JPH0753778B2 - Roofing material and its sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Object of the Invention The present invention relates to a roofing material. More specifically, mechanical properties, workability, heat resistance, cold resistance, which is made of an extremely low density ethylene copolymer obtained by randomly copolymerizing ethylene and α-olefin using a specific catalyst,
(EN) A roofing material excellent in adhesiveness and a sheet thereof.

BACKGROUND OF THE INVENTION Asphalt-based roofing, synthetic polymer-based roofing, or roofing combining these has been conventionally used for waterproofing general buildings and civil engineering structures.

When a polymer roofing material is used, these sheets are joined together to form a single waterproof layer consisting of one sheet. And, the joining between these sheets must be completed completely.

Since the roofing material is installed on the rooftop of the building, it is often applied directly to a relatively rough surface such as concrete where there are undulations, and it has high mechanical strength and elongation to withstand external stress. In addition, since the roofing material is installed outdoors, it is required to have good performance against heat from sunlight in summer and cold in winter.

Furthermore, it is necessary that it does not swell even with water vapor or oil generated from the ground such as concrete or asphalt.

Polymeric roofing materials include ethylene-propylene rubber (EPR), butyl rubber, polyvinyl chloride (PVC),
Vulcanized rubber is used. However, EPR and butyl rubber have weak mechanical strength, and PVC is not desirable because it causes bleeding of plasticizers and the like during long-term use, resulting in reduced mechanical strength. In addition, although vulcanized rubber has mechanical strength, the heat-sealing property between sheets is poor, and even if an adhesive is used, the development of an appropriate adhesive suitable for this is not sufficiently developed. There is.

[Structure of the Invention] From the above, the present inventors have conducted extensive studies to solve the above-mentioned problems, and as a result, these problems can be solved by using a specific ethylene-α-olefin copolymer. The inventors have found that a roofing material and a roofing sheet having excellent performance can be obtained, and arrived at the present invention.

That is, in the present invention, in the presence of a catalyst composed of a solid catalyst component containing at least magnesium and titanium and an organoaluminum compound, ethylene and α having 3 to 12 carbon atoms are used.
-The following (i) obtained by copolymerizing with an olefin:
The present invention relates to a roofing material made of an ethylene-α-olefin copolymer having the property (iv) and a sheet thereof.

(I) Melt index 0.01 to 100g / 10min (ii) Density 0.860 to 0.905g / cm ³ (iii) Maximum peak temperature of 100 ° C or higher by differential scanning calorimetry (DSC) (iv) Boiling n-hexane insoluble matter Is 10% by weight or more [Effect of the invention] The roofing material and the sheet thereof obtained by the present invention have the following operational effects.

(A) Molding is easy because of its excellent fluidity, and the appearance of molded products is excellent.

(B) Since it has high mechanical strength and elongation and is excellent in flexibility, it has good shapeability and can cope with external stress.

(C) Since it has excellent heat resistance, it can be used even at high temperatures due to temperature rise due to direct sunlight.

(D) Since it has excellent low temperature characteristics, it can be used well in cold regions.

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

(F) Since it is thermoplastic, it can be easily and completely bonded by the heat fusion method.

(G) Scrap can be reused.

The ethylene-α-olefin copolymer of the present invention has excellent effects as described above, and is extremely useful as a roofing material and a 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. Specific examples include propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1, decene-1, dodecene-1. Particularly preferred among these are propylene, butene-1, 4-methylpentene-1 and hexene-1. Further, dienes such as butadiene and 1,4-hexadiene can be used in combination as a comonomer. Α in ethylene-α-olefin copolymer
-The olefin content is preferably between 5 and 40 mol%.

The method for producing the ethylene / α-olefin copolymer 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 an organoaluminum compound, and examples of the solid catalyst component include metallic magnesium, magnesium hydroxide, magnesium carbonate, magnesium oxide, magnesium chloride and the like. ,
Further, double salts, double oxides, carbonates, chlorides or hydroxides containing a metal selected from silicon, aluminum and calcium and a magnesium atom, and further these inorganic solid compounds are oxygen-containing compounds and sulfur-containing compounds. , An aromatic hydrocarbon, an inorganic solid compound containing magnesium such as one treated or reacted with a halogen-containing substance, and a titanium compound supported by a known method.

Examples of the oxygen-containing compound include water, alcohol,
Organic oxygen-containing compounds such as phenol, ketone, aldehyde, carboxylic acid, ester, polysiloxane, acid amide,
Examples thereof include inorganic oxygen-containing compounds such as metal alkoxides and metal oxychlorides. As the sulfur-containing compound, thiol, organic sulfur-containing compounds such as thioether,
Examples thereof include inorganic sulfur compounds such as sulfur dioxide, sulfur trioxide, and sulfuric acid. Examples of aromatic hydrocarbons include various monocyclic and polycyclic aromatic hydrocarbon compounds such as benzene, toluene, xylene, anthracene, and phenanthrene. As a halogen-containing substance,
Examples thereof include compounds such as chlorine, hydrogen chloride, metal chlorides and organic halides.

Examples of the titanium compound include titanium halides, alkoxy halides, alkoxides and halogenated oxides. As the titanium compound, a tetravalent titanium compound and a trivalent titanium compound are preferable, and the tetravalent titanium compound is specifically represented by the general formula Ti (OR) _n X _4-n
(Here, R represents an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, and X represents a halogen atom.
Is 0 ≦ n ≦ 4. ) Are preferable, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium,
Monoethoxytrichlorotitanium, diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium. Examples thereof include titanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium and tetraphenoxytitanium. As the trivalent titanium compound, titanium tetrahalide such as titanium tetrachloride and titanium tetrabromide is hydrogen,
Examples thereof include aluminum, titanium, and titanium trihalides obtained by reduction with an organometallic compound of a metal of Group I to III of the periodic table. Further, in the general formula Ti (OR) _m X _4-m (wherein R represents an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, X represents a halogen atom, and m represents 0 <
m <4. And a trivalent titanium compound obtained by reducing the tetravalent halogenated alkoxy titanium represented by the formula (1) with an organometallic compound of a metal of groups I to III of the periodic table.

Of these titanium compounds, tetravalent titanium compounds are particularly preferable.

Specific examples of these catalysts include, for example, MgO-RX-TiCl ₄ system (Japanese Patent Publication No. 51-3514), Mg-SiCl ₄ -ROH-TiCl ₄ system (Japanese Patent Publication No. 50-23864), and MgCl. _2- Al (OR) ₃ -TiCl ₄ system (Japanese Patent Publication No. 51-152,
Sho 52-15111 _{JP), MgCl 2 -SiCl 4 -ROH-} TiCl 4 type (JP 49-106581 _{JP), Mg (OOCR) 2 -Al} (OR) 3 -TiCl 4 system (JP-B 52 −11710
JP), Mg-POCl ₃ -TiCl ₄ system (JP-B 51-153 discloses), MgCl ₂ -AlOCl-TiCl ₄ type (JP-B 54-15316 _{discloses), MgCl 2 -Al (OR)} n X 3 _-n Si (OR ') _m X _4-m -TiCl ₄ system (JP _-A- 56-95909), such as solid catalyst components (in the above formula, R and R'are organic residues, X is a halogen atom) Is shown as an example of a preferable catalyst system.

As an example of another catalyst system, a catalyst system in which a reaction product of an organomagnesium compound such as a so-called Grignard compound and a titanium compound is used as a solid catalyst component and an organoaluminum compound is combined therewith can be exemplified.
Examples of the organomagnesium compound include the general formula RM
Organomagnesium compounds such as gX, R ₂ Mg, RMg (OR) (wherein R is an organic residue having 1 to 20 carbon atoms, X is a halogen), ether complex thereof, and these organomagnesium compounds Further, other organometallic compounds, for example, organosodium, organolithium, organopotassium, organoboron, organocalcium, organozinc and the like, which have been modified and added, can be used.

Specific examples of these catalyst systems, for example, RMgX-TiCl ₄ type (JP-B 50-39470 discloses), RMgX- phenol -TiCl ₄ system (JP-B 54-12953 discloses), RMgX- halogenated phenol −TiCl ₄ series (Japanese Patent Publication No. 54-129
54), RMgX—CO ₂ —TiCl ₄ system (JP-A-57-73009), and the like, and an organoaluminum compound in combination with a solid catalyst component.

As another example of the catalyst system, Si is used as a solid catalyst component.
O ₂ , using a solid substance obtained by contacting the inorganic catalyst such as Al ₂ O ₃ and the above-mentioned solid catalyst component containing at least magnesium and titanium, it is possible to exemplify a combination of an organoaluminum compound it can. Examples of the inorganic oxides include SiO ₂ , Al ₂ O ₃ , CaO, B ₂ O ₃ , SnO _{2 and the} like, and a complex oxide of these oxides can be used without any trouble. As a method for bringing these various inorganic oxides into contact with the solid catalyst component containing magnesium and titanium, known methods can be adopted. That is, the temperature of 20 ~ in the presence or absence of an inert solvent
The reaction may be carried out at 400 ° C., preferably 50 to 300 ° C. for usually 5 minutes to 20 hours, a method by co-milling treatment, or a combination of these methods as appropriate.

Specific examples of these catalyst systems include, for example, SiO _2-
ROH-MgCl ₂ -TiCl ₄ system (JP 56-47407 _{JP), SiO 2 -R-O-} R'-MgO-AlCl 3 -TiCl 4 system (JP 57
-187305 _{discloses), SiO 2 -MgCl 2 -Al (} OR) 3 -TiCl 4 -Si (OR ') 4 system (JP 58-21405 JP) (R during the above formula, R' is a hydrocarbon And a combination of an organoaluminum compound and the like.

In these catalyst systems, the titanium compound can be used as an adduct with the organic carboxylic acid ester, or the inorganic solid compound containing magnesium described above can be used after being contact-treated with the organic carboxylic acid ester. Further, there is no problem even if the organoaluminum compound is used as an adduct with the organic carboxylic acid ester.
Furthermore, in all cases, it is possible to carry out without any problems using a catalyst system prepared in the presence of an organic carboxylic acid ester.

Here, as the organic carboxylic acid ester, various aliphatic,
Alicyclic and aromatic carboxylic acid esters are used, preferably aromatic carboxylic acid esters having 7 to 12 carbon atoms. Specific examples thereof include alkyl esters of benzoic acid, anisic acid, methyl toluic acid, and ethyl.

Specific examples of the organoaluminum compound to be combined with the solid catalyst component described above include the general formula R ₃ Al, R ₂ AlX, R
AlX ₂ , R ₂ AlOR, RAl (OR) X and an organic aluminum compound of R ₃ Al ₂ X ₃ (wherein R represents an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, and X represents a halogen atom, R may be the same or different) are preferred, and triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, diethylaluminum ethoxide, ethylaluminum sesquichloride, and mixtures thereof. Etc.

Although the amount of the organoaluminum compound used is not particularly limited, it can usually be used in an amount of 0.1 to 1000 mol times that of the titanium compound.

Further, by using the above catalyst system in the polymerization reaction after contacting it with the α-olefin, the polymerization activity can be greatly improved, and the operation can be more stable than that in the untreated case. As the α-olefin used at this time, various ones can be used, but the one having 3 to 12 carbon atoms is preferable.
Α-olefin, more preferably having 3 to 3 carbon atoms.
An α-olefin of 8 is desirable. Examples of these α-olefins include propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, decene-1, dodecene-1 and the like, and mixtures thereof. be able to. The temperature and time for contacting the catalyst system with the α-olefin can be selected within a wide range, and for example, the contact treatment can be carried out at 0 to 200 ° C., preferably 0 to 110 ° C. for 1 minute to 24 hours. Contact α
-Although the amount of olefin can be selected in a wide range, it is usually 1 g to 50,000 g, preferably 5 g to 30,000 g per 1 g of the solid catalyst component.
It is preferable to treat the α-olefin with about 1 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 normally it is desirable to contact under a pressure of -1 to 100 kg / cm ² · G.

During the α-olefin treatment, all the organoaluminum compound used was combined with the solid catalyst component and then α-
It may be contacted with an olefin, or a part of the organoaluminum compound used may be combined with the solid catalyst component and then contacted with an α-olefin, and the remaining organoaluminum compound may be added separately during the polymerization. A polymerization reaction may be performed. Further, when the catalyst system and the α-olefin are brought into contact with each other, there is no problem even if hydrogen gas coexists, and there is no problem even if other inert gases such as nitrogen, argon and helium coexist.

The polymerization reaction is carried out in the same manner as the polymerization reaction of olefins using a conventional Ziegler type catalyst. That is, all the reactions are carried out in the gas phase or in the presence of an inert solvent, or using the monomer itself as a solvent, in a state where oxygen, water, etc. are substantially cut off. The olefin polymerization conditions are a temperature of 20 to 300 ° C., preferably 40 to 200 ° C., and a pressure of normal pressure to 70 kg / cm ^2.
G, preferably 2 kg / cm ² · G to 60 kg / cm ² · G. The molecular weight can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but it is effectively performed by adding hydrogen to the polymerization system.
Of course, it is possible to carry out a two-step or multi-step polymerization reaction with different polymerization conditions such as hydrogen concentration and polymerization temperature without any trouble.

Melt index of ethylene-α-olefin copolymer synthesized as above (MI, JIS K6760)
Is 0.01 to 100 g / 10 min, preferably 0.1 to 50 g / 10 min. Density (according to JIS K 6760) is 0.860 to 0.910 g / cm ³ ,
Preferably 0.880 to 0.910 g / cm ³ , more preferably 0.890.
It is about 0.905 g / cm ³ . The maximum peak temperature (Tm) by differential scanning calorimetry (DSC) is 100 ° C or higher, preferably 110
℃ or above. The boiling n-hexane insoluble content is 10% by weight or more, preferably 20 to 97% by weight, more preferably 20 to 95%.
% (DSC and boiling n-hexane insoluble content measurement method described later).

MI of ethylene-α-olefin copolymer is 0.01g / 10min
If it is less than 100%, fluidity is lowered, and if MI exceeds 100 g / 10 min, tensile strength is lowered, which is not desirable. Density is 0.
If it is less than 860 g / cm ³ , the tensile strength will be reduced, the surface of the resin molded product will become sticky, the appearance will be impaired, and the density will be 0.90.
If it exceeds 5 g / cm ³ , elongation is undesirably reduced. If the maximum peak temperature by DSC is less than 100 ° C, the tensile strength will decrease,
In addition, the surface of the resin molded product becomes sticky and the heat resistance is lowered, which is not desirable. When the boiling n-hexane insoluble content is less than 10% by weight, the tensile strength is lowered and the surface of the molded product is undesirably solid.

Further, with respect to a roofing material and a roofing sheet using the ethylene-α-olefin copolymer of the present invention, high-density polyethylene within a range that does not change its performance,
Crystalline polyolefins such as linear low-density polyethylene, high-pressure polyethylene, polypropylene, natural rubber, various synthetic rubbers, thermoplastic elastomers, tackifiers, cross-linking agents, carbon black, calcium carbonate, silica, metal fibers, carbon fibers You may mix | blend various fillers, such as, an antioxidant, a flame retardant, and a coloring agent as needed.

[Manufacture of roofing sheet]

The roofing sheet can be manufactured by using any known technique. As a typical method, there is a method of forming a sheet using a T die. Although the thickness of the sheet varies depending on the purpose of use, a sheet having a thickness of about 1 to 2 mm is usually used.

When the roofing sheet is actually used for the roofing, it is necessary to join some sheets, and any known technique can be used as the method.
For example, a heat fusion method or a method using an adhesive can be used, and the preferable method is the heat fusion method.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. The methods for measuring physical properties in each of the examples and comparative examples will be described below.

[Creation of test sheet]

The resin composition is put into a mold having a thickness of 2 mm and a length × width of 150 mm × 150 mm, preheated at 210 ° C. for 5 minutes, and then at the same temperature of 150 kg / cm ² ·
G was pressed for 5 minutes and then cooled at 30 ° C. under a pressure of 150 kg / cm ² · G for 10 minutes. After it was annealed at 50 ° C. for 20 hours, it was left at room temperature for 24 hours, and the physical properties were measured.

[Tensile test]

According to JIS K6301, a test piece was prepared using a No. 3 dumbbell and measured at a pulling speed of 50 mm / min.

〔hardness〕

Test pieces were prepared according to JIS K6301 and measured using a C-type tester.

[Vicat softening point]

 It was measured according to JIS K7206.

[Flexible temperature]

 It was measured according to JIS K6773.

〔Oil resistance〕

Create a test piece according to JIS K6301 and use JIS No. 3 oil to 2
The volume change rate at 3 ° C for 22 hours was obtained.

[Sheet adhesion]

Sheets having a thickness of 1.5 mm were superposed on each other by about 3 cm, hot air was blown between the two sheets, and the sheets were pressure-bonded with a roller to evaluate the adhesiveness of the portions.

[Method for measuring boiling n-hexane insoluble matter]

A heat press is used to form a sheet with a thickness of 200 μm, and three 20 mm x 30 mm sheets are cut from each of the length and width, and extracted with boiling n-hexane for 5 hours using a double tube Soxhlet extractor. Do. The n-hexane insoluble matter was taken out and dried under vacuum (7 hours, under vacuum, 50 ° C.),
The boiling n-hexane insoluble matter is calculated by the following formula.

[Measurement method by DSC] About 5 mg of sample was precisely weighed from the heat-pressed 100 μm thick film, set it in the DSC device, heated to 170 ° C., and held at that temperature for 15 min, then the cooling rate was 2.5. 0 ℃ at ℃ / min
Cool down. Next, from this state, at a heating rate of 10 ° C / min
Measure at 170 ℃. The temperature at the apex of the maximum peak of the peaks appearing while the temperature was raised from 0 ° C to 170 ° C is defined as Tm.

[Example] Next, an example will be described.

Example 1 Ethylene butene was obtained by copolymerizing ethylene and butene-1 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 content of this ethylene-butene-1 copolymer is 8
7.9 mol%, melt index 1.0g / 10min, density
The maximum peak temperature of DSC was 0.895 g / cm ³ , and the boiling n-hexane insoluble content was 72% by weight. Table 1 shows the evaluation results of various physical properties.

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

The ethylene content of this ethylene-butene-1 copolymer is 9
1.0 mol%, melt index (MI) 5.1g / 10min,
The density was 0.903 g / cm ³ , the maximum peak temperature of DSC was 121 ° C., and the boiling n-hexane insoluble content was 78% by weight. Table 1 shows the evaluation results of various physical properties.

Example 3 An ethylene / propylene copolymer was obtained by copolymerizing ethylene and propylene using a catalyst composed of triethylaluminum and a solid catalyst component obtained from substantially anhydrous magnesium chloride, anthracene and titanium tetrachloride. This ethylene-propylene copolymer has an ethylene content of 88.0 mol%, MI of 1.0 g / 10 min, density of 0.901 g / cm ³ , DS
The maximum peak temperature of C is 121 ℃, boiling n-hexane insoluble matter
It was 79% by weight. The evaluation results are shown in Table 1.

Comparative Example 1 An ethylene-propylene copolymer rubber was synthesized using a VOCl ₃ -ethylaluminum sesquichloride-based catalyst.
The melt index of the copolymer rubber was 2.0 g / 10 min, the ethylene content was 83 mol%, and the density was 0.865 g / cm ³ . DSC
Has a maximum peak temperature of 33 ° C and no boiling n-hexane insoluble matter.
% By weight. The evaluation results are shown in Table 1. From Table 1, the results of Comparative Example 1 are inferior in tensile strength and elongation, and inferior in oil resistance, so that they are inferior to the ethylene-α-olefin copolymer of the present invention in applications of the roofing material and its sheet. It became clear.

Comparative Example 2 Commercially available linear low density polyethylene (Nisseki Linirex AF
2320, Nippon Petrochemical Co., Ltd.) was used to measure the physical properties. The MI of this polyethylene is 1.0g / 10min, and the density is 0.922g.
/ cm ³ , the maximum peak temperature of DSC was 123 ° C, and the boiling n-hexane insoluble content was 97% by weight. The evaluation results are shown in Table 1. Such linear low-density polyethylene has excellent tensile strength and elongation, but is too hard and lacks flexibility, and has poor adhesiveness, and is not always desirable for use as a roofing material or sheet.

Claims (2)

[Claims] 1. The following (i) obtained by copolymerizing ethylene and an α-olefin having 3 to 12 carbon atoms in the presence of a catalyst comprising a solid catalyst component containing at least magnesium and titanium and an organoaluminum compound. ~ (V) (i) Melt index 0.01 to 100 g / 10 min., (Ii) Density 0.860 to 0.905 g / cm ³ , (iii) Maximum peak temperature by differential scanning calorimetry (DSC) is 100 ° C or higher, (iv) ) Boiling n-hexane insoluble matter is 10% by weight or more (v) Roofing consisting of ethylene-α-olefin copolymer having a property that the α-olefin content in the ethylene-α-olefin copolymer is 5-40 mol% Wood and its sheet. 2. The roofing material and its sheet according to claim 1, wherein the α-olefin in the ethylene-α-olefin copolymer is an α-olefin having 3 to 6 carbon atoms.