Liquid additive composition

Abstract

A liquid additive composition comprising a fluoropolymer; an organic phosphite antioxidant; a sterically hindered phenolic antioxidant; and one or more hydrocarbon polymer dispersants, providing improved processing and product appearance in film applications, extrusion blow molding, and as a masterbatch reinforcing agent.

Description

Background Technology

[0001] This invention relates to additive compositions containing fluoropolymers in liquid form, which can be used in a variety of applications, such as polymer preparation. Unlike conventional additive compositions containing fluoropolymers, these are typically available only in solid form (e.g., granular masterbatch). The liquid additive compositions of this invention address needs that conventional solid additives cannot meet by exhibiting unexpectedly superior performance in, for example, film processing and appearance (e.g., blow molding and casting); extrusion blow molding; and as a masterbatch reinforcing agent. This enhanced performance is likely due to the excellent dispersibility of the liquid additive compositions, more predictable amounts of fluoropolymer in the final product, no additive loss during masterbatch compounding, and no thermal history. Summary of the Invention

[0002] One aspect of the present invention relates to an additive composition in liquid form, the composition comprising: a fluoropolymer; an organic phosphite antioxidant; a sterically hindered phenolic antioxidant; and one or more hydrocarbon polymer dispersants.

[0003] In one exemplary embodiment, the viscosity of the liquid additive composition is 3,000 to 20,000 centipoise, for example 4,000 to 18,000 centipoise, for example 5,000 to 16,000 centipoise, for example 6,000 to 15,000 centipoise.

[0004] In one exemplary embodiment, the amount of the fluoropolymer is 10 to 25% by weight, for example 12 to 22% by weight, for example 15 to 20% by weight.

[0005] In one exemplary embodiment, the amount of the organophosphite antioxidant is 15 to 35% by weight, for example 20 to 35% by weight, for example 20 to 30% by weight.

[0006] In one exemplary embodiment, the amount of the sterically hindered phenolic antioxidant is 0.5 to 10% by weight, for example 2 to 8% by weight, for example 3 to 7% by weight.

[0007] In one exemplary embodiment, the amount of one or more hydrocarbon polymer dispersants is 30 to 75% by weight, for example 35 to 65% by weight, for example 40 to 60% by weight, for example 45 to 55% by weight.

[0008] In one exemplary embodiment, the fluoropolymer is polyvinylidene fluoride.

[0009] In a specific embodiment, polyvinylidene fluoride is selected from: Kynar 5300, Kynar 5301, Kynar 3121-50 and Kynar 2821.

[0010] Suitable organic phosphite antioxidants include any commercially available organic phosphite antioxidant. In a specific embodiment, the organic phosphite antioxidant is... 126 and One or more of 168.

[0011] In one specific embodiment, the sterically hindered phenolic antioxidant is one or more of the following: 1010 1035 1076、 1098 1135、 1330 1425, 1520L 1726 245. 245DW 3114、 565, Rianox(Thanox)1076, Rianox(Thanox)1098, Rianox(Thanox)1790 and Rianox(Thanox)3114.

[0012] In one exemplary embodiment, the liquid additive composition includes other antioxidants. In one exemplary embodiment, the other antioxidants are one or more selected from thioethers, lactones, hydroxylamines, vitamin E derivatives, and blended antioxidants.

[0013] In one specific embodiment, the thioether antioxidant is PS 800 or One or more of PS802.

[0014] In one exemplary embodiment, the blended antioxidant is a blend of sterically hindered phenols and organophosphites. In another exemplary embodiment, the blended antioxidant is... B 215 B 225, B 561, B 612 and One or more of B 900.

[0015] In one exemplary embodiment, one or more hydrocarbon polymers are polymerized C4 olefins. In a specific embodiment, the polymerized C4 olefin is polybutene. In a specific embodiment, polybutene is one or more of the following: L-2, L-3, L-6 L-8, L-14 H-7 H-8 H-15 H-25, H-50 H-100 H-300 and H-1200. In one exemplary embodiment, the liquid additive composition comprises two different hydrocarbon polymers. In one exemplary embodiment, the liquid additive composition comprises three different hydrocarbon polymers. In a specific embodiment, the liquid additive composition comprises... L-14 and H-25 (Add-Vis 18), among which, The amount of L-14 is 25 to 55% by weight, for example, 30 to 50% by weight, for example, 35 to 45% by weight, and the amount of Add-Vis 18 is 1 to 12% by weight, for example, 3 to 10% by weight, for example, 4 to 8% by weight.

[0016] In one exemplary embodiment, the liquid additive composition includes other dispersants that are not polymerized C4 olefins. In one exemplary embodiment, the non-polymerized C4 olefin dispersant is a polymeric dispersant. In a specific embodiment, the polymeric dispersant is one or more of the following: Solplus TM K240, Solplus TM K241, Solplus TM K251, Solplus TM DP310, Solplus TM D320, Solplus TM D330 and Solplus TM DP700.

[0017] In an exemplary embodiment, the amount of polymeric dispersant (not polymerized C4 olefin) is 0.1 to 5% by weight, for example 0.3 to 5% by weight, for example 0.5 to 3% by weight, for example 0.5 to 2% by weight, for example 1 to 3% by weight.

[0018] In one exemplary embodiment, the liquid additive composition further comprises a flow promoter, which also functions as a dispersing agent and a rheology modifier. In one exemplary embodiment, the flow promoter is micronized polyethylene or a polyethylene-containing wax. In a specific embodiment, the wax is one or more of the following: 3715 3716TP, 3620 5551 and 9615A.

[0019] In one exemplary embodiment, the amount of micronized polyethylene or polyethylene-containing wax is 0.5 to 6% by weight, for example 1 to 5% by weight, for example 2 to 4% by weight.

[0020] In one exemplary embodiment, the liquid additive composition further comprises a thickener / thixotropic agent / rheology modifier. In a specific embodiment, the thickener / thixotropic agent / rheology modifier is silica (e.g., amorphous calcined or colloidal silica). In a specific embodiment, silica is... N20.

[0021] In an exemplary embodiment, the amount of silicon dioxide is 0.05 to 5% by weight, for example, 0.1 to 3% by weight, for example, 0.3 to 1% by weight.

[0022] In an exemplary embodiment, the liquid additive composition further comprises one or more of the following substances: inorganic fillers, organic fillers, weathering agents, ultraviolet absorbers, heat stabilizers, light stabilizers, antistatic agents, pigments, adsorbents, lubricants, and silicone compounds.

[0023] In one exemplary embodiment, the liquid additive composition comprises: a fluoropolymer; an organic phosphite antioxidant; a sterically hindered phenolic antioxidant; two different polymerized C4 olefin dispersants; a polymer dispersant that is not a polymerized C4 olefin; a micronized polyethylene wax matting agent; and a thixotropic agent.

[0024] In one exemplary embodiment, the liquid additive composition is essentially composed of the following substances: a fluoropolymer; an organic phosphite antioxidant; a sterically hindered phenolic antioxidant; two different polymerized C4 olefin dispersants; a polymer dispersant that is not a polymerized C4 olefin; a micronized polyethylene wax matting agent; and a thixotropic agent.

[0025] In one exemplary embodiment, the liquid additive composition comprises: a fluoropolymer; an organic phosphite antioxidant; a sterically hindered phenolic antioxidant; two different polymerized C4 olefin dispersants; a polymer dispersant that is not a polymerized C4 olefin; a micronized polyethylene wax matting agent; and a thixotropic agent.

[0026] In one exemplary embodiment, the liquid additive composition comprises: polyvinylidene fluoride; an organophosphite antioxidant; a sterically hindered phenolic antioxidant; two different polymerized C4 olefin dispersants; a polymer dispersant that is not a polymerized C4 olefin; and one or more of silica and micronized polyethylene wax matting agents used as thixotropic agents.

[0027] In one exemplary embodiment, the liquid additive composition is essentially composed of the following substances: polyvinylidene fluoride; an organophosphite antioxidant; a sterically hindered phenolic antioxidant; two different polymerized C4 olefin dispersants; a polymer dispersant that is not a polymerized C4 olefin; micronized polyethylene wax used as a matting agent; and silica used as a thixotropic agent.

[0028] In one exemplary embodiment, the liquid additive composition comprises: polyvinylidene fluoride; an organophosphite antioxidant; a sterically hindered phenolic antioxidant; two different polymerized C4 olefin dispersants; a polymer dispersant that is not a polymerized C4 olefin; micronized polyethylene wax used as a matting agent; and silica used as a thixotropic agent.

[0029] In one exemplary embodiment, the liquid additive composition comprises: 12 to 22 wt% polyvinylidene fluoride; 20 to 30 wt% an organophosphite antioxidant; 2 to 8 wt% a sterically hindered phenolic antioxidant; 25 to 65 wt% of two different polymeric C4 olefin dispersants; 0.3 to 3 wt% a polymer dispersant that is not a polymeric C4 olefin; 1 to 5 wt% a micronized polyethylene wax used as a matting agent; and 0.1 to 3 wt% silica used as a thixotropic agent.

[0030] In one exemplary embodiment, the liquid additive composition comprises essentially the following substances: 12 to 22 wt% polyvinylidene fluoride; 20 to 30 wt% an organophosphite antioxidant; 2 to 8 wt% a sterically hindered phenolic antioxidant; 25 to 65 wt% two different polymeric C4 olefin dispersants; a total of 0.3 to 3 wt% a polymeric dispersant that is not a polymeric C4 olefin; 1 to 5 wt% a micronized polyethylene wax used as a matting agent; and 0.1 to 3 wt% silica used as a thixotropic agent.

[0031] In one exemplary embodiment, the liquid additive composition comprises: 12 to 22 wt% polyvinylidene fluoride; 20 to 30 wt% an organophosphite antioxidant; 2 to 8 wt% a sterically hindered phenolic antioxidant; 25 to 65 wt% of two different polymeric C4 olefin dispersants; 0.3 to 3 wt% a polymer dispersant that is not a polymeric C4 olefin; 1 to 5 wt% a micronized polyethylene wax used as a matting agent; and 0.1 to 3 wt% silica used as a thixotropic agent.

[0032] In a specific embodiment, the liquid additive composition comprises: polyvinylidene fluoride; and an organophosphite antioxidant selected from the group consisting of: 126 and 168; Stericly hindered phenolic antioxidants, selected from the following group: 1010 1035 1076、 1098 1135、 1330 1425, 1520L 1726 245. 245DW 3114、 565, Rianox 1076, Rianox 1098, Rianox 1790, and Rianox 3114; two polymerized C4 olefin dispersants selected from the group consisting of: L-2, L-3, L-6 L-8, L-14 H-7 H-8 H-15 H-25, H-50 H-100 H-300 and H-1200; a polymer dispersant selected from the following group: Solplus TM K240, Solplus TM K241, Solplus TM K251, Solplus TM DP310, Solplus TM D320, Solplus TMD330 and Solplus TM DP700; Micronized polyethylene wax matting agent, selected from the following group: 3715 3716TP, 3620 5551 and 9615A; and silica thixotropic agents selected from amorphous calcined or colloidal silica.

[0033] In a specific embodiment, the liquid additive composition is basically composed of the following substances: polyvinylidene fluoride; and an organic phosphite antioxidant selected from the group consisting of: 126 and 168; Stericly hindered phenolic antioxidants, selected from the following group: 1010 1035 1076、 1098 1135、 1330 1425, 1520L 1726 245. 245DW 3114、 565, Rianox 1076, Rianox 1098, Rianox 1790, and Rianox 3114; two polymerized C4 olefin dispersants selected from the group consisting of: L-2, L-3, L-6 L-8, L-14 H-7 H-8 H-15 H-25, H-50 H-100 H-300 and H-1200; a polymer dispersant selected from the following group: Solplus TM K240, Solplus TM K241, Solplus TM K251, Solplus TM DP310, Solplus TM D320, Solplus TMD330 and Solplus TM DP700; Micronized polyethylene wax matting agent, selected from the following group: 3715 3716TP, 3620 5551 and 9615A; and silica thixotropic agents selected from amorphous calcined or colloidal silica.

[0034] In a specific embodiment, the liquid additive composition comprises the following substances: polyvinylidene fluoride; and an organic phosphite antioxidant selected from the group consisting of: 126 and 168; Stericly hindered phenolic antioxidants, selected from the following group: 1010 1035 1076、 1098 1135、 1330 1425, 1520L 1726 245. 245DW 3114、 565, Rianox 1076, Rianox 1098, Rianox 1790, and Rianox 3114; two polymerized C4 olefin dispersants selected from the group consisting of: L-2, L-3, L-6 L-8, L-14 H-7 H-8 H-15 H-25, H-50 H-100 H-300 and H-1200; a polymer dispersant selected from the following group: Solplus TM K240, Solplus TM K241, Solplus TM K251, Solplus TM DP310, Solplus TM D320, Solplus TMD330 and Solplus TM DP700; Micronized polyethylene wax matting agent, selected from the following group: 3715 3716TP, 3620 5551 and 9615A; and silica thixotropic agents selected from amorphous calcined or colloidal silica.

[0035] In a specific embodiment, the liquid additive composition comprises: polyvinylidene fluoride; 168; H-25; Rianox 1076; L-14; Solplus TM K240; 3620; and N20.

[0036] In a specific embodiment, the liquid additive composition is basically composed of the following substance: polyvinylidene fluoride; 168; H-25; Rianox 1076; L-14; Solplus TM K240; 3620; and N20.

[0037] In a specific embodiment, the liquid additive composition comprises the following substance: polyvinylidene fluoride; 168; H-25; Rianox 1076; L-14; Solplus TM K240; 3620; and N20.

[0038] In a specific embodiment, the liquid additive composition comprises: Kynar 3121-50; 168; H-25; Rianox 1076; and L-14.

[0039] In a specific embodiment, the liquid additive composition is basically composed of the following substances: Kynar 3121-50; 168; H-25; Rianox 1076; and L-14.

[0040] In a specific embodiment, the liquid additive composition comprises the following substances: Kynar 3121-50; 168; H-25; Rianox 1076; and L-14.

[0041] In a specific embodiment, the liquid additive composition comprises: Kynar 5301; 168; H-25; Rianox 1076; and L-14.

[0042] In a specific embodiment, the liquid additive composition is basically composed of the following substances: Kynar 5301; 168; H-25; Rianox 1076; and L-14.

[0043] In a specific embodiment, the liquid additive composition comprises the following substances: Kynar 5301; 168; H-25; Rianox 1076; and L-14.

[0044] In a specific embodiment, the liquid additive composition comprises: Kynar 3121-50; 168; H-25; Rianox 1076; L-14; Solplus TM K240; 3620; and N20.

[0045] In a specific embodiment, the liquid additive composition is basically composed of the following substances: Kynar 3121-50; 168; H-25; Rianox 1076; L-14; Solplus TM K240; 3620; and N20.

[0046] In a specific embodiment, the liquid additive composition comprises the following substances: Kynar 3121-50; 168;Add-Vis 18;Rianox 1076; L-14; Solplus TM K240; 3620; and N20.

[0047] In a specific embodiment, the liquid additive composition comprises: Kynar 5301; 168; H-25; Rianox 1076; L-14; Solplus TM K240; 3620; and N20.

[0048] In a specific embodiment, the liquid additive composition is basically composed of the following substances: Kynar 5301; 168; H-25; Rianox 1076; L-14; Solplus TM K240; 3620; and N20.

[0049] In a specific embodiment, the liquid additive composition comprises the following substances: Kynar 5301; 168; H-25; Rianox 1076; L-14; Solplus TM K240; 3620; and N20.

[0050] One aspect of the present invention is an article comprising a liquid additive composition as described herein.

[0051] One aspect of the invention is a polymer comprising a liquid additive composition as described herein.

[0052] One aspect of the present invention is a film comprising a liquid additive composition as described herein.

[0053] In one exemplary embodiment, the amount of liquid additive composition in the article (e.g., polymer, such as film) is 0.001 to 10% let-down ratio (LDR), for example 0.005 to 5% LDR, for example 0.005 to 3% LDR, for example 0.01 to 5% LDR, for example 0.01 to 3% LDR.

[0054] In one exemplary embodiment, the amount of the organophosphite antioxidant component in the liquid additive composition of the article (e.g., polymer, such as film) is 0.002 to 0.50% by weight, for example 0.002 to 0.4% by weight, for example 0.003 to 0.40% by weight, for example 0.003 to 0.3% by weight.

[0055] In one exemplary embodiment, the amount of the sterically hindered phenolic antioxidant component in the liquid additive composition of the article (e.g., polymer, such as film) is 0.0005 to 0.10 wt%, for example 0.0006 to 0.10 wt%, for example 0.0007 to 0.08 wt%, for example 0.0008 to 0.07 wt%.

[0056] In one exemplary embodiment, the amount of one or more hydrocarbon polymer dispersant components of the liquid additive composition in the article (e.g., polymer, such as film) is 0.020 to 1.0 wt%, for example 0.050 to 1.0 wt%, for example 0.050 to 0.8 wt%, for example 0.060 to 0.6 wt%.

[0057] In one exemplary embodiment, the amount of the polymer dispersant (which is not a polymerized C4 olefin) component of the liquid additive composition in the article (e.g., polymer, such as film) is 0.00001 to 0.01 wt%, for example 0.00002 to 0.01 wt%, for example 0.00003 to 0.01 wt%, for example 0.00003 to 0.009 wt%.

[0058] In one exemplary embodiment, the amount of micronized polyethylene or polyethylene-containing wax component of the liquid additive composition in the article (e.g., polymer, such as film) is 0.001 to 0.05% by weight, for example 0.002 to 0.04% by weight, for example 0.003 to 0.03% by weight.

[0059] In one exemplary embodiment, the amount of silica component in the liquid additive composition of the article (e.g., polymer, such as film) is 0.00005 to 0.010% by weight, for example 0.00007 to 0.008% by weight, for example 0.00008 to 0.007% by weight.

[0060] In one exemplary embodiment, the film is a blown film or a cast film.

[0061] One aspect of the present invention is an extruded blow-molded article comprising a liquid additive composition as described herein.

[0062] One aspect of the invention is a masterbatch comprising a liquid additive composition as described herein.

[0063] One aspect of the present invention is a method for improving the clarity of a thin film, the method comprising: adding a liquid additive composition as described herein to a thin film or a thin film precursor.

[0064] One aspect of the present invention is a method for improving the surface appearance of a thin film, the method comprising: adding a liquid additive composition as described herein to a thin film or a thin film precursor.

[0065] One aspect of the present invention is a method for reducing die buildup, increasing productivity, shortening color change transitions, reducing product degradation, improving batch flowability, and reducing or eliminating sharkskin defects, the method comprising adding a liquid additive composition as described herein during the preparation of the manufactured article (e.g., a film).

[0066] In one exemplary embodiment, the liquid additive composition is preferably used at a processing temperature of up to 500℉ (also referred to as a "low-temperature additive composition"). In different exemplary embodiments, the liquid additive composition is preferably used at a processing temperature above 500℉ (also referred to as a "high-temperature additive composition"). In one exemplary embodiment, the low-temperature additive composition provides a moderately clearing effect visually, increases transmittance with increasing tolerance ratio (LDR), and requires third-party pulverization. In contrast, in one exemplary embodiment, the high-temperature additive composition provides a significant clearing effect visually, exhibits optimal transmittance at a lower tolerance ratio (LDR), and does not require pulverization.

[0067] In a specific embodiment, the liquid additive composition preferably used at a processing temperature of up to 500℉ contains Kynar. 5301 is used as a polyvinylidene fluoride component. In a specific embodiment, the liquid additive composition preferably used at processing temperatures greater than 500℉ contains Kynar. 3121 is polyvinylidene fluoride.

[0068] One aspect of the present invention relates to a method for preparing a thin film, the method comprising the step of adding the additive composition of the present invention to a resin.

[0069] In one exemplary embodiment, the film is selected from the group consisting of polypropylene (PP), chlorinated polypropylene (CLPP), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), low-density polyethylene (LDPE), ethylene-vinyl acetate (EVA), and metallocene (mPE). Attached Figure Description

[0070] The following figures only illustrate specific embodiments of the present invention and are not intended to limit the scope of the present invention as described herein in any other way.

[0071] Figure 1 The transmittance results of LLDPE films containing different amounts of the exemplary additive compositions of the present invention are shown.

[0072] Figure 2 The differences in improving the clarity of LLDPE films containing exemplary compositions of the present invention are shown, wherein Kynar 5301 is a polyvinylidene fluoride component, and the composition is present at 0.015% LDR and 1% LDR.

[0073] Figure 3 The differences in improving the clarity of LLDPE films containing exemplary compositions of the present invention are shown, wherein Kynar 3121 is a polyvinylidene fluoride component, and the composition is present at 0.015% LDR and 1% LDR. Invention Details

[0075] The liquid additive compositions of the present invention offer processing and appearance advantages in film applications. In exemplary embodiments, the fluoropolymer component of the liquid additive composition is blended with a suitable resin to produce a variety of different film applications. Objectives for preparing articles containing liquid additive compositions (e.g., films) include minimizing the amount of liquid additive composition required for desired film properties, and achieving lower processing temperatures and faster processing times, which improves the efficiency and productivity of methods for preparing additive-containing articles, while also resulting in reduced energy consumption and waste generation. Small-batch use also increases production flexibility.

[0076] The liquid additive composition of the present invention may be in the form of a solution, a colloid, or a suspension, wherein the form is generally dependent on temperature.

[0077] In an exemplary embodiment, the ideal visual properties of a film containing the liquid additive composition of the present invention include improved clarity and enhanced finished surface on the final article.

[0078] In one exemplary embodiment, the processing advantages of films containing the liquid additive composition of this application include: reduced or eliminated die build-up, increased productivity, uninterrupted film production line processing, reduced degradation due to lower processing temperatures, shorter color change transitions, and reduced film friction (slippage).

[0079] The aforementioned advantages associated with the use of the additive compositions of the present invention are likely due to the fact that the additive compositions have an affinity for metals, which allows for easy coating of processing equipment and dies. This property allows for the formation of a low surface energy coating within the processing equipment, which facilitates the movement of the masterbatch material through the equipment, minimizes or eliminates undesirable defects in the film (e.g., sharkskin), increases slip performance, improves productivity, reduces processing temperature, and reduces torque and psi.

[0080] Fluoropolymer components

[0081] Polyvinylidene fluoride (PVDF) is a preferred fluoropolymer in the liquid additive composition of the present invention, but other suitable fluoropolymers include polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), and ethylene fluoride (PVF). In an exemplary embodiment, the amount of the fluoropolymer component in the liquid additive composition is 12 to 22% by weight, for example 13 to 21% by weight, for example 14 to 21% by weight, for example 15 to 20% by weight, for example 15 to 18% by weight. Preferred polyvinylidene fluoride includes: Kynar 5300, Kynar 5301, Kynar 3121-50 and Kynar 2821.

[0082] Organic phosphite components

[0083] The organic phosphite component of the liquid additive composition of the present invention is used as a processing stabilizer, which protects the polymer from changes in molecular weight and thermal oxidative degradation by decomposing hydrogen peroxide to form non-radical, non-reactive products. 126 and 168 is a preferred organophosphite, which is present in the liquid additive composition in an amount of 15 to 35% by weight, for example 17 to 35% by weight, for example 19 to 33% by weight, for example 20 to 30% by weight, for example 20 to 25% by weight.

[0084] sterically hindered phenolic components

[0085] The sterically hindered phenolic components of the liquid additive compositions of the present invention primarily function as non-discoloring stabilizers to prevent thermal oxidative degradation. Preferred sterically hindered phenols include: 1010 1035 1076、 1098 1135、 1330 1425, 1520L 1726 245. 245DW 3114、 565, Rianox (Thanox) 1076, Rianox (Thanox) 1098, Rianox (Thanox) 1790, and Rianox (Thanox) 3114. The sterically hindered phenols are present in the liquid additive composition in amounts of 0.5 to 10% by weight, for example 1 to 10% by weight, for example 2 to 8% by weight, for example 3 to 7% by weight, for example 4 to 6% by weight.

[0086] hydrocarbon polymer components

[0087] Polymerized C4 olefins (e.g., polybutene) are preferred hydrocarbon components in the liquid additive compositions of the present invention, but other suitable hydrocarbon polymers include copolymers of ethylene and propylene. In a specific embodiment, polybutene is one or more of the following: L-2, L-3, L-6 L-8, L-14 H-7 H-8 H-15 H-25, H-50 H-100 H-300 and H-1200. The amount of the hydrocarbon polymer in the liquid additive composition is 0.5 to 10% by weight, for example 1 to 10% by weight, for example 2 to 8% by weight, for example 3 to 7% by weight, for example 4 to 6% by weight.

[0088] Polymer dispersant components

[0089] The polymeric dispersant component present in various embodiments of the liquid additive composition of the present invention helps to wet particles present in the composition, reduce particle size, and / or stabilize particles. Preferred polymeric dispersants include: Solplus. TM K240, Solplus TM K241, Solplus TM K251, Solplus TM DP310, Solplus TM D320, Solplus TM D330 and Solplus TM DP700, but polyhydroxystearic acid dispersants and polyolefin amide enamine dispersants are also suitable. The amount of polymeric dispersant in the liquid additive composition is 0.1 to 5 wt%, for example 0.3 to 5 wt%, for example 0.5 to 5 wt%, for example 0.5 to 3 wt%, for example 0.5 to 2 wt%, for example 1 to 3 wt%.

[0090] Micronized wax components

[0091] Micronized waxes are typically linear synthetic paraffins with a carbon number greater than 30, providing better anti-slip, abrasion-resistant, and matte finish properties. Preferred micronized wax components present in various embodiments of the liquid additive compositions of this invention are polyethylene or polyethylene-containing waxes, but other suitable micronized waxes include Carnuba, ethylene bis-stearamide, and polypropylene micronized waxes. Preferred micronized polyethylene or polyethylene-containing waxes include: 3715 3716TP, 3620 5551 and 9615A. The amount of micronized polyethylene or polyethylene-containing wax in the liquid additive composition is 0.5 to 6% by weight, for example 1 to 5% by weight, for example 1 to 4% by weight, for example 2 to 4% by weight.

[0092] film

[0093] The liquid additive compositions of this invention unexpectedly improve the clarity and surface appearance of films (e.g., cast or blown films) (e.g., reducing or eliminating sharkskin defects). Furthermore, the presence of the liquid additive compositions during film preparation provides several advantages, such as reducing die head build-up due to the composition's affinity for metals, increasing productivity by forming a low surface energy coating within the processing equipment, shortening color transitions, reducing product degradation, improving batch flowability, and reducing equipment torque and pressure (psi).

[0094] The liquid additive ratio (LDR) provides a method for identifying the concentration usage rate of the liquid additive composition of the present invention. For example, using 1 gram of liquid additive composition (100:1) per 99 grams of polymer / resin to be treated produces a 1% LDR. Using 2 grams of liquid additive composition (50:1) per 98 grams of polymer / resin to be treated produces a 2% LDR, and so on. It has been observed that, for films, desirable results can be obtained at LDRs of 0.005% to 5%, for example 0.005% to 3%, for example 0.01% to 3%, for example 0.01% to 2%, for example 0.01% to 1%.

[0095] It was also unexpectedly observed that Kynar, which is used as a component of polyvinylidene fluoride, The liquid additive composition of 5301 is preferably used at a processing temperature of up to 500°F (i.e., "low-temperature additive composition"), and contains Kynar as a polyvinylidene fluoride component. Embodiments of the liquid additive composition of 3121 are preferably used at processing temperatures above 500°F, for example, up to 2000°F (i.e., "high-temperature additive compositions"). Low-temperature additive compositions are typically observed to provide a moderately clearing effect visually, with increased transmittance as the level-to-difference ratio (LDR) increases, and require third-party pulverization. In contrast, in one exemplary embodiment, high-temperature additive compositions are typically observed to provide a significant clearing effect visually, exhibiting optimal transmittance at lower level-to-difference ratios (LDRs), and do not require pulverization.

[0096] Masterbatch

[0097] The masterbatch consists of a polymer matrix (i.e., a carrier) and a high loading of pigments and / or other additives, wherein the polymer matrix is ​​the same as or compatible with the polymer to be added to the masterbatch. The liquid additive compositions of the present invention are suitable for improving masterbatch properties by promoting the movement of the masterbatch material through processing equipment for preparing plastics. The resulting plastics typically exhibit excellent properties. In exemplary embodiments, the amount of the liquid additive composition in the masterbatch is 0.05 to 90 wt%, for example 1 to 80 wt%, for example 5 to 80 wt%, for example 10 to 70 wt%, for example 15 to 70 wt%, for example 20 to 60 wt%, for example 25 to 55 wt%, wherein the wt% is based on the total weight of the masterbatch.

[0098] Extrusion blow molding

[0099] The advantages obtained by using the liquid additive composition of the present invention during extrusion blow molding are substantially similar to those obtained by using the liquid additive composition in the preparation of the cast or blown films described herein. Example

[0100] The purpose of preparing liquid additive compositions is to obtain uniform rheology, suitable flow rates, and maximum loading of components. A second objective is to develop liquid additive compositions as liquid masterbatches that exhibit minimal or insignificant sedimentation during storage.

[0101] Example 1. Preparation of "Low Temperature" Liquid Additive Composition

[0102] H-25 L-14 and Solplus TM K240 and The 1:1 mixture of L-14 was mixed in a mixing vessel to 110°F, and then added... 168. Rianox 1076. 3620 and crushed Kynar 5301. After mixing, allow the temperature to cool. When the temperature is below 80°F, add... Apply N20 silica until it is evenly dispersed and no visible clumps remain.

[0103] Example 2. Preparation of "High Temperature" Liquid Additive Composition

[0104] H-25, L-14 and Solplus TM K240 and The 1:1 mixture of L-14 was mixed in a mixing vessel to 110°F, and then added... 168. Rianox 1076. 3620 and uncrushed 3121. After mixing, allow the temperature to cool. When the temperature is below 80°F, add... Apply N20 silica until it is evenly dispersed and no visible clumps remain.

[0105] Results and discussion

[0106] Figure 1 The results show that all the tested additive compositions of this invention exhibit improved clarification in LLDPE compared to the original LLDPE. At 0.015% LDR, using Kynar... 3121 achieved the most significant overall clarification effect. (Using Kynar...) 3121 achieved the most significant clarification effect with the lowest LDR. (Using Kynar...) The clarification effect obtained by 5301 is proportionally improved to LDR. Figure 2 and Figure 3 The differences in clarity improvement are shown in LLDPE resins containing different amounts of the exemplary LLDPE additive compositions of the present invention.

[0107] All patents / publications cited in this article are included in full by way of citation.

Claims

1. A liquid additive composition, said composition comprising: Fluoropolymers; Organic phosphite antioxidants; sterically hindered phenolic antioxidants; Hydrocarbon polymer components; and One or more polymer dispersants, wherein the polymer dispersant is not a hydrocarbon polymer component. in, The fluoropolymers include polyvinylidene fluoride, polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), and ethylene fluoride (PVF), and the content of the fluoropolymers is 10 to 25% by weight. The hydrocarbon polymer component includes copolymers of polymerized C4 olefins, ethylene and propylene, and the content of the hydrocarbon polymer component is 0.5 to 10% by weight. The content of one or more polymer dispersants is 0.1 to 10% by weight.

2. The liquid additive composition of claim 1, wherein, The viscosity of the liquid additive composition is from 3,000 to 20,000 centipoise.

3. The liquid additive composition according to claim 1 or claim 2, wherein, The amount of fluoropolymer is 12% to 22% by weight.

4. The liquid additive composition of claim 1, wherein, The amount of organic phosphite antioxidant is 15% to 35% by weight.

5. The liquid additive composition of claim 1, wherein, The amount of sterically hindered phenolic antioxidants is 0.5% to 10% by weight.

6. The liquid additive composition of claim 1, wherein, The amount of one or more hydrocarbon polymer dispersants is from 0.3% to 5% by weight.

7. The liquid additive composition of claim 1, wherein, The fluoropolymer is polyvinylidene fluoride.

8. The liquid additive composition of claim 1, wherein, The composition also contains other antioxidants.

9. The liquid additive composition of claim 1, wherein, One or more polymer dispersants are: Solplus TM K240, Solplus TM K241, Solplus TM K251, Solplus TM DP310, Solplus TM D320, Solplus TM D330 and Solplus TM DP700.

10. The liquid additive composition of claim 1, wherein, One or more polymeric dispersants include polyhydroxystearic acid dispersants and polyolefin amide enamine dispersants.

11. The liquid additive composition of claim 1, wherein, The composition also contains a matting agent.

12. The liquid additive composition of claim 11, wherein, Matting agents are micronized polyethylene or polyethylene-containing waxes.

13. The liquid additive composition of claim 1, wherein, The composition also contains a thixotropic agent.

14. The liquid additive composition of claim 13, wherein, The thixotropic agent is silicon dioxide.

15. The liquid additive composition of claim 1, wherein, The composition comprises: Fluoropolymers; Organic phosphites; sterically hindered phenols; Two different polymerized C4 olefins; Polymer dispersants, which are not polymerized C4 olefins; Micronized polyethylene or polyethylene-containing waxes; and Silicon dioxide.

16. The liquid additive composition of claim 9 or 10, wherein, The composition comprises the following substances composition: Fluoropolymers; Organic phosphites; sterically hindered phenols; Two different polymerized C4 olefins; Polymer dispersants, which are not polymerized C4 olefins; Micronized polyethylene or polyethylene-containing waxes; and Silicon dioxide.

17. An article comprising a liquid additive composition as described in any of the preceding claims.

18. A film comprising the liquid additive composition as described in any one of claims 1 to 16.

19. The thin film of claim 18, wherein, The film is either blown film or cast film.

20. An extruded blow-molded article comprising the liquid additive composition as described in any one of claims 1 to 16.

21. A masterbatch comprising the liquid additive composition as described in any one of claims 1 to 16.

22. A method for improving the clarity of a thin film, the method comprising: The liquid additive composition as described in any one of claims 1 to 16 is added to the film or film precursor.

23. A method for improving the surface appearance of a thin film, the method comprising: The liquid additive composition as described in any one of claims 1 to 16 is added to the film or film precursor.

24. A method for preparing a thin film, the method comprising the step of adding a liquid additive composition as described in any one of claims 1 to 16.

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