KR950011920B1 - Asphalt composition for waterproof sheets - Google Patents

Abstract

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Description

Asphalt composition for waterproof sheet

In the present invention, the number average molecular weight is in the range of 1,000 to 20,000, and the amorphous propylene ethylene random copolymer having an ethylene content of 8 to 30% by weight or the butene-1 content is 10 to 60% by weight. Asphalt composition for water-resistant sheet based on% amorphous propylene butene-1 random high polymer and asphalt.

As the asphalt composition for waterproof sheet of the present invention is inexpensive and has excellent performance, it is widely used in roofing waterproofing of sealing materials between concrete plates in joints, water pipes, etc. Suitable for construction waterproof sheet.

As an asphalt-based waterproof composition, it is known that asphalt is blended with various kinds of raw rubber such as natural rubber, butyl rubber, styrene butadiene rubber, thermoplastic elastomer, or resin such as atactic polypropylene and petroleum resin.

1986년 11월호 112페이지에는 지붕·옥상용 방수시트로서 토치모양의 가스버너로 두께 4mm 전후의 훗겹 방수시트의 뒷면과 밑바탕을 동시에 쐬어서 순간적으로 시트를 붙여가는 토치공법 및 토치공법용 방수시트가 기재돼 있으며, 아스팔트 질의 개량 방법으로서 아탁틱 폴리프로필렌, 스티렌 부타디엔 스티렌 볼록 공중합체를 각각 형편에 따라 사용하는 사례를 기재하고 있다.Especially "waterproof journal"

On November 112, November 1986, a waterproof sheet for torch and torch is used as a waterproof sheet for roofs and roofs. As an improvement method of asphalt quality, examples of use of atactic polypropylene and styrene butadiene styrene convex copolymers according to circumstances are described.

However, these known compositions leave problems such as changes in physical properties with changes in temperature during summer and winter, recoverability against deformation, or workability due to changes in viscosity at work.

In particular, in the case of the waterproof sheet for the torch method, the waterproof sheet modified by adding styrene butadiene styrene block copolymer (SBS) to asphalt is difficult to mix asphalt and SBS, or the viscosity of the asphalt is too high, so that the amount of SBS blended It is difficult to use it in the warm-room area because it is not able to do much, and even if it is added little, it is excellent only in low temperature flexibility, and softening in high temperature area is large.

On the other hand, since the waterproof sheet modified by atactic polypropylene can be easily blended in large quantities, the atactic polypropylene is produced in a crystalline (crystalline) isotactic polypropylene resin even though there is little softening in the high temperature region. A low molecular weight amorphous polymer that is a byproduct in petroleum. It has been used in waterproofing sheet for torch construction because it is cheap because of low viscosity and by-product residue of crystalline polypropylene. There are some shortcomings, though.

In other words, there are three types of homopolymer and random copolymer block copolymers in crystalline isotactic polypropylene, but in terms of composition, propylene alone or random copolymer is only about 5% even if ethylene is copolymerized. Propylene is also only about 5-6% ethylene.

As described above, the atactic polypropylene produced by the homopolypropylene and the random copolymer is difficult to obtain good low temperature properties because propylene is the main component.

On the other hand, in the case of the amorphous polypropylene by-produced in the block copolymer, even though the rubber component to be extracted a lot of ethylene is not a random copolymer because the component is not uniform, the quality is not constant, the use value is low. For this reason, it is difficult to obtain atactic polypropylene having good low temperature properties and high usability.

In addition, since it is a by-product residue, it is difficult to produce the required amount by limiting characteristics such as viscosity, softening point, and hardness, and the desired melt viscosity because the molecular weight of the by-product atactic polypropylene also changes according to the molecular weight of the crystalline isotactic polypropylene. I could not get anything. In addition, since the solvent is used to separate the atactic polypropylene from the crystalline isotactic polypropylene, it is difficult to completely remove the solvent or to remove the catalyst residue. Moreover, as the catalyst of isotactic polypropylene shifts to a highly active type, the production amount of by-product atactic polypropylene is reduced, causing anxiety for stable acquisition in the future.

The waterproof sheet containing the by-product atactic polypropylene having the above drawbacks as the main component of the modifier is inferior in flexibility at low temperatures. It is accompanied by the risk of odor and ignition, and softening point and melting point also have defects such as being difficult to accommodate within a certain range. Moreover, there is also anxiety that the production will be stopped due to the inability to secure raw materials in the future.

Accordingly, an object of the present invention is to provide an asphalt composition which is well suited to the asphalt composition excellent in low temperature flexibility, heat resistance, workability, and quality stability, in particular, a waterproof sheet for a torch method, to eliminate the drawbacks of these known waterproofing material compositions.

That is, the waterproof sheet asphalt composition of the present invention has a number average molecular weight in the range of 1,000 to 20,000, and an amorphous propylene ethylene random copolymer having an ethylene content of 8 to 30% by weight or an amorphous propylene butene having a butene-1 content of 10 to 60% by weight. It is an asphalt composition for waterproof sheets which mix | blends 100-1900 weight part of asphalt with respect to 100 weight part of -1 random copolymers.

The amorphous propylene ethylene random copolymer or amorphous propylene butene-1 random copolymer used in the present invention is, for example, in the presence of hydrogen using a titanium supported catalyst supported on magnesium chloride and 3 ethyl aluminum. Copolymerized by introducing ethylene or liquefied butene-1 into the liquefied propylene. The number average molecular weight is in the range of 1,000 to 20,000, preferably in the range of 1,500 to 18,000 and the ethylene content of the ethylene copolymer is 8 to 30% by weight. It is an amorphous random copolymer of 9-28 weight%-or 10-60 weight% of butene-1 content of a butene-1 copolymer. Unlike by-products of atactic polypropylene, this polymer has good heat resistance of atactic polypropylene because the content of ethylene or butene-1 is in the above range, but it has good low temperature characteristics and softening point and melting point. It can be made within a certain range to make a stable quality. Moreover, the softening point and melt viscosity are set to a fixed value by the copolymerization ratio and molecular weight of propylene and ethylene or butene-1, and can be produced. In addition, since it is a polymerization without using a solvent and there is no treatment process with a solvent, there is no risk of ignition or a problem of odor.

When the number average molecular weight of the random copolymer of the present invention is less than 1,000, the asphalt modification effect is not sufficient, while in the case of 20,000 or more, the melt viscosity is too high, making it difficult to mix with asphalt. In addition, when the ethylene content of the amorphous propylene ethylene random copolymer is less than 8%, it is not expected to improve the low-temperature characteristics, while more than 30% becomes too soft at room temperature or the softening point is too low to be used for high temperature heat-resistant applications. . In addition, the random copolymer with ethylene is used to extract the degree of endothermic peak during crystal melting and soxhle extraction in boiling n-heptane in estimating the temperature increase of a differential scanning calorimeter. Insoluble content is preferably at most 15%. This is because, when the crystallinity is present, the mixing with the asphalt cannot be sufficiently performed.

Asphalt referred to in the present invention may be straight asphalt or bloated asphalt, but is preferably straight asphalt in view of ease of mixing with amorphous propylene ethylene copolymer or amorphous propylene butene-1 random copolymer and inexpensiveness. . Straight asphalt as used here is prescribed | regulated to JISK2207, and a softening point is 30-90 degreeC, Preferably it is 35-80 degreeC.

The blending ratio in the composition of the present invention is 100 to 1900 parts by weight of asphalt, preferably 120 to 160 parts by weight, relative to 100 parts by weight of the amorphous propylene ethylene random copolymer or the amorphous propylene butene-1 random copolymer. If it is less than 100 parts by weight, the asphalt component is less and the waterproofness, saltiness and workability of the asphalt are inferior.

In the composition of this invention, you may mix | blend 1 or more types of synthetic rubber, a polyolefin polymer, and a thermoplastic elastomer as needed.

By blending these polymers, the impact resistance of the waterproof sheet can be increased.For mixing with asphalt and in particular the fluidity of the waterproof sheet for the torch method, an amorphous propylene ethylene random copolymer or an amorphous propylene butene-1 random copolymer 20 parts by weight or less with respect to 100 parts by weight of the composition to be asphalt. When too much, it will not dissolve well when mixing asphalt.

Synthetic rubbers include styrene butadiene copolymer rubber (SBR), isoprene rubber (IR), butadiene rubber (BR), neoprene rubber (NPR), ethylene propylene copolymer rubber (EPR), ethylene propylene diene rubber (EPDM) and butyl rubber. Can be mentioned. Polyolefin polymers include polyethylene, polypropylene, polybutene and ethylene-based copolymers, ie, vinyl esters such as ethylene, propylene, butene, pentene, hexene, heptene, octene, methyl acrylate, ethyl methacrylate and methyl methacrylate. And copolymers with one or more comonomers selected from unsaturated carboxylic acid esters such as ethyl acid and ionomers thereof.

Examples of the thermoplastic elastomers include styrene butadiene styrene block copolymer (SBS), styrene isoprene styrene block copolymer (SIS), and styrene ethylene butylene styrene block copolymer (SEHS).

In the present invention, inorganic fillers such as calcium carbonate, aluminum hydroxide, clay talc, and the like may be appropriately added depending on the application.

In the present invention, a method for mixing an amorphous tropropylene ethylene random copolymer or an amorphous propylene butene-1 random copolymer, asphalt or other additives is conventionally known, for example, after melting and melting asphalt with a mixing brush. Into the amorphous propylene ethylene random copolymer or amorphous propylene butene-1 random copolymer and, if necessary, other additives may be added to dissolve and mix until uniform.

The composition in the present invention can be used as a waterproof sheet by impregnating, coating or compressing the asphalt composition alone or on a roofing base, a woven fabric, a nonwoven fabric, a metal sheet or a gold foil.

Roofing papers of organic or inorganic materials, such as asbestos felt, asbestos roofing, perforated felt, etc .; woven or nonwoven fabrics of inorganic materials such as glass fiber, nylon, vinylon, polyester, and fibrin, or The thing using organic long fiber or short fiber, metal thin plate, or copper foil, iron, aluminum etc. are mentioned.

The waterproof sheet of the present invention is excellent in water resistance, moisture resistance, unity, sound absorption, buffering, elasticity, electrical insulation, weather resistance, chemical resistance, heat resistance, low temperature flexibility, and thus is very useful as a roofing material for various applications, particularly torch construction. It can be used suitably.

The thickness of the electrical waterproof sheet is 0.2 to 10 mm, preferably 0.5 to 8 mm, particularly preferably 1 to 6 mm. In the case of too thin, the waterproofing effect is not sufficient, and in the case of being too thick, construction is difficult. In particular, in the case of the torch method roofing material, the back side of the sheet is melted and pasted while being unwound, so that the sheet may be melt-cut if extremely thin, and at the same time, the loosening and heating may not be performed at the same time.

As described above, the following effects can be obtained by the asphalt composition for waterproof sheet of the present invention.

① The low temperature flexibility of the waterproof sheet is improved so that it does not crack or crack when working under low temperature and after construction.

(2) Because of the good mixing property between the amorphous propylene ethylene random copolymer or the amorphous propylene butene-1 random copolymer and asphalt, a large amount of propylene ethylene random copolymer or amorphous tropropyleneene butene-1 random copolymer can be blended. The softening flow at the high temperature of the composition can be prevented.

③ Waterproof sheet with various properties such as softening point, hardness and fluidity can be obtained.

④ There is no danger of odor or flammability caused by solvent during manufacturing, construction and use.

EXAMPLE

Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these examples.

EXAMPLES 1-8

Comparative Examples 1-3

[Materials used]

(A-1) amorphous propylene ethylene random copolymer:

Rextac, manufactured by El Paso Products, USA

TABLE 1

(A-2) Amorphous Propylene Butene-1 Random Copolymer:

Rextac, manufactured by El Paso Products, USA

TABLE 2

(B) Atactic polypropylene (by-product): Chiba Fine Chemical Co., Ltd.

Softening Point: 110 ℃

Melt Viscosity: 500 (150 ℃)

Ethylene Content: 0%

(C) Styrene butadiene styrene block copolymer: Cellifre Karifurek TR1101

(D) Asphalt: Nippon Petroleum Co., Ltd. straight asphalt 80/100

[Composition Method of Composition]

Mixing the asphalt in the mixing vessel while heating and mixing the amorphous propylene random copolymer or amorphous propylene butene-1 random copolymer, atactic polypropylene, styrene butadiene styrene block copolymer as shown in Table 1 It added at the ratio and mixed melted for 30 minutes, and obtained the composition. These were measured by the following physical property measurement method. The results are shown in Table 3.

[Measurement method of physical property]

(A) Round ball softening point: In accordance with JIS K2207.

(B) Penetration degree (infiltration degree): It measures at 25 degreeC and 40 degreeC based on JISK2207.

(C) Number average molecular weight: GPC method, 135 degreeC, solvent ODCB.

(D) Ethylene content: NMR method.

(E) Low temperature flexibility: The composition was press-molded into a sheet having a thickness of 2 mm, and wound around a rod having a diameter of 10 mm under an atmosphere of -10 ° C to check for breakage. Destroyed samples / test samples.

(F) Melt viscosity: Based on JIS K2207.

TABLE 3

Claims (2)

The number average molecular weight is in the range of 1,000 to 20,000 and the ratio of the ethylene content of 8 to 30% by weight of the amorphous propylene ethylene random copolymer or the butene-1 content of 10 to 60% by weight The asphalt composition for waterproof sheets which mix | blends 100-1900 weight part of asphalt with respect to 100 weight part of qualitative propylene butene-1 random copolymers. The asphalt composition for waterproof sheeting according to claim 1, wherein the amorphous propylene ethylene random copolymer and the amorphous propylene butene-1 random copolymer have an insoluble content of not more than 15% by rapid extraction in boiling n-heptane.