JPS6143376B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to polyolefin compositions, particularly polyolefin compositions that have good adhesion to substrates other than polyolefins. Polyolefins such as polyethylene, polypropylene, and polybutene do not have polar moieties, such as functional groups, in their molecules and are highly crystalline, so they have extremely poor adhesion to aluminum, iron, and the like. Various attempts have been made to improve this adhesiveness. For example, by treating the adhesive surface of polyolefin with a solvent,
Methods of surface treatment such as heated air treatment and acid treatment, methods of mechanically roughening the metal surface to be bonded, and methods of surface oxidation treatment have been proposed. However, in all cases, not only the processing operations were complicated, but also sufficient adhesive strength could not be obtained. In addition, various adhesives have been proposed and some are commercially available, but they require time-consuming work such as preparing the adhesive, applying it to the adhesive surface, and drying, and are also inexpensive and excellent for large-scale adhesive processing. No material with such adhesive ability is known yet. The present inventors have conducted various studies to solve these problems, and as a result, have completed the present invention.
The present invention aims to modify polyolefins and to provide novel polyolefin compositions which themselves exhibit good adhesion to substrates other than polyolefins, such as metals, glass, etc., for example by pressing. According to the present invention, this object is achieved by a polyolefin composition comprising a polyolefin blended with a hydrocarbon polymer having at least one epoxy group and having a saturated or partially saturated main chain. be done. The present invention will be explained in detail below. (1) The polyolefin in the composition of the present invention specifically refers to the following, for example. Polymers and copolymers of α-olefins represented by ethylene, propylene, butene, 4-methylpentene-1, etc., ranging from relatively low molecular weight polymers to high molecular weight polymers. The density ranges from low density products of about 0.86 to 0.
It includes products with a high density of about 97, and also includes products that are virtually amorphous to highly crystalline. For example, polyethylene is produced by a low-density homopolymer with many long chain branches produced by a high-pressure process, a copolymer with ethylene-vinyl acetate, acrylic acid, methacrylic acid, acrylate, and methacrylate, and a copolymer produced by a low-pressure process. Examples include high-density polyethylene or copolymers of ethylene and other olefins produced by a medium-pressure method, and high-density polyethylene or copolymers of ethylene and other olefins produced by a medium-pressure method. Regarding polypropylene, it includes stereoregular polypropylene, that is, isotactic polypropylene, syndiotactic polypropylene with high crystallinity, and atactic polypropylene with low crystallinity. Polymers of olefins higher than propylene include polymers of 1-butene, which also include crystalline polymers with high stereoregularity to non-crystalline polymers. Furthermore, as a polymer of higher olefin, poly 4
-Methylpentene-1, etc. Others, α
- There are no restrictions on the type of olefin, and various olefin polymers can be used. Copolymers of ethylene and propylene, ethylene and butene-1, and ethylene and hexene-1 are also used. In this case, either a random copolymer or a block copolymer may be used. For example, ethylene and propylene are combined with a Ziegler-based catalyst. ethylene-propylene rubber, which is polymerized in the presence of ethylene-propylene rubber, optionally containing further unsaturated components such as dicyclopentadiene, ethylidenenorbornene, or 1.4
-Includes terpolymers containing hexadiene, etc. (2) In the composition of the present invention, a hydrocarbon polymer having at least one epoxy group and whose main chain is saturated or partially saturated (hereinafter simply "having at least one epoxy group") Specifically, the term "saturated hydrocarbon polymer" refers to, for example, the following: That is, the main chain is a fully or partially saturated hydrocarbon chain. Here, "partially saturated" refers to, for example, one in which the 1,4 polyptadiene chain is hydrogenated by 50% or more, preferably 80% or more. The number of epoxy groups per molecule is on average 1.5 to 8.0, especially 1.5 to 3.0
It is preferable that Number average molecular weight is 500~
Preferably it is 20000. Such a saturated hydrocarbon polymer having at least one epoxy group is obtained by reacting a hydrocarbon polymer having at least one hydroxyl group and having a saturated or partially saturated main chain with epihalohydrin. or polyptadiene,
By epoxidizing a hydrogenated product of a polydiene such as polyisoprene with a peracid such as peracetic acid or a peracetic acid-acetaldehyde complex,
Manufactured. A hydrocarbon polymer having at least one hydroxyl group and whose main chain is saturated or partially saturated (hereinafter simply referred to as "a saturated hydrocarbon polymer having at least one hydroxyl group") The method for producing by reacting with epihalohydrin will be described in detail below. The starting polymer is a hydrocarbon chain whose main chain is fully or partially saturated. Here, the term "partially saturated" refers to one in which the double bonds in the main chain, such as a 1.4 polybutane chain, are hydrogenated by 5% or more, preferably 80 or more. The average number of hydroxyl groups is 1.5 to 8.0 per molecule.
In particular, it is preferably 1.5 to 3.0. The number average molecular weight is preferably 500 to 20,000. Moreover, it is preferable that one or more hydroxyl groups exist at the ends of the main chain or long chain branches. However, this saturated hydrocarbon polymer having at least one hydroxyl group can be produced by various methods. For example, polyhydroxy saturated hydrocarbon polymers obtained by completely or almost completely hydrogenating polyhydroxy diene polymers obtained by various methods, and copolymers of isoprene and diene monomers are oxidized and A polyhydroxy saturated hydrocarbon polymer obtained by decomposition treatment and then reduction, a copolymer of α-olefin (e.g. ethylene and propylene) and a non-conjugated diene (or conjugated diene) is oxidized and decomposed. Examples include polyhydroxy saturated hydrocarbon polymers obtained by subsequent reduction. Hydrogenated products of polyhydroxydiene-based polymers can be easily obtained by catalytic hydrogenation of polyhydroxydiene-based polymers in a conventional manner. or by polymerizing a conjugated diene monomer and another monomer such as a vinyl monomer using a hydrogen peroxide initiator or an azobisisonitrile initiator having a hydroxyl group. Conjugated diene monomers used in such polymerization include 1,3-butadiene, isoprene, and 1,3-butadiene.
- Pentadiene, 2,3-dimethylbutiene, etc., and other monomers include general formula (In the formula, R ¹ represents a hydrogen atom or an alkyl group, and R ² represents an aryl group, a carboxyl group, an ester group, a pyridyl group, etc.), such as styrene, acrylonitrile, acrylic acid, methacrylic Examples include acid acrylates, methacrylates and vinylpyridine. The content of other monomers in the resulting copolymer when copolymerized is usually 75% by weight or less, preferably 50% by weight or less. Examples of azobisisonitrile compounds having a hydroxyl group include β,β′-azobis(β-cyano-n-propanol), δ,δ′-azobis(δ
-cyano n-pentanol), etc. A polyhydroxydiene polymer can also be obtained by reacting a living diene polymer with an epoxy compound such as a halogenoalkylene oxide, for example, according to the method disclosed in Japanese Patent Application No. 1982-62822.
Next, the diene-based living polymer was reacted with a halogenoalkylene oxide or a polyepoxy compound, and then further reacted with a monoepoxy compound, according to the method of treatment with protonic acid or the method of Japanese Patent Application No. 1983-65244. rear,
It can also be produced by a method of treatment with protonic acid and various other modified methods of these methods. The living diene polymer used in these methods is a dialkali metal polymer in which an alkali metal is bonded to both ends of the molecule.
Such a living polymer is produced by combining the above-mentioned conjugated diolefin alone, or the conjugated diolefin and another monomer represented by the above general formula (), in the presence of an alkali metal or an organic alkali metal compound according to a known method. It can be easily obtained by polymerization below. Examples of alkali metals used in this polymerization include lithium, sodium, potassium, rubidium, and cesium, and examples of organic alkali metal compounds include alkali metals such as naphthalene complexes, anthracene complexes, biphenyl complexes, diene complexes, and styrene complexes. Organic complexes of metals, or 1,4-dialkali metal butanes, 1,5-
Dialkali metal pentane, 1,10-dialkali metal decane, 1,2-dialkali metal-1,2
Examples include dialkali metal hydrocarbons such as -diphenylethane, 1,4-dialkali metal-1,1,4,4-tetraphenylbutane, and the like. Hydrocarbon solvents such as hexane, heptane, benzene, toluene, xylene, cyclohexane, and methylcyclohexane are used to make the living polymerization proceed smoothly. In particular, when the reaction is to be carried out uniformly, the above hydrocarbon solvent and Lewis A mixed solvent of bases is used. As such Lewis bases, oxygen-containing Lewis bases such as dimethyl ether, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, anizole, and ethyl phenyl ether, and nitrogen-containing Lewis bases such as trimethylamine, triethyl aion, and dimethylaniline are used. be done.
The living diene polymer obtained in this way, which usually has an alkali metal bonded to both ends, is reacted with an epoxy compound based on the method of each of the above patent applications, and then protonated with hydrochloric acid, sulfuric acid, acetic acid, etc. A polyhydroxydiene polymer can be obtained by treatment with an acid. Epoxy compounds to be reacted include monoepoxy compounds such as ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide, and phenyl glycidyl ether; diglycidyl ether of bisphenol A, vinyl cyclohexene diepoxide, butadiene diepoxide, and Cyclopentadiene diepoxide, limonene diepoxide,
Examples include polyepoxy compounds such as bisepoxide of ethylene glycol; halogenoalkylene oxides (ie, haloepoxy compounds) such as epichlorohydrin, methylepichlorohydrin, and epibromohydrin. These epoxy compounds are used in various combinations and in various amounts. For example, when a living polymer is reacted with a monoepoxy compound in an amount more than twice the molar amount, the epoxy compound is ring-opened and bonded to both ends of the living polymer, and the hydroxyl groups generated by the ring opening are bonded to both ends of the living polymer. A polymer having a group in which a hydrogen atom is substituted with an alkali metal, that is, an -OM group (M represents an alkali metal) is produced,
This -OM group is converted to a hydroxyl group by protonic acid treatment. Furthermore, when a polyepoxy compound or a halogenoalkylene oxide is reacted, the molecular weight and number of hydroxyl groups of the resulting polymer vary depending on the reaction ratio. That is, it is usually 0.5 to 2.0 times the mole of the living polymer, especially,
These are reacted within the range of 0.6 to 1.7 times the mole, but in this case, various polymers in which several molecules of living polymers are bonded via ring-opened epoxy group-containing groups are produced, and the opening Since the -OM group is formed in the ring epoxy group,
When this polymer is treated with proton acid, it becomes a polymer having hydroxyl groups at each seam of living polymer units. Furthermore, if a living polymer is reacted with an equimolar amount of a polyepoxy compound or a halogenoalkylene oxide, and then a monoepoxy compound is reacted with the living polymer, each seam and both ends of the living polymer units of the resulting polymer can be reacted. ―
OM groups are formed, and if this polymer is treated with a protonic acid, a polymer having hydroxyl groups at both ends and in the middle (for each seam) of the molecule can be obtained. By hydrogenating polyhydroxydiene polymers obtained by various methods as described above, they can be made into saturated hydrocarbon thread polymers having at least one hydroxyl group. Complete hydrogenation is desirable, but as mentioned above, the hydrogenation rate
There is no problem with partial hydrogenation of 50% or more.
For hydrogenation, commonly used catalytic hydrogenation means can be employed. That is, as the hydrogenation catalyst, a nickel catalyst (for example, Raney nickel), a cobalt, platinum, palladium, ruthenium, or rhodium catalyst, which has been used for a long time, or a mixture or alloy catalyst thereof can be used. These catalysts can be used alone as a solid or soluble homogeneous complex, or supported on carbon, silica, diatomaceous earth, or the like. Furthermore, hydrogenation may be performed using a metal complex obtained by reducing a compound containing nickel, titanium, cobalt, etc. with an organometallic compound (for example, trialkylaluminum, alkyllithium, etc.). As the hydrogen to be used, molecular hydrogen or a gas containing it can be used as long as it does not contain substances that poison the catalyst. There is no difference in hydrogen pressure whether it is a normal pressure blow or a pressurized system. Temperature is room temperature ~
The temperature is 200°C, preferably 180°C or less. The polyhydroxydiene polymer can be used alone or as a solution in a solvent. Such solvents include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons,
Alcohols, aliphatic carboxylic acids, etc. can be used alone or in a mixed system. Another method for producing a saturated hydrocarbon polymer having at least one hydroxyl group includes a method in which a copolymer of α-olefin and another monomer is oxidized and decomposed, and then reduced. For example, if a butyl rubber-based polymer obtained by cationic polymerization of imbutylene and butadiene or 1,3-pentadiene is treated with ozone, and then reduced with lithium aluminum hydride, polyhydroxy polyimbutylene can be obtained. Further, a polyhydroxy polyolefin can be obtained by ozonolyzing a poly α-olefin having an unsaturated bond obtained by copolymerizing ethylene alone or with a diene in the coexistence of propylene, and then reducing it. The raw material saturated hydrocarbon thread polymer having at least one hydroxyl group obtained by various methods as detailed above is reacted with epihalohydrin. As such epihalohydrin, epichlorohydrin is most commonly used, but other epibromohydrin, α-methylepichlorohydrin, etc. can also be used. The reaction with epihalohydrin is usually carried out in a solvent. Although various solvents can be used as such a solvent, hydrocarbon solvents are generally preferably used. For example, hexane, heptane, cyclohexane, benzene, xylene, and mixed solvents thereof are used. Also. The reaction is carried out in the presence of various catalysts. Both acids and alkalis can be used as such catalysts;
Examples of alkaline catalysts include caustic soda and caustic potash; examples of acid catalysts include hydrochloric acid,
Inorganic acids such as sulfuric acid, various solid acids, and organic acids such as formic acid and acetic acid can be used, with acid catalysts being generally more commonly used. However, more preferred catalysts are boron trifluoride, its ether complexes, tin halides, titanium halides, aluminum halides, and the like. When using an alkaline catalyst, at least 1
Introducing an epoxy group into a saturated hydrocarbon polymer having hydroxyl groups through a one-step reaction between the --OH group and epihalohydrin, that is, a glycidyl ether group.

[Formula] is formed, but when an acid catalyst is used, -OH of the polymer is formed.
The reaction of epihalohydrin with groups is a ring-opening/addition reaction, and an epoxy group cannot be introduced in a one-step reaction. In this case, it is necessary to further perform a ring-closing reaction in the presence of an alkali after the first stage reaction. In general, it is easier to introduce epoxy groups quantitatively in a two-stage method than in a one-stage method. If the reaction of these one-step method and two-step method is expressed as an equation, it is estimated that it is as shown in the following equation (the formation of glycidyl ether groups in the obtained polymer was confirmed by infrared absorption spectrum). ). In addition, in the above reaction formula, the hydroxyl group of the polymer is 1
Only one is listed. Other hydroxyl groups are omitted to simplify the formula. The above-mentioned one-stage reaction and the first-stage reaction of the two-stage method usually proceed rapidly at room temperature to 130°C, preferably 50 to 100°C. In addition, the second stage reaction of the two-stage process, that is, the ring-closing reaction, is carried out at a relatively high temperature of 25 to 40°C in the presence of various alkalis, such as an aqueous solution of caustic soda (relatively high concentration ones can also be used). It progresses easily at low temperatures. The saturated hydrocarbon polymer having at least one epoxy group can be blended into the polyolefin described in (1) above, for example, as follows. In order to blend the two and mix them uniformly, any conventionally known kneading machine such as a Brabender plastograph, an extruder, a high-power screw type kneader, or a roll can be used. The temperature depends on the type of raw material, but for example, in the case of high-density polyethylene,
It can be carried out at 150-250°C. The mixing ratio is selected at a ratio that effectively exhibits the properties of the composition of the present invention, which will be described later, but usually 0.05 to 100 parts by weight of a saturated hydrocarbon polymer having at least one epoxy group is used per 100 parts by weight of polyolefin. ,Preferably
Selected from the range of 0.1 to 10 parts by weight. The constituent elements of the composition of the present invention have been explained above using preferable examples, but the composition of the present invention may also contain conventionally commonly used colorants, stabilizers, other additives, and fillers. Needless to say, it's a good thing. Fillers include natural silica such as sand and quartz, synthetic silica produced by wet or dry methods, natural silicates such as kaolin, mica, talc, clay, and asbestos, and synthetic silicates such as calcium silicate and aluminum silicate. , alumina, titania metal oxides, potassium carbonate, potassium sulfate,
Other metal powders such as aluminum and bronze, carbon black, etc. can also be used. Furthermore, the polymer (2) of the present invention may partially coexist with a diene polymer, vinyl polymer, etc. that do not contain a hydroxyl group. The composition of the present invention obtained as described above has extremely good adhesion and printability when molded into a film, sheet, plate, or other shape. In particular, it shows good adhesion to metals such as aluminum and iron, which are inherently difficult to adhere to polyolefins. Note that when adhering the composition of the present invention to metal,
By applying a compound having a group capable of reacting with an epoxy group to the metal surface to be bonded, the adhesive strength can be significantly increased. Groups that can react with these epoxy groups include amino groups, amide groups, carboxyl groups, acid anhydride groups, hydroxyl groups, isocyanate groups, and the like. Specifically, polyamines such as diethylenetriamine and diaminodiphenylmethane, polyamide resins, polycarboxylic acids such as maleic acid, phthalic acid, and hexahydrophthalic acid, and polycarboxylic anhydrides thereof, polyols such as trimethylolpropane, Examples include polyisocyanate compounds such as tolylene diisocyanate and diphenylmethane diisocyanate. These compounds are
It is usually applied to metal as a solution in a diluent such as an organic solvent. Next, examples of the present invention and production examples (reference examples) of raw materials for the composition of the present invention will be described, but the present invention is not restricted by these examples unless the gist of the present invention is exceeded. Reference example (1) Production of polyhydroxy saturated hydrocarbon polymer (hydrogenation of polyhydroxy diene polymer) Polyhydroxy polybutadiene (manufactured by ArCO Chem, R-
45HT, number average molecular weight 3110, [OH] = 0.82meq/
g, cis-1.4: 15%, trans-1.4: 58%,
After charging 3 kg of vinyl (27%), 3 kg of cyclohexane, and 300 g of carbon-supported ruthenium (5%) catalyst (manufactured by Nippon Engelhardt Co., Ltd.), replacing the inside of the system with purified argon gas, high-purity hydrogen gas was introduced into the autoclave. The supply started, and heating started at the same time. It took about 30 minutes for the inside of the autoclave to reach steady conditions (internal temperature 100°C, internal pressure 50 kg/cm ² ). After 15 hours under these conditions, the hydrogenation reaction was stopped, and the polymer was purified and dried according to a conventional method. As a result of analysis by infrared absorption spectrum, the obtained polymer was found to be a hydrocarbon polymer containing almost no double bonds. The amount of --OH groups in the hydrogenated product was 0.81 meq/g.
The number average molecular weight was 3200, and the average number of hydroxyl groups per molecule was 2.6. (2) Epoxidation 50 g of the polyhydroxy saturated hydrocarbon polymer hydrogenated in (1) was dissolved in 200 ml of toluene and charged into a 300 ml flask. Toluene 100ml
After dehydrating the system by heating and distilling off the
_BF3O ( _C2H5 ) _{2 0.1g} , epichlorohydrin
Epichlorohydrin was added by adding 10 g and stirring for 1.0 hour. The above solution was cooled to room temperature, 30 g of 50% NaOH aqueous solution was added, and the mixture was vigorously stirred for 1.0 hour to perform ring-closing epoxidation. After washing thoroughly with water, it was poured into a large amount of methanol to precipitate it, and then dried under vacuum at 50°C. The infrared absorption spectrum of the obtained polymer has
The absorption of -OH group at 3500cm ^-1 disappears, and a new
Absorption appeared at 840, 1260, 1120, and ~1130 cm ^-1 , confirming that epoxy groups were introduced. Since the absorption of OH groups has completely disappeared, epoxidation has progressed to almost 100%, and 1
The average number of epoxy groups per molecule was 2.6. Example 1 Commercially available high-density polyethylene [Novatec
BR002, Novatek are registered trademarks of Mitsubishi Chemical Industries, Ltd.] 100 parts by weight (hereinafter, parts are by weight) and 1 part of the epoxidized product of the reference example were mixed in a Brabender Plus graph for 5 minutes at 160°C. did. Next, thin aluminum plates [manufactured by Nippon Seifaku Co., Ltd., chromate-treated aluminum, 200 mm x 200 mm, each 0.3 mm thick]
Sandwich the above composition between the two and heat press for 230
Pressed for 15 minutes at °C. For press,
A 2.4 mm spacer was used to define the thickness of the laminate. After taking out the pressed pieces and allowing them to cool, cut them into specified dimensions and perform a 180°C peel test (according to ASTM D903-49T).
Served. The adhesive strength was 8 kg/25.4 mm. Example 2 An aluminum-polyethylene laminate was produced in exactly the same manner as in Example 1, except that 3 parts of the epoxide was used instead of 1 part. Its adhesive strength is 10Kg/
It was 25.4mm. Examples 3-5 In exactly the same manner as in Example 1, high density polyethylene compositions containing 1 part of epoxide were produced. on the other hand,
Toluene solution of the compounds shown in Table 1 (0.02g/ml)
2 ml was uniformly applied to the aluminum plate of Example 1 with dimensions of 200 mm x 200 mm and dried. A laminate was produced in the same manner as in Example 1 using these polyethylene compositions and surface-treated aluminum plates. The adhesive strength is shown in Table 1.

[Table] 〓
* Manufactured by Fuji Kasei Kogyo Co., Ltd., Tomide
2400 (Tomide is a trademark)
Comparative Examples 1 to 3 A laminate was produced in the same manner as in Example 1 by sandwiching high-density polyethylene (not containing epoxide) between the surface-treated aluminum plates used in Examples 3 to 5, but no adhesion occurred.

Claims (1)

[Scope of Claims] 1. A polyolefin composition comprising a polyolefin blended with a hydrocarbon polymer having at least one epoxy group and having a saturated or partially saturated main chain. 2 A hydrocarbon polymer having at least one epoxy group and a saturated or partially saturated main chain has at least one hydroxyl group and a saturated or partially saturated main chain. The polyolefin composition according to claim 1, which is the product of reacting a hydrocarbon-based polymer with epihalohydrin. 3. According to claim 2, the hydrocarbon polymer having at least one hydroxyl group and having a saturated or partially saturated main chain is a hydrogenated product of a polyhydroxydiene polymer. polyolefin composition. 4. Claim 2 or 4, wherein the hydrocarbon polymer having at least one hydroxyl group and having a saturated or partially saturated main chain has at least one hydroxyl group at its terminal end. The polyolefin composition according to item 3. 5. Claims 2 to 5, wherein the hydrocarbon polymer having at least one hydroxyl group and having a saturated or partially saturated main chain has an average number of hydroxyl groups per molecule of 1.5 to 8.0. The polyolefin composition according to any one of Item 4. 6. The polyolefin composition according to any one of claims 1 to 5, wherein the polyolefin is polyethylene. 7. Claims in which the blending ratio is 0.05 to 100 parts by weight of a hydrocarbon polymer having at least one epoxy group and whose main chain is saturated or partially saturated, per 100 parts by weight of polyolefin. The polyolefin composition according to any one of Items 1 to 6.