JPS6289712A - Roofing material and sheet therefor - Google Patents

Abstract

PURPOSE:The titled product having improved mechanical characteristics, laying properties, heat resistance, freeze resistance, adhesiveness, flexibility, etc., comprising an extremely low-density ethylene copolymer obtained by copolymerizing ethylene with an alpha-olefin by the use of a specific catalyst. CONSTITUTION:Firstly, ethylene is copolymerized with 3-12 alpha-olefin (preferably propylene, etc.,) in the presence of a catalyst consisting of a solia catalytic component containing Mg and Ti and an organoaluminum compound (preferably triethylaluminum, etc.,), to give an ethylene-alpha-olefin copolymer having 0.01- 100g/10min melt index, 0.86-0.91g/cm<2> density, >=100 deg.C maximum peak tempera ture by differential scanning calorimetry and >=10wt% boiling n-hexane insoluble content. Then, the copolymer is used, to give the aimed product. MgO-RX-TiCl4 (R is organic residue; X is halogen) catalyst is preferably as the catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION OBJECTS OF THE INVENTION The present invention relates to roofing materials. More details include mechanical properties, workability, heat resistance, cold-resistant bamboo, adhesive properties, etc. of an extremely low-density ethylene copolymer obtained by copolymerizing ethylene and α-olefin using a specific catalyst. To provide an excellent roofing material and its sheet.

"Background of the Invention" Conventionally, asphalt-based roofing, synthetic polymer-based roofing, or a combination thereof has been used to waterproof general buildings and civil engineering structures.

When a polymeric roofing material is used, these sheets are joined together to form a single waterproof layer consisting of one layer of sheet 1. And the joining of these sheets must be done perfectly.

Because roofing materials are installed on the roof of a building, they are often installed directly on relatively rough and undulating surfaces, such as concrete, and require mechanical strength and strength to withstand external stress. In addition, since roofing materials are installed outdoors, they are required to have good performance against heat from sunlight in the summer and cold in the winter.

Furthermore, it is necessary that the material does not swell due to water vapor or oil generated from the base material such as concrete or asphalt.

Examples of polymeric roofing materials include ethylene-propylene rubber (EPR), butyl rubber, and polyvinyl chloride ('P
VC), vulcanized rubber, etc. are used. However, EPR and butyl rubber have low mechanical strength, and PVC may bleed out plasticizers after long-term use.
This is undesirable as it may cause a decrease in mechanical strength. Also, although vulcanized rubber has mechanical strength, the heat between the sheets @! It has poor adhesion, and even if an adhesive is used, there are problems such as the development of an appropriate adhesive that is suitable for this purpose.

[Structure of the Invention] Based on the above, the present inventors conducted extensive investigations to solve the problem (a) above, and found that 14 constant ethylene-α-
The inventors have discovered that these problems can be solved by using an olefin copolymer, and that roofing materials and roofing sheets with superior performance can be obtained, and the present invention has been achieved.

That is, in the present invention, in the presence of a catalyst consisting of a solid catalyst component J containing at least magnesium and titanium, and an organoaluminum compound, ethylene and carbon atoms having 3 to 1 carbon atoms are combined.
The present invention relates to a roofing material made of an ethylene-α-A lenoin copolymer having the properties (i) to (iv) below, which is obtained by copolymerizing 111 with the α-olefin of No. 2, and the sheet of A.

(i) Melt index 0.01-100! ? /10m1n (ii) Density 0.860-
0.910'J/car 3 (iii) Indicative & chemothermal falf method (D S C) k: The maximum peak 4 degrees is 100℃ or higher (1V) Boil! The n-helical insoluble matter is 10% by weight or more; d% or more [Effects of the Invention] The roofing material and sheet thereof obtained by the present invention have the following effects.

(b) It has excellent fluidity, which makes it easy to mold, and the appearance of the molded product is excellent.

(b) It has high mechanical strength, high elongation, and excellent flexibility, so it has good shapeability and can handle external stress! (c) It has excellent heat resistance, so it can be used even under high temperatures caused by direct sunlight.

(d) It has excellent low-temperature properties, so it can be used satisfactorily even in cold regions.

(e) Since it does not require additives such as plasticizers and has excellent weather resistance, it does not deteriorate easily even after long use.

(to) It's thermoplastic, so it's hot! Adhesion can be done easily and completely depending on the viewing method.

(1.) Scrap can be reused.

The ethylene-α-olenoin monolithic combination of the present invention has effects superior to those described above, and has extremely high utility value as a roofing material and roofing sheet.

[Detailed Description of the Invention] In the ethylene-α-olefin copolymer used in the present invention, the α-olefin copolymerized with ethylene has 3 to 12 carbon atoms. Specifically, propylene,
Butene-1,4-methylbendene-1, Heyasen-1,
Octene-1, decene-1, dodecene-1, etc. can be mentioned. Particularly preferred among these are propylene, butene-1,4-methylbendene-1 and hexene-1. In addition, dienes, 1
For example, butadiene, 1,4-lysine, and the like can be used. Ethylene-α-olefin JL i
It is preferable that α-=olefin linkage in the U combination is 5 to 40 mol%.

The method for producing the copolymer of ethylene and α-A refine used in the present invention will be described below.

First, the catalyst system used is a combination of a solid catalyst component containing at least magnesium and titanium with various aluminum compounds, and the solid catalyst components include, for example, magnesium metal, magnesium hydroxide, magnesium carbonate, magnesium oxide, and magnesium chloride. Such,
In addition, double salts, double oxides, carbonates, chlorides, or hydroxides containing metals selected from silicon, aluminum, and calcium and magnesium atoms, as well as 2MM compounds and Examples include those in which a titanium compound is supported by a known method on an inorganic solid compound containing magnesium, which has been treated or reacted with a sulfur compound, an aromatic hydrocarbon, or a halogen-containing substance.

Examples of the sulfur-containing compound in L include water, alcohol,
Examples include oxygen-containing compounds such as phenols, ketones, aldehydes, carboxylic acids, esters, polyoxyoxanes, and acid amides, metal alkoxides, and inorganic solid compounds such as metal dichloride chopsticks. Examples of the sulfur-containing compound include organic sulfur-containing compounds such as thiol, thiol, and thiol, and non-sulfur compounds such as sulfur dioxide, IA trioxide, and la acid. Examples of aromatic hydrocarbons include various qt-ring and polycyclic aromatic hydrocarbon compounds such as benzene, toluene, xylene, anthracene, and phenothrene. Halogen-containing substances include chlorine, hydrogen chloride, metal salts,
Examples include compounds such as organic halides.

Examples of the butane compound include titanium halides, alkoxydihalides, alkoxides, and halogenated oxides. As a titanium compound, 4IIl
The titanium compound represented by i and the titanium compound represented by 31j5 are suitable, and the tetravalent titanium compound is specifically represented by the general formula Ti
(OR)
n≦4. ) are preferred, and titanium tetrachloride, titanium tetrabromide, butane tetraiodide, monomethoxytrichlorotitanium, dimethoxydi[10titanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, Toxydichlorotitanium, triethoxymonochlorotitanium, tetramethoxytitanium, monoisopropoxytrichlor1]titanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxytichloritanium, monobento Examples include 1-citrichlorotitanium, monophenoxytrichlorobutane, diphenoxydichlorotitanium, trinoenoxy7-chlorotitanium, and detraphenoxyditane cap. As trivalent titanium compounds, titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide are combined with hydrogen,
Aluminum, titanium or circumference 11J *! Examples include trihalogenated titanium which can be reduced with an organometallic compound of a group In metal.It also represents an alkyl group, an aryl group, or an aralkyl group of the general formula 7.
X represents a halogen atom. m is Q<m<4.

) represents a tetravalent alkoxybutane! ! Examples thereof include trivalent titanium compounds obtained by reduction with organometallic compounds of metals of groups 111IfiiI to II.

Among these titanium compounds, tetravalent titanium compounds are particularly preferred.

Specific examples of these catalysts include, for example, the MOO-RX-T r Cja system (Japanese Patent Publication No. 1983-
3514), M OS + 0 1 4 -- RO
H-T + CI 4 system (Special Public Interest Publication in 1984)
-23864), MCI 012-AI (OR) 3-ri CM
4 series (Special Publication No. 51-1520, Special Publication No. 52-151
11), M(l Cj 2-8i C14-ROH-Ti CI
4 series (Special 1m Publication No. 49-106581), Mg(O
OCR)2-AI (OR)3-T i CL4 series (Special Publication No. 52-11710), Mg-POCJ) 3
-TlCJ, s series (Japanese Patent Publication No. 51-153), MIJ C12-AN OCN -Ti CM 4 series (
Special Publication No. 54-1531 (Publication No. I), M (J Cj 2
-A! J (OR), X3-nSi (OR')
An organoaluminum compound is combined with a solid catalyst component (in the above formula, R1R' is an organic residue and X is a halogen atom) such as Examples of preferred catalyst systems include:

Another example of a catalyst system is a catalyst system in which a reaction product of an organomagnesium compound such as a so-called Grignard A compound and a titanium compound is used as a solid catalyst component, and an organoaluminum compound is combined with this. . Examples of organomagnesium compounds include general formula RMgX.

Organomagnesium compounds such as R2Mg, RMo (OR>, where R is an organic residue having 1 to 2 carbon atoms, and X represents a halogen) and their ether complexes, and these organomagnesium compounds, Organometallic compounds such as chromium, organolithium, 4'
TL! It is possible to use denatured organic compounds by adding various compounds such as potassium, organic boron, organic calcium, and organic zinc.

Specific examples of these catalyst systems include, for example, RMO
X T i Cj! , s series (Special Publication No. 50-3947
0 X3 Publication), RMgX-pheno-ru-r i C
J4 series (Japanese Patent Publication No. 54-12953), RMo X-halogenated phenol Ti0.04 series (
Special Publication No. 54-12954), RM OX CO
2-1' I CfJ, s series (JP-A-57-7300
(No. 9)) Examples include those in which an organoaluminum compound is combined with a solid catalyst component of a cap.

In addition, as an example of another catalyst system, C is a solid catalyst component, and Si
An example is a combination of a solid substance obtained by contacting an inorganic oxide such as O, Al2O2, etc. with the solid catalyst component containing at least magnesium and titanium, and an organoaluminium compound. 1
In addition to SiO and AfJ203, M organic oxides include Ca.
0°B203, Sn02, etc. can be used, and double oxides of these oxides can also be used without any problems. Any known method can be used to bring these various inorganic oxides into contact with the solid catalyst component containing magnesium and titanium. For example, a method of reacting in the presence or absence of an inert solvent at a temperature of 20 to 400°C, preferably 50 to 300°C for usually 5 minutes to 20 hours, a method of co-pulverization, or any of these methods as appropriate. The reaction may be carried out by combining them.

Specific examples of these catalyst systems include, for example, S
i 02 ROHMU CJI 2
Ti Cj 4 system (Japanese Unexamined Patent Publication No. 56-47407), 8102 ROR' M (I 0-AICI3-T
iCN4 series (Japanese Unexamined Patent Publication No. 57-187305), S
i 02 Mcl C4) 2 AN (pull) 3
-Ti CJ4-3i (OR') 4 series (JP-A-58
-21405) (In the above formula, R and R' represent hydrocarbon residues.

), etc. On the right are those made by combining aluminum compounds.

In these catalyst systems, titanium compounds can also be used as adducts with organic carboxylic acid di-L esters, and inorganic solid compounds containing the above-mentioned magnesi 1 cum can be used as ba
Contact with carboxylic acid ester 11! l5II! ! You can also use it after doing so. Furthermore, there is no problem in using the organoaluminum compound as an adduct of any carboxylic acid ester. In addition, it is also perfectly possible in all cases to use a catalyst system prepared in the presence of an organic carvone M,'l-ster.

Here, the organic carboxylic acid esters include various aliphatic,
Alicyclic or aromatic carboxylic acid esters are used, and aromatic carboxylic acid esters having carbon Wi of 7 to 12 are preferably used. Specific examples include alkyl esters of benzoic acid, anisic acid, and toluic acid, such as methyl and ebul.

Specific examples of the aluminum compound to be combined with the solid catalyst component described above include the general formula RΔ, 11.
R, IX, R1! X2゜R2AJ OR, RAJ (O
R) Organoaluminum compound of X and C7RΔ12X3v
)J (where R is an alkyl bond having 1 to 20 carbon atoms, an aryl group or an aral group, X is a halogen atom, and R
may be the same or different), including triedylaluminum, trioctylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminium chloride, diethylaluminum ethoxide, ethylaluminum sesyachloride, and these compounds. Examples include mixtures.

The amount of organoaluminum compound used is not particularly limited, but is usually 0.1 to 1000 mol relative to the titanium compound18
can be used.

Further, by using the above-mentioned catalyst system in a polymerization reaction in contact with an α-olefin, the polymerization activity can be greatly improved, and operation can be made more stable than in the case of no treatment. Various α-olefins can be used at this time, but preferably α-olefins having a carbon number of 3 to 1
α-olefin having 2 carbon atoms, more preferably 3 carbon atoms
~8 α-olefins are preferred. Examples of these α-olefins include propylene, butene-1, pentene-1,4-methylpentene-1, he, 1-hin-
Examples include 1, octene-1, decene-1, dodecene-1, and mixtures thereof. Catalyst system and α
- The temperature during contact with the olefin, 9511, can be selected within a wide range, for example from 0 to 200 °C, preferably t
The contact treatment can be carried out at 0 to 110°C for 1 minute to 24 hours. The amount of α-A-refin to be contacted can be selected from a wide range, but it is usually 1g to 5g per 1g of the solid catalyst component.
It is desirable to treat with an α-olefin of about 0.0OO5F, preferably about 57 to 30.0009, and react with 1 g to 500 g of α-olefin per 1 g of the solid catalyst component. At this time, the pressure at the time of contact can be arbitrarily selected, but it is usually desirable to make the contact under a pressure of -1 to 1003 g/cIi.G.

During the α-A reflex treatment, if the organoaluminum compound used is combined with all 81 solid catalyst components, α-
It may be brought into contact with an olefin, or a part of the organoaluminum compound used in combination with the solid catalyst component may be brought into contact with an α-olefin, and the remaining organoaluminium hexapolymer is added separately during polymerization. The polymerization reaction may be carried out by Further, when the catalyst system is brought into contact with the α-olefin, there is no problem even if hydrogen gas coexists, and there is no problem even if other inert gases such as nitrogen, argon, helium, etc. coexist.

The polymerization reaction is carried out in the same manner as an ordinary olefin polymerization reaction using a Ziegler type catalyst. That is, all reactions are carried out substantially in the absence of oxygen, water, etc., in the gas phase, in the presence of an inert solvent, or using the monomer itself as a solvent. Olefin polymerization conditions are temperature number 120-300
℃, preferably 40 to 200℃, and the pressure is normal pressure to 70 KI/t:d-G s, preferably 2 K'J
/ I: i.G to 608 g/ci.G. Although the molecular weight can be adjusted to some extent by changing polymerization conditions such as polymerization humidity and catalyst molar ratio, it is more effectively carried out by adding hydrogen to the polymerization system. Of course, a two-step or more multi-step polymerization reaction using different polymerization conditions such as hydrogen hydroxide and polymerization temperature can also be carried out without any problem.

Melt index of the ethylene-α-olefin copolymer synthesized as described above (old.

JIS K6760 G: Yoru) u 0.01~10
0g/10m1n.

Preferably it is 0.1-50g/10a+in. Density (JIS K 8760: J Nil) Ha0.880
-0.910g/cttr3, preferably 0.880-
0.910g/cIR3, more preferably 0.890
~0.90! lbi/cttt 3. The maximum peak temperature (◯) measured by differential scanning thermo-thermometry (DSC) is at least 100'C, preferably at least IIO'C. The insoluble matter in boiling water is 10% by weight or more, preferably 2% by weight.
It is 0 to 97% by weight, more preferably 20 to 95% by weight (DSC 5J: method for measuring the hexane insoluble content will be described later).

Ml of ethylene-α-olefin copolymer is 0.01
If Ml is less than 10 g/10 m1n, the fluidity will decrease, and if Ml is less than 1
If it exceeds 00g/10m1n, tensile strength etc. will decrease, which is not desirable. If the density is less than 0.860ff/13, the tensile strength will decrease and the surface of the resin molded product will become sticky, deteriorating the appearance, and if the density is less than 0.910g/c.
If it exceeds m3, the elongation decreases, which is not desirable. If the maximum peak temperature measured by DSC is less than 100° C., the tensile strength will decrease, the surface of the resin molded product will become sticky, and the heat resistance will also deteriorate, which is not desirable. )l181Iln-
If the hexane-insoluble content is less than 10% by weight, the tensile strength will decrease and the surface of the molded product will become sticky, which is not desirable.

In addition, for roofing materials and roofing sheets using the ethylene-α-olefin copolymer of the present invention, high-density polyethylene, linear low-density polyethylene, high-pressure polyethylene, Crystalline polyolefins such as polypropylene, natural rubber, various synthetic rubbers, thermoplastic elastomers, tackifiers, crosslinking agents, carbon black, calcium carbonate, silica,
metal! Various fillers such as carbon fiber, antioxidants, flame retardants, colorants, etc. may be added as necessary.

[Manufacture of roofing sheets]

Roofing sheets can be made by using any known technique. A typical method is to mold the material into a sheet using a die. Sea 1-
Although the thickness varies depending on the purpose of use, a thickness of about 1 to 2 # is usually used.

When roofing is actually carried out using roofing sheets, it is necessary to join several sheets together, and any known technique can be used to do so.

For example, a heat fusion method or a method using an adhesive may be used, but a preferable method is a heat fusion method.

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto. The method for measuring the physical properties of each Example and Comparative Example will be described below.

[Creation of test sheet]

The resin composition has a thickness of 2 tta and a length x width of 150 m
It was placed in a 15G shoe mold, heated at 210°C for 5 molecules, then press-molded at the same temperature for 5 minutes at 150kg/cd-G, and then cooled at 30°C for 10 minutes under a pressure of 150kg/ci-G. After annealing it at 50° C. for 20 hours, it was left to stand at room temperature for 24 hours, and its physical properties were measured.

[Tensile test]

A test piece was prepared using a No. 3 dumbbell according to JIS K6301, and the test piece was measured at a tensile speed of 501 M/min.

[Hardness]

A test piece was prepared according to JIS 6301 and measured using a C-type tester.

[Vicat softening point]

Measured according to JIS 720G.

[Flexible humidity]

Measured according to JIS K6773.

〔Oil resistance〕

A test piece was prepared according to JIS 6301, and JIS 3
The volume change rate was determined using No. 9 oil at 23° C. for 22 hours.

(Adhesiveness of the sheet) 1. Press the two sheets together with a roller while blowing hot air between the two sheets to check the adhesion of the parts. I planned it.

[Measurement method for boiling r1-hexane insoluble matter] Use a heat press to form a sheet with a thickness of 200 μm, cut out three sheets of 20 am x 30 m + lengthwise and widthwise, and use a double-tube Soxhlet extractor. Boil! I! I
Extraction is carried out for 5 hours with n-hekirin. After taking out the n-hexane insoluble matter and vacuum drying (7 hours under vacuum at 50° C.), the boiling n-hexane insoluble matter is calculated using the following formula.

(Measurement method using DSC) Approx.
Precisely weigh the sample at J+5F, put it into a DSC device, raise the temperature to 170°C, hold at that temperature for 151 days, and then cool to 0°C at a cooling rate of 2.5°C/min.

Next, from this state, the product temperature is 1M degrees and 10 degrees Celsius/win.
Measure the temperature of the product down to 0°C. The temperature at the top of the maximum peak that appeared during the product temperature rise from 0°C to 170°C is defined as 6 m.

[Example] Next, an example will be described.

Example 1 Ethylene and butene-1 were copolymerized using a solid catalyst component obtained from substantially anhydrous magnesium chloride, 1,2-dichloroethane, and titanium tetrachloride, and a catalyst consisting of triethylaluminum. -1 copolymer was obtained.

The ethylene n8 of this ethylene-butene-1 copolymer is 8
7.9'L-le%, melt index is 1.0g/1
0m1n, density is 0.895g/cta3, D S
The maximum peak temperature of C was 119°C, and the 11n-hekirin insoluble content was 72% by weight. Table 1 shows the planning results of various physical properties.
It was shown to.

Example 2 Using the same catalyst as in Example 1, ethylene butene-1
A common hair combination was obtained.

The ethylene trivalent number of this ethylene-butene-1 copolymer is 9
1.0 mol%, melt index (MI) 5.1g
/10m1n, density is 0.9039/as3, S
The maximum peak temperature of DC was 121°C, and the boiling point insoluble in 11n-hexane was 78% by weight. Table 1 shows the evaluation results of various physical properties.

Example 3 Ethylene and propylene were copolymerized using a solid catalyst component obtained from substantially anhydrous magnesium chloride, anthracene, and titanium tetrachloride and a catalyst consisting of triethylaluminum to obtain an ethylene-propylene copolymer. The ethylene content of this ethylene-propylene copolymer is 88.0 mol%, the Ml is 1.0 g/10 m1n, and the density is 0.901! J/cm3, the maximum peak temperature of DSC was 121°C, and the insoluble matter in boiling water was 19% by weight. The evaluation results are shown in Table 1.

Comparative Example 1 (1) An ethylene-propylene copolymer rubber was synthesized using a 0Cj3-ethylaluminum sesquichloride catalyst. The melt index of the copolymer rubber is 2. OJ/
The 10sin, x tyrene content was 83 mol%, and the density was 0.865 g/α3. The maximum peak humidity by DSC was 33° C., and the boiling point insoluble matter was 0% by weight. The results of Evaluation III are shown in Table 1.

From Table 1, the results of Comparative Example 1 are inferior in tensile strength and elongation;
In addition, since the oil resistance is poor, it has become clear that the copolymer is inferior to the ethylene-α-olefin copolymer of the present invention for use in roofing materials and sheets thereof.

Comparative Example 2 Commercially available linear low density polyethylene (8 stone Nilex A
Physical properties were measured using F232G, Nippon Petrochemicals@Product). Ml of this polyethylene is 1.0g/10m
1n, the density was 0.922g/cry3, the maximum peak temperature of DSG was 123°C, and the boiling l1n-hexane insoluble content was 971%. The evaluation results are shown in Table 1.

Although such linear low-density polyethylene has excellent tensile strength and elongation, it is too hard, lacks flexibility, and has poor adhesive properties, so it is not necessarily desirable for use in roofing materials and sheets.

Procedural amendment 1. Indication of the case 1985 Patent Application No. 228388 2 Name of the invention Roofing material and its sheet 3 Relationship with the famous case to be amended Applicant name (444) Nippon Oil Co., Ltd. 4 Agent address 107 01-1-5, Minami-Aoyama, Minato-ku, Tokyo
, date of amendment order (voluntary) (shipment date) Showa year, month, day 7, rsDJ on the bottom line of page 23 of the amended statement of contents is amended to fDsj.

that's all

Claims (2)

[Claims] (1) The following (i) to ( iv) (i) Melt index 0.01-100g/10min (ii) Density 0.860-0.910g/cm^3(i
ii) A roofing material made of an ethylene-α-olefin copolymer having a maximum peak temperature of 100°C or higher by differential scanning calorimetry (DSC) (iv) A boiling n-hexane insoluble content of 10% by weight or higher; sheet. (2) α- in the ethylene-α-olefin copolymer
The roofing material and its sheet according to claim 1, wherein the olefin is an α-olefin having 3 to 6 carbon atoms.