Compositions, extruded films, capacitors and metallized films

Abstract

To provide an extrusion composition that exhibits an improved ability to be extruded as a film having a thickness of less than 10 μm. The polycarbonate polysiloxane contains a first carbonate unit derived from bisphenol A, a second carbonate unit derived from bisphenol isophorone, and a third carbonate unit derived from a terminally arylated polysiloxane. The polycarbonate polysiloxane is useful for forming thin extruded films, which are in turn useful for fabricating electrostatic film capacitors.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application was filed on May 1, 2020, both of which are incorporated herein by reference in their entirety. Claiming the benefit of U.S. Provisional Patent Application No. 63 / 023,904, filed September 3, 2020 Priority is claimed to European Patent Application No. 20196451.7 filed on the 16th.

[0002] The present application relates to a heat-resistant extruded film, a film capacitor including the extruded film, and a method for manufacturing the extruded film. The present invention relates to a heat-resistant polycarbonate polysiloxane useful for forming films. [Background technology]

[0003] Electrostatic film capacitors with high volumetric energy density, high operating temperature and long life are essential components in pulsed power, automotive and industrial electronics. essentially a device that has two parallel conductive plates separated by a thin layer of electrically insulating (dielectric) film When a voltage is applied across the plates, the electric field in the dielectric It transfers charge and thus stores energy. Energy stored in a capacitor The amount of dielectric constant and breakdown voltage of the insulating material used to form the film and the dimensions of the film (total area and thickness). To maximize the amount of energy, the dielectric constant and breakdown voltage of the film are maximized, The thickness of the film is minimized. The physical properties of the dielectric material in the capacitor determine the performance of the capacitor. The determining factor is the improvement of one or more of the physical properties of the dielectric material in the capacitor. The improvement can result in a corresponding improvement in performance in capacitor components, typically in electronic devices. This enhances the performance and lifespan of the device system or the product in which it is embedded. Summary of the Invention [Problem to be solved by the invention]

[0004] High temperature polycarbonate copolymers have been used to form electrostatic film capacitors. For example, U.S. Patent Application Publication No. 2016 / 0060403 to Mahood et al. See U.S. Patent Application Publication No. 2019 / 0153217A1 and U.S. Patent Application Publication No. 2019 / 0153217A1. and extrusion compositions that exhibit an improved ability to be extruded as films having thicknesses of less than 10 μm. The finished product is in demand. [Means for solving the problem]

[0005] One embodiment is a polycarbonate polysiloxane in which the total carbonate units are 100 mol %. against [ka] (In the formula, R 1 is C6~C 16 is a divalent aromatic group 20 to 69.95 mol % of a first carbonate unit having the structure [ka] [In the formula, R 2 teeth [ka] JPEG0007779808000004.jpg28126 (in the formula, R f and R g are independently generated for each occurrence, C1 to C 12 Alkyl, C1-C 12 Alkoxy or C2-C 12 alkenyl, and each Rh is hydrogen, or R appears twice h together with the carbon atom to which they are attached to form a carbonyl group, and each Appearance R i are independently C1-C6 alkyl, and R j is hydrogen, C1-C6 alkyl or phenyl optionally substituted with 1, 2, 3, 4 or 5 C1-C6 alkyl groups Nil and R k is independently at each occurrence C1-C3 alkyl or phenyl, preferably Mostly methyl, X b is C6~C 12 Arylene, C4~C 18 Cycloalkylene, C 4~C 18 Cycloalkylidene or -C(R m )(R n )-(wherein, R m is hydrogen, C1 ~C 12 Alkyl or C6-C 12 aryl, and R n is C6~C 10 Alkyl, C 6-C8 cycloalkyl or C6-C 12 aryl), or X b teeth- (Q a ) x -G-(Q b ) y -(in the formula, Q a and Q b are each independently C1 to C3 alkylene, G is C3-C 10 cycloalkylene, x is 0 or 1, and y is 0 or 1), and j, m, and n are each independently 0, 1, 2, 3, or 4) C having the structure 17 ~C 40 is a divalent aromatic group of the formula and 30 to 79.95 mol % of a second carbonate unit having the structure a divalent polysiloxane group, [ka] (wherein each occurrence of R 3 are independently C1 to C 13 is a hydrocarbyl group) 0.05 to 0.4 mole % of the diorganosiloxane having 5 to 60 diorganosiloxane units having the structure and a third carbonate unit of the polycarbonate polysiloxane, Carbonate polysiloxane was compared with the gel immersion test using a bisphenol A polycarbonate standard. Weight average of 18,000 to 35,000 g / mol determined by permeation chromatography a second carbon having a molecular weight of 70 to 79.95 mol % polycarbonate polysiloxane; When the polycarbonate unit is contained, the polycarbonate polysiloxane is 18,000 to 24,000 The polycarbonate polysiloxane has a weight average molecular weight of 0 g / mol.

[0006] Another embodiment is a polycarbonate polysiloxane having 100 moles of total carbonate units. For % [ka] (In the formula, R 1 is C6~C 16 is a divalent aromatic group 20 to 69.95 mol % of a first carbonate unit having the structure [ka] [In the formula, R 2 teeth [ka] JPEG0007779808000009.jpg85169 (in the formula, R f and R g are independently generated for each occurrence, C1 to C 12 Alkyl, C1-C 12 Alkoxy or C2-C 12 alkenyl, and each R h is hydrogen, or R appears twice h together with the carbon atom to which they are attached to form a carbonyl group, and each Appearance R i are independently C1-C6 alkyl, and R j is hydrogen, C1-C6 alkyl or phenyl optionally substituted with 1, 2, 3, 4 or 5 C1-C6 alkyl groups Nil and R k is independently at each occurrence C1-C3 alkyl or phenyl, preferably Mostly methyl, X b is C6~C 12 Arylene, C4~C 18 Cycloalkylene, C 4~C 18 Cycloalkylidene or -C(R m )(R n )-(wherein, R m is hydrogen, C1 ~C 12 Alkyl or C6-C 12 aryl, and R n is C6~C 10 Alkyl, C 6-C8 cycloalkyl or C6-C 12 aryl), or X b teeth- (Q a ) x -G-(Q b ) y -(in the formula, Q a and Q b are each independently C1 to C3 alkylene, G is C3-C 10 cycloalkylene, x is 0 or 1, and y is 0 or 1), and j, m, and n are each independently 0, 1, 2, 3, or 4) C having the structure 17 ~C 40 is a divalent aromatic group of the formula and 30 to 79.95 mol % of second carbonate units each having a divalent carbonate structure. The divalent polysiloxane group is a carboxylate group and a divalent polysiloxane group. [ka] (wherein each occurrence of R 3 are independently C1 to C 13 is a hydrocarbyl group) 0.05 to 0.4 mole % of the diorganosiloxane having 5 to 60 diorganosiloxane units having the structure and a third carbonate unit. Polycarbonate polysiloxane is a standard product of bisphenol A polycarbonate. 18,000-35,000 g / mol as determined by gel permeation chromatography using and the polycarbonate polysiloxane has a weight average molecular weight of 70 to 79.95 mol %. When the polycarbonate polysiloxane contains a second carbonate unit of 18,000, The composition has a weight average molecular weight of about 24,000 g / mol.

[0007] Another embodiment is an extruded film comprising the composition of any of the variations described herein. It is.

[0008] Another embodiment includes an extruded film and a conductive metal layer in contact with the extruded film. , a capacitor.

[0009] These and other embodiments are described in detail below. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present inventors have discovered that a specific amount of polysiloxane carbonate units and two types of aromatic carbonates are Extrusion compositions containing polycarbonate polysiloxanes as their main component, including carbonate units The product was determined to exhibit an improved ability to be extruded as a film having a thickness of 10 μm. did.

[0011] One embodiment is a polycarbonate polysiloxane in which the total carbonate units are 100 mol %. against [ka] (In the formula, R 1 is C6~C 16 is a divalent aromatic group 20 to 69.95 mol % of a first carbonate unit having the structure [ka] [In the formula, R 2 teeth [ka] JPEG0007779808000014.jpg134166 (in the formula, R f and R g are independently generated for each occurrence, C1 to C 12 Alkyl, C1-C 12 Alkoxy or C2-C 12 alkenyl, and each R h is hydrogen, or R appears twice h together with the carbon atom to which they are attached to form a carbonyl group, and each Appearance R i are independently C1-C6 alkyl, and R j is hydrogen, C1-C6 alkyl or phenyl optionally substituted with 1, 2, 3, 4 or 5 C1-C6 alkyl groups Nil and R k is independently at each occurrence C1-C3 alkyl or phenyl, preferably Mostly methyl, X b is C6~C 12 Arylene, C4~C 18 Cycloalkylene, C 4~C 18 Cycloalkylidene or -C(R m )(R n )-(wherein, R m is hydrogen, C1 ~C 12 Alkyl or C6-C 12 aryl, and R n is C6~C 10 Alkyl, C 6-C8 cycloalkyl or C6-C 12 aryl), or X b teeth- (Q a ) x -G-(Q b ) y -(in the formula, Q a and Q b are each independently C1 to C3 alkylene, G is C3-C 10 cycloalkylene, x is 0 or 1, and y is 0 or 1), and j, m, and n are each independently 0, 1, 2, 3, or 4) C having the structure 17 ~C 40 is a divalent aromatic group of the formula and 30 to 79.95 mol % of second carbonate units each having a divalent carbonate structure. The divalent polysiloxane group is a carboxylate group and a divalent polysiloxane group. [ka] (wherein each occurrence of R 3 are independently C1 to C 13is a hydrocarbyl group) 0.05 to 0.4 mole % of the diorganosiloxane having 5 to 60 diorganosiloxane units having the structure and a third carbonate unit of the polycarbonate polysiloxane, Carbonate polysiloxane was compared with the gel immersion test using a bisphenol A polycarbonate standard. Weight average of 18,000 to 35,000 g / mol determined by permeation chromatography a second carbon having a molecular weight of 70 to 79.95 mol % polycarbonate polysiloxane; When the polycarbonate unit is contained, the polycarbonate polysiloxane is 18,000 to 24,000 The polycarbonate polysiloxane has a weight average molecular weight of 0 g / mol. As used herein, the term "hydrocarbyl" may be used by itself or as a prefix, suffix or is used as a fragment of another term, and is also referred to as "substituted hydrocarbyl." Unless specifically identified as such, it refers to a residue containing only carbon and hydrogen. The alkyl residues may be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated or unsaturated. This may include aliphatic, aromatic, straight-chain, cyclic, bicyclic, branched, saturated and unsaturated hydrocarbons. It may also contain a combination of substituents. can contain heteroatoms in addition to carbon and hydrogen.

[0012] The polycarbonate polysiloxane comprises a first carbonate unit, a second carbonate unit, and a and a third carbonate unit. The first (low heat) carbonate unit is [ka] (In the formula, R 1 is C6~C 16 It has the structure of a divalent aromatic group. A homopolymer of 1 carbonate unit is melted at 20°C / Glass transition temperature below 135°C to 155°C, as determined by differential scanning calorimetry at a heating rate of 1 min. This means that it has a transition temperature.

[0013] In some embodiments, the first carbonate unit is [ka] (In the formula, R a and R b are each independently a halogen (i.e., F, Cl, Br, or I) ), C1-C3 alkyl or C1-C3 alkoxyl, and c is 0 or 1; p and q are each independently 0 or 1; a is a single bond, -O-, -S-, -S (O)-, -S(O)2-, -C(O)- or a C1 to C4 divalent hydrocarbylene group which may be cyclic or acyclic, aromatic or non-aromatic, and may contain halogen, oxygen, and further containing one or more heteroatoms selected from nitrogen, sulfur, silicon, and phosphorus. (It may be In some embodiments, c is 0. In other embodiments, c is 1. In some embodiments, c is 1 and X a C3~C6 cycloaliphatic alkylene (e.g., 1,4-cyclohexylene), C3-C6 cycloalkylidene (e.g., For example, cyclohexylidene), the formula -C(R c )(R d )(wherein, R c and R d are each C1-C6 alkylidene of the formula -C(= R e )(wherein, R eis a divalent C1-C5 hydrocarbon group). a oh and each terminal bond of the first carbonate unit is ortho, meta or para (preferably In some embodiments, p and q are each 0. In some embodiments, c is 1, p and q are each 1, and R a and R b are X a The methyl is meta-positioned to form the first carbonate unit. Some illustrative examples of dihydroxy compounds that can be used are described in U.S. Pat. No. 6,233,599 to Sun et al. Publication No. 2014 / 0295363A1 and International Patent Application ... Patent Application No. 2013 / 175448A1 and Fernandez et al. This is described in International Publication No. 2014 / 072923A1.

[0014] In some embodiments, the first carbonate unit is [ka] It is derived from bisphenol A, which has the structure do.

[0015] Polycarbonate polysiloxane is a polycarbonate polysiloxane containing The first (low heat) carbonate is present in an amount of 20 to 69.95 mol % relative to 100 mol % of the carboxylate units. Within this range, the amount of first carbonate units is 30 to 69.95 mol %; It may be 35 to 64.95 mol % or 45 to 64.95 mol %.

[0016] In addition to the first (low heat) carbonate units, the polycarbonate polysiloxane may contain: [ka] (In the formula, R 2 is C 17 ~C 40 is a divalent aromatic group The "high heat" refers to the second carbonate unit having the structure A homopolymer of the hydroxyl group unit was obtained at a heating rate of 20°C / min according to ASTM D3418-15. Glass transition above 155°C or between 155°C and 300°C, as determined by differential scanning calorimetry The second carbonate unit may be, for example, [ka] (In the formula, R f and R g are independently generated for each occurrence, C1 to C 12 Alkyl, C1-C 12 Alkoxy or C2-C 12 alkenyl, and each R h is hydrogen, or R appears twice h together with the carbon atom to which they are attached to form a carbonyl group, and each Appearance R i are independently C1-C6 alkyl, and R j is hydrogen, C1-C6 alkyl or phenyl optionally substituted with 1, 2, 3, 4 or 5 C1-C6 alkyl groups Nil and R k is independently at each occurrence C1-C3 alkyl or phenyl, preferably Mostly methyl, X b is C6~C 12 Arylene, C4~C 18 Cycloalkylene, C 4~C 18 Cycloalkylidene or -C(R m )(R n )-(wherein, R m is hydrogen, C1 ~C 12 Alkyl or C6-C 12 aryl, and R n is C6~C 10 Alkyl, C 6-C8 cycloalkyl or C6-C 12 aryl), or X b teeth- (Q a ) x -G-(Q b ) y -(in the formula, Q a and Q b are each independently C1 to C3 alkylene, G is C3-C 10 cycloalkylene, x is 0 or 1, and y is 0 or 1), and j, m, and n are each independently 0, 1, 2, 3, or 4) In some embodiments, R f and R g is, each independently at each occurrence, C1-C3 alkyl or C1-C3 alkoxyl; i is C1-C3 alkyl, and R j is methyl or phenyl, and each R k is methyl be.

[0017] Exemplary second carbonate units are [ka] JPEG0007779808000022.jpg46170 (in the formula, R f , R g , R j , m and n are defined above, and R m appears independently Each is hydrogen or C1-C4 alkyl, and g is 0, 1, 2, 3, 4, 5, 6, 7, 8 , 9 or 10) In some embodiments, R f and R g are independent of each other and each R is C1-C3 alkyl or C1-C3 alkoxyl. m is methyl , m and n are each independently 0 or 1.

[0018] In some embodiments, the second carbonate unit is [ka] or a combination thereof, wherein the first structure is 2-phenyl-3,3'- Bis(4-hydroxyphenyl)phthalimidine carbonate or PPPBP carbonate The second structure is called bisphenol isophorone carbonate or BPI carbonate. It is called carbonate.

[0019] Polycarbonate polysiloxane is a polycarbonate polysiloxane containing The second (high heat) carbonate is present in an amount of 30 to 79.95 mol % relative to 100 mol % of the carboxylate units. Within this range, the amount of the second carbonate units is 30 to 69.95 mol %; It may be 35 to 64.95 mol % or 35 to 54.95 mol %.

[0020] In addition to the first (low heat) carbonate unit and the second (high heat) carbonate unit, The recarbonate polysiloxane further comprises a third (polysiloxane-containing) carbonate unit. The third carbonate units each contain a divalent carbonate group (-OC(O)O-) and and a divalent polysiloxane group, the divalent polysiloxane group being [ka] (wherein each occurrence of R3 are independently C1 to C 14 is a hydrocarbyl group) It contains 5 to 60 diorganosiloxane units having the structure:

[0021] C1~C 14 The hydrocarbyl group may be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated It may also be aliphatic, aromatic, straight-chain, cyclic, bicyclic, branched, or unsaturated. It may contain saturated and unsaturated hydrocarbon moieties. 3 Examples of the group include C1-C1 4 Alkyl, C1-C 14 Alkoxyl, C2-C 14 Alkenyl, C2-C 14 Arke Nyloxyl, C6-C 14 Aryl, C6-C 14 Aryloxyl, C7-C 14 a Aryl alkyl and C6-C 14 In some embodiments, alkyl is aryl. In each occurrence of R 3 is methyl.

[0022] The third carbonate units each contain 5 to 60 diorganosiloxane units. Within this range, the number of diorganosiloxane units is 10 to 60, 20 to 60, 30 to 60, or 3 It may be 5 to 55.

[0023] In some embodiments, the third carbonate unit is [ka] wherein Ar, at each occurrence, is optionally substituted with 1, 2, 3, or 4 substituents. C6~C 24 each substituent independently represents a halogen (i.e., F, Cl, Br or I), C1-C6 alkyl and C1-C6 alkoxy R 4 is, independently at each occurrence, a C2-C8 divalent aliphatic radical; , R 5 and R 6 are independently generated for each occurrence, C1 to C 12 Alkyl or C6-C 18 a where m, n, and q are independently 0 or 1 for each occurrence, and p is (30 -nq) to (60-nq) or (35-nq) to (55-nq) It has the following structure.

[0024] Examples of Ar groups include 1,3-phenylene, 1,4-phenylene, and 2,2-bis( When each occurrence of m, n, and q is 0, each occurrence of m is 0. The Ar that appears is C6~C 24 Dihydroxyarylene compounds, such as resorcinol, 1 ,1-bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)methane )ethane, 1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane (hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)butane, 2,2- Bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octanol 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis( (4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfide , 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane and 1,1- It can be derived from bis(4-hydroxy-3-t-butylphenyl)propane, etc.

[0025] R 4Examples of groups include dimethylene (-(CH2)2-), trimethylene (-(C H2)3-), hexamethylene (-(CH2)6-), and 1,4-cyclohexylene In some embodiments, each occurrence of R 4 is trimethylene.

[0026] R 5 and R 6 Examples of groups include methyl, ethyl, 1-propyl, cyclohexyl, In some embodiments, each occurrence of R 5 and R 6 is methyl.

[0027] In some embodiments, each occurrence of m, n, and q is 0. In some embodiments, m, n, and q at each occurrence are 1. In some embodiments, p is (35- nq) to (55-nq).

[0028] In some embodiments, the third carbonate unit is [ka] (wherein r is 5 to 60, 5 to 60, 10 to 60, 20 to 60, 30 to 60, or 35 to 5 5) It has the following structure.

[0029] In other embodiments, the third carbonate unit is [ka] (wherein r is 5 to 60, 5 to 60, 10 to 60, 20 to 60, 30 to 60, or 35 to 5 5) It has the following structure.

[0030] In yet another embodiment, the third carbonate unit is [ka] (wherein s is 3 to 58, 8 to 58, 18 to 58, 28 to 58, or 33 to 53) When s is 43, the structure is designated D45 carbonate.

[0031] Polycarbonate polysiloxane is a polycarbonate polysiloxane containing The third carbonate unit is present in an amount of 0.05 to 0.4 mol % relative to 100 mol % of the carbonate units. Within this range, the third carbonate unit may be from 0.05 to 0.35 mol %, from 0.05 to 0.35 mol %, It can be present in an amount of 0.3 mol % or from 0.05 to 0.25 mol %.

[0032] In some embodiments, the polycarbonate polysiloxane is a polycarbonate 30 to 69.95 mol% based on 100 mol% of all carbonate units in the polysiloxane First carbonate units, 30 to 69.95 mole % second carbonate units and 0. and 0.05 to 0.35 mol % of a third carbonate unit.

[0033] In another embodiment, the polycarbonate polysiloxane is a polycarbonate polysiloxane. 35 to 64.95 mol % of the first carbonate unit relative to 100 mol % of the total carbonate units in the oxane carbonate units, 35 to 64.95 mol % of second carbonate units and 0.05 to Contains 0.3 mole percent of third carbonate units.

[0034] In another embodiment, the polycarbonate polysiloxane is a polycarbonate polysiloxane. 45 to 64.95 mol % of the first carbonate unit relative to 100 mol % of the total carbonate units in the oxane carbonate units, 35 to 54.95 mol % of second carbonate units and 0.05 to Contains 0.25 mole percent of third carbonate units.

[0035] In some embodiments, the polycarbonate polysiloxane is bisphenol A 10,0 as determined by gel permeation chromatography using polycarbonate standards The weight average molecular weight is 0.00 to 50,000 g / mol. Within this range, the weight average molecular weight is 15,000-40,000 g / mol or 24,000-30,000 g / mol It's okay.

[0036] In some embodiments of the polycarbonate polysiloxane, the first carbonate The unit is [ka] and the second carbonate unit has the structure [ka] or a combination thereof.

[0037] In some embodiments of the polycarbonate polysiloxane, a third carbonate The unit is [ka] wherein Ar, at each occurrence, is optionally substituted with 1, 2, 3, or 4 substituents. C6~C 24 wherein each substituent is independently selected from halogen, C1 to C6, R is selected from the group consisting of C alkyl and C-C alkoxyl; 4 independently Each occurrence is a C2-C8 divalent aliphatic radical, R 5 and R 6independently for each occurrence , C1~C 12 Alkyl or C6-C 18 aryl, and m, n, and q are independently and each occurrence is 0 or 1, and p is (30-nq) to (60-nq) or (35-nq) to (55-nq) It has the following structure.

[0038] In some embodiments, the polycarbonate polysiloxane has a viscosity of 35 to 64.95 % of the first carbonate unit, 35 to 64.95 mol % of the second carbonate unit, and and 0.05 to 0.3 mol % of a third carbonate unit.

[0039] In a very particular embodiment of the polycarbonate polysiloxane, the first carbonate The unit is [ka] and the second carbonate unit has the structure [ka] or a combination thereof, and the third carbonate unit is [ka] wherein Ar, at each occurrence, is optionally substituted with 1, 2, 3, or 4 substituents. C6~C 24 wherein each substituent is independently selected from halogen, C1 to C6, R is selected from the group consisting of C alkyl and C-C alkoxyl; 4 independently Each occurrence is a C2-C8 divalent aliphatic radical, R 5 and R 6 independently for each occurrence , C1~C 12Alkyl or C6-C 18 aryl, and m, n, and q are independently and each occurrence is 0 or 1, and p is (30-nq) to (60-nq) or (35-nq) to (55-nq) The polycarbonate polysiloxane has a structure of 35 to 64.95 mol % of the first carbonyl group. 35 to 64.95 mol % of a second carbonate unit and 0.05 to 0 0.3 mole % of a third carbonate unit, and the polycarbonate polysiloxane is Determined by gel permeation chromatography using phenol A polycarbonate standards. It has a weight average molecular weight of 20,000 to 35,000 g / mol.

[0040] In another very particular embodiment of the polycarbonate polysiloxane, the first carbon The net unit is [ka] and the second carbonate unit has the structure [ka] or a combination thereof, and the third carbonate unit is [ka] wherein Ar, at each occurrence, is optionally substituted with 1, 2, 3, or 4 substituents. C6~C 24 wherein each substituent is independently selected from halogen, C1 to C6, R is selected from the group consisting of C alkyl and C-C alkoxyl; 4 independently Each occurrence is a C2-C8 divalent aliphatic radical, R 5 and R 6 independently for each occurrence , C1~C 12 Alkyl or C6-C 18 aryl, and m, n, and q are independently and each occurrence is 0 or 1, and p is (30-nq) to (60-nq) or (35-nq) to (55-nq) The polycarbonate polysiloxane has a structure of 45 to 69.95 mol % of the first carbonyl group. 30 to 54.95 mol % of a second carbonate unit and 0.05 to 0 0.16 mole % of a third carbonate unit, and the polycarbonate polysiloxane Determined by gel permeation chromatography using phenol A polycarbonate standards It has a weight average molecular weight of 20,000 to 35,000 g / mol.

[0041] Polycarbonate polysiloxanes are disclosed, for example, in U.S. Pat. No. 6,229,393 to Vaughn. Nos. 3,419,634 and 3,419,635, Merritt et al. No. 3,821,325 against Merritt, No. 3,832 against 419 and 6,072,011 to Hoover They can be prepared using known methods for synthesizing polycarbonate copolymers, including those Detailed procedures for synthesizing recarbonate polysiloxanes are included in the examples below.

[0042] Another embodiment is a polycarbonate polysiloxane in any of its above variations. Thus, one embodiment is a composition comprising a polycarbonate polysiloxane. Based on 100 mol% of all carbonate units in [ka] (In the formula, R 1is C6~C 16 is a divalent aromatic group 20 to 69.95 mol % of a first carbonate unit having the structure [ka] (In the formula, R 2 is C 17 ~C 40 is a divalent aromatic group and 30 to 79.95 mol % of a second carbonate unit having the structure divalent polysiloxane containing a siloxane group (-OC(O)O-) and a divalent polysiloxane group The base [ka] (wherein each occurrence of R 3 are independently C1 to C 13 is a hydrocarbyl group) 0.05 to 0.4 mole % of the diorganosiloxane having 5 to 60 diorganosiloxane units having the structure and a third carbonate unit of the polycarbonate polysiloxane, Carbonate polysiloxane was compared with the gel immersion test using a bisphenol A polycarbonate standard. Weight average of 18,000 to 35,000 g / mol determined by permeation chromatography a second carbon having a molecular weight of 70 to 79.95 mol % polycarbonate polysiloxane; When the polycarbonate unit is contained, the polycarbonate polysiloxane is 18,000 to 24,000 The polycarbonate polysiloxane has a weight average molecular weight of 0 g / mol.

[0043] The composition is useful for forming extruded films. When used for this purpose, the composition Typically, the polycarbonate polycarbonate is present in an amount of 70 to 100% by weight based on the total weight of the composition. Contains Roxane.

[0044] In some embodiments, the composition further comprises a roughening agent. The extruded film has a surface roughening agent, i.e., a physical texture. , for example, synthetic or natural silica, limestone, talc, zeolites, crosslinked silicones, cyclic olefins, Particulate materials comprising olefin copolymers and combinations thereof are also included.

[0045] The roughening agent is a crosslinked silicone, preferably a crosslinked silsesquioxane, more preferably a crosslinked The polymethylsilsesquioxane may include polymethylsilsesquioxane. Silsesquioxane is a compound of Si—O— Silsesquioxanes are cage-like structures with Si bonds and tetrahedral Si vertices. , in molecular form as cages with 10 or 12 Si vertices, and in polymeric form. There may be. The cages are T6, T8, and T 10 and T 12 It may be labeled with (T = tetrahedron vertex). The T8 cage has the formula [R-SiO 1.5 ]8 or equivalently R8Si8O 12 Each Si center is bonded to three oxo groups, which in turn bond to other Si centers. The fourth group on Si is an R group. Each R group is independently C1-C8 alkyl, ... C8 alkenyl, acrylate, methacrylate, hydroxyl or epoxide The crosslinked polymethylsilsesquioxane particles are spherical and have a soft, gel-like consistency. This makes the composition suitable for processing using fine filters. When passing through a melt filter (e.g., a 5 μm filter), the roughening agent It does not clog and avoids the problems encountered when inorganic particulates are used as roughening agents. In some embodiments, the roughening agent is a laser-treated surface according to ISO 13320:2009. 0.1-10 μm, 0.1-5 μm, 0.1-3 μm or 0 μm determined by laser diffraction Contains particulate crosslinked polymethylsilsesquioxane with a median equivalent spherical diameter of 0.2 to 2 μm. Particulate crosslinked polymethylsilsesquioxane is available, for example, in Momentive Perf It is commercially available from Ormance Chemicals under the trade name TOSPEARL.

[0046] When present in the composition, the roughening agent is present in an amount of from 0.05 to 2% by weight relative to the total weight of the composition. Within this range, the amount of the roughening agent can be 0.05 to 1 wt. %, 0.1 to 0.8 wt. %, or % by weight or 0.15 to 0.6% by weight.

[0047] The composition may optionally contain an organic slip agent, which aids in the handling of the extruded film. Suitable organic slip agents include, for example, pentaerythritol tetrastearate. stearate, dipentaerythritol hexastearate, glycerol tristearate, High density polyethylene, polymethylpentene, and combinations thereof. When used, the organic slip agent can be used in an amount of 0.1 to 15% by weight based on the total weight of the composition. Within this range, the amount of organic slip agent may be 0.1 to 5 wt %, 0.1 to 2 wt %, or 0.1 to 5 wt %. It may be 1% by weight.

[0048] The composition may optionally contain one or more additives known in the thermoplastic arts. Additives include, for example, stabilizers, release agents, lubricants, processing aids, anti-drip agents, and nucleating agents. , UV absorbers, colorants (including dyes and pigments), antioxidants, antistatic agents, foaming agents, gold If present, these include metal deactivators, antiblocking agents, and combinations thereof. Such additives typically comprise no more than 10% by weight, preferably 5% by weight, based on the total weight of the composition. or less or in a total amount of 1% by weight or less.

[0049] In very specific embodiments, the composition is 70 to 99.95% by weight of polycarbonate. The coating composition contains polysiloxane and further contains 0.05 to 2% by weight of a surface roughening agent, and is a polycarbonate. The polysiloxane has 35 to 64.95 mole percent of first carbonate units, % by mole of the second carbonate unit and 0.05 to 0.3 mol % of the third carbonate unit The first carbonate unit is [ka] and the second carbonate unit has the structure [ka] or a combination thereof, and the third carbonate unit is [ka] wherein Ar, at each occurrence, is optionally substituted with 1, 2, 3, or 4 substituents. C6~C 24 wherein each substituent is independently selected from halogen, C1 to C6, R is selected from the group consisting of C alkyl and C-C alkoxyl; 4 independently Each occurrence is a C2-C8 divalent aliphatic radical, R 5 and R 6 independently for each occurrence , C1~C 12 Alkyl or C6-C 18 aryl, and m, n, and q are independently and each occurrence is 0 or 1, and p is between (30-nq) and (60-nq). ) structure, and polycarbonate polysiloxane is a bisphenol A polycarbonate. 20,000-35,000 as determined by gel permeation chromatography using a standard 00g / mol, and the surface roughening agent is Particulate crosslinks with median equivalent spherical diameters of 0.1 to 10 μm determined by laser diffraction Contains polymethylsilsesquioxane.

[0050] Another embodiment is an extruded film comprising the composition of any of the above variations thereof. The composition was extruded using an extruder conventionally used for thermoplastic compositions using a flat die. In the extrusion cast film method, the composition is melted in an extruder and The molten composition is conveyed through a flat die with a small lip gap separating it, and optionally, a relatively High winding speeds stretch the film and cool / solidify the film-forming composition to form the final film. The extruder may be of single or twin screw design and may include forming a molten polymer. A pump can be used to provide a constant, non-pulsating flow of polymer through the die. The gap between the rolls can be as small as 100 to 200 μm, and the take-up rollers can be up to 2 It can operate at a speed of 1000m / min. The design also includes an additional heated roll to temper / This may include annealing the material to minimize the development of frozen-in internal stresses. The edges of the film may be trimmed and the film may be wound using a tension-controlled winding mechanism. The die is wound onto a roll. the rheological properties of the polymers used to make the film; The cleanliness of both the film and the mechanical properties of the winding mechanism are all important factors in determining the thickness of the extruded film. In some embodiments, the thickness of the film is between 2 and 15 μm. μm, 2 to 10 μm, 2 to 8 μm, or 2 to 6 μm.

[0051] In some embodiments, the extruded film has a thickness of 2 to 15 μm and the composition is 70 to 99.95% by weight of polycarbonate polysiloxane based on the total weight of the composition; 0.1-10 μm determined by laser diffraction according to ISO 13320:2009 Particulate crosslinked polymethylsilsesquioxane having a median equivalent spherical diameter of 0.05 to and 2% by weight of a surface roughening agent.

[0052] Another embodiment is a method for producing an extruded film comprising the composition of any of the above variations thereof, and an extruded a metallized film (e.g., a film capacitor) comprising a conductive metal layer in contact with the film; A variety of metals and metal alloys are used to form the conductive metal layer depending on the intended use of the film. In some embodiments, the conductive metal layer can be copper, aluminum, silver, Gold, nickel, zinc, titanium, chromium, vanadium, platinum, tantalum, niobium, brass and and combinations thereof. These methods are well known and include, for example, vacuum metal deposition, metal sputtering, plasma These include laser processing, electron beam processing, chemical oxidation or reduction reactions, and electroless wet chemical vapor deposition. The extruded film may be metallized on both sides by conventional electroless plating. A patterned metal layer may be formed on the surface of the film, for example by inkjet printing. The thickness of the conductive metal layer is determined by the intended use of the metallized film, and is, for example, 0.1 to 1 000 nm, 0.5 to 500 nm, or 1 to 10 nm.

[0053] Another embodiment is a composition comprising, based on the total weight of the composition, a homopoly of a first bisphenol monomer. Carbonates were subjected to dynamic mechanical testing at a heating rate of 1°C / min according to ASTM E1640-13. A first bisphenol having a glass transition temperature of less than 155°C as determined by bisphenol A. The first carbonate unit is derived from a monomer, and the second is a homopolymer of a bisphenol monomer. The recarbonate was subjected to dynamic mechanical analysis at a heating rate of 1°C / min according to ASTM E1640-13. A second bisphenol having a glass transition temperature of 155°C or higher as determined by bisphenol A. 65 to 99.95 wt. % of a copolycarbonate containing a second carbonate unit derived from a monomer. Nate and greater than 5 μm as determined by laser diffraction according to ISO 13320:2009 and particulate crosslinked polymethylsilsesquioxane with a median equivalent spherical diameter of 10 μm or less and 0.05 to 2% by weight of a surface roughening agent containing a copolycarbonate. and European Patent Application No. 18, filed November 14, 2018, both of which are incorporated herein by reference. No. 206355.2 and international patent application PCT / US1 filed November 14, 2019 It corresponds to "High Heat Copolycarbonate" in No. 9 / 061477.

[0054] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independent. Each range disclosed herein can be combined with any other range within the disclosed range. This disclosure constitutes a disclosure of any point or subrange within the scope of the present invention.

[0055] The present invention includes at least the following aspects.

[0056] Aspect 1: Per 100 mol% of all carbonate units in the polycarbonate polysiloxane hand [ka] (In the formula, R 1 is C6~C 16 is a divalent aromatic group 20 to 69.95 mol % of a first carbonate unit having the structure [ka] [In the formula, R 2 teeth [ka] (In the formula, R f and R g are independently generated for each occurrence, C1 to C 12 Alkyl, C1-C 12 Alkoxy or C2-C 12 alkenyl, and each R h is hydrogen, or R appears twice h together with the carbon atom to which they are attached to form a carbonyl group, and each Appearance R i are independently C1-C6 alkyl, and R j is hydrogen, C1-C6 alkyl or phenyl optionally substituted with 1, 2, 3, 4 or 5 C1-C6 alkyl groups Nil and R k is independently at each occurrence C1-C3 alkyl or phenyl, preferably Mostly methyl, X b is C6~C 12 Arylene, C4~C 18 Cycloalkylene, C 4~C 18 Cycloalkylidene or -C(R m )(Rn )-(wherein, R m is hydrogen, C1 ~C 12 Alkyl or C6-C 12 aryl, and R n is C6~C 10 Alkyl, C 6-C8 cycloalkyl or C6-C 12 aryl), or X b teeth- (Q a ) x -G-(Q b ) y -(in the formula, Q a and Q b are each independently C1 to C3 alkylene, G is C3-C 10 cycloalkylene, x is 0 or 1, and y is 0 or 1), and j, m, and n are each independently 0, 1, 2, 3, or 4) C having the structure 17 ~C 40 is a divalent aromatic group of the formula and 30 to 79.95 mol % of second carbonate units each having a divalent carbonate structure. The divalent polysiloxane group is a carboxylate group and a divalent polysiloxane group. [ka] (wherein each occurrence of R 3 are independently C1 to C 13 is a hydrocarbyl group) 0.05 to 0.4 mole % of the diorganosiloxane having 5 to 60 diorganosiloxane units having the structure and a third carbonate unit of the polycarbonate polysiloxane, Carbonate polysiloxane was compared with the gel immersion test using a bisphenol A polycarbonate standard. Weight average of 18,000 to 35,000 g / mol determined by permeation chromatography a second carbon having a molecular weight of 70 to 79.95 mol % polycarbonate polysiloxane; When the polycarbonate unit is contained, the polycarbonate polysiloxane is 18,000 to 24,000 Polycarbonate polysiloxane characterized by having a weight average molecular weight of 0 g / mol. .

[0057] Aspect 2: The polycarbonate polysiloxane of aspect 1, wherein the first carbonate The unit is [ka] and the second carbonate unit has the structure [ka] or a combination thereof. Sun.

[0058] Aspect 3: The polycarbonate polysiloxane of aspect 1 or 2, further comprising a third carbonyl group. Carbonate units [ka] wherein Ar, at each occurrence, is optionally substituted with 1, 2, 3, or 4 substituents. C6~C 24 wherein each substituent is independently selected from halogen, C1 to C6, R is selected from the group consisting of C alkyl and C-C alkoxyl; 4 independently Each occurrence is a C2-C8 divalent aliphatic radical, R 5 and R 6 independently for each occurrence , C1~C 12 Alkyl or C6-C 18 aryl, and m, n, and q are independently and each occurrence is 0 or 1, and p is between (30-nq) and (60-nq). ) A polycarbonate polysiloxane characterized by having the following structure:

[0059] Aspect 4: The polycarbonate polysiloxane according to any one of Aspects 1 to 3, , 35 to 64.95 mol% of the first carbonate unit, 35 to 64.95 mol% of the second carbonate units and 0.05 to 0.3 mol % of a third carbonate unit. Polycarbonate polysiloxane characterized by:

[0060] Aspect 5: The polycarbonate polysiloxane of aspect 1, wherein the first carbonate The unit is [ka] and the second carbonate unit has the structure [ka] or a combination thereof, and the third carbonate unit [ka] wherein Ar, at each occurrence, is optionally substituted with 1, 2, 3, or 4 substituents. C6~C 24 wherein each substituent is independently selected from halogen, C1 to C6, R is selected from the group consisting of C alkyl and C-C alkoxyl; 4 independently Each occurrence is a C2-C8 divalent aliphatic radical, R 5 and R 6 independently for each occurrence , C1~C 12 Alkyl or C6-C 18 aryl, and m, n, and q are independently and each occurrence is 0 or 1, and p is between (30-nq) and (60-nq). ) and the first carbon black has a structure in which the polycarbonate polysiloxane is 35 to 64.95 mol %. carbonate units, 35 to 64.95 mol % of second carbonate units and 0.05 to 0. 3 mole % of a third carbonate unit, and the polycarbonate polysiloxane is Determined by gel permeation chromatography using phenol A polycarbonate standards. Poly(ethylene glycol) having a weight average molecular weight of 20,000 to 35,000 g / mol Carbonate polysiloxane.

[0061] Aspect 6: Per 100 mol% of all carbonate units in the polycarbonate polysiloxane hand [ka] (In the formula, R 1 is C6~C 16 is a divalent aromatic group 20 to 69.95 mol % of a first carbonate unit having the structure [ka] [In the formula, R 2 teeth [ka] JPEG0007779808000057.jpg46161 (in the formula, R f and R g are independently generated for each occurrence, C1 to C 12 Alkyl, C1-C 12 Alkoxy or C2-C 12 alkenyl, and each R h is hydrogen, or R appears twice htogether with the carbon atom to which they are attached to form a carbonyl group, and each Appearance R i are independently C1-C6 alkyl, and R j is hydrogen, C1-C6 alkyl or phenyl optionally substituted with 1, 2, 3, 4 or 5 C1-C6 alkyl groups Nil and R k is independently at each occurrence C1-C3 alkyl or phenyl, preferably Mostly methyl, X b is C6~C 12 Arylene, C4~C 18 Cycloalkylene, C 4~C 18 Cycloalkylidene or -C(R m )(R n )-(wherein, R m is hydrogen, C1 ~C 12 Alkyl or C6-C 12 aryl, and R n is C6~C 10 Alkyl, C 6-C8 cycloalkyl or C6-C 12 aryl), or X b teeth- (Q a ) x -G-(Q b ) y -(in the formula, Q a and Q b are each independently C1 to C3 alkylene, G is C3-C 10 cycloalkylene, x is 0 or 1, and y is 0 or 1), and j, m, and n are each independently 0, 1, 2, 3, or 4) C having the structure 17 ~C 40 is a divalent aromatic group of the formula and 30 to 79.95 mol % of second carbonate units each having a divalent carbonate structure. It contains a carbonate group (-OC(O)O-) and a divalent polysiloxane group, The xanthane group [ka] (wherein each occurrence of R 3 are independently C1 to C 13 is a hydrocarbyl group) 0.05 to 0.4 mole % of the diorganosiloxane having 5 to 60 diorganosiloxane units having the structure and a third carbonate unit. Polycarbonate polysiloxane is a standard product of bisphenol A polycarbonate. 18,000-35,000 g / mol as determined by gel permeation chromatography using and the polycarbonate polysiloxane has a weight average molecular weight of 70 to 79.95 mol %. When the polycarbonate polysiloxane contains a second carbonate unit of 18,000, A composition characterized by having a weight average molecular weight of ∼24,000 g / mol.

[0062] Embodiment 7: The composition of embodiment 6, wherein the polycarbonate polysiloxane is 35 to 6 4.95 mol% of the first carbonate unit, 35 to 64.95 mol% of the second carbonate unit % of a third carbonate unit and 0.05 to 0.3 mol % of a third carbonate unit. composition.

[0063] Embodiment 8: The composition of embodiment 6 or 7, wherein the composition has a total weight of 70 to 99 0.95% by weight of polycarbonate polysiloxane and 0.05 to 2% by weight of a surface roughening agent. A composition comprising:

[0064] Embodiment 9. The composition of embodiment 8, wherein the surface roughening agent is in accordance with ISO 13320:2009. The particles have a median equivalent spherical diameter of 0.1 to 10 μm as determined by laser diffraction. A composition comprising a crosslinked polymethylsilsesquioxane.

[0065] Embodiment 10: The composition of embodiment 6, wherein the composition is 70 to 99.95 wt. % polycarbonate. The coating composition contains a carbonate polysiloxane and further contains 0.05 to 2% by weight of a surface roughening agent. The carbonate polysiloxane has 35 to 64.95 mol % of first carbonate units, 64.95 mol % of second carbonate units and 0.05 to 0.3 mol % of third carbonate units a first carbonate unit; [ka] and the second carbonate unit has the structure [ka] or a combination thereof, and the third carbonate unit [ka] wherein Ar, at each occurrence, is optionally substituted with 1, 2, 3, or 4 substituents. C6~C 24 wherein each substituent is independently selected from halogen, C1 to C6, R is selected from the group consisting of C alkyl and C-C alkoxyl; 4 independently Each occurrence is a C2-C8 divalent aliphatic radical, R 5 and R 6 independently for each occurrence , C1~C 12 Alkyl or C6-C 18 aryl, and m, n, and q are independently and each occurrence is 0 or 1, and p is between (30-nq) and (60-nq). ) The polycarbonate polysiloxane has a structure of bisphenol A polycarbonate. 20,000-35,000 as determined by gel permeation chromatography using standards 0 g / mol weight average molecular weight, and the roughening agent is Particulate crosslinked polymers with median equivalent spherical diameters between 0.1 and 10 μm as determined by laser diffraction. A composition comprising methylsilsesquioxane.

[0066] Aspect 11: An extruded film comprising the composition according to any one of aspects 6 to 10. Film.

[0067] Embodiment 12: The extruded film of embodiment 11, wherein the extruded film has a thickness of 2 to 15 μm. The composition has a polycarbonate content of 70 to 99.95% by weight based on the total weight of the composition. and polysiloxanes, as determined by laser diffraction according to ISO 13320:2009. Particulate crosslinked polymethylsilsesquioxane with a median equivalent spherical diameter of 0.1 to 10 μm and 0.05 to 2% by weight of a surface-roughening agent containing methyl acrylate.

[0068] Aspect 13: An extruded film comprising the composition of any one of aspects 6 to 10, and a conductive metal layer in contact with the film.

[0069] Aspect 14: An extruded film comprising the composition of any one of aspects 6 to 10, and a conductive metal layer in contact with the film.

[0070] Aspect 15: A homopolycarbonate of a first bisphenol monomer, based on the total weight of the composition. The nate was subjected to dynamic mechanical analysis at a heating rate of 1°C / min according to ASTM E1640-13. a first bisphenol monomer having a glass transition temperature of less than 155°C as determined and a homopolycarbonate of a second bisphenol monomer. The nate was subjected to dynamic mechanical analysis at a heating rate of 1°C / min according to ASTM E1640-13. a second bisphenol monomer having a glass transition temperature of 155°C or greater, 65 to 99.95 wt. % of a copolycarbonate comprising a second carbonate unit derived from , greater than 5 μm and 1 μm determined by laser diffraction according to ISO 13320:2009 Contains particulate crosslinked polymethylsilsesquioxane with a median equivalent spherical diameter of 0 μm or less and 0.05 to 2% by weight of a surface roughening agent.

[0071] The present invention is further illustrated by the following non-limiting examples. [Example]

[0072] The materials used in these experiments are summarized in Table 1.

[0073] The following is about 62.5 mole % bisphenol isophorone (BPI) carbonate units, about 37.34 mol % bisphenol A (BPA) carbonate units and about 0.16 mol A procedure for synthesizing polycarbonate copolymers containing % D45 carbonate units. Polycarbonate copolymers containing the same carbonate units in different proportions are The synthesis can be carried out by changing the ratio of each monomer. Equipped with a stirrer and a circulation pump. Methylene chloride (18 L), BPI (3157 g) , BPA (1393g), D45 (91g), water (10L), triethylamine (30g ) and sodium gluconate (10 g) were introduced into the reactor. Methylene chloride (800 g A solution of paracumylphenol (PCP, 112 g) in HCl was fed to the reactor at 200 g / min. Phosgene gas (2650 g) was bubbled through the reactor at 90 g / min to form a solution. While vigorously stirring, 33% by weight of aqueous sodium hydroxide solution was added to The H was maintained at 9-10°C. After the phosgene addition was complete, the reaction mixture was stirred for 10 minutes. The pH was stabilized at 9. A sample of the reaction product was diluted with bisphenol A polycarbonate standard. The product was analyzed by gel permeation chromatography (GPC), and the result was 28,665 g / mol weight average molecular weight (M w ) and a number average molecular weight (M n )of The reactor was purged with nitrogen for 5 minutes and then the contents were discharged into the feed tank. The mixture was fed into a series of liquid-liquid centrifuges where the brine phase was separated by methylene chloride. Triethylamine was separated from the polymer solution in ethanol. The residual ions were removed by washing with water. The purified polymer solution was transferred to a feed pot. The polymer solution was contacted with the vapor from the precipitation jet. Isolate the resin by flashing off the methylene chloride and leaving a white wet cake. The resin was placed in a cone dryer and heated nitrogen was passed through the powder for 4 hours to remove water. The yield of the isolated resin powder was 10.2 kg. GPC analysis revealed that M w The copolymer hydrolyzate (terpoly Ultra-high performance liquid chromatography analysis of the hydroxybenzoate (obtained by reacting hydroxybenzoate with potassium hydroxide) The BPI content was 63 mol %. [Table 1] JPEG0007779808000063.jpg196170JPEG0007779808000064.jpg210170JPEG0007779808000065.jpg204170JPEG0007779808000066.jpg114170

[0074] Table 2 summarizes the film extrusion composition properties and film properties. In this context, "copolymer" refers to the copolymer used in the film extrusion composition (copolymer (The explanation of the "polysiloxane carbonate" is in Table 1), and "polysiloxane carbonate (mol%)" is the amount of % by mole of polysiloxane carbonate units relative to the sum of all carbonate units; "BPI carbonate (mol %)" is the percentage of the total carbonate units in the copolymer. % of BPI carbonate units, and "BPA carbonate (mol %)" is the copolymer is the mole % of BPA carbonate units relative to the sum of all carbonate units in the polymer; "M w (kg / mol) is the weight average molecular weight of the copolymer. 99.34% by weight of specific copolymer, 0.3% by weight of PETS, 0.3% by weight of PMS All compositions contained 0.06 wt.% AO and 0.06 wt.% S-2. Werner & Pf with a high die-to-diameter ratio and vacuum ports located near the die face Compounding was carried out in a Leiderer co-rotating twin screw extruder. Compounding was carried out at temperatures between 285 and 330°C. .

[0075] A 25 mm single screw extruder was used, utilizing a melt pump to eliminate pulsating melt flow. The melt pump was operated at a temperature of 330-360°C, where the melt pressure in the die was at its maximum. The melt was poured into a die with a die gap clearance of 100 to 300 μm. The melt curtain was extruded onto a polished chill roll. The gauge was measured using a melt pump in downstream equipment. By matching the output speed of the feeder with the winding speed, the film can be produced uniformly without unevenness. Made it thick.

[0076] Table 2 summarizes the film properties. "Processability" refers to how easily the film can be processed. The rating indicates whether the composition can be extruded to a thickness of 5 μm. A rating of 1 means that the composition could not be extruded to form a film. A rating of 2 means that it was difficult to form an extruded film having a thickness of 5 μm. This means that the composition could be consistently processed to form an extruded film with a thickness of 5 μm. , and rating 3 indicates that the composition was able to be consistently processed to form an extruded film having a thickness of 3 μm. A rating of 2 or 3 is preferred and is used to form thin gauge films for capacitor applications. A robust processing window for achieving this is predicted.

[0077] Tensile elongation (with units of % gauge length), tensile stress at break (MPa) and tensile modulus ( MPa) for a 5 μm thick extruded film according to ASTM D882-02. The film was evaluated at 3°C ​​in both the machine and transverse directions. Good film handling is predicted through the extrusion, metallization and cap wrapping processes of the fabrication. can be.

[0078] The tear strength (unit: N / mm) was measured according to ISO 6383-1 for a 5 μm thick film. Extruded films were evaluated at 23°C in both the machine and transverse directions. Test parameters were as follows: The test conditions were as follows: (1) Test speed: 200 mm / sec, (2) Test elongation: 50 mm, (3 ) Load cell: 10N, (4) Five runs per sample were reported, (5) Blueh Instron Test Rack with ill3 software, (6) film test Material size: 25mm x 200mm strip, (7) To start the tearing site, (8) Each leg of the specimen was clamped using a pneumatic grip. (9) Static electricity was removed from the sample using a deionized air gun. (10) The average tear strength was calculated from the area of ​​the load / elongation curve selected by the operator. High tear strength ensures excellent durability during the extrusion, metallization and cap winding processes of film capacitor manufacturing. Good film handling is predicted by

[0079] "Slipperiness rating" and "slipperiness rank" are subjective measures of the slipperiness of the surface of an extruded film. The slipperiness rating ranges from 1 (sticky) to 3 (slippery), and the displayed value is The slipperiness ranking is the average of the evaluations by five evaluators. The ratings are based on a ranking system in which 1 is the best and 18 is the worst, and the values ​​shown are based on the rankings of five raters. The lubricity is an average of the extrusion process, metallization, capacitor winding and capacitor This is essential for good handling of the film web through the flattening process. This can lead to blocking and wrinkling during the extrusion process, as well as the inability to flatten the capacitor windings. Too much slipperiness can cause problems in the metallization operation and winding problems in the metallization. This creates problems of telescoping and tracking during advance and rewind.

[0080] Surface roughness is an important physical property of the film that directly affects the slipperiness. This is essential for good film web handling through film metallization and capacitor winding. If the surface roughness is insufficient, the film may crack between the windings of subsequent layers in the master roll during extrusion. Blocking and air entrapment may occur. Excessive surface roughness is the primary cause of scoping. The surface roughness characteristics (evaluation of the surface roughness) decrease the efficiency of the film and the dielectric breakdown strength of the film. "Ra" (all units are μm) was determined in accordance with JIS B0601:1994. is the arithmetic mean roughness, "Ry" is the maximum height, "Rz" is the ten-point mean height, and "S" is the average spacing of local peaks, "Sm" is the average spacing of irregularities, and "RMS" is the square of The values ​​in Table 2 represent the average values ​​from five samples. Surface roughness characteristics are expressed as Ke The roughness was determined using a Keynes confocal microscope. Primary roughness images were taken using a 50x objective. The samples were placed on flat polycarbonate plaques and captured with a VK-200. Surface separation was minimized. Using the stage height adjustment in laser measurement mode, The scanning range was changed from more than 1 μm from the top surface of the film to 1 μm from the top surface of the film. The total scan range did not exceed the film thickness. The scanning range is 2 mm to ensure that the bottom surface of the film is not imaged during data collection. The result was ~4 μm. When the entire field of view could not be captured within the target scan range, The sample was moved in the X and Y directions to ensure a flat image. Once set, run Auto Gain to obtain acceptable luminance and brightness across the entire scan range. The contrast settings were established. The double scan option was used under high accuracy settings. The step height was 0.1 μm. Under these settings, the field of view was 280-300 mm x 200 mm. Measurements were taken using a 50x objective, which provides 5 individual measurements for data analysis. The surface roughness measurements were carried out using one 50 mm × 100 mm sample at various positions. The IS B0601:1994 standard calculations were performed on each image. The template for scan analysis was used to generate the data for each of the five individual scans. The average value was calculated and reported. The analysis included 60 lines across each image in the machine direction. , Ra (arithmetic mean roughness), Ry (maximum height), Rz (ten-point mean height) and RMS (double The results were reported as the average root mean square roughness (rms). Pre-processing of the obtained images was performed according to Keyence's recommendations. The following steps are recommended: automatic deskew; automatic noise removal; height cut level; and DC L / BCL levels were included. Roughness curve correction: Height data was calculated by subtracting the roughness curve from the slope corrected surface. The surface roughness was determined from the cross-sectional curve of the line roughness. For surface roughness, the baseline was calculated using the least squares method for the height data. The distance from the baseline to each height data point was calculated. The absolute value of the height difference between the roughness curve and the reference surface was then calculated. The Ry calculation is performed by comparing the distance between the reference surface and each point on the roughness surface to determine the highest peak. This was done by calculating the sum of the peak height (Yp) and the depth of the lowest valley (Yv). The value is the average of the absolute heights of the five highest peaks and the absolute depths of the five lowest valleys. The RMS calculation was calculated as the square root of the sum of the differences between the reference surface and the roughness curve.

[0081] Electrical properties were determined using the Bosch test, which measures the electrical conductivity of a sample per unit thickness. A continuous electrical breakdown test that can measure the number of breakdowns in a film that occur at a specific voltage. The lower the clear count at each voltage level, the better the film Higher quality (i.e. fewer defects, scratches, wrinkles and uneven thickness). Electric clear counts of 150, 200, 250, 300, 350, 400, 450 and The test film was polished with a ground metallization layer on the counter electrode film. The test film and the corresponding grounded metallized film (counter electrode) were sandwiched between steel rollers. ) was wound through the device at 10 m per minute in a roll-to-roll process. The potential of the filter was measured using a BK Precision 1700 with a TREK 20 / 20C amplifier. The 88B power supply was used for control. The Labview software control interface was N Used with the National Instruments Ni-9223 voltage input module Using this, voltage / current spikes were measured at specific voltages to determine the breakdown counts. Edge breakdown counts and location at each voltage for 1m 2 The results were recorded on the film shown in Table 2. The account values ​​represent the average of five tests per sample. Thinner films could not be extruded, so the results are not shown. Regarding these, no results are shown for voltages of 450 and 500 V / μm. For this sample, there were a large number of cows at 400V / μm, where the operator stopped the test. The phenomenon was observed.

[0082] The property results in Table 2 show that the examples of the present invention not only have good processability, but also good processability, tensile strength, tear strength, etc. It also demonstrates a desirable balance of strength, surface roughness, and electrical resistance. The comparative examples in which the carbonate polysiloxanes have a high polysiloxane content are The examples show improved processability overall. Polycarbonate with low polysiloxane content In contrast to the comparative examples incorporating copolymers, polycarbonate polysiloxanes, particularly BPI copolymers, are used. The present examples of low carbonate content polycarbonate polysiloxanes are generally It exhibits improved processability, electrical performance and slip properties. [Table 2] JPEG0007779808000068.jpg247170JPEG0007779808000069.jpg243170JPEG0007779808 000070.jpg251170JPEG0007779808000071.jpg246170JPEG0007779808000072.jpg59170

[0083] In this experiment, tensile properties were measured for as-extruded and aged extruded samples at 150°C for 170 hours. The results are shown in Table 3. The percent change is Calculated as (value after aging - value as extruded) ÷ value as extruded × 100 The results were used in a multi-response optimization model, which resulted in good processability and aging properties. One of the copolymer compositions that shows minimal change in physical properties with respect to 61.3 mole % of bisphenol A carbonate based on the total moles of carbonate units in units, 38.6 mol % BPI carbonate units and 0.078 mol % polysiloxane It was predicted to contain dicarbonate units. [Table 3] JPEG0007779808000074.jpg255166JPEG0007779808000075.jpg165168

Claims

1. based on the total weight of the composition, 70 to 99.95 wt. % of a polycarbonate polysiloxane; 0.05 to 2 wt. % of a surface roughening agent, The polycarbonate siloxane contains 100 mol % of the total carbonate units in the polycarbonate polysiloxane. 35 to 64.95 mole percent of first carbonate units; 35 to 64.95 mole percent of second carbonate units; each containing a divalent carbonate group and a divalent polysiloxane group, wherein the divalent polysiloxane group is 【Chemistry 1】 (wherein each occurrence of R ３ are independently １ ~C １３ is a hydrocarbyl group) and 0.05 to 0.3 mole percent of a third carbonate unit comprising 5 to 60 diorganosiloxane units having the structure A composition comprising a polycarbonate polysiloxane, comprising: The first carbonate unit is 【Chemistry 2】 and a bisphenol A carbonate unit having the structure The second carbonate unit is 【Transformation 3】 The bisphenol isophorone carbonate unit has the structure the polycarbonate polysiloxane has a weight average molecular weight of 18,000 to 35,000 g / mole as determined by gel permeation chromatography using a bisphenol A polycarbonate standard; when the polycarbonate polysiloxane comprises 70 to 79.95 mole percent of the second carbonate units, the polycarbonate polysiloxane has a weight average molecular weight of 18,000 to 24,000 g / mole; 1. A composition, characterized in that the roughening agent comprises a particulate crosslinked polymethylsilsesquioxane having a median equivalent spherical diameter of 0.1 to 10 μm as determined by laser diffraction according to ISO 13320:2009.

2. 10. The composition of claim 1, the polycarbonate polysiloxane comprises 35 to 64.95 mol % of first carbonate units, 35 to 64.95 mol % of second carbonate units, and 0.05 to 0.3 mol % of third carbonate units; the third carbonate unit 【Chemistry 4】 wherein Ar is, independently at each occurrence, a C group optionally substituted with 1, 2, 3, or 4 substituents. ６ ~C ２４ wherein each substituent is independently selected from halogen, C １ ~C ６ Alkyl and C １ ~C ６ alkoxyl; R ４ independently for each occurrence, C ２ ~C ８ is a divalent aliphatic group represented by the formula: ５ independently for each occurrence, C １ ~C １２ Alkyl or C ６ ~C １８ aryl, and R ６ independently for each occurrence, C １ ~C １３ m, n, and q are independently at each occurrence 0 or 1, and p is from (30-nq) to (60-nq). A composition characterized by having the structure:

3. An extruded film comprising the composition of claim 1 or 2.

4. 4. The extruded film of claim 3, An extruded film characterized by having a thickness of 2 to 15 μm.

5. an extruded film comprising the composition of claim 1 or 2; a conductive metal layer in contact with the extruded film; A capacitor comprising:

6. an extruded film comprising the composition of claim 1 or 2; a conductive metal layer in contact with the extruded film; A metallized film comprising:

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