NL2032034B1

NL2032034B1 - Method for colouring a polymeric film and coloured polymeric film

Info

Publication number: NL2032034B1
Application number: NL2032034A
Authority: NL
Inventors: Vos Hendré
Original assignee: Orange Dynamics B V
Priority date: 2022-05-31
Filing date: 2022-05-31
Publication date: 2023-12-12
Also published as: WO2023234776A1

Abstract

The invention relate to a method for colouring a polymeric film and a coloured polymeric ﬁlm. The method comprises the steps of: 5 — a polymeric backbone layer and one or more polymeric layers arranged on the polymeric backbone layer, each of the one or more polymeric layers having a respective glass transition temperature, wherein the one or more polymeric layers that are arranged on a same side of the polymeric backbone layer are arranged in an order of decreasing glass transition temperature starting from said same side, the glass transition temperature of 10 each of said one or more polymeric layers being lower than that of the polymeric backbone layer; and — colouring the one or more polymeric layers in an order of their glass transition temperature starting with the polymeric layer(s) having the highest glass transition temperature.

Description

! ~ METROD FOR COLOURING A POLYMERIC FILM AND COLOURED POLYMERIC FILM

The present invention relates to a method for colouring a pelymeric film and to a coloured polymeric film. Furthermore, the invention relates to a master colour batch obtainable by said method, a ase of smd master colour batch, rigid packaging, and an injected moulded product, such as a hottie.

Plastic articles are useful for a wide variety of applications. Furthermore, the recycling of coloured plastic articles is even more important than ever before, as the volume of plastics discarded has proliferated in the last few decades. There is a great dernand for more and more

IQ complex materials to satisfy the different aspects of the packaging industry.

Plastics are for example nsed extensively for beverage bottles, including bottles for carbonated soft drinks and other liquids, Many of the articles used in this way are coloured by various types of pigments or colorants to enhance their appearance or to protect the contents of the + bottle from ultraviolet radiation.

There is a great need in the recycling industry for better methods aad technologies for colouring plastics and/or removing colourants fram plastics. Conventionally, a plastic material that is to be recycled is typically washed, (faked or pelletized, and then supplied to a solid-state reactor ire the process of converting waste plastic into various articles. The recycling of coloured plastic material into granules leads to dark prey or black granules. One main bottleneck of these granules of recycled plastic material ts that they must be compounded with virgin material to be able to provide the desired colour during further nse. Often this leads to colour differences. The colour differcuces may be reduced by adding other colourants such as titanium dioxide. However, this tmpairs the physical properties and processability of the plastics, which further restricts their range of application. In particular, further recycling is made much more difficult because additional colourants are added with each cycle, and thus further bupairing the physical properties of the polymer.

An objective of the present invention is to provide a roethod for sustainably colouring a plastic in which the abovementioned problem does not occur or at least toa lesser extent,

This objective is achieved with the method for colouring a polymeric film, wherein the method comprises the steps of! — providing 2 polymeric film comprising 4 polymeric backbone layer and one or more polymeric layers arranged on the polymeric backbone layer, each of the one or more polymeric layers having a respective glass transition temperature, wherein the onc-or more poly merie layers that are arranged on « same side of the polymerie backbone layer are arranged in an order of decreasing glass transition temperature starting from said same side, the glass transition temperature of each of said one or more polymeric layers being lower than that of the polymeric backbone layer: and = colouring the one or more polymeric layers in an order of their glass transition temperature starting with the polymeric layer(s) having the highest glass traasition ternperatue, 3 ft is noted that the phrase “adjacent” as used in this application is considered 16 be sinnlar to “divectly adjacent” and/or “contiguous wij” and these phrases are used interchangeably in this application.

Furthermare, 1 1s noted that the glass transition temperature of the polymeric film decreases from the inside to the outside. 1G Further, itis noted that the polyrasrc {thm may coraprise voe or more polymeric layers on pre or both sides of the polymeric backbone ayer, For example, the polymeric film may be formed from a thenuopkstc matedal/polyner,

The method according to the invention may stan with the step of providing @ polymeric film comprising 4 polymeric backbone layer and one or more polymeric layers arranged on the polymeric backbone layer, each of the one or raore polymeric layers having a respeciive glass transition temperature, where the Das or roe polymere layers that ame arranged on 4 same side of the polymede backbone layer are swranged in an order of decreasing glass transition temperature : starting frome said same side, the glass pansion emperature of each of said one or more polyreeric layers being lower than that of the polymeric backbone layer. Said step may than be followed by the step of colouring the one or more polymeric layers ia an order of their glass transition femperatare sting with the polymeric layers having the highest glass transition temporaire.

For example, the order of their glass transition temperature niay be an order starting with a high glass transition temperature to a Tow glass transition temperature. In other words, the glass transition temperatuge of the polymeric backbone layer may be higher compared fo the one or more polymeric layers, wherein the glass transition femperature of the individual layers decreases in a direction extending away rom the polymeric backbone layer,

The colouring of the polymeric film may be performed using a colouring agent, which may be provided to the polymeric fila as a solution. in addition, the polymeric film provided by the method according to the invention comprises

Xa polyastc backbone layer and obo or more polymeris layers, wherein the polypiernic backbone {ayer and each of the one or mare polymeric layers having a respective glass transition temperature, wherein for cach pair of adiacent polymeric layers. the glass transition temperature of the polyraeric layer that is closest to the polymeric backbone layer is higher than that of the other polymeric layer and lower than that of the polymeric backbone layer: Thus. zach layer among the one or more polymeric layers and the polymerie backbone may have iis characteristic morphology, describing the distinction between amorphous and orystalline solids,

; |l tis noted that polymers with an amorphoas morphology Have their atoms held thgetherin á loose structure, but this structure is never orderly or predictable. Therefore, amorphous solids may also refer to amorphous solids having no long-range order or chain entanglement.

Furthermore, it 3s noted that polymers with a crystalline morphology have their atoms held together in a rigid structure, wherein the structure may form folds and form orderly stacks of . folded chains, known as lamellae. Lamellae bring long-range order to polymers,

Thus, the polymer chains of the polymeric backbone layer and/or the one or more polynieric layers are arranged increasingly more randomly throughout the material starting from the polymeric backbone layer to the outer polymeric layer, making atomic positions quasi-random. As a result of decrease in long-range order and decrease of crystallinity {getting more amorphous and less crystalline), the colouring of the different layers may be dependent on when the glass transition teuperature of the effective layer is reached. In addition, the morphology of the one or more polymeric layers enables absorbing the colourant before the one or more polymeric layers reach the liquid state.

In fact, the polymeric backbone layer and/or one or more polymeric layers extending away from the polymeric backbone, reach & range of temperatures over which the material becomes less glassy and more tubber-like or vice versa, As a result, the polymeric backbone layer and/or the one or more polymeric layers do not have a melting point but have a glass transition temperature (Ty).

Without being bond to a specific theory, # is assured that the coleurant, such 28 an organic 29 aromatic eolowring agent, may have the ability to migrate into:the synthetic (polar) polymer material to thereby colour the synthetic (polar) polymer material. A migration of the organic arunalic colondnog agent into the synthetic (polar) polymer material may also slow a migration of the organic aromatic colouring agent out-of the coloured synthetic (polar) polymer material,

Therefore, a decolouring of the colowed nuteria] may be possible. To enable a migration as unhindered as possible, the organic aromatic colouring agent preferably has a rather planar structure and preferably comprises at least one free rotation centre outside the planar structure.

Further in case of ligands andor remnants which may be spatially or sterically demanding, the ligands and/or remnants may be as freely movable as possible. around a centre of rotation. This may give the organic aromatic colouring agent the ability to adapt its shape to the environment given by the matrix of the synthetic (polar) polymer material. Preferably, the organic aromatic . colouring agent may not comprise a spiro-centre and/or the organic aromatic colouring agent may not comprise a large mofety that is rotation impaired. In this application a large moiety that is rotation impaired may mean that the molecular weight of this rotation impaired moisty is in the range of 320 g mol’! to 380 g mel”. : 35 An advantage of the method according to the invention is that the different Jayers of the polymeric film may be coloured on demand. As a result, an efficient colouring process is achieved.

Furthermore, the polymeric film provided in the metbad according to the invention has a rigid core (backbone layer) and one or more less rigid/flexible polymeric layers arranged on the polymeric backbone layer. In particular, the one or more less rigid/flexible polymeric layers arranged on the polymeric backbone Jayer may be efficiently coloured due to the difference in glass transition temperature. As a result, the exposure of the polymeric backbone layer to thermal stress 15 limited to a minimum. Therefore, the strength of the polymeric film is preserved.

In other words, the one or more polyraeric layers arranged on the polymeric backbone layer, each of the one or more polymeric layers having a respective glass transition temperature. wherein for cach pair of adjacent polymeric layers, the glass transition temperature of the polymenic layer

IO that is closest wo the polymeric backbone {ayer is higher than that of the other polymeric layer and lower than that of the polymeric backbone layer enables to selectively colour the different layers.

As a result, the polymere film may be (semi) temporarily coloured. Furthenmore, the polymeric film may be decoloured at a desired moment in time,

Yet another advantage of the method according to the invention is that sustainable and/or environmentally friendly colourants may be used. As a result, the impact of the polymeric film on the environment is reduced compared te conventional polymeric films and/or plastics.

It was found that the colourants ae temporary} incorporated in the polymer raatox of the polymeric backbone ayer and/or the one or mom polymeric layers. Said incorporation includes non-covalent bonds between the celourant and polymeric backbone layer and/or the one or more polymeric layers, preferably the bonding between the colorant and the polymer is 2 dipole-dipole interaction and/or hydrogen bonding. This enables incorporating and/or removing the colourant efficiently and effectively from the polymeric film.

Furthermore, the method according to the invention enables using colourants that yay be extractable from the polymeric film. Therefore, a reusable plastic fil: and/or plastic is achieved.

In a preferred embodiment according to the invention, the step of colouring comprises one or mote respective colouring sub-steps, wherein each sub-step comprises colouring a single layer,

Providing one or more respective colouring sub-steps, wherein cach sub-step comprises colouring a single layer, enables colovring each individual layer of the polymeric film. As a result, the amount of different colouring agents may be reduced. For example, only red, blue, and yellow 39 way be used in arder to obtain all other possible colours,

In a further preferred embodiment according to the invention, the respective colouring sub- steps may be performed m an order from the most inward polymeric layer relative to the polymeric backbone layer to the most outward polymeric layer relative to the polymeric backbone layer,

Preferably, each colouring sub-step may be performed at a decreased temperature relative to a previous colouring sub-step.

: {tis noted that the polymeric backbone layer may also be coloured, preferably coloured before the one or more polymeric layers.

It was found that perfonning the respective colouring sub-steps ii an order front the most inward polymeric layer relative to the polymeric backbone layer to the most outward polymeric 5 layer relative to the polymeric backbone layer provides an efficiently and effectively coloured polymeric film,

In addition, colouring the polymeric film at decreasing temperatures reduces or prevents mixing of colourants in the polymeric film. This enables tuning the desired colour of the polymeric film in an efficient and effective manner,

In a further preferred embodiment according to the invention, the colouring of a polymeric layer of the one or more polymeric layers ray be performed at a temperature that may be substantially equal to the glass transition temperature of said polymeric layer.

It is noted that substantially equal to the glass transition temperature means + 15 °C of the class transition temperature of the desired layer, preferably + 10 °C of the glass transition temperature of the desired layer, more preferably + 5 °C of the glass transition temperature of the desired layer.

Colouring the polymeric backbone layer and/or a polymeric layer of the one or more polymeric layers at a temperature that may be substantially equal to the glass wansition temperature of said polymeric layer enables selectively colouring the different layers. As 4 result, 2 more elficient and effective colauring of a polymeric tim is achieved.

In addition, it was found that colouring the polymeric backbone layer and/or a polymeric layer of the one or more polymeric layers at a temperatore that may be substamtally equal to the glass transition temperature of said polymeric layer reduces or even prevents aggloraeration of the colourants. Fuethermore, decolouring of the polymeric film may also be performed without agglomeration of the colovrants.

In addition, it was found thar an efficient colour master batch may be achieved.

Ta further preferred embodiment according to the invention, the colouring step comprises transporting the polymeric film through one or more colouring baths, Preferably, each of the one or moore colouring baths may be configived to colour a single polymeric layer. itis noted that transporting the polymeric film also relates to dipping the polymeric film in one or more Colouring baths, submerging the polymeric film in one or more colouring baths, and/or contacting the polymeric film in one or mare colouring baths.

Providing the polymeric film to one or more colouring baths enables colouring the polymeric backbone layer and/or a polymeric layer of the one or more polymeric layers separately with a desired (single) colourant.

In fact, it was found that providing multiple colourants to a single layer, for example the polymeric backbone layer and/or a polymeric layer of the one or more polymeric layers, reduces the equal colouring of said layer, and a colour difference appeared in said fayer. Thus, the colourants were not equally distributed.

Furthermore, it was found that repeatedly colouring the different polymeric layers provides a more intense colour of the polymeric film,

Ina further preferred embodiment according to the invention, the method according 16 the invention further comprises the step of shredding the polymeric film.

It is noted that shredding also refers to cutting, slicing, grinding, fragmenting. and the like.

The step of shredding the polymere film may be performed after the step of colouring the one-or more polymeric layers in an order of their glass transition temperature.

The step of shredding the polymeric {ilm enables to form a colour masterbatch, As a result, granulate may be formed Trom the coloured polymeric film,

Shredding the polymeric film may be performed using a hitting knife or piret.

IS Preferably, flakes or strips of 0.15 mm to 20 mm by 0.15 mm to 20 yom by 0.13 mm to 20 mm are achieved, roore preferably 0.25 mai to 20 mm by 0.25 mm to 20 mm by 0,25 mm to 20 mm are achieved, even more 0.5 mm to 20 moby 0.3 mm to 20 mun by 0.5 mun to 20 mun are achieved, most preferably | mm to 20 mm by { mm to 20 am by 1 mm to 20 mm are achieved.

In addition, the shredded polymeric film may be coloured addirionaliy. As a resul, a colour master batch comprising a more intense colour may be achieved.

Tn a further preferred embodiment according to the invention, the method according to the invention further comprises the step of forming a granulate.

The step of forming a granulate ruay be performed after the step of shredding the polymeric film. To form the granulate, the shredded polymeric fil may be fed to an extruder and/or a wor, weir, anddor kneading element.

The granulate may be used as a colour master batch for further use. In addition, it was found that the grannlate comprises a mixture of the colourants defining the desired colour of the granulate.

In a further preferred embodiment according to the invention, the method may further comprise the step of providing a colouring solution comprising a pigment. Preferably. the pigment comprises a quinone, wherein the quinone may be one or more selected from the group of 1,2- beroquinone, 1:4-benzogüinone, 1 A-napthoquinone, 9,10-anthraquinone, §,2-dihvdroxy-9,10- anthraguinone.

The step of colouring the one or more polymeric layers in an order of their glass transition temperature may correspond fo colouring a given polymeric layer among the one or more polymeric layers by contacting said given polymeric film with tie colouring solution while said given polymeric film is at a temperature between the glass transition temperature of said given polymeric layer and the glass transition temperature of an adjacent more inward polymeric layer, and, if such layer is not present, the glass transition temperature of the polymeric backbone layer,

The colouring solution may be provided to a colouring bath, which enables to colour at feast 3 one single polymeric layer. ft was found that the pigment comprising a quinone provides an environmentally friendly, efficient, and effective colouring of the polymeric film.

In a further preferred embodiment according to the invention, the colouring solution comprising a pigment may be an aqueous solution. Prefembly. the pH of the colouring solution comprising a pigment may be in the range of 2 to 12, preferably in the range of 3 to 6, more preferably in the range of 4 to 3.5, even more preferably in the range of dto 5.

It was found that a pH of the colouring solution coraprising a pigment in the range of 2 © 12, preferably in the range of 3 to 6, more preferably in the range of 4 to 5.5, even more preferably in the range of 4 to 5, enables efficiently and effectively colouring of the polymeric film.

Alternatively, or in addinon to the aqueous solution, the colouring solution may comprise acetone and/or an alcohol, such as methanol, ethanol, propanol, and the like.

It was found that a colouring solution comprising acetone and/or an alechol increases the efficiency of the step of colouring the polymeric backbone. layer and/or the one or more polymeric layers, Furthermore, it was found that a constant pH between 4 and 4,5 of the colouring solution and a concentration of atmost | M pigment in sohiion provides efficient and effective colouring of the polymeric backbone layer and/or the one or more polymeric layers.

In a further preferred embodiment according to the inventis, the one or more polymeric layers. cormpnses at least two polymeric layers, preferably comprises two polymeric layers.

Preferably, the polymeric film comprises a polymeric backbone layer, a (first) polymeric layer. and a further (second) polymeric layer. Preferably, the glass transition temperature of the polymeric backbone layer is at least 10 °C higher compared te the first polymeric, wherein the first polymeric layer is at least 10 °C higher compared to the second polymeric backbone layer,

In a further preferred embodiment according to the invention, the method according tothe invention comprises the step of laminating the one or more polymeric layer on the polymeric backbone layer for obtaining the polymeric film.

The method according to the invention may also include laminating one or more polymeric layers on a polymeric backbone layer for obtaining said polymeric film. Said step of laminating the one or more pelymeric layers on the polymeric backbone layer is performed before the step of providing 4 polymeric film,

The step of iaminating the one or more polymeric layers on the polymeric backbone layer may start with laminating 2 polymeric layer comprising a glass transition temperature closest to the polymeric backbone layer on the polymeric backbone layer, Said tamination raay be followed by laminating a further polypieric layer comprising 4 glass transition temperature second closest to the polymeric backbone ayer on the first polymeric layer, As a result, a polymeric film comprising 2 polymeric backbone layer, first polymeric layer, and second polymeric layer is formed, wherein the polymeric backbone layer comprises a glass transition temperature which is higher than the first polymeric layer, and wherein the glass transition temperature of the first polymeric layer is higher than the glass transition temperature of the second polymeric layer, : An advantage of laminating different layer on each other is that an efficient and effective polymeric film suitable for colouring with the method according to the invention is achieved.

In an alternative erabodirent, the different layers of the film may be coloured before larninating.

An advantage of colouring the different layers of the fm before larataating is that the desired colour may be achieved in an efficient and effective manner. In addition, colouring the different layers separately may increase the throughput of colouring the different layers.

For example, the polymeric backbone layer may be colourless, the polymeric layer the / polymeric layer that is closest to the polymeric backbone layer may be coloured blue, and the polymeric layer second closest to the polymeric backbone layer may be coloured yellow.

Laminating the polymeric layer closest to the backbone layer to the backbone layer, and the second closest polymeric layer to the polymeric layer closest to the polymeric backbone layer provides a polymeric film comprising a green colour. Thus, a green master colour batch may he achieved. ina further preferred embodiment according to the invention, the method according to the invention comprises the step of drying the polymeric film.

The step of deying the polymeric film may be performed between and/or after the step of colouring the one or more polymeric layers i an order of their glass transition temperature.

Drying the polymeric film enables efficiently and effectively incorporating the colorants in the different layers of the polymeric film, in a further preferred embodiment according to the invention, the method according to the invention may comprise the step of perforating the polymeric film and/or the step of performing an additional colouring step.

The step of perforating the polymeric film is performed during and/or after the step of colouring the one or more polymeric layers in an order of their glass transition temperature and/or drying the polymeric film. In addition, the step of performing an additional colouring step may be performed, wherein said step is performed after the step of perforating the polymeric film.

The step of perforating 1acludes providing {small heles to the polymeric film andlor polymeric backbone layer and/or the one or more polymeric layers. itis noted that said (small)

holes cornprise a diameter of af most 209 micrometres, preferably at mest 150 micrometres, most : preferably at most 100 micrometres.

Said perforations may be provided to the polymeric film and/or polymeric backbone layer and/or the one or more polymeric layers. using a fuser and/or a mechanical rollerrwaltz/punchidie- out

Perforating the polymeric film and/or polynieric backbone layer and/or the one of more polymeric layers increases the surface area of said film or polymeric layer. An advantage of perforating and/or additionally colouring the polymeric film is that a more intense and/or equally distributed coloured film is achieved. As a.result, the shredded polymeric Film of which a granulate may be formed may form a better coloured end-product,

In a further preferred embodiment according to the invention, the method according to the invention may comprise the step of colouriag the polymeric backbone layer.

The step of colouring the polymeric backbone layer may be performed before the step of laminating the one or more polymeric {ayers on the polymeric backbone layer and/or is part of the iS step of colouring the one ar more polymeric layers in an order of thelr glass transition teraperature. in a further preferred embodiment according to the invention, the glass transition temperaigee of the polymeric backbone layer ray be at least 10 °C higher than the glass transition temperature of the adjacent polymeric layer, and/or wherein for cach pair of adjacent polymeric layers, the glass transition temperatueof the polymeric layer that may be closest to the polymeric 2 backbone layer may be at least 10°C higher than the glass transition temperature of the other polymeric layer.

Thus, the glass transition temperature of the polymeric backbone layer may be at least 20 °C higher than the glass transition temperature of the polymeric layer second closest to the polymeric backbone layer. in a further preferred embodiment according to the invention, the polymeric backbone layer and the one or more polymeric layers each comprise one or more polymers independently selected from the group of polyethylene, polypropylene, polybutylene, polyisobutylene, sthylenevinylacetaat copolymer, ethene-acrylate ester copolymers, ethyl methacrylate copolymer, caprolactone polymer. Preferably, the polymer of the one or more polymers comprise low-density 39 polyethylene more preferably linear Jow-density polyethylene and/or the polymer of the polymeric backbone layer may comprise high-density polyethylene.

It is noted that the caprolacione polymer is a polyester polymer derived from a caprolactone monomer, wherein the molecular weight of said polymer is between 65000 g mot! and 95000 g mol”, has a melting point in the range of 56 °C to 62 °C, and elongation at break between 750%: and 850%. Furthermore, the mett flow index is between 2.5 ¢ per 10 minutes to 3.5 g per 10 minutes with 2.16 kg, 1” polyvinylchioride die at 160 °C. It was found that when the polymeric backbone layer and the one or more polymenc layers each comprise one or more polymers independently selected irom the group of polyethylene, polypropylene, polybutylene, . polyisobutylene, ethylenevinylacetant copolymer, ethene-acrylate ester copolymers, ethyl methacrylate copolymer, caprolactone polymer, a polymeric film ís provided that may be efficiently and effectively coloured,

For example, the polymeric backbone layer may comprise polyethylene, preferably high- density polyethylene, the polymeric layer adjacent to the polymeric backbone layer may be low- density polyethylene, and the polymeric layer adjacent to the polymeric layer comprising high- density polyethylene may comprise ethyl methacrylate copolymer and/or caprolactone polymer.

In an alternative embodiment, the polymeric backbone layer and the ons or more polymeric layers each comprise one or more polymers independentiy selected from the group of: = polybutylene, polybuiyl ethylene, poly cyclohexylethylene, polyethylene, polyisobutene, polyisobutylethylene, poly(propylene), poly{propylethylene), poly{tert-butylethylene): and/or — polyacrylate with methyl {polymethylacrylate), ethyl (polyethylacrylate), propyl 153 (polypropylacrylate), or butyl { polybutylacrylate); and/or — polymethacrylate with methyl (polymethyhnathaerylate), ethyl {polyethylmethacrylate). propyl (polypropylmethacrylate), or butyl (polybutylmethacrylee) and/or — copolymers of acrylic and methacrylic esters including, among others, such as butyl {methjncryiate, pearyliimerhacrylate and Z-ethylbexyi{methjacrviate; (Meth)acrylates derived from : 20 ussaturated alcohols, preferably oleyvi(methiacrylate, 2-propynyl{meth)acrylate, allylmeth)acrylate, vinyKmethaerylate: and/or = arylmeth)acrylates polymers, preferably benzyK(meth)acrylate polymers or phenyi(meth}acrylate polymers, the aryl radicals each being unsubstituted or up to four times substituted; andfor = cycloalky{meth)acrylates polymers, preferably 3-vinyleyclohexyl(methacryiate polymers, bornyl (methacrylate polymers; and/or - hydroxylatkyl (meth)acrylates polymers, preferably 3- hydroaypropy! (methacrylate polymers, 3,4- dihydroxybutyl{meth)acrylaie polymers, 2-hydroxyethyl(meth}acrylate polymers, 2- hydroxypropyl{ methacrylate polymers; and/or : ~ glycol difmeth)acrylates polymers, preferably 1 4-butanediol (meth)acrylate polymers: and/or — (meth)acrylates of ether alcohols polymers, preferably tetrahydrofarfuryl {methjacrylate polymers, vinyloxyethoxyethy{(meth}acrylate polymers; and/or — polymers of amides and nitriles of the {methyacryle acid, preferably N-(3- dinethylaminopropyD{methbacrylamide polymers, N-tdiethylphosphono){(methacrylamide polymers, 1-methacryloylamido-2-methy1-2-propanol polyraers; and/or

— polymers of sulfur-containing methacrylate, preferably ethylsulfinylethylimethjacryiate, 4-thiocyanatobutyl{meth)acrylate polymers. ethylsulfonylethyl(methYacrylate polymers, thiccyanatomethyl{meth acrylate polymers, methyisulfinylmethyl{meth)acrvlate polymers, bis((meth)acryloyloxyethyhsulfide polymers: and/or — polyhydric (meth)acrylates, preferably trnethyloylpropanetrifmeth}acrylate polymers; and/or ~ acrylonitrile polymers: and/or — vinyl ester polymers, preferably vinyl acetate polymers; and/or — styrene polymers, substituted styrenes polymers with an alkyl substituent 10 the side chain, preferably o-methylstyrene and a-ethylstyrene, substituted styrenes polymers with an alkyl substituent on the ring, preferably vinyl toluene, and p-methylstyrene, halogenated styrene polymers, preferably nionochlorostyrene polyoiers, dichlorostyrene polymers, tribromostyrene polymers and tetrabromostyrene polymers; and/or - heteroeyelic vinyl polymers, preferably 2-vinylpyridine polymers, 3-vinylpyridine 153 polymers, 2-methyl-5-vinylpyridine polymers, 3-ethyl-4-vinylpyridine polymers, 2,3-duvethyk5- vinylpyndine polymers, vinyipyrimidine polymers, vinylpiperidine polymers, 9-vinylcarbazole polymers, 3-vinylcarbazole polymers, d-vinylcarbazole polymers, L-vinylimidazole polymers, 2- methyl-l-viaylimidaszole polymers, N-vinylpyrrolidone polymers, Z-vinylpytrolidone polymers, N- vinylpytrolidine polymers, 3-vinylpynolidine polymers.

N-vinylcaprolactam polymers, N- vingdbutyrolactam polymers, vinyl exolsne polymers, vinyl furan polymers, vinyl thiophene polymers, vinylihiolane polymers, vinylihiazoles and hydrogenated vinylthiazoles polymers, ' vinyloxazoles and hydrogenated vinyloxazoles; and/or — polymers of vinyl and isoprenyl ethers; and/or — maleic acid polymers, preferably maleic anhydride polymers, methyl maleic anhydride polymers, maleimide polymers, methyl maleimide; and/or ~ dienes polymers, preferably divinylbenzene polymers; and/or — copolymers of ethylene and propylene with acrylic esters, preferably polyethylen-block-co- palymethylmethacrylat, polypropylen-block-co-polymethylmethacrylat; and/or - aliphatic and/or aromatic polyesters, preferabl, hydroxyl-funcuonal dendotic polyesters, polycaprolactone, polyethylenterephthalate (PET), polytrimethylenterephthala {PTT). polybutylenterephthalat (PBT), glvcolized polyglveolterephthaltat (G-PET), amorphes polyethylenterephthalat (A-PET), polyesters of terephthalic acid, polyspiro-diol-terephthalate, polypentaspiroglycol-terephthatate (PSG), polyeyclohexylenedimethylene-terephthalate, polyester based copolymer including a dicarboxylic acid-derived residue including a residue derived from an aromatic.dicarboxyhic acid and a diol-derived residue including a residue derived from 4- (hydroxymethylhicyclohexyimethyl-4-(hydroxymethyhicyclohexane carboxylate, polyester based copolymer including a dicarboxylic acid-derived residue including a residue derived from.an aromatic dicarboxylic acid and a divl-derived residue including a residue derived from 44- (oxybis(methylene)bis) cyclohexane methanol; and/or : ~ polycarbonate (PC), 2,2-bis5-(4-hydroxypbenyD-propan (bisphenol A) polycarbonate, 2.2- bis-(d-hydroxyphenyl)-butan (bisphenol B} polycarbonate, Ll-bis(d-hydroxyphenyDcyclohexan © {bisphenal OC) polycarbonate, 2,2-melhylendiphenal (bisphenol F) polycarbonate, 2,2-b7s(3.5- dibrom-4-hydroxyphenyDpropan (tetrabrornbisphenol A) polycarbonate und 3,2-445(3,3 dimethyl . 4-hydroxyphenyhpropan (retramethylbisphenol A) polycarbonate, bisphenol S polycarbonate, ° dihydroxydiphenylsulfid polycarbonate, tetramethylbisphenol A polycarbonate, 1,1-Bis(4- hydroxyphenyi)-3,3.5-trimethyleyclohexane (BPTMC) polycarbonate, 11 1-Tris{d- hydroxyphenyD-ethane (THPE) polycarbonate: andor — aliphatic polyamide IPA), preferably PA 6 based onpolycaprolactam, PA 6.6 based on 6,6- hexamethylendiamin and adipic acid, PA 6.66 based on caprolactam, co-poymer of hexamethylendiamin and adipic acid, PA 66.610 based on hexamethylendiamin, copolymer of

IS adipic acid and sebaic acid, PA 4.6, PA 10, PA 12 and PA copolymers; and/or — polyurethane: and/or — polar-copolymere, maleic anhydride-olefin copolymer; and/or — polyalkylenoxide, polyalkylene block copolymer, propyienoxide-cthylenoxide copelymer, {methylene acrylate-maleic anhydride copolymer; and/or — polar-terpolymere, preferably reactie terpolymers of ethylene, acrylic ester and maleic anhydride, or ethylene, methacrylic ester and raaleic anhydride, or ethylene, acrylic esters and glycidyl mmethaceylate, or ethylene, methacrylic esters and glycidyl methacrylate, or ethylene, {methacrylic esters and methyl (methyl(meth)acyylate), ethyl (ethy(meth)-acrylate), propyl {propyllmetiaceylate). or butyl (butylGneth)acrylate), polyamide, polyester-polyamides, or butyl {butyiimeth)acrylate}, polyether-polyamide copolymers; and/or — polar polymer blends, preferably polycarhonate/polyethy lenterephthalar blends (PC/PET blends), polycarbonate/polybutylensterephthalate blends (PC/PBT blends), blends of polycyclohexylene dimethylene terephthalate copolymer, blends of poly(butylene-adipate- terephthalate); and/or. — polyacrylnitni and polyaeryinitril-copolymers, preferably poly acrylonitrile butadiene styrene (ABS), poly styrene-acrylonttrile: and/or : ~ polystyrene and polystyrene copolymers, preferably styreno/butadiene co-polymer (SBR), poly styrene-isoprene-styrene (SIS), poly(glycidyl methacrylate) grafted sulfonamide based polystyrene resin with tertiary aioe; and/or

— polyether, preferably polyethyleneglyeal, polyethyleneglycol with at least one fatty acid coupled to the polyethyleneglycol, terminating functional groups such NHz-terminated polyethers; and/or ~ functionalized polyacrylamide polymers, copolymers and terpofymers, preferably poly(2- acrylamido-Z-aminopropionicacid) {poly AMPA), poly(2-acrylamido-2-amino propane sulfonic acid), paly{N-isopropylacylanide {poly PNIPAM); poly (amidoamine-co-acrylic acid} copolymer, poly(N.N-dimethylacrylamide-co-sodivm acrylate), poly(acryiamide-co-sodium acrylateYpoly{ethylene glycol) semi-IPN, poly(acrylamide-co-sodinm d-styrenesulfonate}, poly{acrylamide-co-sodivn d-styrenesulfoarte)/pely{ethylerie glycol) semt-IPN, poly(dcryiamide- co-scdiom methacrylate), poly(acrylamide-co-sodium methacrylate)/poly{ethylene glycol) semi-

IPN, and/or poly(N-isopropylacrylamide-co-acrylic acid) and poly{acrylamide-co-actylic acid: apdior ~ poly{ether sulfonesi/poly(ethyleneimine) (PES/PED, polyvinylpyrrolidone, preferably poly(N-vinyl-2-pymrolidone), poly (N-vinyl-2-pyrralidone-co-acrylonitale) treated with 18 hydroxylamine-hydrochloride; and/or ~ polyvinyl alcohol; and/or ~ poly i-naphthy laine }-camphossulphouic acid, ina preferred embodiment, the polymeric film is not a blend, but is constructed of separate layers. :

An advantage of a polymeric film constructed of separate layers is that the materials of the different layers may not blend. As a result, the colourants may only incorporate in the desired layer, rather than penetrate all vr a selection of the layers.

In a further preferred embodiment according to the invention, the method according to the invention comprises the step of calibrating the polymeric film, whetein the step of calibrating comprises the step of ealibtating the initial colour of the polymeric film,

The step of calibrating the polymeric film may be performed before the step of colouring the one or more polymeric layers in an order of their glass transition temperature.

Calibrating may refer to calibrating the colour and/or transparency of the polymeric film,

An advantage of the step of calibrating the polymeric Gin is that the initial colour and/or transparency of the polymeric film may be determined before colouring. Therefore, the provided colourant may be adjusted in order to obtain the desired colour in the polymeric film and/or endfintermediate product.

In a further preferred embodiment according to the invention, the polymeric backbone layer and/or the one or more polymeric layers comprises one or more additives selected from the group of polycaprolactore dio! polymer, ethylene-glvcidy! methacrylate copolymer, polyethylene. polyethylene terephthalate. :

Tt was found that the addition of an additive selected from the group of polycaprolactone diol polymer, ethylene and glycidyl methacrylate copolymer, polyethylene, polyethylene terephthalate to the polymeric backbone layer and/or the one or more polymeric layers increases the uptake of colourant in the different polymeric layers, in a further preferred embodiment, the polymeric backbone fayer and/or the one or more polymeric layers may further comprise an additional additive, wherein said additive is one or more selected from the group of a UV protection additive, a flame retardant, odour additive.

In a further preferred embodiment according to the invention, the method according to the invention comprises the step of heating the polymeric film to a temperature in the range of 110 °C

IQ to 180°C, preferably to a temperature in the range of 120°C to 160 °C.

In an alternative-embodiment, the method according to the invention comprises heating sub- steps, wherein the temperature ts adjusted to the glass transition temperature of the polymeric layer which needs to be coloured, For example, the heating sub-steps may comprise heating to a temperature in the range of 140 °C to 180°C, followed by heating to a temperature in the range of 130°C to 140 °C, and heating to a temperature in the range of 110 Cte 130°C.

In a further preferred embodiment according te the invention, the method according to the invention comprises the step of cutting ap a plate material and/or the step of decolouring the cut-up plate material.

It is noted that the step of decolouring the cut-up plate material may also be performed without cutting up the plate material.

The step of cuiting up a plate material and/or the step of decolouring the cut-up plate material may be performed before the step of providing a polymeric film and/or the step of

Tantinating the one or more polymeric layers on the polyrnerie backbone layer. lt is noted that the plate material may be made of the coloured film obtained by the method according ta the invention.

Furthermore, it is noted that the polymeric backbone layer may comprise a blend of : polymeric materials, wherein the material of the polymeric backbone layer may be made from (recyeled/circular) plate material, wherein the plate material is made of a colonted polymeric film, obtained by the method according to the invention. Thus, the polymeric backbone layer may comprise a blend of polymers originating from all polymeric layers, including the polymeric backbone layer.

Experiments showed that the polymeric backbone layer made from (recycledfeircular) plate material may be efficiently and effectively coloured and/or decoloured,

Furthermore, it 1s noted that plate material may refer to bottles, boxes, containers, and the hike. Thus, the plate material may have different shapes.

Therefore, the step of cutting up a plate material and/or the step of decolouring the cut-up plate material enables a circular polyineric film, and thus reduces the impact on the environment,

Inthe context of this invention circular polymeric layer relates to the use of virgin-like polymer which may be used as a replacernent of virgin (fossil based) polymers. As such, the circular polymers may have similar properties compared fo virgin polymers, In otherwords, to obtain a circular polymer, polymeric waste, such as plate material and/or bottles, is recycled wherein the high quality of the polymer is maintained and a Joss of properties if prevented.

Therefore, the circular polymer may be part of (old) circular polymeric film, wherein the products made of the polymeric film may be used as source for circular polymers.

Circular or circularity refers to a systern of closed loops in which raw materials, components, and products Jose as little of their value as possible and are ideally re-used for 100%.

In other words, the system aims at eliminating waste and continuous use of rescurces. Therefore, a civeular polyraerie film refers to a polymeric filnr derived Trom at least 80% raw materials that are waste from a similar or different application. The polymeric foam preferably has the same iS properties and/or had same use. Thus, after being processed to polymeric film, the circular polymer retains the mechanical properties so that it can be processed as, and is mechanically similar to, virgin polymer material.

An advantage of the circular polymer is that said polymers significantly reduce the environmental footprint of packaging material coloured by the method according to the invention,

For example, packaging made of plastic and/or a palymeric film are often disposed and combasted ar recycled in a downgraded manner. | : in a preferred embodiment, the method according to the invention further comprises the steps of } ~ comminuting 3 thermoplastic material into coloured flakes; — subjecting the coloured flakes to an extrusion process for producing coloured extruded material; and ~ decelouring the coloured extruded material using a decolouring substance.

These steps enable to provide decolouring-colapred thermoplastic material. Said steps may be performed before or after the method steps for colouring a polymeric film.

Furthermore, the method according to the invention ray include the mamdactting of a colour master batch of thermoplastic granules or flakes. Said manufacturing comprises the steps of: — decolouring coloured thermoplastic material according to the invention; =~ eolowring the decolovred extruded material using a colouring substance; and ~ commingting the coloured extruded material into thermoplastic granules or flakes. bit other words, the method according to the invention may include the steps to manufacture granulate and/or flakes, and/or decolour said granulate and/or flakes.

The invention alse relates to a coloured polymeric filo comprising: — a polymeric backbone layer and one or more polymeric layers arranged on the polymeric backbone lager. each of the one or more polymeric layers having a respective glass transition temperature, wherein the one or more polymeric layers that are arranged on 2 sarne side of the polymeric backbone layer are arranged in an order of decreasing glass transition temperature starting from said same side, the glass transition temperatute of each of said one or more polymeric Jayers being lower than that of the polymeric backbone layer; and ~ a colorant, wherein the colourant is at least embedded in the one or more polymeric layers.

The coloured polymeric film provides the same or similar effects and advantages as those described for the method according to the invention.

It is noted that the polymeric backbone layer provides stiffness and rigidity to the polymeric film, wherein the one or more polymeric lavers may be used to incorporate a colourant.

IS A further advantage of the polymeric film according to the invention is that each polymeric laver and/or polymeric backbone layer may have another voleurant, As a result, a polymeric film : may be achieved which may be used to form a granulate, also known as a colour master batch, in any desired colour.

In a preferred embodiment according to the invention, the polymeric film may have a thickness in the range of 50 pm fo 3 mm, preferably may have a thickness in the range of 100 jon to 2 mm, more preferably ry have a thickness w the range of 130 gm 10 | mm.

It was found that a polymeric film having a thickness in the range of 50 um to 3 mm, preferably having a thickness 19 the range of 100 gm to 2 mm, more preferably having a thickness wn the range of {50 pmo | min, enables formag a colour master batch efficiently and effectively.

In a further preferred embodiment according to the invention, the crystallinity of the polymeric layer adjacent to the polymeric backbone is in the range of 35% 10 60%, preferably in the range of 40% to 55%. Preferably. the orystallinity of the polymeric backbone layer is in the range of 60% to 90%, more preferably 1n the range of 60% to 75%.

In addition, the crystallinity of the polymeric layer adjacent to the polymeric layer which is adjacent tothe polynietic backbone layers in the range of 13% to 35%. preferably in the range of 25% to 35%.

It is noted that in this application, the crystallinity refers to a polymer’s degree of crystallinity and describes whether the polymer has an amorphous character or a orystalline character. The crystalliniy can range from 0% {entirely amorphous) to 100% {entirely crystalline).

The polymers of the coloured film according to the invention Tall somewhere between those eXIernes.

The crystallinity of the different polymeric layers is determined by 180 1 1357-12009.

Ia a further preferred embodiment according to the invention, the-one or more polymeric layer each comprises an independently selected colourant comprising at least one pigment, wherein the pigment comprises a quinone, wherein the quinone may be preferably one or more selected

S from the group of 1,2-benzoguinone, 1.4-benzoquinone, 1,4-napthoguinone, 9,10-anthraguinone, 1, 2-dihydroxy-9, | (-anthraquinone,

The invention alsorelates to a master colour batch obtainable by the method according te the vention,

The master colour batch provides the same or similar effects and advantages as those

IO described for the method according to the invention and the coloured polymeric film according to the invention,

It was found that the master colour batch according 1e the invention may provide an efficient . and effective material for forming desired products,

In a preferred embodiment according to the invention, the master colour batch may be a

IS granulate.

A master colour batch as granulate may increase the manageability of the master colour batch.

The invention alse relates to a use of the nuster colour batch according to the invention in the process of injection moulding. 24 The use of the master colour batch provides the same or scimitar effects and advantages as those described for the method according to the invention, the coloured polymeric film according to the invention, and the master colour batch according to the luvention.

The invention also relates to an injected moulded product. such as a bottle, comprising the master colour batch according to the invention.

The injected moulded bottle provides the same or similar effects and advantages as those described for the method according to the invention, the coloured polymeric film according to the invention, the master colour batch according to the invention, and the use of the master colour batch according to the wvention,

Furthermore, the invention also relates to a plastic object comprising the master colour batch according to the invention.

The plastic object provides the same or similar effects and advantages as those described for the method according to the invention, the coloured polymeric film according to the invention, the master colour batch according tothe invention, and the vse of the master colour batch according to the invention.

Further advantages, features and details of the invention are elucidated on the basis of preferred embodiments thereof, wherein reference is made to the accompanying drawings, in which — Figure I shows a schematic overview of a method according to the invention; = Figure 2 shows a schematic overview of a polymeric film provided in the method according to the invention; — Figure 3 shows a schematic overview of á coloured polymeric film according to the inveebon; — Figure 4 shows a schematic overview of a bottle made with the coloured polymeric film according to the invention; — Figure § shows a schematic overview of an apparatus for performing said method for : manufacturing and storing an uncoloured extraded maternal by recycling thermoplastic waste products; and — Figure 6 shows a schematic overview of an apparatus for performing said method for manufacturing a colour master batch from an oncoloured extruded material,

Method 10 (Figure 1) for colouring a polymeric fm follows 4 sequence of different steps.

In the Hluswated embodiment method 10 may start with step 12 of providing a polymeric film comprising a polymeric backbone layer and one or more polymeric layers arranged on the polymeric backbone layer, each of the one or more polymeric layers having a respective glass 200 transition temperature, wherein the one or more polymeric layers that are arranged on a same side of the polysnerie backbone layer are arranged in an order of decreasing glass transition temperature starting from said same side, the glass transition temperature of each of said ope or more polymeric . layers being lower than that of the polymerie backbone layer. Step [2 may be followed by step 14 of colouring the one or more polymeric layers in an order of their glass transition temperature starting with the polymeric Jayer{s) having the highest glass transition temperatnre.

Alternatively, method 10 may start with step 16 of cutting up a plate material, wherein the plate material is made of the polymeric film according to the wvention, and/or step 18 of decolouring the {cut-up} plate material. Step 16 and/or step 18 may than be followed by step 20 of laminating the one or more polymeric layers os the polymeric backbone layer.

Step 20 may be followed by step 12 of providing a polymeric film comprising a polymeric backbone layer and one or more polymeric layers arranged on the polymeric backbone layer, each of the one or more polymeric layers having a respective glass transition temperature, wherein the one or more polymeric layers that are arranged on @ some side of the polymeric backbone layer are arranged 19 an order of decreasing glass transition temperature starting from said same side, the dase mansion temperature of each of said poe or more polymeric ayers being lower than that of the polymeric backbone layer,

The colourAransparsncy of the polymeric fia provided in step £2 may optionally be calibrated in step 22 of calibrating the polymeric film. fy addition to step 22, the polymeric film may be heated in step 24 of heating the polymeric film before performing step 14 of colouring the one or more polymeric layers in an order of their glass transition temperature starting with the

S polymedc layer(s) having the highest glass transition temperature,

In addition to step 14, method {0 may comprise step 26 of providing a colouring solution comprising a pigment. Furthennore, step 14 may comprise colouring sub-steps 28, 30, 32 and/or step 34 of colouring the polymeric backbone layer. Step 36 of drying the polymeric film may be perfornied between any one of sub-steps 28, 30, 32 and/or step 34 of colouring the polymeric

I backboue layer and/or after step 14.

Step 14 may optionally be followed by step 38 of perforating the polymedc film and/or step 40 of performing an additional colouriag step aadfor step 42 of drying the additional coloured polymeric ifm.

Step Id, step 38, step 40, or step 42 may be followed by step 44 of shredding the polymeric film and step 46 of forming x granulate.

In an illustrated embodiment polymeric film 30 (Figure 2) comprises polymeric backbone layer 52, first polymeric layer 54 comprising a glass transition temperatuee lower than polymeric backbone layer 52, and second polymeric layer $6 comprising a glass transition temperature lower than first polymeric layer 54,

In an Ylusteated embodiment polymeric film 60 {Figure 3) comprises palymerie backbone layer 62 which is optionally coloured, first coloured polymeric layer 64 comprising a gl ass transition temperature lower than polymeric backbone layer 62, and second coloured polymeric layer 66 comprising a glass transition temperature lower than fist polymeric layer 64. Optionally, the polymeric backbone layer and/or the one or more coloured polymeric layers comprise different colourants,

Furthermore, polymeric film 60 may further comprise perforations 68.

In an illustrated embodiment injected moulded boule 70 (Figure 4) comprises blow motilded polymeric film 72. Polymeric film 72 may be shredded and used to manufacture injected moulded bottle 70.

In an tustrated embodiment (Figure 5) a method for and an apparatus. for performing said method for manufacturing and storing an uncolowred extruded material by recycling thermoplastie waste products is shown, Specifically, a method is shown in which: — thermoplastic waste products A are cofiiminuted to produce mix of flakes B'hy grinder 74; — mix of flakes B is washed in a hot washer 76, resulting in a mix of clean, but wet flakes C: — said mix Cis then dried by dryer 78, resulting in a mix of clean and dry flakes D;

= mix of dried flakes D, together with an additive Et subjected to an exteuding process by extruder 80 for producing an extruded material F:; } ~ extruded material F is decoloured by means 82 for decelouring an extruded material {and using a decolouring substance) and dried by dryer 84, for producing a decoloured extruded materia] 5; and : — decoloured extruded material G is stored by being wound onto a spool by winding unit 86.

In an illustrated embodiment (Figure 6) a method, and an apparatus for performing said method for manufacturing a colour master batch from an uncoloured extruded material is shown,

Specifically, a method is shown in which: — yncoloured extruded material H is retrieved from storage by being unwound from their spool by unwinding unit 88; — the apparatus shown performs the optional step of laminating uncoloured exuded material

H with additional layers using laminater 90; — the apparatus shown further performs the optional step of cutting extruded material H, winch wag stored 3s a foil, into a plurality of filaments before being coloured by means 94, using cutter 92; — pneoloured extruded material H is coloured by means 94 for colouring an extruded material {and using a colouring substance I) and dried by dryer 96, for producing coloured extmuded material I; and = coloured extruded material J is comminoted into colour master batch M by grinder 98, and, when exiting grind 98, may be received by a container 100 or any other suitable storage media.

In a preferred embodiment, uncoloured extruded material H forms the polymeric backbone layer in a method Tor colouring a polymeric film. In this embodinent the aforementioned additional layers are polymeric layers,

According to a further aspect of the invention, a method for colouring a polymeric film is provided, comprising the steps of providing a polymeric film comprising a polymeric backbone layer and ane or more polymeric layers arranged on the polymeric backbone layer, each of the one or more polymeric layers having arespective glass transition temperature, wherein the one or more polymeric layers thar are arranged on a same side of the polymeric backbone layer are arranged in an order of decreasing glass transition temperature starting from said same side, the glass transition fomperatare of each of said one or more polymeric layers being lower than that of the polymeric backbone layer, and colouring the one or more polymeric layers in an order of their glass transition teraperaturs starting with the polymeric Jayer(s) having the highest glass transition temperature,

According fo a further aspect of the invention, also provided is a coloured polymeric film, comprising a polymeric backbone layer and one or more polymeric layers arranged on the polymeris backbone layer, each of the one or more polymeric layers having a respective glass transition temperature, whersin the one or more polymeric layers that are arranged on n same side of the polymeric backbone layer are arranged in an order of decreasing glass transition temperature starting from said same side, the glass transition temperature of each of said one cr more polymeric layers being lower than that of the polymeric backbone layer, and a colorant, wherein the colourant is at least embedded in the ons or more polymeric layers.

For the present disclosure, any step that includes combining {wo or more products {e.g. when 1) mixing mix of flakes D with additive E before extruder 80; e.g. when adding a colouring substance

I to means 94 for colouring thermoplastic extruded matedal), may be at least partially implemented by providing a dosing feeder, configured to provide an appropriate amount of at least one of the aforementioned two or more products that have to be combined,

The present invention is by no means limited to the above described preferred embodiments and/or experiments thereof. The rights sought are defined by the following claims within the scope of which many modifications can be envisaged.

CLAUSES

1. A method for colouring a polymeric film, comprising the steps of: ~ providing a polyreeric filmy comprising a polymeric backbone layer and one or more polvineric layers ananged on the polymeric backbone layer, each of the one or more polymeric layers having a respective glass transition temperature, wherein the one or more polymeric layers that are arranged on a same side of the polymeric backbone layer are arranged in an order of decreasing glass transition temperature starting from said same side, the glass transition temperature of each of said one or more polymeric layers being lower than that of the polymeric backbone layer; and ~ colouring the one or more polymeric layers in an order of their glass transition temperature starting with the polymeric layer(s) having the highest glass transition temperature. 2. The method according to clause 1, wherein the step of colouring comprises one or more respective colouring sub-steps, wherein each sub-step comprises colouring a single polymeric layer. 3. The method according to claim 2, wherein the respective colouriag sub-steps are 2 performed in an order from the mast inward polymeric layer relative to the polymeric backbone layer to the most outward polymere layer relative to the polymeric backbone layer. 4. The method according to clause 3, wherein each colouring sub-step is performed at a decreased temperature relative to a previous colouring sub-step. 5. The method according to Clause 2, 3, or à, wherein the colouring of a polymeric layer of the one or more polymeric layers is performed at a temperature that is substantially equal to the glass transition temperature of said polymeric layer, 6. The method according to any noe of the preceding clauses, wherein the colouring step comprises transporting the polymeric film through one or more colouring baths, 7. The method according to clause 6, wherein each of the one or more colouring baths is configured to colour a single polymeric layer.

} 8 The method according tò any one of the preceding clauses, further comprising the step of shredding the polymeric film,

G. The method according io any one of the preceding clauses, further comprising the step of forming a granulate. 10. The method according 10 any one of the preceding clauses, further comprising the step of providing a colouring solation comprising a pigment. iQ 11. The method according fo clause 10, wherein the pigment comprises a quinone, wherein the quinone is one or more selected from the group of 1,2-benzoquinone, hd-benzoquinone, 1,4- nupthoguinone, 9,1 0-anthraguinone, 1,2-dihydroxy-9, 1 G-anthmguinone. 12. The method according to clause 10 or 11, wherein the colouring solution coraprising a pigment is an aquepus solution. 13, The method according to clause 10, 11, or 12, wherein the pH of the colouring solution comprising a pigment is in the range of 2 10 12, preferably in the range of 3.te 6, mote preferably in the range of 4 to 3.5, even more preferably in the range of 4 to 5. 14. The method according to any ons of the preceding clauses, wherein the one or more polymeric layers comprises at least two polymeric layers, preferably comprises two polymere layers. 15. The method according to any one of the preceding clauses, further comprising the step of . laminating the one.or more polymeric layers on the polymeric backbone layer for obtaining said polymeric film. 16. The method according to any one of the preceding clauses, further comprising the step of drying the polymere film. 17. The method according to any one of the preceding clauses, further comprising the step of perforating the polymeris film and/or the step of performing an additional colouring step, 18. The method according to any one of the preceding clauses, further comprising the step of : colouring the polymeric backbone layer.

19. The method according to any one of the preceding clauses, wherein the glass transition temperature of the polymere backbone layer is at least 19 “U higher than the glass transition temperature of the adjacent polymeric layer, and/or wherein for each pair of adjacent polymeric layers, the glass transition temperature of the polymeric layer that is closest to the polymeric backbone layer ts at least 10 °C higher than the glass transition temperature of the other polymeric layer.

20. The method according to any one Of the preceding clauses, wherein the polymeric backbone layer and the one or more polymeric layers each comprise one or more polymers

1 independently selected from the group of polyethylene, polypropylene, polybutylens, polyisobutylene, ethyienevinyiacetaal copolymer, ethene-acrylate ester copolymers, ethyl methacrylate copolymer, caprolactone pola.

21. The method according to clause 20, wherein the polymer of the one or more polymers comprise low density polyethylene, preferably Basar low-density polyethylene.

22. The method according to clause 20 or 21, wherein the polyiner of the polyrneric backbone layer comprises high density polyethylene.

23. The reethod according to any aoe of fhe preceding clauses, futher comprising the step of calibrating the polymeric film, wherein the step of calibrating comprises the step of calibrating the thd colour of the polymere film.

24, The method according to any one of the preceding clauses, wherein the polymeric

24 backbone layer sado the one or more polyresric layers comprises one or vore additive selected froma the grovp of polycaprolactone diol polymer, ethylene-glycidyl methacrylate copolymer, } polyethylene, polyethylene terephthalate. 25. The method according to any one of the preceding clauses, further coraprsing the step of

3 heatmng the polymeric film to a temperature in the range of 118 "Cio 180 °C, preferably toa temperature in the range of 120°C to 180 °C.

26. The method according to any one of the preceding clauses, further comprising the step of cutting up a plate material and, optionally, the step of decolouring the cut-up plate material.

27, A coloured polymeric Bla, comprising:

: ~ 3 polymeric backbone layer and one or more polymeric layers arranged on the polymeric backbone layer, each of the one or more palymeric layers having a respective glass transition temperature, wherein the one or more polymeric layers that are arranged on a same side of the polymeric backbone layer ave arranged in an order of decreasing glass transition temperature starting from said same side. the glass : transition temperature of each of said one or more polymeric layers being lower than that of the polymeric backbone layer; and

~ a ¢olourant,

wherein the colourant is at least embedded in the one or more polymeric layers.

’

28. The coloured film according 10 clause 27, wherein the polymeric filmi has a thickness in the range of 30 gm to 3 mm, preferably a thickaess in the range of 100 pm to 2 nun, sod more preferably a thickness in the range of 159 ym to 1 mm.

13 29. The coloured film according to clause 27 or 28, wherein the crystallinity of the polymeric layer adjacent to the polymeric backbone is in the range of 353% t0:60%, preferably in the range of 40% to 55%;

30. The coloured film according to clause 27, 28, or 29, wherein the one or more polymedce layer each comprises an independently selected colorant comprising at least one pigment, wherein the pigment comprises a quinone, wherein the quinone is preferably one or more selected from the group of 1 2-benzoguinone, 1 d-benzoquinone, 1 d-napthoquinone, 9,.10-anthraquinone, and 1,2 dihydroiy-9, 10-anthraguinone.

31 A master colour batch obtainable by the method according to any one of the clauses Ì to 26.

32. The master colagr batch according to clause 31, wherein the master colour batch is a granulate,

33. Use of the master colour batch according 10 clause 31 or 32 in the process of injection moulding.

34. An injected moulded product, such as a bottle, comprising the master colour batch

38 according to clause 31 or 32.

Claims

CONCLUSIONS

A method of coloring a polymeric film, comprising the steps of: ~ providing a polymeric film comprising a polymeric backbone layer and one or more polymeric layers applied to the polymeric backbone layer, each of the one or more polymer layers respectively has a glass transition temperature, wherein the one or more polymer layers applied to the same side of the polymer backbone layer are applied in an order of decreasing glass transition temperature starting from the same side, the glass transition temperature of each of the one or more polymer layers is lower than that of the polymeric backbone layer; and ~ coloring the one or more polymeric layers in order of their glass transition temperature starting with the polymer.

A method according to claim 1, wherein the step of coloring comprises one or more color sub-steps, each sub-step comprising coloring a single polymer layer.

The method of claim 2, wherein the respective color sub-steps are performed in an order from the innermost polymeric layer relative to the polymeric backbone layer to the outermost polymeric layer relative to the polymeric backbone layer.

The method of claim 3, wherein each color sub-step is performed at a decreasing temperature relative to a previous color sub-step.

A method according to claim 2, 3, or 4, wherein the coloring of a polymeric layer of the one or more polymeric layers is carried out at a temperature that is substantially equal to the glass transition temperature of the polymeric layer.

A method according to any one of the preceding claims, wherein the coloring step comprises transporting the polymeric film through one or more color baths.

The method of claim 6, wherein each of the one or more dye baths is arranged to dye a single polymeric layer.

Method according to any one of the preceding claims, further comprising the step of shredding the polymeric film.

9. Method according to any one of the preceding claims, further comprising the step of forming a granulate.

A method according to any one of the preceding claims, further comprising the step of providing a color solution comprising a pigment.

A method according to claim 10, wherein the pigment comprises a quinone, wherein the quinone is one or more selected from the group of 1,2-benzoquinone, 4-benzoquinone, 1,4-napthoquinone, 9,10-anthraquinone, 1, 2-dihydroxy-9,10-anthraquinone.

A method according to claim 10 or 11, wherein the coloring solution comprising a pigment is an aqueous solution.

13. Method according to claim 10, 11, or 12, wherein the pH of the coloring solution comprising a pigment is in the range from 2 to 12, preferably in the range from 3 to 6, more preferably in the range range is from 4 to 5.5, even more preferably in the range from 4 to 3.

Method according to any one of the preceding claims, wherein the one or more polymeric layers comprises at least two polymeric layers, preferably two polymeric layers.

A method according to any one of the preceding claims, further comprising the step of laminating the one or more polymeric layers to the polymeric backbone layer to obtain the polymeric film.

A method according to any one of the preceding claims, further comprising the step of drying the polymeric film.

Method according to any one of the preceding claims, further comprising the step of perforating the polymeric film and/or the step of carrying out an additional coloring step.

A method according to any one of the preceding claims, further comprising the step of coloring the polymeric backbone layer.

A method according to any one of the preceding claims, wherein the glass transition temperature of the polymeric backbone layer is at least 10°C higher than the glass transition temperature of the adjacent polymeric layer, and/or wherein for each pair of adjacent polymeric layers, the glass transition temperature of the polymeric layer closer to the polymer backbone layer 53 is at least 10 °C higher than the glass transition temperature of the other polymer layer.

A method according to any one of the preceding claims, wherein the polymeric backbone layer and the one or more polymeric layers each comprise one or more polymers independently selected from the group of polyethylene, polypropylene, polybutylene, polyisobutylene, ethylene-vinyl acetate copolymer, ethylene-acrylate ester copolymers, ethyl methacrylate copolymer, caprolactone polymer.

A method according to claim 20, wherein the polymer of the one or more polymers each independently comprises low density polyethylene, preferably linear low density polyethylene.

The method of claim 20 or 21, wherein the polymer of the polymeric backbone layer comprises high density polyethylene.

A method according to any one of the preceding claims, further comprising the step of calibrating the polymeric film, wherein the calibrating step includes the step of calibrating the starting color of the polymeric film.

A method according to any one of the preceding claims, wherein the polymeric backbone layer and/or the one or more polymeric layers comprise one or more additives selected from the group of polycaprolactone diol polymer, ethylene-glycidyl methacrylate copolymer, polyethylene, polyethylene terephthalate.

A method according to any one of the preceding claims, further comprising the step of heating the polymeric film to a temperature in the range of 110°C to 180°C, preferably to a temperature in the range of 120°C to and with 160 °C.

26. Method according to any of the preceding claims, further comprising the step of cutting a sheet material and, optionally, the step of decolorizing the cut sheet material.

27. Colored polymeric film, comprising:

— a polymeric film comprising a polymeric backbone layer and one or more polymeric layers deposited on the polymeric backbone layer, each of the polymeric layer(s) having a glass transition temperature respectively, the one or more polymeric layers deposited on the same side of the polymer backbone layer are applied in an order of decreasing glass transition temperature starting from the same side, the glass transition temperature of each of the one or more polymer layers being lower than that of the polymer backbone layer; and — a dye, wherein the dye is embedded at least in the one or more polymeric layers.

The colored film according to claim 27, wherein the polymeric film has a thickness in the range of 50 µm to 3 mm, preferably a thickness in the range of 100 µm to 2 mm, and more preferably a thickness has in the range of 150 gm to | mm.

Colored film according to claim 27 or 28, wherein the crystallinity of the polymeric layer adjacent to the polymer backbone layer is in the range of 35% to 60%, preferably in the range of 40% to 55%.

30. Colored film according to claim 27, 28, or 29, wherein the one or more polymeric layers each comprise an independently selected dye comprising at least one pigment, the pigment comprising a quinone, the quinone preferably being one or more selected from the group is of 1,2-benzoquinone, 4-benzoquinone, 1,4-napthoquinone, 9,10-anthraquinone, 1,2-dihydroxy-9,10-anthraquinone.

31. Main color batch obtainable by means of the method according to any of claims 1 to 26.

32. Main color batch according to claim 31, wherein the main color batch is a granulate.

33. Use of a main color batch according to claim 31 or 32 in the injection molding process.

An injection molded product, such as a bottle, comprising the main color batch according to claim 31 or 32.