JPS6169452A - Laminate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a novel laminate, and in detail,
-Methylbutene-1 It relates to a laminate of a polymer or copolymer and another resin or metal.

[Conventional technology]

Conventionally, polyolefin resins such as polyethylene and polypropylene have been used in a variety of applications, taking advantage of their advantages such as transparency, good chemical resistance, good water resistance, excellent moldability, and light weight. It's here. It is also used in various ways in the field of laminates, and when combined with metals, it is applied as a coating material for the purpose of chemical resistance and corrosion protection. It is also used as a metal/plastic/metal composite material to make composite plates that are lighter in weight. On the other hand, as a packaging material, it is being applied by laminating with nylon, ethylene-vinyl alcohol co-merged resin, etc., and taking advantage of the water resistance, chemical resistance, and oil resistance characteristics of polyolefin. However, although these polyethylene and polypropylene resins have the advantage of being easy to process at relatively low temperatures, the front deformation jM[ is about 1 ooc or more
However, it has the disadvantage of poor heat resistance, and also has the disadvantage that its characteristic oil resistance decreases at high temperatures.

[Purpose of the invention]

The inventors of the present invention have sought to provide a laminate that takes advantage of the advantages of polyolefin resins and has greatly improved heat resistance and oil resistance.

[Structure of the invention]

The present invention provides a thermoplastic resin layer or a metal layer on at least one side of a notebook made of a copolymer mainly composed of 3-methylbutene-7 or J-methylbutene-7 with other α-olefins and/or polyenes. The gist of this is a laminate.

The J-methylbutene/polymer used in the present invention is 3-
It is a homopolymer of methylbutene-7 or a copolymer of 3-methylbutene-/ and α-olefin and/i or polyene.

3-Methylbutene-/number of carbon atoms copolymerized with ~α of JO
-Olefins include ethylene, phosphor 51
Robylene, butene-11hexene/, 41-methylpentene/, octene-11styrene, vinylcyclohexane, etc. are used. Examples of the crushed polyene include butadiene, imprene, hexadiene, methylhexadiene, ethylidene norbornene 7, and the like.

The copolymerization method may be so-called random copolymerization or block copolymerization. Among these, preferred are homopolymers of 1Pi3-methylbutene-/, random copolymers of 3-methylbutene-7 and ethylene, butene, butene, etc.
It is a block copolymer, a copolymer of J-methylbutene-/ and Shaoxian diene. The content of these copolymerized components in the polymer is preferably 0% by weight or less, more preferably -0% by weight or less. This is the copolymerization component.

If it is above, the heat resistance of J-methylbuty/-/ copolymer,
Oil resistance, rigidity, strength, etc. are poor and undesirable 0 The catalyst used for polymerization or copolymerization is usually a well-known Ziegler catalyst, but such catalysts are known, for example, from Japanese Patent Publication No. 5J-1, No. 3-1003゜S Dar 2717
/, Same! ! -/QO! Gu, same j kuda! -Cuco, same S7-Monday-da 3, JP-A-1983-tag 7, same 36-/
1320g, same! rK-Jl, 9ko g1 same 47-j dada 7g, same! 9-//JO4 etc. Furthermore, an electron-donating compound such as ether, ester, amine, or amide may be added as a third component if necessary.

Polymerization is carried out in an aliphatic, alicyclic or aromatic hydrocarbon such as hexane, heptane, cyclohexane, benzene, etc., in a liquid olefin, or in the absence of a solvent, using the above catalyst, in the presence or absence of hydrogen. Polymerize mu to o-1s
0° C., and 3-methylbutene-7 is polymerized alone, or J-methylbutene-7 is copolymerized with an α-olefin and/or polyene having a carbon number of λ to JO.

The J-methylbutene/polymer or copolymer (hereinafter sometimes simply referred to as a polymer) used in the present invention may be used as a laminate as it is, but at least a part of the polymer may contain a monomer capable of radical polymerization. It is preferable to use a modified polymer obtained by graft polymerization.

Such monomers include unsaturated carboxylic acids and their derivatives, such as ester derivatives such as heptanocarbo7rR% glycidyl acrylate such as acrylic acid, unsaturated dicarboxylic acids and anhydrides such as maleic acid, maleic anhydride, amides such as maleamide, etc. , unsaturated carboxylic acids such as fatty polyhydric carboxylic acids containing unsaturated bonds, aromatic vinyl compounds such as styrene, α-methylstyrene, etc.
Various monomers are used, including vinyl esters such as vinyl acetate. It is of course also possible to modify with mixtures of these monomers. Many effective heptamers other than those exemplified here have already been proposed, and the known monomers described in applications related to the production of modified polyolefins can be used in the present invention in four ways.

All known modification methods can be applied, but more specifically, the polymer and the graft monomer may be brought into contact under the influence of a catalyst that generates radicals or ionizing radiation.

The grafting method may be a vapor phase method, a melt kneading method, a slurry grafting method, or a solution carrier method, but the vapor phase method, the slurry method, or the melt mixing method is preferable as the method of the present invention.

The graft bond of the graft monomer is the grafted 3-
Usually o, o based on the weight of 1 g of methylbutene
It may be about 1% by weight to 10% by weight, but in some cases 30% by weight.
A graft material of about 60% by weight can also be used.

In the case of unsaturated carboxylic acid modification, it is preferable that the unsaturated carboxylic acid is present in an amount of about 0.0 Cor 1% per L final composition.

Furthermore, during or after the grafting reaction, fillers, stabilizers, metal inhibitors, organic or inorganic fillers, etc.
It is also possible to manufacture by adding flame retardants and other additive components, and it is also possible to carry out treatments such as washing and heat treatment during or after the grafting reaction to remove unreacted monomers. In addition, the modified 3-methylbutene-7 polymer used in the present invention also includes a composition of a J-methylbutene/polymer and a polyolefin resin modified with the graft monomer.

That is, a modified polyolefin other than 3-methylbutene-/polymer is blended within a range that does not significantly impair the heat resistance, oil resistance, etc., which are the characteristics of polyJ methylbutene-/, and 3-methylbutene-/
/ The modified polymer can be used as a polymer composition. Examples of modified polyolefins used include polyethylene modified with the above-mentioned graft monomer, ethylene-α olefin copolymer, polypropylene, propylene-α olefin copolymer, ethylene-vinyl ester, (meth)ac I)kH ester, etc. copolymers, ethylene-α-olefin-diene elastomers, and the like. The blending amount of these modified polyolefins is 0. The amount of the modified graft monomer in the entire composition is preferably about 1,000% by weight, and the amount of the modified graft monomer in the entire composition is preferably about 0.0col/1% by weight.

The J-methylbutene-1 polymer and modified J-methylbutene/polymer produced by this method are laminated with various base material layers.

The first laminate is a laminate with a metal material. Examples of metals to be laminated include iron, aluminum, copper, zinc, etc., but of course metals other than these, alloys, etc. can also be used. Among them, iron, aluminum, and copper are desirable because they have a wide range of applications. As an iron composite, it can be used as a material for bonding with steel, plated steel plates, etc., and as an exterior material for pipes such as steel pipes.

When the 3-methylbuty7-/polymer or the modified J-methylbutene/polymer of the present invention is used as the exterior or protective layer of a steel plate or the like, good heat resistance and solvent resistance are exhibited. Although it depends on the conditions, the Φ layer of the present invention maintains its shape and maintains chemical and oil resistance even at temperatures at which ordinary polyethylene, polypropylene, and robylene coating layers melt or melt. In addition, when used as a metal/plastic/metal composite material, a composite material with high heat deformation resistance temperature can be obtained.
There is little decrease in strength.

The copper composite can be used for printed circuit boards, etc.

The method for producing such a metal/3-methylbutene-1 polymer laminate can generally be applied to a method for producing a polyolefin laminate. Specifically, there is a method of coating while extruding resin with a T die, round die, etc., a method of forming a sheet in advance,
There are methods such as a method of heat-pressing, a method of bringing a powdered modified resin into contact with a sufficiently heated metal molded body, and the like.

When laminating 3-methylbutene-7 polymer and metal, it is preferable to use a modified J-methylbutene/polymer as an adhesive, but the surface of the 3-methylbutene-7 polymer layer may be bonded by corona treatment or chemical treatment. Methods of improving sexual performance are also possible. Furthermore, it is also possible to add 111 methods such as brimer treatment of metal surfaces and methods using a combination of modified 3-methylbutene-1 polymer and various adhesives. When laminating these, J-methylbutene-
Various stabilizers, colorants, graph fibers, fillers such as mica, etc. may be added to the 7fi combined layer and the modified J-methylbutene-7 polymer layer.

Next, a laminate of 3-methylbutene/polymer and a plastic material such as a thermoplastic resin or a thermosetting resin is produced using the same method, such as gluing notebooks together or extrusion lamination onto the surface of the base material. I can do it. Furthermore, it is also possible to form multi-layer film sheets, tubes, bottles, etc. by coextrusion. In laminates with these plastic materials, it is possible to combine the high heat resistance, chemical resistance, and oil resistance of 3-methylbutene/polymer with the hardness, gas barrier properties, and other properties of the base resin. The result is a high-quality, durable composite material that can be used under conditions that were previously unusable and rare. - For example, a container made of M/so body with an ethylene vinyl alcohol copolymer has a higher viscosity than a conventional container made of polypropylene or the like. . . , □1 and □, it can withstand high temperature sterilization, has high oil resistance, and is resistant to oxygen permeation, so it can be used as a retort container, etc.

Such thermoplastic resins may have functions that can enhance the properties of the J-methylbutene/polymer, such as heat resistance, oil resistance, chemical resistance, etc., such as gas barrier properties. Preferably, the structural KFi resin has a polar group.

In addition to ethylene vinyl alcohol copolymer, resins that can be mixed with J-methylbutene-1 polymer note include 6-methylbutene-1 polymer.
Examples include polyamide resins such as nylon and 6.6-nylon, and polyester resins such as polyethylene terephthalate and polyethylene naphthalate.

The thickness of the 3-methylbutene-1 polymer is not particularly limited,
It can be set as appropriate depending on the application, but usually Sμ~/l
It's about 'll+.

The thickness of the resin or metal to be laminated varies depending on the application, but is usually several microns or more. Its form is particularly limited, such as sheet or tubular (Aj Production of homogeneous titanium trichloride solution jf Purified toluene/!real and θm mol of tetande tetrachloride are charged into a 500-volume four-loaf flask purged with dry argon, and then di- 90 mmol of n-butyl ether was added.Titanium tetrachloride and di-n-butyl ether reacted with some heat and uniformly dissolved in toluene to obtain an orange-yellow homogeneous solution.The solution was stirred. While keeping at -5°C, stiffly diethylaluminum monochloride utmmo1'(i=)luene 20
When the dissolved solution was gradually added to the solution, a crushed orange homogeneous solution of titanium trichloride was obtained.

(B) Production of precipitate of titanium trichloride and production of catalyst (
A) The homogeneous solution of titanium Migishika obtained in the step When the temperature was raised to 0.degree. C., a purple titanium trichloride precipitate was observed to form during the temperature rise. After stirring at 95° C. for 60 minutes, the precipitate was separated and washed three times with 100% n-hebutane to obtain a finely divided purple titanium trichloride catalyst complex. Elemental analysis reveals that the catalyst complex has the formula TiC4IALC4,)6.60t4((n
o,)1. '), 0 ] 0.03.

Polymerization Example-7 0.7 kg of the solid titanium trichloride catalyst complex obtained in Catalyst Production Example-7 and 6.0 kg of diisobutylaluminum monochloride were placed in a fully vacuum-dried autoclave with a capacity of 1 t, which was purged with nitrogen. /Arn tool has been installed. Then, after adding liquefied 3-methylbutene-7 to &309,
3. at 0°C. Polymerization was carried out for S hours. Then, isobutyl alcohol coj was added to stop the polymerization, and excess unreacted supernatant was expelled. Then normal hexane 1000
After introducing yd and stirring at 50° C. for 30 minutes 1), the supernatant was extracted and the oil component in the polymer was washed and removed.

0.2 parts of Irganox 1010 as an additive was added to a portion of the obtained poly-3-methylbutene-7, and Ka*7.
After adding P-EPQ, 'fzO, and 2'fz4C (all manufactured by Nippon Ciba Kaiky Co., Ltd.), pelletization was carried out using an extruder at 0°C. The melting point of this thing is JO'
1℃, and the melt viscosity of the press-formed product at 330℃ is 7
It was X/Os Poise.

Polymerization example - Single polymerization side control/polymerization QL at 50°C and catalyst amount at 3.0
1. Amount of diimbutylaluminum monochloride/
0.4 g to mol, and at the same time as the start of polymerization, a small amount of butene-/Qj/L was introduced every 5 minutes, and the amount of butene-/Qj/L! was adjusted to 0.4 g to mol. Direct polymerization was carried out in exactly the same manner as in Polymerization Example 1, except that wt % O copolymerization was carried out and the polymerization time was set to co-hours. The melting point of this product was -SS℃, and the bath melt viscosity was /x10@poise.0 Manufacturing example of modified polymer-/ 1 Polymer powder 10011 obtained in Example-7 (However, it did not contain additives) ) to xylene, I!
; Add anhydrous maleic rll JOI and dicumyl paloxide sp dissolved in 00 cc, and add 13 mL under nitrogen atmosphere.
Heated at 41° C. for q hours. After cooling, unreacted substances were extracted with acetone, and the amount of acid anhydride was determined by an infrared method, and it was found that O and J type photons were present. (Modified polymer A
) Production Example of Modified Polymer - The monopolymer side polymer was treated in the same manner as in Production Example 7 of Modified Polymer. The graft weight was 0.3 weight and 7 weight. (
Modified Polymer B) Production Example of Modified Polymer-3 Polymerization Example-Maleic anhydride/co polymer powder 1001
11. and, ko, 5 dimethyl ko, j ditertiary buti/
I/ Attach baroxyhexane O0/9 and -10
Melt kneading was carried out using a heavy machine with a diameter of 9 rm/9° C. to obtain pellets. The amount of grafting was OI, 2-M%. (Modified Polymer C) Example-l Modified Polymer A was pressure-molded at 30° C. using a hot press to obtain a transparent sheet with a thickness of 0.1 m.

This sheet was stacked with an aluminum plate with a thickness of 0 and a thickness of 100 cm, which had been previously subjected to surface degreasing treatment, and heated at 30°C.
Pressure was applied for 0 seconds to seal.

When the resulting &tM board was cut into short strips with the same width and its peel strength was measured, it showed a value greater than or equal to -, indicating that it had sufficient adhesive strength.

The above laminate was immersed in Nato xylene for 5 minutes for the purpose of a solvent resistance test, but there was no change in the surface.

Comparison row: Commercially available modified polypropylene (a homopolymer modified with maleic anhydride) was pressure-bonded to an aluminum plate at 230°C. This +7 was determined by the peeling strength of the laminate. When this laminate was immersed in xylene in the same manner as in Example 1, dissolution occurred and the surface layer was deformed and bulged out.

Example - Copolymerization example - The polymer of l was press-molded with JcoOC to give 0.3
m sheets were created. Similarly, a 7-sheet sheet of modified polymer C was prepared, and a laminate of polymer sheet/sheet of modified polymer C 7-sheet sheet/aluminum plate was prepared. In this case as well, a laminate was obtained in which a transparent and highly hard coating was formed on the aluminum plate.

To check solvent resistance, an emulsion was prepared by mixing 5 wt% of kerosene and vrt% of kitchen detergent in water, and the mixture was immersed in water heated to 100°C for 30 minutes, but 3-methylbutene-7 There was no 7 conversion to the polymer coating.

Comparative Example-1 When the same alphanumeric process as in Example 11 was carried out on the propylene-coated laminate of Comparative Example-7, swelling and deformation occurred on the surface.

Example = 3 A sheet of O1/1 thickness of 6-nylon which has been crimped and molded and a sheet of O1/1 thickness of modified polymer A. / The Toatsu sheets were aligned and pressed together at 250℃ for about 30 seconds. Modified polymer 0.
A laminated sheet of 09 m and 70.07 m of 6 Nylon was obtained. 1 character crawling strength is /nigu//! It was mn wide and often had a length of 2γ1.

This laminated sheet was immersed in Buddha's xylene for j minutes, but there was no change.

Comparative Example-J When a social film of nylon and modified polypropylene (50μ15θμ thick film formed into bM shape by coextrusion method) was soaked in boiling xylene in the same manner as in Example 3, the polypropylene layer was immersed. The complex did not retain its shape.

Example-Da! Commercially available ethylene vinyl alcohol copolymer film (0 μm) and polyethylene tere 7 tallate film (λ3
μ) and iL respectively modified polymer B sheet (θ, λm+
) and unmodified 3-methylbutene-/ obtained in polymerization example/
A three-layer 7-coat was prepared by pressure bonding a polymer sheet (0.3 m) at a temperature of 0°C.

In both cases, transparent laminates were obtained. Each adhesive strength is /
, Kf/lx, θ, and A k/cm. When these laminates were left in an atmosphere of 750°C for about 3 minutes, some stress occurred, but other appearance A.
There were no changes above.

Comparative example - da, s, a ethylene vinyl alcohol copolymer and polypropylene,
MM bodies of ethylene vinyl alcohol copolymer and polyethylene, and polyethylene terephthalate and polypropylene were all produced by a pressing method. The polyolefin grafted with maleic anhydride was used. The thickness of each polyolefin was /θOμ. 75 of these sheets
When the sheet was left in an atmosphere of 0° C. for 3 minutes, the polyolefin layer softened and became liquid, and the sheet itself could not maintain its shape.

A copolymer of 3-methylbutene/and butene/ was prepared according to Polymerization Example - Co., Ltd. The copolymerization amount of butene-7 is &, &
In terms of wt%, the melting point of the co-monomer was 2°C. Anhydrous maleic rR1s if & xylene as a medium; 00 a2, Ojika/I/Ij? Using dicumyl bar orcytocol as J initiator, /3g℃-
React for J hours and convert maleic anhydride to θ, λ4tIM *
A glutinous graft polymer was obtained. (Modified Polymer D) The same polymer was used, the solvent was dichlorobenzene, and the initiator was dimethyl. ! -di(tertiarybutylperoquine)hexyne-3 and reacted at a reaction temperature of 40°C for 1 hour to obtain a graft polymer containing 11t% of maleic anhydride/7z.

(Modified Polymer E) Example-6 Copper foil manufactured by Mitsui Kinmuhaku Co., Ltd. (grade: JEC-8) and Japan 7
The above modified 3-methylbutene-/
(200μ) of a mixture of 30% (modified polymer D) and 70% of the unmodified polymer obtained in Polymerization Example-1
were overlapped and press-molded at 300°C. When the adhesive strength (T peel strength) of the layer between this glass fiber and poly-3-methylbutene/copper foil was measured, it was found to be Z at i and qy4.

Example 7 A copper foil/glass fiber reinforced polymer laminate similar to Example 7 was prepared using modified polymer E instead of modified polymer D of Example 6, and the adhesive strength was 7.9.
KvcrR 5, Example-g Polymerization Example-/Polymer f was press-molded at 320°C to obtain a transparent sheet with a thickness of 0.2 m. This sheet was subjected to corona treatment for film and corona treatment. Then, an aluminum plate with a thickness of θ, whose surface had been degreased in advance and an epoxy adhesive (CEMEDINE SUPER) f was used, and then left overnight. The polymer layer and the metal adhered well and could not be peeled off by hand.To test the solvent resistance, the 3-methylbutene-iN of the above laminate was mixed with xylene and held for 5 minutes, but the laminate was not removed. 0 [Effect of the Invention] The laminate of the present invention has significantly improved the dryness β resistance without deteriorating the physical properties of polyolefin, which has excellent physical properties such as chemical resistance, water resistance, and moldability. , which has improved oil resistance and is suitable for use as various covering materials, composite plates for structural materials, packaging materials, etc.

Applicant: Sankyen Kasei Kogyo A-type company Representative Chief Patent Attorney in each state - 1 other person

Claims (3)

[Claims] (1) A thermoplastic resin layer or a metal layer on at least one side of a sheet of 3-methylbutene-1 polymer or a copolymer mainly composed of 3-methylbutene-1 and other α-olefins and/or polyenes. Laminated body with (2) The resin layer is made of ethylene vinyl alcohol copolymer,
The laminate according to claim 1, comprising at least one resin selected from polyamide and polyester. (3) The laminate according to claim 1, wherein the metal layer is aluminum or copper.