阅读说明：本技术 在宽的聚合物加工温度范围内有效的着色剂和添加剂浓缩物载体体系 (Colorant and additive concentrate carrier systems effective over a wide range of polymer processing temperatures ) 是由 保罗·莱格内蒂 埃里克·D·莱尔德 路易斯·帕切科 于 2020-03-13 设计创作，主要内容包括：描述了一种用于在宽的加工温度范围内将着色剂和/或其他添加剂添加到树脂配制剂中的浓缩物载体体系。载体体系包括至少20重量％的基础丙烯酸酯共聚物,例如乙基-甲基丙烯酸酯,其与少于30重量％的聚己内酯或类似的开环环酯或醚衍生物组合提供。剩余部分专用于可以包括着色剂、性能增强剂和/或非功能性填料的复合添加剂,该剩余部分可包括任选的有机增塑剂,例如环氧化大豆油。(A concentrate carrier system for adding colorants and/or other additives to resin formulations over a wide range of processing temperatures is described. The carrier system includes at least 20% by weight of a base acrylate copolymer, such as ethyl-methacrylate, provided in combination with less than 30% by weight of polycaprolactone or similar ring-opened cyclic ester or ether derivative. The remainder is dedicated to the compounding additives which may include colorants, performance enhancers and/or non-functional fillers, and may include optional organic plasticizers, such as epoxidized soybean oil.)

1. A concentrate carrier system for a thermoplastic or thermoset resin formulation, said concentrate comprising:

an acrylate copolymer comprising at least 20% but less than 50% by weight of the concentrate;

a polycaprolactone derivative comprising less than 30% by weight of the concentrate, said polycaprolactone comprising at least one selected from: (i) a polymer of functionalized caprolactone, (ii) a polymer of caprolactone, (iii) a polymer of functionalized lactone having a ring structure containing 2 to 6 carbons in the ring structure, (iv) a polymer of lactone having a ring structure containing 2 to 6 carbons in the ring structure, (v) a copolymer of functionalized lactone having a ring structure containing 2 to 6 carbons in the ring structure and at least one branched and/or straight aliphatic monomer having 2 to 20 carbons in total, the monomer further comprising an optional carboxyl and/or hydroxyl functional group, and (vi) a copolymer of lactone having a ring structure containing 2 to 6 carbons in the ring structure and at least one branched and/or straight aliphatic monomer having 1 to 20 carbons in total;

a composite additive comprising the remainder of the concentrate, the composite additive comprising at least one selected from the group consisting of: colorants, performance enhancers, and non-functional fillers; and

wherein the concentrate carrier system remains in solid form at ambient temperature and the additive package remains viable in the low melting resin system and the engineering resin system, respectively, over a processing temperature range of 90 ℃ or less to at least 200 ℃.

2. The concentrate carrier system of claim 1, wherein the polycaprolactone derivative is at least one of: polycaprolactone, polyhydroxyalkanoates, polyglycolide, polylactide, and optionally any of the foregoing having one or more functional groups as a pendant group thereof.

3. The concentrate carrier system of claim 1 or 2, wherein the acrylate polymer comprises an ethyl-methacrylate copolymer.

4. The concentrate carrier system of claim 3, wherein the co-additive is at least 50% by weight of the concentrate.

5. The concentrate carrier system of claim 3, wherein the co-additive comprises at least one selected from the group consisting of: organic and inorganic pigments, dyes, alumina, mica, pearlescent effect additives, laser markers, and metallocene polyethylene.

6. The concentrate carrier system of claim 3, wherein the co-additive comprises at least one selected from the group consisting of: zinc stearate, calcium fatty acid, process modifiers, mold release agents, biocides, ultraviolet light stabilizers, heat stabilizers, antioxidants, free radical scavengers, acid scavengers, antistatic fillers and conductive fillers.

7. The concentrate carrier system of claim 3, wherein the co-additive comprises at least one selected from the group consisting of: calcium carbonate, clay, silica, talc, rice hull ash, and ash.

8. The concentrate carrier system of claim 2, wherein the polycaprolactone derivative consists essentially of polycaprolactone.

9. The concentrate carrier system of claim 1, wherein the polycaprolactone derivative comprises at least one of: a monomer, a polymer of a functionalized caprolactone, a polymer of a functionalized lactone and a copolymer of a functionalized lactone, such that they are provided with at least one functional group selected from the group consisting of: carboxy, hydroxy, methyl, butyl, propyl and isopropyl.

10. The concentrate carrier system of claim 2, further comprising 0.5 to 30.0 wt% of a plasticizer, and wherein the acrylate copolymer is 17.0 to 45.0 wt% of an ethyl-methacrylate copolymer, the polycaprolactone derivative is 3.0 to 5.0 wt%, and the co-additive comprises 2.0-30.0 wt% (relative to the concentrate carrier system) of a colorant, 0.8-18.5 wt% (relative to the concentrate carrier system) of a performance enhancer, and 0.0-41.0 wt% (relative to the concentrate carrier system) of a non-functional filler.

11. The concentrate carrier system of any of claims 1, 8, 9, or 10, wherein the plasticizer consists essentially of epoxidized soybean oil.

Technical Field

The present invention relates to methods and non-liquid compositions for incorporating colorants and other additives into a variety of thermoplastic and/or thermosetting resins (from engineering polymers to ordinary low melting polymers) having a wide range of processing temperatures.

Background

Thermoplastic and thermoset resin systems are widely used in articles of manufacture. Depending on the intended use, these systems need to meet certain structural and/or aesthetic requirements. Thus, there are a variety of colorants and complex additives and concentrates that enable manufacturers to customize resin systems to their particular needs.

One challenge is that these colorants and compounding additives must be compatible with the inherent processing temperatures of the base resin. In this regard, industrial or "engineered" resin systems typically require processing temperatures in excess of 200 ℃. Examples of such engineering plastics include Styrene Acrylonitrile (SAN), high impact Polystyrene (PS), Acrylonitrile Butadiene Styrene (ABS), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), Polyoxymethylene (POM), Polycarbonate (PC), Thermoplastic Polyether (TPE), Thermoplastic Polyurethane (TPU), various polyamides, and other known systems. The individual melting temperatures of each of these resins are known in the art and are specifically disclosed herein. The relatively high processing temperatures of these systems require that the concentrate not degrade or otherwise phase separate and overcoat at these temperatures.

Conversely, lower melting polymer compositions may be preferred based on cost, equipment, ease of use, availability, and/or other requirements. These materials can generally be processed at temperatures of 95 ℃ to 175 ℃ and they comprise a variety of compositions including, but not limited to, Polyethylene (PE), such as peroxide or moisture crosslinkable polyethylene (XLPE) and other highly substituted polyolefins, and lactones, such as polycaprolactone. Notably, these low temperature systems may include thermoplastic and thermoset materials, and their melting temperatures are specifically contemplated and disclosed herein, as described above.

To be an effective colorant or additive concentrate, the carrier resin of the concentrate must liquefy below the minimum required components of the base polymer (i.e., the engineering resin and the low melting point resin), but otherwise remain active (i.e., not degrade) throughout the required temperature range. Thus, many "universal" carrier systems for pigments and other additives have been proposed which are provided in liquid form.

While these liquids can be effective carrier systems for colorants and additives in high and low temperature resins, the use of liquids presents a challenge to formulators. First, it is often difficult to incorporate, uniformly disperse, and retain liquids in a blend of components that are primarily solid resin particles. Examples of such liquid carriers can be found in U.S. Pat. Nos. 4,167,503 and 5,308,395 and Chinese publication CN 102504599A.

Other solutions have been proposed. U.S. patent 3,846,360 describes a pigment carrier for resins that melt in the range of 250 ℃ to 400 ℃, while in U.S. patent 6,713,545 proposes a carrier for styrene-butadiene-styrene (SBS) block copolymers at temperatures above 230 ℃.

In contrast, us patent 4,810,733 discloses a color concentrate based on polypropylene and polypropylene or polyethylene wax. Other carrier and concentrate systems can also be found in U.S. patent publications 2002/0198122 and 2004/0214927 and U.S. patent 7,935,747. Japanese publications JPH5202234 and JPH11106573, and patent Cooperation treaty publications WO2007/138120 and WO2011/014528 are also noteworthy.

As further background, U.S. patent 2,916,481; 3,837,773, respectively; 3,786,018 and 5,589545 describe resin systems, equipment and related/corresponding techniques that can be combined with "universal" concentrates (i.e., solid concentrates/carriers that can be used for both high and low temperature resin/formulations). Furthermore, U.S. patent publications 2008/0317990 and 2016/0017144; patent Cooperation treaty publications WO2002/018487, WO2009/002653 and WO 2014/050580; japanese publication JP 2000248074; and chinese publication CN101831099 are of interest. As can be seen from these disclosures, the coatings of wire and cable are of particular interest, as regulations and standards set very specific conditions for the thickness, composition and physical properties of these polymer coatings.

Disclosure of Invention

A carrier platform for colorants and/or other additives is described. The carrier comprises a base acrylate copolymer used in combination with a ring-opened cyclic ester or ether derivative. In some embodiments, an optional organic plasticizer is provided in combination with a compounding additive that may include colorants, performance enhancers, and non-functional fillers. The resulting concentrate is useful as a solid universal concentrate, suitable for addition to low and high melting resin systems.

In a first embodiment, a solid concentrate carrier system for use in a thermoplastic or thermoset resin formulation is provided. The concentrate carrier system comprises any combination of:

at least 20% by weight of the concentrate of an acrylate copolymer;

a polycaprolactone component comprising at least one of: polycaprolactone, polyhydroxyalkanoates, polyglycolide, polylactide, and optionally any of the foregoing having one or more functional groups as a pendant group thereof, the polycaprolactone component comprising less than 30% by weight of the concentrate;

from 0.5 to 30% by weight of the concentrate of a plasticizer;

a complex additive comprising the remainder of the concentrate, the complex additive comprising at least one selected from: colorants, performance enhancers, and non-functional fillers;

wherein the concentrate remains in solid form at ambient temperature and the additive package remains viable in both low melting and engineering resin systems over a processing temperature range of 90 ℃ or less to at least 200 ℃;

wherein the acrylate polymer comprises an ethyl-methacrylate copolymer;

wherein the acrylate copolymer is less than 50 wt% of the concentrate;

wherein the plasticizer consists essentially of epoxidized soybean oil;

wherein the additive package is at least 50% by weight of the concentrate;

wherein the additive package is at least 75% by weight of the concentrate;

wherein only polycaprolactone is provided and is 5% by weight or less of the total concentrate;

wherein only polycaprolactone is provided;

wherein the polycaprolactone derivative is selected from: polyhydroxyalkanoates, polyglycolides, polylactides, and copolymers of lactones with one or more additional monomers;

wherein the polycaprolactone derivative comprises any one of: (i) a polymer of functionalized caprolactone, a polymer of caprolactone, (ii) a polymer of functionalized lactone having a ring structure containing 2 to 6 carbons in the ring structure, (iii) a polymer of lactone having a ring structure containing 2 to 6 carbons in the ring structure, (iv) a copolymer of functionalized lactone having a ring structure containing 2 to 6 carbons in the ring structure and at least one branched and/or straight chain aliphatic monomer having 2 to 20 carbons in total, the monomer further comprising an optional carboxyl and/or hydroxyl functional group, and (v) a copolymer of lactone having a ring structure containing 2 to 6 carbons in the ring structure and at least one branched and/or straight chain aliphatic monomer having 1 to 20 carbons in total, the monomer further comprising an optional carboxyl and/or hydroxyl functional group;

wherein, when present, the functionalized caprolactone and/or the functionalized lactone comprises at least one functional group selected from: carboxyl, hydroxyl, methyl, butyl, propyl and isopropyl;

wherein at least one monomer is one or more selected from methyl, butyl, propyl and isopropyl structures;

wherein the composite additive comprises at least one selected from the group consisting of: organic and inorganic pigments, dyes, alumina, mica, pearlescent effect additives, laser markers, and metallocene polyethylene;

wherein the composite additive comprises at least one selected from the group consisting of: zinc stearate, calcium fatty acid, process modifiers, mold release agents, biocides, ultraviolet light stabilizers, heat stabilizers, antioxidants, radical scavengers, acid scavengers, antistatic fillers and conductive fillers; and

wherein the composite additive comprises at least one selected from the group consisting of: calcium carbonate, clay, silica, talc, rice hull ash, and ash.

In another embodiment, the solid concentrate carrier system for use in a resin formulation having a processing temperature in the range of 90 ℃ or less to at least 200 ℃ consists essentially of any combination of:

17.0 to 45.0 wt% of an ethyl-methacrylate copolymer;

3.0 to 5.0% by weight of at least one selected from: polycaprolactone, polyhydroxyalkanoates, polyglycolide, polylactide, and optionally any of the foregoing having one or more functional groups as a pendant group thereof;

0.0 to 20.0% by weight of a plasticizer;

a complex additive consisting of 2.0 to 30.0% by weight (relative to the concentrate carrier system) of a colorant, 0.8 to 18.5% by weight (relative to the concentrate carrier system) of a performance enhancer and 0.0 to 41.0% by weight (relative to the concentrate carrier system) of a non-functional filler;

wherein the plasticizer is provided at 0.5 to 20.0 wt.%;

wherein the plasticizer consists essentially of epoxidized soybean oil;

wherein the performance enhancing agent consists of at least one selected from the group consisting of: process modifiers, uv stabilizers and antioxidants;

wherein the process modifier is zinc stearate and/or calcium fatty acid;

wherein the non-functional filler is provided at 27.2 to 41.0 wt%;

wherein the non-functional filler consists essentially of calcium carbonate;

wherein the composite additive includes only the colorant and the performance enhancer; and

wherein the performance enhancing agent is provided at 1.3 wt% or less.

Reference is made in detail to the appended claims and the following description, all of which disclose elements of the present invention. Although specific embodiments are specified, it should be understood that elements from one described aspect may be combined with elements from another specified aspect. In the same way, those of ordinary skill in the art will have the necessary understanding of common processes, components, and methods, and this specification is intended to cover and disclose such common aspects, even if they are not explicitly stated herein.

Drawings

FIG. 1 is a Differential Scanning Calorimetry (DSC) plot of the acrylate and ring-opening components of a premix, according to one aspect of the present invention.

Figure 2 is a thermogravimetric analysis (TGA) thermogram according to one aspect of the present invention.

Detailed Description

Reference may be made in detail to the exemplary embodiments of the invention, some of which are illustrated, exemplified, and/or described herein. Other embodiments and means of practicing the invention may be utilized without departing from the intended scope, including various structural, compositional, and/or functional changes known to those skilled in the art. Accordingly, the following description is presented by way of illustration only and should not limit these alternatives and modifications in any way.

As used herein, the words "example" and "exemplary" mean an example or illustration, but do not necessarily indicate a critical or preferred aspect or embodiment. Unless the context indicates otherwise, the word "or" is intended to be inclusive rather than exclusive. For example, the phrase "A employs B or C" includes any inclusive permutation (e.g., A employs B; A employs C; or A employs B and C). On the other hand, the articles "a" and "an" generally mean "one or more" unless the context dictates otherwise.

As noted above, there is a need for a solid composition that can be used as a platform to make concentrate or masterbatch-type compositions that can be used with equal effectiveness in low melting thermoplastic formulations and in combination with engineering resin systems. Manufacturers would welcome a concentrate system that could meet all of their needs. As used herein, the term colorant or additive concentrate refers to a cured resin-based carrier system formed from a premix (which may include an optional liquid plasticizer) disclosed below, which is subsequently introduced as a solid into any amount of low or high temperature resin formulation.

To this end, a premix of an acrylate copolymer and a ring-opened polymeric cyclic ester or ether is prepared. Generally, the acrylate comprises 20 to 90 weight percent of the premix, while the ring-opening component is provided at less than 30 weight percent of the premix or in other embodiments at 0.1 to 20 weight percent. The remainder includes the colorant and the compounding additives, and optionally a plasticizer, which when present may constitute from 0.5 to 35 weight percent of the premix.

It has been found to be particularly useful in acrylates made from ethylene butyl acrylate, ethyl acrylate and methyl acrylate copolymers. Any combination (or single one) of these acrylates may be used, although ethyl-methacrylate (EMA) copolymers are preferred in certain aspects. Other acrylate copolymers may be used so long as the resulting components provide relatively high temperature stability (compared to the other components of the premix). Preferably, the acrylate component (or the combination of components in general) comprises at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, or at least 80 wt% of the total premix. Rather, these components should be no more than 90 weight percent, no more than 80 weight percent, no more than 70 weight percent, no more than 60 weight percent, no more than 50 weight percent, no more than 40 weight percent, or no more than 30 weight percent of the total premix. Additional limitations and parameters are included in the accompanying examples, all of which form a part of this written disclosure.

Similarly, polycaprolactone and components based on the polycaprolactone ring structure are preferred as ring-opening components. Polycaprolactone is particularly effective because of its broad hansen interaction radius, wide availability and relatively low cost (compared to other ring-opening polymeric esters and ethers). Certain substituted or functionalized derivatives of polycaprolactone and other cyclic ethers are also contemplated. Although an appropriate amount of ring-opening component is required (i.e., at least 0.1 wt% of the premix), it should not exceed 30 wt%. In further embodiments and in the examples indicated below, maximum amounts of polycaprolactone (or other ring-opening component) of 1 wt.%, 5 wt.%, 10 wt.%, 15, 20 and 25 wt.% are contemplated. It is noted that any of these recited intervals can also be considered to be the minimum end point of an acceptable range.

Although polycaprolactone is expected to have particular utility, it is possible to replace or enhance the use of certain polycaprolactone derivatives. As mentioned above, these derivatives may have certain functional groups introduced along the caprolactone ring (or cyclic ether ring). Three, four, five, and six-membered ring structures may be preferred due to their availability and cost. Some examples of derivatives may include: polyhydroxyalkanoates, polyglycolides, polylactides, and copolymers of lactones with one or more additional monomers;

thus, as used herein, "polycaprolactone derivatives" may include polymers of functionalized caprolactone, copolymers of certain lactones and one or more monomers, and/or polymers of those lactones. In particular, the lactones of interest comprise ring structures containing 2, 3,4, 5 or 6 carbons, to which functional groups may be attached to one or more of these carbons. In certain embodiments, the lactone ring has no added functional groups. When used, the monomers of these derivatives are selected from branched and/or straight chain aliphatic structures having any integer number of carbon atoms between 1 and 20 within the structure. These base monomers may include any number of carboxyl or hydroxyl functional groups, as well as methyl, butyl, ethyl, and isopropyl structures (with or without carboxyl and/or hydroxyl functional groups). The functional group of the monomer may also serve as a preferred functional group for the polycaprolactone and/or lactone ring structure.

In some aspects, a plasticizer is provided to the premix to wet the polymer surface, thereby reducing the required processing temperature. For example, Epoxidized Soybean Oil (ESO) can be added in amounts of 0.5 to 35 weight percent of the premix, with additional minimum or maximum levels of 1.0, 5, 10, 15, 20, 25, and 30 weight percent also being disclosed. It is worth noting that while the ESO and other plasticizers may be liquid when introduced during the manufacture of the premix of the concentrate carrier system, the final concentrate carrier itself will be a solid.

When used, the ESO can be mixed directly into the premix or additive package blend. In some embodiments, the premix and the additive package are combined, although a split stream process may be used to separately melt the polymer and additive package prior to forming the concentrate. In this case, it is understood that the plasticizer is involved in the processing of the premix, and any desired characteristics to be imparted to the final formulation using the concentrate should be properly considered as part of the performance enhancing agent in the additive package itself. However, formulators may also choose to use plasticizers, including ESO, in the low or high melting point resin formulations achieved by the carrier system of the present invention.

That is, the complex additive forms an important aspect of the present invention because the acrylate-based and ring-opened components serve only as the base resin carrier. Therefore, it is desirable to optimize and maximize the weight percent of the co-additive relative to the base resin carrier within the constraints of making a stable solid product. In some embodiments, the combined additive component comprises at least 0.1 wt%, more preferably between 45 wt% and 55 wt%, with the remainder of the premix mass constituting the base resin carrier (and plasticizer, if used). In some embodiments, the composite additive is approximately 80 weight percent of the total premix. Further, the additive package can be 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 50 wt%, 65 wt%, 70 wt%, and 75 wt% of the total mass of the premix.

The composite additive itself may include one, two or all three of the following: colorants, performance enhancers, and non-functional fillers. Each is familiar to those skilled in the art, and it will be understood that the substances used in the composite additive must be compatible with each other without detracting from the ultimate intended purpose of the concentrate (as a colorant or additive carrier, and to remain in solid form for general use in low and high temperature resin formulations). Colorants are expected to have particular utility in certain aspects of the present invention, and the present disclosure expressly contemplates the following embodiments: wherein the colorant is the sole purpose of the additive package, or wherein the premix is optimized for the colorant such that the colorant is the major component of the additive package, the additive package contains only minor amounts of process modifiers and/or antioxidants (less than 10 wt%, more preferably less than 5 wt%, of the mass of the additive package).

In general, the colorant can be any combination of organic and inorganic pigments, dyes, alumina, mica, pearlescent effect additives, laser markers, and/or metallocene polyethylene. To the extent that these components are cited or indicated in any publication cited herein, these portions of these publications are incorporated by reference herein to further enrich the disclosure. Furthermore, specific examples are indicated below, but these should not be construed as necessarily limiting the disclosure.

The performance enhancing agent imparts specific characteristics to the final thermoplastic formulation (rather than the premix or concentrate carrier system itself). Thus, to the extent that the performance enhancing agent is included in the additive package of any of the claimed or disclosed embodiments, those properties are imparted to the formulation into which the concentrate is incorporated. Properties of interest typically include process modifiers and mold release agents, as well as biocides, ultraviolet and light stabilizers, heat stabilizers, antioxidants, radical scavengers, acid scavengers, and antistatic or conductive fillers. Combinations of these performance enhancing agents may be included in any given concentrate formulation according to some aspects of the present invention. As with the colorants, certain non-limiting examples are provided below.

Finally, non-functional fillers may be used in the composite additive. These fillers are not intended to change the appearance or otherwise impart specific properties to the concentrate/final resin. Thus, unlike colorants and performance enhancers, these non-functional fillers are intended to facilitate formulation of the concentrate carrier system itself. Examples of non-functional fillers suitable for use in the present invention include calcium carbonate, clay, silica, talc, rice hull ash and certain other non-reactive types of ash. Reasons for relying on such non-functional fillers may be related to controlling costs, improving the manufacture/processing of the carrier system, and/or ensuring that the concentrate is sufficiently solid.

In one aspect of the invention, the co-additive includes a small amount of metallocene polyethylene to facilitate processing of certain aspects of the co-additive itself (in which case the metallocene may be considered a non-functional filler). The components of the compounded additive are premixed in a twin screw extruder and then recombined downstream with the premixed polymer/plasticizer blend. In another embodiment, the composite additive is dry-blended with the premix polymer and plasticizer, and then coagulated in the melt to form a concentrate.

The complex additive itself may be completely identical to the colorant. In other aspects, the colorant comprises a majority (i.e., at least 50 wt%) of the composite additive by weight percentage. Performance enhancing agents and/or non-functional fillers may be added to the colorant. In some cases, the non-functional filler may comprise a majority of the composition. The performance enhancer is typically no more than 50% by weight of the additive package. In preferred embodiments, the colorant comprises at least 2.5 wt%, at least 25.0 wt%, and at most 95.8 wt% of the composite additive. When provided, the non-functional filler can comprise 50.0 to 60.0 wt% of the composition. The performance enhancer may comprise from 2.0 wt% to 25.0 wt% of the additive package.

In another aspect, the pre-mixed polymer, plasticizer, and compounding additive will be combined on a two-roll mill, a compounder, a single or twin screw extruder, or a farel continuous mixer. Combinations of these mixing methods may also be used. After mixing, the mixture is then granulated through a die or a spray head, or cut into pieces as a ribbon.

In this regard, the invention includes methods of making the carrier system and formulations for use in the system. As noted above, other aspects of the invention relate to the subsequent use of the carrier system in combination with a low melt or high melt processing resin.

As mentioned above, the concentrate (including the additive package) formed in this manner has advantages over existing so-called "universal" or multi-functional concentrates. In particular, the concentrates according to the invention can be incorporated into low-temperature resins, such as moisture-curing XLPE, and also into high-temperature engineering resins, in particular PC, ABS and/or nylon 6.

U.S. patent 7,442742 describes a masterbatch composition that relies on a metallocene polymer, while U.S. patent 9,969,881 and the current co-pending continuation application (filed 4/13 in 2018 as U.S. serial No. 15/952,926, now published as U.S. patent publication 2018/0258237) describe a split stream process for preparing such a composition. Certain aspects of these disclosures, including formulations and methods of manufacture, may further enrich some aspects of the invention. Accordingly, these documents are incorporated herein by reference in their entirety.

Finally, a series of disclosures describe polymer blends that may be particularly useful when used in conjunction with certain aspects of the present invention. These documents include: us patent 3,459,834; 3,524,906, respectively; 4,320,212, respectively; 4,404,248, respectively; and 4,908,397, and German publications DE3518538 and DE3662527 and patent Cooperation treaty publication WO 2008/001684.

In practice, using the concentrate of the present invention, two injection manufacturing processes can be achieved in combination with different resin systems (i.e. those with processing temperatures that differ by at least 20 ℃, at least 50 ℃ and up to at least 100 ℃) while relying on the same concentrate platform. Furthermore, because of its flexibility over a wide range of processing temperatures, the risk of degradation or loss of the concentrate (including the required complex additives) is reduced.

An important aspect of the concentrate carrier system described and claimed herein is its ability to remain effective and viable over a wide temperature range. This, in turn, means that the concentrate can be incorporated into a low or high temperature process without fear of the concentrate degrading or failing to function as intended. The viability of the concentrate can be verified by oxidation induction time and/or melt separation tests and known standards of thermogravimetric analysis (e.g., ASTM E1131, E2105, etc.). Generally, the concentrate needs to maintain its integrity and avoid carbon formation or separation during use. The final formulation exhibited lumps, specks and/or other similar characteristics indicating that the concentrate carrier system failed to melt in the formulation as expected/needed.

In other aspects, the proportions of the components within the additive package and the relative proportions of the base resin (i.e., acrylate and polycaprolactone) and the overall additive package are important. Thus, in certain embodiments, all weight percentages disclosed herein may be further combined to form a ratio. In determining such a ratio, the amount of plasticizer introduced into the premix may be ignored. In the same manner, the relative proportions of plasticizer, base resin, and compounding additive are contemplated and within the aspects of these disclosures.

Examples

Table 1 shows three exemplary formulations of premixes and co-additives according to certain aspects of the invention. All ingredients indicated, except the plasticizer, are selected to be in solid form, not liquid or gaseous form.

Table 1 concentrate formulations all values are expressed as weight percent of the total premix

1a combination of 1.0% C.I. pigment Red (48:2), 8.76% C.I. pigment blue (15:1), 0.66% C.I. pigment Black (7, 70nm) and 2.0% C.I. pigment white (6)

1b 0.4% Zinc stearate and 0.4% calcium fatty acid

2a C.I. pigment Black (7)

3a C.I. pigment white (6)

2b and 3b Irganox 1010

Sample 1 was hand mixed and then melt compounded on a two roll mill with the front roll temperature set at 205 ° f and the back roll temperature set at 130 ° f. Of the following polymer resins, sample 1 was shown to provide uniform color at all tested amounts (up to 5 phr): rigid and flexible polyvinyl chloride, XLPE, poly (vinylidene fluoride), high density polyethylene, polypropylene, polyoxymethylene, ABS, general and high impact PS, PC, nylon 6 and TPE.

As a control experiment, comparable concentrates based on the teaching of us patent 6,713,545 were made using styrene and a linear diblock copolymer of ethylene/propylene. This material remains rubbery at lower temperatures and is extremely difficult to composite below 280 ° f. It cannot be compounded with XLPE and overcoating occurs when trying to compound it with PVC.

Differential Scanning Calorimetry (DSC) of ethylene methyl acrylate copolymer (trade name Elvaloy AC1820) and polycaprolactone is shown in figure 1, which indicates that the melting temperature of the material is 92 ℃ (198 ° f). The above-described embodiment of the invention was tested in a melt flow indexer using ASTM D1248, indicating that it can be dispersed at this temperature, which was set at 93 ℃. The melt flow index of this embodiment of the invention was found to be 0.01g/10min (2.16kg, 93 ℃). At 190 deg.C, the melt flow of the material was found to be 2.38g/10min (2.16 kg).

Figure 2 shows a dry air TGA thermogram according to the above embodiment of the present invention. Mass loss was 1% at 305.6 ℃ (582 ° f), with slight degradation occurring at 325.7 ℃ (618.3 ° f). This is sufficient to allow the concentrate to be mixed with a high temperature polymer (e.g., PC) that requires the material to reach 600 ° f in a short period of time.

Sample 2 was produced using a farel continuous mixer and extruder system to produce a pelletized product on an industrial scale. Sample 3 was produced using a two roll mill as described above. Both samples 1 and 3 maintained sufficient integrity and could be cut into uniform pieces from a solid rolled plate. Sample 2 can be pelletized using an underwater cutting pelletizing die.

Although specific embodiments have been illustrated, described, and/or described herein, it should be understood that the invention is not limited to the disclosed embodiments, but is also capable of numerous rearrangements, modifications, and substitutions. The exemplary embodiments have been described with reference to preferred embodiments, but further modifications and changes cover the foregoing detailed description. Such modifications and variations are also within the scope of the appended claims or their equivalents.