阅读说明：本技术 用于光泽度和表面光洁度改性的官能化丙烯酸系加工助剂 (Functionalized acrylic processing aids for gloss and surface finish modification ) 是由 K·R·尤卡 D·A·芒茨 J·M·莱昂斯 于 2017-03-23 设计创作，主要内容包括：一种减小光泽度的方法,该方法得到一种聚氯乙烯(PVC)部件,该部件表现出减小的表面光泽度,其中PVC或其他热塑性树脂部件包含：PVC树脂、一种或多种加工助剂以及任选的至少一种抗冲改性剂,所述加工助剂包含至少一种基础聚合物,并且所述加工助剂中的一种或多种用基于加工助剂总重的约0.5重量％至约35重量％的反应性环氧基、羟基或羧酸官能团官能化。所述PVC或其他热塑性树脂部件与加工助剂未官能化的类似PVC部件相比,在85度以下的角度测得的光泽度减小至少5点。(A method of reducing gloss resulting in a polyvinyl chloride (PVC) part exhibiting reduced surface gloss, wherein the PVC or other thermoplastic resin part comprises: PVC resin, one or more processing aids comprising at least one base polymer, and one or more of the processing aids functionalized with reactive epoxy, hydroxyl, or carboxylic acid functional groups in an amount of from about 0.5 to about 35 weight percent, based on the total weight of the processing aid, and optionally at least one impact modifier. The PVC or other thermoplastic resin part has a reduction in gloss measured at an angle below 85 degrees of at least 5 points as compared to a similar PVC part that has not been functionalized with a processing aid.)

1. A polyvinyl chloride (PVC) part having reduced surface gloss, comprising:

PVC resin, one or more crosslinked functionalized non-core-shell processing aids comprising at least one base polymer, said processing aids functionalized with about 1 to about 25 wt%, based on the total weight of the processing aid, of reactive epoxy or hydroxyl functional groups, and optionally at least one impact modifier; wherein the PVC part has a reduction in gloss measured at an angle below 85 degrees of at least 5 points as compared to a similar PVC part that has not been functionalized with a processing aid; wherein the one or more crosslinked functionalized non-core-shell processing aids have a molecular weight (M) in the filtered or unfiltered state_w) Is more than 50000 g/mol; wherein a portion of the one or more crosslinked functionalized non-core-shell processing aids is insoluble in an organic solvent, the insoluble portion ranging from 1% to about 90% as measured by extraction with acetone as the solvent; wherein the PVC resin and the crosslinked functionalized non-core-shell processing aid do not contain an additional crosslinking agent other than the functional groups on the processing aid.

2. The PVC member of claim 1, wherein the processing aid is present in an amount from about 0.1phr to about 12 phr.

3. The PVC member of claim 1, wherein the one or more processing aids are functionalized with at least 5 wt% of reactive functional groups based on the total weight of the processing aid.

4. The PVC member of claim 1, wherein the PVC member has a reduction in gloss measured at an angle of 60 degrees or less of at least 10 points as compared to a similar PVC member without functionalization of the processing aid.

5. The PVC member of claim 1, wherein the PVC member containing the functionalized processing aid has impact properties comparable to a similar PVC member containing an unfunctionalized processing aid, the impact properties being measured as izod or dart impact properties.

6. The PVC member of claim 1, wherein the reactive epoxy or hydroxyl functional group is derived from one or more of a hydroxy-substituted alkyl ester of (meth) acrylic acid or an epoxy-containing monomer.

7. The PVC member of claim 1, wherein the base polymer of the one or more processing aids comprises an acrylic polymer or copolymer.

8. PVC part according to claim 1, wherein the molecular weight (M) of the one or more processing aids_w) About 100000g/mol or more.

9. PVC part according to claim 7, wherein the acrylic copolymer is derived from monomers comprising vinyl or (meth) acrylic groups; styrene or styrene derivatives; an olefin; a diene; or mixtures thereof.

10. The PVC component according to claim 1, wherein the molecular weight (M) of the one or more crosslinked functionalized non-core-shell processing aids_w) At least 2690000g/mol and at most 15000000 g/mol.

11. The PVC member of claim 1, wherein the insoluble portion of the crosslinked functionalized non-core-shell processing aid is in the range of 4% to about 90%.

12. The PVC member of claim 1, wherein the insoluble portion of the crosslinked functionalized non-core-shell processing aid is in the range of 10% to about 90%.

13. The PVC member of claim 1, wherein the insoluble portion of the crosslinked functionalized non-core-shell processing aid is in the range of 20% to about 90%.

14. The PVC component according to claim 1, wherein the molecular weight (M) of the one or more crosslinked functionalized non-core-shell processing aids_w) In the range of at least 2690000g/mol up to 15000000g/mol, the insoluble portion of the crosslinked functionalized non-core-shell processing aid is in the range of 10% to about 90%.

15. An automotive product, a building material, a household or kitchen item, a medical or office item, a garment, or a packaging material for a personal care product comprising the PVC member of claim 1.

16. A method of reducing surface gloss of a polyvinyl chloride (PVC) part, the method comprising:

providing a PVC resin;

forming at least one base polymer as a non-core-shell processing aid;

functionalizing the at least one base polymer to form a crosslinked functionalized non-core-shell processing aid, wherein the base polymer is functionalized with about 1 wt% to about 25 wt% of reactive epoxy or hydroxyl functional groups based on the total weight of the processing aid;

optionally providing at least one core-shell impact modifier;

producing a PVC formulation from the PVC resin, a crosslinked functionalized non-core-shell processing aid, and optionally a core-shell impact modifier; and

forming a PVC part from the PVC formulation,

wherein the PVC part has a reduction in gloss measured at an angle below 85 degrees of at least 5 points as compared to a similar PVC part that has not been functionalized with a processing aid; wherein the one or more crosslinked functionalized non-core-shell processing aids have a molecular weight (M) in the filtered or unfiltered state_w) Is more than 50000 g/mol; wherein the intersection isA portion of the linked functionalized non-core-shell processing aid is insoluble in an organic solvent, the insoluble portion ranging from 1% to about 90% as measured by extraction with acetone as the solvent; wherein the PVC resin and the crosslinked functionalized non-core-shell processing aid do not contain an additional crosslinking agent other than the functional groups on the processing aid.

17. The method according to claim 16, wherein the processing aid is present in an amount of from about 0.1phr to about 12phr, based on the PVC resin.

18. The method of claim 16, wherein the one or more processing aids are functionalized with at least 5 wt.% of reactive functional groups based on the total weight of the processing aid.

19. The method of claim 16, wherein the PVC member has a reduction in gloss of at least 10 points measured at an angle of 60 degrees or less.

20. The process according to claim 16, wherein the PVC part containing the functionalized processing aid has impact properties comparable to similar PVC parts containing non-functionalized processing aid, said impact properties being measured as izod or dart impact properties.

21. The method of claim 16, wherein the reactive epoxy or hydroxyl functional group is derived from one or more of a hydroxy-substituted alkyl ester of (meth) acrylic acid or an epoxy-containing monomer.

22. The method of claim 16, wherein the base polymer of the one or more processing aids comprises an acrylic polymer or copolymer.

23. The method of claim 16, wherein the one or more functionalized processing aids have a molecular weight (M)_w) About 100000g/mol or more.

24. The method according to claim 22, wherein the acrylic copolymer is derived from a vinyl or (meth) acrylic group containing monomer or derivative thereof; styrene or styrene derivatives; an olefin; a diene; or mixtures thereof.

Technical Field

The present disclosure relates generally to processing aids used in polyvinyl chloride (PVC) formulations and other thermoplastic polymers. More particularly, the present disclosure relates to processing aids capable of reducing the specular gloss of PVC and other thermoplastic polymer parts without sacrificing mechanical properties.

Background

The statements in this section merely provide background information related to the present disclosure and may not constitute prior art.

Polyvinyl chloride (PVC) resins are generally chemically inert, resistant to water and environmental corrosion, provide good insulation and heat-insulating properties, and can maintain performance over a wide temperature range. Commercial polymerization processes and post-polymerization processing techniques (e.g., extrusion, injection molding, blow molding, etc.) for polyvinyl chloride (PVC), often referred to as "vinyl", have matured over the past century. The manufacturing base and the basic properties exhibited by PVC have led to vigorous development of PVC-containing products. For example, in the past decade, the sales volume for vinyl based windows (e.g., approximately 3100 thousands/year) has exceeded the sales volume for wood and aluminum windows. The vinyl product is durable, recyclable, and easy to maintain. They are resistant to fungal and mold growth and are not affected by rot, corrosion, cracking, flaking or insect damage. Vinyl products exhibit excellent fire performance and meet most building codes for flammability, heat release, burn rate, flame spread, and smoke generation. Since vinyl products are generally all-in-one, small scratches do not require painting or repair, and the aesthetics are easily maintained by washing with soap and water. With proper installation and maintenance, vinyl products can provide long-lasting aesthetic, reliable performance, and sustained energy savings.

The dispersion of pigments into PVC formulations can be used to provide color, while the incorporation of a matting agent into the formulation can alter the surface gloss exhibited by the finished PVC product. Matting agents are generally classified into three categories: i) polymeric core/shell impact modifiers having a polybutylacrylate core and a polymethyl acrylate shell, such as Paraloid^TM[ Midland, Mich.) Dow chemical company](ii) a ii) crosslinked polymethyl methacrylate particles with an average size of several micrometers, e.g.MBX K-8[ Sekisui Plastics Co. Ltd. ] (Tokyo Plastics Co., Ltd.)]OrBS 100 particles (alcoma corporation, prince prussian, pa); and iii) polymers such as methyl methacrylate/styrene copolymers, e.g.OP 278[ Essen, Germany, winning Industrial Corp (Evonik Industries)]. However, many of the matting agent technologies used in PVC and other thermoplastic polymers and resins either fail to substantially reduce surface gloss or can adversely affect the mechanical properties associated with the molded PVC parts.

Other thermoplastic resins can also be used with similar potential as PVC resins to produce the final article using similar post-polymerization processing. These resins include acrylic polymers, styrenic, polyolefin, PVC blends, polycarbonate, polyurethane, fluoropolymer and mixtures thereof.

U.S. patent No. 7,557,158 discloses thermoplastic polymer compositions that can be processed into capstocks having a reduced gloss appearance, high impact strength, and excellent weatherability. The thermoplastic polymer composition is said to comprise a core/shell polymer wherein the core is derived from an alkyl acrylate monomer and the shell is a copolymer derived from an alkyl methacrylate monomer and another copolymerizable monomer.

U.S. patent No. 3,301,919 discloses a processing aid for polyvinyl chloride, which essentially comprises a linear copolymer obtained by polymerizing a mixture of 20 to 98.5 wt.% methyl methacrylate, 0.5 to 40 wt.% ethyl acrylate, and 1 to 40 wt.% glycidyl methacrylate, such that the ethylene oxide ring in at least 85% of the glycidyl acrylate units remains intact.

Korean patent No. 101030513 discloses a method for manufacturing a methacrylate copolymer used as a processing aid for vinyl chloride resins. The method comprises the following steps: polymerizing the monomer mixture in the presence of a water-soluble initiator and an emulsifier to prepare a polymer latex; the polymer latex is then cured. The monomer mixture comprises 60 to 85% by weight of methyl methacrylate, 15 to 30% by weight of an alkyl acrylate-based compound and 1 to 10% by weight of an epoxide-based compound.

Summary of The Invention

The present invention generally provides polyvinyl chloride (PVC) and other thermoplastic polymers and resins having reduced surface gloss, and methods of reducing the surface gloss. PVC or other thermoplastic polymers/resins comprise: polymers or resins, such as PVC; one or more processing aids; and optionally at least one impact modifier. Parts made from PVC or other thermoplastic polymers/resins have a reduction in gloss measured at angles below 85 degrees of at least 5 points as compared to similar parts that have not been functionalized with a processing aid. Parts made from PVC or other thermoplastic polymers/resins can be used in automotive products, building materials, household or kitchen goods, medical or office goods, electronics, apparel, or packaging materials for personal care products or other consumer products.

The processing aid comprises at least one base polymer, one or more of which is functionalized with about 0.5 to 35 wt.% of a reactive epoxy, hydroxyl, or carboxylic acid functional group, based on the total weight of the processing aid. The processing aid may be present in the PVC formulation in an amount of about 0.1 to about 12phr, or in other (i.e., non-PVC) thermoplastic resin parts in an amount of about 0.1 to about 20 phr. If desired, the processing aid can be functionalized with at least 1 wt%, based on the total weight of the processing aid, of reactive functional groups. The reactive epoxy, hydroxyl, or carboxylic acid functional groups in the processing aid can be derived from hydroxy-substituted alkyl esters of (meth) acrylic acid; vinyl esters of straight or branched carboxylic acids; unsaturated C₃-C₆Monocarboxylic acids and unsaturated C₄-C₆A dicarboxylic acid; an epoxy-containing monomer; or mixtures thereof.

According to one aspect of the present disclosure, a PVC or other thermoplastic resin component may exhibit at least a 10 point reduction in gloss when measured at angles below 60 degrees. In addition, PVC or other thermoplastic resin parts containing functionalized processing aids and similar PVC parts containing non-functionalized processing aids can exhibit comparable impact properties. This impact property may be, but is not limited to, an Izod (Izod) impact property or a dart impact property.

According to another embodiment of the present disclosure, the processing aid may have an average molecular weight or weight average molar mass of about 50000g/mol or more. The base polymer in the processing aid may comprise an acrylic polymer or copolymer. The acrylic polymer or copolymer may be derived from vinyl or (meth) acrylic group containing monomers; styrene or styrene derivatives; an olefin; a diene; or mixtures thereof. Processing aids aid in crosslinking inside PVC or other thermoplastic resin parts. The processing aid may also contain 0 to about 1 weight percent of a chain transfer or crosslinking agent.

A method of reducing the surface gloss of a polyvinyl chloride (PVC) or other thermoplastic resin component comprising: providing PVC or other base thermoplastic resin; forming at least one base polymer as a processing aid; functionalizing the at least one base polymer to form a functionalized processing aid; optionally providing at least one impact modifier; forming a formulation from a base resin, a functionalized processing aid, and optionally an impact modifier; PVC or other thermoplastic resin parts are formed from the formulation. The base polymer is functionalized with about 0.5 to 35 weight percent of a reactive epoxy, hydroxyl, or carboxylic acid functional group based on the total weight of the processing aid. The resulting PVC part has a gloss reduction measured at an angle below 85 degrees of at least 5 points as compared to a similar PVC part that has not been functionalized with a processing aid. Alternatively, the PVC or other thermoplastic resin part exhibits at least a 10 point reduction in gloss when measured at an angle of 60 degrees or less. PVC or other thermoplastic resin parts containing functionalized processing aids and similar PVC parts containing non-functionalized processing aids can exhibit comparable impact properties. This impact property may be, but is not limited to, measured as an izod or dart impact property.

The method of reducing gloss may further comprise the presence of a processing aid in the PVC formulation in a range of about 0.1 to about 12phr or in other thermoplastic resin formulations in a range of about 0.1 to about 20 phr. If desired, the processing aid can be functionalized with at least 1 wt%, based on the total weight of the processing aid, of reactive functional groups. The reactive epoxy, hydroxyl, or carboxylic acid functional groups in the processing aid can be derived from hydroxy-substituted alkyl esters of (meth) acrylic acid; vinyl esters of straight or branched carboxylic acids; unsaturated C₃-C₆Monocarboxylic acids and unsaturated C₄-C₆A dicarboxylic acid; an epoxy-containing monomer; or mixtures thereof. The base polymer in the processing aid may comprise an acrylic polymer or copolymer. The acrylic polymer or copolymer may be derived from vinyl or (meth) acrylic group containing monomers; styrene or styrene derivatives; an olefin; a diene; or mixtures thereof. The functionalized processing aid can have a molecular weight (M) of about 50000g/mol or greater_w)。

Further areas of applicability will become apparent from the description provided herein. It should be understood that the description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure.

Brief description of the drawings

The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure in any way.

FIG. 1 is a schematic illustration of a method of forming a part from PVC or other thermoplastic polymers/resins in accordance with the teachings of the present disclosure;

FIG. 2 is a graph comparing surface gloss (75 ℃) and impact strength measured for PVC parts made from various PVC formulations of the present disclosure and conventional PVC formulations; and

fig. 3 is another graph comparing the measured surface gloss (60 °) and impact strength of PVC parts prepared from various PVC formulations of the present disclosure and conventional PVC formulations.

Detailed Description

The following description is merely exemplary in nature and is in no way intended to limit the disclosure, its application, or uses. For example, to more fully illustrate the compositions and their uses, polyvinyl chloride (PVC) formulations prepared and used in accordance with the teachings contained in the present disclosure are described throughout the present disclosure in connection with "PVC" or "vinyl" windows and doors. The incorporation and use of such PVC formulations in other applications or products is considered to fall within the scope of the present disclosure. Formulations prepared with other thermoplastic polymers/resins in other applications or products are also considered to fall within the scope of the present disclosure. Such applications may include, but are not limited to, automotive products, building materials, household or kitchen goods, medical or office goods, apparel, or packaging materials for personal care products or other consumer products. It should be understood that throughout the specification, corresponding reference numerals indicate like or corresponding parts and features.

The present disclosure generally provides polyvinyl chloride (PVC) or other thermoplastic resin components that exhibit reduced surface gloss without sacrificing mechanical properties. More specifically, the PVC or other thermoplastic resin component comprises, consists essentially of, or consists of: polyvinyl chloride (PVC) or other thermoplastic resin, one or more processing aids, and optionally at least one impact modifier, wherein at least one of the processing aids is functionalized with about 0.5 to 35 weight percent of reactive epoxy, hydroxyl, or carboxylic acid functional groups, based on the total weight of the processing aid. The PVC or other thermoplastic resin parts formed therefrom have a reduction in gloss, measured at angles below 85 degrees, of at least 5 points, as compared to similar PVC parts not functionalized with a Processing Aid (PA). The functionalized processing aid (f-PA), used alone or in combination with an impact modifier, surprisingly reduces surface gloss and retains the mechanical properties exhibited by PVC or other thermoplastic resin parts, which is beneficial for many applications where aesthetics is important. Mechanical properties that are not substantially affected or enhanced by the functionalization of the processing aid with reactive functional groups include, but are not limited to, impact properties and density, as well as parameters related to the processability (e.g., extrusion) of PVC or other thermoplastic resin formulations.

According to one aspect of the present disclosure, the reduction in surface gloss exhibited by PVC parts comprising the functionalized processing aid (f-PA) as compared to similar PVC parts comprising the conventional Processing Aid (PA) can be alternatively characterized by at least 10 points measured at angles below 60 degrees, or at least 15 points measured at angles below 20 degrees. Alternatively, the change in surface gloss (Δ) between a PVC part containing f-PA and a similar PVC part containing conventional PA is greater than about 5 points measured at any angle; or greater than about 10 points measured at any angle; or greater than 20 points measured at 85 °; or greater than 25 points measured below 60 °; or greater than 30 points measured below 60 deg..

According to another aspect of the present disclosure, a functionalized processing aid synthesized for polyvinyl chloride processing, modified with the above-described functional groups, and further as defined herein, achieves a different effect in the polyvinyl chloride matrix than conventional acrylic processing aids. Functionalized processing aids comprise synthetic acrylic polymers or copolymers containing reactive epoxy, hydroxyl, or carboxylic acid functional groups that are capable of reacting during use to form PVC or other thermoplastic resin parts. Examples of methods capable of forming PVC or other thermoplastic resin components include, but are not limited to, extrusion processes. During extrusion, the reactive functional groups facilitate crosslinking in the presence or absence of an optional chain extender or crosslinker. When desired, crosslinking during extrusion may occur between particles formed by the processing aid (e.g., crosslinking between the processing aid and/or crosslinking between the processing aid and the PVC). Conventional processing aids used in polyvinyl chloride (PVC) formulations typically comprise acrylate and methacrylate monomers, which are not reactive in such processing. The functionalized processing aids of the present disclosure can be prepared according to any method known in the art, including but not limited to emulsion polymerization.

The processing aid can be an "acrylic" polymer or copolymer having a variety of different compositions and molecular weights. They may have a higher molecular weight than the molecular weight of the PVC resin or other thermoplastic resins. In particular in PVC resins, they assist the intergranular mixing of the PVC particles during the initial stage of the fusion, due to their very good compatibility with PVC resins. The processing aids of the present disclosure can have a weight average molecular weight (also referred to as molar mass (M) of greater than about 50000g/mol_w) ); alternatively, the weight average molecular weight of the processing aid is greater than about 100000 g/mol; alternatively, the molecular weight (M) of the processing aid_w) About 250000g/mol or more; or, of processing aids (M)_w) The soluble fraction is between about 50000g/mol to about 15000000g/mol, or between about 750000g/mol to about 12000000 g/mol. Molecular weight can be measured by any known method, including but not limited to gel chromatography (GPC), the procedure of which is further described in example 2. The upper limit for molecular weight measurement can be affected by the cross-linking that occurs between the polymer processing aids.

In one embodiment, the processing aids of the present invention surprisingly exhibit insolubility in organic solvents. The soluble and insoluble portions of the processing aid can be determined by using extraction techniques (see example 2) with solvents such as Tetrahydrofuran (THF) or Methyl Ethyl Ketone (MEK). The insoluble portion of the processing aid is in the range of 1% to about 90%; alternatively, the insoluble fraction is in the range of about 2% to about 70%; alternatively, the insoluble fraction is in the range of about 4% to about 55%, preferably about 10-50%, more preferably about 20-45%, and even more preferably about 25-40%.

The processing aid has a value equal toOr a glass transition temperature (T) greater than 0 ℃ and up to about 150 ℃_g) (ii) a Or T of a processing aid_gIn the range of about 60 ℃ to about 85 ℃. T of processing aid_gMeasured in powder form or in the form of a pressed bar formed from the powder using any known method, including but not limited to Differential Scanning Calorimetry (DSC) analysis as further described in example 3.

The processing aid comprises a base polymer or copolymer derived from ethylenically unsaturated monomers including, but not limited to, vinyl or (meth) acrylic group containing monomers such as linear or branched alkyl esters of acrylic or methacrylic acid; styrene and styrene derivatives; olefins, such as ethylene; dienes, such as butadiene; and mixtures thereof, with linear or branched alkyl esters of acrylic or methacrylic acid being preferred. Several specific examples of monomers comprising vinyl or (meth) acrylic groups include, but are not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate (BMA), 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, and mixtures thereof, with methyl (meth) acrylate, ethyl (meth) acrylate, and glycidyl (meth) acrylate being preferred. Alternatively, the base polymer or copolymer may be polymethyl methacrylate, polybutyl acrylate, polyethyl acrylate, methyl methacrylate-styrene copolymer, or mixtures thereof. Alternatively, the base polymer comprises preferably polymethylmethacrylate for compatibility with the PVC matrix. When desired, other acrylates, such as polybutylacrylate or polyethylacrylate, may be added at levels of 10-30 wt% to control the glass transition temperature (T) of the functionalized processing aid_g) And fusion properties.

At least one of the processing aids used in the PVC or other thermoplastic resin formulation forming the PVC or other thermoplastic resin component is functionalized with about 0.5 to 35 wt% of reactive epoxy, hydroxyl, or carboxylic acid functional groups, based on the total weight of the processing aid. Alternatively, the reactive functional group is present in an amount between about 1% and about 25% by weight; alternatively, the processing aid comprises between at least about 5 wt.% and about 20 wt.% of reactive functional groups, based on the total weight of the one or more processing aids. Not all processing aids employed in the formulation need be functionalized. In other words, the conventional Processing Aid (PA) and the functionalized processing aid (f-PA) may be used in combination. The ratio of PA to f-PA can range from 0:100 to about 75: 25; alternatively, from about 0:100 to about 50: 50; alternatively, 0:100 to about 25: 75.

The processing aid may be used in powder or granular form. The powder or particles may be solid particles comprising a base polymer substantially functionalized with reactive functional groups, or the powder or particles may be pseudo-core/shell particles. The functionalized processing aid (f-PA) may be prepared by a multi-step polymerization process such that the functionalized processing aid resembles a pseudo core/shell particle comprising a core made of a non-functionalized base polymer, at least a portion of the core being encapsulated by a shell comprising reactive epoxy, hydroxyl or carboxylic acid functional groups.

The reactive epoxy, hydroxyl, or carboxylic acid functional groups may result from the addition of an epoxy, hydroxyl, or carboxylic acid containing monomer to the base polymer. Examples of such monomers include, but are not limited to, hydroxy-substituted alkyl (meth) acrylates, such as 2-hydroxyethyl (meth) acrylate; vinyl esters of straight-chain or branched carboxylic acids, e.g. vinyl valerate, unsaturated carboxylic acids, including unsaturated C₃-C₆Monocarboxylic acids, e.g. Acrylic Acid (AA), unsaturated C₄-C₆Dicarboxylic acids such as maleic acid and itaconic acid; and epoxy group-containing monomers such as glycidyl acrylate or Glycidyl Methacrylate (GMA). Preferably unsaturated C₃-C₆Monocarboxylic acids, e.g. Acrylic Acid (AA), unsaturated C₄-C₆Dicarboxylic acids such as maleic acid and itaconic acid, and epoxy group-containing monomers such as glycidyl acrylate or Glycidyl Methacrylate (GMA), with acrylic acid, glycidyl acrylate, and Glycidyl Methacrylate (GMA) being more preferred. Alternatively, the functional groups may be incorporated into the base polymer of the process aid by the addition of most preferably Acrylic Acid (AA), Glycidyl Methacrylate (GMA), or mixtures thereof.

The amount of processing aid in the PVC formulation may range from about 0.1phr to about 12phr in the PVC formulation, or from 0.1phr to about 20phr in other thermoplastic resin parts; alternatively, from about 0.1phr to about 7phr in PVC formulations, or from about 0.1phr to about 10phr in other thermoplastic resinous parts; alternatively, greater than or equal to 1 phr. In the context of the present disclosure, the term "phr" means parts in 100 parts of PVC or other thermoplastic base resin. The amount of processing aid in the PVC or other thermoplastic resin formulation may also be expressed as a weight percentage based on the total weight of the PVC or other thermoplastic resin formulation. The amount of processing aid used in the PVC formulation may vary depending on the type of PVC formulation selected and the specifications set for the application for which the PVC or other thermoplastic resin part is to be utilized. In other words, the amount of processing aid in the formulation can be predetermined based on the level of usage required to reduce the surface gloss to a level that matches the color requirements of a given application (i.e., siding, window profile, pipe or foam sheet, etc.).

Without intending to be bound by any theory, the processing aid facilitates the fusing of the PVC resin by modifying the melt rheology of the PVC formulation during extrusion. The processing aid also helps to facilitate mixing of the components as the PVC resin is melted, to increase the strength of the molten polymer blend, to control the volume increase or expansion (e.g., die swell) of the molten polymer blend immediately after it exits the die orifice, to reduce the incidence of segregation and crystallization, and to increase long term impact strength and weatherability. Generally, processing aids with higher molecular weights tend to give higher die swell. Higher die swell may be beneficial in the preparation of foamed PVC parts.

The functionalized processing aid (f-PA) is also capable of promoting crosslinking during the formation of PVC parts from PVC formulations. This crosslinking may occur in the presence or absence of a chain transfer agent or a crosslinking agent. When desired, the optional chain transfer or crosslinking agent may be added to the processing aid in an amount greater than 0 wt% and less than or equal to about 1 wt%, based on the total weight of the processing aid. Several examples of such chain transfer or crosslinking agents include, but are not limited to, mercaptans, polythiols, alcohols, and halogen-containing compounds, with mercaptans and polythiols being preferred.

In other thermoplastic resins, the purpose of the processing aid is to reduce gloss.

PVC resins can be produced at many different molecular weights by any method known in the art including, but not limited to, solution, suspension, or emulsion polymerization. The PVC resin may include, but is not limited to, rigid PVC resins, flexible PVC resins, PVC plastisols, and mixtures or combinations thereof with one or more other thermoplastic and/or thermoset resins. PVC resins can be characterized by their molecular weight, which is usually reported as Intrinsic Viscosity (IV) or K-value. In general, the higher the IV or K-value of a PVC resin, the greater the impact strength of the PVC or other thermoplastic resin part made therefrom. However, PVC resins with high molecular weights are also more difficult to fuse and polymer flow without using excessive heat or shear. The molecular weight of the PVC resin used in the formulation used to make the PVC part may be predetermined according to the mechanical properties and economic factors required for the final product. Resins having K-values in the range of about 56-72 or in the range of about 63-67 or about 65 are typically used to form PVC parts having a rigid distribution and a relatively low molecular weight for foam applications. The molecular weight of the PVC resin is generally less than the molecular weight of the processing aid with which it is used. The amount of PVC resin used in the formulation used to form the PVC or other thermoplastic resin component may range from about 30% to about 85% by weight of the entire PVC formulation, or from about 50% to about 80% by weight.

Other thermoplastics that may be used in the present invention as, for example, a cap layer on a substrate include, but are not limited to, acrylic polymers, styrenic polymers, polyolefins, polyvinyl chloride (PVC), Polycarbonate (PC), Polyurethane (PU), polyvinylidene fluoride Polymer (PVDF), polylactic acid (PLA), and the like, and mixtures thereof. Such other thermoplastics described herein may be used in combination with PVC, or in any combination thereof, with or without PVC, and further comprise the processing aid of the present invention to form parts having reduced surface gloss.

Styrenic polymers, as used herein, include, but are not limited to, polystyrene, High Impact Polystyrene (HIPS), acrylonitrile-butadiene-styrene (ABS) copolymers, acrylonitrile-styrene-acrylate (ASA) copolymers, styrene-acrylonitrile (SAN) copolymers, methacrylate-acrylonitrile-butadiene-styrene (MABS) copolymers, styrene-butadiene copolymers (SB), styrene-butadiene-Styrene Block (SBs) copolymers and partially or fully hydrogenated derivatives thereof, styrene-isoprene copolymers, styrene-isoprene-styrene (SIS) block copolymers and partially or fully hydrogenated derivatives thereof, styrene- (meth) acrylate copolymers [ such as styrene-methyl methacrylate copolymer (S/MMA) ] and mixtures thereof. The preferred styrenic polymer is ASA. The styrenic copolymers of the present invention have a styrene monomer content of at least 10 wt%, preferably at least 25 wt%.

Styrenic polymers may also be blended with other polymers to form compatible blends. Examples include ASA blended with PVC, and SAN blended with PMMA.

As used herein, acrylic polymers include, but are not limited to, homopolymers, copolymers, and terpolymers containing alkyl (meth) acrylates.

The alkyl methacrylate monomer is preferably methyl methacrylate, which may comprise 60 to 100% of the monomer mixture. Other acrylate, methacrylate and/or other vinyl monomers may also be present in the monomer mixture in an amount of 0-40%. Other methacrylates, acrylates and other vinyl monomers that may be used in the monomer mixture include, but are not limited to, methyl acrylate, ethyl acrylate and methacrylate, butyl acrylate and methacrylate, isooctyl methacrylate and isooctyl acrylate, lauryl acrylate and methacrylate, stearyl acrylate and methacrylate, isobornyl acrylate and methacrylate, methoxyethyl acrylate and methacrylate, 2-ethoxyethyl acrylate and 2-ethoxyethyl methacrylate, dimethylaminoethyl acrylate and methacrylate, styrene and derivatives thereof. Alkyl (meth) acrylic acids such as (meth) acrylic acid and acrylic acid may be used for the monomer mixture. Also hasLow levels of multifunctional monomers, such as cross-linking agents, can be used. Preferred acrylic polymers are methyl methacrylate with 2-16% of one or more C_1-4Copolymers of acrylic esters.

The thermoplastic polymers of the present invention can be made by any means known in the art, including emulsion polymerization, solution polymerization, and suspension polymerization. In one embodiment, the thermoplastic matrix has a weight average molecular weight of between 50000-500000g/mol, preferably 75000-150000g/mol, as determined by Gel Permeation Chromatography (GPC). The molecular weight distribution of the thermoplastic matrix may be unimodal or multimodal with a polydispersity index of greater than 1.5.

Particularly preferred thermoplastics for the matrix polymer are styrenic polymers (including SAN, ABS, MABS, ASA, HIPS), acrylic polymers and PVDF polymers.

The PVC formulations used to form PVC or other thermoplastic resin parts may optionally contain at least one impact modifier, when desired. Impact modifiers increase the toughness of the final product and improve its resistance to cracking or chipping during any subsequent manufacturing operations performed on PVC or other thermoplastic resin parts, such as cutting sections of the part or drilling holes therein. Impact modifiers generally function by absorbing energy and/or dissipating the energy of a propagating crack. The impact modifier may comprise any compatible polymeric particle, including block copolymers and "core/shell particle" polymers having a soft rubbery core (Tg <0 ℃) or a hard core (Tg >0 ℃) with limited compatibility with PVC resins, and a grafted compatible polymeric shell. The polymeric particles or compatible polymeric shells may comprise methacrylate/butadiene/styrene (MBS), acrylic polymers (e.g., acrylic polymers known as acrylic impact modifiers [ AIM ]), or acrylate/butadiene/methacrylate, and acrylonitrile/butadiene/styrene (ABS), semi-compatible polymers such as Chlorinated Polyethylene (CPE) and Ethylene Vinyl Acetate (EVA) polymers, and other polymers such as ethylene/vinyl acetate/carbon monoxide terpolymers, ethylene/propylene/carbon monoxide terpolymers, polymers of olefins and acrylates, various copolymers of butadiene and acrylonitrile, methacrylate or other rubbers, and even silicone-promoted materials. A preferred shell comprises polymethyl methacrylate (PMMA).

The PVC or other thermoplastic resin formulation may also optionally contain one or more inorganic fillers or particles, pigments, lubricants, stabilizers, or other desired additives. For example, ultrafine CaCO₃The particles can be used as fillers to improve the low temperature impact resistance of rigid PVC products and to increase UV stability. Synthetic amorphous silica particles may also be added to PVC formulations, which also improve impact resistance and provide improved flow properties. Other solid fillers including, but not limited to, kaolin, talc, mica, wollastonite, and calcium metasilicate, may also be added to the formulation in order to simply reduce the cost of the formulation without materially affecting the properties of the PVC or other thermoplastic resin component.

Various pigments may be added to provide color to the PVC or other thermoplastic resin components. These pigments generally exhibit stability at elevated temperatures and in the presence of hydrogen chloride. These pigments may include, but are not limited to, various organic pigments or ceramic pigments, such as titanium dioxide and other metal oxides, with or without a silica or alumina surface treatment.

Various lubricants may be added to the PVC formulation at relatively small levels in order to reduce the resistance to flow of the polymer chains and other ingredients present. These lubricants may be used as external lubricants or metal release (smoothing) agents to promote the flow of "hot" material through the processing equipment, or as internal lubricants to reduce the melt viscosity of the material being processed. Lubricants are the major additional components that can be added to the formulation to aid or promote the fusing of the PVC resin. Several examples of lubricants include, but are not limited to, paraffin waxes and long chain carboxylic acids or their esters, amides, and salts. The amount of lubricant used is generally below the level that would cause bleeding. Bleeding can occur if the lubricant present in the formulation is extruded out of the hot bulk material as the extrudate exits the die or passes through the vacuum calibrator, causing the material to plug or deposit.

Various stabilizers may be added to the PVC formulation or other thermoplastic formulations to increase resistance to heat or UV light, and the like. The heat stabilizer may include, but is not limited to, lead-based compounds or organotin compounds, mixed metal stabilizers, or organic stabilizers such as epoxides. The UV stabilizer may include, but is not limited to, hindered amines or phenols.

According to another aspect of the present disclosure, a method (10) of reducing specular gloss of a polyvinyl chloride (PVC) or other thermoplastic resin component is provided. Referring to fig. 1, the method (10) generally comprises: providing (15) PVC or other thermoplastic base resin; forming (20) at least one base polymer as a processing aid; functionalizing (25) the base polymer with reactive functional groups to form a functionalized processing aid; producing (30) a PVC or other thermoplastic resin formulation from the base resin and functionalized processing aid; forming (35) a PVC or other thermoplastic resin component from the PVC or other thermoplastic resin formulation. More specific information regarding PVC formulations and their compositions has been discussed above and is further defined below. The base polymer is functionalized with about 0.5 to 35 weight percent of reactive epoxy, hydroxyl, or carboxylic acid functional groups. Optionally, at least one impact modifier may also be provided (40) and added to the PVC or other thermoplastic resin formulation (30). The resulting PVC or other thermoplastic resin part has a surface gloss measured at 85 ℃ or less that is reduced by at least 5 points.

Other embodiments of the invention

1. A polyvinyl chloride (PVC) part having reduced surface gloss, comprising:

PVC resin, one or more processing aids comprising at least one base polymer, one or more of said processing aids functionalized with about 0.5 to about 35 weight percent of reactive epoxy, hydroxyl, or carboxylic acid functional groups, based on the total weight of the processing aid, and optionally at least one impact modifier; wherein the PVC part has a reduction in gloss measured at an angle of 85 degrees or less of at least 5 points as compared to a similar PVC part that has not been functionalized with a processing aid.

2. The PVC member of claim 1, wherein the processing aid is present in an amount from about 0.1phr to about 12 phr.

3. The PVC member of claim 1 or 2, wherein the one or more processing aids are functionalized with at least 5 wt% of reactive functional groups based on the total weight of the processing aid and the PVC member has a reduction in gloss measured at an angle of 60 degrees or less of at least 10 points.

4. PVC part according to any of claims 1 to 3, wherein the PVC part comprising a functionalized processing aid has comparable impact properties as a similar PVC part comprising an unfunctionalized processing aid, the impact properties being measured as Izod or Dart impact properties.

5. The PVC part according to any one of claims 1 to 4, wherein the reactive epoxy, hydroxyl or carboxylic acid functional groups are derived from hydroxy-substituted alkyl esters of (meth) acrylic acid; vinyl esters of straight or branched carboxylic acids; unsaturated C₃-C₆Monocarboxylic acids and unsaturated C₄-C₆A dicarboxylic acid; an epoxy-containing monomer; or mixtures thereof.

6. PVC part according to any of claims 1 to 5, wherein the base polymer of the one or more processing aids comprises an acrylic polymer or copolymer, the molecular weight (M) of the processing aid(s)_w) About 50000g/mol or more.

7. PVC part according to any of claims 1 to 6, wherein the acrylic polymer or copolymer is derived from monomers comprising vinyl or (meth) acrylic groups; styrene or styrene derivatives; an olefin; a diene; or mixtures thereof.

8. The PVC component according to any one of claims 1 to 7, wherein the one or more functionalized processing aids promote crosslinking within the PVC component, the functionalized processing aids further comprising from 0 to about 1 weight percent of a chain transfer or crosslinking agent.

9. Use of a PVC part according to any one of claims 1 to 8 in: automotive products, building materials, household or kitchen goods, medical or office goods, clothing, or packaging materials for personal care products or other consumer products.

10. A method of reducing surface gloss of a polyvinyl chloride (PVC) part, the method comprising:

providing a PVC resin; forming at least one base polymer as a processing aid;

functionalizing said at least one base polymer to form a functionalized processing aid, wherein said base polymer is functionalized with about 0.5 wt% to about 35 wt% of reactive epoxy, hydroxyl, or carboxylic acid functional groups based on the total weight of the processing aid; optionally providing at least one impact modifier; producing a PVC formulation from the PVC resin, a functionalized processing aid, and optionally an impact modifier; and

forming a PVC part from the PVC formulation, wherein the PVC part has a reduction in gloss measured at an angle below 85 degrees of at least 5 points as compared to a similar PVC part that has not been functionalized with a processing aid.

11. The method according to claim 11, wherein the processing aid is present in an amount from about 0.1phr to about 12 phr.

12. The method according to claim 10 or 11, wherein the one or more processing aids are functionalized with at least 5 wt% of reactive functional groups based on the total weight of the processing aid and the gloss of the PVC part is reduced by at least 10 points measured at angles below 60 degrees.

13. The process according to any one of claims 10 to 12, wherein the PVC part containing the functionalized processing aid has impact properties comparable to similar PVC parts containing non-functionalized processing aid, said impact properties being measured as izod or dart impact properties.

14. The method of any one of claims 10-13, wherein the reactive epoxy, hydroxyl, or carboxylic acid functional group is derived from a hydroxy-substituted alkyl ester of (meth) acrylic acid; vinyl esters of straight or branched carboxylic acids; unsaturated C₃-C₆Monocarboxylic acids and unsaturated C₄-C₆A dicarboxylic acid; an epoxy-containing monomer; or mixtures thereof, and the base polymer of the one or more processing aids comprises an acrylic polymer or copolymer, an acrylic polymer or copolymer derived from vinyl and (meth) acrylic functional group containing monomers, styrene and styrene derivatives, olefins, dienes, or mixtures thereof.

15. The method of any one of claims 10-14, wherein the one or more functionalized processing aids promote crosslinking within the PVC member, the one or more functionalized processing aids having a molecular weight (M) of about 50000g/mol or greater_w) The functionalized processing aid further comprises 0 to about 1 weight percent of a chain transfer agent or a crosslinking agent.

Example 1 Overall Experimental conditions and test protocols

Both the functionalized processing aids and the conventional processing aids were evaluated in PVC formulations to observe and compare mechanical properties including processability and gloss levels. Polymer processing was done using a Brabender rheometer with blended PVC formulations (powders) containing either control acrylic processing aids or acrylic processing aids functionalized with reactive species and measured for fusion torque, fusion time, fusion temperature and equilibrium torque. The method for measuring the fusion properties of PVC compounds using a torque rheometer was carried out according to the standard procedures of ASTM D2538-02[2010, ASTM International, West Conshaken, Pa. (West Consho-hocken) ].

Pellets made from the PVC formulation were then used in an injection molding apparatus to prepare injection molded test strips and plates or sheets. After the test strips and panels were prepared, their impact strength was measured and their gloss was measured using a gloss meter and the ability of the surface of each sample to reflect light was recorded. The izod impact property is defined as the kinetic energy required to initiate a crack and to sustain the crack until the sample fractures. The Ellevode test specimens were notched and measured as specified in ASTM D256-10e1(ASTM International, West Corschoeken, Pa.). The impact strength or toughness of plastics can also be measured according to the dart drop (Gardner) impact property method specified in ASTM D4226 and ASTM D5420(ASTM International, West Corschschoeken, Pa.).

Gloss is related to the ability of a surface to reflect more light in a direction approaching specular. The test strips and panels exhibited specular gloss as measured at various angles according to the standard test method described in ASTM D523(2014, ASTM international, west corneschoenkken, pennsylvania). The measured gloss ratings were obtained by comparing the specular reflectance of the test strips or plates to the specular reflectance of the black glass standards.

The amount of soluble or remaining insoluble fraction in each processing aid can be determined by extraction with a solvent such as acetone, THF, or MEK. A predetermined total amount of powder was added to the flask along with about 35 grams of solvent. The powder/solvent mixture was stirred or shaken for 22 hours, during which time about 30 grams of solvent was added to the flask, followed by stirring or shaking for an additional 1.5 hours. Then, about 30 g of the mixture solution was placed in a centrifuge tube and placed under centrifugal force at a speed of 16500rpm at a temperature of 5 ℃ for 3 to 5 hours. The upper part of the separated mixture solution was added to another tube, and then centrifuged again under similar conditions. The clear supernatant present in the centrifuge tube was collected and 10mL of this supernatant was placed into an aluminum dish using a serological pipette. The supernatant in the aluminum pan was dried by heating and the percentage of insoluble fraction was determined according to equation 1, where W_fIs the final total amount of aluminum pan, W_iIs the starting weight of the aluminum pan, W_{Powder of}Is the weight of a predetermined amount of powder put in a flask, V_Solvent(s)Is the total volume of solvent placed in the flask, V_{Supernatant fluid}Is the volume of supernatant transferred to the aluminum dish.

EXAMPLE 2 measurement of the molecular weight of the processing aid

The molecular weight associated with the processing aid can be determined by various known methods and procedures using Gel Permeation Chromatography (GPC). One such method employs a differential refractometer equipped with two PL gel mixing A columns and a guard column. A THF solution at a concentration of 1.5mg/mL of the soluble portion of the processing aid was injected into the column at a temperature of 35 deg.C in an injection volume of 150 microliters (L). The process aid was eluted through the column using THF solvent (HPLC grade) at a flow rate of 1.0 mL/min. Each sample of processing aid can be tested in either the filtered or unfiltered state. Chromatograms for each test sample were obtained and analyzed, and molar mass values were calculated relative to a Polymethylmethacrylate (PMMA) calibration curve. For more information on GPC methods, see ASTM D4001-13 (ASTM International, West Corschoeken, Pa.).

The molar mass averages for the filtered and unfiltered samples may differ slightly from each other. In other words, filtration of the sample through a 1.0 μm PTFE membrane may affect the measured molecular weight distribution. Filtration of the sample removes the very high molar mass species, thereby reducing the high end portion of the molar mass distribution. Filtering the sample can also lead to degradation of high molar mass substances, thereby increasing the number of lower molar mass substances, resulting in a higher number average and/or weight average molar mass mean. The molar mass mean is a weighted average based on the number of molecules per slice, so increasing or decreasing the number of molecules of a given molar mass affects the molar mass mean and distribution.

The molecular weight of the soluble portion of a total of 13 different process aid samples prepared according to the teachings of the present disclosure was measured. Each sample was co-injected three times and averaged to give the average molecular weight (M)_w). The molecular weight of each of the different process aid samples was obtained in both the unfiltered and filtered states. Average molecular weight (M) of the samples measured in the unfiltered and filtered state_w) All in the range of 50000g/mol to about 15000000 g/mol. The polydispersity is measured for each sample tested between about 10 and about 60, where polydispersity is defined as the ratio of weight average molecular weight to number average molecular weight (M)_w/M_n). For example, one particular sample of processing aid has a weight average molecular weight (M) of 2690000g/mol in the unfiltered state_w) And a polydispersity of 54.2, with M in the filtered state of 2110000g/mol_wAnd a polydispersity of 15.5.

EXAMPLE 3 measurement of glass transition temperature of processing aid

Determination of glass transition temperature (T) of processing aids prepared in accordance with the teachings of the present disclosure using Differential Scanning Calorimetry (DSC)_g). Each DSC measurement was obtained at a temperature in the range of-75 ℃ to 160 ℃ using a heating rate of 20 ℃/min and a cooling rate of 10 ℃/min. T is_gDetermined as the average of at least two measurements made from each sample formulation.For more description of the DSC method, see ASTM E1356-08(2014) (ASTM international, west corneschoeken, pa).

Glass transition temperature (T) of processing aid_g) The determination may be made with a powder or a test strip formed from a powder. The powder may be placed under high pressure (e.g. 25 tons) at elevated temperature (e.g. 215 ℃), from which a sample strip is pressed. In total, 10 different processing aid samples were analyzed, with an average T for each sample_gIn the range of 0 ℃ to about 150 ℃. No significant difference was observed between the glass transition temperatures measured with the sample strip and with the powder. For example, one particular processing aid sample exhibited a glass transition temperature of 85.0 ℃ in the sample bar form and 83.4 ℃ in the powder form.

Example 4-PVC formulations and parts prepared and tested with a processing aid functionalized with Glycidyl Methacrylate (GMA)

An 29014.52 gram (116.3phr) polyvinyl chloride (PVC) formulation masterbatch was prepared containing 24948 grams (100phr) of PVC resin [ PVC-5385, Exxocel (Axall) Inc., Prozobia Gulf Inc. (Georgia Gulf), Atlanta, Georgia]249.48 g (1.0phr) tin stabilizer [ T-161, PMC organometallic (Organometallix) Inc., Caronton, Kentucky]299.38 g (1.2phr) calcium stearate, 249.48 g (1.0phr) Lubricant [ [ solution ] ]RL-165, Honeywell International Inc., N.J.]24.95 grams (0.1phr) secondary polyethylene lubricant (AC629A, HONEYWELL INTERNATIONAL INC., N.J.), 748.44 grams (3.0phr) calcium carbonate, and 2494.8 grams (10phr) titanium dioxide. This PVC masterbatch is then utilized to prepare PVC formulations comprising various combinations of conventional processing aids (c-PA) and functionalized processing aids (f-PA) with either conventional impact modifiers (c-IM) or functionalized impact modifiers (f-IM). The conventional impact modifier (c-IM) used in this experiment was an acrylic polymer [ alpha ], [ alpha ] was a ] anD-350, Achima, Prussian, Pa. (King of Prussia)]The conventional processing aid (c-PA) used in this experiment was an acrylic polymer (C-PA)550, available from akoma corporation, prussian, pa). The functionalized impact modifier (f-IM) and functionalized processing aid (f-PA) used in this experiment were prepared by functionalizing conventional IM and PA with about 16 weight percent Glycidyl Methacrylate (GMA).

Table 1 below summarizes the processing aids and impact modifiers present in four comparable samples (Nos. C1-C4) and two tested samples (Nos. R1 and R2) prepared and tested. The amount of impact modifier used in each of the comparative and test samples was 4 phr. The amount of processing aid used in each of the comparable and test samples was 1phr or 3 phr. Thus, the total amount of impact modifier and processing aid added to the PVC masterbatch is about 5phr or 7 phr.

TABLE 1

The PVC formulations containing the impact modifier and processing aid were then evaluated using a brabender rheometer to measure the density, izod impact properties, and surface gloss at various angles of the injection molded bars or plaques formed therefrom. Table 2 below summarizes the test results. Similar performance was observed for the test samples (nos. R1 and R2) in terms of density, fusion time, fusion torque, fusion temperature, and equilibrium torque.

TABLE 2

At all angles, comparable samples containing the functionalized impact modifier (C2 and C4) were observed to exhibit similar gloss levels as comparable samples containing the conventional impact modifier (C1 and C3). However, a shift in gloss was observed at all angles for the test samples (R1 and R2) relative to the comparable samples (C1-C4). More specifically, the test sample (R1) containing 1phr of functionalized processing aid showed a decrease in gloss compared to comparable samples (C1 and C2) by the following: about 38-46 points at an angle of 20 deg., about 16-18 points at an angle of 60 deg., and about 7-9 points at an angle of 85 deg.. Similarly, the test sample (R2) containing 3phr of functionalized processing aid showed a decrease in gloss compared to the comparable samples (C3 and C4) by the following: about 50-56 points at an angle of 20 deg., about 68-70 points at an angle of 60 deg., and about 33 points at an angle of 85 deg.. Furthermore, the Izod impact properties of the test samples (R1 and R2) were not inferior to the comparable samples (C1-C4).

This example shows that PVC formulations containing functionalized processing aids can form PVC parts with reduced gloss at 20 °,60 ° and 85 ° angles, as compared to similar PVC parts containing only conventional non-functionalized processing aids. This example also shows that similar functionalization of the impact modifier does not provide the beneficial effects on gloss reduction as observed with the use of functionalized processing aids. In addition, the use of functionalized impact modifiers reduces the impact properties of PVC or other thermoplastic resin parts (see C1/C3 vs. C2/C4). On the other hand, the use of functionalized processing aids maintains the mechanical properties of the PVC formulations at similar levels observed for PVC formulations and parts formed with conventional processing aids throughout processing and after formation of the PVC parts.

EXAMPLE 5 preparation of a Process aid functionalized with Acrylic Acid (AA) and Glycidyl Methacrylate (GMA)

f-PA functionalized with GMAA5 l heating mantle polymerization reactor equipped with a stirrer and a reflux condenser was charged with 848.7g of distilled water, 31.34g of sodium dodecylbenzenesulfonate and 0.48g of sodium carbonate. Preparation of 320.0 g of Methyl Methacrylate (MMA), 100.0 g of Butyl Acrylate (BA) and 80.0 g of Glycidyl Methacrylate (GMA) (MM)64/20/16 weight percent A/BA/GMA) and then added to the reactor. The reaction temperature was set to 45 ℃ while purging the reactor with nitrogen for 20 minutes. 20.45g of a distilled aqueous solution of 4% potassium persulfate and 12.12g of a distilled aqueous solution of 5% metabisulfite were added under a nitrogen atmosphere to initiate the reaction. After 12 minutes a peak temperature of 86 ℃ was observed. The reaction temperature was set to 80 ℃ and 1.25g of a distilled aqueous solution of 4% potassium persulfate was added to the reactor. The batch was held at 80 ℃ for 30 minutes and then cooled to room temperature. The average latex particle size Dv was measured using a Nicomp model 380 ZLS and was found to be approximately 100 nm. The solids content was about 36%. Latex particles of f-PA functionalized with GMA were isolated by spray drying.

f-PA functionalized with AAPreparation of a processing aid functionalized with Acrylic Acid (AA) following the same procedure described above for GMA functionalization of a processing aid, except that acrylic acid is used instead of the GMA comonomer. Thus, the monomer mixture used contained 324.6 g of Methyl Methacrylate (MMA), 100.0 g of Butyl Acrylate (BA), 75.0 g of Acrylic Acid (AA) and 0.375 g of tert-dodecyl mercaptan (t-DDM), the MMA/BA/AA/t-DDM weight percentage being 64.925/20/15/0.075. 18 minutes after the initiator addition, a peak temperature of 79.5 ℃ was observed. The average latex particle size was found to be about 165 nm. The solids content was about 35.7%. Latex particles of f-PA functionalized with AA were isolated by spray drying.

EXAMPLE 6 preparation and testing of PVC formulations and parts Using the processing aid prepared in experiment 2

Two master batches containing 3090 grams (123.6phr) of a polyvinyl chloride (PVC) formulation were prepared, pigmented with white pigment or beige pigment. Each master batch contained 2500.0 grams (100phr) PVC (SE-950, N.C., Houston, Tex.), 25.0 grams (1.0phr) tin stabilizer161, PMC group shares company, Laurushan, New Jersey (Mount Laurel)]25.0 grams (1.2phr) calcium stearate, 2.5 grams (0.1phr) lubricant (Epoline E-14, West lake chemical, Houston, Tex.), 112.5 grams (4.5phr) impact modifier (C) (A)D-350, available from Achima, Prussian, Pa.), 125.0 grams (5.0phr) of calcium carbonate, 250.0 grams (10.0phr) of titanium dioxide, and 25.0 grams (1.0phr) of white or beige pigment. These PVC masterbatches were then used to prepare various PVC formulations (nos. R3-R7) containing various combinations of functionalized processing aids prepared in experiment 2, and to prepare control samples (control No. C5) containing conventional unfunctionalized processing aids.

Table 3 summarizes the processing aid composition added to the masterbatch to form the PVC formulation. Each of the test samples (Nos. R3-R7) and the control sample (control No. C5) contained a total of 25.0 grams (1.0phr) of processing aid. The processing aid in the control sample (C5) was a conventional acrylic polymer (C)550, available from akoma corporation, prussian, pa). The f-PA used in the sample numbered R3 consisted entirely of the processing aid functionalized with Acrylic Acid (AA) in experiment 2. Similarly, the f-PA used in the sample numbered R7 consisted entirely of the processing aid functionalized with Glycidyl Methacrylate (GMA) in experiment 2. The f-PA used in the samples numbered R4-R6 comprised a mixture of the AA and GMA functionalized processing aids of experiment 2. The AA/GMA processing aid ratios used in samples numbered 4,5, and 6 were 1/3,2/2, and 3/1, respectively. Each of the test samples (Nos. R3-R7) and the control sample (control No. C5) included two test specimens, one using a white pigment and the other using a beige pigment.

TABLE 3

The PVC formulations containing the functionalized processing aid (Nos. R3-R7) and the conventional processing aid (control No. C5) were then formed into sheets (0.040 inch by 4.5 inch) using a Brabender conical twin-screw extruder, and the surface gloss of the sheets was measured at various angles. No difference was observed in sheet processing. Table 4 below summarizes the average gloss measurements obtained for each test sample. The reported average gloss represents the average of 60 measurements taken from the top, bottom, left and right sides of the sheet.

All test sheets (nos. R3-R7) containing white or beige functionalized processing aids had significantly reduced gloss at all angles compared to the gloss measured on a comparable sheet (control No. C5) containing conventional unfunctionalized processing aid. The gloss reduction of the test sheet (R3-R7) with white pigment compared to a comparable sheet (control No. C5) was: about 34 to 39 points at an angle of 20 degrees, about 35 to 55 points at an angle of 60 degrees, about 13 to 20 points at an angle of 75 degrees, and about 20 to 27 points at an angle of 85 degrees. Similarly, the reduction in gloss for the test sheet with beige pigment (R3-R7) compared to a comparable sheet (control No. C5) was: about 23 to 30 points at an angle of 20 degrees, about 27 to 46 points at an angle of 60 degrees, about 12 to 19 points at an angle of 75 degrees, and about 11 to 20 points at an angle of 85 degrees.

TABLE 4

It was also observed that the amount of f-PA functionalized with GMA or F-PA functionalized with AA affected the decrease in gloss. In general, as the ratio of GMA/AA is increased, an increase in the decrease in gloss measured by the test sheet or part is observed. For example, a test sheet completely containing GMA functionalized f-PA (No. R7) had a greater reduction in gloss than a test sheet completely containing AA functionalized f-PA (No. R3), measured at an angle of 20 ° to 75 °, whether a white or beige part.

Referring now to fig. 2 and 3, the gloss values measured at 60 ° and 75 ° angles, respectively, for the test sheets or parts (nos. R3-R7) were graphically compared to the gloss values measured for a comparable sheet (control No. C5). Further, dart drop test impact results for each sheet were also compared. It was found that the addition of f-PA to PVC or other thermoplastic resin parts reduced gloss, but had no effect on the impact strength of the parts compared to the impact properties exhibited by PVC parts containing only conventional, non-functionalized processing aids.

This example shows that PVC formulations containing functionalized processing aids can form PVC parts with reduced gloss at 20 °,60 ° and 85 ° angles, as compared to similar PVC parts containing only conventional non-functionalized processing aids. This example also shows that the functionalization of the processing aid can be accomplished using GMA, AA, or mixtures thereof. The comparison between the gloss reduction exhibited by test parts containing an f-PA functionalized with GMA versus test parts containing an f-PA functionalized with AA indicates that GMA functionalization may be more effective than AA functionalization in reducing the gloss of the parts. This example also shows that a reduction in gloss is observed for differently colored PVC parts due to the addition of the functionalized processing aid.

Example 7-preparation and testing of further PVC formulations and parts with the processing aid prepared in experiment 2

A2526.0 gram (126.3phr) polyvinyl chloride (PVC) formulation masterbatch was prepared containing 2000 grams (100phr) of PVC resin [ SE-950, N.K., Inc., Houston, Tex]20.0 g (1.0phr) of a tin stabilizer161, PMC group stocks, Laurushan, N.J.]24.0 g (1.2phr) calcium stearate, 20.0 g (0.1phr) lubricant: (RL-165, Holnwell International, N.J.), 2.0 grams (0.1phr) of secondary polyethylene lubricant (AC629A, Holnwell International, N.J.), 90.0 grams (4.5phr) of impact modifier(s) ((R)D-350, available from Achima, Prussian, Pa.), 100.0 grams (5.0phr) of calcium carbonate and 200.0 grams (10.0phr) of titanium dioxide, and 70.0 grams (3.5phr) of beige pigment. This PVC masterbatch was then used to prepare various PVC formulations (Nos. R8-R12) containingThere were various combinations of functionalized processing aids prepared in experiment 2, and a control formulation (control nos. C6-C14) was prepared that contained a conventional unfunctionalized processing aid.

Table 5 summarizes the processing aid composition added to the masterbatch to form the PVC formulation. Each of the test samples (Nos. R8-R11) and the control samples (controls Nos. C6-C14) contained a total of 20.1 grams (1.0phr) of processing aid. The processing aids in the control samples C6-C9 and C11-C13 were conventional acrylic polymers (C)550, available from akoma corporation, prussian, pa). Impact modifier [ Paraloid ] was used in control samples C7-C10^TMEXL-5136, Dow chemical company, Midland, Mich]. The impact modifier is a polymeric core/shell impact modifier having a polybutylacrylate core and a polymethyl acrylate shell. Another impact modifier (C11-C14) was used in control samples C11-C14BS-130, Achima, Prussian, Pa.). The impact modifier is crosslinked polymethylmethacrylate particles having an average particle size of several micrometers. The f-PA used in the sample numbered R8 consisted entirely of the processing aid functionalized with Acrylic Acid (AA) in experiment 2. Similarly, the f-PA used in the sample numbered R9 consisted entirely of the processing aid functionalized with Glycidyl Methacrylate (GMA) in experiment 2. The f-PA used in the sample numbered R10 comprised a 50:50 mixture of the AA and GMA functionalized processing aids of experiment 2. Finally, the f-PA used in the sample numbered R11 comprised the AA functionalized processing aid of experiment 2 and a conventional acrylic polymer (R) ((R))550, available from akoma corporation, prussian, pa) at a 50:50 ratio.

TABLE 5

The PVC formulations containing impact modifiers and/or processing aids were then evaluated using a brabender rheometer to measure the density, gardner impact properties, and surface gloss at various angles of the injection molded bars or plaques formed therefrom. Table 6 summarizes bulk density, fusion time, fusion torque, fusion temperature, and equilibrium torque. Similar performance was observed for the test samples (nos. R8-R11) and the comparative samples (control nos. C6-C14) in terms of density, fusion time, fusion torque, and fusion temperature. However, the equilibrium torque of the test sample (C6-C14) was substantially increased compared to the comparative sample (control Nos. C6-C14). Thus, PVC formulations containing functionalized processing aids (Nos. R8-R10) or mixtures of functionalized processing aids and non-functionalized processing aids (No. R11) exhibit better mechanical properties than PVC formulations containing non-functionalized processing aids (No. C6), mixtures of conventional non-functionalized processing aids and impact modifiers (Nos. C7-C9 and C11-C13), or impact modifiers only (Nos. C10 and C14).

TABLE 6

The PVC formulations containing the functionalized processing aid (Nos. R8-R11) and conventional processing aid and/or impact modifier (controls Nos. C5-C14) were then formed into sheets (0.040 inch x6 inch) using a Brabender conical twin-screw extruder, and the surface gloss of the sheets was measured at a 60 ° angle. Table 7 below summarizes the average gloss measurements obtained for each of the test samples. The reported average gloss represents the average of 20 measurements made from the top and bottom of the sheet.

All test sheets (Nos. R8-R11) containing functionalized processing aids exhibited reduced gloss or improved impact properties as compared to the gloss measured for a comparable sheet (controls C6-C14) containing non-functionalized processing aid, conventional impact modifier, or mixtures thereof. The test sheets (Nos. R3-R7) exhibited improved Gardner impact performance compared to control sheets containing either the conventional impact modifiers alone (Nos. C10 and C14) or a mixture of impact modifiers with conventional processing aids (Nos. C7-C9 and C11-C13). Further, the gloss ratio of the test sheet (Nos. R3-R7) at an angle of 60 ℃ was reduced by about 10 points or more compared to the comparative sheet (control Nos. C6-C14), measured on top of the sheet. Similarly, the test sheets (Nos. R3-R7) have the same or lower gloss at an angle of 60 ℃ as measured at the bottom of the sheet as compared to a comparable sheet (controls Nos. C6-C14).

TABLE 7

This example shows that PVC formulations containing functionalized processing aids can form PVC parts with reduced gloss or improved impact properties at an angle of 60 ℃ compared to similar PVC parts containing only conventional non-functionalized processing aids, mixtures of conventional processing aids and impact modifiers, or only impact modifiers. This example also shows that the functionalization of the processing aid can be accomplished using GMA, AA, or mixtures thereof. Finally, this example demonstrates that PVC parts containing functionalized processing aids have improved performance over prior art matting agent technologies currently put into commercial use in the PVC door and window and siding industry (control nos. C7-C14).

In this specification, various embodiments have been described in a manner that enables them to be clearly and concisely written, but it should be understood that it is intended that the various embodiments can be combined in various ways without departing from the invention. For example, it should be understood that all of the preferred features described herein apply to the various aspects of the invention described herein.

The foregoing description of various forms of the invention has been presented for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Many modifications and variations are possible in light of the above teaching. The form or forms discussed were chosen and described to provide the best illustration of the principles of the invention and its practical application to thereby enable one of ordinary skill in the art to utilize the invention in various forms and with various modifications as are suited to the particular use contemplated. All such modifications and variations are within the scope of the invention as determined by the appended claims when interpreted in accordance with the breadth to which they are fairly, legally and equitably entitled.

Example 8 (prophetic example) -preparation and testing of PVC-acrylic formulations Using the processing aid prepared in experiment 2

A1262 gram (63.1phr) polyvinyl chloride (PVC) formulation masterbatch was prepared containing 1000 grams (50phr) of PVC resin [ SE-950, N.K., Inc., Houston, Tex.)]24 g (1.2phr) of a tin stabilizer [ alpha ], [ beta ] or a mixture of [ beta ], [ beta ] and [ beta ], [ beta ] and [ beta ], [ beta ] or a172, PMC group stocks, Laurushan, N.J.]24 g (1.2phr) of lubricant (bRL-165, hounwell international, nj), 12 grams (0.6phr) calcium stearate, 2 grams (0.1phr) secondary polyethylene lubricant (AC629A, hounwell international, nj), and 200 grams (10phr) titanium dioxide.

Together with the PVC masterbatch, 1000 g (50phr) of acrylic resin(s) are addedPB, akoma, prasuwang, pa) and 100 grams (5phr) of the processing aid prepared in experiment 2, and blended to form a PVC-acrylic formulation.

Example 9 (prophetic example) -preparation and testing of acrylic formulations Using the processing aid prepared in experiment 2

For the preparation of acrylic formulationsThis was supplemented with 2000 grams (100phr) of acrylic resin (100phr) with 100 grams (5phr) of the processing aid prepared in example 2P600, akoma, inc., prussian, pa).