Polymer materials and additives therefor

Abstract

The formulation for reducing the aldehyde content in the polymer material comprises a compound containing at least three moieties of formula (A), each moiety (A) containing an amine moiety (-NH2) bonded ortho or meta to an amide moiety (-CONH), each R 1 independently represents a substituent, m is an integer from 0 to 4, and the three moieties (A) are bonded to the respective carbon atoms of the main fragment via their respective amide nitrogen atoms, this main fragment containing only carbon and hydrogen atoms and being saturated. TIFF2025521482000028.tif25170

Description

Technical Field

[0001] The present invention relates to polymer materials in which aldehydes may undesirably accompany, for example, during production, downstream melt processing and / or use. In particular, without excluding others, it relates to polymer materials such as polyesters, polyoxymethylene (POM), polyolefins, polyketones and polyurethanes. This polymer material may also include recycled materials that may be contaminated with aldehydes. This may particularly apply to recycled HDPE and / or PP.

Background Art

[0002] Polyethylene terephthalate (PET) is widely used on a large scale for the production of food packages such as bottles. Such bottles are widely used for packaging beverages such as carbonated soft drinks, beer, or mineral water. The technology generally used to manufacture bottles from PET (i.e., to convert PET from the raw material stage into a predetermined shape) generally includes a two-step process. In the first step, PET granules are injection molded to produce preforms. In the second step, these preforms are blow molded into the desired shape.

[0003] PET has a high softening point. Therefore, the typical temperatures required for processing PET are in the range of 260 - 285 °C. A problem recognized in the industry is that under the high-temperature and high-shear conditions required for injection molding to produce preforms and blow molding of preforms to produce bottles, PET tends to deteriorate and form acetaldehyde. The presence of acetaldehyde in the material of the finished bottle is undesirable, especially when the bottle is used for products consumed by humans. This is because acetaldehyde can migrate from the packaging material or the wall of the bottle to its contents, which may adversely affect the flavor and aroma characteristics of the food product. The formation of acetaldehyde in bottles made from virgin PET is an ongoing problem, but the formation of acetaldehyde is even more likely in bottles made from recycled PET (rPET). This is because the PET has multiple thermal histories.

[0004] The migration of acetaldehyde from PET bottles to flavored beverages is undesirable, but usually, trace amounts of acetaldehyde are often acceptable because the taste and aroma of the beverage are not significantly affected. However, the presence of even trace amounts of acetaldehyde in either carbonated or non-carbonated beverages, such as mineral water, tends to impart very undesirable off-tastes and odors to the beverage.

[0005] To capture acetaldehyde that may be generated by the degradation of PET, it is known to add an acetaldehyde scavenger to PET before or during melt processing. However, there are various competing requirements related to the selection and use of acetaldehyde scavengers. For example, the weight of the acetaldehyde scavenger incorporated into PET needs to be high enough to capture a large amount of acetaldehyde. However, higher levels of additives incorporated into PET can be harmful to the optical properties of PET. For example, high levels of additives can have an adverse effect on L * , a * or b * (i.e., L* Regarding L * there is a possibility of reducing), each of which is undesirable, especially when PET is used for mineral water bottles where aesthetics are particularly important. In addition, unfortunately, since the aldehyde scavenger may penetrate into the beverage contained in the bottle made of PET, it is important that the aldehyde scavenger itself does not significantly migrate from PET.

[0006] WO 2017 / 033117 A1 (Colormatrix) discloses a method for reducing the aldehyde content in polymer materials, such as polyethylene terephthalate. This document specifically exemplifies the range of aldehyde scavengers and evaluates the properties of the scavengers in Examples 6 to 13. However, even the scavenger showing the lowest level of migration (Example 6) still shows a relatively high migration, and the optical properties of the bottle incorporating the scavenger are considered to be improvable.

[0007] The present invention is based on the discovery of an improved aldehyde scavenger with respect to the scavengers described in WO 2017 / 033117 A1.

[0008] Aldehydes, especially formaldehyde, may also be generated during the production, processing and / or use of polyoxymethylene (POM) and other polymers. Aldehyde scavengers may be used to capture formaldehyde.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0010] The object of the present invention is to address issues related to aldehydes, such as the generation of formaldehyde or acetaldehyde in polymer materials.

[0011] The object of the present invention is to provide an aldehyde scavenger that is improved compared to the scavengers described in WO 2017 / 033117 A1.

Means for Solving the Problems

[0012] According to a first aspect of the present invention, there is provided a formulation for reducing the aldehyde content in a polymer material, for example, the formulation comprising a compound XX containing at least three moieties of the following formula:

Chemical formula

[0013] Compound XX shows an advantageous compromise in providing high-level aldehyde scavenging at an acceptable addition rate in polymer materials, such as polyesters, without significantly affecting the optical properties (e.g., L * , a * and / or b * ). Advantageously, it has been found to show a relatively low level of migration from the polymer. Compound XX is surprisingly more advantageous than the compounds disclosed in WO 2017 / 033117 A1.

[0014] One R 1 or each R 1may be selected from a halogen atom, or an optionally substituted hydrocarbon group, alkoxy group, amine group, amide group, phenol group or carboxylic acid group. The optionally substituted hydrocarbon may be substituted with one or more halogen atoms or an alkoxy group, amine group, amide group, phenol group or carboxylic acid group. The optionally substituted hydrocarbon is preferably unsubstituted.

[0015] One R 1 Or each R 1 is an optionally substituted, preferably unsubstituted alkyl group, for example an optionally substituted, preferably unsubstituted C 1~20 such as C 1~10 alkyl group. R 1 may be configured to improve the compatibility of compound XX in a polymer material in which compound XX may be incorporated by including a relevant functional group for improving compatibility (compatibility) in R 1

[0016] One m or each m may be 0 or 1. Preferably, each m is 0. That is, except for the amine part and the amide part, each part (A) is unsubstituted.

[0017] Preferably, in compound XX, at least one part (A) contains an amine part (-NH2) bonded ortho to the amide part (-CONH). Preferably, in each part (A) in compound XX, the amine part is bonded ortho to the amide part. In this case, it is preferable that m = 0.

[0018] Preferably, the above main fragment does not contain any cyclic or aromatic part. Preferably, this main fragment contains a straight chain or a branched chain.

[0019] The above main fragment may contain 3 to 20 carbon atoms. Preferably, the main fragment contains 5 to 15 carbon atoms, more preferably 7 to 12 carbon atoms, especially 8 to 10 carbon atoms. When the number of carbon atoms is n, the number of hydrogen atoms may be equal to 2n - 1. Preferably, this main fragment contains 5 to 39 hydrogen atoms. Preferably, the main fragment contains 9 to 29 hydrogen atoms, more preferably 13 to 23 hydrogen atoms, especially 15 to 19 hydrogen atoms.

[0020] In a preferred embodiment, the above main fragment is C9H 17 moiety.

[0021] The above main fragment may contain a straight chain having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms. This straight chain may contain a branch point to which a chain containing 1 to 4 carbon atoms is attached.

[0022] The above main fragment has the following general formula

Chemical formula

[0023] Preferably, the sum of the integers p, q and r is at least 4, preferably at least 6, more preferably at least 7. This sum may be less than 20, preferably less than 15, more preferably less than 10.

[0024] In compound XX, preferably the nitrogen atom of the amide moiety (-CONH) is separated by at least 2, preferably at least 4, carbon atoms and preferably no more than 10, for example no more than 7, carbon atoms.

[0025] The above compound XX has the following formula

Chemical formula

[0026] The above compound XX is preferably

Chemical formula

[0027] The above formulation may contain at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, especially at least 75% by weight of the carrier. This formulation may contain less than 80% by weight of the above carrier.

[0028] The above formulation may contain 50 to 95% by weight of the carrier, 5 to 50% by weight of the above compound XX, and 0 to 30% by weight of other additives. These other additives may be selected from colorants, antioxidants, thickeners, process stabilizers, UV additives and reheat additives. In one preferred embodiment, the above formulation contains 0.5 to 10% by weight of one or more colorants, for example, at least one blue colorant. In another embodiment, the above formulation contains 0.5 to 10% by weight of one or more reheat additives, for example, titanium nitride or tungsten oxide (especially the latter) described in WO 2016 / 063013 pamphlet, the content of WO 2016 / 063013 pamphlet is incorporated herein by reference insofar as it relates to titanium nitride and tungsten oxide. In a preferred embodiment, the above formulation contains at least some colorant, for example, a blue colorant.

[0029] The colorants described in this specification may be dyes or pigments.

[0030] Preferably, in the above formulation, the total weight percentage of the carrier and compound XX is at least 80% by weight, at least 90% by weight or at least 95% by weight.

[0031] The above-mentioned composition may be a solid masterbatch or a liquid composition. When the composition is a solid masterbatch, the solid masterbatch may contain 60 to 95% by weight of a thermoplastic polymer. This thermoplastic polymer may be selected from polyester, polyoxymethylene (POM), polyolefin, polyketone, and polyurethane. This thermoplastic polymer is preferably compatible with the functional groups in the polymer material treated to reduce the aldehyde content as described herein and / or contains the same functional groups as such functional groups.

[0032] The above-mentioned composition may contain 10 to 40% by weight of Compound XX and 60 to 90% by weight of a thermoplastic polymer.

[0033] The solid masterbatch may contain up to 60% by weight of a colorant. This colorant may be a dye or a pigment. The solid masterbatch may contain 0 to 10% by weight, preferably 0.5 to 10% by weight, of one or more colorants, such as one or more inorganic pigments.

[0034] When the above-mentioned complex is a liquid formulation, this formulation may contain 50 to 90% by weight (for example, 50 to 80% by weight) of a liquid carrier and 10 to 50% by weight (for example, 20 to 50% by weight) of Compound XX. This liquid carrier may preferably be liquid at 25°C and atmospheric pressure. A carrier that has good solubility in the polymer material to which it is added is suitable. It may contain an oil (for example, vegetable oil or mineral oil) or a glycol. A polymer material-compatible organic liquid carrier may be an oily vehicle (especially when the polymer material is a polyester). Examples of such vehicles are materials sold as Clearslip (trademark) 2, Clearslip (trademark) 3 and Process Aid-1 by ColorMatrix Europe Ltd, Units 9-11 Unity Grove, Knowsley Business Park, Merseyside, L34 9GT.

[0035] When the above-mentioned formulation is a solid formulation (i.e., a masterbatch), a polymer resin may be used as the carrier. Such carriers may be polyesters, polyacetals (POM), TPE, polyvinyl butyral (PVB), polyolefins or waxes.

[0036] The specific compound of Formula XX is considered to be novel. Thus, in a second aspect, a novel compound of Formula XX containing at least three moieties of the following formula:

Chemical formula

[0037] Preferably, the novel compound is [Chemical formula] as follows.

[0038] According to a third aspect of the present invention, there is provided a method for reducing the aldehyde content in a polymer material, which method comprises contacting the polymer material, or a monomer, oligomer or prepolymer involved in the preparation of the polymer material, with the compound XX described in the first and / or second aspects.

[0039] The polymer material to be contacted in the method may be any polymer material capable of incorporating aldehydes that need to be trapped or otherwise reduced. This polymer material may include polyester (especially poly(ethylene terephthalate)), polyurethane, polyoxymethylene (POM), polyketone or polyolefin. Preferably, the polymer material includes polyester (especially poly(ethylene terephthalate)). This polymer material may include unused material or recycled material. The latter may be particularly relevant to HDPE and / or PP.

[0040] References herein to "ppm" refer to "parts per million" by weight.

[0041] A method for measuring acetaldehyde in industrially injection-molded polyethylene terephthalate preforms is described by Fl Villian et al., Journal of Polymer Science, Vol. 52, 55 - 60 (1994).

[0042] The above contacting step may be carried out using a polymer material in a molten state. Alternatively, the above compound may suitably be added to a solid polymer material at a temperature lower than the melting point of the polymer material, where the polymer material is not in a fluid state and / or a molten state. In one less preferred embodiment, compound XX may be added to a monomer, oligomer or prepolymer involved in the preparation of the above polymer material. This may be particularly relevant to processes involving polyoxymethylene (POM), polyvinyl butyral (PVB), polyolefins and polyurethanes.

[0043] Advantageously, the use of the method can lead to environmental improvement, lower global emissions and sublimation, and an improved oxygen induction time.

[0044] Prior to the above contacting step, the polymer material is preferably selected when it is in the above-mentioned solid state. This selected polymer material is preferably present in a state where the monomers used in the preparation of the polymer material are substantially absent. This selected polymer material is preferably in a state isolated from the reaction mixture from which it was formed. The polymer material is preferably an isolated polymer material. The method may include a step of drying the polymer material prior to the above contacting step. The above selected polymer material is preferably in particulate form, for example in the form of pellets, granules or flakes.

[0045] The amount of compound XX in contact with the above polymer material may be selected based on the level of performance required in the polymer material. In a preferred embodiment, the total ppm of compound XX in contact with the above polymer material (based on the weight of the above polymer material) is preferably at least 100 ppm, preferably 200 ppm, more preferably at least 450 ppm. This total ppm may be less than 2000 ppm or less than 1000 ppm.

[0046] The above compound XX may be part of the formulation described according to the first aspect. In a preferred embodiment, compound XX is combined, for example mixed, with an organic liquid carrier that is compatible with the above polymer material. Typical carriers include hydrocarbons, hydrocarbon mixtures, alcohols, esters, polyethers, and mixtures of two or more of these.

[0047] The polymer material-compatible organic liquid carrier may be (especially when the polymer material is a polyester) an oily vehicle. Examples of such vehicles are materials sold as Clearslip™ 2, Clearslip™ 3, and Process Aid-1 by ColorMatrix Europe Ltd, Units 9-11 Unity Grove, Knowsley Business Park, Merseyside, L34 9GT.

[0048] When the polymer material is preferably polyester, the polyester is preferably polyethylene terephthalate, and this term is intended to include copolyethylene terephthalate in the context of this specification. The copolyethylene terephthalate of polyethylene terephthalate may contain repeating units from at least 85 mol% of terephthalic acid and at least 85 mol% of ethylene glycol. The dicarboxylic acids that may be included with terephthalic acid are exemplified by phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, cyclohexanedicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4'-dicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, and sebacic acid. In addition to ethylene glycol, other diols that may be incorporated into copolyethylene terephthalate include diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, 3-methylpentane-2,4-diol, 2-methylpentane-1,4-diol, 2,2,4-trimethylpentane-1,3-diol, 2-ethylhexane-1,3-diol, 2,2-diethylpropane-1,3-diol, hexane-1,3-diol, 1,4-di(hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, 2,2-bis-(3-hydroxyethoxyphenyl)-propane, and 2,2-bis-(4-hydroxypropoxyphenyl)-propane. In a preferred embodiment, the polyethylene terephthalate has less than 10 mol%, more preferably less than 6 mol%, especially less than 2 mol% of comonomer substitution. Preferably, this copolyethylene terephthalate does not contain copolyethylene terephthalate, and it preferably substantially comprises a homopolymer produced by esterifying or transesterifying terephthalic acid or dimethyl terephthalate with ethylene glycol to produce bis(2-hydroxyethyl) terephthalate, and then polycondensing this in the presence of a catalyst, in vacuo, at a high temperature.

[0049] As used herein, the term "IV" refers to the intrinsic viscosity of the polymeric material. This may be measured in a solution of 0.5 g of the polymer dissolved in 100 ml of a mixture of phenol (60% by volume) and tetrachloroethane (40% by volume).

[0050] When the polymeric material is a polyester, the IV of the polyester upon contact with the compound XX is preferably greater than 0.5 dL / g, more preferably greater than 0.65 dL / g.

[0051] When the polymeric material is a polyester, this polyester may be particularly suitable for use in extrusion blow molding (EBM). Such adaptation is known to those skilled in the art and includes an increase in the amount of comonomer, changes in IV and structure.

[0052] The polymeric material is preferably part of an article, such as a molded article, and / or defines an article, such as a molded article. This article may be selected from a preform, a container, a bottle, a cup, a tray, a thermoformed sheet, or other desired shapes.

[0053] After contacting the polymeric material with the compound XX, the polymeric material may contain 50 to 1000 ppm of the compound XX, preferably 100 to 700 ppm or 150 to 600 ppm of the compound XX, based on the amount of the polymeric material, such as polyester.

[0054] According to a fourth aspect of the present invention, there is provided a method for producing an article, such as a molded article, from a polymeric material, comprising (a) selecting the compound XX described in the first aspect and / or the second aspect; (b) contacting the polymeric material with the compound XX; and (c) shaping the polymeric material into an article, such as a molded article is provided.

[0055] Preferably, step (b) is carried out when the polymeric material is not in a fluid state, such as a molten state. Thereafter, in step (c), the polymeric material is suitably melt-processed to define the above article.

[0056] The above article may be defined by any process known in the art. For example, this process may include injection molding, blow molding or thermoforming. For example, injection molding may be used to form a preform used to blow mold bottles, food / drink containers, trays or other desired shapes. Also, the above process may include the manufacture of a sheet that may later be thermoformed to define an article, such as a receptacle like a cup or tray. Alternatively, a melt polymeric material may be used in an extrusion blow molding operation to provide bottles, food containers, etc. A melt polymeric material melt may similarly be supplied to an extruder to manufacture films, sheets, profiles, pipes, etc.

[0057] Preferably, the above article preferably includes a container or a preform for a container made from the described polyester. More preferably, the above molded article includes a preform for a bottle, such as a beverage bottle.

[0058] The above article may include one or more colorants, such as at least one blue colorant. After contacting the polymeric material with Compound XX, the polymeric material may contain 1 to 1000 ppm of a colorant (such as a blue colorant), preferably 5 to 500 ppm of a colorant (such as a blue colorant), and this ppm is based on the amount of this polymeric material, such as polyester. The colorants described herein may be dyes or pigments.

[0059] The above-mentioned article may contain one or more reheating additives, for example, titanium nitride or tungsten oxide (especially the latter) described in WO 2016 / 063013 pamphlet. The content of WO 2016 / 063013 pamphlet is incorporated herein by reference insofar as it relates to titanium nitride and tungsten oxide. After the above-mentioned polymer material is contacted with compound XX, this polymer material may contain 1 to 1000 ppm of reheating additive (for example, titanium nitride or tungsten oxide), preferably, it contains 5 to 500 ppm of reheating additive (for example, titanium nitride or tungsten oxide), and this ppm is based on the amount of the above-mentioned polymer material, such as polyester.

[0060] Preferably, in the above-mentioned molded article, the total weight percentage of the amount of the polymer material, such as polyester, and the amount of compound XX is at least 90 wt%, at least 95 wt% or at least 98 wt%.

[0061] According to the fifth aspect of the present invention, there is provided a polymer material, such as polyester, having a reduced aldehyde level, for example, an acetaldehyde level, wherein this polymer material, such as polyester, incorporates compound XX according to the first and / or second aspect or a reaction product of compound XX and an aldehyde, such as acetaldehyde.

[0062] The reaction product of compound XX and an aldehyde, such as acetaldehyde, suitably contains a fragment derived from part (A) described in the fragment of the first aspect below.

Chemical formula

[0063] The reaction product preferably contains the following part.

Chemical formula

[0064] The nitrogen atom adjacent to the carbonyl group is appropriately bonded to the main fragment described according to the first aspect.

[0065] Any aspect of any of the inventions described herein may be modified where appropriate and combined with any other aspect of any of the inventions described herein.

BEST MODE FOR CARRYING OUT THE INVENTION

[0066] Next, specific embodiments of the present invention will be described by way of example.

[0067] The following materials are referred to hereinafter. A polyetheramine having the general structure shown below, JEFFAMINE (trademark) T-403

CHEMICAL

CHEMICAL

[0068] Broadly speaking, an aldehyde scavenger is contacted and mixed with a polyester, particularly PET, and the combination is injection molded (along with any other additives present) to produce a container preform. Preforms are well known. They preferably have a test tube-shaped body and a threaded neck adjacent to the open end, with a cap flange associated with the neck. The preform is blow molded to form a container, such as a beverage container that can be closed by a cap releasably engaging the threaded neck.

[0069] The aldehyde scavengers described may be solid or liquid. When they are solid, they may be provided as a dispersion in a carrier, such as mineral oil or another carrier compatible with the polyester into which the scavenger is incorporated. When they are liquid, the liquid may be used directly or may be diluted by a carrier as described above. In some embodiments, the carrier for the acetaldehyde scavenger may be solid at 25°C.

[0070] The acetaldehyde scavenger may be prepared as described in Examples 1-3, the preform may be prepared as described in Example 4, and the scavenger may be evaluated as described in the subsequent examples.

Examples

[0071] Example 1 - Preparation of a Comparative Acetaldehyde Scavenger Based on Jeffamine™ (referred to as "Scavenger C1") Jeffamine T-403 was reacted with phthalic anhydride to produce Scavenger C1, which is detailed below. The amount of phthalic anhydride was selected to derivatize all of the primary amine functional groups of Jeffamine.

Chemical formula

[0072] This scavenger is identical to Example 7 in WO 2017 / 033117 pamphlet.

[0073] Example 2 - Preparation of a Comparative Acetaldehyde Scavenger Based on Tris(2-aminoethyl)amine (Referred to as "Scavenger C2") Tris(2-aminoethyl)amine was reacted with isatoic anhydride to produce Scavenger C2, which is detailed below. The amount of isatoic anhydride was selected to derivatize all the primary amine functional groups of Jeffamine.

Chemical Structure

[0074] This scavenger was the same as Example 6 in WO 2017 / 033117 Pamphlet and had a melting point of 146 - 148°C.

[0075] Example 3 - Preparation of the Acetaldehyde Scavenger N,N'-(2-(4-(2-aminobenzamide)butyl)pentane-1,5-diyl)bis(2-aminobenzamide) (Referred to as "Scavenger EG3") Scavenger EG3 has the following structure.

Chemical Structure

[0076] It was prepared as follows. 2H-Benzothieno[3,2-d][1,3]oxazine-2,4(1H)-dione (98.84 g, 3.5 eq., 605.9 mmol) was dissolved in dimethylformamide (500 mL) at room temperature. To this reaction mixture, a solution of 4-(aminomethyl)octane-1,8-diamine (30.00 g, 1 eq., 173.1 mmol) in dimethylformamide (250 mL) was added dropwise. The reaction mixture was stirred overnight at room temperature until complete conversion was evident by LC-MS. Dimethylformamide was removed under reduced pressure to afford a dark brown oil. Water (1 L) and ammonium hydroxide (25%, 50 mL) were added thereto, and the product was extracted with dichloromethane. Dichloromethane was removed under reduced pressure, and the product was recrystallized from a mixture of methanol and acetonitrile. The solid was collected by filtration and dried to give N,N'-(2-(4-(2-aminobenzamido)butyl)pentane-1,5-diyl)bis(2-aminobenzamide) (51.0 g, 55.5% yield). The structure of this compound was confirmed by NMR and LC-MS, and the melting point was 160 °C.

[0077] Example 4 - General Procedure for the Preparation of Preforms The C93 PET resin is dried at 160 °C for at least 4 hours using a Con-Air™ dryer prior to use.

[0078] The selected amount of scavenger was contacted with the hot dried C93 PET in the presence of 1000 ppm (relative to C93 PET) of the acetic acid ester of monoglyceride made from fully hydrogenated castor oil. This acetic acid ester is the carrier. In practice, a liquid formulation containing the carrier and the scavenger would be used, but the separate addition of the scavenger and carrier described is convenient for the experimental procedure.

[0079] The above blend was added to the hopper of a Husky 160T Injection Molder having the following parameters to produce 34 g PET preforms.

[0080]

Table 1

[0081] Example 5 - General Procedure for Determining the Acetaldehyde Content of Preform Samples The acetaldehyde content of the sample is determined for preform samples cryogenically milled to less than 1 mm. The level of acetaldehyde is determined using a ThermoFisher 22 Scientific Trace 1310 gas chromatograph equipped with a Triplus 500 headspace autosampler and an FID detector. The reduction of acetaldehyde is calculated based on the percentage reduction in the acetaldehyde level of the preform containing the additive compared to the preform without the additive.

[0082] Example 6 - Procedure for Measuring Optical Properties Samples are taken from the sidewall of the preform, and relevant controls are prepared. The optical properties (i.e., L * , a * and b * ) are evaluated using a Minolta CM-3700d spectrophotometer in transmission mode equipped with a D65 / 10° light source.

[0083] Example 7 - Procedure for Determining the Migration of Acetaldehyde Scavengers from PET Bottles blow-molded from preforms incorporating the selected acetaldehyde scavenger, along with relevant controls, are filled with 20% ethanol / water (in accordance with standard EU acceptance test conditions) and placed in an oven at 60 °C for 10 days. At various time points, water is sampled and the level of migration of the acetaldehyde scavenger into the water (if migration occurs) is determined using LC-MS. Multiple bottles are evaluated for each scavenger tested, and the average migration value is calculated.

[0084] Example 8 - Evaluation of the Acetaldehyde Scavenging Ability of Selected Materials Using the general procedure described in Example 4, preforms were made using the compounds within the described ranges, and the aldehyde scavenging ability of the compounds was evaluated as described in Example 5. The results are shown below. Note that based on other experiments (not reported), the addition amount of each scavenger was selected based on the level required to achieve aldehyde reduction equivalent to that when anthranilamide, a commercially available aldehyde scavenger at 500 ppm, was used.

[0085] The results regarding the aldehyde scavenging ability of the aldehyde scavengers of Examples 1 to 3 and anthranilamide against the control (made of C93 PET) are shown in the following table.

[0086] [Table 2] n / a means "not applicable".

[0087] Example 9 - Evaluation of the Optical Properties of the Selected Materials The preforms mentioned in Example 8 were evaluated as described in Example 6. The results regarding the optical properties (L * , a * , b * ) are shown in the following table.

[0088] [Table 3]

[0089] Example 10 - Evaluation of the Migration of the Aldehyde Scavenger The preforms mentioned in Example 8 were evaluated as described in Example 7. The results regarding the level of migration in "parts per billion" (ppb) by weight are shown in the following table.

[0090] [Table 4] n / a means "not applicable".

[0091] Example 11 - Calculation for Comparing the Effectiveness of Acetaldehyde Scavengers Based on the previous examples and results, the following calculations were performed to illustrate the advantageous properties of the scavenger EG3. (i) The amount of acetaldehyde scavenger for treating 1 Kg of PET. For this, it is desirable that the amount is relatively small while achieving a high level of acetaldehyde reduction. (ii) The molecular weight (MW) of the scavenger. (iii) The millimoles (mmol) of acetaldehyde scavenger used to achieve a specific level of scavenging. A low value is preferred. (iv) The millimoles of nitrogen-containing active centers for achieving a specific level of scavenging. (v) The millimoles of nitrogen-containing active centers divided by the % of acetaldehyde reduction for achieving a specific level of scavenging. A low value is preferred. (vi) The millimoles of nitrogen-containing active centers divided by the shift in ppb units of acetaldehyde reduction for achieving a specific level of scavenging. A high value is preferred.

[0092] [Table 5]

[0093] Discussion From the above, the scavenger EG3 has a very low shift according to (vi) and is the best in class effectiveness (see (iii) and (v)), with a higher L * and a lower b * compared to other low-shift scavengers. It should be noted that it has these properties.

[0094] The present invention is not limited to the details of the above-described embodiments. The present invention extends to any novel one of the features disclosed herein (including the appended claims, abstract, and drawings), or any novel combination thereof, or any novel one of the steps of any method or process disclosed as such, or any novel combination thereof.

Claims

1. For example, a formulation for reducing the aldehyde content in a polymer material, wherein the formulation comprises a compound XX having at least three parts of the following formula: 【Chemistry 1】 Each portion (A) is an amine portion (-NH) bonded to the amide portion (-CONH) in an ortho or meta manner. ２ ) including, Each R １ Each of the following independently represents a substituent, and m is an integer from 0 to 4. A composition in which the three parts (A) are bonded to each carbon atom of the main fragment via their respective amide nitrogen atoms, and the main fragment contains only carbon and hydrogen atoms and is saturated.

2. One R １ or each R １ The compound according to claim 1, wherein the halogen atom is selected from a halogen atom, or an optionally substituted hydrocarbon group, alkoxy group, amine group, amide group, phenol group, or carboxylic acid group.

3. The formulation according to claim 1, wherein each m is 0.

4. The compound according to claim 1, wherein in each portion (A) of compound XX, the amine portion is ortho-bonded to the amide portion.

5. The formulation according to claim 1, wherein the main fragment does not contain any cyclic or aromatic portion, and / or the main fragment contains a linear or branched chain.

6. The formulation according to claim 1, wherein the main fragment comprises 3 to 20 carbon atoms and / or 5 to 39 hydrogen atoms.

7. The aforementioned main fragment is of the following general formula: 【Chemistry 2】 The formulation according to claim 1, wherein p, q, and r are integers in the range of 1 to 10, preferably 1 to 5.

8. The formulation according to claim 7, wherein p is in the range of 2 to 4, q is in the range of 1 to 3, r is in the range of 2 to 6, and / or the sum of integers p, q and r is at least 4, preferably at least 6, and the sum is less than 20, preferably less than 15.

9. The compound according to claim 7, wherein the compound XX is of the following formula. 【Transformation 3】

10. The compound XX is 【Chemistry 4】 The compound according to claim 1.

11. The formulation according to claim 1, comprising 50 to 95% by weight of a carrier, 5 to 50% by weight of the compound XX, and 0 to 30% by weight of other additives.

12. The formulation according to claim 1, comprising 0.5 to 10% by weight of one or more colorants, for example, at least one blue colorant.

13. The formulation according to claim 1, wherein the total weight percent of the carrier and compound XX is at least 80% by weight, at least 90% by weight, or at least 95% by weight.

14. The formulation according to claim 1, wherein the formulation is a solid masterbatch comprising 60 to 95% by weight of a thermoplastic polymer selected from polyester, polyoxymethylene (POM), polyolefin, polyketone, polyvinyl butyral (PVB), and polyurethane, and 0 to 10% by weight, preferably 0.5 to 10% by weight, of one or more colorants.

15. The formulation according to claim 1, wherein the formulation is a liquid formulation comprising 50 to 90% by weight (for example, 50 to 80% by weight) of a liquid carrier and 10 to 50% by weight (for example, 20 to 50% by weight) of compound XX.

16. A novel compound of formula XX comprising at least three parts of the following formula, 【Transformation 5】 Each portion (A) is an amine portion (-NH) bonded to the amide portion (-CONH) in an ortho or meta manner. ２ ) including, Each R １ Each of the following independently represents a substituent, and m is an integer from 0 to 4. A compound in which the three parts (A) are bonded to each carbon atom of the main fragment via their respective amide nitrogen atoms, and the main fragment contains only carbon and hydrogen atoms and is saturated.

17. The aforementioned compound, 【Transformation 6】 The compound according to claim 16.

18. A method for reducing the aldehyde content in a polymer material, comprising the step of contacting the polymer material, or a monomer, oligomer, or prepolymer involved in the preparation of the polymer material, with a compound XX according to any one of claims 1 to 17.

19. The method according to claim 18, wherein the polymer material to be brought into contact in the method is any polymer material that can incorporate an aldehyde that needs to be captured or otherwise reduced, and / or the polymer material comprises polyester (particularly poly(ethylene terephthalate)), polyurethane, polyoxymethylene (POM), polyketone or polyolefin.

20. The method according to claim 18, wherein the polymer material to be brought into contact in the above method is polyester (particularly poly(ethylene terephthalate)).

21. The method according to claim 18, wherein the total ppm (based on the weight of the polymer material) of compound XX in contact with the polymer material is at least 100 ppm, preferably 200 ppm, more preferably at least 450 ppm, and / or the total ppm is less than 2000 ppm or less than 1000 ppm.

22. The method according to claim 18, wherein the compound XX is part of the formulation described in any one of claims 1 to 15.

23. The method according to claim 18, wherein the polymer material is part of an article, for example, a molded article, and / or defines the article, for example, a molded article, the article may be selected from a preform, a container, a bottle, a cup, a tray, or a thermoformed sheet.

24. A method for manufacturing articles, such as molded articles, from polymer materials, (a) A step of selecting compound XX according to any one of claims 1 to 17, (b) A step of bringing the polymer material into contact with the compound XX, (c) A step of molding the polymer material into an article, for example, a molded article. A method that includes this.

25. The method according to claim 24, wherein the article comprises a container or a preform for a container.

26. A polymer material, such as polyester, having a reduced level of aldehyde, such as acetaldehyde, wherein the polymer material, such as polyester, incorporates compound XX according to any one of claims 1 to 17, or a polymer material having a reaction product of compound XX with an aldehyde, such as acetaldehyde.

27. The product of the reaction between compound XX and an aldehyde, such as acetaldehyde, includes a fragment derived from portion (A) of any one of claims 1 to 17 below. 【Transformation 7】 In the formula, R ３０ refers to the aldehyde residue, and preferably, when the aldehyde is acetaldehyde, it is a methyl group. The polymer material according to claim 26.

28. The polymer material according to claim 26, wherein the product of the above reaction includes the following portion. 【Transformation 8】

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