Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
  • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
  • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond

Definitions

• This invention relates to laminated structures in which at least one adhesive layer is a melt-stable, titanium dioxide-containing composition of one or more copolymers of ethylene with
• alpha,beta-unsaturated carboxylic acids such as, e.g., toothpaste tubes, where metal foil is laminated to a printable plastic layer on which the name of the product or other similar information is to be printed.
• Ethylene copolymers with alpha,beta-unsaturated carboxylic acids are known to be very good hot melt adhesives, which are suitable for bonding the outer layer to the metal foil or to another plastic layer.
• the outer layer is a clear or at least
• the adhesive layer be white-pigmented, so that the white color may show through.
• Another typical application for such white-pigments copolymers is in condiment pouches.
• titanium dioxide has been used as white pigment for plastics and for other purposes.
• commercial titanium dioxide particles normally are coated on their surface with alumina, which improves the pigment's flowability.
• copolymer is exposed to high temperatures, such, for example, as are encountered during extrusion, the copolymer appears to be reacting with the alumina coating, as evidenced by a decrease of the polymer's melt index. Further reduction of melt index occurs on storage. Such lowering of the melt index is
• composition said laminate structure comprising at least two nonadhesive layers and at least one
• white-pigmented adhesive layer which adhesive layer is made of a composition stabilized against thermal crosslinking and consequent decrease of its melt index consisting substantially of a uniform dispersion of alumina-coated titanium dioxide pigment in a blend of a matrix polymer with a stabilizing polymer,
• the matrix polymer being a copolymer
• E stands for ethylene
• X stands for a C 3 -C 7 alpha,beta-unsaturated carboxylic acid
• Y which is optional, stands for another copolymerizable comonomer selected from the group consisting of C 3 -C 7 alpha,beta-unsaturated carboxylic acids, C 1 -C 10 alkyl esters of such acids, vinyl esters, vinyl ethers, acrylonitrile,
• the stabilizing polymer being a high melt index copolymer of ethylene with an unsaturated carboxylic acid selected from the group consisting of acrylic acid (E/AA copolymer) and methacrylic acid (E/MAA copolymer), said high melt index copolymer having a melt index of at least about 5,000 dg/min, but preferably at least 10,000 dg/min, determined according to ASTM D1238, condition E, and containing at least about 5 weight percent, preferably at least 9 weight percent, of carboxylic acid monomer;
• the relative weight ratio of matrix polymer to stabilizing polymer being about 95:5 to 80:20, and the amount of titanium dioxide in the blend being about 5 to 20 weight percent.
• composition may be further compounded to incorporate minor amounts of conventional additives such as, e.g., stabilizers, antioxidants, and slip improving agents. It can be additionally formulated with further additives such as, for example,
• plasticizers and unreactive fire retardants such as halogenated hydrocarbons, the total amount of
• plasticizers if present, being no more than about 15 weight percent, but preferably 5-15 weight percent of the final composition; and the amount of fire
• retardants if any, being about 10 to 30 weight percent of the final composition, depending on the level of fire resistance desired.
• the drawing represents a plot of intitial melt index of representative compositions of the present invention as well as of some compositions outside the scope of the present invention vs. weight percent of high melt index copolymer in those
• the E/X/Y copolymers suitable in the compositions of the present invention either are available commercially or can be made according to known processes from readily available monomers.
• Copolymers of ethylene with unsaturated carboxylic acids are described in U.S. Patents 4,351,931 to Armitage, 4,252,954 to Chatterjee, 3,264,272 to Rees, 3,520,861 to Thomson et al., 3,884,857 to Ballard et al., and 3,658,741 to Knutson et al.
• Terpolymers of ethylene with unsaturated carboxylic acids and with alkyl esters of unsaturated carboxylic acids are described in U.S. Patent 3,264,272 to Rees;
• terpolymers of ethylene with carbon monoxide and unsaturated carboxylic acids are disclosed in U.S. Patent 3,780,140 to Hammer, while terpolymers with sulfur dioxide and unsaturated carboxylic acids are described in U.S. Patent 3,784,140 to Hammer.
• Various ethylene copolymers with methacrylic acid are sold by E. I. du Pont de Nemours and Company under the trademark NUCREL ® .
• Ethylene copolymers with acrylic acid are sold by Dow Chemical Company under the trademark Primacor ® .
• monocarboxylic acids also include monoesters of alpha,beta-unsaturated dicarboxylic acids such as, e.g., maleic, fumaric, and itaconic acids.
• Typical alkyl esters of alpha,beta-unsaturated carboxylic acids include methyl, ethyl, butyl, pentyl, hexyl, octyl, and decyl esters, both linear and branched, as well as diesters of dicarboxylic acids.
• High melt index copolymers of ethylene with acrylic acid are available, for example, from Allied Signal Corporation under the trademark A-C ®
• Copolymers Such copolymers also can be made.
• High melt index copolymers of ethylene with methacrylic acid also can be made according to known methods, as illustrated by means of examples herein.
• Titanium dioxide is available from several sources, including E. I. du Pont de Nemours and
• Preferred matrix dipolymers are dipolymers of ethylene with methacrylic acid (X is methacrylic acid and Y is absent) and especially those in which the weight proportion of methacrylic acid is about 3- 30%, preferably 4-15% by weight.
• Preferred matrix terpolymers are terpolymers of ethylene in which X is methacrylic acid and Y is vinyl acetate, n-butyl acrylate, or isobutyl acrylate.
• the type and amount of the stabilizing polymer such that the resulting initial melt index of the composition is close to the melt index of the matrix polymer itself. As will be seen below, this objective can be met for the preferred compositions with moderate amounts, 15% or less, of stabilizing polymer.
• Laminates of the present invention comprise a substrate, for example, metal foil, sheet of
• plastic or sheet of kraft paper, at least one
• Such laminates can be made in a number of ways, all of which are generally known to the art, such as, for example, film casting,
• WPAC white pigmented acid copolymer
• Film casting is a continuous process by which a thermoplastic material is extruded through a slot die onto a chill roll, where it is quenched and solidified.
• the molten film normally exits the extruder vertically through a slot die and
• Extrusion lamination is an adaptation of this technique, wherein the film is cast onto a substrate such as kraft paper, aluminum foil, polyester film, or low density polyethylene (LDPE) film.
• a substrate such as kraft paper, aluminum foil, polyester film, or low density polyethylene (LDPE) film.
• LDPE low density polyethylene
• the WPAC compositions of the present invention normally are used as adhesive or bonding layers in laminate structures, the WPAC film is cast between two substrates.
• a typical laminate may thus be, for example, aluminum foil//WPAC//clear LDPE or kraft paper//WPAC//clear LDPE.
• more than one WPAC bonding layers may be present.
• thermoplastic materials Another commmon process for producing films of thermoplastic materials is blown film extrusion.
• a molten tube of polymer is
• the hot tube is cooled by high velocity air from an air ring on the outside and sometimes also on the inside of the tube. Normally, the tube is formed and drawn in a vertical and upward direction.
• multilayer laminate structures are formed through coextrusion.
• a multiplicity of extruders usually from two to seven, feed individual polymers into a coextrusion head, where a multilayer laminate is extruded.
• This may be a flat film or sheet laminate or a hollow tube
• WPAC compositions of this invention can be used as the adhesive layer in structures such as, for example, ethylene/vinyl alcohol
• Compression molding is the simplest process for producing laminates.
• the apparatus, or molding press consists of two platens that close together. Heat and pressure are applied to form the material into the desired shape.
• a typical laminate that can be made in such equipment has the following layers: aluminum foil//WPAC//clear polyester. The two outer layers are higher melting than the inner layer, so that under the press conditions only the adhesive inner layer is activated.
• a typical press temperature is about 200oC. Compression force can reach as much as 1000 tons.
• Laminates in sheet or film form can be used for making a variety of articles such as, for example, the aforementioned toothpaste tubes, and condiment pouches, where the substrate is either metal foil or a plastic sheet, and the top coat is clear plastic on which appropriate information is printed; traffic road signs, where the substrate is either plastic or metal, and the top coat is clear plastic; and roadway lane marking tapes, in which both the botom layer and the top layer are made of plastics.
• Other types of laminated articles which can be formed directly, for example, by compression molding or by coextrusion and blow molding, comprise containers of various types, including bottles.
• the high melt index stabilizing polymer and titanium dioxide may first be blended in a suitable equipment above the melt temperature of the polymer to form a masterbatch containing about 50 - 75 weight percent of TiO2 uniformly dispersed in the polymer matrix. This masterbatch is then again melt-blended in the desired proportions with the matrix polymer.
• all three components may be
• TiO 2 used in all the examples was a commercial product of E. I. du Pont de Nemours and Company sold under the
• Ti-Pure ® R101 It had an average particle size of 0.18 micrometer and was coated on its surface with aluminum oxide.
• MI Melt Index
• melt index was determined, according to ASTM D1238, condition E, which requires a temperature of 190°C and a 2,160 g weight.
• High MI acid copolymers E through M were prepared according to the general disclosure of U.S. 3,264,272 to Rees.
• Commercial ethylene and acrylic acid (AA) or methacrylic acid (MAA) were fed in a continuous manner to a stirred pressure vessel.
• Free radical initiator t-butyl peroxyacetate was fed by a separate line.
• the flow of monomers was adjusted to give constant mole ratios, and the feed rate was the same as the rate of discharge of polymer and of unpolymerized monomers from the reactor.
• Table I represents the state of the art of compounding pigmented compositions containing TiO 2 and gives melt index stability data for representative compositions containing an E/MAA copolymer as the matrix polymer and a commercial dispersion of titanium dioxide in either an ethylene/methyl acrylate
• Samples 1-3 were the matrix polymers, and samples 4 and 5 were the Ampacet Ti ⁇ 2 concentrates.
• Samples 6 through 11 were made by extruder-blending 25 parts of Ampacet concentrate with 75 parts of matrix polymer at 170°C. The resulting blends had initial Mis of 11.0 to 5.4, but those dropped considerably after mixing at 280°C in the Haake Mixer.
• Samples 13 and 14 were made by directly compounding 30 parts of Ampacet concentrates with 70 parts of matrix polymer in the Haake Mixer. The blends had very low Mis, suggesting a rather high degree of crosslinking.
• Sample 12 was a control, made by direct blending of matrix polymer with TiO 2 . This sample had a higher MI than samples 13 and 14, which were made via the concentrates.
• Table II lists the matrix copolymers
• Table III lists the high melt index stabilizing E/AA and E/MAA copolymers.
• the matrix copolymers are identified by Roman numerals I through IV.
• High melt index stabilizing copolymers are designated by letters A-G. Those designated H and J-P have melt indices below 5,000 dg/min and are outside the scope of the present invention; they are included for comparison purposes only.
• Table IV lists representative pigmented compositions obtained from matrix polymer I by
• Samples 15-18, 33, and 41 were controls containing no high MI copolymer.
• Samples 15-32 contained 15% of TiO 2 ; samples 33-40 contained 9% of TiO 2 ; and samples 41-42 contained 8% of TiO 2 .
• Samples 38-40 are outside the scope of the invention.
• Table V similarly lists representative pigmented compositions obtained from matrix polymer II.
• samples 43-55 contained 15% of TiO 2 ;
• samples 56-63 contained 9% of TiO 2 ; and samples 64-69 contained 6% of TiO 2 .
• Samples 43 and 56 were
• the drawing is a plot comparing the effectiveness of representative high MI copolymers in increasing the initial MI of TiO 2 -containing matrix polymer II compositions. It shows the superiority of copolymers B and C, which had Mi's in excess of
• Table VI presents data correlating the melt index of lower MI copolymers, outside the scope of the invention, with the melt index stability of the blends. All the blends were prepared on the Haake System 40 Mixer at 280°C. All the copolymers in this table had Mi's between 1000 and 2400 dg/min but this still was not high enough for optimum effectiveness. It can be seen, for example, that while the Mi's were reasonably stable, increasing the amount of the high MI copolymer did not in most cases significantly increase the MI of the blend.
• Table VII presents similar data as Table VI, except that all the high MI copolymers have Mis of at least 10,000. In this case, both high Mis and high MI stabilities are obtained for the blends; and, further, increase of the level of high MI copolymer
• sample 113 in this table was of the same composition as sample 92 in Table VI. Yet, at same level of high MI copolymer, the blend MI in the former case was 10.2, but in the latter case it was only 7.6.
• Table VIII summarizes the preparation of TiO 2 concentrates for the practice of this invention.
• Samples 132-138 were prepared using the Haake System 40 Mixer. Those compositions were then scaled up on a 30 mm twin screw extruder. Comparison of the initial Mis of samples 132 and 139 and samples 133 and 140 shows good initial MI reproducibility on scale-up.
• compositions were compounded using a Haake System 40 Mixer.
• Table IX demonstrates that the invention can be practiced in two steps, using Ti ⁇ 2 concentrates, to the same extent as by blending individual components in a one-step operation.
• the concentrates were blended with either Matrix Polymer I or Matrix Polymer II in such amounts that the resulting blends contained either 9% or 15% of TiO 2 .
• the initial Mis of the final blends were comparable to those of the
• Adhesive strength of laminates was determined according to the following test (with indicated variants).
• Example 2 A specimen, 2.54 cm wide and 12.7 cm long (in Example 1) or 15 mm wide and 25.4 cm long (in Example 2) was used for the test. About 2.5 cm of the coating was manually peeled from the substrate. The coating was placed in the upper jaw of the Instron Tensile Tester (in Example 1) or of the Zwick Model 1410 testing machine (in Example 2), and the substrate was placed in the lower jaw. The specimen was peeled at a 90° angle either at a crosshead speed of 30.5 cm per minute (in Example 1) or of 10 cm per minute (in Example 2). The load required to peel the coating away from the substrate was measured in units of force (or weight) per unit of width. In each test,
• compositions designated respectively as Compound 1A and Compound IB, were compounded as follows:
• E/MAA copolymer I from Table II 75.0% TiO2 (Ti-Pure ® R101) 15.0%
• E/AA copolymer C from Table III (high MI) 10.0% These compounds were extruded and laminated onto untreated 51 micrometer thick aluminum foil using an 11.4 cm Egan Laminator Coater ® .
• the extruder was fitted with a two-stage mixing screw having a
• L/D length-to-diameter
• the extruder temperature settings were 177-304°C, the polymer melt temperature being 285-305°C.
• Each compound was extruded through a 122 cm wide ER-WA-PA ® coat hanger die with a 508 micrometer opening.
• the extruded polymer film was laminated to the aluminum foil substrate using a matte finish chill roll. Line speed determined the ultimate coating thickness.
• the laminates were stored at ambient temperature for either 13 days or 57 days.
• the adhesive strength of the pigmented material was measured using the 90° peel test. The results are given below in Table X.
• Ti02 (Ti-Pure ® R101) 9.0%
• the laminates were prepared using a 9 cm Egan Laminator Coater ® (mixing screw of L/D ratio of 30:1) with temperature settings of 170°C, 210°C,
• the laminate from Test 1 was passed through the laminating line for the second time to give the following structure (from bottom to top) :
• the adhesive strength of 15 mm-wide test strips was determined in the 90° peel test.
• the average adhesion strength, in N/15 mm, was as follows:

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Laminated Bodies (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Cosmetics (AREA)

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• 1989
  • 1989-11-14 US US07/436,467 patent/US4992486A/en not_active Expired - Lifetime
• 1990
  • 1990-04-17 BR BR909001782A patent/BR9001782A/pt not_active Application Discontinuation
  • 1990-04-18 CA CA002014801A patent/CA2014801A1/en not_active Abandoned
  • 1990-04-18 MX MX20354A patent/MX164801B/es unknown
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