JPS6229225B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to thermoplastic resin laminates with improved surface hardness, surface gloss and abrasion resistance, particularly polyolefin laminates coated with organosilicon compounds. In general, thermoplastic resins, regardless of whether they are transparent or opaque, have a lower surface hardness than metals, glass, etc., and are weak against scratches and abrasions and are easily damaged on the surface. Polymethyl methacrylate, which has the particular advantage of transparency,
Polycarbonate, polystyrene or poly4
-Polyolefins such as -methyl-1-pentene and polypropylene have poor scratch resistance, which is a major drawback and has become an obstacle in practical use. 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. Therefore, the present inventors studied ways to improve the surface properties of polyolefin, and as a result, they arrived at the present invention. That is, the present invention is a polyolefin laminate with improved surface properties, comprising a polyolefin, a rubber-like substance grafted with an organosilicon compound having a group having an olefinic unsaturated bond and a hydrolyzable organic group, 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, 4-methyl-1-pentene, etc., or a copolymer consisting 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 polyolefin laminate of the present invention has a rubber-like substance (B) layer grafted with an organosilicon compound having a group having an olefinic unsaturated bond and a hydrolyzable organic group on the polyolefin (A) layer described above, A silicone resin (C) layer is formed. Among the components constituting layer (B) above, 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, 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, allyl, butenyl, cyclohexenyl, and cyclopentadienyl, with terminal olefinically unsaturated groups being particularly preferred. Another preferred example has an ester bond of a terminal unsaturated acid. _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 , 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, such as vinyltolylmethoxysilane,
Examples include vinyltriethoxysilane and vinyltris(methoxyethoxy)silane. However, vinylmethyldiethoxysilane, vinylphenyldimethoxysilane, etc. can be used as well. Examples of the rubber-like substance for the substrate to which the organosilicon compound is grafted include 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 rubbery substance referred to in the present invention is an amorphous polymer or a low crystalline polymer with a crystallinity of 0 or 30% or less based on X-rays. In order to produce a 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 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℃
℃, especially in the range of about 140℃ to 200℃,
The reaction time is usually 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 rubbery material. Further, 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-gum is preferred, especially 0.5mM to 5mM/min/Kg-gum. This reaction method allows for homogeneous grafting 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 simply by 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, or 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. In addition, 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 is used that can create radical sites in the rubber-like material under organosilicon modification reaction conditions. These compounds include organic peroxides, organic peresters such as benzoyl oxide, 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 rubbery material (B) grafted with an organic silicon compound is poor, and if it exceeds 25% by weight, it is a grafted material with a polyolefin (A) and an organic silicon compound. rubbery substance
Adhesion with (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. The method for laminating the organosilicon compound grafted rubbery material on polyolefin is to melt the organosilicon compound grafted rubbery material and, if the grafted rubbery material has a low molecular weight, use a roll, brush, spray, etc. Alternatively, examples include a method in which the grafted rubbery material is directly immersed in a melt of the grafted rubbery material to form a layer, 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, aliphatic hydrocarbon solvents such as n-hexane, cyclohexane, and n-heptane, carbon tetrachloride, 1,1,1-trichloroethane, Examples include chlorine-based solvents such as 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, 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 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 that the softening temperature of the polyolefin to be laminated is not exceeded. 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. 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 a silicone resin,
In addition to being lightweight, polyolefin has surface hardness, surface gloss, and transparency, so it can be used to protect windows of automobiles, ships, buildings, etc., machine covers, windshields, safety glasses, goggles, sunglasses, etc. It is useful for applications such as store displays, transparent toys, stationery, see-through panels, and lenses for optical equipment. 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 graft material) Ethylene-propylene random copolymer (ethylene 60 mol%, 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, 30 g of vinyltrimethoxysilane (hereinafter referred to as VTMS) as an organosilicon compound and 2,5-dimethyl-2,5-di (tert.
1 g of -butylperoxy)hexyne-3 was added over 2 hours, and the reaction was further continued for 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 9.9% by weight, and the melt index was 15g/
It was hot in 10 minutes. (Manufacture of laminate) 4-methyl-1-pentene-1-hexadecene-1-octadecene ternary copolymer (1-hexadecene 4.5 wt%, 1-octadecene 4.5 wt%, melt index 70 g/10 min: ASTM D1238T , hereinafter referred to as PHO-), and a 2 mm thick thin plate was produced using a 7 oz injection molding machine. Next, the thin plate was immersed in a 1 g/100 ml toluene solution of VTM-EPR- for 10 seconds and then dried, followed by a mixed solution of trimethoxysilane compound in isopropyl alcohol acetone (trade name "X-12-917" Shin-Etsu Chemical KK). product) for 10 seconds, dried, and heated in an oven at 80°C for 50 minutes to harden the surface to obtain a laminate. The following tests were conducted using the obtained laminate. Adhesion: 11 on the surface of the laminate at 1mm intervals on 10mm squares
Scratch the 11 lines with a cutter, stick a 100 mm long cellophane adhesive tape (Cello Tape No. 250, manufactured by Nichiban Co., Ltd.) on the scratched surface, rub it back and forth 10 times vertically and horizontally with a 20 mm φ glass rod, and then apply the cellophane adhesive tape to the scratched surface. Peel off the adhesive tape from the front,
Count the number of remaining pieces, perform the above test three times, and evaluate as number of remaining pieces/100. Light transmittance: Measured by ASTM D1003 method. Glossiness: Measured by ASTM D523 method. Pencil hardness: Measured by JIS K5400 method. Abrasion resistance: Taber abrasion test ASTM D1044 250g
Evaluation was made by the decrease in light transmittance (△%) after rotating 100 times with CS-10 abrasive paper under load. Examples 2 and 3 The same procedure as in Example 1 was carried out except that the grafting amount of VTMS of Example 1 with respect to EPR was changed as shown in Table 1. The results are shown in Table 1. Examples 4 and 5 The same procedure as in Example 1 was carried out except that the 1 g/100 ml toluene solution of VTM-EPR- in Example 1 was changed to p-xylene and benzene. Results first
Shown in the table. Examples 6 to 8 In place of PHO- in Example 1, the amount of copolymerization of 1-hexadecene and 1-octadecene was 3wt%.
and 3wt% (hereinafter referred to as PHO-)
The same procedure as in Examples 1, 4 and 5 was carried out except that . The results are shown in Table 1. Examples 9 to 11 Instead of VTMS in Example 1, vinyltriethoxysilane (hereinafter referred to as VTES), vinyltributoxysilane (hereinafter referred to as VTBS) and γ-methacryloxypropyltrimethoxysilane (hereinafter referred to as γ
- MMS) was used to determine the amount of each graft.
The same procedure as in Example 1 was carried out except that the values shown in the table were used. The results are shown in Table 2. Example 12 Polypropylene (melt index 11g/10min: ASTM
The same procedure as in Example 1 was carried out except that D1238L (hereinafter referred to as PP) was used. The results are shown in Table 2. Example 13 Instead of EPR in Example 1, ethylene-1-
Butene/ethylidene norbornene terpolymer (ethylene 93 mol%, iodine number: 15, melt index 540 g/10 min: ASTM D 1238D, below)
Table 2 shows the results obtained in the same manner as in Example 1 except for using EBE (referred to as EBE). Example 14 Instead of the trimethoxysilane compound of Example 1, an isopropanol solution of an equimolar partial hydrolysis reaction product of γ-glycidoxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane was used, and the drying conditions were 100°C. The same procedure as in Example 1 was carried out except that the time was 60 minutes. The results are shown in Table 2. Comparative Example 1 The same procedure as in Example 1 was carried out except that the VTM-EPR- undercoating step of Example 1 was omitted. The results are shown in Table 2. However, since the silicone resin layer peels off easily, in Comparative Examples 1 to 3 below, only the values of pencil hardness and abrasion resistance were obtained for the base material. Comparative Example 2 The same procedure as in Example 1 was conducted except that a hydrolyzate of vinyltrimethoxysilane was used instead of VTM-EPR- in Example 1. The results are shown in Table 2. Comparative Example 3 Instead of VTM-ERR- in Example 1, a 20wt% butanol solution of a reaction product of γ-aminopropyltriethoxysilane and maleic anhydride (hereinafter referred to as γ
-APTE/MAH) was used in the same manner as in Example 1. The results are shown in Table 2. Examples 15 to 17, Comparative Example 4 The laminates of Examples 5, 9, 13 and Blank 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 17 hours. Heat treatment: The laminate was left in an oven at 160°C for 30 minutes for heat treatment. The results are shown in Table 3.

【table】

【table】

【table】

[Table] Examples 18 to 25 (Production of organosilicon compound grafted rubber material) The same procedure as Example 1 was carried out except that the EPR of Example 1 was used and the VTMS was 100 g, and vinyltrimethoxysilane grafted ethylene/propylene random copolymer was used. A polymer (hereinafter referred to as VTM-EPR-) was obtained.
The grafting amount of VTMS of the obtained VTM-EPR- was 24.2% by weight, and the melt index was 8g/
It was hot in 10 minutes. (Manufacture of laminate) 4-methyl-1-pentene-1-decene copolymer (1-decene 3wt%, melt index 70
g/10min: ASTM D1238T (hereinafter referred to as PHO-) and a 7-ounce injection molding machine to produce a 2 mm thick thin plate. Then, the thin plate was subjected to VTM-EPR
-1g/10ml-1,1,1-trichloroethane solution for 10 seconds and then dried, followed by a mixed solution of trimethoxysilane compound in isopropyl alcohol acetone (trade name "X-12-917" Shin-Etsu Chemical KK product) for 10 seconds and then dried at room temperature.
After some progress in curing, the sample was immersed again in the trimethoxysilane compound solution for 10 seconds. After repeating the above steps the number of times shown in Table 4, the laminate was heated in an oven at 80° C. for 50 minutes to completely harden the surface. The obtained laminate was evaluated in the same manner as in Example 1. The results are shown in Table 4. Examples 26-33, Comparative Example 4 The laminates of Examples 18-25 and Blank 4 were subjected to hot water treatment and heat treatment in the same manner as in Examples 15-19. The results are shown in Table 5.

【table】

【table】

Claims (1)

[Claims] 1. A polyolefin (A), a rubbery substance (B) grafted with an organosilicon compound having a group having an olefinic unsaturated bond and a hydrolyzable organic group, and a silicone resin (C). Polyolefin laminate. 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.