DE19639865A1 - Thermoplastic olefin elastomer film, laminate comprising the film and use thereof - Google Patents

Abstract

A sheet comprising an olefin thermoplastic elastomer obtained by dynamically heat-treating 100 parts by weight of a mixture of 40 - 90 % by weight of (A) an olefin polymer rubber having a Mooney viscosity at 100{C (ML 1+4 100{C) of 5 - 100 and substantially free from unconjugated diene and 60 - 10 % by weight of (B) an olefin polymer in the presence of 0.005 - 0.5 part by weight of an organic peroxide and 0.05 - 4 parts by weight of N,N'-m-phenylenebismaleimide or divinylbenzene is excellent in light resistance and thermal aging resistance. A laminate comprising said sheet and a foamed sheet is also provided.

Description

The present invention relates to a film comprising a thermoplastic olefin elastomer with excellent lightfastness and thermal aging resistance comprises a laminate comprising the film and the use thereof. More specifically concerns the invention a film which is a thermoplastic olefin elastomer with excellent Durability properties, especially light resistance or the like is characterized in appearance and feel or the like, and with the polyvinyl chloride material Plasticizer can be replaced; a laminate comprising the film, and one the film or the interior trim material for motor vehicles comprising the laminate.

Thermoplastic elastomers are widely used in industrial products, including automotive parts, parts for electrical equipment and various articles since the time-consuming vulcanization step in their manufacture is not required and they using a conventional thermoplastic resin molding machine can be processed.

On the other hand, moldings with improved quality are known to date, which are made by Laminating a surface layer material onto a molded thermoplastic resin were made to give them an improved look and soft feel. As  For example, surface layer material became a soft polyvinyl chloride material Macher used that with a foamed layer of polyolefin or polyurethane is lined to give it damping properties.

However, the polyvinyl chloride surface layer material has the problem that it has a high specific density and is poorer in light resistance. Therefore, its surface appearance will deteriorate significantly if it is used as a surface Layer material is used for a motor vehicle part that is directly exposed to sunlight is exposed. Because it is softened by containing a large amount of plasticizer it also has the problem; that the windshield and the like Plasticizer is fogged up when used as an interior finish surface material is used for motor vehicles.

In addition, because of its chemical structure, polyvinyl chloride Burning hydrogen chloride gas creates another problem that its combustion after use from the environmental point of view should not be allowed and that it tends to erode various processing equipment.

To solve the problems described above, it has been proposed to Surface layer material using an olefin thermoplastic elastomer to produce the non-conjugated ethylene-α-olefin as a rubber component Diene copolymer rubber includes (JP-A-4-73 112).

However, when ethylidene norbomene deteriorated as the non-conjugated diene deteriorated the properties of the product were used within a short period of time Expose to light.

When dicyclopentadiene was used as the non-conjugated diene, the was Property deterioration less noticeable in a short period of time (JP-A-5-279524), but there was still a problem that the thermal aging durability of the product was not sufficient. Therefore, if a thermoplastic Elastomeric film containing one of these non-conjugated dienes for use is used where light resistance is particularly required, such as as a top surface layer material for the dashboard of the motor vehicle, a large amount of Light stabilizers can be used to prevent light aging. As a result Problems arise that have to be solved by the film on the surface of the film deposited light stabilizer becomes dirty or the windshield through sub limited light stabilizer mists up.

The object of the present invention is therefore to overcome these problems of the prior art Technique to solve and provide a film that is a thermoplastic olefin elastomer with excellent lightfastness and heat resistance properties,  a laminate comprising the film and an interior material for motor vehicles, comprising the film or the laminate.

As a solution to these problems, it has been found that light decomposition and Heat decomposition is less evident when taking a thermoplastic olefin elastomer Use of an olefin polymer rubber that is free of non-conjugated diene, and using certain amounts of a special crosslinking agent and one special cross-linking agent is produced.

The present invention provides a film comprising a thermoplastic olefin elastomer which is obtained by dynamic heat treatment of 100 parts by weight of a mixture of 40-90 wt.% (A) of an olefin polymer rubber having a Mooney viscosity at 100 ° C ( ML _{1 + 4} 100 ° C) of 5-100, which is essentially free of non-conjugated diene, and 60-10 wt .-% (B) of an olefin polymer in the presence of 0.005-0.5 parts by weight of an organic peroxide and 0.05-4 parts by weight of N, N'-m-phenylene bismaleimide, divinylbenzene or a mixture thereof is available.

The film according to the invention preferably has a thickness in the range of 0.1- 5 mm, in particular 0.2-2 mm.

The present invention further provides a laminate comprising a thermoplastic olefin elastomer according to the invention and a laminated thereon Foam or a foamed sheet material laminated thereon. The laminate can through Laminating a foam or a foamed sheet made of a material such as poly ethylene, polypropylene and polyurethane, on the thermoplastic olefin elastomer film be preserved.

The present invention further provides an interior trim material for Motor vehicle ready, which comprises the film or the laminate.

The present invention will now be described in detail.

First, the thermoplastic olefin elastomer film according to the invention is next described below.

The olefin polymer rubber (A) used in the present invention is an olefin polymer rubber having a Mooney viscosity at 100 ° C (ML _{1 + 4} 100 ° C) of 5-100, preferably 10-70, and is substantially free of non-conjugated diene .

If the Mooney viscosity at 100 ° C (ML _{1 + 4} 100 ° C) is less than 5, the advantageous mechanical properties cannot be obtained, and if it is higher than 100, the appearance of the molded product is worse. Therefore, this is not preferred.

The olefin polymer rubber (A) used in the present invention includes, for example, amorphous statistical elastic copolymers that are considered an olefin Main ingredient included selected from ethylene-propylene copolymer rubber, Ethylene-1-butene copolymer rubber and propylene-1-butene copolymer rubber. The  amorphous static elastic copolymers preferably contain the olefin in one Amount of at least 50% by weight. Among them, ethylene propylene Copolymer rubber (hereinafter referred to as "EPM") preferred and ethylene Propylene copolymer rubber with a propylene content of 10-40% by weight, especially 20-35% by weight, more preferred.

Preferably, the olefin polymer used in the present invention is (B) polypropylene or a copolymer of propylene and an α-olefin other than Propylene. The α-olefin other than propylene includes, for example, ethylene, 1-butene, 1- Pentene, 3-methyl-1-butene, 1-hexene, 1-decene, 3-methyl-1-pentene, 4-methyl-1-pentene and 1-octene. The polymer has a melt flow rate usually in the range of 0.1-100 g / 10 minutes and preferably 0.5-50 g / 10 Minutes on.

The olefin thermoplastic elastomer used in the present invention can be obtained by dynamic heat treatment of a mixture comprising (A) an olefin polymer rubber and (B) an olefin polymer in the presence of an organic peroxide obtained as a special crosslinking agent and a special crosslinking aid will.

The organic peroxide includes, for example, 2,5-dimethyl-2,5-di (tert-butylper oxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexy-3,1,3-bis (tert-butylperoxy-yiso propyl) benzene, 1,1-di (tert-butyiperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5- di (peroxybenzoyl) hexin-3 and dicumyl peroxide. Among them is 2,5-dimethyl-2,5- di (tert-butylperoxy) hexane or 2,5-dimethyl-2,5-di (tert-butylperoxy) hexin-3 of Ge the smell and the light-off properties of the cross-linking prefers.

The amount of the organic peroxide can range from 0.005-0.5 parts by weight, preferably 0.01-0.1 part by weight, per 100 parts by weight of the total amount of Olefin polymer rubber (A) and the olefin polymer (B) can be selected.

An amount of the organic peroxide less than 0.005 part by weight is not preferred because the crosslinking becomes non-uniform. If the amount is more than 0.5 part by weight the strength of the film becomes lower.

In the production of the thermoplastic olefin elastomer according to the invention a special crosslinking aid in a certain amount in addition to the organic peroxide added.

The special cross-linking aid is N, N'-m-phenylene bismaleimide or di vinylbenzene.

Using such a connection occurs a uniform and moderate Crosslinking reaction, and it can even be used for the olefin polymer rubber used in the  is essentially free of non-conjugated diene, an improvement in mechanical Properties can be achieved.

The amount of crosslinking aid is in the range of 0.05-4 parts by weight, preferably 0.1-2 parts by weight, per 100 parts by weight of the total amount of the oil polymer rubber (A) and the olefin polymer (B).

If the amount of the crosslinking aid is less than 0.05 part by weight, postforming, such as vacuum forming, is not performed properly, and if the Amount is more than 4 parts by weight, the fluidity decreases, which the molding process processing impaired.

The olefin thermoplastic elastomer used in the present invention can be of the partially networked type or of the fully networked type, but is preferably of the partially cross-linked type.

The thermoplastic olefin elastomer according to the invention can by dynamic Heat treatment of a mixture comprising 40-90 parts by weight, preferably 60-80 Parts by weight, (A) of an olefin polymer rubber and 60-10 parts by weight, preferably 40- 20 parts by weight, (B) of an olefin polymer (the amounts being chosen so that the Sum (A) + (B) is 100 parts by weight), in the presence of an organic peroxide and of the above-mentioned special crosslinking aid.

If the amount of the (A) olefin polymer rubber is less than 40 parts by weight, a flexible olefin thermoplastic elastomer cannot be obtained, and a 90th Amounts in excess of parts by weight are not preferred because the fluidity lowers becomes what affects the processing into a film.

The process for producing a film from that described above thermoplastic elastomer is not particularly limited and includes, for example Process in which the thermoplastic elastomer from an extruder at about 150- 250 ° C is extruded using a T-shape process, and a process in which the elastomer the calendering to form a film at a temperature in same area.

The laminate comprising the film according to the invention and the use thereof are illustrated below.

The laminate according to the invention is a laminate which is the one described above Foil and a foam laminated thereon or a foamed foil of a material, comprises, with polyethylene, polypropylene and polyurethane being preferred as the material.

The process for producing the laminate according to the invention is not special it also limits and includes, for example, a method in which a melted Foil under foil molds with a foam or a foamed foil of a material, such as polyethylene, polypropylene and polyurethane, can be combined in layers  and they pass the distance between a pair of rollers. With this procedure the thermoplastic elastomer film is preferably in contact with an embossing roller brought and the foam or the foamed sheet is preferably with a ordinary roller that is not heated.

If necessary, an olefin resin can be added to the thermoplastic olefin elastomer mixed, which was obtained as above. The amount to be mixed is in an area that does not affect the flexibility of the thermoplastic olefin elastomer impaired, and is preferably less than 50 wt .-%. The olefin resin is not particularly limited and includes, for example, polyethylene and polypropylene. Under they prefer low density polyethylene.

Examples of end products using the thermoplastic olefinela stomer film or the laminate comprising the film include the following introduced interior materials for automobiles.

Examples of the interior materials include interior materials such as Dashboard, console case, armrest, headrest, door trims, rear cover clothing, column decorations, sun visor, trims from the trunk, trims from Luggage compartment lid, air bag container, seat buckles, glove compartment, steering wheel cover and material for the blanket.

Examples of other uses for the thermoplastic olefin elastomer film or the laminate comprising the film according to the invention includes parts for electrical Household and office equipment, parts for buildings and houses and parts for others industrial use where light resistance and heat resistance are required are as listed below.

Regarding the parts for electrical household appliances and office equipment, the suitable use for example materials for televisions, VCRs, washing machine, dryer, vacuum cleaner, cooler, air conditioner, remote control housing, electronic equipment, toaster, coffee maker, pot; Vessel, dishwasher, staff Computer, typewriter, projector, telephone, copier, facsimile, teleprinter and other housings and office supplies where light resistance and Heat resistance is required.

With regard to parts for buildings and houses, the appropriate use includes Example material for furnishings, table, armchairs, wall ornaments, ceiling ornaments and Curtain wall and the like, interior flooring for the kitchen, washroom and toilet and the like, outdoor flooring for porch, patio, balcony and carport and the like, carpet-like fabrics such as doormats, tablecloths, coasters and Ashtray rag, a.  

With regard to parts for other industrial use, an appropriate one includes Use, for example, a handle of an electrical tool.

Other suitable uses include, for example, bag materials, Suitcase, index box, notebook, album, stationery, camera body, dolls and other toys and materials for picture frames.

The olefin thermoplastic elastomer used in the present invention If necessary, additives such as filler, lubricant, antioxidant, UV-Ab sorbents and lightfastness agents.

Examples

The present invention is illustrated by the examples, which are not considered Limitation of the scope of the invention should be understood.

The test methods used to measure the properties in the Examples and comparative examples are illustrated below.

(1) Mooney viscosity at 100 ° C (ML _{1 + 4} 100 ° C)

The measurement was carried out according to ASTM D927-57T. For the oil-stretched ethylene-propylene-ethylidene norbornene copolymer rubber (hereinafter referred to as EPDM) used in the comparative examples, the value was calculated using the following equation:
log (ML₁ / ML₂) = 0.0066 (ΔPHR)
ML₁: Mooney viscosity of EPDM
ML₂: Mooney viscosity of oil-extended EPDM
ΔPHR: amount of oil stretching per 100 parts by weight of EPDM

(2) Melt Flow Rate (MFR)

The measurement was carried out according to JIS K-7210 at 230 ° C and 10 kg.

(3) Elongation at break and ratio of maintaining elongation when the train breaks

Elongation at break was measured according to JIS K-6301 using a JIS No. 3 dumbbell test sample at an elongation rate of 200 mm / minute measured.

The ratio of maintaining the elongation at tensile break was calculated using the following equation:
Ratio of elongation at break (%) = (elongation at break after examination of light or heat resistance) / (elongation at break before examination).

example 1

Using a Banbury mixer, 70 parts by weight of ethylene-propylene copolymer rubber [EPM-1, propylene content = 22% by weight, ML _{1 + 4} 100 ° C = 35], 30 parts by weight of polypropylene (MFR = 2.0 g / 10 minutes, homotype), 0.4 part by weight of N, N′-m-phenylenebismaleinimide (Sumifine BM, manufactured by Sumitomo Chemical Co., Ltd.) as a crosslinking aid, 0.2 part by weight of Sumisorb 300 (manufactured by Sumitomo Chemical Co., Ltd.), 0.2 part by weight of Sanol LS-700 (manufactured by Sankyo Ltd.), 0.1 part by weight of Tinuvin 622 (manufactured by Ciba-Geigy Corp.) as light stabilizers and 0.1 part by weight Kneaded Irganox 1010 as a heat stabilizer for 7 minutes at 170-200 ° C. Then they were molded with an extruder to produce a master batch in pellet form. 100 parts by weight of the masterbatch were uniformly mixed with 0.04 part by weight of 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane in a Henschel mixer for 3 minutes.

The mixture was run at 240-260 ° C in a double cut for about 30 seconds Kneading extruder (TEX-44HC, manufactured by Nippon Seikosho Co.) dynamically heat acts, receiving pellets of a partially crosslinked thermoplastic elastomer were.

Then the thermoplastic elastomer was made using an extruder film machine with a 25 mm (diameter) T-shape formed into a film. A Sample was punched out of the film thus obtained with a JIS No. 3 dumbbell and the Light test with a Sunshine Weather-O-Meter (S.W.O.M.) (manufactured by Suga Test Instruments Co., Ltd.) under a blackboard temperature of 83 ° C without water subjected to and the light resistance through the ratio of maintaining the stretch determined in the event of a broken train after a specified period of time. The results of the Determination are listed in Table 1.

Comparative Example 1 Manufacture of oil-extended EPDM-1

To a 5% (wt .-%) solution of ethylene-propylene-ethylidene norbornene (ENB) copolymer rubber [EPDM-1, iodine number = 12, propylene content = 28 wt .-%, ML _{1 + 4} 100 ° C = 242] 100 parts by weight of mineral oil (Diana process oil PW-380, manufactured by Idemitsu Kosan Co.) was added to hexane per 100 parts by weight of EPDM-1. Then the solvent was removed by steam stripping to give oil-extended EPDM-1 (ML _{1 + 4} 100 ° C = 53).

The procedure of Example 1 was repeated except that EPM-1 was replaced by the Oil-stretched EPDM-1 obtained above was replaced. The results of the assessment are shown in Table 1.

Example 2

The procedure of Example 1 was repeated except that the amounts of Sumi sorb 300 as light stabilizer and Irganox 1010 as heat stabilizer to 0.05 parts by weight or 0.05 parts by weight were changed and Sanol LS-770 and Tinuvin 622 were not added were given and the examination of the light resistance by an examination of the Heat aging resistance with the ratio of maintaining the elongation when Pull break replaced with a GPH-200 gear oven (manufactured by Tabai Espec Corp.) which was measured at 140 ° C for 500 hours. The results of the assessment are shown in Table 2.

Comparative Example 2 Manufacture of oil-extended EPDM-2

To a 5% (wt .-%) solution of ethylene-propylene-ethylidene norbornene copolymer rubber [EPDM-2, iodine number = 5.5, propylene content = 28 wt .-%, ML _{1 + 4} 100 ° C = 242] in hexane 100 parts by weight of mineral oil (Diana process oil PW-380, manufactured by Idemitsu Kosan Co.) per 100 parts by weight of EPDM-2. The solvent was then removed by steam stripping to give oil-extended EPDM-2 (ML _{1 + 4} 100 ° C = 53).

The procedure of Example 2 was repeated except that EPM-1 was replaced by the Oil-stretched EPDM-2 obtained above was replaced. The results of the assessment are shown in Table 2.

Example 3

Joitac AD-471B (manufactured by Tokushushikiryo Kogyo Co.) was on one side the T-shape extruded film produced in Example 2 for adhesion with urethane applied. A semi-hard porous urethane foam with a density of 0.16 g / cm³, formed from a 1: 2 mixture of an isocyanate and a polyol, manufactured by Su mitomo Bayer Urethane Co., was applied to obtain a laminate. A sample was punched out of the laminate with a JIS No. 3 dumbbell and the light test with a Sunshine Weather-O-Meter (S.W.O.M.) manufactured by Suga Test Instruments Co., Ltd., subjected to a blackboard temperature of 83 ° C without water and the lightfastness due to the ratio of maintaining the elongation at break determined after removal of the urethane foam after a specified period of time. The Results of the determination are shown in Table 3.  

Comparative Example 3

The procedure in Example 3 was repeated except that the T-shape extrusion foil using 70 parts by weight of the same oil stretched EPDM-1 as in Comparative Example 1 used instead of EPM-1 produced in Example 2 Get laminate. The results of the determination are shown in Table 3.

Table 1

Table 2

Table 3

As described above, according to the present invention, a thermoplastic olefin elastomer film with excellent light resistance and ther mixer aging resistance, a laminate comprising the film and a use of which provided.

Claims (4)

1. A film comprising a thermoplastic olefin elastomer obtained by dynamic heat treatment of 100 parts by weight of a mixture of 40-90% by weight (A) of an olefin polymer rubber with a Mooney viscosity at 100 ° C (ML _{1 + 4} 100 ° C) of 5-100, which is essentially free of non-conjugated diene, and 60-10 wt .-% (B) of an olefin polymer in the presence of 0.005-0.5 parts by weight of an organic peroxide and 0.05 - 4 wt. -Share N, N'-m-phenylene bismaleimide, divinylbenzene or a mixture thereof is available. 2. A film according to claim 1, in which the organic peroxide is 2,5-dimethyl-2,5-di (tert butylperoxy) hexane or 2,5-dimethyl-2,5-di (tert-butylperoxy) hexin-3. 3. Laminate comprising a thermoplastic olefin elastomer film according to claim 1 or 2 and a foam laminated thereon or a foamed sheet of material, selected from polyethylene, polypropylene and polyurethane. 4. Interior trim material for motor vehicles, comprising a thermoplastic Olefin elastomer film according to claim 1 or 2 or a laminate according to claim 3.