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WO2018073123A1 - Composés polymères pour la fabrication de feuilles de polyester présentant une conductibilité thermique augmentée - Google Patents

Composés polymères pour la fabrication de feuilles de polyester présentant une conductibilité thermique augmentée Download PDF

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Publication number
WO2018073123A1
WO2018073123A1 PCT/EP2017/076199 EP2017076199W WO2018073123A1 WO 2018073123 A1 WO2018073123 A1 WO 2018073123A1 EP 2017076199 W EP2017076199 W EP 2017076199W WO 2018073123 A1 WO2018073123 A1 WO 2018073123A1
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Prior art keywords
polymer compound
filler
less
film
polymer
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German (de)
English (en)
Inventor
Matthias WUCHTER
Christian HENNE
Andreas Bork
Holger Kliesch
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Ensinger GmbH
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Ensinger GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
    • H10F19/85—Protective back sheets
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
    • H01B3/421—Polyesters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to polymer compounds for the production of polyester films, on the one hand have an increased thermal conductivity, on the other hand, however, are usable as Elektroisoliermaterial.
  • the invention further relates to the use of these polymer compounds for the production of in particular at least uniaxially oriented polyester films.
  • Films in electrical insulation applications must meet a number of requirements. On the one hand, they must have a high electrical insulation effect (dielectric strength, creep resistance) and, on the other hand, they must dissipate the heat generated by the electric current flow in order to avoid overheating of the live parts.
  • the thermal conductivity of many classical electrical insulating materials is therefore rather low.
  • the biaxially oriented polyethylene terephthalate films frequently used because of their high electrical breakdown strength have a thermal conductivity of less than or equal to 0.2 W m.sup.- 1 K.sup.- 1 .
  • the values given in each case refer to measurements perpendicular to the film plane (measuring method TIMA).
  • Polyester molding compounds with increased thermal conductivity are e.g. from the
  • polyester films as electrical insulator
  • dielectric strength of polyethylene terephthalate (PET) can be significantly increased by at least monoaxial, preferably biaxial stretching.
  • the increased hydrolysis stability and the thermooxidative stability of the polyester are also important.
  • the object of the present invention is to propose a polyester-based polymer compound with which polyester films with increased thermal conductivity of about 0.3 W m "1 K " 1 or more can be produced on existing polyester film systems which are at least uniaxially orientable and which furthermore have a dielectric strength of about 90 kV mm -1 or more in accordance with DIN 40634 (at 23 ° C. and AC voltage (AC)).
  • This object is achieved by a polymer compound according to claim 1.
  • Films which can be produced from the compound according to the invention have in particular an elongation at break of about 5% or more in each film direction and a relative temperature index (RTI) of about 90 ° C. or more.
  • the relative temperature index RTI is determined according to UL 746B and is based on the elongation at break measured according to DIN EN ISO 572-1 and -3.
  • the RTI value correlates with the temperature in ° C at which the film fails in continuous use.
  • Films can be up to approx. 5% at filler contents of the polymer compound.
  • the polymer compound according to the invention can also be processed into films with admixture of further, in particular substantially filler-free polymer material, in which case the polymer compound serves as a masterbatch.
  • the thicknesses of the films are about 9 to about 400 pm.
  • Films made of the compound of the invention are particularly suitable as electrical insulation, z. B. as a backsheet for solar modules, as a motor insulation film, as an insulating film in computers and electronic devices of all kinds.
  • the polymer compound according to the invention contains about 7 to about 80% by weight of a particulate first filler which comprises crystalline Si0 2 and / or crystalline silicate, in particular selected from quartz, kyanite and cristobalite, and mixtures thereof.
  • a particulate first filler which comprises crystalline Si0 2 and / or crystalline silicate, in particular selected from quartz, kyanite and cristobalite, and mixtures thereof.
  • the lower limit for the content of the first filler is preferably approx.
  • the upper limit of the content of the first filler is preferred, in particular when used for film production, at about 60 wt .-% and more preferably at about 45 wt .-%.
  • the requirement that the polymer compound should be both heat-conducting and electrically insulating makes the selection of materials in the fillers difficult.
  • ceramic fillers such as hexagonal boron nitride (hBN), aluminum oxide (Al 2 0 3 ) or silicon carbide (SiC) come into question.
  • hBN hexagonal boron nitride
  • Al 2 0 3 aluminum oxide
  • SiC silicon carbide
  • the suitable particles to increase the thermal conductivity When selecting the suitable particles to increase the thermal conductivity, the simultaneously high, functional dielectric strength, which is required in the films to be produced, must be taken into account. Therefore, the use of metal particles prohibits from the outset, as well as the use of carbon-based fillers, such.
  • carbon-based fillers As graphite, carbon black, carbon fibers or carbon nanotubes (CNT). These conduct the electric current, and the required dielectric strength of about 90 kV mm “1 or more according to DIN 40634 (at 23 ° C and alternating voltage (AC)) with good thermal conductivity is not achievable with these fillers Quantities up to 8 wt .-% are introduced into a film without the electrical breakdown strength drops significantly, but at these levels no appreciable increase in the thermal conductivity is achieved.
  • Periclase and MgO spinels also prove to be less suitable as fillers for polymer compounds according to the invention, which are designed for film production, since these may react with the polyesters used according to the invention in the film production and, on the one hand, to a large molecular weight decrease due to hydrolysis of the polymer Polyester can lead (therefore, the production of the film is problematic or impossible), and on the other hand, even by the superficial conversion of the MgO component in Mg (OH) 2 , the particles lose significantly in thermal conductivity.
  • hBN hexagonal boron nitride Due to the inert structure of the hexagonal boron nitride (hBN), the interactions at its interface can not be significantly increased with the help of compatibilizers (such as aminosilanes). Such compatibilizers can not sufficiently interact with hBN, whether through covalent bonding or van der Waals forces.
  • compatibilizers such as aminosilanes
  • rutile results in increased abrasion on the film extrusion tools, although this is still tolerable.
  • rutile is also formed Voids (bubbles) to parts of the particles, so that through the use of rutile also no appreciably increased thermal conductivity can be achieved in the films.
  • Crystalline Si0 2 and / or crystalline silicates such as quartz, kyanite or cristobalite, have surprisingly proven to be suitable for the first filler, while amorphous SiO 2 and amorphous silicates do not lead to an increase in the thermal conductivity.
  • Cristobalite is z. Available as filler from Quarzwerke GmbH (Frechen, Germany) under the brand name Silbond® Cristobalit (eg 8000 RST).
  • the filler has the same thermal conductivity in all spatial directions and is thus particularly well suited for polymer compounds for the production of films.
  • the Mohs hardness of cristobalite of about 6.5 is comparable to that of glass fibers. Due to the cubic filler form, however, the wear behavior of the filler compared to glass fibers is much lower and thus more favorable.
  • suitable thermally conductive particles are also crystalline aluminosilicate, preferably Al 2 O 3 -SiO 2 , particularly preferably in the form of kyanite.
  • Kyanite proves to be particularly suitable due to its high thermal conductivity in all directions and its relatively low Mohs hardness of 4.5 - 7 (depending on the crystal direction) and especially its good integration into the polyester matrix.
  • Suitable Kyanitp particles are z. B. from Quarzwerke GmbH under the brand name Silatherm® available.
  • polymer compounds in which the kyanite particles have a triclinic crystal structure and / or the cristobalite particles have a tetragonal or cubic crystal structure are particularly preferred.
  • Quartz is also suitable as a filler of the polymer compounds according to the invention, but has a slightly lower thermal conductivity compared with cristobalite and kyanite.
  • the Mohs hardness is about 7.
  • the polymer content of the polymer compound is preferably about 50% by weight or more.
  • the proportion of the thermoplastic polyester in the polymer content of the polymer compound is preferably about 75% by weight or more.
  • thermoplastic polyester In addition to the thermoplastic polyester other polymers such. As polyamides, polyimides, polyetherimides (such. As Ultem ® from Sabic) or Polycarbona- te be contained in the inventive polymer compound.
  • polyamides polyimides
  • polyetherimides such as Ultem ® from Sabic
  • Polycarbona- te be contained in the inventive polymer compound.
  • their shares lead, except for the proportions of polyetherimides, almost always due to their poor miscibility with polyesters to a significantly deteriorated running safety of the extrusion equipment and a poorer thermal conductivity or possibly significantly higher costs (as in particular Poiyetherimiden).
  • the plastic material of the compound preferably consists predominantly of polyethylene terephthalate, but this preferably contains at least one co-monomer.
  • thermoplastic polyester preferably about 80 mol .-%, more preferably to about 83 mole% or more, more preferably about 88 mole% or more, of ethylene glycol and terephthalic acid units.
  • naphthalene-2,6-dicarboxylic acid has over the use of terephthalic acid the advantage of a higher long-term heat resistance at significantly higher raw material price, so that - due to the higher price of naphthalene-2,6-dicarboxylic acid - this is usually dispensed with.
  • the remaining monomer units are referred to as co-monomers and are preferably selected from other aliphatic, cycloaliphatic or aromatic diols or dicarboxylic acids.
  • Suitable other aliphatic diols are, for example, diethylene glycol, triethylene glycol, aliphatic diols of the general formula HO- (CH 2 ) n -OH, where n is preferably less than 10, for example butanediol and propanediol, and the cycloaliphatic cyclohexanedimethanol.
  • Suitable other dicarboxylic acids are, for. B. isophthalic acid, adipic acid, etc.
  • the diol component of the thermoplastic polyester is about 5 mol% or less, preferably about 3 mol% or less
  • the dicarboxylic acid component of the thermoplastic polyester to about 12 mol .-% or less, preferably to about 10 mol .-% or less, and ideally to about
  • IPA isophthalic acid
  • the diol component of the thermoplastic polyester to about 2 mol .-% or less, ideally to about
  • the stretchability of the film to be produced and the incorporation of the particles of the filler can be on the other hand by the use of co-monomers, such as. As isophthalic acid and diethylene glycol, improve.
  • the diethylene glycol content is therefore about 0.6 mol% or more, more preferably about 0.9 mol% or more, and ideally about 1.3 mol% or more, each based on the diol component of the thermoplastic polyester.
  • the isophthalic acid content based on the dicarboxylic acid component, in preferred embodiments is about 1 mol% or more, preferably about 1.5 mol% or more, and ideally about 2 mol%. % or more.
  • the filler particles used according to the invention can be used with and without surface modification.
  • surface modification preference is given to using organosilanes, in particular methacrylsilanes, trimethylsilanes and methylsilanes, and more preferably epoxysilanes and aminosilanes, and in each case combinations thereof.
  • the incorporation of the filler particles into the polyester matrix can be further improved, resulting in a further reduction in voids formation. Furthermore, surface modification also improves the uniformity of the distribution of the filler particles in the polyester matrix. This also has a positive effect on mechanical properties such. As tensile strength, Young's modulus, elongation at break, elongation at break and impact resistance.
  • the filler particles of the first filler have a particle size distribution with a d 50 value of about 15 ⁇ m or less, preferably about 10 ⁇ m or less, and particularly preferably about 6 ⁇ m or less.
  • the d 50 value is preferably above about 0.1 ⁇ m, and particularly preferably at about 0.5 ⁇ m or more.
  • the d 98 value of the particle size distribution of the particles is about 40 pm or less, preferably about 25 pm or less and more preferably about 15 pm or less.
  • the dgs value is more than about 40 pm, the largest particle fraction causes breaks in the stretching process.
  • variations in the melt viscosity and the melt pressure result.
  • the melt film is subject to width variations, which makes it difficult to insert the film into the clip chain of the combination frame.
  • the polymer compound according to the invention may also contain a second filler which is selected in particular from boron nitride, more preferably hexagonal boron nitride, and optionally magnesium oxide. If appropriate, larger d 50 values in the particle size distribution can also be tolerated for the second filler. The upper limit for the d 5 o value is about 60 pm.
  • magnesium oxide is generally less suitable for polymer compounds according to the invention which are used for film production.
  • the polymer compound comprises as the first filler about 10 to about 30% by weight of crystalline SiO 2 and / or silicate particles and as the second filler about 5 to about 15% by weight of hexagonal particulate Boron nitride, preferably about 12 to about 25 wt .-% crystalline Si0 2 - and / or silicate particles and about 6 to about 10 wt .-% hexagonal particulate boron nitride.
  • the hexagonal boron nitride preferably has a particle size distribution with a d 5 o value of about 15 pm or less, preferably of about 6 pm or less.
  • the polymer compound according to the invention may contain at least one radical scavenger, wherein the content of radical scavenger in the range of about 100 to about 5000 ppm, preferably from about 400 to about 2000 ppm, more preferably from about 500 to about 1200 ppm, in each case based on the mass of the polymer compound.
  • the radical scavenger preferably contains a phenolic antioxidant having the structural element (I) (I) wherein R is an organic radical, and wherein the molecular weight of the radical scavenger is about 300 g / mol or more, preferably about 500 g / mol or more, more preferably about 700 g / mol or more.
  • Polymer compounds according to the invention preferably have a thermal conductivity of about 0.3 W m "1 " “1 or more, preferably of about 0.35 W m “ 1 " “ 1 or more, particularly preferably about 0.45 W m “1 " “1 or more (measured on a specimen prepared from the polymer compound (engineering film) having a thickness of 150 ⁇ m, perpendicular to the specimen-body plane).
  • the polymer compound according to the invention should have a low electrical conductivity, so that an electrical breakdown strength of the test piece produced from the polymer compound with a thickness of 150 pm of about 90 kV mm "1 or more according to DIN 40634 (at 23 ° C and AC), the test piece having a unidirectional orientation.
  • the polymer compounds according to the invention are used according to the invention for the production of at least monoaxially oriented, single- or multilayer polyester films, which in particular have a thermal conductivity of about 0.3 W m "1 K " 1 or more perpendicular to the film plane.
  • the films preferably contain about 10 to about 45 wt .-% of a particulate filler having a particle size distribution with a d 5 o value of about 0.1 to about 15 m.
  • the polymer content of the film is preferably approx.
  • thermoplastic polyester 50 wt .-% or more, which in turn preferably consists of about 75 wt .-% of a thermoplastic polyester.
  • the polymer compound according to the invention can be used at Golfstoffblock up to about 45 wt .-% easily directly for the production of films, at higher Rudstoffpol the polymer compound of the invention is often processed as a masterbatch together with other polymer portions to films.
  • the total film thickness is typically about 9 pm to about 400 pm.
  • the film thickness is about 100 pm to about 350 pm, most preferably about 120 pm to about 300 pm. If the film thickness is less than about 9 pm, then the film with the above-described fill levels of crystalline Si0 2 and / or silicate particles can not be produced in a process-safe manner and is moreover suitable only for low-voltage applications. Above a film thickness of about 400 pm, production on existing polyester systems is no longer economical, and the films can no longer be cooled sufficiently fast on a cooling roller.
  • foils than 400 .mu.m are required for high-voltage applications, preferably several layers of the foil according to the invention are glued or laminated together using suitable methods.
  • the films of the polymer compounds according to the invention have a thermal conductivity of preferably about 0.35 W m "1 K “ 1 or more and ideally of about 0.45 W m "1 K “ 1 or more.
  • a thermal conductivity preferably about 0.35 W m "1 K “ 1 or more and ideally of about 0.45 W m "1 K “ 1 or more.
  • the advantage that is achieved by the higher thermal conductivity is usually no longer sufficiently large to compensate for the economic disadvantage caused by the introduction of large amounts of particles.
  • These amounts of particles reduce both the mechanical strength and the dielectric strength of the films and increase the cost of production both by the proportion of costs attributable to them and by a reduction in the running safety of the film systems.
  • the proportion of particles introduced to increase the thermal conductivity is about 10% by weight or more, preferably about 12% by weight or more, and ideally about 13% by weight or more.
  • the upper limit of the proportion of the particles used in the invention in the film is often about 45 wt .-% or less, preferably about 40 wt .-% or less, and ideally about 37 wt .-% or less.
  • thermal conductivity of the film does not lead to a significant increase in the thermal conductivity of the film for the reasons described above. Surprisingly, however, a further increase in the thermal conductivity can be achieved in combination with the crystalline particles used according to the invention.
  • the particle size (d 50 value) of boron nitride is about 15 ⁇ or less, preferably about 6 ⁇ or less, and ideally about 3 microns or less.
  • Suitable BN particles are z. B. as NX1 from Momentive Materials available.
  • the films produced from the polymer compounds according to the invention are either single-layered or multi-layered, it being necessary to ensure in the case of a multi-layered structure that the Si0 2 and / or silicate particles used according to the invention are distributed as evenly as possible over the respective layers.
  • concentration of the Si0 2 and / or silicate particles in one or both outer layer (s) can be increased while the content of the Si0 2 and / or silicate particles in the outer layer (s) is increased Inner layer / s, are reduced, wherein about 90% of the film thickness or more should be represented by the at least one or more inner layer / s. Care must be taken to ensure that the entire content of thermally conductive filler within the range according to the invention of about 10 to about
  • the film is single-layered, since in single-layer embodiments, the homogeneous distribution of the thermally conductive filler according to the invention can be realized particularly efficiently.
  • the film is at least two-layered, with at least one of these layers making up less than about 10% of the total thickness, this layer being a cover layer (outer layer) and less than about 10% by weight of the SiO 2 used according to the invention and / or silicate particles and preferably contains less than about 5 wt .-% of Si0 2 - and / or silicate particles used in the invention.
  • this causes a slight deterioration of the thermal conductivity of the film, but leads to a significant improvement in the elongation at break and dielectric strength of the film.
  • the polymer compound according to the invention can be modified for this purpose with an additional polymer fraction.
  • the so-called SV value of the film is of great importance.
  • the SV value is defined in more detail in the context of the examples.
  • the mean value of the SV value of the polyester raw materials used is therefore about 600 or more, preferably about 700 or more and in particular about 750 or more.
  • the SV value of the raw materials used is preferably about 1000 SV or less, more preferably about 950 SV or less and in particular about 920 SV or less. If the value is more than 1000, usually no economic production is possible on conventional polyester film systems, since the extruders exceed their maximum power consumption at the usual throughputs and therefore the throughputs would have to be greatly reduced.
  • the degradation is about 150 or less, preferably about 100 or less and in particular about 50 SV units or less (see also conditions of the manufacturing process in the following examples).
  • the RTI can be positively influenced by further measures.
  • the polymer compound about 100 to about 5000 ppm of a radical scavenger (a thermal oxidation stabilizer) are added, the content preferably about 400 about 2000 ppm and in particular about 500 to about 1200 ppm.
  • a radical scavenger a thermal oxidation stabilizer
  • Lower contents than about 50 ppm lead to no measurable improvement in the thermal stability and higher contents than about 5000 ppm have no further improving effect on the thermal stability of the film to be produced and therefore only reduce the economic efficiency.
  • Contents above about 1200 ppm also tend to lead to the formation of gels with a high stabilizer content and a yellowish tinge.
  • radical scavengers it is possible to use-preferably-a compound as well as, less preferably, a mixture of different radical scavengers.
  • the radical scavenger (s) used are preferably selected from the group of the phenolic antioxidants or from the group of the antioxidants which contain at least the following structural element:
  • R is various organic radicals, which are explained in the context of the following examples.
  • radical scavengers have low toxicity and good properties as radical scavengers and are therefore preferred radical scavengers for the purposes of the invention: a) 5,7-di-tert-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2 -one (80 to
  • CAS-No. 88-24-4 2,2'-methylenebis (4-ethyl-6-tert-butylphenol);
  • CAS-No. 991-84-4 2,4-bis (octylmercapto) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine;
  • CAS-No. 1709-70-2 1, 3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene;
  • CAS-No. 4130-42-1 2,6-di-tert-butyl-4-ethylphenol
  • CAS-No. 25013-16-5 tert -butyl-4-hydroxyanisole
  • CAS-No. 27676-62-6 1, 3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H ) -trione;
  • CAS-No. 32509-66-3 ethylene glycol bis [3,3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate];
  • CAS-No. 32687-78-8 N, N'-bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propynyl) hydrazide;
  • CAS-No. 35074-77-2 1,6-hexamethylene-bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate),
  • CAS-No. 35958-30-6 1,1-bis (2-hydroxy-3,5-di-tert-butylphenyl) ethane;
  • CAS-No. 36443-68-2 triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate];
  • CAS-No. 36443-68-2 triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate];
  • CAS-No. 40601-76-1 thiodiethanol bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate);
  • CAS-No. 57569-40-1 terephthalic acid
  • CAS-No. 70331-94-1 2,2'-oxamido-bis [ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate];
  • CAS-No. 110675-26-8 2,4-bis (dodecylthiomethyl) -6-methylphenol.
  • Radical scavengers with the structural element preferred according to the invention should have a molecular weight of about 300 g / mol or more and more preferably of about 500 g / mol or more, and ideally of about 700 g / mol or more, since compounds with lower molecular weights among the for polyester typical processing temperatures have too high volatility and so partially evaporate during film production. This can lead to problems in the production (vapor development, odor, blistering in the film, etc.) and also has the disadvantage of a higher migration tendency from the film. This applies, inter alia, to the compounds with the CAS numbers mentioned in the above list: 2082-79-6, 25013-16-5, 128-37-0.
  • Compounds having a molecular weight below 300 g / mol are therefore preferably used at less than 500 ppm and more preferably at less than 300 ppm, and ideally not at all.
  • Compounds having a molecular weight of about 500 g / mol or less are therefore preferably used at about 1000 ppm or less and more preferably at about 500 ppm or less, and ideally not at all.
  • radical scavengers with nitrogen in the empirical formula are preferably used at about 1000 ppm or less, more preferably at about 500 ppm or less, and ideally not at all.
  • Radical scavengers with sulfur in the empirical formula have a characteristic, rather unpleasant odor in the manufacture of the film and are therefore less preferred. Radical scavengers with sulfur in the empirical formula are preferably used at about 500 ppm or less, more preferably at about 300 ppm or less, and ideally not at all.
  • the radical scavenger (s) can be added to the polyester both directly during polymer preparation and later by incorporating the compounds into a finished polymer. lyester be added. When incorporated into a finished polyester, CAS no. 1709-70-2 (Irganox 1330) proved to be particularly suitable, as no blistering or vapor evolution was observed.
  • thermoplastic polyester of the film has a low carboxyl end group content (CEG). In a preferred embodiment, this is about 40 mmol / kg or less for the polymer compound processed to the film, more preferably about 30 mmol / kg or less, and ideally about 27 mmol / kg or less.
  • Low carboxyl endgroup contents may be e.g. B. by using polyester raw materials with Carbox xylenend phenomenon contents of about 20 mmol / kg or less in the polymer compound and subsequent gentle extrusion can be achieved.
  • Gentle extrusion means low temperature, preferably below 300 ° C., in the discharge zones of the extruders used and high extruder fill levels at low speed (applies to twin-screw extruders) or good predrying (single-screw extruder) and degassing of the melt (twin-screw extruder ).
  • the low CEG value may also preferably be obtained via a catalytic decarboxylation, such as e.g. in EP 2 251 371 A2, can be achieved. Less preference is given to the setting of low CEG contents by adding a hydrolysis protection agent, as described, for example, in EP 2 184 311 A1.
  • the film is oriented at least uniaxially.
  • the RTI value no longer increases. Below a surface stretch ratio of about 2, neither the inventive RTI values nor the dielectric strength according to the invention can be achieved.
  • the area stretch ratio is therefore included about 2 or more, preferably about 3 or more, and ideally about 5 or more.
  • the area stretch ratio is about 16 or less, more preferably about 14 or less, and ideally about 13 or less.
  • the elongation at break of the film is preferably in the longitudinal and transverse directions at about 5% or more, more preferably at about 15% or more, and ideally at about 20% or more. If the elongation at break is less than 5%, the film in the further processing, such as. B. in the folding in engine foil (insulating film in the engine), break easily and is therefore no longer usable for most applications.
  • modulus of elasticity is at least one film direction at about 1000 N mm “2 or more, preferably about 1500 N mm" 2 or more and most preferably about 2000 N mm “2 or more. Particularly preferred achieved in both directions on the film.
  • an e-modulus of about 1000 N mm "2 or less consists in processing processes, the danger of excessive Verstre- ckung of the film, which would lead to a significant decrease in the electrical breakdown strength.
  • the novel polymer compound processed into polyester films preferably has a dielectric strength of about 90 kV mm -1 or more, more preferably about 100 kV mm -1 or more, and ideally about 110 kV mm -1 or more.
  • the dielectric strength according to the invention is achieved by setting the surface stretch ratios in the range according to the invention, wherein the dielectric strength increases up to an area stretch ratio of about 5, but decreases again above about 12.
  • the dielectric strength is further adjusted by the targeted selection of the co-monomers (molar ratio) in the range according to the invention.
  • the dielectric strength is significantly lower. If contents of thermally conductive particles are used above the ranges according to the invention, the dielectric strength desired according to the invention can not be achieved.
  • the polyester film of the present invention has a Relative Temperature Index (RTI value) of about 90 or more.
  • the RTI value correlates with the temperature in ° C at which the film fails in continuous use.
  • the RTI value of the film is about 90 or more, preferably about 95 or more and ideally about 105.
  • the RTI value increases with increasing draw ratio and decreases with increasing co-monomer content , Within the ranges of these values according to the invention, the RTI values desired according to the invention are achieved.
  • the RTI value is, as described above, further positively influenced by the use of thermal oxidation stabilizers and the use of hydrolysis-stable fillers or stabilizers.
  • the film to be produced according to the invention is outstandingly suitable for use in backside laminates of solar modules, the film in this case having a thickness of about 100 ⁇ m or more.
  • the film according to the invention is the use as a motor foil for electrical insulation of electric motors.
  • the film is about 96 ⁇ m thick or more, preferably about 150 ⁇ m thick or more.
  • the Heat can be dissipated from the motor faster, reducing the resistance in the motor coil and consuming less power from the motor. In addition, overheating of the engine is avoided.
  • the thickness here is usually about 50 pm or less.
  • Bulbs such. B. LED lamps.
  • the surface and the contact to the next medium for the heat dissipation are of crucial importance.
  • the contact between the film and the next surface should be as gap-free as possible and without trapping air.
  • the polyester film is modified and provided with a described contact medium in order to improve the contact and thus the heat dissipation to the next surface.
  • this surface is the encapsulation material, for example made of EVA or silicone, or, in the case of motor insulation, another insulation material for improving the thermal class.
  • polyester polymers of the individual layers are prepared by polycondensation, either starting from dicarboxylic acids and diols or else starting from the esters of dicarboxylic acids, preferably the dimethyl esters, and a diol.
  • Suitable polyesters preferably have so-called SV values in the range from about 500 to about 1300, the individual values being less important, but the average SV value of the raw materials used must be about 600 or greater and preferably about 1000 or less is.
  • thermally conductive fillers also referred to below as heat-conducting pigments, as well as any additional additives which may be present, can already be added during the preparation of the polyester.
  • the particles are dispersed in the diol, optionally ground, decanted and the reactor - either in (re) esterification or polycondensation - added.
  • a concentrated particle-containing or additive-containing polyester masterbatch can be prepared with a twin-screw extruder and diluted in the film extrusion with particle-free polyester. It has proved to be advantageous if no masterbatch is used which contains less than 30 wt .-% polyester.
  • the masterbatch containing Si0 2 and / or silicate particles should not be more than 50% by weight of Si0 2 and / or silicate (because of the risk of gel formation).
  • Another possibility is to add particles and additives directly during film extrusion in a twin-bladed extruder.
  • the polyester or the polyester mixture of the layer - or in multilayer films the individual layers - compressed in extruders and liquefied.
  • the melt (s) are / are added in a single or multi-layer die formed flat melt films, pressed through a slot die and withdrawn on a chill roll and one or more take-off rolls, wherein it cools and solidifies / en.
  • the melt at the respective extruder outputs should not be warmer than 305 ° C., preferably not warmer than 300 ° C., since this facilitates the achievement of the RTI values according to the invention. These temperatures are achieved by cooling the discharge zones of the extruder and / or by setting a low extruder speed while maintaining a high degree of filling of the extruder (applies to twin-screw extruder).
  • the film according to the invention is oriented at least uniaxially, ie. at least uniaxially stretched.
  • stretching is most often performed sequentially.
  • the stretching in the longitudinal direction can be carried out with the help of two according to the desired stretch ratio at different speeds rolling.
  • a corresponding clip frame For cross-stretching is generally used a corresponding clip frame.
  • the temperature at which the stretching is carried out may vary within a relatively wide range and depends on the desired properties of the film.
  • the stretching is carried out in the longitudinal direction in a temperature range of 80 to 130 ° C (heating temperatures 80 to 130 ° C) and in the transverse direction in a temperature range of 90 ° C (start of stretching) to 140 ° C (end of stretching).
  • the stretching temperature in MD and TD
  • the stretching temperature is below 125 ° C., preferably below 118 ° C.
  • one or both surfaces of the film can be coated in-line according to the methods known per se.
  • the in-line coating can be used, for example, to apply an adhesion promoter or to apply a coating.
  • the film is stretched over a period of about 0.1 to 10 s under tension at a temperature of about 0.1 to 10 s. temperature of 150 to 250 ° C and to achieve the desired
  • Shrinkage and elongation values relaxed by at least 1%, preferably at least 3% and particularly preferably at least 4% in the transverse direction, if a transverse orientation was carried out.
  • This relaxation preferably takes place in a temperature range from 150 to 190.degree. Subsequently, the film is wound in the usual manner.
  • the film according to the invention obtained by the process described above, preferably at 150 ° C has a shrinkage in the longitudinal and transverse directions of less than 6%, preferably less than 2% and particularly preferably less than 1.5%.
  • This film also has at 100 ° C a thermal expansion of less than 3%, preferably less than 1% and more preferably less than 0.3%.
  • This dimensional stability can be obtained, for example, by suitable relaxation of the film before winding (see process description). This dimensional stability is important in order to avoid re-shrinking of the strip cut film when used in motors, which could lead to a lack of electrical insulation at the edges of the motor.
  • the compounds of the invention are suitable not only for the production of films, but also for the production of moldings for a variety of applications in which both a good thermal conductivity and a sufficient dielectric strength is important.
  • the preferred production methods for such molded articles include injection molding, profile extrusion, sheet or panel extrusion, pipe extrusion, cable extrusion, spun yarn and monofilament making, calendering, pressing, extrusion blow molding, injection blow molding, stretch blow molding, die casting Thermoforming and rotational molding.
  • filler materials for the second filler do not apply or only to a lesser extent.
  • MgO materials, including spinel can be used as the second filler in the polymer compounds according to the invention.
  • the determination of the mean diameter d 50 is carried out by means of a Malvern Master Sizer 2000 on the particulate filler to be used.
  • the samples are then placed in a cuvette with water and then placed in the meter.
  • the dispersion is determined by laser and the particle size distribution is determined from the signal by comparison with a calibration curve.
  • the measuring process is automatic and includes the mathematical determination of the d 50 value.
  • the d 50 value is determined from the (relative) cumulative curve of the particle size distribution: the intersection of the 50% ordinate value with the cumulative curve gives the desired d 5 o value on the abscissa axis.
  • the dgs value is defined by the intersection of the 98% ordinate value.
  • the standard viscosity in dilute solution SV was measured, based on DIN 53 728 part 3, in an Ubbelohde viscometer at (25 ⁇ 0.05) ° C.
  • the solvent used was dichloroacetic acid (DCE).
  • the concentration of the dissolved polymer was 1 g of polymer / 100 ml of pure solvent.
  • the proportion of particles in the film or the polymer raw material was determined by means of ash determination and corrected by appropriate extra scale. That :
  • the mechanical properties were determined by means of a tensile test based on DIN EN ISO 572-1 and -3 (specimen type 2) on 100 mm ⁇ 15 mm film strips.
  • the thermal shrinkage was determined on square film samples with an edge length of 10 cm. The samples were cut so that one edge ran parallel to the machine direction and one edge perpendicular to the machine direction. Samples were accurately measured (edge length L 0 was determined for each machine direction TD and MD, L 0 TD and L 0 MD ) and annealed for 15 minutes at the specified shrinkage temperature (here 150 ° C) in a convection oven. The samples were taken and measured accurately at room temperature (edge length L TD and L MD ) - The shrinkage results from the equations:
  • Thermal Interface Material To determine the thermal conductivity of films, the "Thermal Interface Material” process is used on the TIMA device from Powell Nanoest und Design GmbH, described in WO 2012/107355 A1.
  • the film surface is first coated on both sides with a paste to exclude surface effects such as roughness and to produce the best possible contact between the sample and the meter.
  • the paste has a known thermal conductivity.
  • Suitable for this is, for example, the silicone thermal compound "Dow Corning® 340 Heat Sink Compound".
  • the thus prepared sample is clamped at a constant pressure of 600 kPa and room temperature between two reference bodies per CuZn - CuZn.
  • the contact area is 132.7 mm 2 .
  • a reference body is in turn connected to a heating source, which is heated to 100 ° C.
  • the other reference body is located on a réelleabieiter with a temperature of 15 ° C.
  • the temperature profile is measured. This results in the thermal interface resistance of the system Rth, totai, from which one obtains the thermal interface resistance of the sample R t h, fiim.
  • the thermal conductivity ⁇ can be determined perpendicular to the sample plane.
  • the samples are stored in a U m Kunststoff oven at least three different temperatures.
  • a property value elongation at break, referred to the initial value before being fitted in the U ml air heating cabinet
  • the respective time is determined at which this property value has reached a defined limit value ( ⁇ 2%).
  • the elongation at break is determined on the basis of DIN EN ISO 572-1 and -3 (test specimen type 2) on 100 mm ⁇ 15 mm wide film strips.
  • the evaluation of such tests is carried out by plotting the property value over the storage period.
  • the storage times at which the samples fail at the respective temperature are plotted semilogarithmically against reciprocal storage temperature (in K -1 )
  • the temperature is read from the diagram, which corresponds to a service life of 20,000 hours, and named as the temperature index RTI.
  • the dielectric strength is measured according to DI N 53481-3 (taking into account DIN 40634 for the special foil instructions). It is measured by means of ball / plate (electrode diameter 49.5 mm) at a sinusoidal alternating voltage of 50 Hz at 23 ° C and 50 relative air humidity in air. The dielectric strength is measured according to IEC 60674 with 20 mm ball, 50 mm plate and 50 Hz AC and averaged over 10 measuring points.
  • the polymer compounds are melted at 292 ° C and applied electrostatically through a slot die on a cooled to 50 ° C cooling roller. It is then stretched longitudinally and then transversely under the following conditions:
  • PET1 polyethylene terephthalate of ethylene glycol and terephthalic acid with an SV value of 1100 and DEG content of 0.9 mol% (diethylene glycol content with respect to the diol component).
  • PET2 polyethylene terephthalate from ethylene glycol and terephthalic acid with an SV value of 840.
  • PET3 polyethylene terephthalate having an SV value of 830 and containing 22.4 mol% of isophthalic acid (with respect to the dicarboxylic acid component).
  • PEN polyethylene naphthalate with an SV value of 580.
  • PET4 polyethylene terephthalate with an SV value of 580 and a content of 50% by weight aluminum nitride AB 253753 AIN with a d 50 value of 55 ⁇ m (H C. Starck, Kunststoff Germany). The particles were incorporated into the polyethylene terephthalate PET1 in a twin-screw extruder.
  • PET5 polyethylene terephthalate with an SV value of 550 and a content of 50% by weight of hexagonal boron nitride BN GRADE B50 with a d 50 value of the primary particles of 10 ⁇ m (HC Starck, Kunststoff, Germany). The particles were incorporated into the polyethylene terephthalate PET1 in a twin-screw extruder.
  • PET6 polyethylene terephthalate with an SV value of 580 and a content of 50% by weight SILBOND® 8000 RST silicon dioxide particles with a d 50 value of 2 ⁇ m (Quarzwerke GmbH, Frechen Germany). The Si0 2 particles were incorporated into the polyethylene terephthalate PET1 in a twin-screw extruder.
  • PET7 polyethylene terephthalate of ethylene glycol and terephthalic acid having an SV of 870 and a carboxyl end group of 10 mmol / kg.
  • PET8 polyethylene terephthalate with 5000 ppm Irganox 1330 CAS no. 1709-70-2 (manufacturer: BASF Switzerland), incorporated by means of a twin-screw extruder in PETl, SV value 780.
  • Example V2 which has not proved to be suitable for the film production, is very well suited according to the invention for the production of moldings, in the manufacturing process, the running safety of a film extruder and the occasional observed in films outlines have no meaning.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un composé polymère à base de polyester, qui permet de fabriquer des corps façonnés et en particulier des feuilles de polyester présentant une conductibilité thermique augmentée d'environ 0,3 W m-1 K-1 ou plus, les feuilles pouvant être orientées au moins de manière uniaxiale et présentant en outre une rigidité diélectrique d'environ 90 kV mm-1 ou plus selon la norme DIN 40634 (à 23°C et avec une tension alternative (AC)). Le composé polymère comprend un polyester thermoplastique et une première charge en une proportion d'environ 7 à environ 80 % en poids, par rapport au poids total du composé, la première charge présentant une répartition granulométrique présentant une valeur d50 d'environ 0,1 à environ 15 μm et la première charge comprenant du SiO2 cristallin et/ou un silicate cristallin, en particulier choisi parmi le quartz, la kyanite et la cristobalite.
PCT/EP2017/076199 2016-10-17 2017-10-13 Composés polymères pour la fabrication de feuilles de polyester présentant une conductibilité thermique augmentée Ceased WO2018073123A1 (fr)

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DE102016119751.3A DE102016119751A1 (de) 2016-10-17 2016-10-17 Polymer-Compounds für die Herstellung von Polyester-Folien mit erhöhter Wärmeleitfähigkeit

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EP3904048A4 (fr) * 2018-12-27 2022-09-28 Oji Holdings Corporation Film de résine thermoplastique amorphe, film métallisé de condensateur, rouleau de film et condensateur

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WO2009064873A1 (fr) 2007-11-16 2009-05-22 E. I. Du Pont De Nemours And Company Composition de résine plastique thermoconductrice
EP2184311A1 (fr) 2008-11-11 2010-05-12 Mitsubishi Polyester Film GmbH Feuille de polyester résistante à l'hydrolyse orientée de manière bi-axiale contenant des dérivés d'acide gras époxydes et un prolongateur de chaîne, ainsi que son procédé de fabrication et d'utilisation
EP2251371A2 (fr) 2009-05-15 2010-11-17 Mitsubishi Polyester Film GmbH Feuille de polyester étirée biaxialement comprenant un catalyseur de décarboxylation, son procédé de fabrication et utilisation dans des applications d'isolation électrique
DE102010005020A1 (de) * 2010-01-19 2011-09-01 Continental Automotive Gmbh Wärmeleitendes Kompositmaterial, Formkörper hieraus sowie Verwendungszwecke
WO2012107355A1 (fr) 2011-02-09 2012-08-16 Robert Bosch Gmbh Procédé et système de mesure pour la caractérisation d'un matériau d'interface thermique
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EP2184311A1 (fr) 2008-11-11 2010-05-12 Mitsubishi Polyester Film GmbH Feuille de polyester résistante à l'hydrolyse orientée de manière bi-axiale contenant des dérivés d'acide gras époxydes et un prolongateur de chaîne, ainsi que son procédé de fabrication et d'utilisation
EP2251371A2 (fr) 2009-05-15 2010-11-17 Mitsubishi Polyester Film GmbH Feuille de polyester étirée biaxialement comprenant un catalyseur de décarboxylation, son procédé de fabrication et utilisation dans des applications d'isolation électrique
DE102010005020A1 (de) * 2010-01-19 2011-09-01 Continental Automotive Gmbh Wärmeleitendes Kompositmaterial, Formkörper hieraus sowie Verwendungszwecke
WO2012107355A1 (fr) 2011-02-09 2012-08-16 Robert Bosch Gmbh Procédé et système de mesure pour la caractérisation d'un matériau d'interface thermique
EP2878619A1 (fr) * 2013-12-02 2015-06-03 LANXESS Deutschland GmbH Compositions de polyester
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