JPS6230103B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyolefin laminates coated with organosilicon compounds that have improved surface hardness, surface gloss, abrasion resistance, transparency, and weather resistance. In general, thermoplastic resins, regardless of whether they are transparent or opaque, have lower surface hardness than metals, glass, etc., are weak against scratches and abrasions, have easily damaged surfaces, and have poor weather resistance. In particular, for polyolefins such as polymethyl methacrylate, polycarbonate, polystyrene, poly4-methyl-1-pentene, and polypropylene, which have an advantage of transparency, their poor scratch resistance is a major drawback and is a practical obstacle. It's getting old. Many methods have been proposed to improve these drawbacks, one of which is to add silicone resin to the resin surface.
There is a method of coating and laminating a hydrolyzate of an organic silicon compound, and in this case, proposals have also been made regarding an undercoat to increase the adhesive strength of the silicone resin to the resin. However, most of these proposals are effective for thermoplastic resins that have polar groups in their molecules, such as polymethyl methacrylate and polycarbonate, and these methods cannot be applied to polyolefins that do not have polar groups in their molecules. However, the coating easily peels off, making it impossible to obtain a product suitable for practical use. on the other hand,
Polyolefins such as poly4-methyl-1-pentene and polypropylene have a lower density than polymethyl methacrylate, polycarbonate, polyvinyl chloride (hard), etc., which have polar groups in the molecule, so they are lightweight and have acid and alkali resistance. It has the advantage of being excellent in surface properties, and it is desired to improve its surface properties. In view of the current situation, the present inventors investigated a method for forming a surface property improving layer with good adhesion on polyolefin, and found that a group having an olefinic unsaturated bond between polyolefin and silicone resin and a hydrolyzable A method was discovered in which a rubber-like material grafted with an organosilicon compound having an organic group was found and proposed in Japanese Patent Application No. 55-68874.
However, even if this proposed method is carried out without hesitation, there is a problem in that the adhesion deteriorates under harsh conditions such as long-term outdoor exposure, which may be inconvenient depending on the application. The present invention improves the above-mentioned proposal and provides a method for preventing a decrease in adhesion using simple means. This is a polyolefin laminate consisting of a rubber-like substance grafted with an organosilicon compound having a decomposable organic group and containing a weathering stabilizer, and a silicone resin. The polyolefin referred to in the present invention refers to ethylene,
It is a homopolymer of olefins such as propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene, or a copolymer of two or more types of olefins. Among them, polypropylene and poly4-methyl-1-pentene are preferred because of their excellent transparency. In addition to the homopolymer of propylene, the above-mentioned polypropylene includes copolymers of propylene and 10 mol% or less of other α-olefins such as ethylene, 1-butene, 1-hexene, etc. -Methyl-1-pentene means 4-methyl-1
-In addition to pentene homopolymers, 4-methyl-1-
Pentene and 20 mol% or less of α with 6 to 18 carbon atoms
-Olefins, such as 1-hexene, 3-methyl-1-pentene, 1-octene, 1-decene, 1
-Includes copolymers with one or more of tetradecene, 1-octadecene, etc. The polyolefin laminate of the present invention is obtained by grafting an organosilicon compound having a group having an olefinic unsaturated bond and a hydrolyzable organic group onto the polyolefin (A) layer described above, and containing a weathering stabilizer. A silicone resin (C) layer is formed through a rubbery substance (B) layer. Among the components constituting the layer (B), the organosilicon compound to be grafted onto the rubbery substance may be an organosilicon compound having a group having an olefinic unsaturated bond and a hydrolyzable organic group,
It is represented by the general formula R ¹ R ² SiY ¹ Y ² , R ¹ XSiY ¹ Y ² or R ¹ SiY ¹ Y ² Y ³ . In the formula, R ¹ and R ² have an olefinic unsaturated bond, are composed of carbon, hydrogen and optionally oxygen, are the same or different groups, and are reactive with the free radical site generated in the polyolefin. Examples of such groups include vinyl, allyl, butenyl, cyclohexenyl, and cyclopentadienyl, with terminal olefinically unsaturated groups being particularly preferred. Other preferred examples include _CH2 =C( _CH3 )COO( _CH2 ) _3- , _CH2 =C( _CH3 )COO( _CH2 ) ₂ -O-(CH2), which has an ester bond of a terminal unsaturated acid. ₂ ) _3- , _CH2 =C( _{CH3 ) COOCH2OCH2CH2 (} OH) _CH2O ( _CH2 ) _3- , etc. Among these, vinyl groups are most suitable. X is an organic group having no olefinic unsaturated bond, such as monovalent hydrocarbon groups such as methyl, ethyl, propyl, tetradecyl, octadecyl, phenyl, benzyl, tolyl, etc. , or a halogen-substituted hydrocarbon group. The groups Y ¹ , Y ² , Y ³ are each the same or different hydrolyzable groups, such as alkoxy groups such as methoxy, ethoxy, butoxy, methoxyethoxy, alkoxyalkoxy groups, formyloxy, acetoxy, propionoxy, etc. Acyloxy group, oxime, e.g.
ON=C( _CH3 ) ₂ , _-ON = _CHCH2C2H5 and _-
ON=C( _C6H5 ) ₂ or _substituted amino and arylamino groups such _{as -NHCH3} , _-NHC2H5 and _-NH ( _C6H5 ), and any other hydrolyzable organic It is the basis. The organosilicon compound preferably used in the present invention is a compound represented by the general formula R ¹ SiY ¹ Y ² Y ³ , in particular groups Y ¹ , Y ² ,
Organosilicon compounds with equal Y ³ are suitable. Among these, vinyltris alkoxysilane is preferred, and examples include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris(methoxyethoxy)silane. However, vinylmethyldiethoxysilane, vinylphenyldimethoxysilane, etc. can be used as well. Basic rubbery substances to which organosilicon compounds are grafted include, for example, polyisoprene, styrene, etc.
Butadiene rubber, polybutadiene, acrylonitrile-butadiene rubber, polychloroprene, butyl rubber, polyether rubber, silicone rubber, acrylic rubber, ethylene/α-olefin (carbon number 3 to 8) random copolymer, ethylene/α-olefin (carbon number 3-8) Diene random copolymer, halogenated polyethylene, ethylene/vinyl acetate copolymer, 4-methyl-1-pentene/α-
Olefin (6 to 18 carbon atoms) random copolymer,
Examples include halogenated poly-4-methyl-1-pentene, halogenated 4-methyl-1-pentene-α-olefin (carbon number 6 to 18) random copolymer, and the like. Among them, ethylene/α-olefin (carbon number 3 to 8) random copolymer, ethylene/α-olefin (carbon number 3 to 8) diene random copolymer, halogenated polyethylene, ethylene/vinyl acetate copolymer, 4- Methyl-1-pentene α-
Olefin (6 to 18 carbon atoms) random copolymer,
Olefin rubbers such as halogenated poly-4-methyl-1-pentene and halogenated 4-methyl-1-pentene/α-olefin (carbon number 6 to 18) random copolymer are preferred because they are compatible with polyolefins. In addition, the rubbery material of the graft raw material is
It is preferable to graft a certain amount of an organosilicon compound having a group having an olefinic unsaturated bond and a hydrolyzable organic group and then use it as an undercoat to the polyolefin. Since it is suitable to use it by dissolving it in a liquid, it is preferable that it is not crystalline, and for example, it is preferable that the degree of crystallinity based on X-rays is 0 or 30% or less. Note that the rubber-like substance referred to in the present invention is an amorphous polymer or a low crystallinity polymer whose crystallinity based on X-rays is 0 or 30% or less. In order to produce the grafted rubbery material constituting layer (B) by grafting the organosilicon compound onto the base rubbery material, the base rubbery material and the organosilicon compound are mixed in an inert gas atmosphere in the substantial absence of oxygen. It is preferable to carry out the reaction under non-extrusion reaction conditions in the presence of a radical initiator in an atmosphere. In order to uniformly graft an organosilicon compound, the graft reaction is usually carried out using a reactor. It is preferable that the graft reaction is carried out by heating the rubber-like substance and under strong stirring. Reaction temperature is 100℃ or higher 300℃
°C, especially in the range of about 140 °C to 200 °C,
The reaction time is usually 1 to 20 hours. The reaction operation may be carried out either batchwise or continuously, but batchwise is preferred in order to achieve uniform grafting. In the present invention, it is preferable to carry out the graft reaction while sequentially adding the organosilicon compound to the rubbery material. Moreover, it is preferable to add the radical initiator simultaneously and sequentially. Specifically, the addition rate of the organosilicon compound is 0.1mM to 10mM/min/
Kg-rubber is preferred, especially 0.5mM to 5mM/min/Kg-rubber. By this reaction method, it is possible to graft homogeneously onto rubber-like substance molecules with a high grafting yield (ratio of the amount of grafted monomer to the amount of monomer charged), and the formation of homopolymers of organosilicon compounds is extremely suppressed. After the reaction is complete, it can be used for normal purposes by simply removing a small amount of unreacted monomers, radical initiators, and volatile components such as their decomposition products under vacuum, but purification can lead to increased production costs such as dissolution, precipitation, and extraction. The process can be omitted. The amount of organosilicon compound and radical initiator added to the rubbery material can be varied within a wide range depending on the type of rubbery material, the reaction temperature, and the desired amount of grafting. The preferred range is rubbery substances.
Based on 100 parts by weight, the amount of the organosilicon compound is 0.5 to 150 parts by weight, especially about 10 to 100 parts by weight, and the radical initiator is 0.01 to 10 parts by weight, especially about 0.03 to 5 parts by weight. Also, the molar ratio of the radical initiator to the organosilicon compound is 1/200 to 1, preferably 1/
It is preferable to set it as 100-1/5. As the radical initiator, one that can create radical sites in the rubber-like material under organosilicon modification reaction conditions is used. These compounds include organic peroxides, organic peresters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(peroxybenzoate) hexyne-3 , 1・4-
Bis(tert-butylperoxyisopropyl)benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,2.
5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert
-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl perpivalate and tert-butyl perdiethyl acetate, other azo compounds such as azobis-isobutylnitrile, dimethylazoisobutyrate There is. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-di(tert- Dialkyl peroxides such as butylperoxy)hexane and 1,4-bis(tert-butylperoxyisopropyl)benzene are preferred. The grafting amount of the organosilicon compound having a group having an olefinic unsaturated bond and a hydrolyzable organic group to the rubbery material is 0.5 to 50% by weight;
In particular, it is preferably in the range of 5 to 25% by weight. If it is less than 5% by weight, the adhesion between the silicone resin (C) and the rubber-like material (B) grafted with the organic silicon compound will be poor, and if it exceeds 25% by weight, the adhesion between the silicone resin (C) and the organic silicon compound grafted will be poor. Adhesion with the grafted rubbery substance (A) is poor. A layer of a rubbery substance (B) grafted with an organosilicon compound having a group having an olefinic unsaturated bond and a hydrolyzable organic group is interposed between the polyolefin (A) layer and the silicone resin as a surface improving material. This is absolutely necessary in order to improve the adhesion between the polyolefin and the silicone resin (C) layer. Without the organosilicon compound grafted rubbery substance layer, the polyolefin and silicone resin would not adhere completely and would peel off during use, which would be a practical problem. As the weathering stabilizer to be contained in the organosilicon compound grafted rubbery material, any known weathering stabilizer can be used. Examples of weathering stabilizers include phenyl salicylate, monoglycol salicylate, p-
Salicylic acid ester compounds such as tert-butylphenyl salicylate; 2(2'-hydroxy-5'-methylphenyl)benzotriazole, 2(2'-hydroxy-3'·5'-di-tertbutylphenyl)benzotriazole, 2(2'-hydroxy-3'-
tertbutyl-5'-methylphenyl)benzotriazole, 2(2'-hydroxy-3'-tertbutyl-
5′-methylphenyl)-5-chlorobenzotriazole, 2(2′-hydroxy-3′・5′-ditertbutyl-phenyl)-5-chlorobenzotriazole, 2(2′-hydroxy-3′・5′) -Dipentyl-
Benzotriazole compounds such as phenyl)-benzotriazole; resorcinol monobenzoate; 2'-ethyl-hexyl-2-cyano-3-
Phenyl cinnamate; bis(2, 2, 6, 6-
Tetramethyl-4-piperidine) sebacate, 4
-Piperidine compounds such as benzoyloxy-2,2,6,6-tetramethyl-piperidine; and 2-hydroxy-4-methoxy-4'-chloro-
Benzophenone, 2-hydroxy-4-methoxy-2'-carboxy-benzophenone, 2-hydroxy-4-methoxy-4'-methyl-benzophenone, 2,4-dihydroxy-benzophenone,
Examples include benzophenone compounds such as 2,2-dihydroxy-4,4'-dimethoxy-benzophenone, 2,2',4,4'-tetrahydroxy-benzophenone, and 2-hydroxy-4-n octoxy-benzophenone. The above weathering stabilizers may be used alone or in combination of two or more.
The amount of weathering stabilizer added to the organosilicon compound-grafted rubbery material is preferably from 5 to 200% by weight, particularly preferably from 50 to 150% by weight. If it is less than 5% by weight, there is no effect of improving weather resistance, and if it is less than 200% by weight.
If it exceeds this amount, the weathering stabilizer will aggregate and the transparency will be significantly impaired. The weathering stabilizer can be added to the organosilicon compound-grafted rubbery material by adding it directly to the rubbery material and melt-mixing it, or by adding it when the rubbery material is dissolved in the solvent described below and melting and mixing it. Examples include methods. The method for laminating the organosilicon compound grafted rubbery material on polyolefin is to melt the organosilicon compound grafted rubbery material containing a weathering stabilizer, and if the grafted rubbery material has a low molecular weight, it can be directly coated with a roll or a brush. , using spray etc.
Alternatively, examples include a method in which the grafted rubbery material is directly immersed in a molten solution and laminated, or a method in which the grafted rubbery material is diluted in a solvent and applied by the method described above, and the solvent is removed. Among these, the method of diluting it in a solvent and applying it is preferred because it allows the graft rubber-like material to be uniformly layered and coated on the polyolefin. The solvent used to dilute the grafted rubbery material is preferably a solvent that dissolves the grafted rubbery material and does not devitrify the polyolefin. Examples of such solvents include aromatic hydrocarbon solvents such as benzene, toluene, and xylene, and n-
Examples include aliphatic hydrocarbon solvents such as hexane, cyclohexane, and n-heptane, and chlorine-based solvents such as carbon tetrachloride, 1,1,1-trichloroethane, 1-chlorobutane, and trichloroethylene. As the silicon resin (C) used in the present invention, any crosslinked silicon resin that has a surface improving effect can be used. Examples of crosslinked silicone resins include organotrialkoxysilane, tetraalkoxysilane,
Organotriasiloxysilane, vinyltrialkoxysilane, aminoalkylalkoxysilane, epoxyalkylalkoxysilane, silicon-functional polysiloxane, carbon-functional polysiloxane, or a mixture of one or more of these partial hydrolysis products or oligomers. Examples include those that have been hardened. Specifically, the organotrialkoxysilane includes methyltrimethoxysilane, ethyltrimethoxysilane, n-butyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, Tetraalkoxysilanes include methyltripropoxysilane, methyltributoxysilane, etc.; tetraalkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraptoxysilane, etc.
Examples of organotriasiloxysilane include methyltriacetoxysilane, ethyltriacetoxysilane, isopropyltriacetoxysilane, phenyltriacetoxysilane, vinyltriacetoxysilane, methyltripropionyloxysilane, ethyltripropionyloxysilane, and vinyltrialkoxysilane. Examples of aminoalkylalkoxysilane include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltributoxysilane; examples of aminoalkylalkoxysilane include aminomethyltriethoxysilane, N-β-aminoethylaminomethyltrimethoxysilane, and γ-aminopropyltriethoxysilane. Examples of epoxyalkylalkoxysilane such as silane include γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropylmethyldimethoxysilane; examples of silicon-functional polysiloxane include 1,3-dimethoxytetramethyldisiloxane, 1・5-dimethoxyhexamethyltrisiloxane, 1,7-dimethoxyoctamethyltetrasiloxane, 1,9-dimethoxydecamethylpentasiloxane, 1,3-diethoxytetramethyldisiloxane, 1,5-diethoxyhexamethyltrisiloxane , 1,7-diethoxyoctamethyltetrasiloxane, 1,9-diethoxydecamethylpentasiloxane, 1,3-dimethoxyhexaethyltrisiloxane, etc., 1,3-bis(hydroxymethyl )-1,1,3,3-tetramethyldisiloxane, etc. can be exemplified. The organosilicon compound, its oligomer, or a partial hydrolyzate thereof, which serves as a raw material for silicone resin, can be applied directly to the polyolefin laminated with the organosilicon compound-grafted rubbery material, but it can be dissolved in a solvent and used in an amount of 5 to 50% by weight. It is preferable to apply the solution in the form of a solution having a concentration of . The solvent includes ethyl alcohol, propyl alcohol, butyl alcohol,
Alcohols such as amyl alcohol, ethers such as propyl ether, butyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ketones such as methyl ethyl ketone and diethyl ketone, ethyl acetate,
One or a mixture of two or more of esters such as propyl acetate, butyl acetate, and ethyl propionate, and aromatic hydrocarbons such as benzene, toluene, and p-xylene are used. The organic silicon compound etc. can be applied using a roll, a brush,
This is carried out using a spray or the like, or by immersion in a solution of the organosilicon compound or the like. After the organic silicon compound or the like is applied, it is cured to form a hard film of silicone resin on the polyolefin. The conditions for heat treatment (crosslinking reaction treatment) of the organosilicon compound etc. vary depending on the type of polyolefin to be laminated, but are usually
Preferably it is carried out at a temperature of 60 to 150°C. However, it is desirable not to exceed the softening temperature of the polyolefin to be laminated. This is because polyolefin may be deformed if treated at a temperature exceeding its softening temperature. Incidentally, the application of the organic silicon compound etc. may be repeated several times as necessary.
At this time, unless the organic silicon compound is semi-cured or after curing, the previously applied organic silicon compound may dissolve during recoating. The laminate of the present invention is characterized in that the weathering stabilizer is contained in the organic silicon compound grafted rubber material layer, which is the intermediate layer. The weather resistance of polyolefin can be improved by adding the above-mentioned weather stabilizer to the polyolefin, but this laminate can improve weather resistance with a smaller amount of weather stabilizer added than the amount added to the polyolefin. There are things that can be improved. In addition, since silicone resin is laminated on the outer layer of the organosilicon compound grafted rubber material layer containing a weathering stabilizer, it will not be washed away by rainwater even if exposed outdoors for a long period of time, so it can be used for a long time. It has the following characteristics. A polyolefin laminate comprising the polyolefin of the present invention, a rubbery substance grafted with an organosilicon compound having a group having an olefinic unsaturated bond and a hydrolyzable organic group, and containing a weathering stabilizer, and a silicone resin. In addition to the light weight of polyolefin, polyolefin has surface hardness, surface gloss, and transparency, and is also excellent in weather resistance, so it is used for window glass of automobiles, ships, buildings, etc., machine covers, windshield glasses, safety glasses, goggles, It is useful for protecting sunglasses, display displays for stores, transparent toys, stationery, lenses for optical equipment, etc. Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples unless the gist thereof is exceeded. Example 1 (Production of organosilicon compound grafted rubber material) Ethylene-propylene random copolymer (ethylene 60 mol%, melt index 30 g/
10min: ASTM D 1238E, hereinafter referred to as EPR)
100 g was charged into a glass reactor with a capacity of 300 ml. Next, after nitrogen purging, the system was heated to 150°C, and while stirring, 100 g of vinyltrimethoxysilane (hereinafter referred to as VTMS) as an organosilicon compound and 2,5-dimethyl-2,5-di (tert. -butylperoxy)hexyne-3 1g
was added over 2 hours, and the reaction was continued for an additional 2 hours. Next, the reaction product was dissolved in p-xylene, precipitated in a large excess of acetone, and dried separately to obtain a vinyltrimethoxysilane grafted ethylene/propylene random copolymer (hereinafter referred to as VTM-EPR-). The grafting amount of VTMS of the obtained VTM-EPR- was 17.9% by weight, and the melt index was 8.
g/10min. (Manufacture of laminate) 4-methyl-1-pentene/1-decene copolymer (1-decene 3.0wt%, melt index 70
g/10min: ASTM D 1238T), and a 2 mm thick thin plate was produced using a 7 ounce injection molding machine. The thin plate was then treated with 2(2'-hydroxy-3'-
tert-butyl-5'-methyl-phenyl)-5-chlorobenzotriazole (trade name Tinuvin 326; manufactured by Ciba-Geigy) 1 g and the above VTM-EPR
- Immerse 1 g in 100 ml of 1,1,1-trichloroethane for 30 seconds and dry, then dry the isopropyl alcohol-methyl alcohol mixed solution of trimethoxysilane compound (trade name X-12-940, Shin-Etsu) (manufactured by Kagaku Kogyo Co., Ltd.) for 10 seconds, dried, and heated in an oven at 80° C. for 120 minutes to harden the surface to obtain a laminate. The thickness of each layer of the obtained laminate was 0.1μ for the VTM−EPR− layer;
There are 3 layers of trimethoxysilane compound, which is silicone resin.
~5μ, 4-methyl-1-pentene 1-
This corresponds to approximately 0.01g of weathering stabilizer added to 100g of decene copolymer. Next, the following tests were conducted. Adhesion: 11 on the surface of the laminate at 1mm intervals on 10mm squares
Scratch 11 lines with a cutter, apply cellophane adhesive tape P (Cello Tape No. 250, manufactured by Nichiban Co., Ltd.) approximately 100 mm long to the scratched surface, and rub it vertically and horizontally 10 times with a 20 mm φ glass rod.
Peel off the Cellophane adhesive tape from the front, count the number of pieces remaining, perform the above test three times, and evaluate as the number of pieces left/100. Light transmittance: Measured by ASTM D 1003 method. Appearance: Visual judgment Pencil hardness: Measured according to JIS K 5400 method. Wear resistance: Taper wear test ASTM D 1044 250
Evaluation was made by the decrease in light transmittance (△%) after rotating 100 times with a CS-10 abrasive paper under a load of g. Weather resistance: Tested according to JIS A 1415 method. Note that a sunshine carbon arc lamp was used as a light source. Tensile test: Elongation (%) according to JIS K 6760 method
was measured. The results are shown in Table 1. Example 2 Tinuvin of VTM-EPR- used in Example 1
Instead of the 1,1,1-trichloroethane solution containing 327, 1 g of VTM-EPR-; and 1 g of Tinuvin 326 as a weathering stabilizer and bis(2,2,6,
Same as Example 1 except that a solution of 0.1 g of 6-tetramethyl-4-piperidine) sebacate (trade name Sanol LS-770; manufactured by Sankyo Co., Ltd.) dissolved in 100 ml of 1,1,1-trichloroethane was used. I went to
The results are shown in Table 1. Comparative Example 1 Tinuvin of VTM-EPR used in Example 1
Same as Example 1 except that instead of the 327-containing 1,1,1-trichloroethane solution, a solution prepared by dissolving 1 g of VTM-EPR- in 100 ml of 1,1,1-trichloroethane without adding a weathering stabilizer was used. I went to The results are shown in Table 1. Reference example 1 4-methyl-1-pentene used in Example 1
Example 1 was carried out in the same manner as in Example 1, except that a single layer plate of 2 mm thick thin plate of 1-decene copolymer was used without laminating a graft rubber layer or the like. The results are shown in Table 1. Reference example 2 4-methyl-1-pentene used in Example 1
Comparative Example 1 was carried out in the same manner as in Comparative Example 1, except that a thin plate formed by adding 0.5 g of Tinuvin 326, the weathering stabilizer used in Example 1, to 100 g of the 1-decene copolymer was used.
The results are shown in Table 1. 【table】

Claims (1)

[Scope of Claims] 1. A rubber-like material (B) obtained by grafting a polyolefin (A) with an organosilicon compound having a group having an olefinic unsaturated bond and a hydrolyzable organic group, and containing a weathering stabilizer. ), and a polyolefin laminate consisting of silicone resin (C). 2. The polyolefin laminate according to claim 1, wherein the rubbery substance is a polyolefin rubber. 3. The grafting amount of the organosilicon compound having a group having an olefinic unsaturated bond and a hydrolyzable organic group to the rubbery material is 0.5 to 30% by weight.
The polyolefin laminate according to claim 1. 4 The content of weathering stabilizer is 5% relative to the rubbery substance.
2. The polyolefin laminate according to claim 1, wherein the polyolefin laminate contains from 200% to 200% by weight.