymer of vinyl chloride and acrylate. Further, ethylene / vinyl acetate copolymer, polyacrylate, chlorinated polyethylene and the like obtained by graft-polymerizing vinyl chloride can also be used together. In addition, stabilizers, anti-aging agents, plasticizers, process oils, fillers, colorants, pigments, and other chemicals (for example, flame retardants, antistatic agents, fungicides, foaming agents, etc.) are added to these vinyl chloride resins. Those to which is appropriately added are also used. Also, vinyl chloride resin products that can be recycled are used.

In addition to the above materials, stabilizers, antioxidants, fillers, colorants, flame retardants, etc. used for blending vinyl chloride resin are included in the blending of bituminous vinyl chloride resin composition, in addition to the above materials. Antistatic agents, antifungal agents, foaming agents and the like are also used as necessary.

For adding petroleum pitch, plasticizer, process oil, other stabilizers, antiaging agents, fillers, coloring agents, other chemicals, etc. to vinyl chloride resin, mixing, kneading, and manufacturing of products, ordinary vinyl chloride is used. Machines and devices used for resin are used. For example, for mixing and kneading, a blender, a Banbury mixer, a kneading roll, a kneading extruder with a pelletizer,
Sheeting rolls, pelletizers (granulators), and the like, and calender rolls, extruders, injection molding machines, presses, etc. are used for manufacturing products.

Mixing petroleum pitch with vinyl chloride resin is used in combination with plasticizer and process oil. It is also possible to handle powdered petroleum pitch in the same manner as the filler, and to prepare a blend of the bituminous vinyl chloride resin composition by a usual method,
As a method for improving the mixing dispersibility and miscibility of petroleum pitch powder with vinyl chloride resin, petroleum pitch powder is used as a plasticizer,
It is preferable to use one dispersed in process oil, or one moistened with a plasticizer or process oil. In particular, petroleum pitch powder is preferably added to and mixed with a plasticizer and process oil in advance, and pulverized and dispersed through a grinder, a mill or the like.

The admixture of the vinyl chloride resin composition containing bitumen of the present invention may be formed into a granular shape such as a square, a cylinder or an amorphous shape, and used as a raw material for a sheet or other molded products. This blend of bituminous vinyl chloride resin composition can be used to make sheets and other molded products using a calendar roll, an extruder, an injection molding machine, a press and the like. Further, after the admixture of the vinyl chloride resin composition containing bitumen of the present invention is produced, a sheet such as a sheet can be subsequently produced using a calendar roll, an extruder, an injection molding machine, a press or the like.

The features, functions and effects of the bituminous vinyl chloride resin composition of the present invention and the method for producing the same are summarized as follows.

(1) The bituminous-containing vinyl chloride resin composition of the present invention is a bituminous resin having a softening point of 130 ° C. or higher and a fixed carbon of 40% by weight or more, which is mainly composed of petroleum pitch. There is.

Petroleum pitch is rich in aromaticity, has excellent affinity with vinyl chloride resin, and has thermoplasticity and high softening point, and therefore does not impair the heat resistance of vinyl chloride resin. Moreover, since about 1/2 or more of the oil pitch is fixed carbon, the auxiliary effect is great. Further, by using a process oil such as an aromatic system as a plasticizer and a process oil used in combination with petroleum pitch, the petroleum pitch is partially dissolved or swelled in them, and thus mixed with vinyl chloride resin. The mixing of is better. The petroleum pitch mixed in the bituminous vinyl chloride resin composition has a good binding property, so that the petroleum pitch does not fall off and there is no contamination.
In addition, the product has no odor such as tar odor or asphalt odor.

It is also chemically stable. Further, when processed into a sheet or the like, it has a vibration and soundproof effect. Since it is possible to mix bituminous to a considerable amount, it is possible to obtain one having stable physical properties and to reduce the cost, so it is economical and expected to be applied to various products.

(2) The petroleum pitch powder is dispersed in the plasticizer and the process oil in advance (particularly, it is preferable to disperse it while grinding), or the petroleum pitch powder is wetted in the plasticizer and the process oil, and then the vinyl chloride resin. When kneaded with, the petroleum pitch powder mixes the plasticizer and process oil together with the vinyl chloride resin, so that good dispersion and mixing are possible, and the affinity and binding are better, and stable bituminous vinyl chloride is used. A resin composition can be produced.

 Next, examples of the present invention will be described.

 The properties of the petroleum pitch used are as follows.

Example 1 52 parts by weight of petroleum pitch sample No. 1 and 48 parts by weight of DOP are mixed while crushing petroleum pitch through a grinder to prepare a viscous dispersion liquid having a petroleum pitch concentration of 52% by weight.

Blender, vinyl chloride resin (average degree of polymerization 1000, vinyl acetate 3%) 100 parts by weight, DOP 10 parts by weight, epoxidized soybean oil 5 parts by weight, stabilizer 3 parts by weight, calcium carbonate powder
80 parts by weight and 50 parts by weight of the above-mentioned petroleum pitch dispersion are mixed and then kneaded with a kneading roll, and then a black odorless bituminous vinyl chloride resin sheet (thickness: about 1.6 mm) is passed through a calendar roll. It was

Example 2. Petroleum pitch sample No. 2 52 parts by weight, petroleum-based aromatic process oil (specific gravity 1.001, flash point 212 ° C., aromatic component 43)
%, Naphthene component 32%, paraffin component 25%) 18 parts by weight, DOP 30 parts by weight, and the mixture is passed through a grinder to pulverize and mix the oil pitch to disperse the oil pitch into fine particles. Make a 52% by weight dispersion.

Kneading roll, PVC film scrap 60
Parts by weight, 15 parts by weight of calcium carbonate powder, petroleum pitch dispersion
Knead 25 parts by weight. Then, an odorless bituminous vinyl chloride resin sheet was obtained through a calendar roll.

Example 3 100 parts by weight of petroleum pitch sample No. 1 was mixed with 25 parts by weight of the mixture of 10 parts by weight of the aromatic process oil used in Example 2 and 15 parts by weight of DOP, and the mixture was wetted with a plasticizer, a process oil and the like. Build the oil pitch.

Blender, vinyl chloride resin (average degree of polymerization 1000) 10
0 parts by weight, 15 parts by weight of GOP, 5 parts by weight of epoxidized soybean oil, 3 parts by weight of stabilizer, 80 parts by weight of the petroleum pitch wet product, and 20 parts by weight of calcium carbonate powder were mixed and then kneaded with a kneading roll. A blue vinyl chloride resin composition was obtained. This was passed through a calendar roll to obtain an odorless vinyl chloride resin sheet containing bitumen.

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Claims (2)

(57) [Claims] 1. A softening point of 130 ° C. or higher and a fixed carbon of 4
A bituminous vinyl chloride resin composition comprising 0% by weight or more of petroleum pitch kneaded in a vinyl chloride resin together with a plasticizer and a process oil and uniformly mixed. 2. A softening point of 130 ° C. or higher and a fixed carbon of 4
0% by weight or more of petroleum pitch is dissolved in a plasticizer or process oil or dispersed in fine particles, or a plasticizer,
A method for producing a vinyl chloride resin composition containing bitumen, characterized in that the petroleum pitch is kneaded with a plasticizer and a process oil into a vinyl chloride resin and uniformly mixed after being moistened with the process oil.