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    • 专利摘要:
    hot melt adhesive an adhesive for use on porous substrates, wherein the hot melt adhesive has a) about 10% to about 70% > by weight of a polypropylene homopolymer having a dsc melting point of less than 100°C, b) about 10% to about 60% of a first tackifier resin having a ring & ball softening point of about 95°C to about 140°C; c) about 0% to about 65% of a second tackifier resin which is different than the first tackifier resin; d) about 5% to about 50% of a plasticizer; e) about 1% to about 40% by weight of a secondary polymer which is either a semicrystalline polymer or a wax with an enthalpy of melting greater than 30 joules/gram; f) about 0.1% to about 5% of a stabilizer or antioxidant; wherein the components total 100% by weight of the composition and the viscosity of the composition is equal to or less than about 20,000 centipoise (cp) at 163°c (325°f).
    公开号:BR112015029180B1
    申请号:R112015029180-5
    申请日:2014-05-21
    公开日:2021-09-08
    发明作者:Richard Hamann；Lianne Rachow
    申请人:Bostik, Inc；
    IPC主号:
    专利说明:

    FOR USE ON POROUS SUBSTRATES" DESCRIPTIVE REPORT FUNDAMENTALS OF THE INVENTION
    [001] The present invention relates to hot melt adhesives, and more particularly to a hot melt adhesive using low molecular weight, low modulus polypropylene polymers. This adhesive gives high initial bond strength despite the long crystallization time of the polypropylene polymer.
    [002] Additives are used in combination with polypropylene polymer to increase adhesive crystallization time and setting speed. This is necessary for applications where high green strength or low throughput bleed is required.
    [003] Hot melt adhesives are used to bond a wide variety of substrates together in a range of industrial processes. Some of these end uses include corrugated box and box sealing, labels for a wide variety of applications, and assembling disposable diapers. For some applications hot melt is a solid, flexible, hard material with no surface added immediately after application of adhesive. An example would be a box sealing application where the product needs to “set” or solidify quickly to hold the box flaps in place seconds after the hot melt application. For other applications, the hot melt needs to have appreciable surface added after it cools down, for example when used as a pressure sensitive tape or label where the adhesive must bond to another substrate at room temperature.
    [004] For some other applications such as diaper constructions, the adhesive is applied to the substrate in a molten state but must immediately build up strength so that it will hold the article together even if there are forces acting on the adhesive bond. A common purpose of use for hot melts is to attach the elastic straps on a diaper in place. The adhesive must be able to resist the contractive force of the elastic straps, since the elastic straps are stretched before being attached to the diaper. Another challenge is to ensure that the adhesive does not leak - even though substrates are in contact with it. Non-woven fabrics are often used in the production of disposable items and care must be used so that the adhesive does not leak - through the non-woven fabric. If this occurs, it can form into rollers or compression sections of the diaper line. Many of the adhesives used to make disposable articles are pressure sensitive in nature since this tends to give the hot melt a wider process window. So a balance must be struck between relatively low viscosity for ease of application, rapid build-up of internal strength to hold substrates together immediately after being applied, and resistance to breakthrough bleed even if the adhesive is soft and/or pressure sensitive.
    [005] Typically hot melt adhesives can be based on polymers such as polyolefins (eg ethylene or propylene based polymers), or functionalized polyolefins (ethylene or propylene copolymers with oxygen-containing monomers), or styrenic block copolymers containing at least one rubber phase, styrene-isoprene type (SIS), or styrene-butadiene-styrene polymers (SBS).
    [006] Styrenic block copolymers are commonly used for diaper construction where non-woven fabrics are frequently used. They tend to be very resistant to cross-bleeding in these materials. This is thought to be due to the speed at which the finished styrene blocks reform after application, which happens very quickly as the hot melt cools. Hot melts that are not based on styrenic block copolymers must cool and recrystallize after application to a few degrees to resist through bleed.
    [007] Over the years, many different olefinic polymers have been used in the formulation of hot melt adhesives used in the construction of disposable soft goods. One type is amorphous polyalpha olefins, also known as APAO. They were first produced using Ziegler-Natta catalysts and can be made using a variety of monomers, including, but not limited to, propylene, ethylene and butene. Many different types of APAO copolymers and terpolymers are produced by a number of manufacturers. They include Evonik, which makes Vestoplast® polymers; REXtac, LLC, which produces range of Rextac® RT and Eastman Chemical materials, makers of the Eastoflex® product line. They are all characterized by having a very low degree of crystallinity as measured by DSC. As commercially produced, they are random polymers having broad molecular weight distributions.
    [008] When formulated in hot melt adhesives for the construction of disposable articles, APAO has some deficiencies due to its amorphous character. While they are useful for diaper construction applications (bonding the nonwoven to polyethylene) they do not have the high temperature creep resistance level required for elastic bonding application. Another shortcoming is that they tend not to spray well using hot melt application equipment.
    [009] Older Ziegler-Natta catalyzed polyolefins such as polyethylene or polypropylene have not been widely used for diaper construction applications. While these polymers are used in hot melt adhesives for packaging applications (eg case and box sealing), they lose the adhesion, open time and sprayability required for disposable article construction applications. Examples of these types of polymers include Epolene® polymers from Westlake Chemical Company, although many other manufacturers produce these types of polyolefin polymers.
    [010] These older types of Ziegler-Natta catalyzed polyolefin polymers typically have very high melting points because of their level of crystallinity. This gives a hot melt that has a very high melting point which in turn means that the adhesive needs to be applied at very high temperatures, eg higher than 160°C or up to 170°C. This is undesirable since many of the substrates used in the non-woven industry are very thin and are very sensitive to high temperatures.
    [011] More recently, polyolefins have been made using metallocene catalysis instead of Ziegler-Natta catalysis. Some of these new polymers have found use in the development of hot melt adhesives. However, they have not found wide use in the manufacture of disposable items since they tend not to spray very well, their application temperature window is narrow and their adhesion to certain substrates has been poor.
    [012] The standard in the disposable industry in terms of spreadability has been hot melt based styrenic block copolymers, particularly styrene-isoprene-styrene (SIS) block copolymers. No olefin-based polymer has been able to match the characteristics of styrenic block copolymers in terms of easy spreadability, performance and application temperature window.
    [013] In recent years, there have been significant changes in the way energy has been produced, particularly in the United States. There has been a tremendous increase in the amount of natural gas that is produced because of the increase in "hydraulic fracturing" or "fracturing". When natural gas is processed, there is a much higher ratio of low molecular weight constituents (C2, C3 and C4) produced versus higher molecular weight materials (C5 and higher). This translates into better availability and lower costs for olefins like polyethylene and polypropylene versus other materials where C5 to C9 monomers are required (eg isoprene, styrene and other aromatic monomers).
    [014] So, a need exists to have a hot melt adhesive that is based on olefins, such as ethylene and propylene, to take advantage of the increased availability of natural gas and other cracking feeds of lower molecular weight, but which has better performance and application characteristics than currently available polyolefin polymers. SUMMARY OF THE INVENTION
    [015] A new type of polyolefin polymer was developed by Idemitsu Petrochemical, Ltd. They are described as their grades L-MODU, which is the abbreviation for Low Molecular Weight Low Modulus Polyolefin. Although they are entirely based on polypropylene, they have properties not normally associated with polypropylene polymers. Conventional polypropylene homopolymers tend to be very high in crystallinity and melting point. This is true whether or not they were prepared using metallocene or Zeigler-Natta catalyst technology. The new L-MODU variants are made using a single metallocene catalyst, which controls the stereoregularity of the polymer. This results in a new type of polymer that imparts properties that were previously unattainable.
    [016] The present invention uses novel L-MODU polymers from Idemitsu as the base polymer(s) in the formulated hot melt adhesive. L-MODU polymer is used at a level of from about 10 percent to about 70 percent by weight. An adhesive resin is also a critical part of the formulation and is present from about 10 percent to about 60 percent by weight. Another essential component is a plasticizer which is used from about 5 percent to about 50 percent by weight. The fourth major component is from about 1 percent to about 40 percent by weight of a secondary additive, such as a wax or semicrystalline polymer that is used to increase the drying rate of the adhesive. Without this component, the adhesive's open time is very long, which causes a weak bond to form initially, and can also cause infiltration if the adhesive is used on a porous substrate, such as a non-woven fabric.
    [017] The present invention solves the important problem of having an olefin-based, sprayable hot melt adhesive using the same application parameters as currently used, such as coating techniques and coupling levels while providing the same expected level of performance with current technologies based on SIS and SBS, (ie high bond strength, creep resistance, deformation strength and heat resistance levels). When formulated in a hot melt adhesive, these polypropylene polymers offer better spray characteristics compared to hot melt adhesives based on APAO or those based on older Ziegler-Natta or metallocene catalyzed generations of polyolefins. In particular, when formulated in combination with a semi-crystalline material, such as a semi-crystalline polymer or wax, a hot melt adhesive can be produced with a unique combination of adhesion, high temperature resistance, sprayability and the bleed resistance of crossing porous substrates. This combination of properties has not previously been achieved in a hot melt without using a styrene block copolymer as the base polymer. Furthermore, compared to conventional SIS-based or SBS-based adhesives, L-MODU polymers offer better viscosity stability when stored at elevated temperatures for extended periods of time (eg 48 hours at 177°C ). DETAILED DESCRIPTION OF THE INVENTION
    [018] A new type of polyolefin has been developed by Idemitsu Petrochemical, Ltd. They have been described as their grades L-MODU, which is short for Low Molecular Weight and Low Modulus Polyolefin. Although they are based entirely on polypropylene, they have properties not normally associated with polypropylene. Conventional polypropylene homopolymers tend to be very high in crystallinity and melting point. This is true whether or not they were prepared using Zeigler-Natta or metallocene catalyst technology. The new L-MODU variants are made using a single metallocene catalyst, which controls the stereoregularity of the polymer. This results in a new type of polymer that imparts properties that were previously unattainable. For example, the melting points of these new polymers are much lower than any other metallocene catalyzed polypropylene homopolymer. Typical polypropylene homopolymers have melting peaks of about 130°C to 170°C when measured by differential scanning calorimetry as in ASTM E794-01. The new L-MODU polymers have Ring and Ball softening points of 130 °C when measured in accordance with ASTM E-28-99. When measured using Differential Scanning Calorimetry (DSC) in accordance with ASTM E-794-01, they have melting points below 100°C and more preferably between 60°C and 90°C.
    [019] The process for making these polymers is described in detail in United States Patent 6,797,774 (assigned to Idemitsui Petrochemical Co., Ltd. of Tokyo, JP), along with various hot melt adhesive formulations. As they have such low melting points and long recrystallization times, special considerations have to be taken into account when processing them using underwater pelletizing equipment. This is described in US Patent 7,776,242 issued to Idemitsui Kosan Co., Ltd. of Tokyo, JP. The disclosures found in US Patent No. 6,797,774 and US Patent No. 7.776,242 are both specifically incorporated into the present application by reference.
    [020] However, it has been found that when L-MODUIdemitsu polymers are used as the only polymer in the hot melt formulation, since they are in the prior art reference to US 6,797,774 mentioned above, the drying speed it is too slow and there is not a high tendency to spread through. We have found that this can be remedied by adding a secondary additive such as a wax or semi-crystalline polymer to increase assembly speed and minimize or eliminate through-bleeding. The secondary additive can simply recrystallize on its own to stop the through-bleeding or it can nucleate the L-MODU polymer to make it crystallize quickly. They can also bloom on the surface to prevent sticking to the substrate.
    [021] Although L-MODU polymers are polypropylene homopolymers, they are very different from traditional polypropylene polymers as mentioned earlier. In addition to having much lower melting points when measured by DSC, their enthalpy of melting values are also much lower than traditional polypropylene grades. When analyzed in accordance with ASTM E793-01 "Standard Test Method for Enthalpies of Melting and Crystallization by Differential Scanning Calorimetry", the following results are obtained. The test was slightly modified to use a scanning temperature of 20°C per minute instead of 10°C per minute.

    [022] Both melt peak and melt enthalpy values are very low compared to most traditional polypropylene-based homopolymers. Typical polypropylene homopolymers have melting points of from about 130°C to 171°C and enthalpy of melting values of about 80 J/g or more. L-MODU polymers have a unique combination of melting point and melting enthalpy. However, to make a hot melt adhesive using these suitable materials as a base polymer requires the use of an additional semi-crystalline polymer as a secondary additive.
    [023] The reason that through bleed is such an important issue is that it can cause significant equipment downtime, defective product, increased scrap level, as well as consumer complaints. If through-bleed bleed builds up on the equipment, on the rollers, for example, it can cause substrates to stick to the rollers, which can result in tearing of the substrates or finished products. This can cause increased reject rates as well as equipment downtime when the production line needs to be stopped for cleaning. When the equipment runs at a thousand feet per minute and produces hundreds of finished articles per minute, any downtime is very costly. If the sticker builds up and is transferred to the finished article and ends up in the consumer's package, this can also lead to customer complaints as well.
    [024] A wide variety of waxes and other semi-crystalline polymers can be used as a secondary additive to provide this function. Typical waxes such as paraffin wax, microcrystalline wax, Fischer-Tropsch wax, or polyethylene or polypropylene waxes can be used. Polyolefin polymers can also be used to provide this function. They are produced in a wide range of molecular weights, monomers, densities and levels of crystallinity. They are also made using an increasing range of catalysts, including Ziegler-Natta, metallocene and other single-site catalysts.
    [025] Polymers in general can vary in crystallinity from very low, such as amorphous polypropylene or amorphous poly-alpha-olefins to those that are very high, such as isotactic polypropylene. The crystallinity of a polymer can be determined by Differential Scanning Calorimetry (DSC) or by X-ray diffraction techniques. DSC is the most widely used technique in the adhesive industry. The enthalpy of fusion (also known as latent heat of fusion or enthalpy of fusion) can be measured and quantified using ASTM E793-01, entitled "Differential Scanning Calorimetry Crystallization and Melting Enthalpies Standard Test Method". The enthalpy of fusion is the amount of energy needed to fuse the crystalline part of the polymer. This value is usually reported in Joules/gram (J/g).
    [026] This number varies widely between almost zero and more than 250 Joules/gram, depending on the crystallinity of the polymer. Theoretically, an amorphous polymer would truly have no crystallinity, no melting point, and hence an enthalpy of melting of zero. As stated in US Patent 7,524,911 issued to Dow Global Technologies (column 8, lines 30-33), “The term 'amorphous' refers to a polymer without a crystalline melting point as determined by differential scanning calorimetry (DSC) or equivalent technique”.
    [027] As a practical matter, most polymers that are sold as “amorphous poly-alpha-olefins” (APAO) have some low level of crystallinity. On the other hand, polymers that are considered crystalline are not 100 percent crystalline. In the Dow 911 patent it is stated at column 8, lines 26-30, “The term 'crystalline' refers to a polymer that has a first order transition or crystalline melting point (Tm) as determined by differential scanning calorimetry (DSC) or technical equivalent and this term may be used interchangeably with the term 'semi-crystalline'”.
    [028] It is useful to have some quantifiable boundary between a polymer that is considered an “amorphous” polymer and those considered “semicrystalline” or “crystalline”. United States Patent 6,747,114 (assigned to ExxonMobil Chemical Patents Inc. of Houston, TX) states at column 8, lines 9-14, "The semicrystalline polymer preferably has a heat of fusion of about 30 J/ g to about 80 J/g, as determined by DSC, preferably more than about 40 J/g to about 70 J/g, as determined by DSC, and most preferably from about 50 J/g to about 65 J/g as determined by DSC”.
    [029] Bostik's own internal analysis correlates with the above descriptions. "Amorphous poly-alpha olefins" are not, in fact, completely amorphous, but have a very low level of crystallinity as measured by DSC. Analysis of many of the grades marketed by Eastman Chemical Co. as “amorphous” polyolefins under the trade name Eastoflex® and those sold by Evonik Industries as “amorphous poly-alpha olefins” under the trade name VESTOPLAST® and those manufactured by REXtac, LLC. like REXtac® RT show that they all have an enthalpy (or heat) of fusion of less than 25 Joules/gram. The single highest value obtained was 20.4 Joules/gram for VESTOPLAST® 708. One of the two types shown in US Patent 7,517,579 (assigned to Kimberly Clark Worldwide, Inc.) is RT2730, which has a heat of fusion of 9.4 Joules/gram. The other category mentioned is RT2723, which according to the normal nomenclature of REXtac should be a lower viscosity version of RT2730 with the same proportions of monomers. Therefore, the enthalpy of fusion should be similar to RT2730. In summary, currently available data strongly indicates that any grade of polymer currently sold as an "amorphous poly-alpha-olefin" would have a melt enthalpy value of less than about 25 Joules/gram.
    [030] A wide range of other polyolefins are produced by a variety of manufacturers that fall under the category of “semi-crystalline polymers”. They have heat fusion values greater than about 30 Joules/gram, which puts them outside the APAO range. For example, ethylene vinyl acetate copolymers in the range of about 35 Joules/gram for a high grade of vinyl acetate (40% vinyl acetate) and about 73 Joules/gram for a lower grade of vinyl acetate ( 18% vinyl acetate). Polyalphaolefins such as Dow's Affinity® grades (metallocene catalyzed ethylene/octene copolymers) range between about 52 Joules/gram for Affinity® 8200, a relatively low grade of density (0.870 g/cc, MI = 5) and 77 J /g for a higher degree of density (0.900 g / cc, MI = 6) called Affinity® PL 1280. Dow also manufactures a high degree of melt index (0.870 g/cc, M 1 = 1000) called GA1900 specifically for adhesives hot melt that has a heat of fusion of 57 Joules/gram. Clearly, these Affinity® polymers could not be considered to be amorphous and are not amorphous poly-alpha-olefins.
    [031] A more recent development in the area of polyolefins is what are referred to as “block copolymers or olefins” OBC. This is an entirely new class of polyolefin polymer produced using a shuttle-chain catalysis technology that produces a linear block structure of the monomers rather than a random polymer produced by traditional metallocene or Ziegler-Natta technology. At this time, they are manufactured by Dow Chemical under the trade name Infuse®. OBC consist of crystallisable (hard) ethylene-octene blocks with a very low comonomer content and high melting temperature alternating with amorphous (soft) ethylene-octene blocks with high comonomer content and low glass transition temperature. This gives the polymer much better high temperature resistance and elasticity compared to a typical metallocene random polymer of similar density. While some of the Infuse® grades have low heat of fusion (about 20 Joules/gram) they could not be considered amorphous poly-alpha-olefins because the polymer architecture is completely different (ie against random block) and it is specifically bred to have crystalline regions.
    [032] For the purposes of the present invention, the L-MODU polypropylene homopolymer is mixed with a secondary additive, such as a wax, or other semi-crystalline polymer, which has a heat of fusion greater than 30 joules per gram, when measured using procedure ASTM E793-01. Additives that are greater than 30 J/g provide the finished adhesive with a short enough open time to minimize infiltration while increasing setting speed and heat resistance.
    [033] Consequently, the present invention provides a hot melt adhesive composition, comprising a mixture of the following components: about 10% to about 70%, preferably about 15% to about 60%, and with greater preferably, about 20% to about 50%, by weight, of a polypropylene homopolymer having a DSC melting point of less than 100°C; about 10% to about 60%, preferably about 15% to about 55%, and more preferably about 20% to about 50%, by weight, of a first adhesive resin having a softening point of at least about 95°C and preferably a softening point of about 95°C to about 140°C; about 0% to about 65% of an adhesive resin which is second different from the first adhesive resin; about 5% to about 50%, preferably about 10% to about 45%, more preferably about from 15% to about 40%, by weight, of a plasticizer; about 0.1% to about 5% of a stabilizer or antioxidant; and about 1% to about 40%, preferably about 2% to about 35%, and more preferably about 2% to about 30%, by weight, of a secondary additive other than polypropylene homopolymer, the former and second adhesive resins and the plasticizer, said secondary additive being a semi-crystalline material with a melting enthalpy greater than 30 Joules/gram, wherein the components total 100% by weight of the composition, and the viscosity (measured by ASTM D3236 -88) of the composition is equal to or less than about 20,000 centipoise (cP) at 163 °C (325 °F), preferably equal to or less than 15,000 cP at 163 °C, and more preferably equal to or less than 12,000 cP at 163°C.
    [034] The hot melt adhesive compositions of the present invention also comprise a solid tackifier that is compatible with the low melting point of polypropylene homopolymer. Representative resins include C5/C9 hydrocarbon resins, synthetic polyterpenes, rosin, rosin esters, natural terpenes, and the like. More particularly, useful tackifying resins include any compatible resins or mixtures thereof such as (1) natural and modified resins which include gum rosin, wood rosin, high oil rosin, distilled rosin, hydrogenated rosin, dimerized rosin and rosin polymerized; (2) glycerol and esters of natural and modified pentaerythritol resins, including pale glycerol ester, wood resin, glycerol ester of hydrogenated rosin, glycerol ester of polymerized rosin, pentaerythritol ester of hydrogenated rosin, and resin phenolic ester modified pentaerythritol; (3) copolymers and terpolymers of natural terpenes, such as styrene/terpene and alpha-methyl-styrene/terpene; (4) polyterpene resins generally resulting from the polymerization of terepene hydrocarbons, such as the bicyclic monoterpene known as pinene, in the presence of Friedel-Crafts catalysts at moderately low temperatures; also included are hydrogenated polyterpene resins; (5) modified phenolic terpene resins and their hydrogenated derivatives such as, for example, as the resin product resulting from the condensation, in acidic medium, of a bicyclic terpene and a phenol; (6) aliphatic petroleum hydrocarbon resins that result from the polymerization of monomers consisting primarily of olefins and diolefins; also included are hydrogenated aliphatic petroleum hydrocarbon resins; and (7) cyclic petroleum hydrocarbon resins and their hydrogenated derivatives. Mixtures of two or more of the adhesive resins described above may be necessary for some formulations. Also included are C5 cyclic or acyclic and modified acyclic aromatic resins or cyclic resins.
    [035] The adhesive resin should have a Ringe Ball softening point (measured according to ASTM E28) of at least about 95 °C and preferably between about 95 °C and about 140 °C and, more preferably, the softening point is between about 95°C and about 130°C. A preferred tackifier is an aromatic modified hydrogenated dicyclopentadiene resin having a Ring and Ball softening point between about 95°C to 130°C. Adhesive resins are most preferred fully hydrogenated resins, regardless of type as aliphatic or cycloaliphatic hydrocarbon resins, such as Eastotac® H100W, or Sukorez® SU210 resins, a pure aromatic monomer resin such as REGALREZ 1094, and dicyclopentadiene (DCPD) resins with non-aromatic content such as Escorez 5400.
    [036] Also, other preferred tackifying resins are partially hydrogenated, such as Eastotac H100L and Eastotac H100R aliphatic hydrocarbons, as well as non-hydrogenated aliphatic C5 resins and aromatic modified C5 resins with low aromaticity, such as Piccotac 1095 and Piccotac 9095, respectively.
    [037] The tackifier resins can be present in amounts of about 10 to 60% by weight of the composition, preferably about 15 to 55% by weight are used, and more preferably about 20 to 50 % by weight. Mixtures of two or more adhesive resins can also be used. For example, a mixture of a first adhesive resin and a second adhesive resin that is different from the first adhesive resin can also be employed. From about 0% to about 65% by weight of one or more adhesive resins can be blended together with the first adhesive resin, if desired.
    [038] The hot melt adhesive formulas according to the present invention also contain about 5% to about 50%, preferably about 10 to about 50%, and more preferably about 15% to about 40% by weight of a plasticizer. A suitable plasticizer can be selected from the group which includes not only the usual plasticizer oils, such as mineral oil, but also olefin oligomers and low molecular weight polymers, glycol benzoates, as well as vegetable and animal oil and derivatives thereof oils. Petroleum oils which can be employed are relatively high boiling temperature materials which contain only a minor proportion of aromatic hydrocarbons. In this regard, aromatic hydrocarbons should preferably be less than 30%, and more particularly less than 15%, by weight of the oil. Alternatively, the oil can be completely non-aromatic. The oligomers can be polypropylene, polybutenes, hydrogenated polyisoprene, hydrogenated butadiene, or the like, having average molecular weights between about 100 and about 10,000 g/mol. Suitable vegetable and animal oils include the glycerol esters of fatty acids and customary polymerization products thereof. Other plasticizers can be used as long as they have adequate compatibility. Nyflex 222B, a naphthenic mineral oil manufactured by Nynas Corporation, has also been found to be a suitable plasticizing agent. As will be appreciated, plasticizers have typically been used to lower the viscosity of the total adhesive composition without substantially lowering the adhesive strength and/or service temperature of the adhesive. The choice of plasticizer can be useful in formulating for specific end uses (such as wet strength core applications). Due to the economics involved in production and material cost, as plasticizers are generally less costly than other materials involved in formulation such as polymers and adhesive resins, the amount of plasticizer in the adhesive must be maximized for cost considerations.
    [039] The adhesive also typically includes about 0.1% to about 5% of a stabilizer or antioxidant. Stabilizers that are useful in the hot melt adhesive compositions of the present invention are incorporated to help protect the aforementioned polymers, and thus the total adhesive system, from the effects of thermal and oxidative degradation, which normally occur during manufacturing and application of the adhesive, as well as the normal exposure of the final product to the surrounding environment. Such degradation is usually manifested by a deterioration in the appearance, physical properties and performance characteristics of the adhesive. A particularly preferred antioxidant is Irganox 1010, a tetrakis-(methylene-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)) methane manufactured by Ciba-Geigy. Among the applicable stabilizers are high molecular weight phenols hindered and multifunctional phenols, such as sulfur and phosphorus containing phenols. Hindered phenols are well known to those skilled in the art and can be characterized as phenolic compounds which also contain sterically bulky radicals in close proximity to the phenolic hydroxyl group thereof. In particular, tertiary butyl groups are generally substituted on the benzene ring in at least one of the ortho positions to the phenolic hydroxyl group. The presence of these bulky sterically substituted radicals in the vicinity of the hydroxyl group serves to retard their elongation frequency and, correspondingly, their reactivity; this steric hindrance thus providing the phenolic compound with its stabilizing properties. Representative hindered phenols include:- 1,3,5-trimethyl-2,4,6-tris(3-5-di-tert-butyl-4-hydroxybenzyl)benzene;- pentaerythritol tetrakis-3(3,5-di- tert-butyl-4-hydroxyphenyl)propionate; - n-octadecyl-3 (3,5-di-tert-butyl-4-hydroxyphenyl)propionate; - 4,4'-methylenebis(4-methyl-6-tert-butylphenol); - 4,4'-thiobis (6-tert-butyl-o-cresol); - 2,6-di-tert-butylphenol; - 6-(4-hydroxyphenoxy)-2,4-bis(n-octylthio)-1,3,5-triazine; - 2,4,6-tris(4-hydroxy-3,5-di-tert-butyl-phenoxy)-1,3,5-triazine; - di-n-octadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate; - 2-(n-octylthio)ethyl-3,5-di-tert-butyl-4-hydroxybenzoate; and - sorbitol hexa-(3,3,5-di-tert-butyl-4-hydroxy-phenyl)propionate.
    [040] The performance of these stabilizers can be further increased through the use, together with such synergistic agents such as, for example, thiodipropionate esters and phosphites.
    [041] The adhesive composition useful in the method of the present invention can be produced using any of the techniques known in the art. A representative example of the procedure involves placing all substances in a jacketed mixing boiler, and preferably in a Baker-Perkins or Day type heavy jacketed mixer, and which is equipped with rotors and subsequently increases the temperature of the mixture present in a range of 120 °C to 177 °C. It should be understood that the exact temperature to be used in this step will depend on the melting point of the particular ingredients. The resulting adhesive composition is agitated until the polymers completely dissolve. A vacuum is then applied to remove any trapped air.
    [042] Up to 25% of the optional ingredients can be incorporated into the adhesive composition in order to modify the particular physical properties. These ingredients can include colorants such as titanium dioxide and fillers such as talc, calcium carbonate and clay, crosslinking agents, reactive mineral compounds, fire retardant or organic agents, as well as ultraviolet (UV) light agents. UV absorption and fluorescent agents. These optional ingredients are well known in the art.
    [043] Polyolefin nucleating agents may also be present in the invention. Nucleating agents accelerate the crystallization of a polyolefin, providing a place for crystals to form. The result is that the polymer not only recrystallises faster, but also more completely, which results in the adhesive having a high Ring & Ball softening point and better heat resistance. The nucleating agent appears to be more effective when there is a secondary semi-crystalline additive present than when it is absent. Nucleating agents suitable for this invention are generally from the subclass of nucleating agents known as clarifying agents which are commonly used in polyolefin additive packages to promote rapid crystallization. Suitable materials include dibenzylidene sorbitol derivatives such as Millad 3988 and Millad NX8000 supplied by Milliken, as well as Irgaclear D produced by BASF. Other suitable agents include aromatic systems such as NJ Star amide NU-100 supplied by New Japan Chemical Company.
    [044] The nucleating agent is generally present in the adhesive compositions in amounts of about 0.05 to 5.0% by weight of the composition, preferably about 0.1 to 2.5% by weight, are used, and more preferably about 0.2 to 1.0% by weight. Mixtures of two or more nucleating agents can also be used. For example, a mixture of a nucleating agent and a second nucleating agent that is different from the first nucleating agent can also be employed. From about 0.05% to about 5.0% by weight of a nucleating agent or more can be mixed together with the first nucleating agent, if desired. The nucleating agent can be used directly as a powder, as a suspension in a part of a suitable plasticizing agent, or as a component of a masterbatch of a suitable polymer, such as Milliken NX-10.
    [045] Various methods are conventionally used for coating a relatively low viscosity hot melt adhesive onto a substrate. This can be done by roller coating or any printing type method, or by slot coating, extrusion or spray gun. Spray spraying techniques are numerous and can be done with or without the aid of compressed air which forms the adhesive spray, and hence the adhesive pattern. The hot melt adhesive material is generally allowed to melt in tanks, and then pumped through hoses to the final coating location on the substrates. EXAMPLES
    [046] Hot melt adhesives were prepared with the ingredients and mixing procedures described herein below. A total of 2000 grams of each were made and mixing was carried out at about 150 °C to 190 °C under carbon dioxide atmosphere in a laboratory type mixer consisting of a propeller driven by a motor, a heating mantle , a temperature control unit and a container about 1 gallon in size. Appropriate amounts of each component, calculated according to the relationships indicated in the following tables, were added to the container in an appropriate sequence to allow for mixing, when limiting the heat of shear or degradation of the ingredients. After the ingredients in the container were completely melted and thoroughly mixed to ensure good homogeneity, the samples were properly stored for testing.
    [047] The base polymer was one of the L-MODU Idemitsu polypropylene homopolymers listed in Table One.
    # DSC softening points were performed by Bostik Analytical Laboratory. The other values were reported by Idemitsu on their website. * MFR = 50 g/10 min per 2.16 kg of L-MODU S901 at 230 °C.
    [048] Formulations were prepared as listed in Patent US6,797,774 as shown in Table 2. The best match of polymer P1 viscosity given in Table 1 of 774, it was determined that a mixture of 1 part L-MODU S600 to 4 parts of L-MODU S400 was required. TABLE TWO (State of the Art)

    [049] The melt viscosity of Example 1, 2 & 3 are shown in Table two of US patent 6,797,774. TABLE THREE (Inventive)

    Raw materials used in Tables
    [050] I-MARV adhesive resins are fully hydrogenated hydrocarbon resins produced by Idemitsu Kosan Co., Ltd. The “P” indicates that the product is completely hydrogenated and the number in the name is the resin's softening point in degrees Celsius.
    [051] Escorez 5400 is a fully hydrogenated hydrocarbon resin with a softening point of 100 °C. It is manufactured by ExxonMobil Chemical Co.
    [052] Sukorez SU-210 is a hydrogenated C5/cyclic hydrocarbon resin with an R&B Softening Point of 110°C. It is available from Kolon Industries of South Korea.
    [053] Piccotac 9095 is a common aromatic modified C5 resin R&B softening point 94°C. It is available from Eastman Chemical Co.
    [054] Eastotac H-100R is a hydrogenated hydrocarbon resin with an R&B Softening Point of 100°C R&B and a Cast Gardner Color of 4. It is available from Eastman Chemical Co.
    [055] P1 is the polymer as described in US patent 6,797,774. Since Bostik cannot polymerize exact polymer, a mixture of commercially available polymers of the same type from Idemitsu was used. The ratio of available types was selected to double the viscosity of polymer P1 as much as possible.
    [056] L-MODU grades were obtained from Idemitsu Co.Japan. The physical properties of these types are shown in Table One.
    [057] Pro-fax RP501V is a high-flow, propylene impact copolymer that contains isotactic polypropylene and an ethylene-propylene rubber phase. It is produced by LyondellBasell Polymers. It has a melt flow of 100 g/10 minutes when measured in accordance with ASTM D-1238 using a weight of 2.16 kg and a test temperature of 230°C. Polymer density is 0.90 g/cc. It has a melting peak of 163 °C and a melting enthalpy of 81.1 Joules/gram when measured by differential scanning calorimetry. The test procedures used are ASTM E793-01 and ASTM E794-01 respectively.
    [058] Pro-fax RP591V is a high flow, random polypropylene copolymer produced by LyondellBasell Polymers. It has a melt flow of 100 g/10 minutes when measured in accordance with ASTM D-1238 using a weight of 2.16 kg and a test temperature of 230°C. The polymer density is 0.90 g/cc. It has a melting peak of 142 °C and a melting enthalpy of 74.0 Joules/gram when measured by differential scanning calorimetry. The test procedures used are ASTM E793-01 and ASTM E794-01 respectively.
    [059] 104N is a low molecular weight, high density polyethylene wax produced by Hana Corporation. It has a DSC melting peak of 118°C, a melting enthalpy of 185 Joules/gram, a viscosity of 330 centipoise at 140°C, and a density of 0.93 grams/cm at room temperature.
    [060] 150 MP Paraffin Wax is a 66 °C (150 °F) softening point paraffin wax, available from a number of suppliers. The enthalpy of fusion is 187 Joules/gram as measured by DSC.
    [061] AC-1089 is a polypropylene homopolymer wax sold by Honeywell International Inc. It has a Ring & Ball Softening Point of 146°C, a viscosity of 45 centipoise at 190°C, and a density of 0.91 grams /cm at room temperature.
    [062] L-Crysta 7000 is a semi-crystalline polyolefin with a DSC melting point of 75°C and a melting enthalpy of 131 Joules/gram as measured by DSC. It is manufactured by Idemitsu Kosan Co. of Japan.
    [063] Kraton G-1657 is a styrene-ethylene/butylene-styrene block copolymer sold by Kraton Polymers. It has a styrene content of 13%, contains 30% diblock and has a solution viscosity (20% in toluene) of 1200 to 1800 centipoises at 25 °C.
    [064] Paraffinic Process Oil is Diana Process Oil PW-90 manufactured by Idemitsu Kosan Co., Ltd. of Japan.
    [065] Nyflex 222B is a severely hydrogen treated naphthenic process oil available from Nynas Corporation.
    [066] Irganox 1010 is a hindered phenol-type antioxidant. It is commercially available from Ciba Specialty Chemicals of Tarrytown, New York. Crossing Bleeding Studies Conducted on Nonwoven Fabrics
    [067] Several of the prior art blends shown in Table Two, and all of the inventive blends of Table Three, were used to coat a nonwoven fabric to determine its through-bleed level at various temperatures. Blends 1A, 2A and 3A (prior art), as well as blends A, B, C, D, E and F (inventive), were run to see how these variables effect their ability to resist infiltration of a non-woven material pattern.
    [068] The products were coated using an Acumeter LH-1 using a spiral spray adapter to apply the adhesive between a non-woven fabric and a polyethylene film. Adhesives were applied at a complement of 16.3 grams per square meter (gsm) level to the non-woven and after an opening time of 0.2 seconds were combined to the polyethylene film using steel to steel pinch rollers using a consistent amount of compression. Since different adhesive application temperatures were used, the heated air used to spray the hot melt was also varied and was maintained at 50°F greater than the adhesive temperature for a given test. The non-woven fabric was a Fibertex 17 gsm SMS (woven fabric/porous fabric/woven fabric) non-woven fabric. The film was a 19 gsm embossed polyethylene film designated BR 134 and was obtained from Clopay Plastic Products Co. As the adhesive was applied to make the non-woven film/laminate, the amount of bleed through was observed along with the degree of adhesive build-up on the steel roll. After the roll of laminate was produced, the amount of blocking and adhesion that occurred when the roll was unrolled was also checked. If the adhesive leaks through the non-woven fabric, it will stick with the polyethylene layer adjacent to it on the laminate roll. TABLE FOUR (State of the Art)

    [069] The throughput bleed levels in the three prior art products (1A, 2A and 3A) of US 6,797,774 have opposed these to being run in a commercial setting without significant amounts of downtime and scrap rates. FIVE (Inventive) Non-Woven Fabric Crossing Bleeding Assessments

    [070] All of the examples in Table Five showed much improved through-bleed resistance in the non-woven fabric against prior art products without secondary polymer or wax to promote crystallization. Note: “Very Mild” in Table Five means “Very Mild”. So, not only where effective inventive formulations for bonding a film and non-woven substrate into a laminate, but they did it without any significant through-bleeding of the non-woven substrate.
    [071] The method used to determine density is ASTM D-792-00. The method for determining Melt Index and Melt Flow Rates is ASTM D-1238-04. The reported molecular weight is the weight average molecular weight and is determined in accordance with ASTM D-6474-99.
    [072] The following Tables Six, Seven and Eight illustrate additional inventive compositions (Examples 1-17) and compare them to three different mixtures (Comp.1, Comp.2, and Comp.3). Comparative examples 1-3 do not contain the low melting polypropylene homopolymer, or a combination of the low melting polypropylene homopolymer with another semi-crystalline polymer, and are therefore extremely soft as measured by a needle penetrometer. Compositions having a needle penetrometer of about 85 dmm or greater, preferably about 90 dmm or greater, are considered soft. TABLE SIX Additional Blends Using Low Melting Polypropylene Homopolymers


    TABLE SEVEN

    TABLE EIGHT

    权利要求:
    Claims (15)
    [0001]
    1. Hot Melt Adhesive For Use On Porous Substrates, characterized in that the hot melt adhesive comprises: a) 10% to 70% by weight of a polypropylene homopolymer having a DSC melting point of less than 100°C;b ) 10% to 60% of a first tackifier resin having a Ring & Ball Softening Point of 95°C to 140°C; c) 0% to 65% of a second tackifier resin which is different than the first tackifier resin d) 5% to 50% of a plasticizer; e) 2% to 35% by weight of a secondary additive which is different from the polypropylene homopolymer, the first and second tackifier resins and the plasticizer, said secondary additive being selected from the group consisting of waxes with a melting enthalpy greater than 30 Joules/gram and semi-crystalline polymers with a melting enthalpy greater than 65 Joules/gram, wherein semi-crystalline polymers are selected from the group which consists of a polypropylene impact copolymer and a polypropylene impact copolymer. ipropylene; f) optionally 0.1% to 5% of a stabilizer or antioxidant; wherein the components total 100% by weight of the composition and the viscosity of the composition is equal to or less than 20,000 centipoise (cP) at 163°C ( 325°F).
    [0002]
    2. Hot Melt Adhesive For Use On Porous Substrates, according to Claim 1, characterized in that it comprises 2% to 35% by weight of a secondary additive which is different from polypropylene homopolymer, the first and second tackifier resins and the plasticizer, said secondary additive being selected from the group consisting of waxes with a melting enthalpy greater than 30 Joules/gram.
    [0003]
    3. Hot Melt Adhesive For Use On Porous Substrates, according to Claim 1, characterized in that it comprises semi-crystalline polymers with a melting enthalpy greater than 65 Joules/gram, wherein the semi-crystalline polymers are selected from from the group consisting of a polypropylene impact copolymer and a polypropylene copolymer.
    [0004]
    4. Hot Melt Adhesive For Use On Porous Substrates, according to Claim 1, characterized in that the viscosity of the composition is equal to or less than 15,000 cP at 163°C, advantageously equal to or less than 12,000 cP at 163° Ç.
    [0005]
    5. Hot Melt Adhesive For Use On Porous Substrates, according to Claim 1, characterized in that the polypropylene homopolymer has a DSC melting point of between 60°C and 90°C.
    [0006]
    Hot Melt Adhesive For Use On Porous Substrates, according to Claim 1, characterized in that the composition comprises 15% to 60%, advantageously 20% to 50% by weight of the polypropylene homopolymer.
    [0007]
    Hot Melt Adhesive For Use On Porous Substrates, according to Claim 1, characterized in that the composition comprises 15% to 55%, advantageously 20% to 50% by weight of the first tackifier resin.
    [0008]
    8. Hot Melt Adhesive For Use On Porous Substrates, according to Claim 1, characterized in that the first tackifying resin has a Ring and Ball softening point of 95°C to 130°C.
    [0009]
    9. Hot Melt Adhesive For Use On Porous Substrates, according to Claim 1, characterized in that the first tackifying resin is selected from the group consisting of (1) natural and modified resins including gum resin, resin. wood, liquid resin, distilled resin, hydrogenated resin, dimerized resin and polymerized resin; (2) glycerol and pentaerythritol esters of natural and modified resins, including glycerol ester of pale wood rosin, glycerol ester of hydrogenated rosin, glycerol ester of polymerized rosin, pentaerythritol ester of hydrogenated rosin, and phenolic-modified pentaerythritol resin ester; (3) copolymers and terpolymers of natural terpenes, such as styrene/terpene and alpha methyl styrene/terpene; (4) polyterpene resins resulting from the polymerization of terpene hydrocarbons, such as bicyclic monoterpene known as pinene, in the presence of Friedel-Crafts catalysts at moderately low temperatures as well as hydrogenated polyterpene resins; (5) phenolic-modified terpene resins and hydrogenated derivatives thereof; (6) aliphatic petroleum hydrocarbon resins resulting from the polymerization of monomers consisting primarily of olefins and diolefins as well as hydrogenated aliphatic petroleum hydrocarbon resins; (7) cyclic petroleum hydrocarbon resins and the hydrogenated derivatives thereof; and (8) blends of two or more of the above-described resins.
    [0010]
    10. Hot Melt Adhesive For Use On Porous Substrates, according to Claim 1, characterized in that the second tackifying resin is selected from the group consisting of (1) natural and modified resins including gum resin, resin. wood, liquid resin, distilled resin, hydrogenated resin, dimerized resin and polymerized resin; (2) glycerol and pentaerythritol esters of natural and modified resins, including glycerol ester of pale wood rosin, glycerol ester of hydrogenated rosin, glycerol ester of polymerized rosin, pentaerythritol ester of hydrogenated rosin, and phenolic-modified pentaerythritol resin ester; (3) copolymers and terpolymers of natural terpenes, such as styrene/terpene and alpha methyl styrene/terpene; (4) polyterpene resins resulting from the polymerization of deterpene hydrocarbons, such as bicyclic monoterpene known as pinene, in the presence of Friedel-Crafts catalysts at moderately low temperatures as well as hydrogenated polyterpene resins; (5) phenolic-modified terpene resins and hydrogenated derivatives thereof; (6) aliphatic petroleum hydrocarbon resins resulting from the polymerization of monomers consisting primarily of olefins and diolefins as well as hydrogenated aliphatic petroleum hydrocarbon resins; (7) cyclic petroleum hydrocarbon resins and the hydrogenated derivatives thereof; and (8) blends of two or more of the above-described resins.
    [0011]
    Hot Melt Adhesive For Use On Porous Substrates, according to Claim 1, characterized in that the composition comprises 10% to 45%, 15% to 40% by weight of the plasticizer.
    [0012]
    12. Hot Melt Adhesive For Use On Porous Substrates, according to Claim 1, characterized in that the plasticizer is selected from the group consisting of mineral oil and polybutene.
    [0013]
    Hot Melt Adhesive For Use On Porous Substrates, according to Claim 1, characterized in that the composition comprises 2% to 30% by weight of the secondary additive.
    [0014]
    14. Hot Melt Adhesive For Use On Porous Substrates, according to Claim 1, characterized in that the secondary additive is a semi-crystalline polymer with a melting heat of 65 Joules/gram to 80 Joules/gram, advantageously of 65 Joules/gram gram at 70 Joules/gram.
    [0015]
    Hot Melt Adhesive For Use On Porous Substrates, according to Claim 1, characterized in that the composition further comprises 0.05% to 5.0% by weight of a nucleating agent, said nucleating agent advantageously selected from the group consisting of dibenzylidene sorbitol derivatives and aromatic amides.
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    WO2014190098A1|2014-11-27|
    BR112015029180A2|2017-07-25|
    JP6618895B2|2019-12-11|
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    法律状态:
    2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-11-05| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-07-20| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    2021-08-10| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-09-08| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/05/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201361855775P| true| 2013-05-23|2013-05-23|
    US61/855,775|2013-05-23|
    PCT/US2014/039041|WO2014190098A1|2013-05-23|2014-05-21|Hot melt adhesive based on low melting point polypropylene homopolymers|
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