JPH04369537A - Polybutadiene-metal layered structure - Google Patents

Abstract

PURPOSE: To enable effective bonding of a polyethylene layer with a metal by using an adhesive composition particularly consisting of an acidic functional block copolymer. CONSTITUTION: A liminate consisting of a polybutadiene and a metallic laver contains at least one piece of metal, an adhesive layer and at least one piece of a polybuthylene layer laminated in that order. The adhesive to be employed is partially hydrogenated and a modified block copolymer is obtained through modification by grafting a maleic acid compound on a block copolymer structure. That is, the block copolymer is at least one kind of functional block copolymer having at least one block which is composed mainly of at least a unit to be derived from a monoalkenyle aromatic hydrocarbon monomer and at least one block composed mainly of at least a hydrogenated unit which can be derived from a conjugated diolefin monomer.

Description

[Detailed description of the invention]

0001

TECHNICAL FIELD This invention relates to laminate structures comprising metal-polybutylene structures having functionalized block copolymer bond layers.

0002

TECHNICAL BACKGROUND OF THE INVENTION Laminated structures consisting of a plurality of polymer layers are well known and are described, for example, in US-
A-4,058,647, US-A-4,198,32
7, US-A-4,332,858, US-A-4,3
41,837, US-A-4,588,648 and J.
Reference is made to P-A-58 [1983]-13242. US-A-4,332,858 and US-A-4,
341,837 describes various polymeric materials such as olefin homopolymers; olefin copolymers such as copolymers of ethylene and vinyl alcohol; and polycarbonates, modified but not hydrogenated block copolymers. ,
For example, it is taught that a maleated block copolymer of styrene and butadiene can be used for adhesion. US-
No. 4,588,648 discloses that certain polymeric materials, such as polypropylene and ethylene/vinyl alcohol copolymers, can be laminated with an adhesive layer consisting of a grafted copolymer of olefin and maleic anhydride and ungrafted polypropylene. is teaching. However, none of these documents describes or suggests how to bond polybutylene to metals.

Adhesives and similar compositions are known which can consist of block copolymers containing at least one monoalkenyl aromatic hydrocarbon block and at least one hydrogenated conjugated diolefin block. Polymer compositions that may contain hydrogenated block copolymers are described, for example, in US-A-3,607,977, US-A-3,970.
, 711 and EP-A-0169987. US-A-3,607,977 requires at least 2
a block copolymer containing at least one monoalkenyl aromatic hydrocarbon polymer block and at least one monoalkenyl aromatic hydrocarbon polymer block in which at least 10% of the initial unsaturation introduces polar groups. teaches compositions containing block copolymers that have been reacted as described above. These block copolymers may each independently be intact or hydrogenated. The polar group may be an oxygen-containing group such as a carboxyl group. Compositions containing oxygen-containing groups are said to be particularly useful as adhesives for polar fabrics such as cellulose. but,
There is no indication that these adhesives would be useful in producing polymeric laminates consisting of metal and polybutylene layers.

Problems with adhesion of polybutylene to metal substrates have been a problem for many years. Therefore, there is still a need for metal-polybutylene laminate structures.

[0005]

OBJECTS OF THE INVENTION The present invention has been made in view of the current situation, and it is an object of the present invention to provide a polybutadiene-metal laminate having a metal layer, a polybutylene layer, and an adhesive layer for bonding the two layers.

[0006]

SUMMARY OF THE INVENTION A laminate structure comprising polybutadiene and a metal layer according to the present invention is a laminate structure comprising at least one metal, an adhesive layer and at least one polybutylene layer in this order, The agent layer has at least one block composed at least predominantly of units derivable from monoalkenyl aromatic hydrocarbon monomers and at least one block composed at least predominantly of hydrogenated units derivable from conjugated diolefin monomers. It is characterized in that it consists of at least one functionalized block copolymer having 1 block.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The polybutadiene-metal laminate structure according to the present invention will be specifically described below.

The adhesive employed in accordance with the present invention is a modified block copolymer that is partially hydrogenated and further modified by grafting a maleic acid compound onto the block copolymer structure. The term "block copolymer" refers to at least one block (block A) composed at least predominantly of polymerized vinyl aromatic hydrocarbon units and at least predominantly composed of hydrogenated and polymerized conjugated alkadiene units. used to denote a thermoplastic elastomer characterized by at least one block (block B) constituted by

The vinyl aromatic hydrocarbons used as precursors of the A block are vinyl groups having up to 12 carbon atoms directly bonded to the aromatic ring, such as -CH═CH
It has 2 groups. Preferred vinyl aromatic hydrocarbons are styrene and styrene homologs, such as those of the formula:

00
10]

[Chemical formula 1]

(In the formula, each R is independently a hydrogen atom or 4
is an alkyl group having up to 1 carbon atoms). Examples of such compounds are styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, p
-ethylstyrene, m-propylstyrene and α-,
4-dimethylstyrene. Styrene and alpha-methylstyrene are preferred, with styrene particularly preferred.

The A block of the block copolymer is preferably a homopolymer block, but it is a block obtained by copolymerizing some of the monomers of the B block with a vinyl aromatic hydrocarbon monomer which is the main component of the block A. Good too. Such blocks are called tapered and have at least 85 mol%, preferably at least 93 mol%, of polymerized vinyl aromatic hydrocarbons;
The remainder is, for example, the conjugated alkadiene used to provide block B. A blocks containing mixtures of vinyl aromatic hydrocarbons are also suitable, but less preferred. The average molecular weight of the A block is typically 5,000 to
125,000, preferably 7,000-125,00
It is 0.

Each B block is derived at least primarily from a polymerized conjugated alkadiene. The alkadiene used as monomer for the B block may be a conjugated alkadiene having up to 8 carbon atoms, for example as shown in the following formula.

[0014]

[Case 2]

Such alkadienes (wherein each R is as defined above) include butadiene,
Isoprene, 2,3-dimethylbutadiene, 1,3-octadiene, 1,3-pentadiene and 2-methyl-
An example is 1,3-hexadiene. Preferred conjugated alkadienes are butadiene and isoprene, with butadiene being particularly preferred. Each B block has at least a main component of polymerized alkadiene, and in the case of a tapered block, B
The blocks are preferably polymerized with at least 85 mol %, especially at least 93 mol % of the alkadiene, the remainder being vinyl aromatic hydrocarbons of the A block. Homopolymer blocks are preferred for each B block, but tapered blocks and blocks of polymerized mixed alkadienes are also sufficient. Among polymerized alkadienes, two modes of polymerization are possible and commonly observed. 1,4
- In what is called polymerization, each carbon atom of the four-carbon alkadiene moiety is incorporated into a polymer chain, which then contains two carbon atoms joined by an ethylene bond. In what is called 1,2-polymerization, only one carbon-carbon double bond of the conjugated alkadiene participates in the polymerization. The carbon atoms of this bond are incorporated into the polymer chain,
This in turn contains pendant unsaturated groups. Control of these two modes of polymerization is within the knowledge of those skilled in the art. Preferred block copolymers contain 25% to 55% of each B block.
The unit of % is derived from 1,2-polymerization. The average molecular weight of the B block is preferably 10,000 to 300,0
00, preferably 30,000 to 150,000.

[0016] The A block is a block copolymer consisting of
A total of 2 to 55% by weight, preferably 10 to 35% by weight, based on the total block copolymer, is suitable. The average total molecular weight of the block copolymer is 25,000 to 350
,000, preferably 35,000 to 300,000. These average molecular weights are determined by conventional techniques such as tritium counting or osmometry.

The structure of the block copolymer depends on the polymerization method employed to produce the block copolymer. In one embodiment, block copolymers are referred to as linear and are produced by sequential polymerization of blocks. As an example of producing a 3-block or triblock polymer, an A-block vinyl aromatic hydrocarbon is polymerized using an initiator, preferably an alkyllithium compound. The conjugated alkadiene of block B is then introduced, followed by the required vinyl hydrocarbon in the second A block. Such block copolymers are characterized as ABA. Two-block or diblock polymers can be prepared using, for example, a lithium initiator.
It is produced by polymerizing the blocks and subsequently introducing a second block of conjugated alkadienes. Such a polymer is A
It is characterized as B. Homopolymer blocks will be formed when the monomers of each block polymerize substantially completely before introducing the monomers of the next block. Introducing the monomers of the next block before any one block is completely polymerized will result in a tapered block. Adopting similar sequential polymerization techniques, ABABA, AB
Block copolymers characterized as AB, ABABABA, or copolymers with larger numbers of blocks can also be produced. The production of block copolymers, especially those with a relatively large number of blocks, can also be achieved by using coupling agents such as dihaloalkanes, resulting in the production of linear polymers, but with three or more blocks. The use of coupling agents with functionality, such as silicon tetrahalides or dicarboxylic acid dialkyl esters, results in the formation of polymers that are called radial or branched, respectively.

These block copolymers are well known in the art, and the characterization and preparation of such polymers is described in US-A-3,251,905, US-A-3,251,905,
-A-3,390,207, US-A-3,598,8
87, and US-A-4,219,627.

The block copolymers used as precursors of the formulation components of the present invention are preferably linear polymers of the following type. Polystyrene-polybutadiene (SB), polystyrene-polyisoprene (SI), polystyrene-polybutadiene-polystyrene (SBS), polystyrene-polyisoprene-polystyrene (SIS), poly(α
-methylstyrene)-polybutadiene-poly(α-methylstyrene) and poly(α-methylstyrene)-polyisoprene-poly(α-methylstyrene). Particularly preferred are SBS type block copolymers. These block copolymers are now common and many are commercially available, such as those manufactured by Shell Chemical Co.
It is commercially available as KRATON® thermoplastic rubber from Mpany.

To prepare the adhesive component, the block copolymer is partially hydrogenated and then further modified by reaction with a maleic acid compound. Hydrogenation of block copolymers is also well known in the art and includes catalytic hydrogenation in the presence of Raney nickel or finely divided forms of elemental metals such as finely divided platinum or palladium. Such hydrogenation typically results in hydrogenation of most, if not all, of the aromatic unsaturation of the A block as well as the ethylenic unsaturation of the aliphatic B block. In preparing the components of the adhesives used in this invention, it is helpful to hydrogenate most of the unsaturation in each aliphatic B block, but to eliminate a substantial degree of unsaturation in the aromatic rings of the A block. Partial hydrogenation without hydrogenation is adopted. The hydrogenation method is described in US-A-3,113,986 and US-A-4,2
26,952. Suitable partially hydrogenated block copolymers have no more than 25%, preferably no more than 5%, of the aromatic unsaturation hydrogenated and no residual unsaturation in the polymerized conjugated alkadiene blocks that are hydrogenated. 0.1% to 20% of unsaturation before hydrogenation.

Partially hydrogenated block copolymers often differ in the structure of the block copolymer precursor and the aliphatic blocks (
one or more "apparent" structures. Therefore, partial hydrogenation of SBS block copolymers can be combined with a hydrogenated or ethylene (E) central block produced by 1,4-polymerization and a portion of 1,2-polymerization and a portion of 1,4-polymerization. ethylene/butylene copolymer in the case of central block units produced in portions. These things are SES or SEBS respectively
is shown as Polymers produced by partial hydrogenation of SIS block copolymers with a high degree of 1,4-polymerization in the central block are similar to ethylene/propylene copolymers because, when hydrogenated, the central block resembles an ethylene/propylene copolymer. ,
It is called SEPS. Preferred maleated partially hydrogenated block copolymers as components of the formulations of the present invention contain 45% hydrogenated butadiene units in the central block.
It is produced from a partially hydrogenated block polymer of the SEBS type with ~65% ethylene type (1,4-addition) and the remainder of the butylene type (1,2-addition). These types of partially hydrogenated block copolymers are also well known in the art, and many are commercially available. For example, certain partially hydrogenated block copolymers are available from Shell Chemical
KRATON (registered trademark) from al Company
It is commercially available as G thermoplastic rubber.

The maleated partially hydrogenated block copolymer employed as a component in the formulations of the present invention is an adduct of a partially hydrogenated block copolymer and a maleic acid compound. Maleated polymers, by way of example, add a hydrogen atom on a carbon atom that is allylic to the residual unsaturation of a partially hydrogenated block copolymer to a carbon-carbon double bond of a maleic compound, and It is produced by forming carbon-carbon bonds between an acid compound and a polymer chain of a partially hydrogenated block copolymer. By way of illustration and without wishing to be associated with any particular reaction theory, the production of maleated block copolymers is carried out according to the reaction scheme shown below, in which the wavy lines indicate continuous polymer chains.

[0023]

[Chemical formula 3]

Maleic acid compounds suitably employed in the production of the maleated partially hydrogenated block copolymer include maleic acid, maleic anhydride, and monoalkyl esters of maleic acid [note that the alkyl group has 4 or less carbon atoms]. lower alkyl group having an alkyl atom], maleic acid monoamide and maleic acid imide. Among these maleic acid compounds, it is preferable to use maleic anhydride.

Maleated partially hydrogenated block copolymers are known in the art, as are methods of making them. Generally, the process for making maleated products is a grafting process in which the maleic acid compound is grafted onto the aliphatic portion of the partially hydrogenated block copolymer chain. In one embodiment, the partially hydrogenated block copolymer and maleic acid compound are contacted in the presence of a free radical initiator, preferably a peroxy compound. Contacting is carried out at a temperature sufficient to melt the reactants and decompose the initiator, such as from 75°C to 450°C, more often from 200°C to 30°C.
It is carried out at a temperature of 0°C. Such reactions are often carried out without solvents or reaction diluents and in extruders that serve to melt mix the reactants and heat the mixture to the desired elevated temperature. In another embodiment, the partially hydrogenated block copolymer and the maleic acid compound are dissolved in a suitable solvent and heated to 150°C to 200°C.
Contacting is carried out in the absence of a free radical initiator at an elevated temperature of . In these latter embodiments, free radical inhibitors are often added to prevent gelation.

The degree of maleation of the partially hydrogenated block copolymer depends on the degree of maleation of the polymer aliphatic block (one or several).
depends in part on the degree of residual unsaturation. For said polymers, the moieties derived from maleic acid grafted onto the aliphatic portions of the partially hydrogenated block copolymer range from 0.02 to 20% by weight, based on the total polymer, preferably 0.1%. Sufficient maleic acid compound is reacted with the partially hydrogenated block copolymer to form a maleated derivative included in an amount of ˜10% by weight, more preferably 0.2-5% by weight.

In general, solventless "extruder type" maleation processes are preferred. Such methods are now commonly disclosed and are disclosed in US-A-4,292,414; US-A-4;
427,828, US-A-4,628,072, US
-A-4,657,970 and US-A-4,657
, 971. Another method is US-A-4,57
8,429 and US-A-4,670,173.

A number of maleated partially hydrogenated block copolymers have been commercialized, some of which are
l Chemical Company by KR
It is commercially available as ATON® G thermoplastic rubber. A particularly preferred maleated partially hydrogenated block copolymer is commercially available as KRATON® FG1901X thermoplastic rubber with a styrene content of 28% by weight, a specific gravity of 0.91 and a maleic acid functionality of 2 as the grafted maleic anhydride. It is characterized as a maleated block copolymer of the SEBS type with a weight %.

The polybutylene used to provide the layers in the laminates of the present invention is the product of a stereoselective polymerization operation and is referred to as an "isotactic" or "stereoselective"polymer; In a polymer, the repeating units of all of the polymer chains have a stereochemical configuration along the chain. This can be contrasted with "atactic" polymers in which the repeating units of the polymer chain vary in a random arrangement along the chain. The stereochemical properties of isotactic polybutylene for use in the present invention can be easily observed from its structural formula shown below.

[0030]

[C4]

The high molecular weight isotactic polybutylene utilized in the novel structure of the present invention is prepared by stereoselective polymerization of the monomer butene-1. Methods for carrying out such polymerization operations are well known to those skilled in the art, and typical procedures are disclosed in US-A-3,197,452 and NL-A-6,507,546. . These methods generally involve the use of polymerization initiators or catalysts to polymerize the monomer butene-1 into high molecular weight polymers. Among the preferred catalyst systems utilized in such procedures are metal alkyl compounds, such as triethylaluminum, and heavy metal compounds, such as titanium, vanadium, chromium, zirconium, molybdenum and tungsten, from Periodic Table IV-VI. Examples include reaction products of group metals with trihalides. The formation of a polymer exhibiting substantial isotactic properties and the change in its molecular weight depends on the nature of the polymerization catalyst used, the nature of co-reactants in the system and the reaction conditions.

The preferred isotactic polybutylene is
They are relatively hard while in their plastic form, but flow rapidly when heated. As mentioned earlier, these need to have a high molecular weight. Therefore, when expressing the molecular weight in terms of "melt flow", the applicable isotactic polybutylene ranges from 0.2 to 300, preferably 0.
．． It should exhibit a melt flow in the range of 4 to 40.0. These latter melt flow values are ASTM D 12
determined by the method described in 36-62 Te,
It has an inverse relationship with molecular weight, ie the lower the melt flow value the higher the molecular weight. In addition, alpha-olefins such as ethylene and propylene may be present in butene-1 in small amounts, i.e., up to about 5% by weight, so as not to substantially impair the desirable properties described above exhibited by the product from essentially a single polymer system. It should be noted that it can be present in the polymerization system.

The term polybutylene as used herein therefore refers to butene-1 homopolymers and butene-1 and olefins such as ethylene, propylene, carbon atoms, etc.
It refers to a polymer containing a copolymer with an α-olefin.

Butene-1 can be copolymerized with various α-olefins to form useful copolymers, such as US-A-3,362.
, 940. Generally, any method known in the art that is useful for manufacturing laminate structures can be used to manufacture the laminate structures of the present invention. In this case, the preferred manufacturing method includes; extruding the separate layers of polybutylene and adhesive separately, then laminating them together as they pass through a multilayer die, and simultaneously or subsequently adding a metal structure such as a metal foil or Coextrusion method for bonding with preformed structures; an adhesive layer is preformed into a film or sheet and then placed between the preformed polybutylene layer and the metal substrate;
A method of bonding the adhesive film to the polybutylene layer and the metal by heating and pressing, for example using a hot press; the adhesive is melted and then applied to one or several polymeric structures; A high temperature lamination method in which the adhesive is pressed onto a metal film or structure and cooled; the adhesive is dissolved in a solvent and applied to the polymer or metal structure to be laminated;
Solvent lamination methods in which the solvent is evaporated and the laminate is then heated and pressed to effect the desired bonding; and wet lamination methods in which the adhesive is used as a latex to bond several layers of a laminated structure. Among these several methods, coextrusion is preferred. This is because the adhesive exhibits a relatively wide range of operating temperatures, allowing the necessary flow properties to be adjusted by the temperature changes required to enable the formation of uniform laminate structures. It is.

The laminate structure of the present invention can be used in any of the applications known in the prior art for such laminates. In this case, suitable applications include packaging films in the form of films and sheets, or any application where it is desired to adhere polybutylene to metal.

In a preferred embodiment of the invention, the adhesive composition comprises at least one styrene block and 0.1
at least one functionalized block copolymer comprised of at least one butadiene or isoprene block containing ~2.5% by weight maleic acid units. In a preferred embodiment, the block copolymer is selectively hydrogenated such that at least 98% of the ethylenic unsaturation originally contained therein is changed (saturated). In a preferred embodiment, the block copolymer contained in the adhesive composition contains 90 to 65% by weight of either butadiene or isoprene. Also, in another preferred embodiment of the invention, the adhesive composition is used to form a laminate consisting of one metal layer and one polybutylene layer. In this preferred embodiment, the laminate is coextruded such that the adhesive forms a bonding layer between the metal layer and the polybutylene.

Blends of block copolymers can be used that have better flow properties for coextrusion than at least most block copolymers when used alone. In this embodiment, the block copolymer blend comprises at least one triblock copolymer having polystyrene end blocks and a central hydrogenated polybutadiene or hydrogenated polyisoprene block.
0 to 93% by weight and 20 to 3% by weight of at least one diblock copolymer having one polystyrene block and one hydrogenated polybutadiene or hydrogenated polyisoprene block. The weight average molecular weight of the polystyrene blocks in the triblock and diblock copolymers is preferably 4,000 to 15,000. The weight average molecular weight of the hydrogenated conjugated diolefin blocks in both polymers is preferably 10,000 to 100,000.

[0038] The adhesive layer can be applied at any functional thickness. The preferred thickness is 25-1270μ
m (0.001 to 0.050 inch). The thickness is
There may be wide variations, especially if the metal structure has a non-uniform surface or shape.

Next, the present invention will be explained with reference to the following examples.

[0040]

According to the present invention, an acid having at least a major amount of at least one monoalkenyl aromatic hydrocarbon polymer block and at least a major amount of at least one hydrogenated conjugated diolefin polymer block is provided. By using an adhesive composition made of a mechanized block copolymer, it is possible to provide a laminate in which a polybutylene layer and a metal layer are well bonded.

[0041]

[Example] Steel/maleated styrene-hydrogenated butadiene-styrene block copolymer/polybutylene/
A peel test was conducted on the maleated styrene-hydrogenated butadiene-styrene block copolymer/steel structure. Peel testing was performed at room temperature according to the procedure outlined in ASTM D 903. Thickness 25 μm (0
．． 001 inch) adhesive film and 127 μm (
0.005 inch) adhesive films were tested at heat seal times of 5 seconds, 10 seconds and 15 seconds and seal temperatures of 245°C and 260°C.

The adhesive used in these examples was She
The rubber was KRATON® FG1901X rubber available from Ill Chemical Company. The adhesive was solvent cast onto a 2.54 x 15.2 cm (1 x 6 inch) steel strip 0.08 mm (0.003 inch) thick.

A 25 μm (0.001 inch) thick coating of adhesive was applied to KRATON® FG1901X.
A 25% by weight solution of the rubber in toluene was used to apply it to steel cleaned with isopropyl alcohol. The applied coating film is dried to a thickness of 25 to 38 μm (0.001 to 0.0
An adhesive layer of 0.015 inch) was formed. 127μ of adhesive
0.005 inch (0.005 inch) coatings were applied using a 25 weight percent solids toluene solution. Thickness: 127 μm (0.0
05 inches) is dried to a thickness of 127 to 152μ.
A coating film of 0.005 to 0.006 inch was formed.

[0044] The laminated structure is
It was formed using a 0.8 mm (0.030 inch) thick sheet of polybutylene DP2420 available from Cal Company and pressed between two adhesive coated steel strips. 245 of these structures
or 260°C at a pressure of 0.28 MPa (40 psi) for 5 seconds, 10 seconds or 15 seconds.

[0045] These laminated structures were tested according to ASTM D 90
3 at room temperature and the maximum load was recorded. An adhesive-free steel-polybutylene-steel laminate structure was produced under the conditions described above. These layers were not adhered and no peel strength test values could be obtained.

[0046]

[Table 1]
Table 1
Peel strength, Kg/cm (pounds/linear inch)

5 seconds 10 seconds
15 seconds 25μm (0.001 inch) -245℃ 0.52 (2.9)
1.08 (6.1) 1.94
(10.9)
0.23 (1.3)
0.93 (5.2) 1.45 (8
．． 2)
0.43 (2.4) 0.
80 (4.5) 2.10 (11.8)

0.41 (2.3) 0.73
(4.1) 2.67 (15.0)
0
．． 27 (1.5) 1.10 (6
．． 2) 1.55 (8.7)
Average 0.37
(2.1) 0.93 (5.2)
1.94 (10.9) Standard deviation 0.11 (0.6)
0.16 (0.9) 0.48
(2.7) 25 μm (0.001 inch) -26
0℃ 1.88 (10.6) 1
．． 17 (6.6) 1.17 (6.6
)
2.03 (11.4) 1.80
(10.1) 1.23 (6.9)

1.10 (6.2) 1.37 (
7.7) 1.14 (6.4)
1.4
4 (8.1) 1.62 (9.1
) 1.08 (6.1)
0.96
(5.4) 1.01 (5.7)
1.39 (7.8) flat
Average 1.48 (8.3)
1.39 (7.8) 1.
21 (6.8) standard deviation
0.48 (2.7)
0.32 (1.8) 0.11 (0.
6) 127 μm (0.005 inch) -254℃
1.88 (10.6) 2.05 (
11.5) 3.10 (17.4)
1.
51 (8.5) 2.30 (12.
9) 2.35 (13.2)
2.42
(13.6) 1.94 (10.9)
2.33 (13.1)
2.01 (11
．． 3) 2.62 (14.7)
2.44 (13.7)
1.89 (10.6)
3.51 (19.7) 1.
96 (11.0) Average
1.94 (10.9)
2.47 (13.9) 2.44 (1
3.7) Standard deviation
0.32 (1.8) 0.62
(3.5) 0.41 (2.3) 12
7 μm (0.005 inch) -260℃ 1.83
(10.3) 2.26 (12.7)
2.05 (11.5)
1.67 (
9.4) 2.28 (12.8)
2.31 (13.0)
2.46 (13.8
) 2.62 (14.7) 2
．． 85 (16.0)
2.58 (14.5)
2.95 (16.6) 2.14
(12.0)
2.72 (15.3)
3.26 (18.3) 2.10 (1
1.8) Average
2.26 (12.7) 2.6
7 (15.0) 2.30 (12.9)
Standard deviation 0.4
6 (2.6) 0.43 (2.4
) 0.34 (1.9) The data are summarized in Table 2.

[0047]

[Table 2]

Another group of samples was aged for two weeks and the test was repeated. The results are shown in Table 3.

[0049]

[Table 3]
Table 3
Peel strength, Kg/cm (pounds/linear inch)

2 week aging sample
5 seconds
10 seconds 15 seconds 25
μm (0.001 inch) -245℃ 0.17
(0.95) 0.94 (5.3)
1.30 (7.3)
0.34 (
1.9) 1.19 (6.7)
0.61 (3.4)
0.30 (1.7
) 0.50 (2.8) 1
．． 14 (6.4)
0.93 (5.2)
0.62 (3.5) 0.55
(3.1)
0.48 (2.7)
1.03 (5.8) 1.00 (
5.6) Average
0.48 (2.7) 0.8
5 (4.8) 0.93 (5.2)
Standard deviation 0.2
8 (1.6) 0.28 (1.6
) 0.34 (1.9) 25 μm (0.
001 inch) -260℃ 0.62 (3.
5) 0.96 (5.4)
0.87 (4.9)
0.37 (2.1)
1.28 (7.2) 1.0
0 (5.6)
0.34 (1.9)
1.10 (6.2) 1.01
(5.7)
0.32 (1.8)
1.12 (6.3) 1.16 (6.
5)
0.50 (2.8) 1.0
5 (5.9) 0.98 (5.5)
Average 0
．． 43 (2.4) 1.10 (6
．． 2) 1.01 (5.7)
Standard deviation 0.12 (0
．． 7) 0.12 (0.7)
0.36 (0.6) 127 μm (0.005
inch) -245℃ 1.44 (8.1)
1.23 (6.9) 2.14
(12.0)
1.66 (9.3)
1.78 (10.0) 1.74 (9
．． 8)
2.15 (12.1) 2.
31 (13.0) 1.82 (10.2)

1.62 (9.1) 1.87
(10.5) 2.23 (12.5)
1
．． 73 (9.7) 1.78 (10
．． 0) 1.62 (9.1)
Average 1.73
(9.7) 1.80 (10.1)
1.90 (10.7) Standard deviation 0.27 (1.5)
0.39 (2.2) 0.27
(1.5) 127 μm (0.005 inch) -
260℃ 1.87 (10.5) 1
．． 83 (10.3) 1.60 (9.0
)
2.42 (13.6) 1.21
(6.8) 1.67 (9.4)

1.60 (9.0) 1.87 (1
0.5) 2.15 (12.1)
1.9
8 (11.1) 1.46 (8.2
) 1.50 (8.4)
−
2.28 (12.8)
1.67 (9.4) flat
Average 1.96 (11.0)
1.73 (9.7) 1.7
3 (9.7) standard deviation
0.36 (2.0) 0
．． 41 (2.3) 0.25 (1.4
) The data are summarized in Table 4.

[0050]

[Table 4]

From Tables 1 and 2, 2.67Kg/cm
It can be seen that peel strengths of less than (15 pounds per linear inch) can be obtained by using a maleated block copolymer tie layer or adhesive on a steel-polybutylene-steel laminate. Tables 3 and 4 show that the two week aged laminate construction still exhibits good peel strength up to 11 pounds per inch. Without adhesive no measurable adhesion between the layers was obtained.

Claims (1)

[Claims] 1. A laminate structure comprising, in this order, at least one metal, an adhesive layer and at least one polybutylene layer, the adhesive layer comprising units derivable from monoalkenyl aromatic hydrocarbon monomers. and at least one block composed at least predominantly of hydrogenated units derivable from conjugated diolefin monomers. A polybutadiene-metal laminate structure made of a block copolymer.