WO2018153665A1 - Solution de stabilisation uv pour le traitement de la couche de surface d'un article polymère - Google Patents

Solution de stabilisation uv pour le traitement de la couche de surface d'un article polymère Download PDF

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Publication number
WO2018153665A1
WO2018153665A1 PCT/EP2018/053003 EP2018053003W WO2018153665A1 WO 2018153665 A1 WO2018153665 A1 WO 2018153665A1 EP 2018053003 W EP2018053003 W EP 2018053003W WO 2018153665 A1 WO2018153665 A1 WO 2018153665A1
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Prior art keywords
polymer
alkyl
mol
alkoxy
article
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PCT/EP2018/053003
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English (en)
Inventor
Joel POLLINO
Stéphane JEOL
Jonathan Schwartz
Marco Apostolo
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Syensqo Specialty Polymers USA LLC
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Solvay Specialty Polymers USA LLC
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Priority to US16/488,145 priority Critical patent/US20200002493A1/en
Priority to CN201880012381.1A priority patent/CN110337462B/zh
Priority to EP18703776.7A priority patent/EP3585830B1/fr
Priority to JP2019545299A priority patent/JP7237842B2/ja
Publication of WO2018153665A1 publication Critical patent/WO2018153665A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • C08J7/065—Low-molecular-weight organic substances, e.g. absorption of additives in the surface of the article
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/04—Polysulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/06—Polysulfones; Polyethersulfones

Definitions

  • the present invention relates to a process for treating the surface of a polymer article with a UV-stabilizer solution which comprises an effective amount of a UV-absorber compound dissolved in a solvent, and optionally a radical scavenger.
  • the present invention also relates to a process for preparing a UV-stabilized polymer article which comprises a step consisting in contacting the surface layer of a polymer article with the UV stabilizer solution.
  • the present invention also provides UV-stabilized polymer articles, that-is-to-say polymer articles which are resistant to color change upon exposure to UV light.
  • the treatment process of the present invention is very well-suited for injection molded or extruded parts, which will then for example be exposed to outdoor or indoor light.
  • the polymer articles can be used in the following applications: electronic or electronic devices, automotive parts, aeronautic parts, sporting equipment, face shields, lenses and architectural components.
  • UV-absorbers are molecules designed to convert photochemical energy into heat energy, thereby serving as photon inhibitors. These compounds are designed to absorb UV radiation more efficiently than the polymers that they protect. UV-absorbers can be categorized by their chemical structure and include for example 2-hydroxy benzotriazoles, 2-hydroxy benzophenones, and 2- hydroxy triazines. Each molecule possesses its own UV absorbance characteristics (e.g. magnitude of extinction coefficient and position lambda max).
  • UV-absorbers Incorporating UV-absorbers into a polymer by melt compounding results in the UV-absorbers being homogeneously distributed throughout the polymer volume. In general, the higher the amount of UV-absorbers is incorporated into a polymer, the better the UV-stabilization is. However, there exists an upper limit to how much UV-absorbers can be
  • the majority of the UV-absorber compounds are positioned inside the molded article instead of at the surface where the most of the photodegradation occurs. This is especially true for most aromatic polymers because they possess chromophores that are highly efficient at absorbing UV light. In these systems, almost all of the UV light is captured at the outermost surface layer (10 ⁇ depth) before ever reaching the inner part of the molded article.
  • impregnating the surface layer of the polymer article with UV-absorbers The impregnating methods of the prior art, also called infusion methods or penetration methods, are described in relation to certain polymers and their efficiency depends on several parameters that characterized the polymer material to be treated, such as the degree of crystallinity of the polymer or the susceptibility of the polymer to UV radiation.
  • impregnating methods also sometimes suffer from the fact that the polymer article surface must be heated to the melting point to allow the UV absorbers to diffuse into the polymer surfaces.
  • the process of the present invention is a process for treating at least one surface of a polymer article with a UV-absorber solution, the polymer material being for example selected from the group consisting of poly(aryl ether ketone) (PAEK), poly(aryl ether sulfone) (PAES) and polyarylene sulfide (PAS).
  • PAEK poly(aryl ether ketone)
  • PAES poly(aryl ether sulfone)
  • PAS polyarylene sulfide
  • the process of the present invention is also characterized by the fact that the process does not necessarily need a heating step.
  • the UV-absorbers, optionally with radical scavengers are positioned in the surface layer of the polymer article.
  • the present invention relates to a process, continuous or sequential, for treating the surface of a polymer article with a UV-stabilizer solution which comprises an effective amount of a UV-absorber compound dissolved in a solvent, and optionally a radical scavenger.
  • the UV-stabilizer solution of the present invention comprises:
  • UV-absorber compound selected from the group consisting of
  • R a is H; halogen; C1 -C4 alkyl; C1 -C4 alkoxy; or -COOR d ; and Rb, Rc and Rd, independently from one another, are H; C1 -C24 alkyl; C7-C16 alkylphenyl; or C5-C12 cycloalkyl;
  • Ri to R6 independently from one another, are H; OH; C1 -C12 alkyl; C2-C6 alkenyl; C1-C12 alkoxy; C2-C18 alkenoxy; halogen; trifluoromethyl C7-C1 I phenylalkyI; phenyl; phenyl which is substituted by C1 -C18 alkyl, C1 -C18 alkoxy or halogen; phenoxy; phenoxy which is substituted by C1- C18 alkyl, C1 -C18 alkoxy or halogen; C1 -C18 alkoxy; C1 -C18 alkoxy which is substituted by -COOR 7 or OH;
  • R 7 is H; C1 -C24 alkyl; C7-C16 alkylphenyl; or C5-C12 cycloalkyl; an Re is H; C1 -C18 alkyl; or C1-C18 alkoxy which may substituted by - COOR 7 or OH; and
  • R n is H; or C1 -C24 alkyl
  • DMF dimethylformamyde
  • NMP N-Methyl-2-pyrrolidone
  • DMAc dimethylacetamide
  • THF tetrahydrofuran
  • RS radical scavenger compound
  • the present invention also relates to a process for preparing a UV- stabilized polymer article which comprises a step consisting in contacting the surface layer of a polymer article with the UV stabilizer solution.
  • the present invention also provides UV-stabilized polymer articles, that-is- to-say polymer articles which are resistant to color change upon exposure to UV light.
  • the present invention also relates to the use of the UV-absorber solution to treat the surface layer of polymer articles, for example polymer articles made at least in part from a polymer composition (C) comprising a polymer selected from the group consisting of poly(aryl ether ketone) (PAEK), poly(aryl ether sulfone) (PAES) and polyarylene sulfide (PAS).
  • a polymer composition comprising a polymer selected from the group consisting of poly(aryl ether ketone) (PAEK), poly(aryl ether sulfone) (PAES) and polyarylene sulfide (PAS).
  • PAEK poly(aryl ether ketone)
  • PAES poly(aryl ether sulfone)
  • PAS polyarylene sulfide
  • the present invention relates to a process for treating the surface of a
  • the polymer article comprising a step consisting in contacting the surface of the article with a UV-stabilizer solution.
  • the UV-stabilizer solution of the invention comprises at least one UV-absorber, a solvent and optionally a radical scavenger.
  • UV-absorber or “UV-absorber compound” is used within the context of the present invention according to its usual meaning, i.e. to designate an organic compound possessing absorption bands in the region ranging from 250 to 400 nm.
  • the expression “radical scavenger” or “radical scavenger compound” is used within the context of the present invention to designate an organic compound capable of reacting with a radical formed during the
  • the expression "treating” or “treatment” is used within the context of the present invention according to its usual meaning and encompasses any process and technology that can be used to incorporate the UV-absorber compounds (UV), possibly the radical scavenger compounds (RS), within the layer surface of the polymer article.
  • the process of the present invention comprises an essential step which consists in contacting at least one surface of a polymer article with the UV- absorber solution.
  • the contact step can be implemented by any means, such as for example by coating, spraying or immersion.
  • the process of treating the layer of the polymer article can be continuous or sequential.
  • the treatment can last from a few seconds to several hours depending notably on the degree of crystallinity of the polymer material, the shape of the article, and the UV-susceptibility of the polymer article as defined below.
  • the contacting step can, for example, be 10 to 60 second long.
  • the treatment advantageously takes place at room temperature, but can also take place below or above room temperature.
  • the step of contacting occurs between 10 and 30°C, for example between 15 and 25°C.
  • the process of the present invention may also further comprise one step or several steps consisting of rinsing the surface of the polymer article and/or one step or several steps consisting of drying the article.
  • the process of the present invention does not comprise a step of heating the polymer article, for example at a temperature higher than 30°C.
  • the UV-stabilizer solution of the present invention comprises:
  • UV-absorber compound selected from the group consisting of
  • R a is H; CI; C1 -C4 alkyl; C1 -C4 alkoxy; or -COOR d ;
  • Rb, Rc and Rd independently from one another, are H; C1 -C24 alkyl; C7-C16 alkylphenyl; or C5-C12 cycloalkyl;
  • Ri to R6 independently from one another, are H; OH; C1 -C12 alkyl; C2-C6 alkenyl; C1-C12 alkoxy; C2-C18 alkenoxy; halogen; trifluoromethyl C7-C1 I phenylalkyI; phenyl; phenyl which is substituted by C1 -C18 alkyl, C1 -C18 alkoxy or halogen; phenoxy; phenoxy which is substituted by C1- C18 alkyl, C1 -C18 alkoxy or halogen; C1 -C18 alkoxy; C1 -C18 alkoxy which is substituted by -COOR 7 or OH;
  • R 7 is H; C1 -C24 alkyl; C7-C16 alkylphenyl; or C5-C12 cycloalkyl; an
  • Re is H; C1 -C18 alkyl; or C1-C18 alkoxy which may substituted by - COOR 7 or OH;
  • R n is H; or C1 -C24 alkyl; b) at least one solvent selected from the group consisting of dimethylformamyde (DMF), A/-Methyl-2-pyrrolidone (NMP),
  • DMAc dimethylacetamide
  • THF tetrahydrofuran
  • UV-absorber compounds (UV) used in the UV-stabilizer solution of the present invention ranges from 1.5 to 15 mol. %, based on the total number of moles of the solution.
  • the amount of UV-absorber compounds (UV) used in the UV-stabilizer solution of the present invention ranges from 2 to 10 mol. % or from 2.2 to 8 mol. %, based on the total number of moles of the solution.
  • the UV-stabilizer solution of the present invention can comprise one UV- absorber compound (UV) or more than one, for example two or three distinct UV-absorber compound (UV).
  • the UV-stabilizer solution of the present invention can for example comprise one UV-absorber compound of formula (I) and one UV-absorber compound of formula (II).
  • the amount of radical scavenger compounds (RS), which can be used in the UV-stabilizer solution of the present invention, can range from as little as 0.01 mol. % to 15 mol. %, based on the total number of moles of the solution.
  • moles % is hereby defined as moles of solvent, moles of UV-absorber compounds and moles of radical scavenger compounds.
  • the amount of radical scavenger compounds (RS) used in the UV-stabilizer solution of the present invention ranges from 0.1 to 10 mol. %, from 0.5 to 8 mol. %, or from 0.8 to 5 mol. %, based on the total number of moles of the solution.
  • the UV-stabilizer solution of the present invention can comprise one
  • radical scavenger compound or more than one, for example two or three distinct radical scavenger compounds (RS).
  • the UV-absorber compound (UV) of the UV- stabilizer solution is a 2-hydroxyphenyl benzotriazole compound of formula (I):
  • R a is H; CI; C1 -C4 alkyl; C1 -C4 alkoxy; or -COOR d ;
  • Rb, Rc and Rd independently from one another, are H; C1 -C24 alkyl;
  • the UV-absorber compound (UV) of the UV-stabilizer solution is a phenyl benzotriazole compound of formula (I):
  • R a is H; or CI;
  • Rb and R c independently from one another, are H; C1 -C24 alkyl; or C7- C16 alkylphenyl.
  • the UV-stabilizer solution of the present invention can comprise one 2- hydroxyphenyl benzotriazole compound formula (I) or more than one, for example two or three distinct 2-hydroxyphenyl benzotriazole compounds formula (I).
  • the UV-absorber compound (UV) of the UV-stabilizer solution is selected from the group consisting of compound of formula (IA), (IB) and (IC) below:
  • the 2-hydroxyphenyl benzotriazole [0032] According to an embodiment, the 2-hydroxyphenyl benzotriazole
  • compound is a compound of formula (IA), (IB) or (IC) above. These compounds are notably commercially available under the trade names Tinuvin® 234, Tinuvin® 326 and Tinuvin® P from BASF.
  • phenyl benzotriazole compounds are also commercially available under the trade names Tinuvin® 329, Tinuvin® 328, Tinuvin® 360 and Tinuvin® 320 from BASF.
  • the UV-absorber compound (UV) of the UV- stabilizer solution is a 2-hydroxy phenyl triazine compound of formula (II):
  • Ri to R6 independently from one another, are H; OH; C1 -C12 alkyl; C2-C6 alkenyl; C1 -C12 alkoxy; C2-C18 alkenoxy; halogen; trifluoromethyl; C7- C1 1 phenylalkyl; phenyl; phenyl which is substituted by C1 -C18 alkyl, C1 - C18 alkoxy or halogen; phenoxy; phenoxy which is substituted by C1 -C18 alkyl, C1 -C18 alkoxy or halogen; C1 -C18 alkoxy; C1 -C18 alkoxy which is substituted by -COOR/ or OH;
  • R 7 is H; C1 -C24 alkyl; C7-C16 alkylphenyl; C5-C12 cycloalkyl;
  • Rs is H; C1 -C18 alkyl; C1 -C18 alkoxy which may substituted by -COOR 7 or
  • the UV-absorber compound (UV) of the UV-stabilizer solution is a 2-hydroxy phenyl triazine compound of formula (II):
  • Ri to R6 independently from one another, are H; or C1 -C12 alkyl; ; R 7 is H; and
  • Re is H; C1 -C18 alkyl; or C1-C18 alkoxy which may substituted by -
  • the UV-absorber solution of the present invention can comprise one 2- hydroxy phenyl triazine compound of formula (II) or more than one, for example two or three distinct 2-hydroxy phenyl triazine compounds of formula (I).
  • the UV-absorber compound (UV) of the UV-stabilizer solution is a compound of formula (I I A):
  • the phenyl triazine compound is a 2- hydroxyphenyl triazine compound of formula (I I A) above.
  • This compound is notably commercially available under the trade name Chiguard® 1064 from BASF.
  • phenyl triazine compounds are also commercially available under the trade names Tinuvin® 1577, Tinuvin® 400, Tinuvin® 460, Cyasorb® UV 1 164 and Cyasorb® UV 1 164L.
  • the UV-absorber compound (UV) of the UV- stabilizer solution is 2-hydroxy benzophenone compound of formula (III):
  • the UV-absorber compound (UV) of the UV-stabilizer solution is a compound of formula (IIIA), (1MB) or (1MB):
  • the present invention employs a UV-absorber compound - solvent
  • the solution penetrates the surface layer of the polymer, allowing for the sub-surface deposition of the UV stabilizer compounds (UV), and radical scavenger compounds (RS) (if also present in the solution).
  • UV UV stabilizer compounds
  • RS radical scavenger compounds
  • the solvent useful in the practice of the present invention should be able to appropriately dissolve, at room temperature, the UV-absorbers compounds (UV), and radical scavenger compounds (RS) (if also present in the solution).
  • UV UV-absorbers compounds
  • RS radical scavenger compounds
  • the solution comprises at least one solvent selected from the group consisting of dimethylformamyde (DMF), A/-Methyl-2-pyrrolidone (NMP), dimethylacetamide (DM Ac) and tetrahydrofuran (THF).
  • the solution may also comprise two, three or four distinct solvents from the list. The most preferred solvent is THF.
  • THF is the preferred solvent according to the present invention.
  • THF is less dependent on the concentration than other solvents, for example dichloromethane (CH2CI2).
  • the UV-stabilizer solution of the present invention may comprise one
  • radical scavenger compound RS
  • RS radical scavenger compound
  • RS radical scavenger compound
  • RS radical scavenger compound
  • radical scavengers may be selected from the group consisting of hindered amine light stabilizers (HALS) and hindered phenol antioxidants (HPA).
  • HALS hindered amine light stabilizers
  • HPA hindered phenol antioxidants
  • HALS compounds which can be added to the UV-stabilizer solution of this invention include 2,2,6,6-tetraalkylpiperidine compounds of formula (IV), or polymers including the same:
  • Rt and R p are independently from one another, H or substituents.
  • the UV-stabilizer solution of this invention include 2,2,6,6-tetraalkylpiperidine compounds of formula (III), or polymers including the same, in which:
  • R P is H or a C1 -C18 alkyl
  • Rt is an alkyl, an aryl or a cycloalkyl, all possibly substituted with heteroatom(s) such as N, S or O.
  • HALS hindered amine light stabilizers
  • Chiguard® 944 and Chiguard® 770 from BASF.
  • HPA compounds which can be added to the UV-stabilizer solution of this invention include 2,6-dialkylphenol derivative compounds of formula (V), or polymers including the sa
  • the UV-stabilizer solution of this invention include 2,2,6,6-tetraalkylpiperidine compounds of formula (III), or polymers including the same, in which:
  • Rj and R m are independently from each other, a C1 -C18 alkyl
  • HPA hindered phenolic antioxidant
  • Irganox® 1076 and Irganox® 1010 from Ciba Specialty Chemicals.
  • the method according to the present invention is effective in treating
  • polymer articles having a UV-susceptibility such that their ⁇ value is comprised between 5 and 50, after a 5-day exposure to filtered xenon arc light (using an Atlas ci4000 Xenon Weather-Ometer® configured with a Type S Borosilicate inner filter, a Type S Borosilicate outer filter, a irradiance at 340 nm setting of 0.3 W/m 2 set, a relative humidity setting of 54 %, and a temperature of 38°C) according to ASTM G155-04.
  • the UV-susceptibility of a polymer is determined by (i) exposing a desired polymer to accelerated weathering conditions, i.e. filtered xenon arc light, during 5 days and (ii) evaluating the color change(s) by standard methods known in the art.
  • accelerated weathering conditions i.e. filtered xenon arc light
  • color changes may be quantified according to the Hunterlab system which expresses color change based on the ⁇ value, or according to the CIElab system which quantifies color changes based on the ⁇ *.
  • the L coordinate represents the lightness (black to white) scale
  • the a coordinate represents the green-red chromaticity
  • the b coordinate represents the blue-yellow chromaticity.
  • the polymer of the present invention can be amorphous or semi- crystalline.
  • the polymer is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • PAEK poly(aryl ether ketone)
  • PAES poly(aryl ether sulfone)
  • PAS polyarylene sulfide
  • the recurring units (RPAEK) are selected from the group consisting of units of formulae (J-A) to (J-D) below :
  • each of R' is selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; and
  • - j' is zero or an integer ranging from 1 to 4.
  • the phenylene moieties independently have 1 ,2-, 1 ,4- or 1 ,3-linkages to the other moieties different from R' in the recurring unit (RPAEK).
  • the phenylene moieties have 1 ,3- or 1 ,4- linkages, more preferably they have a 1 ,4-linkage.
  • j' is preferably at each occurrence zero so that the phenylene moieties have no other substituents than those linking the main chain of the polymer.
  • the PAEK is poly(ether ether ketone) (PEEK).
  • PEEK poly(ether ether ketone)
  • RPAEK recurring units of formula J'-A
  • At least 60 mol. %, 70 mol. %, 80 mol. %, 90 mol. %, 95 mol. %, 99 mol. %, and most preferably all of recurring units (RPAEK) are recurring units (J'-A).
  • the PAEK is poly(ether ketone
  • PEKK poly(ether ketone ketone)
  • RPAEK mol. % of the recurring units
  • At least 60 mol. %, 70 mol. %, 80 mol. %, 90 mol. %, 95 mol. %, 99 mol. %, and most preferably all of recurring units (RPAEK) are a combination of recurring units (J'-B) and (J"-B).
  • the PAEK is poly(ether
  • PEK poly(ether ketone)
  • RPAEK recurring units of formula (J'-C)
  • At least 60 mol. %, 70 mol. %, 80 mol. %, 90 mol. %, 95 mol. %, 99 mol. %, and most preferably all of recurring units (RPAEK) are recurring units (J'-C).
  • the PAEK is a PEEK-PEDEK copolymer.
  • a "PEEK-PEDEK copolymer” denotes any polymer of which more than 50 mol. % of the recurring units (RPAEK) are both recurring units of formula J'-A (PEEK) and formula J'-D (poly(diphenyl ether
  • the PEEK-PEDEK copolymer may include relative molar proportions of recurring units J'-A and J'-D (PEEK/PEDEK) ranging from 95/5 to 60/40.
  • the sum of recurring units J'-A and J'-D represents at least 60 mol. %, 70 mol. %, 80 mol. %, 90 mol. %, 95 mol. %, 99 mol. %, of recurring units in the PAEK.
  • recurring units J'-A and J'-D represent all of the recurring units in the PAEK.
  • the PAEK is PEEK or PEEK-PEDEK. KETASPIRE®
  • PEEK is commercially available from Solvay Specialty Polymers USA, LLC.
  • PAES sulfone
  • each R is selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium;
  • each h equal to or different from each other, is an integer ranging from 0 to 4.
  • T is selected from the group consisting of a bond, a sulfone group
  • Rj and Rk are selected from a hydrogen, a halogen, an alkyl, an alkenyl, an alkynyl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium.
  • Rj and Rk are preferably methyl groups.
  • At least 60 mol. %, 70 mol. %, 80 mol. %, 90 mol. %, 95 mol. %, 99 mol. %, and most preferably all of recurring units in the PAES are recurring units (RPAES).
  • the PAES is a polyphenylsulfone (PPSU).
  • PPSU polyphenylsulfone
  • a "polyphenylsulfone (PPSU)" denotes any polymer of which more than 50 mol. % of the recurring units are recurring units of formula
  • At least 60 mol. %, 70 mol. %, 80 mol. %, 90 mol. %, 95 mol. %, 99 mol. %, and most preferably all of the recurring units in the PPSU are recurring units of formula (K'-A).
  • PPSU can be prepared by known methods and is notably available as RADEL® PPSU from Solvay Specialty Polymers USA, L.L.C.
  • the PAES is a polyethersulfone (PES).
  • PES polyethersulfone
  • a "polyethersulfone (PES)" denotes any polymer of which at least 50 mol. % of the recurring units are recurring units of formula (K'-B), the mol. % being based on the total number of moles in the polymer:
  • PES can be prepared by known methods and is notably available as
  • the PAES is a polysulfone (PSU).
  • PSU polysulfone
  • a "polysulfone (PSU)" denotes any polymer of which at least 50 mol. % of the recurring units are recurring units of formula (K'-C), the mol. % being based on the total number of moles in the polymer:
  • At least 60 mol. %, 70 mol. %, 80 mol. %, 90 mol. %, 95 mol. %, 99 mol. %, and most preferably all of the recurring units in the PSU are recurring units of formula (K'-C).
  • PSU can be prepared by known methods and is available as UDEL® PSU from Solvay Specialty Polymers USA, L.L.C.
  • PAS sulfide
  • recurring units 50 mol. % of the recurring units are recurring units (RPAS) of formula -(Ar'- S)-, where Ar' is an aromatic group.
  • At least 60 mol. %, 70 mol. %, 80 mol. %, 90 mol. %, 95 mol. %, 99 mol. %, and most preferably all of the recurring units in the PAS are recurring units (RPAS).
  • Non-limiting examples of PAS include poly(2,4-toluene sulfide),
  • the PAS is poly(para-phenylene sulfide) (PPS).
  • PPS poly(para-phenylene sulfide)
  • a "poly(para-phenylene sulfide) (PPS)” denotes any polymer of which at least 50 mol. % of the recurring units are recurring units (Rpps) of formula (L), the mol. % being based on the total number of moles in the polymer:
  • At least 60 mol. %, 70 mol. %, 80 mol. %, 90 mol. %, 95 mol. %, 99 mol. %, and most preferably all of the recurring units in the PPS are recurring units (Rpps).
  • PPS is manufactured and sold under the trade name Ryton® PPS by
  • the polymer is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • PPSU polyphenylsulfone
  • PES polyethersulfone
  • PSU polysulfone
  • PEEK poly(ether ether ketone)
  • PPS poly(para-phenylene sulfide)
  • the polymer article of the present invention can be made at least in part from a polymer composition (C) comprising a polymer (P) selected from the group consisting of polyphenylsulfone (PPSU), polyethersulfone (PES), polysulfone (PSU), poly(ether ether ketone) (PEEK) and poly(para-phenylene sulfide) (PPS), optionally reinforcing agents.
  • PPSU polyphenylsulfone
  • PES polyethersulfone
  • PSU polysulfone
  • PEEK poly(ether ether ketone)
  • PPS poly(para-phenylene sulfide)
  • composition (C) can for example comprises up to 60 wt. % of
  • the % being based on the total weight of the
  • the optional reinforcing agents also called reinforcing fibers or fillers, may be selected from fibrous and particulate reinforcing agents.
  • a fibrous reinforcing filler is considered herein to be a material having length, width and thickness, wherein the average length is significantly larger than both the width and thickness. Generally, such a material has an aspect ratio, defined as the average ratio between the length and the largest of the width and thickness of at least 5, at least 10, at least 20 or at least 50.
  • the reinforcing filler may be selected from mineral fillers (such as talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate), glass fibers, carbon fibers, synthetic polymeric fibers, aramid fibers, aluminum fibers, titanium fibers,
  • the reinforcing agents may be present in the composition (C) in a total amount of greater than 0.5 wt. %, greater than 1 wt. % by weight, greater than 1.5 wt. % or greater than 2 wt. %, based on the total weight of the polymer composition (C).
  • the reinforcing agents may be present in the composition (C) in a total amount of less than 50 wt. %, less than
  • the polymer composition (C) may also comprises optional components, for example selected from the group consisting of plasticizers, colorants, pigments (e.g. black pigments such as carbon black and nigrosine), antistatic agents, dyes, lubricants (e.g. linear low density polyethylene, calcium or magnesium stearate or sodium montanate), thermal stabilizers, light stabilizers, flame retardants, nucleating agents and antioxidants.
  • plasticizers for example selected from the group consisting of plasticizers, colorants, pigments (e.g. black pigments such as carbon black and nigrosine), antistatic agents, dyes, lubricants (e.g. linear low density polyethylene, calcium or magnesium stearate or sodium montanate), thermal stabilizers, light stabilizers, flame retardants, nucleating agents and antioxidants.
  • colorants e.g. black pigments such as carbon black and nigrosine
  • antistatic agents e.g. black pigments such as carbon black and nigrosine
  • dyes e.
  • composition (C) may comprise one or more distinct polymers, as long as the polymer article incorporating the same has a UV-susceptibility, such that their ⁇ value is comprised between 5 and 50, after a 5-day exposure to filtered xenon arc light (using an Atlas ci4000 Xenon Weather-Ometer® configured with a Type S Borosilicate inner filter, a Type S Borosilicate outer filter, a irradiance at 340 nm setting of 0.3 W/m 2 set, a relative humidity setting of 54 %, and a temperature of 38°C), according to ASTM G 155-04.
  • the present invention also relates to a process for preparing a UV- stabilized polymer article which comprises a step consisting in contacting the surface layer of a polymer article with the UV stabilizer solution.
  • the present invention also provides UV-stabilized polymer articles,
  • UV- stabilized polymer articles are also called treated polymer articles, in comparison with polymer articles which have not be contacted with the UV-stabilizer solution of the invention and serve as a reference to assess the efficiency of the process of the present invention to impart resistance to color change to the polymer articles at stake.
  • color changes were determined according to the Hunterlab system. However, the particular manner that color change is expressed is not essential to the invention. All that is essential is that the color change be offset as a result of the treatment of the polymer article with the UV-absorber solution. Thus, if the Hunterlab or CIElab system is used to express color change, it is desirable that the ⁇ or ⁇ * value be as low as possible, ideally zero.
  • the L coordinate represents the lightness (black to white) scale
  • the a coordinate represents the green-red chromaticity
  • the b coordinate represents the blue-yellow chromaticity.
  • the ⁇ of the treated articles should be as low as possible.
  • the ⁇ of the treated article is reduced by at least 50 %, in comparison to the ⁇ of non-treated articles, after a 5-day exposure to filtered xenon arc light using an Atlas ci4000 Xenon Weather-Ometer® configured with a Type S Borosilicate inner filter, a Type S Borosilicate outer filter, a irradiance at 340 nm setting of 0.3 W/m 2 set, a relative humidity setting of 54 %, and a temperature of 38°C, in accordance with ASTM G155-04, it is considered according to the present invention that the polymer article is UV-stabilized.
  • the polymer article is said to be UV-stabilized following the process of the present invention, when its ⁇ (or ⁇ *) is reduced by at least 50 % in comparison to ⁇ (or ⁇ *) of the non-treated polymer article, after a 5-day exposure to filtered xenon arc light, using an Atlas ci4000 Xenon Weather-Ometer® configured with a Type S Borosilicate inner filter, a Type S Borosilicate outer filter, a irradiance at 340 nm setting of 0.3 W/m 2 set, a relative humidity setting of 54 %, and a temperature of 38°C, in accordance with ASTM G155-04.
  • the ⁇ of the treated article is reduced by at least 60 %, in comparison to the ⁇ of non-treated articles, after a 5-day exposure to filtered xenon arc light using an Atlas ci4000 Xenon Weather- Ometer® configured with a Type S Borosilicate inner filter, a Type S Borosilicate outer filter, a irradiance at 340 nm setting of 0.3 W/m 2 set, a relative humidity setting of 54 %, and a temperature of 38°C, in
  • the treated polymer article incorporate UV-stabilizer compounds (UV) in the surface layer of the polymer article, as detected by photoacoustic FTIR analysis of the surface.
  • UV UV-stabilizer compounds
  • the surface layer of the article is the depth of polymer material extending from the surface of the article wherein UV-stabilizer compounds (UV), optionally radical scavengers compounds (RS), can be detected after treatment.
  • UV UV-stabilizer compounds
  • RS radical scavengers compounds
  • the polymer article may have several layers.
  • the process of the present invention may be applied to one surface layer only or several, depending on the expected effect and/or the process used to treat the articles (e.g. coating, spraying, bath immersion).
  • the surface layer extends to a depth of 20 m from the surface of the article, a depth of 50 ⁇ or a depth of 100 m.
  • the concentration of active compounds may vary within the surface layer, for example being maximum adjacent to the surface and decreases progressively to zero within the depth of the surface layer, that- is-to-say within 20 ⁇ from the surface of the article, a depth of 50 ⁇ , a depth of 100 ⁇ from the surface of the article.
  • the present invention also relates to the use of the UV-absorber solution as defined above to treat the surface layer of polymer article having a UV- susceptibility, such that its ⁇ value is comprised between 5 and 50, after a 5-day exposure to filtered xenon arc light, using an Atlas ci4000 Xenon Weather-Ometer® configured with a Type S Borosilicate inner filter, a Type S Borosilicate outer filter, a irradiance at 340 nm setting of 0.3 W/m 2 set, a relative humidity setting of 54 %, and a temperature of 38°C in accordance with ASTM G 155-04.
  • the UV-absorber solution as defined above is used to treat the surface layer of polymer article having a Insusceptibility, such that its ⁇ value is comprised between 5 and 40, or between 5 and 30, after a 5-day exposure to filtered xenon arc light, using an Atlas ci4000 Xenon Weather-Ometer® configured with a Type S
  • Borosilicate inner filter a Type S Borosilicate outer filter, a irradiance at 340 nm setting of 0.3 W/m 2 set, a relative humidity setting of 54 %, and a temperature of 38°C, in accordance with ASTM G155-04.
  • Polymer-1 Radel ® R-5100 NT is a poly(biphenyl ether sulfone) (PPSU) from Solvay Specialty Polymers USA, L.L.C.
  • PPSU poly(biphenyl ether sulfone)
  • Polymer-2 Udel ® P-1700 is a polysulfone (PSU) from Solvay Specialty
  • KetaSpire ® KT 880 is a poly(ether ether ketone) (PEEK) from
  • Polymer-4 Ryton ® PPS is a poly(para-phenylene sulphide) from Solvay
  • T1O2 Ti-Pure ® R-105 is a maximum-durability grade of T1O2 from DuPont ® .
  • UV-1 Tinuvin ® 234 is a 2-hydroxyphenyl benzotriazole UV-absorber of formula (IA), as above detailed, from BASF.
  • UV-2 Tinuvin ® P is a 2-hydroxyphenyl benzotriazole UV-absorber of
  • UV-3 Chiguard ® 1064 is a hydroxyphenyl triazine UV-absorber of formula
  • RS-1 Chiguard® 944 is a hindered amine radical scavenger of formula
  • RS-2 Chiguard® 770 is a hindered amine radical scavenger of formula
  • Molded articles (M1 -M9) were prepared by injection molding of melt compounded blends comprised of one or two polymers and, optionally ⁇ 2 as defined in Table 1. Melt blending was carried out using a
  • UV-stabilizer solutions were prepared by dissolving a quantity of UV absorber (UV) and, optionally a quantity of radical scavenger (RS) into a defined quantity of solvent.
  • the molded articles were submerged into a glass jar containing a UV-stabilizer solution for a dip time ranging from 30 seconds to 2 hours. Following submersion, the molded article was removed and then allow to dry at ambient temperature and pressure in air for at least 16 h.
  • UV exposure was carried out using an Atlas ci4000 Xenon Weather- Ometer® configured with a Type S Borosilicate inner filter, a Type S Borosilicate outer filter, a irradiance at 340 nm setting of 0.3 W/m 2 set, a relative humidity setting of 54 %, and a temperature of 38°C, according to ASTM G 155-04.
  • treated and untreated specimens were mounted to a sample holder, placed in the weathering chamber, and exposed to radiation for 5 days. At the end of each exposure period, colorimetery measurement was performed on each sample.
  • the L coordinate represents the lightness (black to white) scale
  • the a coordinate represents the green-red chromaticity
  • the b coordinate represents the blue-yellow chromaticity.
  • Example 1 UV susceptibility of untreated molded articles
  • Polymer composition (C) comprising a polymer (P) selected from the
  • PPSU polyphenylsulfone
  • PES polyethersulfone
  • PSU polysulfone
  • PEEK poly(ether ether ketone)
  • PPS poly(para- phenylene sulfide)
  • optionally reinforcing agents have a ⁇ value is comprised between 5 and 50, after a 5-day exposure to filtered xenon arc light, using an Atlas ci4000 Xenon Weather-Ometer® configured with a Type S Borosilicate inner filter, a Type S Borosilicate outer filter, a irradiance at 340 nm setting of 0.3 W/m 2 set, a relative humidity setting of 54 %, and a temperature of 38°C, in accordance with ASTM G155-04, and qualify as UV-susceptible polymer articles according to the present invention.
  • Polycarbonate articles (M9) are not UV-susceptible polymer articles
  • UV-stabilizer solutions were tested on M2 molded articles (30 sec treatment).
  • the UV-stabilizer solutions and ⁇ measurements are detailed in Table 3-6 below.
  • Ex 1 C corresponds to the untreated article M2.
  • UV- stabilizer Mol. % 2.5 2.5 2.5 2.5 2.5 2.5 solutions RS RS-1 RS-3 RS-2 RS-2
  • UV-stabilizer solutions were tested on M3 molded articles (30 sec treatment).
  • the UV-stabilizer solutions and ⁇ measurements are detailed in Tables 7-8 below.
  • UV-stabilizer solutions were tested on several molded articles, unfilled or filled, as described in Table 9 (treatment time: 30 sec) and Table 10 (treatment time: 1 hour) below.
  • molded articles made from different polymer compositions can be effectively surface treated with the UV- stabilizer solutions of the invention. All of the examples led to a substantial ⁇ reduction (%) in comparison to their respective untreated molded article, with a % of ⁇ reduction greater than 50 % (i.e. threshold according to which the polymer article is considered UV-stabilized according to the present invention).

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention concerne un procédé de traitement de la surface d'un article polymère avec une solution de stabilisation UV qui comprend une quantité efficace d'un composé absorbant les UV dissous dans un solvant, et éventuellement un piégeur de radicaux. La présente invention concerne également un procédé de préparation d'un article polymère stabilisé contre les UV qui comprend une étape consistant à mettre en contact la couche de surface d'un article polymère avec la solution de stabilisation UV. La présente invention concerne également des articles polymères stabilisés contre les UV, c'est-à-dire des articles polymères qui sont résistants à un changement de couleur lors de l'exposition à une lumière UV.
PCT/EP2018/053003 2017-02-24 2018-02-07 Solution de stabilisation uv pour le traitement de la couche de surface d'un article polymère Ceased WO2018153665A1 (fr)

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US16/488,145 US20200002493A1 (en) 2017-02-24 2018-02-07 Uv-stabilizer solution for treating the surface layer of a polymer article
CN201880012381.1A CN110337462B (zh) 2017-02-24 2018-02-07 用于处理聚合物制品的表面层的uv稳定剂溶液
EP18703776.7A EP3585830B1 (fr) 2017-02-24 2018-02-07 Solution de stabilisant uv pour le traitement de la couche de surface d'un article polymère
JP2019545299A JP7237842B2 (ja) 2017-02-24 2018-02-07 ポリマー物品の表面層を処理するためのｕｖ安定剤溶液

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3778222B1 (fr) 2018-03-29 2024-07-31 Dai Nippon Printing Co., Ltd. Feuille décorative et matériau décoratif utilisant celle-ci

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US4636408A (en) * 1984-01-30 1987-01-13 General Electric Company Ultraviolet radiation stabilized polymer compositions
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P.K. DAS ET AL: "Photostabilization of poly (p-phenylene sulfide)", POLYMER DEGRADATION AND STABILITY, vol. 48, no. 1, 1 January 1995 (1995-01-01), GB, pages 1 - 10, XP055412854, ISSN: 0141-3910, DOI: 10.1016/0141-3910(95)00032-H *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3778222B1 (fr) 2018-03-29 2024-07-31 Dai Nippon Printing Co., Ltd. Feuille décorative et matériau décoratif utilisant celle-ci

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