# US 11,306,227 B2 · Hot-melt adhesives comprising a bimodal polymer composition formed by polyolefins having low stereospecificity

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- Number: US 11,306,227 B2
- Document ID: US11306227B2
- Status: Granted
- Kind: B2
- Application number: 17/057,314
- Filed: 2019-05-20
- Published: 2021-06-24
- Granted: 2022-04-19
- Earliest claimed: 2018-05-28
- Assignees: Savarè I.C. S.R.L.
- Applicants: Savare' I.C. S.P.A.
- Inventors: Italo Corzani
- Web page: https://patentgrep.com/patent/US11306227B2

## CPC

- C09J 123/14: Copolymers of propene (C09J123/16 takes precedence)
- A61F 13/15577: {Apparatus or processes for manufacturing}
- B32B 3/266: {characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12}
- B32B 5/02: characterised by structural features of a {fibrous or filamentary} layer {(layer formed of metallic wires B32B15/02; layer formed of natural mineral fibres B32B19/02; layer formed of wood fibres B32B21/02)}
- B32B 7/12: using interposed adhesives or interposed materials with bonding properties
- A61F 13/15585: {of babies' napkins, e.g. diapers (A61F13/15617 - A61F13/15804 take precedence)}
- A61F 13/472: specially adapted for female use
- A61F 13/496: in the form of pants or briefs
- A61F 2013/1591: {via adhesive}
- A61F 2013/53908: {with adhesive}
- C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H)
- A61F: FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS (dental prosthetics A61C)
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM

## Abstract

The present application discloses novel hot-melt adhesive formulations, with excellent processability, even in processes at high line-speed and at a relatively low temperature, the formulations suitable for strongly bonding substrates that have openings, holes, voids or pores, both macroscopic and microscopic ones, like perforated plastic films, both with bidimensional or tridimensional structure; fibrous substrates, both woven and non-woven; porous plastic films, and the like, all mentioned substrates being widely used for the manufacturing of absorbent hygienic articles. The hot-melt formulations include, as their main or even unique constituent, at least one polymer composition formed by two polyolefins, substantially non-stereospecific, as showed by the low value of their crystallization enthalpy at time zero, the polyolefins having average Number Molecular Weights Mn that do not differ for more than about 6,000 g/mole, being the single average Number Molecular Weights of said polyolefins ranging from about 3,000 g/mole and about 30,000 g/mole.

## Claims

### Claim 1

A hot-melt adhesive formulation, characterised in that it comprises a polymer composition formed by two non-stereospecific polyolefins, said polymer composition having a melt flow rate (MFR) ranging between 10 dg/minute and 6,000 dg/minute, measured at 190° C. and under a weight of 2.16 kg, and comprising:
A) a first non stereospecific polymer formed by a homopolymer of an olefin selected from ethylene, propylene, butene-1 or hexene, or by a copolymer among the same olefins, said polymer A) being characterised by a crystallisation enthalpy from the melt at time zero not greater than 15 J/g and by an average number molecular weight Mn(A) ranging from 3,000 g/mole to 30,000 g/mole;
B) a second non stereospecific polymer formed by a homopolymer of an olefin selected from ethylene, propylene, butene-1 or hexene, or by a copolymer among the same olefins, said polymer B) being characterised by a crystallisation enthalpy from the melt at time zero not greater than 15 J/g and by an average number molecular weight Mn(B) ranging from 3,000 g/mole to 30,000 g/mole;
and where said polymer composition has a ratio by weight between the first polymeric constituent A) and the second polymeric constituent B) ranging from 1:20 to 20:1, said polymeric constituents A) and B) being selected in such a way that the difference between the average number molecular weights of A) and B), Mn(A)−Mn(B), is not greater than 3,000 g/mole
said hot-melt adhesive formulation being further characterised by the fact that:
it shows a crystallisation enthalpy from the melt at time zero not greater than 12 J/g, measured by differential scanning calorimetry (DSC) at the cooling rate of 1° C./minute;
it shows a solidification rate around its rheological setting point not greater than 3,000 Pa/° C.;
it shows a decreasing rate of its rheological parameter tan delta around its own rheological setting point, that is not greater than 0.1 (° C.)−1, and
when applied between two substrates, of which at least one is a fibrous substrate or a porous plastic film or a perforated plastic film, at a basis weight comprised between 0.5 g/m2 and 50 g/m2, it gives to the bonded structure an adhesive peel strength, measured after seven days of aging at 23° C. and 50% relative humidity, that is greater than 0.25 N per 50 mm of width.

### Claim 2 (depends on 1)

The hot-melt adhesive formulation according to claim 1), wherein the two polymeric constituents of the polymer composition, A) and B), are selected in such a way that their average mass molecular weights Mw are ranging from 15,000 g/mole to 200,000 g/mole, and the difference between said average mass molecular weights, Mw(A)−Mw(B), is not greater than 10,000 g/mole.

### Claim 3 (depends on 1)

The hot-melt adhesive formulation according to claim 1), wherein the polymer composition formed by the two non-stereospecific polymers A) and B), constitutes from 50% by weight to 100% by weight of said hot-melt adhesive formulation.

### Claim 4 (depends on 1)

The hot-melt adhesive formulation according to claim 1) further comprising a polymeric viscosity modifier, that is non-solid at room temperature and that has an initial crystallisation enthalpy not greater than 2 J/g in the differential scanning calorimetry (DSC) measurement of crystallisation enthalpy and at the cooling rate of 1° C./minute.

### Claim 5 (depends on 4)

The hot-melt adhesive formulation according to claim 4), wherein the polymeric viscosity modifier that is non-solid at room temperature, has a viscosity that at 50° C. is not lower than 15,000 mPa·s and at 190° C. is not lower than 200 mPa·s.

### Claim 6 (depends on 4)

The hot-melt adhesive formulation according to claim 4), wherein the viscosity modifier that is non-solid at room temperature is a metallocenic non-stereospecific polymer of propylene or a metallocenic non-stereospecific copolymer of propylene-ethylene.

### Claim 7 (depends on 4)

The hot-melt adhesive formulation according to claim 4), wherein the viscosity modifier that is non-solid at room temperature, constitutes from zero to 10% by weight of said hot-melt adhesive formulation.

### Claim 8 (depends on 1)

The hot-melt adhesive formulation according to claim 1), that comprises from zero to 5% by weight of a tackifier or of a blend of tackifiers having a ring & ball softening point ranging from 5° C. to 160° C.

### Claim 9 (depends on 8)

The hot-melt adhesive formulation according to claim 8), wherein the tackifier or the blend of tackifiers is selected from the group consisting of aliphatic hydrocarbon tackifiers, partially hydrogenated aliphatic hydrocarbon tackifier derivatives, fully hydrogenated aliphatic hydrocarbon tackifier derivatives, aromatic hydrocarbon tackifiers, partially hydrogenated aromatic hydrocarbon tackifier derivatives, fully hydrogenated aromatic hydrocarbon tackifier derivatives, tackifiers formed from blends of aliphatic and aromatic hydrocarbon monomers, terpene tackifiers, partially hydrogenated terpene tackifier derivatives, fully hydrogenated terpene tackifier derivatives, rosins, rosin esters, partially hydrogenated rosin derivatives, and fully hydrogenated rosin derivatives.

### Claim 10 (depends on 8)

The hot-melt adhesive formulation according to claim 8), wherein the tackifier or the blend of tackifiers have a volatile organic compound (VOC) value not higher than 1,000 ppm as determined according to the standard test method VDA 278.

### Claim 11 (depends on 1)

The hot-melt adhesive formulation according to claim 1), that comprises from zero to 8% by weight, of the total adhesive formulation, of a liquid plasticiser or of a blend of liquid plasticisers, having a viscosity not greater than 10,000 mPa·s at 50° C. and selected from the group consisting of paraffinic mineral oils, naphthenic mineral oils, vegetable oils, liquid poly-iso-butylene oils (PIB), liquid esters, phthalates, benzoates, sebacates, and combinations thereof.

### Claim 12 (depends on 1)

The hot-melt adhesive formulation according to claim 1), that comprises from zero to 3% by weight, of a wax or of a blend of waxes wherein said wax or blend of waxes has a Brookfield viscosity at 190° C. not greater than 300 mPa·s.

### Claim 13 (depends on 12)

The hot-melt adhesive formulation according to claim 12), wherein the wax or the blend of waxes is constituted by polyolefin waxes.

### Claim 14 (depends on 13)

The hot-melt adhesive formulation according to claim 13), wherein the polyolefin waxes are modified with maleic anhydride.

### Claim 15 (depends on 1)

The hot-melt adhesive formulation according to claim 1), that comprises a further non-stereospecific polyolefinic copolymer, derived from mono-olefins from C2 to C6, that has an initial crystallisation enthalpy not greater than 15 J/g.

### Claim 16 (depends on 15)

The hot-melt adhesive formulation according to claim 15), wherein the further non-stereospecific polyolefinic copolymer constitutes from zero to 15% by weight of the total final adhesive formulation.

### Claim 17 (depends on 1)

The hot-melt adhesive formulation according to claim 1), further comprising polymeric and oligomeric constituents, except for the non-stereospecific polymers A) and B) forming the polymer composition of claim 1), exclusively derived from mono-olefins from C2 to C6 and their blend, and that is substantially free from other polymeric and oligomeric compounds, synthetic or natural, that originate from monomers that are different from the mono-olefins from C2 to C6.

### Claim 18 (depends on 1)

The hot-melt adhesive formulation according to claim 1), that has a rheological setting point ranging from 40° C. to 100° C.

### Claim 19 (depends on 1)

The hot-melt adhesive formulation according to claim 1), that has a Brookfield viscosity at 170° C. not greater than 6,000 mPa·s.

### Claim 20 (depends on 1)

The hot-melt adhesive formulation according to claim 1), that has a Brookfield viscosity at 150° C. not greater than 10,000 mPa·s.

### Claim 21 (depends on 1)

The hot-melt adhesive formulation according to claim 1), that has a shear viscosity at 160° C. and at the shear rate of 100,000 (s)−1 that is not higher than 650 mPa·s.

### Claim 22 (depends on 1)

The hot-melt adhesive formulation according to claim 1), that has a ring & ball softening point not higher than 125° C.

### Claim 23 (depends on 1)

The hot-melt adhesive formulation according to claim 1), that has a needle penetration, measured at 55° C., that is not smaller than 40 dmm.

### Claim 24 (depends on 1)

The hot-melt adhesive formulation according to claim 1), that has an open time ranging from 1.5 minutes and 600 minutes.

### Claim 25 (depends on 1)

The hot-melt adhesive formulation according to claim 1), that after seven days of aging at 23° C. and 50% relative humidity, shows a crystallisation enthalpy, measured in a differential scanning calorimetry (DSC) melting cycle at the heating rate of 1° C./minute, that compared with the crystallization enthalpy at time zero is at least 50% higher.

### Claim 26 (depends on 1)

The hot-melt adhesive formulation according to claim 1), that after seven days of aging at 23° C. and 50% relative humidity, shows an elastic modulus G′, measured at 23° C. and 1 Hz, that compared with the elastic modulus G′ at time zero and in the same conditions of test, is at least 50% higher.

### Claim 27 (depends on 1)

The hot-melt adhesive formulation according to claim 1), that after seven days of aging at 23° C. and 50% relative humidity, shows an elastic modulus G′, measured at 23° C. and 1 Hz, that is not lower than 1.3 MPa.

### Claim 28 (depends on 1)

The hot-melt adhesive formulation according to claim 1), that after seven days of aging at 23° C. and 50% relative humidity, shows a tan delta, measured at 23° C. and 1 Hz, that compared with the tan delta at time zero and in the same conditions of test, is at least 30% lower.

### Claim 29 (depends on 1)

The hot-melt adhesive formulation according to claim 1), that after seven days of aging at 23° C. and 50% relative humidity, shows a tan delta, measured at 23° C. and 1 Hz, that is not higher than 0.4.

### Claim 30 (depends on 1)

The hot-melt adhesive formulation according to claim 1), that after seven days of aging at 23° C. and 50% relative humidity, shows an elastic nodulus G′, measured at 37° C. and 0.01 Hz, that is not lower than 30,000 Pa.

### Claim 31 (depends on 1)

The hot-melt adhesive formulation according to claim 1), that comprises from 0.01% by weight and 10% by weight of at least one stabiliser selected from the group consisting of antioxidants, UV-stabilisers, photo-stabilisers, and combinations thereof.

### Claim 32 (depends on 1)

The hot-melt adhesive formulation according to claim 1), that comprises from zero to 10% by weight of additional constituents selected from the group consisting of mineral fillers, pigments, dyes, perfumes, surfactants, and antistatic agents.

### Claim 33 (depends on 1)

A bonded structure comprising:
a.i. a first substrate;
a.ii. a second substrate;
a.iii. a hot-melt adhesive formulation according to claim 1), that bonds the first and the second substrate, and that, if applied at a basis weight ranging from 0.5 g/m2 to 50 g/m2, gives to the bonded structure an adhesive peel strength, measured after seven days of aging at 23° C. and 50% relative humidity, not lower than 0.25 N per 50 mm of width.

### Claim 34 (depends on 33)

The bonded structure according to claim 33), in which at least one substrate is a porous fibrous substrate or a porous film or a perforated film.

### Claim 35 (depends on 34)

The bonded structure according to claim 34), that is manufactured with a line speed not slower than 250 m/minute and with an adhesive basis weight ranging from 1.5 g/m2 and 20 g/m2, and in which the adhesive peel strength, measured after seven days of aging at 23° C. and 50% relative humidity, is not lower than 0.5 N/inch.

### Claim 36 (depends on 1)

A hygienic absorbent article, comprising the hot-melt adhesive formulation according to claim 1).

### Claim 37 (depends on 33)

A hygienic absorbent article, comprising a bonded structure according to claim 33).

### Claim 38 (depends on 36)

The article according to claim 36), wherein said article is a baby-diaper or a training pant diaper or a diaper for incontinent adults or a feminine catamenial pad.

### Claim 39 (depends on 36)

The absorbent hygienic article according to claim 36, wherein the hot-melt adhesive formulation is used for at least one of the following uses: i) general construction adhesive of the whole article; ii) for bonding elastic components; iii) for strengthening and ensuring, even in use, the integrity of an absorbent core of the absorbent hygienic article; iv) for the bonding of perforated films both with a bidimensional or tridimensional structure.

### Claim 40 (depends on 1)

An article comprising the hot-melt adhesive formulation according to claim 1), wherein said article is an absorbent surgical mattress or sheet or a surgery laminate for medical use or a wound-dressing product.

### Claim 41 (depends on 1)

An article comprising the hot-melt adhesive formulation according to claim 1), wherein said article is a mattress or a component thereof.