MX339901B

Free radical initiator modified hot melt adhesive composition including functionalized polyethylene and propylene-alpha-olefin polymer.

Abstract

A hot melt adhesive composition that includes a first copolymer that includes the reaction product of a functionalized polyethylene, a propylene-alpha-olefin polymer that includes at least 50 mole % propylene and has a viscosity of no greater than 10,000 centipoise at 190 °C, a ratio of z average molecular weight (Mz) to number average molecular weight (Mn) (Mz/Mn) of greater than 20, and a ratio of Mz to weight average molecular weight (Mw) (Mz/Mw) of greater than 3.0, and a free radical initiator.

MX339901B, drawing sheet 1 — Sheet 1 of 44

Term

5.7 yearsleft in the term

Expires 21 June 2032.

11 claims: 4 independent, 7 dependent

1
CLAIMS REIVINDICACIONES IMPI IMPI INSTITUTO mexicano OE LA rROPIEDAU Mexican INSTITUTE OE LA rROPIEDAU INDUSTRIA!. INDUSTRY!. 1. Una composición adhesiva de fusión por calor caracterizada porque comprende:one. A heat fusion adhesive composition characterized in that it comprises: a first copolymer comprising the reaction product of a functionalized polyethylene comprising at least one polar functional group, a propylene-alpha-olefin polymer comprising at least 50 mol% propylene and having a viscosity of not more than 10,000 centipoise at 190 ° C, a ratio between the average molecular weight z (Mz) and the numerical average molecular weight (Mn) (Mz / Mn) greater than 20, and a ratio of Mz to weight average molecular weight (Mw) (Mz / Mw) greater than 3.0, and a free radical initiator. un primer copolímero que comprende el producto de reacción de un polietileno funcionalizado que comprende al menos un grupo funcional polar, un polímero de propileno-alfa-olefina que comprende al menos 50 mol % de propileno y que tiene una viscosidad no mayor que 10,000 centipoise a 190 °C, una relación entre el peso molecular promedio z (Mz) y el peso molecular promedio numérico (Mn) (Mz/Mn) mayor que 20, y una relación entre el Mz y el peso molecular promedio en peso (Mw) (Mz/Mw) mayor que 3.0, y un iniciador de radicales libres.
4
La composición adhesiva de conformidSi9ST''ttt>n reivindicación 1, caracterizada porque el primer copoii'fHSfU'· se forma de al menos 2 % en peso del polietileno funcionalizado en base al peso del primer copolimero. Four. The adhesive composition of conformidSi9ST'' ttt> n claim 1, characterized in that the first copoii'fHSfU '· is formed of at least 2% by weight of the functionalized polyethylene based on the weight of the first copolymer.
8
The adhesive composition in accordance with 8. La composición adhesiva de conformidad con la 20 reivindicación 1, que además comprende al menos una de cera twenty Claim 1, further comprising at least one wax Fischer Tropsch, Polyethylene Wax, Polypropylene Wax, and Polypropylene Maleate Wax. Fischer Tropsch, cera de polietileno, cera de polipropileno, y cera de maleato de polipropileno.
11
14, caracterizado porque el polietileno funcionalizado comprende cera de maleato de polietileno y la mezcla comprende al menos aproximadamente 2 % en peso de la cera de maleato de polietileno. 14, characterized in that the functionalized polyethylene comprises polyethylene maleate wax and the mixture comprises at least about 2% by weight of the polyethylene maleate wax.

Independent claims4

515 paragraphs in 63 sections, as filed

(54) Title: HOT FUSING ADHESIVE COMPOSITION MODIFIED BY A FREE RADICAL STARTER INCLUDING PROPYLENE-ALPHA-OLEPHINE POLYMER AND FUNCTIONALIZED POLYETHYLENE.

(54) Title: FREE RADICAL INITIATOR MODIFIED HOT MELT ADHESIVE COMPOSITION INCLUDING FUNCTIONALIZED POLYETHYLENE AND PROPYLENE-ALPHA-OLEFIN POLYMER.

(57) Summary

A heat-melt adhesive composition that includes a first copolymer that includes the reaction product of a functionalized polyethylene, a propylene-alpha-olefin polymer that includes at least 50 mol% propylene and has a viscosity of not more than 10,000 centipoise at 190 ° C, a relationship between the average molecular weight z (Mz) and the numerical average molecular weight (Mn) (Mz / Mn) greater than 20, and a relationship between Mz and the weight average molecular weight (Mw) ( Mz / Mw) greater than 3.0, and a free radical initiator.

(57) Abstract

A hot melt adhesive composition that ineludes a first copolymer that ineludes the reaction product of a functionalized polyethylene, a propylene-alpha-olefin polymer that ineludes at least 50 mole% propylene and has a viscosity of no greater than 10,000 centipoise at 190 ° C, a ratio of z average molecular weight (Mz) to number average molecular weight (Mn) (Mz / Mn) of greater than 20, and a ratio of Mz to weight average molecular weight (Mw) (Mz / Mw) of greater than 3.0 , and a free radical initiator.

Institute

Mexican Property

Industrial

Yes

PATENT TITLE NO. 339901

Owner (s): HB FULLER COMPANY

Address: 1200 Willow Lake Blvd., PO Box 64683, St. Paul, Minnesota, 55164-0683, USA

Name: HOT FUSION ADHESIVE COMPOSITION MODIFIED BY A UDIRAL RADICALS INITIATOR INCLUDING PROPYLENE-ALPHA-OLEPHINE POLYMER AND FUNCTIONALIZED POLYETHYLENE.

Classification: lntCI.8: C09J123 / 14; C09J123 / 30; C09J151 / 06

Iiwontoríes): RICHARD A MILLER; KEVINDAVIS; STEPHEN M. WILLGING; SHARF U.

AHMED; TIMOTHY W. ROSKA

Number:

MX / a / 2013/015169 '

Country:

US

Validity: Twenty years

REQUEST

Presentation date intemaeioneis June 21, 2012

PRIORITY

Date: Number:

June 2011 61 / 501,585

Expiration Date: June 21, 2032

The reference patent is granted based on articles 1, 2 fraction V, 6 fraction HI, and 59 of the Industrial Property Law.

In accordance with article 23 of the Industrial Property Law, this patent has a non-extendable term of twenty years, counted from the date of filing of the international application and will be subject to payment (Jeta fee to maintain the rights in force .

Whoever subscribes to this title does so based on the provisions of article * 6 fractions III and 7 'bis 2 of the Industrial Property Law (Official Gazette of the Federation (DOF) 27706/1991, retarma & r on 08/02 / 1994, 10/25/1996, 12/26/1997, 05/17/1999, 01/26/2004, 06/16/2005, 01/25/2006, 06/05/2009, 06/01/2010 '8/002010. ¿8/06/2010. 27/01/2012. 04/09/2012); articles 1 ·. 3rd fraction V subsection a), 4th and 12th fractions I and lll of the Regulations of the Mexican Institute of Industrial Property (DOF 14/12/1999, amended on 07/01/2002, 07/15/2004; 28 / 07/2064 and 09/07/2007); articles 1, 3, 4, 5, section Vínciso a), 16 sections I and III and 30 of the EÚatuto Orgânico del InsttMpMewnede de la Propiedad Industrial (DOF 12/27/1999, amended on 16 () 0 / 2002,2β / β7 «004, 08/04/2904 and 13/69/2007); 1st. 3rd and 5th Clause áj of the Agreement which delegates powers to the Deputy Directors General, Coordinator. Divisional Directors, Regional Office Holders, Divisional Deputy Directors, Departmental Coordinators and other subordinates of the Mexican Institute of Industrial Property. (DOF 12/15/1999, amended on 02/04/2000, 07/29/2004, 08/04/2004 and 09/13/2007).

Issue Date: June 16, 2016

MX / 2016/46912 i

IMPI

HOT FUSING ADHESIVE COMPOSITION ΜΟΡΦΡ} Κ3ΑΡΑνΡΟ

INDUSTRIAL

FREE RADICALS INITIATOR INCLUDING THE POLYMER OF

PROPYLENE-ALPHA-OLEPHINE AND FUNCTIONALIZED POLYETHYLENE

This application claims the benefit of the US provisional application. USA no. 61 / 501,585 filed on June 27, 2011, which is incorporated herein.

BACKGROUND

The invention is directed to formulating hot melt adhesive compositions based on propylene-alpha-olefin polymers.

The hot melt adhesive compositions are used in different applications that require the bonding of two substrates including, for example, applications for packaging (for example, corrugated cardboard and cardboard), applications for nonwoven fabric (for example, articles of single use), binding and shoemaking. A hot melt adhesive composition is generally applied in a molten state and forms a bond when it cools and solidifies. The time required for a

IMPI

MEXICAN INSTITUTE OF PROPERTY

heat melt adhesive cool to] S * trffí? bL en'-qtre 'has enough resistance to formát 1 tlhá union 3Γ5 unión calls “hardening time”. Hardening time is an important parameter in applications that require high speed processing operations such as packaging and binding operations. For many packaging applications, the joint needs to be formed quickly; otherwise, the resulting packaging will be poorly sealed or not even sealed.

It is important that the adhesives used in packaging applications exhibit good bond strength over a wide range of temperatures and fast cure times.

Amorphous polypropylene polymers have been formulated into heat melt adhesive compositions for different applications. Many amorphous polypropylene polymers exhibit long open time, are quite tacky immediately after solidification from the molten state, and remain tacky for an undesirable period of time after solidification. These properties are not suitable for applications that require short open times and non-stick properties after solidification.

brief description of the invention

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

In one aspect, the invention —— holy piffia one.

heat-melt adhesive composition including a first copolymer including the reaction product of a functionalized polyethylene, a propylene-alpha-olefin polymer comprising at least 50 mol% of propylene and having a viscosity of not more than 10,000 centipoise at 190 ° C, a ratio between the average molecular weight z (Mz) and the numerical average molecular weight (Mn) (Mz / Mn) greater than 20, a ratio of Mz to weight average molecular weight (Mw) (Mz / Mw) greater than 3.0, and a free radical initiator. In one embodiment, the adhesive composition has a viscosity of not more than about 2,000 centipoise at 177 ° C. In another embodiment, the adhesive composition has a viscosity of from about 400 to about

2,000 centipoise at 177 ° C. In some embodiments, the adhesive composition exhibits a fiber break bond at -29 ° C (Celsius) and at +60 ° C. In other embodiments, the adhesive composition exhibits at least 50% fiber breakage at -29 ° C and at +60 ° C.

In some embodiments, the first copolymer is formed from at least 2% by weight of functionalized polyethylene based on the weight of the first copolymer. In other embodiments, the first copolymer is formed from at least about 4% by weight of weight-based functionalized polyethylene

IMPI

MEXICAN INSTITUTE of the first copolymer. In other modalities' pj copolymer is formed of at least 10% by weight1 of functionalized polyethylene based on the weight of the first copolymer. In one embodiment, the first copolymer includes the reaction product of at least 2% by weight of polyethylene maleate and at least about 80% by weight of the propylene-alpha-olefin polymer. In another embodiment, the first copolymer includes the reaction product of at least 4% by weight of polyethylene maleate and at least about% by weight of the propylene-alpha-olefin polymer. In another embodiment, the first copolymer includes the reaction product of at least 10% by weight of polyethylene maleate and at least about 85% by weight of propylene-alpha-olefin polymer.

In some embodiments, the adhesive composition is homogeneous after 96 hours aging at 177 ° C.

In one embodiment, the adhesive composition exhibits a unique thermal fusion transition temperature when tested using differential scanning calorimetry.

In another embodiment, the adhesive composition has an initial Gardner color of not greater than 3. In some embodiments, the adhesive composition has a color

Gardner after 72 hours aging at 177 ° C of not more than 5.

MEXICAN INSTITUTE

In one embodiment, the initiator of ra ^ ir *0'1- * ΙΜΡΙ

includes peroxide.

In some embodiments, the propylene alpha-olefin polymer includes at least one of ethylene, butene, pentene, hexene, heptene, octene, niene, decene, and dodecene. In other embodiments, the propylene alpha-olefin polymer includes at least 25 mol% butene.

In one embodiment, the adhesive composition further includes at least one of Fisher Tropsch wax, polyethylene wax, polypropylene wax, and polypropylene maleate wax. In other embodiments, the functionalized polyethylene includes polyethylene maleate, and the composition further includes at least one of Fischer wax.

Tropsch, polyethylene wax, and polypropylene maleate wax. In other embodiments, functionalized includes polyethylene maleate and the composition further includes a Fischer Tropsch wax. In some embodiments, the composition further includes an olefin polymer. In another embodiment, the adhesive composition further includes at least about 5% by weight wax. In some embodiments, the adhesive composition further includes at least about 5% by weight of wax selected from the group consisting of polyethylene wax, polypropylene maleate wax, and polyethylene wax

Fischer Tropsch.

IMPI

EROFIEDAU MEXICAN INSTITUTE

In one embodiment, the adhesive composition has a hardening time of less than 15 'SSTJÜlTaóS. Pir. — Pirra modality, the adhesive composition has a hardening time of less than 10 seconds. In other embodiments, the adhesive composition has a cure time of less than 8.5 seconds.

In other embodiments, the first copolymer includes the reaction product of at least 2% by weight of polyethylene maleate and at least about 80% by weight of propylene-alpha-olefin polymer, the adhesive composition further includes at least about 5% by weight wax, and the adhesive composition has a viscosity of not more than 2,000 centipoise at 177 ° C. In another embodiment, the first copolymer includes the reaction product of at least 3 wt% polyethylene maleate and at least about wt% propylene-alpha-olefin polymer, the adhesive composition further includes at least about 5 wt% wax, and the adhesive composition has a viscosity of not more than 2,000 centipoise at

177 ° C.

In some embodiments, the adhesive composition exhibits an Mz / Mn greater than 18, and an Mz / Mw of 2.3 to not greater than 6. In other embodiments, the adhesive composition exhibits an Mz / Mn of at least 27 and an Mz / Mw from 2.3 to no

greater than 4.

IMPI ™

In other modalities

MEXICAN INSTITUTE Ot INDUSTRIAL PROPERTY

the adhesive composition further includes a bonding agent. In some embodiments, the adhesive composition further includes at least 15% by weight of bonding agent. In another embodiment, the adhesive composition further includes from 15% by weight to about% by weight of bonding agent. In another embodiment, the first copolymer is formed from a reaction mixture that further includes a polyfunctional acid.

In one embodiment, the adhesive composition includes at least about 55% by weight (or even at least about 70% by weight) of the copolymer and further includes an adhesion agent and at least one of Fischer Tropsch wax, polyethylene wax, wax polypropylene and polypropylene maleate wax.

In another aspect, the invention features a method of making a heat-melt adhesive composition, the method includes heating a mixture that includes at least about 80% by weight of propylene-alpha-olefin polymer that includes at least 50 mol% of propylene, wherein the propylene-alpha-olefin polymer is derived from propylene and from a definition including at least one of two carbon atoms and four carbon atoms and having a viscosity of not more than 1, 000 centipoise at 190 ° C, a relationship between the average molecular weight z (Mz) and the numerical average molecular weight (Mw) (Mz / Mn) greater than 20, and a relationship between Mz and

IMPI

MEXICAN INSTITUTE OE LA PROTIinAD

the weight average molecular weight (Mw) (Mz / Mw) ma ^ W ^ what ^ * ?? - © ^ functionalized polyethylene and a Tadldáltít initiator!1 free. '

In one embodiment, the functionalized polyethylene includes functionalized polyethylene wax. In other embodiments, the functionalized polyethylene includes polyethylene maleate wax and The blend includes at least 2% by weight of polyethylene maleate wax. In another embodiment, the functionalized polyethylene includes polyethylene maleate wax and the blend comprises at least 4% by weight of polyethylene maleate wax. In some embodiments, the heat melt adhesive composition exhibits a fiber break bond at 29 ° C and + 60 ° C. In other embodiments, the mixture further includes a polyfunctional acid.

In other aspects, the invention features a heat melt adhesive composition that includes a copolymer that includes the reaction product of a functionalized polyethylene, a propylene-alpha-olefin polymer comprising at least 50 mol% propylene, and a free radical initiator , the heat-melt adhesive composition has a ratio between the average molecular weight (Mz) and the numerical average molecular weight (Mn) (Mz / Mn) greater than 18, and a ratio between Mz and the average molecular weight (Mw) (Mz / Mw) of 2.3 to not greater than 6. In one embodiment, the Mz / Mn is at least 27 and the Mz / Mw is 2.5 to not greater than 6. In other modalities, the adhesive composition

IMPI

INSTITUTO MEXICANO DE LA PRQRUOAD presents at least 50% fiber breakage at -29 ° C

In other modalities, functional polyethylene! zacíó include

functionalized polyethylene wax. In another embodiment, the composition further includes the filler.

The adhesive composition exhibits good thermal stability and fiber break properties at a wide range of temperatures.

Other features and advantages will become apparent from the following description of the preferred embodiments and from the claims.

GLOSSARY

With reference to the invention, these terms have the meanings set forth below:

The term "wax" refers to a polymer that has crystallinity and a weight average molecular weight (Mw) of less than 10,000 g / mol.

For ease of reference, when referring to a polymer including or comprising an olefin, the term "olefin" refers to the polymerized form of the olefin in the polymer.

DETAILED DESCRIPTION MFl

INx'TtTjjTO MEXICANO nc INDUSTRIAL PROPERTY

The heat melt adhesive composition includes the reaction product of a functionalized polyethylene, a propylene-alpha-olefin polymer, a free radical initiator, and optionally a polyfunctional acid. The heat melt adhesive composition has a viscosity of not more than 2,000 centipoise (cps), not more than

1,500 cps, not greater than 1,200 cps, not greater than 1,000 cps, not greater than 900 cps, or even from about 400 cps to about 2,000 cps at 177 ° C. The heat-melt adhesive composition further forms a fiber break bond at -29 ° C and +60 ° C and preferably exhibits at least about 50% fiber break at -29 ° C and + 60 ° C, at least about 80% fiber break at 2 9 ° C and +60 ° C, at least about 90% fiber break

<td>fiber to -29</td><td>° C already</td><td>+60 ° C, or</td><td>even at least 100</td><td colspan="2">% breakage</td>

<td>fiber to</td><td>-29 ° C</td><td>already +60</td><td>'C. The composition</td><td>adhesive</td><td>of</td>

<td>merger by</td><td>hot</td><td>presents,</td><td>preferably a</td><td>weather</td><td>of</td>

hardening not greater than 15 seconds, not greater than 10 seconds, not greater than 7 seconds, or even not greater than 5 seconds. The heat melt adhesive composition has an average molecular weight z (Mz) of not more than 100,000 g / mol, not more than about 90,000 g / mol, not more than about 80,000 g / mol, not more than about

70,000 g / mol, not greater than about 60.0üe 's1^ / mol °? ~ aT minus 20,000 g / mol, or even at least approximately

25,000 g / mol.

The heat melt adhesive composition preferably has a weight average molecular weight (Mw) of not more than about 50,000 g / mol, not more than about 40,000 g / mol, not more than about 35,000 g / mol, not more than approximately

30,000 g / mol, or even not greater than about

25,000 g / mol, a numerical average molecular weight (Mn) not greater than 5,000 g / mol, not greater than approximately

4,000 g / mol, not greater than about 3,500 g / mol, not greater than approximately 3,000 g / mol, or even not greater than 2,500 g / mol, an Mz / Mn of at least 15, at least 18, at least 20, at least 25, at least 27, or even at least 30, an Mz / Mw of at least 2.2, at least 2.5, at least 2.6, not greater than 6, not greater than 5.5, not greater than 5, or even not greater than 4.5, and an Mw / Mn of at least 6, at least 7.5, at least 9, or even at least 10.

The heat melt adhesive composition is preferably homogeneous and is thermally stable for an extended period of time. The thermal stability of a heat-melt adhesive composition can be determined by different methods, including evaluating the clarity, homogeneity, and Gardner color of the composition.

Preferably, the homogeneous calorie melt adhesive composition after storage at elevated temperatures for 48 hours, 72 hours, or even 96 hours, and is visibly clear and free of phase separation, charring, and gelation after hours storage, 72 hours, or even 96 hours at 177 ° C.

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MEXICAN INSTITUTE OF THE FROFIF.LMD. , INDUSTRIAL

The heat fusion product preferably has an initial Gardner color of not more than 3, not more than 2, or even not more than 1, and a Gardner color of not more than 6, not more than 5, or even not more than 4 after aging for 48 hours, 72 hours, or even 96 hours, at 177 ° C.

The heat melt adhesive composition is preferably not tacky at room temperature, but can be formulated to be tacky at room temperature.

The heat melt adhesive composition preferably has a specific gravity less than 0.930, not more than 0.8 90, not more than 0.8 85, not more than 0.8 80, or even not more than 0.875, a glass transition temperature (Tg ) less than -10 ° C, less than -20 ° C, or even less than -30 ° C, and a melting temperature (Tm) of at least about 105 ° C, at least 110 ° C, or even at least 115 ° C.

Reaction product

MEXICAN INSTITUTE OF FROFIEDAD

INDUSTRIAL

The melt adhesive composition μϋΓΤΗΙδΓ i'ftólüye at least 50% by weight, at least about 55% by weight, at least about 60% by weight, at least about 70% by weight, at least about 75% by weight, at least about 80% by weight, at least about 85% by weight, at least about 90% by weight, from about 75% by weight to about

100 % by weight, from about 75% by weight to about 95% by weight, or even from about 80% by weight to about 90% by weight of the reaction product of a functionalized polyethylene, a propylene-alpha-olefin polymer, a free radical initiator and, optionally, a polyfunctional acid.

The reaction product preferably exhibits a single thermal fusion transition temperature when tested by means of differential scanning calorimetry. The reaction product preferably has a single thermal melting transition temperature of from about 100 ° C to about 130 ° C, or even from about 110 ° C to about 116 'C.

The reaction product is preferably clear, has an initial Gardner color of not more than 3, not more than 2, or even not more than 1, and after aging for 48 hours at 177 ° C, has,

IMPI

preferably a Gardner color not greater than S ^, ST* hb

than 4, or even not greater than 3.

The reaction product has an average molecular weight z (Mz) not greater than 100,000 g / mol, not greater than approximately 90,000 g / mol, not greater than approximately 80,000 g / mol, not greater than approximately 70,000 g / mol, not greater 'that approximately 60,000 g / mol, at least

20,000 g / mol, or even at least about 25,000 g / mol.

The reaction product preferably has a weight average molecular weight (Mw) of not more than about 50,000 g / mol, not more than about 40,000 g / mol, not more than about 35,000 g / mol, not more than about 30,000 g / mol, or even not greater than about 25,000 g / mol, a numerical average molecular weight (Mn) not greater than 5,000 g / mol, not greater than approximately 4,000 g / mol, not greater than approximately 3,500 g / mol, not more than about 3,000 g / mol, or even not more than 2,500 g / mol, an Mz / Mn of at least 15, at least 18, at least 20, at least 25, at least 27, or even at least 30, an Mz / Mw of at least 2.2, at least

2.5, at least 2.6, not greater than 6, not greater than 5.5, not greater than 5, or even not greater than 4.5, and an Mw / Mn of at least 6, at least 7.5, at least 9, or even at least 10.

IMPI

MEXICAN INSTITUTE

Without being limited by theory, what ^DThe inventors deduce that the reaction product is a functionalized polyethylene copolymer and the propylene-alpha-olefin polymer.

Functionalized polyethylene

Useful functionalized polyethylenes include at least one polar functional group. Examples of useful functional groups include alcohol, ketone, aldehyde, acid, anhydride, ester, amine, amide, thiol, and combinations thereof. Useful functionalized polyethylenes include polyethylene polymers, polyethylene waxes, and combinations thereof. Useful functionalized polyethylenes include polyethylene maleate (ie, maieic acid and modified maleic anhydride), oxidized polyethylene, and combinations thereof. In some embodiments, a functionalized polyethylene wax is preferred.

Polyethylene maleates preferably include functional groups of at least 0.8 mol%, at least 1.6 mol%, or even from about 0.8 mol% to about 3.2 mol%. Useful functionalized polyethylenes have an acid number of from about 2 to about 40, from about 2 to about

10, or even from about 3 to about 8.

IS

IMPI ^

MEXICAN INSTITUTE OF PROPERTY

Useful functionalized polyethylenes Wen ^ iascrystallinity of at least 10%, at least 30 * '% u luclusn1 at least 50% and a thermal melt of at least 70 J / g, at least 85 J / g or even at least 94 J / g, and can be linear or branched.

Useful functionalized polyethylene waxes

<td>they have a</td><td colspan="2">melting point</td><td>of</td><td>at least 100</td><td>'C, and</td><td>a</td>

<td>viscosity</td><td>of</td><td colspan="2">approximately</td><td colspan="3">20 cps at approximately</td>

<td>1,500 cps,</td><td>or</td><td>even from</td><td colspan="2">approximately</td><td>200 cps</td><td>to</td>

<td colspan="2">approximately</td><td>800 cps.</td><td>The</td><td>waxes</td><td colspan="2">polyethylene</td>

<td colspan="2">functionalized</td><td>useful have</td><td>a</td><td>molecular weight</td><td>average</td><td>in</td>

<td>weight (Mw)</td><td>not</td><td colspan="4">greater than about 10,000 g / mol,</td><td>to the</td>

minus approximately 1,000 g / mol, from approximately 500 g / mol to approximately 20,000 g / mol, or even from approximately 4,000 g / mol to approximately 9,500 g / mol.

An example of a useful maleate wax is ACX 1783 polyethylene maleate wax, which is marketed under the trade designation AC 577P by Honeywell.

International Inc. (Morristown, New Jersey).

The reaction product is formed from at least 2% by weight, at least about 3% by weight, at least about 4% by weight, at least about 5% by weight, at least about 7% by weight, from 2% by weight. weight to about 20% by weight, from about 3% by weight to about 20% by weight, from about 5% by weight to

about 15% by weight, by weight to about functionalized based on weight

INSTITUTO MEXICANO DE LA EROPIEDAP or even approximately 100% by weight of the reaction product.

Propylene-alpha-olefin polymer

The propylene-alpha-olefin polymer has a viscosity of at least about 1,000 cps, at least about 3,000 cps, at least about 5,000 cps, not more than about 20,000 cps, not more than about 15,000 cps, or even not more than about 10,000 cps at 190 ° C, at Mz / Mn of at least 40, greater than 45, greater than 50, or even greater than 55, and an Mz / Mw of at least 2.5, at least 2.8, at least 3.0, or even at least 3.2. The propylene-alpha-olefin polymer preferably has a glass transition temperature (Tg) less than -10 ° C, less than -20 ° C, or even less than -30 ° C.

Useful propylene-alpha-olefin polymers also have a number average molecular weight (Mn) of at least about 1,500 g / mol, not more than about 7,500 g / mol, or even not more than about 5,000 g / mol, a weight average molecular weight (Mw) of not more than about 65,000 g / mol, not more than about 60,000 g / mol, at least about 20,000 g / 'mol, or even at least about 30,000 g / mol, and a molecular weight averaged z

IMPI

MEXICAN INSTITUTE. . _ _, OF THE RATIO (Mz) not greater than approximately 250,000 g / mo! B7l,sTiíip ©

than approximately 240,000 g / mol, nu greater than .....-- than approximately 210,000 g / mol, not greater than approximately

200,000 g / mol, or even not greater than about 175,000 g / mol.

Useful propylene-alpha-olefin polymers have a crystallinity of at least 5%, at least about 10%, not more than about 30%, or even not more than about 20%, and a heat of fusion of not more than 60 J / g, not greater than 30 J / g, or even not greater than 20 J / g.

Useful propylene-alpha-olefin polymers include homopolymers, copolymers (i.e., higher order copolymers, terpolymers, and polymers), and combinations thereof. Useful propylene-alphaolefin polymers are derived from propylene and at least one alpha-olefin comonomer having two carbon atoms, or even at least four carbon atoms, including, for example, ethylene, butene, pentene, hexene, heptene , octene, noneno, decene, dodecene, and combinations of these.

Useful propylene-alpha-olefin polymers include at least 50 mol%, at least about 60 mol%, not more than about 8 0 mol%, or even from about 50 mol% to about 70 mol% propylene, and at least 2 mol%, at least 5 mol%, at least

IMPI »

INSTITUTO MEXICANO DE LA FROFIE »AD approximately 10 mol%, at least approximatelyD'T0 *Lmor * ~ rFr at least about 25 mol%, at least 'agiTÓRlUlá'dállléllLtí mol%, not greater than about 50 mol%, or even about 20 mol% to about 50 mol% of at least one alpha olefin comonomer.

The propylene-alpha-olefin polymer is preferably free of functional groups but includes functional groups (eg, maleic anhydride modified propylene-alphaolefin polymer). The propylene-alpha-olefin polymer furthermore preferably has a

<td colspan="6">zero acid number.</td>

<td></td><td>The</td><td>polymers</td><td>of</td><td>propylene-alpha-olefin</td><td>I know</td>

<td colspan="2">they find in</td><td>the market</td><td>low</td><td>different designations</td><td>than</td>

<td>include,</td><td>by</td><td>example the</td><td>Serie</td><td colspan="2">REXTAC 2000 designations</td>

products of Rextac LLC (Odessa, Texas), including REXTAC RT 2765 propylene-butene copolymer, REXTAC RT 2788 propylene-butene copolymer, REXTAC RT 2780 propylene-butene copolymer, REXTAC RT 2215 propylene ethylene copolymer the propylene-ethylene copolymer

REXTAC RT 2385, the propylene-ethylene copolymer REXTAC RT

2535, and the propylene-ethylene copolymer REXTAC RT 2585, the EASTOFLEX series of trade names from Eastman

Chemical Co. (Kingsport, Tennessee), including propylene-ethylene copolymer EASTOFLEX E1060, and the VESTOPLAST series of trade names from Evonik Industries

IMPI ^

MEXICAN INSTITUTE (Mari, Germany), which include terpolymer D& QNDpj ^ piS§® £ ^ butene-ethylene VESTOPLAST EP NC 702 and torpolymer-eepropylene-butene-ethylene VESTOPLAST 608 and combinations thereof.

The reaction product is formed from at least about 70% by weight, at least about 75% by weight, at least about 80% by weight, at least about 85% by weight, at least about 90% by weight, about 75 % by weight to about 95% by weight, or even from about 80% by weight to about 90% by weight of propylene-alphaolefin polymer based on the weight of the reaction product.

Free radical initiator

Useful free radical initiators include, for example, peroxide type compounds, azo type compounds, and mixtures thereof. Examples of suitable peroxide compounds include diacyl peroxides, peroxy esters, peroxyketals, dialkyl peroxides, and hydroperoxides, specifically hydrogen peroxide, benzoyl peroxide, deconoyl peroxide, lauroyl peroxide, succinic acid peroxide, cumer hydroxide, t-butylhydroperoxide , t-butyl peroxyacetate, 2,2 di (t-butyl peroxy) butane diallyl peroxide), 2,5-dimethyl-2,5-di (tert-butyl peroxide) hexane, cumyl peroxide, and combinations

IMPI ^

M £ X1CANO INSTITUTE »E LA FROFIEDA» of these. Suitable hexanes of 2,5-dimethyl-2,5'-2) 5T,tbut,? ± · tertiary peroxy) are marketed under the trade name

LUPERSOL 101 from United Initiator Incorporated (Elyria,

Ohio).

Examples of suitable azo compounds include azobisisobutyronitrile (AIBN), 2,2'-azobis (N, N '~ dimethylene isobutyramide) dihydrochloride (an example of which is marketed under the tradename VA-044 by Wako

Chemical Co.), 2,2'-azobis (2,4-dimethyl valeronitrile) (an example of which is marketed under the trade name V65 by Wako Chemical Co.), VAZO 64 2,2azobis (isobutyronitrile) and VAZO 67 2, 2 '-azobis (2-methylbutyronitrile), both marketed by du Pont de

Nemours and Company (Wilmington, Delaware), l, l'-azobis (1-cyclohexane carbonitrile), azo-functional acid initiators, eg, 4,4'-azobis (4-cyanopentanoic acid), and combinations thereof.

Optional polyfunctional acid

The reaction mixture optionally includes a polyfunctional acid. Examples of suitable polyfunctional acids include dicarboxylic acids and tricarboxylic acids including, for example, aromatic dicarboxylic acids (eg, methylhexahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, and

IMPI

MEXICAN INSTITUTE OF PROPERTY (hexahydrophthalic anhydride), dicarboxylic acidsltoIDUSTi (eg. , maleic acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, pimelic acid, sumeric acid, acelaic acid, sebacic acid, chlorendic acid, 1,2,4-butane-tricarboxylic acid, decanedicarboxylic acid, octadecanedicarboxylic acid, hexahydrophthalic acid, acids methylhexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, dimeric acid and fumaric acid), alicyclic dicarboxylic acids (for example, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid), and combinations thereof. Corresponding acid anhydrides, acid esters and chlorides, and combinations thereof, of these acids are included in the term "dicarboxylic acid".

The reaction product is formed from 0% by weight to not more than about 7% by weight, at least about 1% by weight, at least about 3% by weight, not more than about 5% by weight, from about 1% by weight to about 7% by weight, or even from about 1% by weight to about 5% by weight of polyfunctional acid based on the weight of the reaction product.

Process

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MEXICAN INSTITUTE OF INDUSTRIAL PRORIITY

The reaction product was prepared by treating a mixture of the propylene-alpha-olefin polymer, functionalized polyethylene, and optional polyfunctional acid with the free radical initiator at an elevated temperature. The treatment alters the weight average molecular weight and the z average molecular weight of the propylene-alpha-olefin polymer. The treatment causes a reduction in the melt viscosity of the propylene-alpha-olefin polymer.

Reaction conditions preferably include from about 0.005% by weight to about 10% by weight of the free radical initiator, or even from about 0.01% by weight to about 5% by weight of the free radical initiator based on the weight of the polymer, functionalized polyethylene, and optional polyfunctional acid being treated, and a temperature of from about 150 ° C to about 250 ° C, or even from about 175 ° C to about 225 ° C. The reaction time can vary from less than one minute to several hours depending on the temperature used and the half-life of the free radical initiator used.

The reaction product can be prepared by using a suitable method that includes, for example, continuous processes and batch processes. The right continuous processes

IMPI

MEXICAN INSTITUTE! '

PROPERTY include, for example, processes using extrLf £ © 5? Ai4 example, single screw, double screw, 1 dé '<ül§óü, of · reciprocating single screw and endless single screw) and processes using serial extrusion techniques. Suitable batch processes include, for example, processes using reaction vessels. Suitable reaction vessels include those made of glass or metal. For example, reactions can be performed in glass flasks, in glass-lined reactors, in steel autoclaves, extruders, Brabender plastometers, and Banbury mixers. Reactions can be performed in the presence of air or under inert gases such as nitrogen. Although it is not required, it is also possible to carry out the treatment in the presence of an inert solvent such as benzene.

Optional wax

The heat melt adhesive composition optionally includes a wax. Classes of useful waxes include, for example, functionalized waxes, non-functionalized waxes, and mixtures thereof. Useful functionalized waxes include, for example, functionalized polyethylene wax (for example, polyethylene maleate wax and oxidized polyethylene wax), functionalized polypropylene wax), polar waxes, functionalized stearamide waxes (for example, hydroxystearamide, N ( 2-hydroxyethyl) -12-hydroxystearamide, Ν, Ν'-ethylene bis 1225

ΙΜΡΙ

INSTITUTO MEXICANO hydroxystearamide, and 12-hydroxy stearic acid (ffit bis stearamide), and combinations thereof., Sacas-ao.

Useful functionalized include, for example, Fischer waxes

Tropsch, polyolefin waxes (for example, polypropylene waxes and polyethylene waxes), stearamide waxes, benzoate ester waxes, animal waxes, plant waxes, paraffin waxes, microcrystalline waxes, metallocene waxes, glycerin monostearate, monostearate sorbitan, and combinations of these.

The optional wax preferably has a melting point of at least about 100 ° C, a viscosity of about 20 cps to about 500 cps at 140 ° C, a density of about 0.90 g / cm3 at about 0.95 g / cm3, and a heat of fusion of at least about 70 J / g, at least about 85 J / g or even at least about 94 J / g. The optional wax can be linear or branched. Useful waxes further include waxes with a softening point greater than about 140 ° C and a viscosity of about

twenty cps at approximately 1,000 cps at 190 ° C.

Commercialized useful functionalized waxes include, for example, AC 597P polypropylene maleate wax and AC 1325 polypropylene maleate wax, both available from Honeywell International Inc.

IMPI

MEXICAN INSTITUTE

Non-functionalized waxes

include linear polyethylene wax • fiPQLENgn M-21… .da, Westlake Chemical Corporation, and linear polyethylene waxes AC-8 and AC-9, both marketed by Honeywell

International (Morristown, New Jersey), and FischerTropsch PX105 wax from Baker Hughes Incorporated (Houston, Texas).

The optional wax, when present in the heat melt adhesive composition, is preferably present in an amount of at least 0.2% by weight, at least 2% by weight, at least about 5% by weight, at least about 10% by weight, not more than about 30% by weight, not more than about 25% by weight, from about 5% by weight to about 15% by weight, or even from about% by weight to about 10% by weight.

Additives

The heat melt adhesive composition optionally includes additional components including, for example, additional waxes, stabilizers, oil (eg, aliphatic naphthenic oil, white oil, and combinations thereof), antioxidants, additional polymers, bonding agents, photoinitiators , plasticizers, adhesion promoters, UV stabilizers, rheology modifiers, biocides, corrosion inhibitors,

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY dehydrating agents, colorants (for example, pigments and dyes),

flame, bis (2,4-di-tertdi-stearyl-3,3'-filler) agents, surfactants, crystallizer retardants, and combinations thereof.

Useful antioxidants include, for example, pentaerythritol tetrakis [3, (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2'-methylene bis (4-methyl-6-tertbutylphenol), phosphites, including , for example, tris- (pnonylphenyl) -phosphite (TNPP) and butylphenyl) 4,4'-diphenylene diphosphonite, thiodipropionate (DSTDP), and combinations thereof. Useful antioxidants were marketed under different trade names including, for example, the IRGANOX trade name series including, for example, hindered phenolic antioxidants IRGANOX 1010, IRGANOX 565, and IRGANOX 1076 and phosphite antioxidant IRGAFOS.

168, all marketed by BASF Corporation (Florham

Park, New Jersey), and ETILO 702 4,4'-methylene bis (2,6-ditert-butylphenol). When present, the adhesive composition preferably includes from about 0.1% by weight to about 2% by weight of antioxidant.

Useful additional polymers include, for example, homopolymers and copolymers, thermoplastic polymers including, eg. ex. polyolefins (eg, polyethylene, polypropylene, metallocene catalyzed polyolefins (eg, propylene-ethylene copolymers), and combinations thereof),

IMPI

MEXICAN INSTITUTE η,. , η. DE LA RROPrEBAU elastomers include, e.g. ex. copolymer »» Elastomeric HisnfeL (eg styrene-butadiene-ootyrGno, · catircTKr · ”isoprene-styrene, styrene-ethylene-butene-styrene, styrene-ethylene-propylene-styrene, block copolymers based on metallocene, and combinations of these) and functionalized versions of these, and combinations of these. Examples of suitable polymers include, for example, EPOLENE C-18 branched polyethylene maleate, EPOLENE C-15 branched polyethylene, and EPOLENE C-10 branched polyethylene, available from Westlake Chemical Corporation (Houston, Texas), and the copolymer of metallocene propylene-ethylene VERSIFY 4200 (Dow Chemical, Midland, Michigan).

The optional polymer, when present in the heat-melt adhesive composition, is preferably present in an amount of not more than about 5% by weight, not more than about% by weight, or even about 1% by weight at about 4% by weight.

Useful tackifiers have a ring and ball softening point of less than about 140 ° C, less than about 130 ° C, or even less than about 100 ° C. Classes of bonding agents eg, hydrocarbon {cycloaliphatic resins, suitable resins include, eg.

aromatic, aliphatic, modified aromatic and mixed aliphatic hydrocarbons,

ΙΝ5ΤΓΠΙΤΌ MUfCAA *)

DE LA FRÓRtiOAO modified aliphatic hydrocarbon resins aTdfflSWicaS ^ -and hydrogenated versions of these; terpenes, teiperius moiitflL'aclOS and hydrogenated versions of these; natural rosins, modified rosins, rosin esters and hydrogenated versions thereof; low molecular weight polylactic acid; and combinations of these. Examples of useful natural and modified rosins include rubber rosin, wood rosin, high oil rosin, distilled rosin, hydrogenated rosin, dimerized rosin, and polymerized rosin. Examples of useful rosin esters include, for example, light wood rosin glycerol esters, hydrogenated rosin glycerol esters, polymerized rosin glycerol esters, modified and natural rosin pentaerythritol esters, including pentaerythritol esters of light wood rosin, hydrogenated rosin pentaerythritol esters, high oil rosin pentaerythritol esters, and phenolic modified pentaerythritol rosin esters. Examples of useful polyterpene resins include polyterpene resins having a softening point, determined by the ASTM E2858T method, of about 10 ° C to about 140 ° C, hydrogenated polyterpene resins and copolymers and terpolymers of natural soils (eg styrene -terpene, alpha-methyl sterene-terpene and vinyl toluene-terpene). Examples of useful aliphatic and cycloaliphatic petroleum hydrocarbon resins include hydrocarbon resins of

ΙΜ

MUK INSTITUTE • É LA MOWi

aliphatic and cycloaliphatic petroleum having approximate ball and ring softening at 10 0,,F 140 ° C (eg, modified and unmodified C5 resins, C9 resins, and CIO resins) and hydrogenated derivatives thereof.

Useful bonding agents are marketed under different trade names including, for example, the ESCOREZ series of trade names from Exxon Mobil Chemical.

Company (Houston, Texas) including ESCOREZ 5400, ESCOREZ 5415, ESCOREZ 5600, ESCOREZ 5615, and ESCOREZ 5690, the series

EASTOTAC for trade names of Eastman Chemical (Kingsport, Tennessee) including EASTOTAC H-100R, EASTOTAC H100L, and EASTOTAC H130W, the WINGTACK series of trade names for Cray Valley HSC (Exton, Pennsylvania) including WINGTACK 86, WINGTACK EXTRA, and WINGTACK 95 and the series

PICCOTAC for trade names of Eastman Chemical Company (Kingsport, Tennessee) including, for example, PICCOTAC

8095.

When an adhesion agent is present in the adhesive composition, the adhesive composition preferably includes not more than about 50% by weight, not more than about 40% by weight, not more than about 30% by weight, not more than about 20% by weight, not more than about 10% by weight, not more than about 5% by weight, at least about 1% by weight, at least about 15% by weight, at least

from about 1 '^ SfFpe' to about 13 '"^ - éR' · a or even from about 1% about 20% by weight, about 30% by weight, about 30% by weight, about 10% by weight of bonding agent.

Useful photoinitiators have the ability to promote free radical polymerization, crosslinking, or both, of the ethylenically unsaturated portion on exposure to radiation of a suitable wavelength and intensity. The photoinitiator can be used alone or in combination with a suitable donor compound or a suitable coinitiator. The photoinitiator and the amount thereof are preferably selected to achieve a uniform reaction conversion, as a function of the thickness of the composition being cured, in addition to a sufficiently high degree of total conversion to achieve the desired initial handling strength ( that is, resistance in green).

Useful photoinitiators include, for example, "diva je alpha-type" photoinitiators including, for example, benzyl dimethyl ketal, benzoin ethers, hydroxy alkyl phenyl ketones, benzoyl cyclohexanol, dialkoxy acetophenones, 1hydrocyclohexyl phenyl ketone, trimethylbenzoyl phosphine oxides, uncle phenyl morpholino ketones and morpholino phenyl amino ketones. photoinitiators by hydrogen abstraction; and combinations of these.

Commercial photoinitiators are available under different commercial-eteeignaoiones including, eg. ex. ketone amino phenyl morpholino

IRGACURE 369, IRGACURE 819 bis (2,4,6-trimethylbenzoyl) -phenylphosphine bis (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) phosphine oxide, IRGACURE CGI 403, benzyl dimethyl ketal IRGACURE 651, and benzoyl cyclohexanol IRGACURE

184, all marketed by BASF Corporation (Florham Park, New Jersey), hydroxy alkyl phenyl ketones DAROCUR 1173, mixture of 2-hydroxy-2-methyl-l-phenylpropan-l-one and 2,4,6-oxide of trimethylbenzoyldiphenylphosphine DAROCUR 4265 50:50, and a mixture of bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine and 2-hydroxy-2-methyl-l-phenylpropan-l-one CGI1700 25:75, sold by Ciba-Geigy Corp. (Ardsley, NY).

When present, the photoinitiator is preferably present in the composition in an amount sufficient to provide the desired photopolymerization rate. The amount will depend, in part, on the light source, the thickness of the layer that will be exposed to radiant energy, and the extinction coefficient of the wavelength photoinitiator. Typically, the photoinitiator component is present in an amount of from about 0.01% by weight to about 5% by weight, more preferably, from about 0.1% by weight to about 1% by weight.

IMPÍ

MEXICAN INSTITUTE »AND INDUSTRIAL PROPERTY

Applications .............. .

The hot melt adhesive composition is useful for bonding different substrates including, eg. Eg, cardboard, coated cardboard, cardboard, fiberboard, virgin or recycled kraft, high or low density kraft, pressed, kraft and pressed treated and coated, and corrugated versions of these, stock of clay-coated pressed cardboard, composites, leather, polymer film (eg, polyolefin, polyester, metallized polymer films, multilayer films, and combinations thereof), fiber substrates (eg, virgin fibers, recycled fibers and combinations thereof), and combinations thereof. Useful compounds include, for example, foil laminated pressing (eg, aluminum foil), which can optionally be laminated to at least one layer of polymer film, film bonded pressing, film bonded kraft (e.g. the polyethylene film), and combinations of these.

The hot melt adhesive composition is useful in forming adhesive bonds for different items including, for example, bags, drawers, cardboard boxes, trays, cases, multi-layer bags, items including accessories (eg, straws attached to the boxes beverage), ream wrapper, cigarettes, (for example,

IMPI

INSTITUT MEXICANO filter paper), filters (for example, fold

filter frames), binding, and, .. £ nhr.i cari An He footwear, and combinations thereof.

The hot melt adhesive composition is further useful in bonding the first substrate, for example, as in the lamination of porous substrates and polymer film, as used in the manufacture of disposable articles including, for example, surgical wipes, surgical aprons, bed sheets, feminine hygiene items, diapers, adult incontinence items, absorbent wipes (for example, for animals (for example, sanitary napkins for pets) and for people (for example, bodies and dead bodies) and a variety of substrates including, for example, porous substrates (for example, non-woven fabrics and perforated films), films (for example, polymer films for example, polyethylene, polypropylene, polyvinylidene chloride, ethylene vinyl acetate, and polyester films), and combinations thereof.

The composition of the heat-melt adhesive can be applied to a substrate in any useful way including, for example, a coating (eg, continuous or discontinuous coating), a film, eg, a continuous or discontinuous film), a pattern (a spray pattern), randomly, and combinations of these, using a suitable application method that

IMPL · ^,

INSTITUTO MEXICANO includes, for example, the covering M^ á'ájsTrÍMm '

spray coating (for example, roo i-act '' »on Oopiral ·, random spray and random fiber (for example, melt blowing process)), foaming, extrusion (for example, application of fine line, microsphere extrusion , single screw extrusion, double screw extrusion), wheel application, non-contact coating, contact coating, photo-etching, engraved laminate, roller coating, transfer coating, screen printing, flexographic and combinations of these.

In some embodiments, the heat melt adhesive composition is radiation curable. The radiation curable heat melt adhesive composition can be cured by using radiation from different sources, including, for example, ultraviolet light (i.e., UV), electron beam, and combinations thereof. The composition of the radiation-curable heat-melting adhesive can be exposed to radiation at any suitable point including, for example, simultaneously with the coating of the composition, after coating the composition (eg, after coating the composition of a first substrate and before contacting the composition with a second substrate), after contacting the composition coated with a substrate, and combinations thereof.

IMPI

MEXICAN INSTITUTE> E THE PROPERTY

The invention will now be described by it1·

following examples. All parts, ratios, percentages, and amounts indicated in the examples are by weight, unless otherwise specified.

EXAMPLES

Test procedures

The test procedures used in the examples include the following. All ratios and percentages are by weight, unless otherwise indicated.

Thermal stability

Thermal conditioning procedure

<td></td><td>A</td><td>to sample</td><td>200 grams</td><td>(g)</td><td>of</td><td>composition</td><td>of</td>

<td>fusion</td><td>by</td><td>heat it</td><td>placed in a</td><td>Cup</td><td>of</td><td>hasty</td><td>of</td>

<td>glass</td><td>and</td><td>maintains</td><td>at 177 ° C (350</td><td>° F)</td><td colspan="2">during periods</td><td>of</td>

hours, 48 hours, 72 hours, and 96 hours.

Gardner Color

A sample is conditioned according to the thermal conditioning procedure and then tested (in the molten state) to determine the Gardner color

IMPI

INSTITUTO MEXICANO 1,,,,,, M LA PROHEDAL) by comparing the color of the sample G ^ rner color standards specified tfñ 'id nuiiua A3TM B—

1544. The comparison is made with a color comparator

Gardner Delta equipped with an illuminator marketed by

Pacific Scientific (Bethesda, Maryland).

Clarity

The procedure is observed to record the particles, the separation indicative of conditioning a sample according to that of thermal conditioning, and then clarity is determined with the naked eye. Be visual observations. The presence of sedimentation of the polymer "seeds", and of phases (eg visible layers) are a lack of homogeneity.

Differential scanning colorimetry (DSC) test method

The glass transition temperature (Tg), the melting temperature (Tm), the heat of fusion (Af) and the crystallization were determined by differential scanning calorimetry according to ASTM E-793-01 titled, “Method standard test for heats of fusion and crystallization by differential scanning calorimetry ”, using the following conditions: heating the sample to 160 ° C, keeping it for 5 minutes at 160 ° C,

IMPI

INSTITUTO MEXICANO cool it quickly to -60 C and then give ° C to 160 ° C at a speed of 10 ° C per minute. The results are recorded in degrees Celsius, Joules per gram and% for Tg and Tm, ΔΗ and crystallinity, respectively.

Viscosity test method

ASTM D-3236 entitled, “Standard Test Method for Apparent Viscosity of Heat-melt Adhesives and Coating Materials,” (1988) using the Brookfield Thermosel Model RVDV 2+ Viscometer and an amount of 27 turns at 20 rotations per minute. The results are recorded in centipoise ("cps").

Molecular weight determination method

Molecular weights (Mn, Mw, and Mz) are determined by a Polymer Labs PL-GPC 220 high-temperature size exclusion chromatograph (ΗΤ-SEC) operating at 160 ° C with 1,2,4-trichlorobenzene ( TCB) as a mobile phase. The system contains three serial PL-gel mixed B columns and is equipped with a refractive index (IR) detector. The SEC operates at a flow rate of 1.0 ml / min with an injection volume of 100 μΐ. All samples

SEC-SEC are prepared at a concentration of 4.0 mg / ml. Molecular weights are calculated based on the MarkHouwink ratio using polystyrene standards

IMPIAS

KNOWN MEXICAN INSTITUTE. For polystyrene the parameters *L$ fé®Í8 '* lioEw3K5? are K = 0.000121 and a = 0.707; For the potipToprlen the Mark-Houwink parameters are K = 0.000190 and = 0.725. The results are recorded in grams per mole (g / mol).

Fiber breakage percentage test method

The fiber breakage percentage is the percentage of the fiber that comprises the area of the adhesive after two substrates, which had previously been joined by the adhesive, are forcibly separated. The fiber breakage percentage is determined as follows. An adhesive composition microsphere measuring 15.24 cm (6 inches) x 0.24 cm (3/32 inches) is applied to a first high performance Inland 100% virgin Newton (57 lb) liner sheet substrate, using a Waldorf junction simulator at the specific application temperature. Two seconds after the adhesive microsphere is applied to the first substrate, the adhesive microsphere contacts the second Inland high performance 20 Newton virgin (57 lb) 100% liner sheet substrate, which is pressed against the adhesive and the first substrate with a pressure of

0.21 Mpa (30 pounds per square inch (psi)) for a period of 2 seconds. The resulting construction is then conditioned as a specific test temperature for at least 24 hours. Construction substrates are separated from each other,

IMPI

MEXICAN INSTITUTE. . ... ,, OE THE RRORIEDAD afterwards, by pulling the two substrates to'Ntw-siepa manually. The surface area of the adhesive composition is observed and the percentage of the surface area of the adhesive composition that is covered by fibers is determined and recorded. A minimum of five samples are prepared and tested for each sample composition.

Hardening time test method

An adhesive composition microsphere measuring 15.24 cm (6 inches) x 0.24 cm (3/32 inches) is applied to a first high performance Inland 100% virgin Newton (57 lb) liner sheet substrate, using a Waldorf junction simulator at the specific application temperature. Two seconds after the adhesive microsphere is applied to the first substrate, the adhesive microsphere contacts the second 57-pound Inland high-performance 100% virgin Newton liner sheet substrate, which is pressed against the adhesive and- the first substrate with a pressure of 0.21 Mpa (30 pounds per square inch (psi)) for a period of 2 seconds. A stopwatch is started while the microsphere is applied to the first substrate. When the stopwatch reaches 5 seconds, the joint that has formed is separated. If the joint results in fiber failure less than 100%, another joint is prepared and separated after 5.5 seconds. In this way, one continues

IMPI

INSTITUTO MEXICANO increasing the time, before pulling the joint, from 0.5 seconds until reaching the time of ^ £ diu ^ o¿iax £ tt & Q ~ - ~ £ J, setting time is the shortest amount of time in which the joint pulled results in fiber failure

100 %. Once the hardening time has been reached, the test is repeated once more to confirm the result. If the joint provides 100% fiber failure within 5 seconds, the hardening time is recorded as no greater than 5 seconds.

Propylene-alpha-olefin copolymers

Polymer 1: 65% by weight of propylene copolymer and 35% by weight of butene with a viscosity of 6500 cps at 190 ° C, a Mn of 2610, a Mw of 39, 100, a Mz of 145, 000, a Mz / Mn of 55.6, and a Mz / Mw of 3.7.

Polymer 2: 65% by weight of propylene copolymer and% by weight of butene with a viscosity of 8,500 cps at

190 ° C, a Mn of 3420, Mw of 45,200, Mz of 154,000, Mz / Mn of 45.0, and an Mz / Mw of 3.4.

Polymer 3: 55% by weight of propylene copolymer and 45% by weight of butene with a viscosity of 8,500 cps at

190 ° C,

Polymer 4: 50% by weight of propylene copolymer and 50% by weight of butene with a viscosity of 8,500 cps at 190 ° C, Mn of 4,390, Mw of 57,600, Mz of 232,000, an index of

IMPIOS

MEXICAN INSTITUTE OF PROPERTY polydispersity of 13.1, a Mz / Mn of 52.8, and fficP'tóz / Mbr ~ tfe 4.0. ~

Polymer 5: 65% by weight of propylene copolymer and 35% by weight with a viscosity of 8,000 cps at 190 ° C, an Mn of 4,880, Mw of 55,600, Mz of 233,000, Mz / Mn of 47.7, and

Mz / Mw of 4.2.

Bases 1 to 8 and 11 to 12

The Bases of Heat Fusion Compositions

one a 8 and 11 a 12 were prepared by treating a propylene-alpha-olefin copolymer and, where indicated, a wax, containing 92% 2,5-dimethyl-2,5di (tertbutylperoxy) hexane (United Initiator Incorporated, Elyria, Ohio) under vacuum by applying a pressure of approximately 98.2 kPa (29 inches of mercury (Hg)) and at a temperature of approximately 175 ° C to approximately 190 ° C for a period of approximately 45 minutes.

The type and amount of polymer, wax, and peroxide were as specified in Table 1.

Mz, Mw, Mn, Mz / Mw and Mz / Mn were determined for bases 1, 2 and 12 and are specified in Table 1.

Base 9

The base of the heat melt composition 9 was prepared by treating 65% by weight of

IMPI

MEXICAN INSTITUTE OF THE 'OFFICE.Propylene copolymer 35% by weight of butane ^' Tea ^

Polymer 1) with 1.5 wt% peroxide 'OTíJeinióó L'U'PRÉSÜL ”101 (United Initiator Incorporated, Elyria, Ohio) in an extruder at a temperature of 204.4 ° C (400 ° F) for a residence time of 90 seconds.

Table

<td>Peroxide (% in weigh)</td><td> 1.7</td><td> 1.7</td><td> 1.7</td><td> 1.7</td><td> 1 -1-·1</td><td> 1.7</td><td> 1.7</td><td> 1.7</td><td> 1.7</td><td> 1.5</td><td>r- rd</td><td> 1.7</td><td> 1-1</td>

<td>Polymer (% in weigh)</td><td>the CO</td><td> 95</td><td> 95</td><td>THE σ</td><td> 95</td><td>THE σ</td><td> 06</td><td> 85</td><td>OR 00</td><td>οοτ</td><td> 100</td><td> 85</td><td> 95</td>

<td>Polymer no.</td><td>rd</td><td>rd</td><td>rd</td><td>rd</td><td>rd</td><td>CM</td><td>CO</td><td></td><td>(Ό</td><td>rd</td><td>CM</td><td>THE</td><td>CM</td>

<td>Shows</td><td>Base 1</td><td>Base 2</td><td>Base 3</td><td>Base 4</td><td>Base 5</td><td>Base 6</td><td>Base 7</td><td>Base 8</td><td>Base 8a</td><td>Base 9</td><td>Base 10</td><td>Base 11</td><td>Base 12</td>

THE

OR r — 1 <0>

JMPI ¡^ Mexican Institute OE LA PROPIEDA · * INDUSTRIAL

Or what

Φ <Ü

LO, —I

Controls 1 to 4

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

.Cal-4 © -Ies Controls 1 to 4 fusion compositions were prepared with Bases 3, 4 and 9 to 10, melt blended with 1.0 wt% antioxidant

IRGAFOS 168, 0.5% by weight of antioxidant IRGANOX 1010 and, optionally, additional components as needed and in the amounts specified in Table 2. The heat melt compositions of Controls 1 to 4 were tested according to the methods of Viscosity test, fiber breakage, hardening time, clarity and Gardner color, and the results are specified in Table 3.

Examples 1 to 18

The heat melt adhesive compositions of Examples 1 to 18 were prepared from Bases 1, 2, 5, 6, 7, 8,

8a, 10, 11 and 12, mixed by fusion with 1.0% by weight of antioxidant IRGAFOS 168, 0.5% by weight of antioxidant

IRGANOX 1010 and, optionally, additional components (eg, wax and polymer) in the amounts (% by weight) specified in Table 2. The heat melt adhesive composition of Examples 1 to 14 were tested according to Viscosity, fiber break, and cure time test methods and results are specified in Table 3. Initial clarity and clarity observed after 48

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MEXICAN INSTITUTE hours and 96 hours at 177 ° C (350 ° F) also be me! Wn

Table 3. __

Table

FT = fiber break lD

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Example 19

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MEXICAN INSTITUTE OF INDUSTRIAL RHOTIEDAO

An Hp .fusion pnr adhesive composition was prepared.

radiation curable heat by treating a composition that included 70.85 wt% propylene copolymer 65 wt% and 35 wt% butene-propylene alpha-olefin with a viscosity of 6,500 cps at 190 ° C, 4.48% in weight of linear low density polyethylene maleate wax ACX 1783, 3.00% by weight adipic acid, and 0.45% by weight of antioxidant IRGANOX 1010 with 1.0% by weight of organic peroxide LÜPEROX 101 under vacuum when applying a pressure of approximately 98.2 kPa (29 inches of mercury (Hg)) and at a temperature of approximately 175 ° C to approximately 190 ° C for a period of approximately 45 minutes. Then, the product resulting from the reaction was combined with 3% by weight of IRGACURE 18 4, 10.00% by weight of bonding agent EASTOTAC H-100E, 8.52% by weight of polyethylene wax N21, 1.20% by weight of polypropylene maleate

AC596, and 0.50% by weight of antioxidant IRGANOX 1010.

The composition was then exposed to UV radiation having a wavelength of 280nm to 360nm. The resulting composition was determined to have a Mw of 27,100 g / mol, a Mn of 3,360, and a Mz of 64,500, and had a tensile strength of 1392.7 kPa (202 psi) and 40% elongation.

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All patents present description are described.

Other modalities

MEXICAN INSTITUTE and references merfe'fá ^^ s

incorporate an .... .....— picasent »e.

are covered by the claims.

Contents63

10 members in 6 offices

This recordMember, by publication datePriority claim

Priority claims7

Priority claims
Document	Office	Kind	Date
201161501585	United States of America	P	2011-06-27
61501585	United States of America	–	2011-06-27
2012043585	United States of America	W	2012-06-21
61501585	–	–	–
PCTUS2012043585	–	–	–
US201161501585P	–	–	–
WO2012US43585	–	–	–

Members10

Family members, oldest first
Document	Office	Kind
US2012329929A1	United States of America	A1	2012-12-27
WO2013003197A1	World Intellectual Property Organization (WIPO)	A1	2013-01-03
CN103649258A	China	A	2014-03-19
MX2013015169A	Mexico	A	2014-03-31
EP2723825A1	European Patent Office (EPO)	A1	2014-04-30
US8765851B2	United States of America	B2	2014-07-01
EP2723825B1	European Patent Office (EPO)	B1	2015-08-26
MX339901BThis record	Mexico	B	2016-06-16
CN103649258B	China	B	2016-07-06
BR112013033143A2	Brazil	A2	2017-01-24

Abstract

Term

PATENT TITLE NO. 339901

AHMED; TIMOTHY W. ROSKA

US

REQUEST

PRIORITY

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INDUSTRIAL

FREE RADICALS INITIATOR INCLUDING THE POLYMER OF

PROPYLENE-ALPHA-OLEPHINE AND FUNCTIONALIZED POLYETHYLENE

CROSS REFERENCE TO RELATED REQUESTS

BACKGROUND

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MEXICAN INSTITUTE OF PROPERTY

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

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MEXICAN INSTITUTE

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EROFIEDAU MEXICAN INSTITUTE

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GLOSSARY

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MEXICAN INSTITUTE OF THE FROFIF.LMD. , INDUSTRIAL

MEXICAN INSTITUTE OF FROFIEDAD

INDUSTRIAL

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MEXICAN INSTITUTE

IS

MEXICAN INSTITUTE OF PROPERTY

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MEXICAN INSTITUTE OF INDUSTRIAL PRORIITY

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MEXICAN INSTITUTE

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EXAMPLES

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THE

LO, —I

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

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OR

OR

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

THE

OR

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MEXICAN INSTITUTE OF INDUSTRIAL RHOTIEDAO

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Priority claims7

Members10

Events

Numbers

Titles3

Classification