JPH0320381A - Peelable hotmelt adhesive based on butene-1 polymer and laminated structure - Google Patents

Abstract

PURPOSE:To obtain a peeldable hot-melt adhesive by adding a specified amt. of a stabilizer to a polymer consisting of a large amt. of an ethylene homopolymer or copolymer and a small amt. of a butene-1 homopolymer or copolymer. CONSTITUTION:The subject adhesive is prepared by adding about up to 1 pt. stabilizer (e.g. Irganox 1010) to 100 pts. polymer consisting of about 50-95wt.% ethylene homopolymer or copolymer (e.g. ethylene-vinyl acetate copolymer) and about 50-5wt.% butene-1 homopolymer or copolymer (e.g. ethylene-butene-1 copolymer).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a peelable adhesive bond (
adhesive bond) can be generated,
and hot melt adhesives consisting essentially of butene-1 homopolymers or copolymers or ethylene homopolymers or copolymers. It is expected that this hot melt adhesive will exhibit good polymer-to-polymer bonding.

Additionally, the present invention provides a laminated structure produced using a novel hot-melt adhesive capable of producing a removable seal.
r structure).

Although hot melt adhesives can be prepared to be pressure sensitive, these adhesives are usually soft, tacky, and have limited strength and adhesion.

Common hot melt materials such as ethylene-vinyl acetate copolymer (
EVA), polyethylene (PE), polyamide or polyester are rigid, produce good strong bonds to certain substrates, and generally cannot be peeled off.

Solvent-loaded contact adhesives provide good bonding strength, but these require the use of solvents that can be either toxic or contaminated or non-flammable. Additionally, some of these adhesives may have "peelability" as defined below.

The novel polypropylene hot melt adhesives of the present invention are unique because they require no solvents, are releasable, and can bond to a variety of substrates.

A "peelable seal or bond" or a "peelable" seal or bond may be heat sealing, impact (i.e.
A seal or bond between two films or other types of substrates produced either as a thermal melt between two surfaces with the bond thus produced Thread cutting (w) in the material in which the bonding of two films is carried out
It is defined as being capable of cleavage at the original plane that joins two films together under the action of an attractive force, without opening of the bond resulting in wrenching off or tearing.

For purposes of this invention, a peelable seal or bond is used to surround liquid or solid items or materials during storage and transportation until the user of the packaged product requires the contents of the sealed package. It must have sufficient mechanical resistance to tearing or "peeling" to maintain a tight seal. The mechanical durability of the peelable seal must be low enough to allow the bond to be easily cleaved by hand, ie, without the use of auxiliary equipment to break the bond.

The term "releasable" herein refers to a sealed location of the adhesive where the adhesive is bonded to a substrate. Adhesive release properties are measured by the degree of force applied. Such hot melt adhesive peelability may be measured by ASTM Test Method D-1876 for 180' peel, [T-peel test] and also ASTM Test Method D-903 for 1806 peel.

The present invention relates to formulations that can be used as hot melt adhesives in packaging applications and to methods for their production. The present invention relates to laminates made using these hot melt adhesives and characterized by long term heat sealing or substantially constant peel strength over the application temperature. The formulations, films and/or laminates of the present invention provide a more consistent processing product with predictable and constant peel strength regardless of the inevitable changes in heat sealing or application temperatures used in the manufacture of such packages. Enables the production of objects.

In the past, various thermoplastics have been used in the production of films capable of forming peelable seals.

For example, (1) a copolymer of about 80 to 96% by weight of ethylene and about 4 to 20% by weight of ethylenically unsaturated ester;
and (2) about 10 to 50% by weight of crystalline intactic polybutylene.
U.S. Patent No. 4,18 by Meri'can Can)
See No. 9.519. Although a peel seal may be produced, the film of that patent consists of polybutylene as a minor component. The patented formulation is a high-density polyethylene (
HDPE) and will not bond to polypropylene without an adhesive.

Mobil Oil Corp.
US Pat. No. 3,900.534 by Ration) discloses a thermoplastic shrink film with good heat-sealing properties and good optical properties, but the patent does not indicate a need for a peel-seal film. .

UCB S. A. Belgian U.S. Patent No. 3,87
No. 9.492 discloses blends consisting of polybutylene, styrene-butadiene copolymer, low density polyethylene, high density polyethylene and polyisoptylene.

E. I. DuPont de Nemours
tdo Nemours & Co. U.S. Pat. No. 4,539,263 by J.D.) discloses a peelable seal based on a propylene/sigma copolymer. It's broken. The patent does not appear to provide any disclosure regarding polybutylene polymers.

U.S. Pat. No. 4,665.130 and U.S. Pat. No. 4.666,
No. 778 discloses a blend of polybutylene and EVA (or polyethylene) and polypropylene,
The polypropylene is then less than 15% by weight in the formulation. However, these references do not teach a novel invention.

No. 3,573,240 describes hot melt adhesive compositions for rigid single bindings. In column 4, lines 1-7 of that patent, small amounts, i.e., up to about 5% by weight, of alpha olefin comonomers such as ethylene and propylene are produced without substantial loss of the desired properties exhibited by the essentially homogeneous polymerization system. teaches that it can be present in butene-1 polymerization systems. The patent also indicates in column 2, lines 61-63 that the hot melt binder adhesive exhibits good thermal stability and rapid curing speed. Although the patent states that up to about 5% by weight of ethylene can be added to a substantially butene-1 polymerization system,
No releasable hot melt adhesives are disclosed. Thus, the patent is not contrary to the teachings of the present invention which describe the use of ethylene homopolymers or copolymers with butene-1 homopolymers or copolymers in creating peelable bonds. .

The present invention recognizes that conventional multilayer peel seal films or sheets consist of a peelable seal where the substrate and sealant are not of the hot melt type. The present invention teaches novel hot melt adhesive formulations and methods of making packaging film systems that are removable upon opening the package. The present invention avoids delaminated layers when separating sealed layers. In certain embodiments, a tie adhesive is used to bond incompatible substrates using a novel hot melt adhesive that has releasable properties.

Butene-1 homopolymers and copolymers are a group of polymers that are unique because of their slow crystallization rates. The extremely slow crystallization rate of butene-1 polymers compared to that of other polyole7ine crystalline polymers such as EVA, polyethylene, and polypropylene is due to the extremely slow crystallization rate of the butene-1 polymers on various substrates (
It has been found to be advantageous in formulating new hot melt adhesives that have good adhesion to metals such as stainless steel and cathodized aluminum.

The polybutylene homopolymers and copolymers useful in this invention are primarily linear molecules with a normally and spatially arranged arrangement of ethyl side groups; occurs when polymerizing through 1.2 carbon double bonds along the chain backbone (e.g., U.S. Pat. No. 3,362,94).
(See No. 0).

On cooling from the melt, the ethyl side groups initially align in a tetrahedral configuration and progress to just over half of the final crystallinity (n-type) of the polymer. With time, the tetrahedral crystalline phase Form II transitions to a stable hexahedral spatial configuration and subsequently progresses further to Crystalline Form I.

Butene-l copolymers are one of various alpha olefins.
For example, U.S. Pat.
See the butene-1 copolymers shown in No. 362.940.

Luftene-1/ethylene copolymers with ethylene comonomer in the range of 11 to 20 mole percent have been shown to produce an amorphous phase with a low glass transition temperature (Tg) and further reduce the rate of crystallization of the adhesive. , and are expected to be particularly useful in hot melt adhesives according to the present invention for further reducing the degree of ultimate crystallization in the polymer. By developing the hot melt adhesives of the present invention with these novel release properties, a variety of other adhesives such as adhesive resins, waxes, oils, stabilizers, and other additives such as actuctic polypropylene homogeneous It can be made into a composition with a polymer or copolymer.

The present invention was developed to provide a blend of two incompatible polymers in creating a bond with controllable cohesive strength. “Incompatible polymers” are
Defined as a polymer that separates into two separate phases. "Controllable cohesive strength" refers to an adhesive whose cohesive strength can be varied or controlled by changing the ratio of incompatible components.

In the present invention, the peelable hot melt adhesive is butene-1
Homopolymers or copolymers with about 5 to about 50% by weight of ethylenic homopolymers or copolymers or alternatively ethylenic homopolymers or about 5 to about 50% by weight of butene-1
Homogeneous polymer or copolymer with copolymer; 30 phr
wax up to 15 phr, atactic propylene homopolymer up to 15 phr, tacky resin in varying amounts depending on other components used in the adhesive, and small amounts of stabilizers (1 phr
).

The present invention also uses this releasable hot melt adhesive on compatible substrates of nylon, polycarbonate, stainless steel, and other similar materials, as well as on certain non-compatible substrates. Using laminated structures or closures
ure) could be used to grow.

Within the scope of the present invention, ethylenic homopolymers or copolymers are linear low density polyethylene (LLDPE), low density polyethylene (LDPE), medium density polyethylene (MD
PE), ethylene vinyl acetate copolymer (EVA), ethylene-methyl acrylate copolymer (HMA), high density polyethylene (HDPE) or ethylene-acrylic acid copolymer. Most preferably, either low density polyethylene or ethylene vinyl acetate copolymer is the novel ethylene polymer component.

The butene-1 polymers of the present invention consist of butene-1 homopolymers or propylene, ethylene or Al-7 aolefins having 5 to 8 carbon atoms, with comonomer moles ranging from 1 to 30 mol %, based on the total copolymer. Butene-1 copolymer with comonomer having %.

For example, when a butene-1 copolymer is used with ethylene as a comonomer, a suitable mole percent comonomer is about 1
It is expected that the butene-1 copolymers as the butene-1 fraction, which is 1, will be most preferred for use within the scope of the present invention.

Butene-1 homopolymers and copolymers that can be used within the scope of the present invention can be selected from a wide range of melt flow polymers.

Stabilizers which can be used within the scope of the invention include sterically hindered phenols such as Ciba Geigy
Irganox l manufactured by
O 1 0, Ethyl Corporation
Stabilizers such as Ethanox or RinPace from ion) such as Irgafos l 6 from Ciba Geigy
It can be 8. When used in the present invention, Irganox l
O l O is the most preferred stabilizer. The amount of stabilizer that may be used within the scope of the present invention is expressed as parts per 100 parts of the total weight of the stabilizer in the hot melt adhesive expressed in weight percent (phr.
). Ethanox 330 is l. 3.5-trimethyl-2.4.6-tris[3.5-di-t-butyl-4-hydroxypendynole]benzene. I
rganox l O I O is commonly represented as tetrakis[methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane. 0.
It is preferred to use 3 phr of stabilizer, but about 0.3 phr.
1 to about 2 phr may also be used within the scope of this invention.

Adhesive resins that may be used within the scope of the present invention may be either compatible with an ethylene homopolymer or copolymer component or compatible with a butene-1 homopolymer or copolymer component. . When an ethylene copolymer compatible adhesive resin is used in the present invention, it is usually selected from polar adhesive resins. When using ethylene homopolymer compatible tacky resins, rosin esters or aliphatic hydrocarbon resins may be used within the scope of this invention. Examples of ethylene copolymer compatible resins include those manufactured by Arizona Chemical Company.
Zonester 85 (glycerin ester of disproportionated tall oil rosin) and Zonester
l O O s or Hercules
KristaIe manufactured by es Corporation
x3070 (al-7 amethylstyrene paced resin).

When a butene-1 homopolymer or copolymer compatible adhesive resin is used in the present invention, the adhesive resin is non-polar, such as Regalrez 1 078 (hydrogenated hydrocarbon resin) manufactured by Hercules, Exxon Chemical Company. (Exxo
Esco manufactured by n Chemical Company
rez1304 (hydrocarbon resin), all made by Goodyear Tire & Rubber
Wingtack 9 made by re andRubber)
5 (synthetic polyterbene resin) or Wingtac
Preferably, it is k85. Also within the scope of the invention are partially hydrogenated C.-based hydrocarbon resins having a softening point in the range from 70 to 125.degree. Members of the group consisting of siream resins and polyterpenes can be incorporated into the adhesive in amounts of about 20 to about 60% by weight, preferably 50% by weight.

The wax of the present invention may be a microcrystalline wax, although other waxes may also be used within the scope of the present invention. Waxes are optional and may be used in amounts up to 30 phr (parts per hundred) based on the total adhesive composition. Shallwax' l O O, 300 and 50
0 is an example of a wax suitable for use within the scope of the present invention. A sufficient amount of wax, from lO to 30 phr, preferably 20 phr, should be used in the present invention and that will reduce the viscosity in the overall adhesive composition without substantially reducing the operating temperature of the adhesive. give you the advantage of

In some cases, atactic polypropylene (e.g. AF manufactured by Hercules, Wilmington, Delaware)
AX 5 1 0) about 15p of the entire adhesive preparation
It may be added to the novel composition in amounts ranging up to hr. Most preferably, 15 phr of Afax 5 10 is added to provide the benefit of (l) improved processability of the overall adhesive system by acting as a diluent, and (2) reduced cost of the resulting adhesive. use

The amount of atactic polypropylene that may be used within the scope of this invention is the same as the method used in expressing the amount of stabilizer that may be used within the scope of this invention.
It is expressed as

Plasticizers, such as She I Ifflex, may also be used to reduce manufacturing costs in producing the final strippable product.
Oils such as '371 may be added to the composition.

These plasticizers can also enhance the processability of the adhesive.

The invention can also act as an adhesive in laminated structures in a continuous or discontinuous manner. If the adhesive is applied continuously, the substrate should accommodate some of the bulk of the adhesive. If the adhesive is applied intermittently, the substrate may be either compatible or non-compatible with the bulk of the adhesive. The laminate structure can contain as a substrate one of the following: nylon, polyester, polyvinyl chloride (PVC), high density polyester (HDPE), polypropylene (PP), polycarbonate (PC), polystyrene (PS). ), polyacrylonitrile (PAN), paper or aluminum foil or poly-4-methylpentyl. The layered structure is not limited only to the above-mentioned compounds, but any compound that can be used as a substrate within the scope of the invention is also considered.

The laminated structure can be manufactured by coating at least one surface of a substrate with the hot-melt adhesive of the present invention.

Sanderch-shaped laminates are also within the scope of the present invention.

It has been found that hot melt adhesives can be made using a ratio of ethylene or butene-1 homopolymer or copolymer to tackifying resin in the range of 70:30 to 30:70. These ranges are more preferably 60 each:
The ratio may vary from 40 to 40:60. The most preferred embodiment of the invention is a ratio of butene-1 or ethylene polymer component to the respective compatible adhesive resin of 50:50.

The adhesive composition described above contains a tackifying resin and optionally additional components of atactic propylene homopolymer, waxes and/or other stabilizers, and a small amount of butene-l homopolymer or copolymer and a large amount of When consisting of a composition consisting of some ethylene, the composition may consist of preparations such as those shown below: (1) from about 66.6 to about 15% by weight of an ethylene homopolymer or copolymer, from about 15 to about 66.5% by weight ethylene compatible adhesive resin, about 5 to about 50% by weight butene-1 homopolymer or copolymer, up to 1 phr stabilizer, and optionally up to 30 phr wax, and/or 15 phr up to atactic polypropylene, and furthermore for ethylene homopolymers or copolymers. Preparations in which the ratio of adhesive resins is from 30:70 to 70:30.

(II) about 57 to about 201 weight percent ethylenic homopolymer or copolymer, about 5 to about 50 weight percent butene-1 homopolymer or copolymer, up to about 1 phr stabilizer;
and from about 57 to about 20% by weight tacky resin, and optionally up to 30 phr of wax and/or (1
5 phr), and the composition ratio of adhesive resin to ethylene homopolymer or copolymer is from 40:60 to 60:4.
Preparations that are within the range of 0.

When the ratio of resin to ethylene is l:l, the preparation contains from about 47.5 to about 25% by weight ethylenic homopolymer or copolymer, from about 5 to about 50% by weight butene-l homogeneous. polymer or copolymer, up to about 1 phr stabilizer;
and about 25 to about 47.5% by weight tacky resin; and optionally up to 30 phr wax and/or 1
It can consist of up to 5 phr of atactic polypropylene, the composition ratio of adhesive resin to ethylene homopolymer or copolymer being 1:1.

The adhesive composition comprises a wax and also a stabilizer, and the composition contains a small amount of ethylene and a large amount of butene-1.
When consisting of a homopolymer or copolymer, the composition may consist of a preparation such as: (III) from about 5 to about 50% by weight of an ethylenic homopolymer or copolymer, about 66.5% by weight of an ethylenic homopolymer or copolymer; ~about 15% by weight butene
I homopolymer or copolymer, up to about Iphr stabilizer, and about 15 to about 66.5% by weight tackifying resin, optionally 20phr wax and/or 15phr
Preparation consisting of atactic polypropylene up to r and further comprising a composition ratio of adhesive resin to butene-1 homopolymer or copolymer in the range from 30:70 to 70:30.

(■) about 5 to about 50 weight percent ethylenic homopolymer or copolymer, about 57 to about 20 weight percent butene-1 homopolymer or copolymer, up to about 1 phr stabilizer, and about 20 to about 57% by weight tacky resin, optionally up to 3 Qphr wax and/or up to 15 phr atactic polypropylene resin, and further composition ratio of tacky resin to butene-1 homopolymer or copolymer. is within the range of 40:60 to 60:40.

When the ratio of resin to ethylene is 1:1, the preparation contains from about 5 to about 50% by weight of the ethylenic homopolymer or copolymer, from about 47.5 to about 25% by weight of the butene-1
homopolymer or copolymer, up to about 1 phr stabilizer, and about 25 to about 47.5 wt% tacky resin, and optionally up to 30 phr wax and/or up to 15 phr atactic polybrobylene. It can consist of

Example I Adhesive Production Adhesives were produced using either a compact Brabender compounding head (approximately 50 cc capacity) or a one-tooth Sigma Blade mixer. Preheated equipment (170-180℃
), the test preparations were easily formulated by introducing the polybutylene polymer and mixing until a soft, homogeneous mass formed, then gradually introducing the remaining ingredients. Mixing time was approximately 20 minutes.

Example 2 Adhesive film was release coated (rel
ease coated) on polyester film (
Thin adhesive films (125-200 microns) could be prepared by casting (onto the release coated surface). Pour the preheated adhesive (at about 130°C) onto the polyester film and heat the nip.
I was able to pull it by hand through the roll. Alternatively, the adhesive can be poured onto the substrate and the adhesive can be drawn (dr) using a doctor blade to create a uniform coverage on the substrate.
awdown) I was able to do J. Other methods of applying hot melt adhesives could also be used. For continuous or intermittent application, techniques such as spraying the adhesive or extruding the adhesive using a hot melt gun to apply the adhesive could be used. Using the first technique above, a small amount (<
609) could be produced and thus very small amounts of adhesive could be evaluated.

Once cooled and cured, these adhesives could be used to make test specimens. For example, cut a square of adhesive from a polyester film, peel it off, place the adhesive between pieces of paper,
and hot bar sealer
Kraft paper to kraft paper, polypropylene to polypropylene, and polyethylene to polyethylene bonding could be achieved by heat sealing using a thermosetting resin (time, pressure, and temperature can be adjusted). Alternatively, an adhesive square or piece of adhesive may be placed on a small piece of plastic or metal substrate, melted with a heat gun (or in a dryer), and then bonded under suitable contact pressure to create a T-beer, wrap, or Lap shear or SAFT bonded substrate specimens could be produced.

Test method l. The hot melt viscosity of the adhesive is the RVT head and No.
．． Brookfield thermocell with 29 spindles (ASTM D3236)
d Thermocell) can be measured at 177° C. in a viscometer; for low viscosity preparations No. 27
A spindle could be used.

2. Beer Strength Test Substrates, a 25 mm x 1 50 mm laminated sandwich inch could be fabricated using adhesive as an intermediate layer between the substrate surfaces. Place one side of the laminate into the lower jaw and place it in the Instron (Instron).
sLron) during the test. The jaws were released at a speed of 25 cm/min. The force required to peel the surface was continuously recorded. Maximum and minimum values and destruction (fBilure)
The mode of failure was recorded: adhesion, cohesion or a combination thereof. ．． This test estimated a beer angle of approximately 180°C.

Table 1 shows the differences between adhesives consisting of a large amount of butene-1 and a large amount of ethylene, as well as known adhesives.

Next Toyofune Butene-1 polymer 1) Butene-111 coalescence》 Ethylene polymer +31 Adhesive resin 1'' Adhesive resin 31 Wax 11 Stabilizer (1) Substrate Jinichi chopstick beer strength, ”+1) 1+ A 37 .5 12.5 50.0 0.3 phr pp book 3.7 B 37.5 12.5 Table 1 Hot melt adhesive C 33.3 33.3 l2.5 37.5 33.3 33.3 50 33.3 25 phr 50.0 0.3 phr 0.3 phr AI Hayashi AI Honmoto 4.1 1.1 0.3 phr O. 3 phrHDPE Book Paper 33.3 25 phr 0.3 phr Paper 2.6 1.3 1.0 33.3 33.3 33.3 25 phr O. 3 phr HDPE*Kyomoto 1.0-.

The aspects of the invention can be summarized and described as follows.

1. Ethylene homogeneous polymer or copolymer about 50 to about 9
5% by weight; about 50% butene-1 homopolymer or copolymer
~5% by weight; and up to about 1 part per hundred (phr) of a stabilizer.

2. Ethylenic homopolymer or copolymer from about 60 to about 8
0% by weight; about 40% butene-1 homopolymer or copolymer
and up to about 1 part per hundred (phr) of a stabilizer.

3. from about 50 to about 5% by weight of an ethylenic homopolymer or copolymer; from about 50 to about 95% by weight of a butene-1 homopolymer or copolymer; and up to about 1 part per lOO (phr) of a stabilizer. A releasable hot melt adhesive comprising a large amount of butene-1 homopolymer or copolymer.

4. Ethylenic homopolymer or copolymer about 40-20
Weight %: Butene-1 homopolymer or copolymer about 60~
A releasable hot melt adhesive comprising a large amount of butene-1 homopolymer or copolymer comprising about 80% by weight; and up to about 1 part per hundred (phr) of a stabilizer.

5. Ethylenic homopolymer or copolymer from about 66.5 to
about 15% by weight; about 5 to about 50% by weight of a butene-1 homopolymer or copolymer; up to about 1 phr of a stabilizer; and about 15 to about 66.5% by weight of a tackifying resin; Furthermore, a releasable hot-melt adhesive in which the composition of the adhesive resin to the ethylene homopolymer or copolymer is in the range of 30:70 to 70:30.

6. Ethylenic homopolymer or copolymer from about 57 to about 2
0% by weight; butene-1 homopolymer or copolymer approx.
about 50% by weight: up to about 1 phr of stabilizer: and about 20 to about 57% by weight of a tackifying resin; and further comprising a composition of tackifying resin for the ethylene homopolymer or copolymer of 4020 phr. Peelable hot melt adhesive in the range 0 to 60:40.

7. Ethylenic homopolymer or copolymer from about 47.5 to
about 25% by weight of a butene-1 homopolymer or copolymer; about 5 to about 50% by weight of a butene-1 homopolymer or copolymer; up to about 1 phr of a stabilizer; and about 25 to about 47.5% by weight of a tackifying resin; And furthermore, a releasable hot melt adhesive in which the composition of adhesive resin to ethylene homopolymer or copolymer is in a ratio of 1:1.

8. Ethylenic homopolymer or copolymer from about 5 to about 50
Weight %; butene-1 homopolymer or copolymer approx. 66.
5 to about 15% by weight; up to about 1 phr of a stabilizer; and about 15 to about 66.5% by weight of a tackifier resin for the butene-1 homopolymer or copolymer. A releasable hot melt adhesive having a composition in the range of 30:70 to 70:30.

9. Ethylenic homopolymer or copolymer from about 5 to about 50
Weight %; butene-1 homopolymer or copolymer from about 57 to
about 20% by weight; up to about 1 phr of stabilizer; and about 20 to about 57% by weight of a tackifying resin; =60-60: in the range of 40,
Peelable hot melt adhesive.

10. Ethylenic homopolymer or copolymer from about 5 to about 5
0% by weight; about 47 butene-1 homopolymer or copolymer
．． 5 to about 25% by weight; up to about 1 phr of a stabilizer; and about 25 to about 47.5% by weight of a tackifying resin;
and furthermore a releasable hot melt adhesive in which the composition of adhesive resin to butene-1 homopolymer or copolymer is in a ratio of 1:1.

11. Furthermore, it contains up to 30 phr of wax.
The adhesive described in item 1 and item 3 above.

12. The ethylenic homopolymer or copolymer can be used as linear low density polyethylene, low density polyethylene, medium density polyethylene, ethylene vinyl acetate copolymer, ethylene methyl acrylate copolymer, high density polyethylene and ethylene acrylic acid copolymer. Adhesive according to items 1 and 3 above, selected from the group of polymers.

13. 3. Adhesive according to item 1 and item 3 above, wherein the butene-1 copolymer comprises a comonomer that is a member of the group consisting of ethylene, propylene and alphaole7yne having 5 to 8 carbon atoms.

14. The adhesive of paragraphs 1 and 3 above, wherein the butene-1 copolymer comprises between about 1 and about 30 mole percent of at least one comonomer.

15. The adhesive according to items 1 and 3 above, wherein the stabilizer is a sterically hindered phenol.

16. 16. The adhesive according to item 15, wherein the sterically hindered phenol is tetrakis[methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane.

17. The adhesive of paragraphs 1 and 3 above, further comprising O to about 15 phr atactic polypropylene.

18. the ethylene-compatible adhesive resin is a member of the group consisting of aliphatic hydrocarbons, including ester al-7-amethylstyrene-based resins of disproportionated tall oil rosin;
The adhesive according to any of the above items 5 to 7.

19. The adhesive according to any of paragraphs 8 to 10 above, wherein the adhesive resin that is compatible with adhesives is a member of the group consisting of non-polar resins, partially hydrogenated hydrocarbon resins, polyterbenes, and stream resins. agent.

20. 12. The adhesive of claim 11 further comprising up to 30 phr of microcrystalline wax.

21. a substrate bonded with a releasable hot melt adhesive, the adhesive comprising from about 50 to about 95% by weight of an ethylenic homopolymer or copolymer; a butene-1 homopolymer or copolymer; About 50 to about 5% by weight combined: and 100
A laminate structure containing up to about 1 part per part (phr) of stabilizer.

22. a substrate bonded with a releasable hot melt adhesive, the adhesive comprising from about 60 to about 80% by weight of an ethylenic homopolymer or copolymer; a butene-1 homopolymer or copolymer; about 40 to about 20% by weight combined; and 10
A laminate structure containing up to about 1 part per 0 (phr) of stabilizer.

23. a substrate bonded with a releasable hot melt adhesive, the adhesive comprising from about 50 to about 5% by weight of an ethylenic homopolymer or copolymer; butene-■ homopolymer or copolymer; About 50 to about 95% by weight combined: and 100%
A laminate structure containing up to about 1 part per part (phr) of stabilizer.

24. a substrate bonded with a releasable hot melt adhesive, the adhesive comprising from about 40 to about 20% by weight of an ethylenic homopolymer or copolymer; a butene-1 homopolymer or copolymer; about 60 to about 80% by weight combined; and 10
A laminate structure containing up to about 1 part per 0 (phr) of stabilizer.

25. a substrate bonded with a releasable hot melt adhesive, the adhesive comprising from about 66.5 to about 15% by weight of an ethylenic homopolymer or copolymer; butene-1
About 5 to about 50% by weight of homogeneous polymer or copolymer: about 1
stabilizer up to phr; and tackifying resin from about 15 to about 66 phr.
5% by weight; and furthermore, the composition of the adhesive resin for the ethylene homopolymer or copolymer is 30% by weight:
Laminated structure in the range of 70 to 70:30.

26. from about 57 to about 20% by weight of an ethylenic homopolymer or copolymer: a butene-1 homopolymer or copolymer; About 5 to about 50% by weight combined; about 1 ph
stabilizer up to r; and from about 20 to about 57% by weight tacky resin.
furthermore, the composition of the adhesive resin to the ethylene homopolymer or copolymer is 40:60 to 60.
: Laminated structure in the range of 40.

27. a substrate bonded with a releasable hot melt adhesive, the adhesive comprising from about 47.5 to about 25% by weight of an ethylenic homopolymer or copolymer; butene-1;
About 5 to about 50% by weight homopolymer or copolymer; about 1
stabilizer up to phr; and tackifying resin from about 25 to about 47 phr.
5% by weight: and further in which the composition of adhesive resin to ethylene homopolymer or copolymer is in the ratio l=1.

28. from about 5 to about 50% by weight of an ethylenic homopolymer or copolymer: a butene-1 homopolymer or copolymer; About 66.5 to about 15% by weight combined; about 1
stabilizer up to phr; and tackifying resin from about 15 to about 66 phr.
and furthermore, the composition of the adhesive resin to the butene-1 homopolymer or copolymer is 30:70 to 5% by weight;
Laminated structure in the 70:30 range.

29. a substrate bonded with a releasable hot melt adhesive, the adhesive comprising from about 5 to about 50% by weight of an ethylenic homopolymer or copolymer; a butene-1 homopolymer or copolymer; About 57 to about 20% by weight; about 1 ph
stabilizer up to r; and from about 20 to about 57% by weight tacky resin.
furthermore, the composition of the adhesive resin to the butene-1 homopolymer or copolymer is 40:60 to 6.
Laminated structure in the range of 0:40.

30. a substrate bonded with a releasable hot melt adhesive, the adhesive comprising from about 5 to about 50% by weight of an ethylenic homopolymer or copolymer; a butene-1 homopolymer or copolymer; About 47.5 to about 25% by weight combined; about 1
stabilizer up to phr; and tackifying resin from about 25 to about 47 phr.
and furthermore, the composition of the adhesive resin to the butene-1 homopolymer or copolymer is l:l.
A laminated structure with a ratio of

31. Items 21 and 23 above, wherein the substrate is selected from the group consisting of nylon, polyester, polyvinyl chloride, high density polyethylene, polypropylene, paper, aluminum foil, polystyrene, polyacrylonitrile, polycarbonate or poly-4-methylbentene. Laminated structure.

32. The ethylenic homopolymer or copolymer is linear low density polyethylene, low density polyethylene, medium density polyethylene, ethylene vinyl acetate copolymer, ethylene methyl acrylate copolymer, high density polyethylene and ethylene acrylic acid. The laminated structure according to items 2l and 23 above, which is selected from the group of copolymers.

33. 24. A laminate structure according to items 21 and 23, wherein the butene-1 copolymer comprises a comonomer that is a member of the group consisting of ethylene, propylene and alpha olefins having 5 to 8 carbon atoms.

34. 2l and 23 above, wherein the butene-1 copolymer comprises a comonomer that is a member of the group consisting of ethylene, propylene, and alpha olefins having 5 to 8 carbon atoms, and the comonomer is between about 1 and 30 mole percent. Laminated structure as described in section.

35. The laminated structure according to items 21 and 23 above, wherein the stabilizer is a sterically hindered phenol.

36. The stabilizer is tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)]
The laminated structure according to item 35 above, which is methane.

37. Any of paragraphs 25 to 27 above, wherein the ethylene compatible adhesive resin is a member of the group consisting of aliphatic hydrocarbons, including esters of disproportionated tall oil rosin and al-7amethylstyrene-based resins. A laminated structure described in Crab.

38. 28-3 above, wherein the butene-compatible tacky resin is a member of the group consisting of non-polar resins, partially hydrogenated hydrocarbon resins, polyterpenes, and stream resins.
The laminated structure according to any one of item 0.

39. The laminated structure according to items 2l and 23 above, wherein the adhesive further comprises wax.

40. 40. The laminated structure according to item 39, wherein the adhesive comprises microcrystalline wax.

41. The laminate structure of paragraphs 21 and 23 above, wherein the adhesive further comprises about 15 phr of atactic polypropylene.

1 other person

Claims (1)

[Claims] 1. Ethylene homopolymer or copolymer from about 50 to about 9
5% by weight; about 50% butene-1 homopolymer or copolymer
~5% by weight; and up to about 1 part per hundred (phr) of a stabilizer. 2. About 50 to 5% by weight of an ethylenic homopolymer or copolymer; about 50 to about 95% by weight of a butene-1 homopolymer or copolymer; and up to about 1 part per hundred (phr) of a stabilizer. A releasable hot melt adhesive comprising a large amount of butene-1 homopolymer or copolymer containing. 3. Ethylene homogeneous polymer or copolymer about 66.5~
about 15% by weight; about 5% to about 50% by weight of a butene-1 homopolymer or copolymer; up to about 1 phr of a stabilizer; and about 15% to about 66.5% by weight of a tackifying resin; and Furthermore, the composition of the adhesive resin to the ethylene homopolymer or copolymer is in the range of 30:70 to 70:30.
Peelable hot melt adhesive. 4. Ethylene homopolymer or copolymer about 5 to about 50
Weight %; butene-1 homopolymer or copolymer approximately 66.
5 to about 15% by weight; up to about 1 phr of stabilizer; and about 15 to about 66.5% by weight of tackifier resin; Peelable hot melt adhesive ranging from :70 to 70:30. 5. comprising a substrate bonded with a releasable hot melt adhesive, the adhesive comprising from about 50 to about 95% by weight of an ethylenic homopolymer or copolymer; a butene-1 homopolymer or A laminate structure comprising from about 50 to about 5% by weight of a copolymer; and up to about 1 part per hundred (phr) of a stabilizer. 6. a substrate bonded with a releasable hot melt adhesive, and the adhesive comprises from about 50 to about 5% by weight of an ethylenic homopolymer or copolymer; a butene-1 homopolymer, or A laminate structure comprising from about 50 to about 95% by weight of a copolymer; and up to about 1 part per hundred (phr) of a stabilizer. 7. comprising a substrate bonded with a releasable hot melt adhesive, the adhesive comprising from about 66.5 to about 15% by weight of an ethylenic homopolymer or copolymer; butene-1 homopolymer; About 5 to about 50% by weight of the polymer or copolymer; about 1 ph
and about 15 to about 66.5 wt.
Laminated structure in the range of 30. 8. comprising a substrate bonded with a releasable hot melt adhesive, the adhesive comprising from about 5 to about 50% by weight of an ethylenic homopolymer or copolymer; a butene-1 homopolymer or About 66.5 to about 15% by weight of copolymer; about 1ph
and about 15 to about 66.5 wt.
: Laminated structure in the range of 30.