JPS645539B2 - - 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, acid resistant, and resistant to acids. It has the advantage of being highly alkaline, 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 He discovered a method of interposing a rubber-like substance grafted with an organosilicon compound having a possible organic group, and published Japanese Patent Application No. 55-68874 and Japanese Patent Application No. 56-22198.
proposed as a number. However, there was a need for something with even more sufficient surface hardness, and as a result of extensive research, the present inventors discovered a polyolefin laminate with a hardness superior to that of the invention described above, and completed the present invention. . That is, the present invention provides polyolefin (A), a polyolefin (A) grafted with an organosilicon compound having a group having an olefinic unsaturated bond and an organic group capable of reacting with a silicone resin, and optionally containing a weathering stabilizer.
-A polyolefin laminate consisting of methyl-1-pentene (B) and silicone resin (C). 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 the pentene homopolymer, 4-methyl-1-pentene and 20 mol% or less of α- having 6 to 18 carbon atoms
Olefins, e.g. 1-hexene, 3-methyl-
1-pentene, 1-octene, 1-decene, 1-
It includes one or more copolymers of tetradecene, 1-octadecene, etc. The organosilicon compound to be grafted onto poly-4-methyl-1-pentene may be any organosilicon compound having a group having an olefinic unsaturated bond and an organic group capable of reacting with a silicone resin, and has 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, alkali, butenyl, cyclohexenyl, and cyclopentadienyl, with terminal olefinically unsaturated groups being particularly preferred. Other preferred examples have a terminally saturated ester bond. _CH2 =C( _CH3 )COO( _CH2 ) _3- , _CH2 =C( _CH3 )COO( _CH2 ) _2- O-( _CH2 ) _3- , _CH2 =C( _CH3 ) _COOCH2 Examples include OCH ₂ CH ₂ (OH) CH ₂ O (CH ₂ ) ₃ −. 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 , and Y ³ are each groups capable of reacting with the same or different silicone resins, and examples of such groups include, for example, hydrolyzable groups. Examples of such groups include alkoxy groups such as methoxy, ethoxy, butoxy, methoxyethoxy, alkoxyalkoxy groups, acyloxy groups such as formyloxy, acetoxy, propionoxy, oximes such as -ON=C
( _CH3 ) ₂ , _-ON = _CHCH2C2H5 and -ON ₌ C
( _C6H5 ) ₂ or substituted amino groups and arylamino groups, such _{as -NHCH3} , _{-NHC2H5 and} -
Examples include NH (C ₆ H ₅ ), and any other hydrolyzable organic group may be used. 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 vinyltrimethoxycin, vinyltriethoxysilane, and vinyltris(methoxyethoxy)silane. However, vinylmethyldiethoxysilane, vinylphenyldimethoxysilane, etc. can be used as well. Poly4- as the substrate to which the organosilicon compound is grafted
Methyl-1-pentene is not only a homopolymer of 4-methyl-1-pentene, but also 4-methyl-1-pentene.
- pentene and up to 20 mol % of other alpha-olefins, preferably alpha-olefins having 6 to 18 carbon atoms, such as 1-hexene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-tetradecene , 1-octadecene, etc., or a copolymer of two or more thereof. To produce grafted poly-4-methyl-1-pentene constituting layer (B) by grafting the organosilicon compound onto poly-4-methyl-1-pentene,
The reaction is carried out by reacting poly-4-methyl-1-pentene and an organosilicon compound in the solvent described below in the substantial absence of oxygen, in an inert gas atmosphere, in the presence of a radical initiator, and under non-extrusion molding reaction conditions. is preferred. The solvents used here include aromatic hydrocarbon solvents such as benzene, toluene, and xylene, aliphatic hydrocarbon solvents such as n-hexane, cyclohexane, and n-heptane, chlorobenzene, bromobenzene, iodobenzene, and O- Halogenated aromatic hydrocarbon solvents such as bromotoluene, carbon tetrachloride,
Examples include halogenated aliphatic hydrocarbon solvents such as 1,1,1-trichloroethane, tetrachlorethylene, trichloroethylene, and 1-chlorobutane. Further, in order to uniformly graft the organosilicon compound, the graft reaction is usually carried out using a reactor. In the grafting reaction, poly4-methyl-1-pentene is preferably 50 to 500% using the above solvent.
It is preferable to use a solution adjusted to have a concentration of 1.5 g/g/g/g/g/g/g/g under strong stirring. The reaction temperature is preferably from 80°C to 200°C, particularly from about 120°C to 160°C, and the reaction time is usually from 1 to 20 hours. The reaction operation may be carried out either batchwise or continuously, but the batchwise method 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 poly-4-methyl-1-pentene solution. Further, it is preferable to add the radical initiator simultaneously and sequentially. Specifically, the addition rate of the organosilicon compound is
0.1mM to 10 ¹ /min/-poly4-methyl-
1-pentene solutions are preferred, especially 0.5mM/
min/-poly4-methyl-1-pentene solution is preferred. This reaction method enables homogeneous grafting to poly-4-methyl-1-pentene molecules at a high grafting yield (ratio of the amount of grafted monomer to the amount of monomer charged). The amount of the organosilicon compound and radical initiator added to the poly-4-methyl-1-pentene solution depends on the type of poly-4-methyl-1-pentene, the type of solvent, the reaction temperature, and the desired amount of grafting.
It can be varied within a wide range. The preferred range is based on 100 parts by weight of poly4-methyl-1-pentene,
5 to 600 parts by weight of an organosilicon compound, especially about 50 to 400 parts by weight
parts by weight, 1 to 200 parts by weight of a radical initiator,
In particular about 10 to 150 parts by weight. In addition, the molar ratio of the radical initiator to the organosilicon compound is set to 1/200.
The ratio is preferably 1/50 to 2, preferably 1/50 to 1. As the radical initiator, one that can create a radical site in poly-4-methyl-1-pentene under organosilicon modification reaction conditions is used. These compounds include organic perthioxides, organic peresters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(beroxybenzoate).
Hexyne-3,1,4-bis(tert-butylperoxyisopropyl)benzene, lauroyl peroxide, tert-butel 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 perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert
-butyl perpivalate, cumyl perpivalate and tert-butyl perdiethyl acetate, as well as other azo compounds such as azobis-isobutylnitrile, dimethylazoisobutyrate. Among these are dicumyl peroxide, di-tert
-butylperoxide, 2,5-dimethyl-di(tert-butylperoxy)hexyne 3,2,5
Dialkyl peroxides such as -dimethyl-2,5-di(tert-butylperoxy)hexane and 1,4-bis(tert-butylperoxyisopropyl)benzene are preferred. In addition, the organosilicon compound graft 4-methyl-1 obtained in this way
-Pentene is easily dissolved in the solvent described below. Poly4, an organosilicon compound having a group having an olefinic unsaturated bond and a hydrolyzable organic group
-The amount of grafting to methyl-1-pentene is
A range of 0.5 to 50% by weight, especially 5 to 25% by weight is preferred. If it is less than 5% by weight, the adhesion between the silicone resin (C) and poly-4-methyl-1-pentene (B) grafted with an organosilicon compound will be poor, and if it is more than 25% by weight, it will not be suitable for polyolefin.
The adhesion between (A) and poly-4-methyl-1-pentene (B) grafted with an organic silicon compound is poor. The poly4-methyl-1-pentene (B) layer grafted with the organosilicon compound having a group having an olefinic unsaturated bond and a hydrolyzable organic group is combined with the polyolefin (A) layer and a silicon resin as a surface improving material. It is absolutely necessary to intervene between the polyolefin and the silicone resin (C) layer in order to improve the adhesion between the polyolefin and the silicone resin (C) layer. Without the organosilicon compound-grafted poly4-methyl-1-pentene layer, the polyolefin and silicone resin would not adhere completely and would peel off during use, which would be a practical problem. The polyolefin laminate of the present invention exhibits sufficient adhesion just by interposing the organosilicon compound grafted poly4-methyl-1-pentene layer between the polyolefin and the silicone resin, but in addition, the organosilicon compound grafted poly4-methyl-1-pentene layer is also interposed between the polyolefin and the silicone resin. It is preferable to add a weathering stabilizer to the 1-pentene layer because the adhesion will not deteriorate even during long-term outdoor exposure. As such a weathering stabilizer, a 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'-tert
Butyl-5'-methylphenyl)benzotriazole, 2(2'-hydroxy-3'-tertbutyl-5'-methylphenyl)-5-chlorobenzotriazole,
2(2′-hydroxy-3′,5′-ditertbutyl-phenyl)-5-chlorobenzotriazole, 2(2′-
Benzotriazole compounds such as hydroxy-3',5'-dipentylphenyl)-benzotriazole; resorcinol monobenzoate; 2'-ethyl-hexyl-2-cyano-3-phenylcinnamate; bis(2,2, 6,6-tetramethyl-
piperidine compounds such as 4-piperidine) sebacate, 4-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, 2,2-dihydroxy-4,4'-dimethoxy-benzophenone,
Examples include benzophenone compounds such as 2,2',4,4'-tetrahydroxy-benzophenone and 2-hydroxy-4-n octoxy-benzophenone. The above weathering stabilizers may be used alone or in combination.
A mixture of more than one species may be used. The amount of weathering stabilizer added to the organosilicon compound-grafted poly4-methyl-1-pentene is preferably 5 to 200% by weight, particularly preferably 50 to 150% by weight.
If it is less than 5% by weight, there is no improvement in weather resistance;
If the amount exceeds % by weight, the weathering stabilizer will aggregate and the transparency will be significantly impaired. The weathering stabilizer can be added to the organosilicon compound grafted poly-4-methyl-1-pentene by directly adding it to the poly-4-methyl-1-pentene and melt-mixing it, or by adding it directly to the poly-4-methyl-1-pentene and melt-mixing it.
Examples include a method of adding methyl-1-pentene to a solvent described later and dissolving and mixing. The organosilicon compound grafted poly-4-methyl-
The method for laminating 1-pentene on polyolefin is to dissolve the grafted poly-4-methyl-1-pentene, to which a weathering stabilizer is added if necessary, in a solvent, apply it with a brush, spray, dip, etc., and remove the solvent. Examples include methods for doing so. The graft poly 4-
The solvent used to dissolve methyl-1-pentene is preferably a solvent that dissolves the grafted poly-4-methyl-1-pentene and does not devitrify the polyolefin. Examples of such solvents include aromatic hydrocarbon solvents such as benzene, toluene, and xylene, aliphatic hydrocarbon solvents such as n-hexane, cyclohexane, and n-heptane, carbon tetrachloride,
Examples include halogenated aliphatic hydrocarbon solvents such as 1,1,1-trichloroethane, 1-chlorobutane, trichlorethylene, and tetrachloroethylene, and halogenated aromatic hydrocarbon solvents such as chlorobenzene, bromobenzene, iodobenzene, and O-bromotoluene. 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, Examples of tetraalkoxysilane include methyltripropoxysilane, methyltributoxysilane, etc., tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, 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 epoxyalkylalkoxysilanes such as silane include γ-glycidopropyltrimethoxysilane and γ-glycidpropylmethyldimethoxysilane; examples of silicon-functional polysiloxanes 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., carbon-functional polysiloxanes include 1,3-bis(hydroxymethyl)
Examples include -1,1,3,3-tetramethyldisiloxane. The organosilicon compound or its oligomer or partial hydrolyzate thereof, which is a silicon resin raw material, is an organosilicon compound grafted poly-4-methyl-1
-Although pentene can be applied directly to the laminated polyolefin, it is preferable to dissolve it in a solvent and apply it as a solution with a concentration of 5 to 50% by weight in terms of surface finishing effects and coating operations. Examples of the solvent include alcohols such as ethyl alcohol, propyl alcohol, butyl alcohol, and amyl alcohol; ethers such as propyl ether, butyl ether, ethylene glycol monoethyl ether, and ethylene glycol monomethyl ether; ketones such as methyl ethyl ketone and diethyl ketone; and acetic acid. One or a mixture of two or more of esters such as ethyl, 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. In the laminate of the present invention, the weathering stabilizer is an organosilicon compound grafted poly-4-methyl-
It is preferably contained in the 1-pentene layer.
In order to improve the weather resistance of polyolefin, it can be improved by adding the weathering stabilizer to the polyolefin, but in the case of a laminate like the one described above, the amount of weathering stabilizer added is smaller than the amount added to the polyolefin. can improve weather resistance. In addition, in this case, since silicone resin is laminated on the outer layer of the organosilicon compound grafted poly-4-methyl-1-pentene layer containing a weathering stabilizer, it will not be washed away by rainwater etc. even if exposed outdoors for a long time. It has a long practical life because it does not get damaged. The polyolefin of the present invention, a poly(4-methyl-1-) grafted with an organosilicon compound having a group having an olefinic unsaturated bond and an organic group capable of reacting with a silicone resin, and optionally containing a weathering stabilizer. A polyolefin laminate composed of pentene and silicone resin has not only the lightness of polyolefin, but also high surface hardness due to surface gloss, transparency, and high crystallinity of organosilicon compound grafted poly-4-methyl-1-pentene. Moreover, it has excellent weather resistance, so it can be used as window glass for automobiles, ships, buildings, etc.
Machine covers, windshields, 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 (organosilicon compound grafted poly-4-methyl-1-
Production of pentene) 4-methyl-1-pentene/1-decene copolymer (1-decene 3.0% by weight, melt index
20g/10min: 50g of ASTM D1238T (hereinafter referred to as PMP) and 450ml of toluene were charged into a pressure-resistant glass reactor with a capacity of 1500ml. Next, replace the system with nitrogen.
While heating to 145°C and stirring at 300 rpm, add nyltrimethoxysilane (hereinafter referred to as
50 ml of a toluene solution containing 148 g (referred to as VTMS) and 43.8 g of di-tert-butyl peroxide as a radical initiator was added over 4 hours, and the reaction was continued for an additional 2 hours. The reaction product was then precipitated in acetone and dried separately to obtain a vinyltrimethoxysilane grafted 4-methyl-1-pentene/1-decene copolymer (hereinafter referred to as VTM-PMP). The grafting amount of VTMS in the obtained VTM-PMP was 138% by weight. (Manufacture of laminate) 4-methyl-1-pentene/1-decene copolymer (1-decene 3.0% by weight, melt index
70g/10min: ASTM D1238T) 2(2'-Hydroxy-3-tert-butyl-5'-methyl-phenyl)-5-chlorobenzotoluazole (trade name Tinuvin 326; Ciba Geigy KK) as a weathering stabilizer for 100g. A thin plate with a thickness of 2 mm was produced using a 7-ounce injection molding machine. Next, add 100 ml of 1 g of VTM-PMP to the thin plate.
1,1,1-trichloroethane dissolved in 1,1,1-trichloroethane for 30 seconds and then dried, and then a mixed solution of trimethoxysilane compound in isopropyl alcohol and methyl alcohol (trade name x-12-940,
Shin-Etsu Chemical Co., Ltd.) for 10 seconds, then dry at 80℃.
The laminate was heated in an oven for 120 minutes to harden the surface. The thickness of each layer of the obtained laminate is
The VTM-PMP layer had a thickness of 0.1μ, and the silicone resin trimethoxysilane compound layer had a thickness of 3 to 5μ. 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 wire cutter, paste approximately 100 mm of cellophane adhesive tape (Cello Tape No. 250, Nichiban KK) on the scratched surface, and
Rub the cellophane adhesive tape back and forth 10 times vertically and horizontally with a mmφ glass rod, count the number of pieces remaining, and repeat the above test three times.
Rated at 100. Light transmittance: Measured by ASTM D1003 method. Appearance: Visual judgment Pencil hardness: Measured by JIS K5400 method. Abrasion resistance: Taber abrasion test ASTM D1044 Evaluated by decrease in light transmittance (△%) after 100 rotations with CS-10 abrasive paper under 250 load. Weather resistance: Performed using JIS A1415 method. Note that a sunshine carbon arc lamp was used as a light source. The results are shown in Table 1. Example 2 Weathering stabilizer 2 (2'-hydroxy-3'-tertbutyl-5'-methylphenyl)-5-chlorobenzotriazole (trade name Tinuvin 326; Ciba Geigy) during VTM-PMP coating during the production of laminates
The same procedure as in Example 1 was carried out, except that 1 g of 4-methyl-1-pentene/1-decene copolymer was used and no weathering stabilizer was added to the 4-methyl-1-pentene/1-decene copolymer.
The thickness of each layer of the obtained laminate is VTM-
The PMP layer has a thickness of 0.2μ, the silicone resin trimethoxysilane compound layer has a thickness of 3 to 5μ, and the 4-methyl-1
-For 100g of pentene/1-decene copolymer,
This corresponds to the addition of approximately 0.01g of weathering stabilizer. The results are shown in Table 1. Comparative Example 1 The same procedure as in Example 1 was carried out except that the VTM-PMP undercoating step of Example 1 was omitted. However, since the silicone resin layer was easily peeled off, the values of pencil hardness and abrasion resistance could only be obtained from the base material. Reference Example 1 (Manufacture of organosilicon compound grafted rubber material) Ethylene-propylene random copolymer (60 mol% ethylene, melt index 30 g/
10min: ASTM D1238E, 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) as a radical initiator were added. -Butylperoxy)hexyne-31g 2
The mixture was added at a certain time, 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 amount of VTMS grafted in the obtained VTM-EPR was 17.9
The weight percent and melt index were 8 g/10 min. (Manufacture of laminate) 4-methyl-1-pentene used in Example 1
A 2 mm thick thin plate of 1-decene copolymer was 2(2'-hydroxy-3'-tertbutyl-5'-methylphenyl)-
1 g of 5-chlorobenzotriazole and the above
1 g of VTM-EPR was immersed in a solution of 100 ml of 1,1,1-trichloroethane for 30 seconds, then dried, and then immersed in the same isopropyl alcohol-methyl alcohol mixed solution of the trimethoxysilane compound as in Example 1 for 10 seconds. After drying, the laminate was heated in an oven at 80° C. for 120 minutes to harden the surface. The same test as in Example 1 was conducted using the obtained laminate. The results are shown in Table 1.

[Table] Examples 3 and 4, Comparative Example 2 The laminates of Examples 1 and 2 and Comparative Example 1 were each treated under the following conditions, and adhesion and other tests were conducted. Hot water treatment: The laminate was immersed in hot water at 80°C for 10 days. Heat cycle treatment: The process of leaving the laminate in a high temperature bath at 80℃ for 20 minutes and then leaving it in a low temperature bath at -20℃ for 20 minutes is repeated.
Repeated times. The results are shown in Table 2.

【table】

Claims (1)

[Scope of Claims] 1. A polyolefin prepared by grafting polyolefin (A) with an organosilicon compound having a group having an olefinic unsaturated bond and an organic group capable of reacting with a silicone resin, and optionally containing a weathering stabilizer. A polyolefin laminate comprising -4-methyl-1-pentene (B) and a silicone resin (C). 2. Claim 1, wherein the grafting amount of the organosilicon compound having a group having an olefinic unsaturated bond and an organic group capable of reacting with a silicone resin to poly-4-methyl-1-pentene is 0.5 to 30% by weight. The polyolefin laminate described in Section 1. 3 The content of weathering stabilizer is poly-4-methyl-1
- A polyolefin laminate according to claim 1, in an amount of 5 to 200% by weight, based on pentene.