Polyolefin-based hot melt adhesive composition

Abstract

In this disclosure, (A) A copolymer of butene-1 having a copolymer comonomer content of 0.5 to 8.0% by weight and a melt flow rate of 200 g / 10 min or more (MFR(A) ISO 1133:2011, 190°C / 2.16 kg), and at least one comonomer selected from ethylene, propylene, C5-C10α-olefins, and combinations thereof, in a copolymer of 25% to 50% by weight. (B) 30-60% by weight of tackifier, (C) Contains 5-30% by weight of polypropylene wax, Here, the amounts of (A), (B), and (C) are based on the total weight of (A) + (B) + (C), providing a hot melt adhesive composition. Articles containing the HMA composition are also provided.

Description

[Technical Field]

[0001] This disclosure relates to polyolefin-based hot melt adhesive (HMA) compositions, and more particularly to HMA compositions comprising high melt-flow polybutene-1, a tackifier, and a specific type of wax, namely a polypropylene-based wax. [Background technology]

[0002] Hot-melt plastic adhesives are a type of thermoplastic adhesive that is applied in a molten state and solidifies upon cooling. Due to their rapid hardening, ease of use, and strong bonding ability, they are widely used for numerous applications in various industries, such as packaging, woodworking, product assembly, crafts, and textiles.

[0003] For example, hot-melt adhesive compositions containing highly fluid butene-1 homopolymers or copolymers are well known in the art from European Patent Application No. EP671431 (Himont Inc.) or EP314495 (Shell Oil Company). These references disclose butene-1 polymers that have been bis-break treated with peroxides to achieve low viscosity values. However, peroxide decomposition is known to result in several drawbacks, such as an unpleasant odor and a high yellowness index, which may prevent the use of peroxide-decomposed compositions in some art applications, such as food packaging.

[0004] High-fluidity polybutene-1 immediately after the reactor (untreated) is also known to be suitable for use in hot-melt adhesive compositions.

[0005] US2008190541A1 discloses a hot-melt adhesive composition containing at least two butene-1 copolymers derived from a metallocene catalyst, wherein the copolymers have different melt flow indices. Low-melt index components are essential for achieving a balance in the properties of the hot-melt adhesive.

[0006] Butene-1 copolymers having an MFR in the range of 200 to 1500 g / 10 min, suitable for use in HMA compositions, are known from international patent application WO2015 / 074830A1. International patent application WO2020 / 016143A1 discloses an HMA composition combining polybutene-1 having an MFR of 200 to 1500 g / 10 min with a tackifier and Fischer-Tropsch wax. These compositions are known to exhibit a good compromise between rheological and thermal properties.

[0007] In this context, polyolefin-based hot-melt adhesives that offer a good balance between adhesive and mechanical properties are still considered necessary. [Overview of the project]

[0008] This disclosure is, (A) By the method described in the Examples section, the total copolymer comonomer content is measured by IR spectroscopy and has a melt flow rate MFR(A) of 200 g / 10 min or more, measured according to ISO 1133-1:2011 (190°C, 2.16 kg), and the copolymer is 25% to 50% by weight of butene-1 and at least one comonomer selected from ethylene, propylene, C5-C10α-olefins, and combinations thereof. (B) 30% to 60% by weight of a tackifier, (C) Contains 5-30% by weight of polypropylene wax, Here, the amounts of (A), (B), and (C) are based on the total weight of (A) + (B) + (C) for a hot melt adhesive composition.

[0009] The polyolefin-based hot melt adhesives of this disclosure are endowed with a good balance of properties, including good mechanical properties, SAFT, open time and set time, and softening properties, as indicated by the ring-and-ball test values.

[0010] In a further embodiment, the present disclosure relates to an article comprising a first substrate and a second substrate, wherein the first substrate is bonded to the second substrate by a hot-melt adhesive composition of the present disclosure sandwiched between the first substrate and the second substrate.

[0011] While several embodiments are disclosed, further embodiments will become apparent to those skilled in the art from the following detailed description. As will be apparent, the specific embodiments disclosed herein can be modified in various obvious aspects without departing from the spirit and scope of the claims presented herein. Therefore, the following detailed description should be considered as illustrative and not limiting in nature. [Modes for carrying out the invention]

[0012] In the context of this disclosure, Percentages are expressed by weight unless otherwise specified.

[0013] Unless otherwise specified, the total weight of the polymer composition is 100% by weight.

[0014] The term “contains” when referring to a polymer, or a polymer composition, mixture, or blend should be interpreted as “contains, or essentially consists of.”

[0015] The term "essentially composed" means that, in addition to the essential components, other components may be present in the material as long as their presence does not substantially affect the essential properties of the material. Examples of components that, when present in normal amounts, do not substantially affect the properties of the polymer or polyolefin composition, mixture, or blend include catalyst residues, antistatic agents, and processing aids.

[0016] The term "copolymer" refers to a polymer obtained from the intentional polymerization of at least two different comonomers; in other words, the term "copolymer" includes terpolymers.

[0017] The term "film" refers to a thin layer of material having a thickness of 2,000 micrometers or less.

[0018] The term "sheet" refers to a layer of material having a thickness exceeding 2,000 micrometers.

[0019] Accordingly, the object of the present disclosure is: (A) 25 wt% to 50 wt% of a copolymer of butene-1 and at least one comonomer selected from ethylene, propylene, C5-C10 α-olefins, and combinations thereof, wherein the copolymer has a copolymerized comonomer content of 0.5 wt% to 8.0 wt%, and a melt flow rate MFR (A) of 200 g / 10 min or more as measured in accordance with ISO 1133-1:2011 (190°C, 2.16 kg); (B) 30 wt% to 60 wt% of a tackifier; and (C) 5 wt% to 30 wt%, preferably 15 wt% to 30 wt% of polypropylene wax, wherein the amounts of (A), (B) and (C) are based on the total weight of (A)+(B)+(C), which relates to a hot melt adhesive composition.

[0020] The individual components (A), (B) and (C) of the HMA composition are defined in further detail below. The individual components may be included in the HMA composition in any combination.

[0021] Preferably, the butene-1 copolymer (A) has a melt flow rate MFR (A) of from 200 to 3,000 g / 10 min, more preferably from 400 to 1,700 g / 10 min, still more preferably from 500 to 1,600 g / 10 min, as measured in accordance with ISO 1133-1:2011 (190°C / 2.16 kg).

[0022] Preferably, the butene-1 copolymer (A) has a (total) copolymerized comonomer content of from 0.7 wt% to 7.0 wt%, based on the total weight of the butene-1 copolymer (A).

[0023] Butene-1 copolymer (A) preferably contains a comonomer selected from ethylene, propylene, hexene-1, octene-1, and combinations thereof, with ethylene being particularly preferred.

[0024] In a preferred embodiment, butene-1 copolymer (A) is Based on the weight of the fraction (A1) of butene-1 homopolymer, or a fraction (A1) of comonomers selected from ethylene, propylene, C5-C10α-olefins, and combinations thereof, a fraction (A1) containing less than 3% by weight of butene-1 copolymer, The fraction (A2) comprises, based on the weight of a fraction (A2) of comonomers selected from ethylene, propylene, C5-C10α-olefins, and combinations thereof, a fraction (A2) containing a copolymer of butene-1 in an amount of 3% to 10% by weight. Here, butene-1 copolymer (A) is The total copolymerization comonomer content is 0.5% to 8.0% by weight, preferably 0.7% to 7.0% by weight, based on the total weight of fractions (A1) and (A2); According to ISO 1133-1:2011 (190°C, 2.16 kg), the melt flow rate MFR(I) is 200 g / 10 min or higher; and Based on the total weight of fractions (A1) and (A2), and measured by the method described in the Examples section, the content of xylene-soluble fractions is 80% by weight or less, preferably in the range of 20% to 80% by weight, at 0°C. Here, the comonomer content is measured by IR spectroscopy using the method described in the Examples section.

[0025] Butene-1 copolymer (A) preferably contains fraction (A1) of 15% to 70% by weight, particularly 20% to 65% by weight, and fraction (A2) of 30% to 85% by weight, particularly 35% to 80% by weight, where the amounts of fractions (A1) and (A) are based on the total weight of fractions (A1) and (A2).

[0026] Preferably, the comonomer optionally contained in the butene-1 copolymer fraction (A1) and the butene-1 copolymer fraction (A2) is ethylene.

[0027] Butene-1 copolymer (A) preferably has at least one, more preferably all, of the following additional features: (a) A molecular weight distribution (Mw / Mn) less than 4, preferably less than 3, more preferably less than 2.5 (in all cases, the lower limit is 1.5, and the molecular weight distribution is measured by NMR by the method described in the Examples chapter); and / or (b) Having one or more melt peaks Tm(II) at a temperature of 110°C or lower, preferably 105°C or lower, more preferably in the range of 80°C to 103°C, where Tm(II) is measured by DSC by the method described in the Examples chapter; and / or (c) Glass transition temperature (Tg) in the range of -40°C to -10°C, preferably -30°C to -10°C (where Tg is measured by DSC by the method described in the Examples chapter); and / or (d) Brookfield viscosity of 15,000 mPa·s at 190°C, preferably in the range of 3,000 to 15,000 mPa·s; and / or (e) X-ray crystallinity in the range of 20-60%, preferably in the range of 25-50%; (f) 0.89~0.91 g / cm³ 3 The density of the range; and / or (g) Yellowness index less than 0, especially in the range of -1 to -5.

[0028] In one embodiment, butene-1 copolymer (A) may have all of the features (a) to (g).

[0029] Butene-1 copolymer (A) can be obtained by copolymerizing butene-1 and a comonomer in the presence of a catalytic system that can be obtained by contacting the following: Stereolithic metallocene compounds, Compounds capable of forming aluminoxane or alkylmetallocene cations, and optionally Organic aluminum compounds.

[0030] Patent applications WO2004 / 099269, WO2006 / 045687, WO2015 / 074830, WO2018 / 007279, and WO2022 / 0084081, which are incorporated herein by reference, describe processes and catalyst systems suitable for producing butene-1 copolymer (A).

[0031] Butene-1 copolymer (A) can be obtained by a polymerization process carried out in one or more reactors connected in series. In the latter case, the catalyst may be added to the first reactor only, or to multiple reactors. As described in WO2004 / 099269, the polymerization process may be carried out in the liquid phase, optionally in the presence of an inert hydrocarbon solvent, or in the gas phase, using a fluidized bed or a mechanically agitated gas-phase reactor. Preferably, the polymerization process is carried out using liquid butene-1 as the polymerization medium. The polymerization temperature range is typically 20°C to 150°C, preferably 50°C to 90°C, and more preferably 65°C to 82°C.

[0032] As described in WO2006 / 045687, the molecular weight of the butene-1 copolymer can be controlled by advantageously utilizing hydrogen. The hydrogen concentration during the polymerization reaction carried out in the liquid phase is greater than 1,800 mol ppm and less than 6,000 mol ppm, preferably in the range of 2,000 mol ppm to 6,000 mol ppm.

[0033] Butene-1 copolymers with low melting points can be obtained by appropriately selecting the copolymerized comonomer content, particularly the ethylene content. Therefore, butene-1 copolymer (A) can be obtained in a polymerization process in which the amount of comonomer, particularly ethylene, in the liquid phase is in the range of 0.1% to 8% by weight, preferably 0.2% to 6% by weight, relative to the total weight of butene-1 monomer present in the polymerization reactor.

[0034] If the butene-1 copolymer (A) is a butene-1 copolymer composition (I) comprising components (A1) and (A2), the butene-1 copolymer composition (I) is obtained by melt-mixing components (A1) and (A2) in appropriate amounts. Alternatively, and preferably, the butene-1 copolymer composition (I) is obtained by a polymerization process comprising at least two polymerization steps carried out in at least two reactors connected in series. If component (A1) is a copolymer, with respect to the preparation of component (A1), the amount of comonomer in the liquid phase may be in the range of 0% to 1.2% by weight, while with respect to the preparation of component (A2), the amount of comonomer in the liquid phase of the second step may be in the range of 1% to 10% by weight.

[0035] The hot-melt adhesive composition of this disclosure comprises at least one tackifier (B). The tackifier (B) is preferably solid at a temperature of 25°C ± 1°C.

[0036] The tackifier (B) is preferably selected from hydrogenated hydrocarbon resins and their derivatives, such as aliphatic hydrocarbon resins, aromatic hydrocarbon resins, and aliphatic / aromatic hydrocarbon resins; terpene-derived resins, such as polyterpenes and terpene / phenol resins; natural resins and natural resin esters, such as rosin, rosin esters, and tall oil rosin esters; and mixtures thereof. Preferably, the tackifier (B) is a hydrogenated hydrocarbon resin, and more preferably, an alicyclic hydrocarbon resin.

[0037] In a preferred embodiment, the tackifier (B) has a softening point higher than 100°C.

[0038] Suitable tackifiers for use as component (B) in the HMA composition disclosed herein are well known in the art, for example, ExxonMobil's Escorez (商標) For example, Escorez (商標) It is sold commercially for 5400.

[0039] The HMA composition of this disclosure further comprises polypropylene wax (C). In preferred embodiments, the HMA composition of this disclosure does not contain any wax other than polypropylene wax (C). More preferably, the HMA composition does not contain Fischer-Tropsch wax.

[0040] Polypropylene wax (C) may be a modified polypropylene wax, such as maleic anhydride grafted polypropylene wax.

[0041] The polypropylene wax (C) preferably has a weight-average molecular weight Mw of 10,000 g / mol or less, preferably 8,000 g / mol or less, and more preferably in the range of 3,000 to 7,000 g / mol, as measured by GPC, and / or a molecular weight distribution Mw / Mn in the range of 3.0 to 6.0 as measured by GPC.

[0042] The polypropylene wax (C) also preferably has a dropping melting point (similar to DGF M-III 3, DIN 51801) of 140°C to 157°C, preferably 145°C to 155°C.

[0043] The polypropylene wax (C) preferably also has a thickness in the range of 2 to 7 dmm (DIN 51579:2010).

[0044] Optionally, the HMA composition of this disclosure may include an additional component (D) selected from plasticizers, such as plasticizing oils (e.g., mineral oil), olefin oligomers, or low molecular weight polyolefins (e.g., liquid polybutylene); amorphous poly-α-olefins, thermoplastic polyurethanes, ethylene / (meth)acrylate copolymers, ethylene / vinyl acetate copolymers, and combinations thereof, distinct from the polybutene-1 component (A). The amount of the additional component (D) is in the range of 0% to 15% by weight, based on the total weight of the HMA composition (including the additional component).

[0045] Optionally, the HMA composition may contain, at a rate of 0.05% to 5.0% by weight of the total weight of the HMA composition, an additive (E) selected from additives commonly used in HMA compositions, such as antioxidants, light stabilizers, and combinations thereof.

[0046] The viscosity of the hot melt adhesive compositions of this disclosure can be tailored, thereby optimizing the compositions for various applications. The hot melt adhesive compositions of this disclosure are therefore suitable for use in the woodworking industry, general assembly; and especially for packaging in the assembly industries of electrical equipment, ceramics, furniture, textiles, upholstery materials, leather, plastics, paper, and cardboard components.

[0047] Accordingly, in a further embodiment, the present disclosure relates to the use of hot-melt adhesive compositions for general assembly of bonded articles in the woodworking industry; in particular, for packaging in the assembly industry of electrical equipment, ceramics, furniture, textiles, upholstery materials, leather, plastics, paper, and cardboard components.

[0048] In a further embodiment, the present disclosure relates to an article comprising a first substrate and a second substrate, wherein the first substrate is bonded to the second substrate by a hot-melt adhesive composition of the present disclosure sandwiched between the first substrate and the second substrate.

[0049] Preferably, the first and second substrates are made of materials independently selected from wood, paper, cardboard, natural leather, plastic materials, natural fibers (such as cotton or linen), and combinations thereof.

[0050] Preferably, the first and second substrates are independently selected from films, sheets, panels, woven fabrics, and nonwoven fabrics.

[0051] In one embodiment, the hot melt adhesive composition of the present disclosure preferably has a rotational (Brookfield) viscosity of 7,000 mPa·s or less, more preferably less than 5,000 mPa·s, and even more preferably less than 2,000 mPa / s at 180°C. In one embodiment, the lower limit for each upper limit is 500 mPa·s. HMA compositions with viscosities in these ranges are particularly suitable for use in packaging applications such as assembling paper, cardboard, etc.

[0052] The hot-melt adhesive composition of this disclosure exhibits very good thermal stability.

[0053] The compositions of the present invention can be prepared by known methods and apparatus, such as melting and mixing the constituent components in a stirring tank or a single-screw or twin-screw extruder.

[0054] The features describing the subject matter of this disclosure are not closely related to one another. Therefore, a feature within a preferred range can be combined with another feature within a more or less preferred range, regardless of the level of preference.

[0055] The following examples are for illustrative purposes only and are not intended to limit the scope of the present invention in any way. Examples

[0056] Characterization Methods: The following methods are used to determine the characteristics described in the specification, claims, and examples.

[0057] The melt flow rate (MFR) was measured according to ISO 1133-1:2011 (190°C, 2.16 kg, unless different loads and temperatures are specified).

[0058] Comonomer content (by weight) measured by IR spectroscopy.

[0059] The spectrum of the polymer press film was recorded using absorbance versus wavenumber (cm²). -1). The ethylene content was calculated using the following measurements: a) 4482~3950 cm used for spectroscopic normalization of film thickness -1 Area of the composite absorption band between (At); b) Subtraction coefficient for digital subtraction between the spectrum of a polymer sample and the absorption band due to methylene group sequences BEE and BEB (B: 1-butene unit, E: ethylene unit) (FCR C2 ) (CH2 scissoring vibration).

[0060] c) Area of the remaining band after subtracting the C2PB spectrum (A C2,block ). It is derived from methylene group sequence EEE (CH2 rocking vibration). Apparatus

[0061] A Fourier transform infrared spectrophotometer (FTIR) capable of providing the above-described spectral measurements was used. A hydraulic press (Carver or equivalent) having platens heatable to 200°C is used. Method Calibration of (BEB + BEE) sequences

[0062] % (BEB + BEE) by weight versus FCR C2 / A t A calibration straight line is obtained by plotting . The slope Gr and intercept Lr are calculated by linear regression. Calibration of EEE sequences

[0063] % (EEE) by weight versus A C2、ブロック / A t A calibration straight line is obtained by plotting . Slope G H and intercept I H are calculated by linear regression. Sample preparation

[0064] A thick sheet is obtained by pressing approximately 1.5 g of the sample between two sheets of aluminum foil using a hydraulic press. If uniformity is an issue, it is suggested to perform the pressing operation at least twice. A small portion is cut from this sheet to form a film. The recommended film thickness is 0.1 to 0.3 mm. The pressing temperature is 140 ± 10 °C. Since changes in the crystalline phase occur over time, it is suggested to collect the IR spectrum of the sample film immediately after forming. procedure

[0065] The parameters for acquiring device data are as follows: Purge time: Minimum 30 seconds.

[0066] Collection time: Minimum 3 minutes.

[0067] Apodization: Happ-Genzel.

[0068] Resolution: 2cm -1 .

[0069] The IR spectra of the sample against an air background were collected. calculation

[0070] The gravimetric concentration of the BEE+BEB sequence for ethylene units was calculated.

[0071]

number

[0072] The gravimetric concentration of the EEE sequence in ethylene units was calculated.

[0073]

number

[0074]

number

[0075] For butene / ethylene copolymers, as far as data evaluation is concerned, for each sample, it was assumed that the composition was constant across the entire molecular weight range, and the K value of the Mark-Houwink relation was calculated using a linear combination as reported below.

[0076]

number

number

number

number

[0077] Thermal properties were measured using a differential scanning calorimeter (DSC) on a Perkin Elmer DSC-7 instrument. The melting temperatures of the butene-1 copolymer and the HMA composition were measured according to the following method: TmII (Melting temperature(s) measured during the second heating run): A weighted sample (5-10 mg) obtained by polymerization (or a weighted sample of the HMA composition) was sealed in an aluminum pan and heated at a scanning rate corresponding to 10°C / min. The sample was held at 200°C for 5 minutes to completely melt all microcrystals and eliminate the sample's thermal history. Next, it was cooled to -20°C at a scanning rate corresponding to 10°C / min, and the peak temperature was taken as the crystal temperature (Tc). After standing at -20°C for 5 minutes, the sample was heated a second time at 200°C at a scanning rate corresponding to 10°C / min. The peak temperature measured during this second heating run was marked as (TmII). If multiple peaks were present, the highest (strongest) peak was taken as TmII. The area at the peak (or multiple peaks) was taken as the total enthalpy of melt (DH TmII).

[0078] The enthalpy of melt and melting temperature after aging were also measured by differential scanning calorimetry (DSC) using a PerkinElmer DSC-7 instrument as follows: A weighted sample (5-10 mg) obtained by polymerization (or a weighted sample of the HMA composition) was sealed in an aluminum pan and heated at 200°C at a scanning rate corresponding to 10°C / min. The sample was maintained at 200°C for 5 minutes to completely melt all crystallites, and then cooled to 20°C at a cooling rate of 10°C / min. The sample was then stored at room temperature for 10 days. After 10 days, the sample was subjected to DSC, cooled to -20°C, and heated at 200°C at a scanning rate corresponding to 10°C / min. During this heating operation, the peak temperature was recorded as the melting temperature (TmI). If multiple peaks were present, the highest (strongest) peak was taken as TmI. The area at the peak (or multiple peaks) was taken as the total enthalpy of melt (DH TmI) after 10 days.

[0079] Glass transition temperature (Tg) determined by dynamic mechanical thermal analysis (DMTA). A molded workpiece measuring 76 mm × 13 mm × 1 mm was fixed to a DMTA machine for tensile stress. The tension of the sample and the dependent frequency were fixed at 1 Hz. The DMTA converts the elastic response of the sample from -100°C to 130°C. In this way, a graph of the elastic response to temperature can be created. The elastic modulus of a viscoelastic material is defined as E = E' + iE''. The DMTA can separate the temperature into two components E' and E'' via their resonances and graphs E' and E' / E'' = tan(δ). The glass transition point Tg is assumed to be the temperature of the curve E' / E'' = tan(δ) with respect to the maximum temperature.

[0080] Brookfield viscosity of butene-1 copolymer: Measured at 190°C using a cylindrical axial rotational viscometer HA, Ametek / Benelux scientific model DV2T, equipped with a drive motor capable of varying the test speed and a set of axials capable of achieving and maintaining approximately 80% of the torque. The selected axial / chamber combination was SC4-27 / SC4-13R / RP. The sample was rotated in stages until approximately 80% of the torque value was reached and maintained. Rotation was started at 10 rpm and then gradually increased by 2 rpm every 5 seconds. Brookfield viscosity [mPa*s] was calculated as the shear stress (mPa) / shear rate (sec⁻¹) ratio and measured from the results obtained during the last 20 minutes of acquisition (1 data point / min).

[0081] Brookfield viscosity relative to HMA was measured at 180°C using a cylindrical axial rotational viscometer HA, Ametek Scientific Model DV2T, equipped with a drive motor capable of varying the test speed and a set of axials capable of achieving and maintaining approximately 50% of the torque. The selected axial / chamber combination was SC4 / 27. During the test, the sample (10.5g) was passed through progressively increasing rotations until approximately 50% of the torque value was reached and maintained. The rotation was started at 5 rpm and increased to a maximum of 20 rpm while maintaining a stable rotation for 20 minutes. Brookfield viscosity [mPa*s] was calculated as the shear stress (mPa) / shear rate (sec⁻¹) ratio and measured from the results obtained during the last 20 minutes of acquisition (1 data point / min).

[0082] The degree of crystallinity was measured by X-ray diffraction using a powder X-ray diffraction analyzer with a fixed slit that uses Cu-Kα1 radiation and can collect spectra between diffraction angles 2θ=5° and 2θ=35° at 6-second intervals with a step size of 0.1°.

[0083] The samples are diskettes manufactured by press molding, with a thickness of approximately 1.5 to 2.5 mm and a diameter of 2.5 to 4.0 cm. The diskettes are aged at 23°C for 96 hours.

[0084] After preparation, the test specimen is inserted into the XRPD sample holder. The XRPD instrument is set up to collect the XRPD spectrum of the sample in steps of 0.1° from diffraction angles 2θ=5° to 2θ=35° using a counting time of 6 seconds, and to collect the final spectrum at the end.

[0085] Ta is defined as the total area between the spectral profile and a reference expressed in terms of several / second·2θ; Aa is defined as the total amorphous area expressed in terms of several / second·2θ; and Ca is the total crystalline area expressed in terms of several / second·2θ.

[0086] The spectrum or diffraction pattern is analyzed using the following procedure.

[0087] 1) Define a suitable linear baseline for the entire spectrum and calculate the total area (Ta) between the spectral contour and the baseline. 2) Based on the two-phase model, define an appropriate amorphous profile along the entire spectrum to separate the amorphous region from the crystalline region. 3) Calculate the amorphous area (Aa), which is the area between the amorphous contour and the baseline. 4) Calculate the crystal area (Ca), for example Ca=Ta-Aa, as the area between the spectral contour and the amorphous contour. 5) Calculate the degree of crystallinity of the sample using the following formula: %Cr = 100 x Ca / Ta Density: Measured according to norm ISO 1183-1, Method A, Part 1: Immersion method. Test specimens were obtained by compression molding pellets. The density of polybutene-1 was measured 10 days after conditioning.

[0088] Soluble and insoluble fractions of xylene at 0°C: 2.5 g of polymer composition, and 250 cm 3 o-xylene is introduced into a glass flask equipped with a refrigerator and a magnetic stirrer. The temperature is raised to the boiling point of the solvent over 30 minutes. The resulting clear solution is then stirred under reflux for another 30 minutes. The closed flask is then cooled in air to 100°C for 10-15 minutes while stirring, and then maintained in a 0°C constant temperature water bath for 30 minutes, and similarly for 60 minutes. The resulting solid is filtered at 0°C through quick filter paper. 100 cm 3 The filtered liquid is poured into a pre-measured aluminum container and heated on a heating plate under a nitrogen stream to remove the solvent by evaporation. Therefore, the fraction (weight %) of polymer soluble in xylene (XS) is calculated from the average weight of the residue. The fraction of polymer insoluble in o-xylene at 0°C (XI) is calculated as XI (%) = 100 - XS (%).

[0089] Yellowness index measured according to ASTM method D1925.

[0090] Tensile stress and elongation at yield. Sample preparation: Preheat oven to 175°C. Fill an aluminum cup with the adhesive to be tested, place the cup in the oven, and melt for approximately 1 hour. Pour the molten adhesive onto a silicone paper sheet and allow to cool to 23±1°C. Cut out approximately 10g squares from each sample. Turn on the hot press and set the plate temperature to 85°C. Place the pre-measured square adhesive in the center of two sheets of silicone paper, and place two 0.5mm metal shims on each side of the sheet. Press for approximately 2 minutes, then release the press and verify that a flat, homogeneous surface with a thickness of approximately 0.5mm±0.05mm is obtained. If not, repeat the procedure with a new sample. Allow to cool to 23±1°C. After 24 hours, cut standard dumbbell-shaped test specimens of the following dimensions: [Table 1]

[0091] Condition the specimen at 23°C for at least 24 hours and reconfirm the thickness using a micrometer. Test method: Set the separation speed to 60 mm / min and the elongation limit to 300 mm on a dynamometer. Connect the specimen to the forceps of the dynamometer, start the traction, and plot the stress-strain curve. The yield point is the first point on the stress-strain curve where the strain increases without an increase in stress. The tensile stress at yield is the stress value at the yield point; the elongation at yield is the percentage of deformation at the yield point.

[0092] Ring and Ball Softening Point. The softening point is defined as the temperature at which, when the sample is heated in a glycerin bath at 5°C / min, the disc of the sample held in a horizontal ring is pushed down to a distance of 25.4 mm under the weight of a steel ball (diameter: 9.5 mm; weight: 3.5 ± 0.05 g). This test method is for measuring the softening point of hot melt adhesives and hot melt materials using a ring and ball apparatus HERZOG mod HRB 754. The adhesive sample is melted in an oven and filled into the ring. It is conditioned at 23 ± 1°C for at least 4 hours. The ring is precisely inserted into the holder, a guide cage for the beads is placed to ensure that the beads move freely, and then immersed in a glycerin-containing bath. A beaker is placed on the heating plate of the instrument, and the holder with the ring and the instrument's thermometer are immersed. Sample identification data (name and batch number) is set on the control panel, and the measurement is started. At the end of the analysis, the instrument displays the detected temperature. The result is expressed in °C.

[0093] Cloud point. The cloud point is the temperature at which the HMA composition becomes cloudy when cooled. The HMA composition is melted at 170°C, a thermometer is immersed in the molten adhesive mass, and the adhesive mass is allowed to cool. The temperature measured by the thermometer when the adhesive becomes cloudy is recorded as the cloud point of the adhesive.

[0094] Open time. Open time is defined as the maximum time that an adhesive material remains bondable. Open time is the time after application of the adhesive during which a usable bond is formed. 70 x 50 mm, single-sided coated cardboard (400 g / cm²) 2The following materials are used in the test: A uniform layer of 10 x 50 mm adhesive, melted at 180°C, is applied to the first cardboard sheet using a spray gun at a pressure of 1 bar. After a 1-second time interval (holding time), the second cardboard sheet is pressed for 1 second at a pressure of 0.8 bar to bond it to the first cardboard sheet. Immediately after pressing, the second substrate is pulled perpendicular to the first cardboard sheet at a speed of 3000 mm / min. If a usable bond is formed, 100% of the fibers within the bonded area will peel off. The test is repeated while increasing the holding time by 1 second at a time. The open time is the holding time at which less than 100% of the cardboard fibers peel off. The average open time was determined from five tests conducted with the same HMA composition.

[0095] Set Time: Set time is the time required for an acceptable bond to form when two substrates are joined with adhesive. A uniform layer of 10 x 50 mm adhesive, molten at 180°C, is applied to the first cardboard sheet using a spray gun at a pressure of 1 bar. After 1 second, the second cardboard sheet is pressed against the first cardboard sheet for 0.05 seconds at a pressure of 0.8 bar to bond it to the first cardboard sheet. After pressing, the second substrate is pulled perpendicular to the first cardboard sheet at a speed of 3000 mm / min. The pressing time is increased by 0.02 seconds increments until all the cardboard fibers are detached (set time). The average set time was determined from five tests conducted with the same HMA composition.

[0096] Shear bond failure temperature (SAFT). The test method measures the temperature at which the object bonded with hot melt adhesive delaminates under shear load. The test specimen is prepared as follows: A 10 x 50 mm linear hot melt adhesive is applied to a 70 x 50 mm, single-sided coated first cardboard (400 g / m²). 2 ); A second cardboard sheet measuring 70 x 50 mm, coated on one side (400 g / cm²), bonded to the first cardboard sheet with a pressure of 0.8 bar. 2The adhesive is applied to the surface using a spray gun operating at a pressure of 1 bar at a temperature of 180°C. At least five test specimens are prepared for each adhesive and conditioned for 24 hours at 23°C and 50% relative humidity. The oven is preheated to 50°C, and one end of the test specimen is suspended in the oven, with the other end suspended by a weight of 500g. The oven temperature is increased at a rate of 5°C / hour. The temperature at which the adhesive falls (delaminates) is recorded as the shear bond failure temperature.

[0097] The flexural modulus was measured according to ISO 178. The specimens for the bending test were cut from a compression-type plaque pressed at 200°C and aged for 10 days at 25°C ± 1°C. The thickness of the specimens was 4 mm. raw materials

[0098] Tackifier: Escorez, commercially available from ExxonMobil, with a softening point of 103.4°C and a melt viscosity of 800 mPa·s at 160°C. (商標) 5400 Alicyclic hydrocarbon resin.

[0099] PP wax: Polypropylene wax having a dropping melting point of 150°C, a through-hole of 3dmm, a weight-average molecular weight (Mw) of 5,781, and a Mw / Mn ratio of 4.2; commercially available from Deurex AG as Deurex® P 3815 M.

[0100] FT wax (1): Sasolwax H1, a high-melting-point Fischer-Tropsch wax commercially available from Sasol, having a dropping melting point of 112°C, a penetration depth of 1 dmm, a weight-average molecular weight Mw of 1,863, and a Mw / Mn ratio of 1.3.

[0101] FT wax (2): Sasolwax C80M, a low-melting-point Fischer-Tropsch wax commercially available from Sasol, having a dropping melting point of 97°C, a penetration depth of 7 dmm, a weight-average molecular weight of 1,145 Mw, and a Mw / Mn ratio of 1.1.

[0102] Preparation of catalyst component: Dimethylsilyl{(2,4,7-trimethyl-1-indenyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene)}zirconium dichloride (metallocene A-1) was prepared according to Example 32 of WO01 / 47939.

[0103] Preparation of catalyst solution: Under a nitrogen atmosphere, a 20 L jacketed glass reactor was filled with a 33 g / L solution of triisobutylaluminum (TIBA) in isododecane and a 30% wt / wt solution of methylaluminoxane (MAO) in toluene (567 g). The mixture was stirred with an anchor stirrer and the reaction was carried out at 25°C for approximately 1 hour. After this time, 1.27 g of metallocene A-1 was added and dissolved with stirring for approximately 30 minutes. The final solution was discharged from the reactor into a cylinder via a filter to remove the final solid residue. Composition of the obtained solution: [Table 2]

[0104] Preparation of Butene-1 Copolymer [(Component (A))]: Polymerization was carried out in two stirred reactors operating in series, with liquid butene-1 constituting the liquid medium. The catalyst system described above was injected into both reactors, and polymerization was carried out continuously.

[0105] PB(1) was prepared according to Example 1 of WO2020 / 016143A1, and PB(2) was prepared according to the preparation of butene-1 polymer B)-1 as described in Table 1 of WO2022 / 084081. PB(3) was prepared under the following conditions according to the polymerization process described in WO2020 / 016143A1. [Table 3]

[0106] The butene-1 copolymer was recovered from the solution as a molten material and cut into pellets. The copolymer was further characterized, and the data are recorded in Table 2. [Table 4] *BV: Brookfield viscosity

[0107] Preparation of hot melt adhesive composition: The components are melted in an aluminum can in a melting apparatus at 175°C, and the molten composition is mixed at 175°C at 200 rpm for 2 hours using a small mixer IKA RW20 equipped with a stirring rod. Examples E1-E3

[0108] A hot-melt adhesive composition in accordance with this disclosure was prepared as described above, using the formulations shown in Table 3. The results of tests conducted with the composition are summarized in the same Table 3. [Table 5] *BV: Brookfield viscosity Comparative Examples CE4~CE9

[0109] A hot-melt adhesive composition containing Fischer-Tropsch wax was prepared for comparison according to the method described above. The formulations and test results are summarized in Table 4. [Table 6] *BV: Brookfield viscosity

[0110] The HMA compositions of this disclosure exhibit a best balance of properties, including an improved combination of mechanical properties, SAFT, open time and set time, and ring-and-ball softening point.

Claims

1. A hot melt adhesive composition, (A) A copolymer comprising 25% to 50% by weight of butene-1, having a copolymer comonomer content of 0.5% to 8.0% by weight as measured by IR spectroscopy, and a melt flow rate MFR (A) of 200 g / 10 min or more as measured according to ISO 1133-1:2011 (190°C, 2.16 kg), and at least one comonomer selected from ethylene, propylene, and C5-C10α-olefins, and combinations thereof, as measured by IR spectroscopy, (B) 30% to 60% by weight of a tackifier, (C) comprising 5 to 30% by weight of polypropylene wax, Here, the amounts of (A), (B), and (C) are based on the total weight of (A) + (B) + (C) in the hot melt adhesive composition.

2. The hot melt adhesive composition according to claim 1, wherein the butene-1 copolymer (A) has a melt flow rate MFR (A) (ISO 1133-1:2011, 190°C / 2.16 kg) of 200 to 3,000 g / 10 min, preferably 400 to 1,700 g / 10 min, and more preferably 500 to 1,600 g / 10 min.

3. The hot melt adhesive composition according to claim 1 or 2, wherein the butene-1 copolymer (A) has a total copolymer comonomer content of 0.7% to 7.0% by weight, based on the total weight of the butene-1 copolymer (A), and the comonomer content is measured by IR spectroscopy.

4. The hot melt adhesive composition according to any one of the prior claims, wherein the butene-1 copolymer (A) contains a comonomer selected from ethylene, propylene, hexene-1, octene-1, and combinations thereof, and is particularly preferably ethylene.

5. The butene-1 copolymer (A) is Based on the weight of the fraction (A1) of butene-1 homopolymer, or a fraction (A1) of comonomers selected from ethylene, propylene, C5-C10α-olefins, and combinations thereof, a fraction (A1) containing less than 3% by weight of butene-1 copolymer, The material comprises a fraction (A2) containing a butene-1 copolymer in an amount of 3% to 10% by weight, based on the weight of the fraction (A2) of comonomers selected from ethylene, propylene, C5-C10α-olefins, and combinations thereof, Here, the butene-1 copolymer (A) is The total copolymer comonomer content is 0.5% to 8.0% by weight, preferably 0.7% to 7.0% by weight, based on the total weight of fractions (A1) and (A2); A melt flow rate MFR(I) of 200 g / 10 min or more, as measured according to ISO 1133-1:2011 (190°C, 2.16 kg); and Based on the total weight of fractions (A1) and (A2), and measured by the method described in the Examples section, the content of xylene-soluble fractions is 80% by weight or less, preferably in the range of 20% to 80% by weight, at 0°C. The comonomer content is measured by IR spectroscopy, according to the hot melt adhesive composition according to any one of the prior claims.

6. The hot melt adhesive composition according to claim 5, wherein the butene-1 copolymer (A) comprises a fraction (A1) of 15% to 70% by weight, particularly 20% to 65% by weight, and a fraction (A2) of 30% to 85% by weight, particularly 35% to 80% by weight, and the amounts of fractions (A1) and (A) are based on the total weight of fractions (A1) and (A2).

7. The hot melt adhesive composition according to claim 5 or 6, wherein the comonomer is ethylene.

8. The butene-1 copolymer (A) is (a) A molecular weight distribution Mw / Mn less than 4, preferably less than 3, more preferably less than 2.5 (in all cases, the lower limit is 1.5, and the molecular weight distribution is measured by NMR); and / or (b) Having one or more melting peaks Tm(II) at a temperature of 110°C or lower, preferably 105°C or lower, more preferably in the range of 80°C to 103°C, where Tm(II) is measured by DSC; and / or (c) A glass transition temperature (Tg) measured by DSC in the range of -40°C to -10°C, preferably -30°C to -10°C; and / or (d) Brookfield viscosity of 15,000 mPa·s at 190°C, preferably in the range of 3,000 to 15,000 mPa·s; and / or (e) X-ray crystallinity in the range of 20 to 60%, preferably in the range of 25 to 50%; (f) 0.89-0.91g / cm ３ The density of the range; and / or (g) A hot melt adhesive composition according to any one of the prior claims, having at least one of the following characteristics: a yellowness index of less than 0, particularly in the range of -1 to -5.

9. The hot melt adhesive composition according to any one of the prior claims, wherein the tackifier (B) is solid at a temperature of 25°C ± 1°C and preferably has a softening point above 100°C.

10. The hot melt adhesive composition according to any one of the prior claims, wherein the polypropylene wax (C) has a weight-average molecular weight Mw in the range of 10,000 g / mol or less, preferably 8,000 g / mol or less, more preferably 3,000 to 7,000 g / mol, as measured by GPC, and / or has a molecular weight distribution Mw / Mn in the range of 3.0 to 6.0, as measured by GPC.

11. The hot melt adhesive composition according to any one of the prior claims, wherein the polypropylene wax (C) also has a dropping melting point (similar to DGF M-III 3, DIN 51801) of 140°C to 157°C, preferably 145°C to 155°C.

12. A hot melt adhesive composition according to any one of the prior claims, further comprising a plasticizer, an olefin oligomer or low molecular weight polyolefin, an amorphous poly-αolefin different from polybutene-1 component (A), a thermoplastic polyurethane, an ethylene / (meth)acrylate copolymer, an ethylene / vinyl acetate copolymer, and a component (D) selected from combinations thereof.

13. The hot melt adhesive composition according to claim 12, wherein the amount of component (D) is in the range of 0% by weight to 15% by weight, based on the total weight of the HMA composition.

14. A hot melt adhesive composition according to any one of the prior claims, further comprising 0.05% to 5.0% by weight of an additive (E), preferably selected from antioxidants, light stabilizers, and combinations thereof, based on the total weight of the HMA composition.

15. An article comprising a first substrate and a second substrate, wherein the first substrate is bonded to the second substrate by a hot-melt adhesive composition according to any one of claims 1 to 14, sandwiched between the first substrate and the second substrate.

16. The article according to claim 15, wherein the first and second substrates are made of materials independently selected from wood, paper, cardboard, natural leather, plastic materials, natural fibers (such as cotton or linen), and combinations thereof.

17. The article according to claim 15 or 16, wherein the first and second substrates are independently selected from films, sheets, panels, woven fabrics, and nonwoven fabrics.

18. The article according to claim 15, wherein the first and second substrates are made of paper or cardboard, and the hot melt adhesive composition according to any one of claims 1 to 14 is sandwiched between the first substrate and the second substrate, and has a rotational (Brookfield) viscosity of 7,000 mPa·s or less, more preferably less than 5,000 mPa·s, and even more preferably less than 2,000 mPa / s at 180°C.

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