Polyvinyl chloride, polycarbonate and copolyester compositions, and articles made using these compositions

Abstract

The present disclosure relates to novel polyvinyl chloride compositions comprising a polyvinyl chloride resin, a polycarbonate resin, and a copolyester resin. More particularly, the present disclosure relates to polyvinyl chloride compositions comprising a blend of a polycarbonate and a high glass transition temperature (Tg) copolyester to increase the Tg and heat distortion temperature under load (HDTUL) of the polyvinyl chloride composition.

Description

Technical Field

[0001]

[0001] This disclosure relates to a novel polyvinyl chloride composition. More specifically, this disclosure relates to a novel composition comprising a polyvinyl chloride resin, a polycarbonate resin, and a copolyester resin. More specifically, this disclosure relates to a polyvinyl chloride composition comprising a blend of a polycarbonate resin and a high glass transition temperature (Tg) copolyester resin to increase the Tg and heat deflection temperature under load (HDTUL) of the polyvinyl chloride composition.

Background Art

[0002]

[0002] Rigid polyvinyl chloride (PVC) formulations have been used for many years to make articles such as vinyl siding, window profiles, decking profiles, fencing, and railing materials. These products are typically limited to lighter colors such as white, off-white, beige, or bright pastel greens, blues, and yellows, and darker, richer colors are not typically offered. The reason for the limitation to lighter colors is that these formulations risk exceeding the glass transition temperature (Tg) and heat deflection temperature under load (HDTUL) of the rigid PVC formulation due to absorption of the infrared portion of the high temperature and solar spectrum.

[0003]

[0003] Manufacturers of these products have had to limit the range of designs and colors offered to reduce product distortion. Alternatively, manufacturers have attempted to use materials such as alpha-methylstyrene acrylonitrile copolymer (AMSAN) to increase the Tg and HDTUL of PVC formulations. These options have drawbacks, often limiting the geographical area in which these products can be used, or creating processing and product defects that must be addressed. For example, AMSAN results in reduced thermal stability, increased yellowing, and loss of impact properties. Surprisingly, in this disclosure, it has been found that several polycarbonate resins and high-Tg copolyester compositions are melt-workable at typical rigid PVC processing temperatures without adverse effects on processing properties, as well as increasing Tg and HDTUL without loss of impact properties. [Overview of the project] [Means for solving the problem]

[0004]

[0004] The polyvinyl chloride compositions of this disclosure comprise at least one polyvinyl chloride resin, at least one polycarbonate resin, and at least one copolyester resin.

[0005] One embodiment of the present disclosure is a polyvinyl chloride composition comprising at least one polyvinyl chloride resin, at least one polycarbonate resin, and at least one copolyester resin, wherein the at least one copolyester resin is (a) (i) Approximately 90 to 100 mol% of terephthalic acid residues, (ii) Aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, present in amounts of approximately 0 to 10 mol% A dicarboxylic acid component containing, (b) (i) Approximately 20 to 60 mol% of a modification glycol consisting of 2 to 20 carbon atoms, and (ii) A second modified glycol consisting of 2 to 20 carbon atoms, in an amount of approximately 40 to 80 mol% Glycol components containing This is a polyvinyl chloride composition containing a total mol% of the dicarboxylic acid component and a total mol% of the glycol component, with the latter being 100 mol%.

[0005]

[0006] One embodiment of the present disclosure is a polyvinyl chloride composition comprising at least one polyvinyl chloride resin, at least one polycarbonate resin, and at least one copolyester resin, wherein the at least one copolyester resin is (a) (i) Approximately 50 to 100 mol% of terephthalic acid residues, (ii) Aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, in amounts of approximately 0 to approximately 50 mol% A dicarboxylic acid component containing, (b) (i) Approximately 60 to 100 mol% of a modification glycol consisting of 2 to 20 carbon atoms, and (ii) A second modified glycol consisting of 2 to 20 carbon atoms, in an amount of approximately 0 to 40 mol% Glycol components containing This is a polyvinyl chloride composition containing a total mol% of the dicarboxylic acid component and a total mol% of the glycol component, with the latter being 100 mol%.

[0006]

[0007] In one embodiment, the Tg of the copolyester is at least about 90°C or higher.

[0008] In one embodiment, the Tg of the copolyester is at least about 100°C or higher.

[0007]

[0009] In one embodiment, the copolyester is amorphous.

[0010] In one embodiment, the copolyester has a semi-crystallization time of about 5 minutes or more.

[0011] In one embodiment, the copolyester resin content in the PVC composition is about 1 to about 100 parts (phr) per 100 parts of resin relative to the PVC resin content in the composition.

[0008]

[0012] In one embodiment, the polycarbonate resin content in the PVC composition is approximately 1 to approximately 50 parts (phr) per 100 parts of resin relative to the total PVC resin content in the composition.

[0013] In one embodiment, the polycarbonate resin content in the PVC composition is about 1 to about 50 parts (phr) per 100 parts of resin, and the copolyester resin content is about 1 to about 100 parts (phr) per 100 parts of resin, relative to the PVC resin content in the PVC composition.

[0009]

[0014] In one embodiment, the polyvinyl chloride composition is rigid.

[0015] In one embodiment, the polyvinyl chloride resin is a polyvinyl chloride resin, a chlorinated polyvinyl chloride resin, or an alloy thereof.

[0010]

[0016] In one embodiment, the polycarbonate resin is a bisphenol-based polycarbonate resin.

[0017] The composition according to claim 1 or 2, wherein the ratio of polyvinyl chloride resin to copolyester based on weight fraction is greater than about 1.

[0011]

[0018] The composition according to claim 1 or 2, wherein the ratio of polyvinyl chloride resin:copolyester and polycarbonate based on weight fraction is greater than about 1.

[0019] One embodiment of the present disclosure is a method for producing a polyvinyl chloride composition, comprising the steps of extruding at least one polyvinyl chloride resin composition, at least one polycarbonate resin and at least one copolyester to produce a viscous blend of thermoplastic materials, wherein at least one copolyester is (a) (i) Approximately 90 to 100 mol% of terephthalic acid residues, (ii) Aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, present in amounts of approximately 0 to 10 mol% A dicarboxylic acid component comprising (b) (i) About 20 to about 60 mol% of a modifying glycol having 2 to 20 carbon atoms, and (ii) About 40 to about 80 mol% of a second modifying glycol having 2 to 20 carbon atoms A glycol component comprising Comprising, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the glycol component is 100 mol%, a step; Introducing a blend of the thermoplastic material into a calendering, extrusion or injection molding process to produce a polyvinyl chloride article A method comprising.

[0012]

[0020] One embodiment of the present disclosure is a method for producing a polyvinyl chloride composition, comprising extruding at least one polyvinyl chloride resin composition, at least one polycarbonate resin and at least one copolyester to produce a viscous blend of thermoplastic materials, wherein at least one copolyester is (a) (i) About 50 to about 100 mol% of terephthalic acid residues, and (ii) About 0 to about 50 mol% of aromatic and / or aliphatic dicarboxylic acid residues having a maximum of 20 carbon atoms A dicarboxylic acid component comprising (b) (i) About 60 to about 100 mol% of a modifying glycol having 2 to 20 carbon atoms, and (ii) About 0 to about 40 mol% of a second modifying glycol having 2 to 20 carbon atoms A glycol component comprising Comprising, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the glycol component is 100 mol%, a step; Introducing a blend of the thermoplastic material into a calendering, extrusion or injection molding process to produce a polyvinyl chloride article A method comprising.

[0013]

[0021] One embodiment of the present disclosure is a method for producing a polyvinyl chloride composition, comprising the step of compounding a miscible mixture of at least one polycarbonate resin and at least one copolyester resin to produce a viscous thermoplastic material, wherein the at least one copolyester resin is (a) (i) Approximately 90 to 100 mol% of terephthalic acid residues, (ii) Aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, present in amounts of approximately 0 to 10 mol% A dicarboxylic acid component containing, (b) (i) Approximately 20 to 60 mol% of a modification glycol consisting of 2 to 20 carbon atoms, and (ii) A second modified glycol consisting of 2 to 20 carbon atoms, in an amount of approximately 40 to 80 mol% Glycol components containing The step includes a mixture containing a total mol% of the dicarboxylic acid component, where the total mol% of the glycol component is 100 mol%, and the step is to include a mixture containing a total mol% of the glycol component, A step of blending the compound with at least one polyvinyl chloride resin composition, The steps include introducing the blend into a calendering, extrusion, or injection molding process to produce polyvinyl chloride articles and This method includes [something].

[0014]

[0022] One embodiment of the present disclosure is a method for producing a polyvinyl chloride composition, The step is to produce a viscous thermoplastic material by compounding at least one polycarbonate resin and at least one copolyester resin, wherein at least one copolyester resin is (a) (i) Approximately 50 to 100 mol% of terephthalic acid residues, (ii) Aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, in amounts of approximately 0 to approximately 50 mol% A dicarboxylic acid component containing, (b) (i) Approximately 60 to 100 mol% of a modification glycol consisting of 2 to 20 carbon atoms, and (ii) A second modified glycol consisting of 2 to 20 carbon atoms, in an amount of approximately 0 to 40 mol% Glycol components containing The step includes a mixture containing a total mol% of the dicarboxylic acid component, where the total mol% of the glycol component is 100 mol%, and the step is to include a mixture containing a total mol% of the glycol component, A step of blending the compound into at least one polyvinyl chloride resin composition, The steps include introducing the blend into a calendering, extrusion, or injection molding process to produce polyvinyl chloride articles and This method includes [something].

[0015]

[0023] One embodiment of the present disclosure is a polyvinyl chloride article in which Tg and HDTUL (heat distortion temperature under load) are increased by at least 3°C.

[0024] One embodiment of the present disclosure is a polyvinyl chloride article having a maximum Tg of 110°C or a maximum HDTUL of 130°C. [Brief explanation of the drawing]

[0016] [Figure 1]

[0025] This graph shows that when polycarbonate / copolyester blends are blended with PVC compositions, they tend to lower the complex viscosity (mPa) compared to the PVC control at all measured shear rates. [Figure 2]

[0026] This graph shows that when high glass transition temperature copolyester / polycarbonate admixtures are blended with PVC compositions, the complex viscosity (mPa) tends to increase compared to the PVC control at all measured shear rates. [Figure 3]

[0027] This graph shows that when a 50% copolyester and 50% polycarbonate mixture is blended with a PVC composition, the storage modulus (mPa) versus temperature increases compared to the PVC control, indicating that the glass transition temperature increases as the amount of the mixture increases. [Figure 4]

[0028] This graph shows that when a 50% copolyester and 50% polycarbonate mixture is blended with a PVC composition, a single tan delta peak is produced that increases at higher load levels, indicating the presence of a single glass transition temperature and demonstrating that the mixture is miscible with PVC. [Figure 5]

[0029] This graph shows that when a mixture of 25% copolyester and 75% polycarbonate is blended with a PVC composition, the storage modulus (mPa) versus temperature increases compared to the PVC control, indicating that the glass transition temperature increases as the amount of the mixture increases. [Figure 6]

[0030] This graph shows that when a mixture of 25% copolyester and 75% polycarbonate is blended with a PVC composition, a single tan delta peak is produced that increases at higher load levels, indicating the presence of a single glass transition temperature and demonstrating that the mixture is miscible with PVC. [Figure 7]

[0031] This graph shows that PVC and polycarbonate are immiscible and do not have a single glass transition temperature, but rather two different glass transition temperatures exist as the amount of polycarbonate increases, as indicated by the tandelta readings. [Modes for carrying out the invention]

[0017]

[0032] The polyvinyl alcohol composition of this disclosure comprises at least one polyvinyl chloride resin, at least one polycarbonate resin, and at least one copolyester.

[0018]

[0033] One embodiment of the present disclosure is a polyvinyl chloride composition comprising at least one polyvinyl chloride resin, at least one polycarbonate resin, and at least one copolyester, wherein the at least one copolyester is (a) (i) Approximately 90 to 100 mol% of terephthalic acid residues, (ii) Aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, present in amounts of approximately 0 to 10 mol% A dicarboxylic acid component containing, (b) (i) Approximately 20 to 60 mol% of a modification glycol consisting of 2 to 20 carbon atoms, and (ii) A second modified glycol consisting of 2 to 20 carbon atoms, in an amount of approximately 40 to 80 mol% This is a polyvinyl chloride composition containing a glycol component, wherein the total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the glycol component is 100 mol%.

[0019]

[0034] One embodiment of the present disclosure is a polyvinyl chloride composition comprising at least one polyvinyl chloride resin, at least one polycarbonate resin, and at least one copolyester, wherein the at least one copolyester is (a) (i) Approximately 50 to 100 mol% of terephthalic acid residues, (ii) Aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, in amounts of approximately 0 to approximately 50 mol% A dicarboxylic acid component containing, (b) (i) Approximately 60 to 100 mol% of a modification glycol consisting of 2 to 20 carbon atoms, and (ii) A second modified glycol consisting of 2 to 20 carbon atoms, in an amount of approximately 0 to 40 mol% Glycol components containing This is a polyvinyl chloride composition comprising at least one copolyester, wherein the total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the glycol component is 100 mol%.

[0020]

[0035] Any amorphous or essentially amorphous copolyester is suitable for use in this disclosure. For example, in one embodiment, any copolyester may be used in this disclosure provided that it is essentially amorphous and has a minimum semi-crystallization time of at least about 5 minutes or at least about 7 minutes. In one embodiment, any copolyester may be used provided that it has a minimum semi-crystallization time of at least about 8 minutes. In another embodiment, any copolyester may be used provided that it has a semi-crystallization time of at least about 10 minutes. Amorphous copolyesters in this disclosure may have a semi-crystallization time of up to infinity in some embodiments. In one embodiment of this disclosure, a blend of an amorphous copolyester with other polymers (including other polyesters and copolyesters) is suitable for use provided that it has a minimum semi-crystallization time of at least about 5 minutes.

[0021]

[0036] The semi-crystallization time can be measured using a differential scanning calorimeter following the procedure below. Approximately 10.0 mg of the copolyester sample is sealed in an aluminum pot and heated to approximately 290°C at a rate of approximately 20°C / min, and held in a helium atmosphere for approximately 2 minutes. The sample is then immediately cooled at a rate of approximately 20°C / min to an isothermal crystallization temperature in the range of approximately 140°C to approximately 200°C in increments of approximately 10°C. The semi-crystallization time at each temperature is then determined as the time required to reach the peak of the exothermic curve. The minimum semi-crystallization time is the temperature at which the crystallization rate is fastest.

[0022]

[0037] In one embodiment of this disclosure, copolyester is (a) (i) Approximately 50 to 100 mol% of terephthalic acid residues, (ii) Aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, in amounts of approximately 0 to approximately 50 mol% A dicarboxylic acid component containing, (b) (i) Approximately 20 to 60 mol% of a modification glycol consisting of 2 to 20 carbon atoms, and (ii) A second modified glycol consisting of 2 to 20 carbon atoms, in an amount of approximately 40 to 80 mol% Glycol components containing It contains a total molar percentage of the dicarboxylic acid component, and a total molar percentage of the glycol component, both of which are 100 mol%.

[0023]

[0038] In another embodiment, the copolyester is (a) (i) Approximately 50 to 100 mol% of terephthalic acid residues, (ii) Aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, in amounts of approximately 0 to approximately 50 mol% A dicarboxylic acid component containing, (b) (i) Approximately 60 to 100 mol% of a modification glycol consisting of 2 to 20 carbon atoms, and (ii) A second modified glycol consisting of 2 to 20 carbon atoms, in an amount of approximately 0 to 40 mol% Glycol components containing It contains a total molar percentage of the dicarboxylic acid component, and a total molar percentage of the glycol component, both of which are 100 mol%.

[0024]

[0039] Unless the context explicitly indicates otherwise, the terms “polyester” and “copolyester” are used synonymously herein. The term “polyester” is understood to encompass “copolyester” and to mean a synthetic polymer prepared by polycondensation of one or more difunctional carboxylic acids (or diacids) and one or more difunctional hydroxyl compounds (or diols). In one embodiment, the difunctional carboxylic acid is a dicarboxylic acid, and the difunctional hydroxyl compound is a dihydric alcohol, such as a glycol or a diol.

[0025]

[0040] The term "residue" refers to any organic structure incorporated into a polymer through a polycondensation reaction involving the corresponding monomer. The term "repeating unit" refers to an organic structure having dicarboxylic acid residues (or diacid components) and diol residues (or diol components) linked through a carbonyloxy group. Therefore, dicarboxylic acid residues can originate from dicarboxylic acid monomers or their related acid halides, esters, salts, anhydrides, or mixtures thereof.

[0026]

[0041] In one embodiment, the copolyester of the disclosure is amorphous. In one embodiment, the copolyester of the disclosure is essentially amorphous.

[0042] In one embodiment, the copolyester comprises repeating units derived from a dicarboxylic acid based on 100 mole percent of dicarboxylic acid residues and a diol based on 100 mole percent of diol residues.

[0027]

[0043] In one embodiment, the diacid component contains at least about 50 mole percent of aromatic dicarboxylic acid residues having about 8 to about 14 carbon atoms. The copolyester may be optionally modified with one or more different dicarboxylic acid residues other than aromatic dicarboxylic acids, such as saturated aliphatic dicarboxylic acids having 4 to 12 carbon atoms or alicyclic dicarboxylic acids having 8 to 12 carbon atoms, up to about 50 mole percent of 100 mole percent of dicarboxylic acid residues. Specific examples of dicarboxylic acids include terephthalic acid, phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4'-dicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, and sebacic acid. The polyester can be prepared from one or more of the above dicarboxylic acids.

[0028]

[0044] It should be understood that the use of the corresponding acid anhydrides, esters, and acid chlorides of these acids is encompassed within the term "dicarboxylic acid."

[0045] In one embodiment, the diol component comprises at least about 60 mole percent of diol residues containing 2 to 20 carbon atoms. Furthermore, the diol component may optionally be modified with up to about 40 mole percent of one or more other diol residues relative to 100 mole percent of diol residues. Specific examples of diols include ethylene glycol, diethylene glycol, triethylene glycol, isosorbide, propane-1,3-diol, butane-1,4-diol, 2,2-dimethylpropane-1,3-diol (neopentyl glycol), 2,2,4,4-tetramethyl-1,3-cyclobutanediol, pentane-1,5-diol, hexane-1,6-diol, 1,4-cyclohexanedimethanol, 3-methylpentanediol-(2,4), 2-methylpentanediol-(1,4), 2,2 Examples include 4-trimethylpentane-diol-(1,3), 2-ethylhexanediol-(1,3), 2,2-diethylpropane-diol-(1,3), hexanediol-(1,3), 1,4-di-(hydroxyethoxy)benzene, 2,2-bis-(4-hydroxycyclohexyl)propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis-(3-hydroxyethoxyphenyl)propane, and 2,2-bis-(4-hydroxypropoxyphenyl)propane. Polyesters can be prepared from one or more of the above diols.

[0029]

[0046] In one embodiment, the diacid component contains at least about 90 mole percent of aromatic dicarboxylic acid residues having up to about 20 carbon atoms. The copolyester may optionally be modified with one or more different dicarboxylic acid residues other than aromatic dicarboxylic acids, such as saturated aliphatic dicarboxylic acids having 4 to 12 carbon atoms or alicyclic dicarboxylic acids having 8 to 12 carbon atoms, at up to about 10 mole percent of the dicarboxylic acid residues. Specific examples of dicarboxylic acids include terephthalic acid, phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4'-dicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, and sebacic acid. The polyester can be prepared from one or more of the above dicarboxylic acids.

[0030]

[0047] It should be understood that the use of the corresponding acid anhydrides, esters, and acid chlorides of these acids is encompassed within the term "dicarboxylic acid."

[0048] In one embodiment, the diol component comprises at least about 20 mole percent of diol residues containing 2 to 20 carbon atoms. Furthermore, the diol component may be optionally modified with up to about 80 mole percent of one or more other diol residues relative to 100 mole percent of diol residues. Specific examples of diols include ethylene glycol, diethylene glycol, triethylene glycol, isosorbide, propane-1,3-diol, butane-1,4-diol, 2,2-dimethylpropane-1,3-diol (neopentyl glycol), 2,2,4,4-tetramethyl-1,3-cyclobutanediol, pentane-1,5-diol, hexane-1,6-diol, 1,4-cyclohexanedimethanol, 3-methylpentanediol-(2,4), 2-methylpentanediol-(1,4), 2,2, Examples include 4-trimethylpentane-diol-(1,3), 2-ethylhexanediol-(1,3), 2,2-diethylpropane-diol-(1,3), hexanediol-(1,3), 1,4-di-(hydroxyethoxy)benzene, 2,2-bis-(4-hydroxycyclohexyl)propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis-(3-hydroxyethoxyphenyl)propane, and 2,2-bis-(4-hydroxypropoxyphenyl)propane. Polyesters can be prepared from one or more of the above diols.

[0031]

[0049] The polyester may also contain small amounts of trifunctional or tetrafunctional comonomers such as trimellitic anhydride, trimethylolpropane, pyromellitic dianhydride, pentaerythritol, and other polyester-forming polyacids or polyols commonly known in the art.

[0032]

[0050] In one embodiment, the copolyester comprises (i) a diacid component comprising at least about 50 mole percent of residues of terephthalic acid, naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, isophthalic acid, or a mixture thereof; and (ii) a diol component comprising at least about 80 mole percent of residues of a diol containing 2 to 10 carbon atoms. In one embodiment, the diacid component of the copolyester comprises at least about 80 mole percent of residues of terephthalic acid, naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, isophthalic acid, or a mixture thereof. In another embodiment, the diol component of the copolyester comprises residues of ethylene glycol, 1,4-cyclohexanedimethanol, diethylene glycol, neopentyl glycol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, or a mixture thereof.

[0033]

[0051] In another embodiment, the copolyester comprises (i) a diacid component comprising at least about 80 mole percent of terephthalic acid residues, and (ii) a diol component comprising at least about 80 mole percent of ethylene glycol and 1,4-cyclohexanedimethanol residues. In yet another embodiment, the copolyester comprises (i) a diacid component comprising at least about 80 mole percent of terephthalic acid residues, and (ii) a diol component comprising at least about 80 mole percent of ethylene glycol, 1,4-cyclohexanedimethanol, and diethylene glycol residues. In yet another embodiment, the copolyester comprises (i) a diacid component comprising at least about 80 mole percent of terephthalic acid residues, and (ii) a diol component comprising at least about 80 mole percent of ethylene glycol and neopentyl glycol residues. In yet another embodiment, the copolyester comprises (i) a diacid component comprising at least about 80 mole percent of terephthalic acid residues, and (ii) a diol component comprising at least about 80 mole percent of 1,4-cyclohexanedimethanol and 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

[0034]

[0052] In one embodiment, the copolyester composition is (a) (i) 70-100 mol% of terephthalic acid residues, and (ii) 0 to 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms A dicarboxylic acid component containing, (b) (i) 0 to 40 mol% of 2,2-dimethylpropane-1,3-diol (neopentyl glycol or NPG) residues, (ii) 0 to 100 mol% of 1,4-cyclohexanedimethanol (CHDM) residues, (iii) 0-70 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues, (iv) 0-40 mol% of diethylene glycol (DEG) residues, whether formed in situ or not. It is a glycol component containing, and the remainder of the glycol component is (v) ethylene glycol residues, and (vi) Optionally, 0 to 10 mol% of residues of at least one other denaturing glycol. Glycol components and It contains at least one polyester having a total mol% of the dicarboxylic acid component and a total mol% of the glycol component.

[0035]

[0053] In one embodiment, the copolyester composition is (a) (i) 70-100 mol% of terephthalic acid residues, and (ii) 0 to 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms A dicarboxylic acid component containing, (b) (i) 10-70 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues, (ii) 0-40 mol% of 1,4-cyclohexanedimethanol (CHDM) residues, (iii) 0-10 mol% of diethylene glycol (DEG) residues, whether in-situ or otherwise formed. It is a glycol component containing, and the remainder of the glycol component is (iv) ethylene glycol residues, and (v) Optionally, 0 to 10 mol% of residues of at least one other denaturing glycol. Glycol components and It contains at least one polyester having a total mol% of the dicarboxylic acid component and a total mol% of the glycol component.

[0036]

[0054] In one embodiment, the copolyester composition is (a) (i) 70-100 mol% of terephthalic acid residues, and (ii) 0 to 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms A dicarboxylic acid component containing, (b) (i) 10-70 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues, (ii) 30-90 mol% of 1,4-cyclohexanedimethanol (CHDM) residues, (iii) 0-10 mol% of diethylene glycol (DEG) residues, whether in-situ or otherwise formed. It is a glycol component containing, and the remainder of the glycol component is (iv) ethylene glycol residues, and (v) Optionally, 0 to 10 mol% of residues of at least one other denaturing glycol. Glycol components and It contains at least one polyester having a total mol% of the dicarboxylic acid component and a total mol% of the glycol component.

[0037]

[0055] In one embodiment, the copolyester composition is (a) (i) 70-100 mol% of terephthalic acid residues, and (ii) 0 to 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms A dicarboxylic acid component containing, (b) (i) 20-60 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues, (ii) 40-80 mol% of 1,4-cyclohexanedimethanol (CHDM) residues, (iii) 0-10 mol% of diethylene glycol (DEG) residues, whether in-situ or otherwise formed. It is a glycol component containing, and the remainder of the glycol component is (iv) ethylene glycol residues, and (v) Optionally, 0 to 10 mol% of residues of at least one other denaturing glycol. Glycol components and It contains at least one polyester having a total mol% of the dicarboxylic acid component and a total mol% of the glycol component.

[0038]

[0056] In one embodiment, the copolyester composition is (a) (i) 70-100 mol% of terephthalic acid residues, and (ii) 0 to 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms A dicarboxylic acid component containing, (b) (i) 20-40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues, (ii) 60-80 mol% of 1,4-cyclohexanedimethanol (CHDM) residues, (iii) 0-10 mol% of diethylene glycol (DEG) residues, whether in-situ or otherwise formed. It is a glycol component containing, and the remainder of the glycol component is (iv) ethylene glycol residues, and (v) Optionally, 0 to 10 mol% of residues of at least one other denaturing glycol. Glycol components and It contains at least one polyester having a total mol% of the dicarboxylic acid component and a total mol% of the glycol component.

[0039]

[0057] In certain embodiments, the condensed polymer contains at least two diol residues. In certain embodiments, the condensed polymer is a polyester containing at least one dicarboxylic acid or its ester and at least two diols, where the total amount of acid residues and the total amount of diol residues are 100 mol%. In certain embodiments, the condensed polymer, e.g., polyester, contains a 1,4-cyclohexanedimethanol residue.

[0040]

[0058] For example, in the case of TMCD-CHDM copolyester (a polymer containing 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-cyclohexanedimethanol, and terephthalic acid residues), the modifying glycol can be ethylene glycol and / or isosorbide residues.

[0041]

[0059] In one embodiment of TMCD copolyester, ethylene glycol is excluded as a modifying diol. In the case of modified PETG and modified PCTG polymers, the modifying glycol can be, for example, a glycol other than ethylene glycol and 1,4-cyclohexanedimethanol.

[0042]

[0060] Polymers and / or polyesters useful in the present invention contain 1,4-cyclohexanedimethanol residues in the following amounts: 0.01-100 mol%; 0.01-100 mol%; 0.01-99.99 mol%; 0.10-99 mol%; 0.10-99 mol%; 0.10-95 mol%; 0.10-90 mol%; 0.10-85 mol%; 0.10-80 mol%; 0.10-70 mol%; 0.10-60 mol%; 0.10-50 mol%; 0.10-40 mol%; 0.10-35 mol%; 0.10-30 mol%; 0.10-25 mol%; 0.10-20 mol%; 0. 10-15 mol%; 0.10-10 mol%; 0.10-5 mol%; 1-100 mol%; 1-99 mol%; 1-95 mol%; 1-90 mol%; 1-85 mol%; 1-80 mol%; 1-70 mol%; 1-60 mol%; 1-50 mol%; 1-40 mol%; 1-35 mol%; 1-30 mol%; 1-25 mol%; 1-20 mol%; 1-15 mol%; 1-10 mol%; 1-5 mol%; 5-100 mol%; 5-99 mol%; 5-95 mol%; 5-90 mol%; 5-85 mol%; 5-80 mol%; 5-70 mol%; 5-60 mol%; 5-50 mol%; 5-40 mol%; 5- 35 mol%; 5-30 mol%; 5-25 mol%; 5-20 mol%; and 5-15 mol%; 5-10 mol%; 10-100 mol%; 10-99 mol%; 10-95 mol%; 10-90 mol%; 10-85 mol%; 10-80 mol%; 10-70 mol%; 10-60 mol%; 10-50 mol%; 10-40 mol%; 10-35 mol%; 10-30 mol%; 10-25 mol%; 10-20 mol%; 10-15 mol%; 20-100 mol%; 20-99 mol%; 20-95 mol%; 20-90 mol%; 20-85 mol%; 20-80 mol%; 20-70 mol%; 20-60 mol%; 20-50 mol%; 20-40 mol%; 20-35 mol%; 20-30 mol%; and 20-25 mol%; 30-100 mol%; 30-99 mol%; 30-95 mol%; 30-90 mol%; 30-85 mol%; 30-80 mol%; 30-70 mol%; 30-60 mol%; 30-50 mol%; 30-40 mol%; 30-35 mol%; 40-100 mol%; 40-99 mol%; 40-95 mol%; 40-90 mol%; 40-85 mol%; 40-80 mol%; 40-70 mol%; 40-60 mol%; 40-50 mol%; 50-100 mol%;50-99 mol%; 50-95 mol%; 50-90 mol%; 50-85 mol%; 50-80 mol%; 50-70 mol%; 50-60 mol%; 60-100 mol%; 60-99 mol%; 60-95 mol%; 60-90 mol%; 60-85 mol%; 60-80 mol%; 60-70 mol%; 70-100 mol%; 70-99 mol%; 70-95 mol%; 70- It may contain any amount including, but is not limited to, at least one of the following: 90 mol%; 70-85 mol%; 70-80 mol%; 60-70 mol%; 80-100 mol%; 80-99 mol%; 80-95 mol%; 80-90 mol%; 90-100 mol%; 90-99 mol%; 90-95 mol%; 95-100 mol%; or 95-99 mol%.

[0043]

[0061] A useful polymer composition in the present invention may be either a glycol-modified PET (PETG) or a traditional composition described as glycol-modified poly(cyclohexylenediethylene terephthalate) (PCTG), and any of the above polymers may also be modified with 2,2,4,4-tetramethylcyclobutane-1,3-diol (TMCD polyester).

[0044]

[0062] In one embodiment, a polyester useful in the polymer composition of the present invention comprises an isosorbide residue. In one embodiment, the isosorbide polymer may also comprise an ethylene glycol and / or cyclohexanedimethanol residue. In a particular embodiment, the polyester comprises an isosorbide and 1,4-cyclohexanedimethanol residue, and optionally an ethylene glycol residue. In a particular embodiment, the polyester comprises an isosorbide and ethylene glycol residue, and optionally an 1,4-cyclohexanedimethanol residue.

[0045]

[0063] In certain embodiments, the polymer composition of the present invention may include a copolyester comprising 1,4-cyclohexanedimethanol and optionally ethylene glycol.

[0046]

[0064] In a particular embodiment, the polymer composition of the present invention optionally comprises 0.01 to 30 mol%, or 0.01 to 20 mol%, or 0.01 to 10 mol%, or 0.01 to 5 mol%, of terephthalic acid and / or isophthalic acid, or their esters and / or mixtures thereof, and a diol component comprising: (a) less than 20 to 50 mol% of 1,4-cyclohexanedimethanol residues and more than 50 mol% to 80 mol% of ethylene glycol residues; or 20 to 40 mol% of 1,4-cyclohexanedimethanol. (b) dimethanol residues and 60-80 mol% ethylene glycol residues, or 20-40 mol% 1,4-cyclohexanedimethanol residues and 60-80 mol% ethylene glycol residues, or 25-40 mol% 1,4-cyclohexanedimethanol residues and 60-75 mol% ethylene glycol residues, or 25-35 mol% 1,4-cyclohexanedimethanol residues and 65-75 mol% ethylene glycol residues (PETG); or (b) 50 mol%-99.99 mol%, and This includes 55 mol% to 99.99 mol%, or 60 mol% to 99.99 mol%, or 65 mol% to 99.99 mol%, or 70 mol% to 99.99 mol%, or 75 mol% to 99.99 mol%, or 80 mol% to 99.99 mol%, or 85 mol% to 99.99 mol%, or 90 mol% to 99.99 mol%, or 95 mol% to 99.99 mol%, of 1,4-cyclohexanedimethanol residue and 0.01 mol% to 50 mol%, or 0.01 mol% to 45 mol%, or 0.01 mol% to 40 mol% (c) 95-99.99 mol% of 1,4-cyclohexanedimethanol residues, 0.01-10 mol% or 0.01-30 mol%, or 0.01-25 mol%, or 0.01-20 mol%, or 0.01-15 mol%, or 0.01-10 mol%, or 0.01-5 mol% of ethylene glycol residues (PCTG); or (c) 95-99.99 mol% of 1,4-cyclohexanedimethanol residues, 0.01-10 mol% or 0.01-5 mol% of isophthalic acid residues, and 0.01-10 mol% or 0.(d) 0-20 mol% ethylene glycol residues (PCTA), or (e) 0-20 mol% 1,4-cyclohexanedimethanol residues and 80-100 mol% ethylene glycol residues (PET or glycol-modified PET), or (e) TMCD copolyester containing 20-60 mol% TMCD residues and 40-80 mol% 1,4-cyclohexanedimethanol residues, along with 0-40 mol% denaturing glycol residues; or TMCD copolyester containing 15-40 mol% TMCD residues and 60-85 mol% 1,4-cyclohexanedimethanol residues, along with 0-35 mol% denaturing glycol residues; or containing 20-40 mol% TMCD residues and 60-80 mol% 1,4-cyclohexanedimethanol residues. The copolyester may include (f) an isosorbide polymer containing ethylene glycol, or (g) (PCT as defined herein), or (h) an isosorbide polymer containing 1,4-cyclohexanedimethanol and optionally ethylene glycol.

[0047]

[0065] Copolyesters useful in this disclosure may have an inherent viscosity of about 0.4 to about 1.2 dL / g. As used herein, inherent viscosity (or IhV) is the viscosity of a diluted solution of the polymer, specifically IhV is the viscosity determined by ASTM 4603 at about 25°C or about 30°C with a concentration of about 0.25 g of polyester per 50 ml of a phenol / tetrachloroethane 60 / 40 (wt% / wt%) solution. This viscosity measurement is representative of the molecular weight of the polymer.

[0048]

[0066] For example, in one embodiment, the copolyester has an inherent viscosity of about 0.45 to about 0.9 dL / g or about 0.60 to about 0.90 dL / g, measured at about 25°C using 0.50 grams of polymer per 100 mL of a solvent consisting of 60% by weight of phenol and 40% by weight of tetrachloroethane.

[0049]

[0067] In one embodiment, a copolyester useful in this disclosure has a glass transition temperature of about 30°C to about 155°C. For example, in one embodiment, the glass transition temperature of the copolyester is about 90°C to about 120°C. In one embodiment, the glass transition temperature of the copolyester is about 95°C to about 140°C. In another embodiment, the glass transition temperature of the copolyester is about 100°C to about 150°C. In one embodiment, a copolyester useful in this disclosure has a glass transition temperature of at least about 90°C. In one embodiment, the copolyester has a glass transition temperature of at least about 100°C, or at least about 110°C, or at least about 120°C.

[0050]

[0068] Copolyesters can be prepared by conventional polycondensation procedures well known in the art. Such methods include direct condensation of dicarboxylic acids and diols or transesterification using dialkyldicarboxylates. For example, dialkylterephthalates such as dimethyl terephthalate are transesterified with diols at high temperatures in the presence of a catalyst. The polyester may also be subjected to solid-phase polymerization. A preferred method involves reacting one or more dicarboxylic acids with one or more glycols at a temperature of about 100°C to about 315°C and a pressure of about 0.1 to about 760 mmHg for a time sufficient to form a polyester. For a method of producing polyesters, see U.S. Patent No. 3,772,405. Disclosures of such methods are incorporated herein by reference.

[0051]

[0069] Copolyesters suitable for use in this disclosure can be obtained commercially from Eastman Chemical Company.

[0070] Any polycarbonate ("PC") polymer resin is suitable for use in this disclosure. For example, in one embodiment, an aromatic polycarbonate is a polycarbonate resin useful in this disclosure. Suitable aromatic polycarbonates for the compositions of this disclosure include, for example, polymers derived from diphenols such as bisphenol A, 1,1(4-hydroxyphenol) ketone, bis-(4-hydroxyphenyl)methane, 1,1-bis-(hydroxyphenyl)-ethane, phenolphthalein, and 1,1-bis(hydroxyphenol)sulfone; as well as aromatic polycarbonates having alkyl or halogen substituents on the phenyl ring.In another embodiment, suitable aromatic polycarbonates for the compositions of the present disclosure include, for example, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A); 1,1-bis(4-hydroxyphenyl)-1-phenylethane (bisphenol AP); 2,2-bis(4-hydroxyphenyl)hexafluoropropane (bisphenol AF); 2,2-bis(4-hydroxyphenyl)butane (bisphenol B); bis-(4-hydroxyphenyl)diphenylmethane (bisphenol BP); 2,2-bis(3-methyl-4-hydroxyphenyl)propane (bisphenol C); bis(4-hydroxyphenyl)-2,2-dichloroethylene (bisphenol C2); 1,1-bis(4-hydroxyphenyl)ethane (bisphenol E); bis(4-hydroxyphenyl)methane (bisphenol F); 2,2-bis(4-hydroxy-3-isopropyl-phenyl) Examples of polymers derived from diphenols include bisphenol G (propane); 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene (bisphenol M); bis(4-hydroxyphenyl)sulfone (bisphenol S); 1,4-bis(2-(4-hydroxyphenyl)-2-propyl)benzene (bisphenol P); 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-ol]propane (bisphenol PH); 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC); 1,1-bis(4-hydroxyphenyl)-cyclohexane (bisphenol Z); 2,2-bis(4-hydroxy-3-nitrophenyl)propane (dinitrobisphenol A); and 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane (tetrabromobisphenol A).

[0052]

[0071] In one embodiment, the polycarbonate is a high molecular weight thermoplastic aromatic polycarbonate, and includes homopolycarbonates, copolicarbonates, and mixtures thereof having a number average molecular weight of about 8,000 to over 200,000 or about 10,000 to 80,000 when dissolved in methylene chloride at 25°C and an intrinsic viscosity of 0.30 to 1.0 deciliters per gram (dl / g). Polycarbonates are derived from divalent phenols such as 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 4,4-bis(4-hydroxyphenyl)heptane, 2,2-(3,5,3',5-tetrachloro-4,4'-dihydroxyphenyl)propane, 2,2-(3,5,3',5-tetrabromo-4,4'-dihydroxydiphenyl)propane, and (3,3'-dichloro-4,4'-dihydroxydiphenyl)propane, as well as (3,3'-dichloro-4,4'-dihydroxydiphenyl)methane. Other divalent phenols for use in the preparation of the above polycarbonates are disclosed in U.S. Patents 2,999,835; 3,028,365; 3,334,154 and 4,134,575, which are incorporated herein by reference.

[0053]

[0072] In one embodiment, the polycarbonate resin in this disclosure is a bisphenol-based polycarbonate. In one embodiment, the polycarbonate resin in this disclosure is a bisphenol A-based polycarbonate. In one embodiment, the polycarbonate resin in this disclosure is a bisphenol S-based polycarbonate. In one embodiment, the polycarbonate resin in this disclosure is a bisphenol C-based polycarbonate. In one embodiment, the polycarbonate resin is a bisphenol A-based polycarbonate having a melt flow of approximately 3 to approximately 80 g / 10 min at 300°C and a load of 3.8 kg (ASTM).

[0054]

[0073] Polycarbonates can be produced by known methods. For example, in one embodiment, polycarbonates can be produced by reacting a divalent phenol with a carbonate precursor such as phosgene, according to the methods described in the above-mentioned literature and U.S. Patents No. 3,989,672; No. 4,018,750 and No. 4,123,436, or transesterification methods such as those disclosed in U.S. Patent No. 3,153,008, or other methods known to those skilled in the art (all of which are incorporated herein by reference).

[0055]

[0074] In one embodiment, the polycarbonate is an aromatic polycarbonate, such as a polymer derivative of divalent phenol, dicarboxylic acid, and carbonic acid, as disclosed in U.S. Patent No. 3,169,121.

[0056]

[0075] In one embodiment, a carbonate copolymer or interpolymer is used instead of a homopolymer in the preparation of an aromatic polycarbonate. In this embodiment, two or more different divalent phenols, or copolymers of divalent phenols with glycols or acid-terminated polyesters, or dibasic acids can be used. Any blend of the above materials is acceptable.

[0057]

[0076] In one embodiment, branched polycarbonates, such as those described in U.S. Patent No. 4,001,184, can be used to create a blend of linear and branched polycarbonates.

[0058]

[0077] In one embodiment, the polymer is produced by reacting a divalent phenol, such as 2,2-bis(4-hydroxyphenyl)propane, with a carbonate precursor, such as phosgene, in the presence of an acid binder. In one embodiment, the polycarbonate resin is derived from the reaction of bisphenol A with phosgene. In one embodiment, these polycarbonates have an intrinsic viscosity of 0.3 to 1.0 dl / g or 0.40 to 0.65 dl / g, as measured at 25°C in methylene chloride or a similar solvent.

[0059]

[0078] Any polyvinyl chloride ("PVC") polymer resin is suitable for use in this disclosure. For example, in one embodiment, polyvinyl chloride polymers useful in this disclosure are those listed under the heading "Vinyl Chloride Polymers" in the Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 24, 4th edition, (1997), pp. 1017-1053, which are incorporated herein by reference.

[0060]

[0079] In some embodiments of this disclosure, suitable PVC polymers include polyvinyl chloride homopolymers, polyvinyl chloride copolymers, and mixtures thereof.

[0061]

[0080] In some embodiments, the polyvinyl chloride resin is a polyvinyl chloride resin, a chlorinated polyvinyl chloride resin, or an alloy thereof.

[0081] In some embodiments, a copolymer of vinyl chloride is formed by copolymerization of vinyl chloride with other monomers or monomer blends. In some embodiments, suitable monomers include vinyl acetate, ethylene, propylene, maleate, methacrylate, acrylate, high-alcohol vinyl ester, urethane, chlorinated urethane, methyl methacrylate, and mixtures thereof. In some embodiments, examples of monomer blends include ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene terpolymer, acrylonitrile-butadiene copolymer, and mixtures thereof.

[0062]

[0082] For example, in some embodiments, PVC polymers useful according to this disclosure include vinyl chloride homopolymers and vinyl chloride polymer resins having repeating units polymerized from at least about 70% by weight of vinyl chloride monomers, or repeating units polymerized from at least about 80% by weight, or at least about 90% by weight, or even about 95% by weight, or more than that of vinyl chloride monomers.

[0063]

[0083] In some embodiments, the polyvinyl chloride polymer compositions of the present disclosure may include repeating units polymerized from vinyl chloride monomers, and comonomers may include, but are not limited to, esters of acrylic acid, such as methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, cyanoethyl acrylate; vinyl esters such as vinyl acetate and vinyl propionate; methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate. The copolymer may also contain up to about 30 weight percent of one or more of the copolymers from mixtures of monomers having a suitable reactivity ratio with other copolymerizable monomers or vinyl chlorides known to those skilled in the art, including esters of methacrylic acid such as acrylate and butyl methacrylate; nitriles such as acrylonitrile and methacrylonitrile; acrylamides such as methylacrylamide, N-methylolacrylamide, and N-butoxymethacrylamide; halogen-containing vinyl monomers such as vinylidene chloride, vinylidene fluoride, and vinyl bromide; vinyl ethers such as ethyl vinyl ether and chloroethyl vinyl ether; styrene derivatives including vinyl ketones, α-methylstyrene, vinyltoluene, and chlorostyrene; vinylnaphthalene; olefins such as ethylene, butene, isobutylene, propylene, and hexene; and mixtures of monomers having a suitable reactivity ratio with other copolymerizable monomers or vinyl chlorides known to those skilled in the art.

[0064]

[0084] In one embodiment, the copolymer may include, but is not limited to, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride maleate and fumarate copolymer, vinyl chloride-olefin copolymer, vinyl chloride-acrylonitrile copolymer, and combinations thereof.

[0065]

[0085] Some embodiments of this disclosure may employ a PVC blend with crosslinked PVC or crosslinked PVC alone. Crosslinked PVC polymers can be prepared by polymerizing vinyl chloride in the presence of crosslinkable monomers such as diallyl isophthalate, trimethylolpropane triacrylate, and allyl methacrylate, as taught in U.S. Patent Nos. 4,755,699 and 5,248,546 (relevant portions of which are incorporated herein by reference).

[0066]

[0086] The homopolymers and copolymers described are commercially available and can also be produced by any preferred polymerization method, including suspension, dispersion, or blending. For example, in one embodiment, a polyvinyl chloride polymer prepared using the suspension method is suitable for use in this disclosure.

[0067]

[0087] In some embodiments, the PVC composition is rigid. Any rigid PVC composition is suitable for use in this disclosure. For example, in some embodiments, the rigid composition is neither modified nor plasticized, or the PVC contains little to no plasticizer. In some embodiments, the rigid composition contains plasticizer or plasticizing additives at about 12 phr or less. On the other hand, flexible or plasticized PVC can typically contain plasticizers at levels greater than about 12 phr. Thus, the rigid PVC according to this disclosure is characterized by having a higher level of tensile strength than modified PVC compositions classified as flexible. In this specification, “parts per 100 parts of resin” refers to the amount of component relative to the weight of the resin and is abbreviated as “phr”.

[0068]

[0088] Furthermore, according to this disclosure, rigid PVC refers to the property of a given compound having a tensile coefficient higher than a certain tensile coefficient. For example, PVC can be characterized as rigid when it has a tensile coefficient greater than about 105 psi (or about 689 MPa), semi-rigid when its tensile coefficient is between about 105 psi and about 3000 psi (about 20.7 MPa), and soft when it has a tensile coefficient less than about 3000 psi (or about 20.7 MPa) (tensile coefficient values ​​are based on ASTM standard conditions of 23°C and 50% relative humidity). Thus, rigid PVC according to this disclosure can have tensile coefficient values ​​that vary over a wide range, for example, the tensile coefficient value can be between about 800 MPa and about 1000 MPa, or between about 1000 MPa and up to about 2000 MPa, or even up to 3000 MPa or more.

[0069]

[0089] In some embodiments, the PVC compositions of this disclosure are suitable for use in a variety of applications, including, for example, buildings and construction, corner profiles, decking, fencing, railing, soffits, vinyl siding, cladding, window profiles, door frames, siding, fences, gutters, pipes, piping, fixtures, electrical and electronic enclosures, electrical junction boxes, automotive interiors and exteriors, fixtures, office equipment, sign enclosures, medical devices, aircraft interiors, and other high-temperature applications.

[0070]

[0090] In some embodiments, the polyvinyl chloride resin composition contains additives, such as processing aids, plasticizers, stabilizers, impact modifiers, biocides, flame retardants, foaming agents, blowing agents, UV stabilizers, UV absorbers, heat stabilizers, minerals, pigments, dyes, colorants, fillers, fibers, waxes, fusion accelerators, antioxidants, antistatic agents, release agents, lubricants, additional resins, heat distortion temperature modifiers, and possibly other additives. In some embodiments, the amount of polyvinyl chloride in the commercially available rigid polyvinyl chloride resin composition used is typically less than about 100%.

[0071]

[0091] Any type of PVC resin known in the art may be useful as an ingredient in the compositions of the present disclosure. In some embodiments, the PVC resin may be in the form of a plastisol or a dry blend. Furthermore, in some embodiments, the compositions of the present disclosure may include virgin PVC, recycled PVC such as PVC recycled from various roofing products, and combinations of virgin PVC and recycled PVC.

[0072]

[0092] In one embodiment, the PVC resin in this disclosure has an inherent viscosity of about 0.50 to about 1.60 dl / g or higher, for example, about 0.65 to about 1.40 dl / g, for example, about 0.83 to about 1.00 dl / g, as determined by ASTM D1243.

[0073]

[0093] In one embodiment, the polyvinyl chloride resin has a Tg of about 75°C to about 80°C. In one embodiment, the polyvinyl chloride resin has a heat distortion temperature (HDT) of about 60°C to about 75°C.

[0074]

[0094] In one aspect of this disclosure, when the Tg of the copolyester is higher than about 90°C, the Tg of the PVC resin composition increases, and the HDT of the composition improves.

[0095] For example, in some embodiments, polyvinyl chloride articles prepared using the compositions of the present disclosure have a maximum Tg of 110°C or a maximum HDT of 130°C while maintaining impact strength. In some embodiments, the articles have an increase of at least 3°C ​​in both Tg and HDT while maintaining impact strength.

[0075]

[0096] In some embodiments, the ratio based on the weight fraction of PVC resin to copolyester is greater than about 1.

[0097] In some embodiments, the ratio of PVC resin to copolyester and polycarbonate based on weight fractions is greater than about 1.

[0076]

[0098] In some embodiments, when polyvinyl chloride resin and copolyester are added in appropriate concentrations to produce a PVC composition, the resulting composition exhibits increased tensile strength and modulus of elasticity, as determined by ASTM D638, and increased flexural strength and modulus of elasticity, as determined by ASTM D790.

[0077]

[0099] The copolyesters in this disclosure are miscible with PVC. The term “miscible” refers to a blend or mixture of two or more polymers that are molecularly homogeneous, behave as a single-phase mixture, and exhibit a single glass transition temperature (Tg).

[0078]

[0100] The PVC compositions obtained herein can be processed using any standard PVC processing equipment and any standard PVC processing method, such as extrusion, injection molding, morph extrusion, and sheet extrusion, at any standard PVC processing temperature (approximately 170°C to approximately 230°C).

[0079]

[0101] In some embodiments, the copolyesters of the Disclosure have a Tg of about 75°C to about 120°C. In some embodiments, the copolyesters of the Disclosure have a Tg of at least about 90°C. In some embodiments, the copolyesters of the Disclosure have a Tg of at least about 100°C. In some embodiments, the copolyesters of the Disclosure have a Tg of at least about 110°C.

[0080]

[0102] The copolyesters used in certain embodiments of this disclosure do not have a distinct melting point, but instead their viscosity decreases as the processing temperature rises above their glass transition temperature. By using copolyesters with lower molecular weights, copolyesters with lower viscosity can be obtained.

[0081]

[0103] In one embodiment of the present disclosure, the copolyester has a viscosity range of approximately 100 to approximately 100,000 Pa·s (approximately 1,000 to approximately 1,000,000 poise), or approximately 1,000 to approximately 50,000 Pa·s (approximately 10,000 to approximately 500,000 poise), or approximately 2,000 to approximately 30,000 Pa·s (approximately 20,000 to approximately 300,000 poise), measured at approximately 170°C to approximately 200°C and a shear rate of 10¹ / s. Viscosity measurements in this embodiment of the present disclosure are performed by conducting small amplitude vibrational shear (SAOS) experiments using a Rheometrics RDA II rheometer and performing frequency sweeps over a range of 1 to 400 s⁻¹ at multiple temperatures above the Tg determined by ASTM D4440. In some embodiments, viscosity is measured at a PVC processing temperature of approximately 170°C to approximately 230°C.

[0082]

[0104] In one embodiment of the present disclosure, the copolyester has a semi-crystallization time of more than about 5 minutes, a glass transition temperature of at least about 90°C, a viscosity range of about 100 to about 100,000 Pa·s (about 1,000 to about 1,000,000 poise) measured at about 170 to about 230°C and a shear rate of 10¹ / s.

[0083]

[0105] In another embodiment of the present disclosure, the copolyester composition has a semicrystallization time of more than about 5 minutes, a glass transition temperature of at least 100°C, and a viscosity range of about 100 to about 100,000 Pa·s (about 1,000 to about 1,000,000 poise) measured at about 170°C to about 230°C and a shear rate of 10¹ / s.

[0084]

[0106] In some embodiments, the PVC resin is combined with other additives, such as processing aids, plasticizers, stabilizers, impact modifiers, biocides, flame retardants, foaming agents, foaming agents, heat stabilizers, UV stabilizers, UV absorbers, minerals, pigments, dyes, colorants, fillers, fibers, waxes, fusion accelerators, antioxidants, antistatic agents, release agents, lubricants, additional resins, heat distortion temperature modifiers, and possibly other additives.

[0085]

[0107] One embodiment of the present disclosure is a method for producing a polyvinyl chloride composition, comprising the steps of: compounding a miscible admixture of at least one polycarbonate resin and at least one copolyester to produce a viscous thermoplastic material, wherein at least one copolyester comprises: (a) a dicarboxylic acid component comprising (i) about 90 to about 100 mol% of terephthalic acid residues and (ii) about 0 to about 10 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a glycol component comprising (i) about 20 to about 60 mol% of a modifying glycol consisting of 2 to 20 carbon atoms and (ii) about 40 to about 80 mol% of a second modifying glycol consisting of 2 to 20 carbon atoms; blending the compound with at least one polyvinyl chloride resin composition; and introducing the blend into a calendering, extrusion or injection molding process to produce a polyvinyl chloride article.

[0086]

[0108] Another embodiment of the present disclosure is a method for producing a polyvinyl chloride composition, comprising the steps of: compounding at least one polyvinyl chloride resin with at least one copolyester to produce a viscous thermoplastic material, wherein at least one copolyester comprises: (a) a dicarboxylic acid component comprising (i) about 90 to about 100 mol% of terephthalic acid residues and (ii) about 0 to about 10 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a glycol component comprising (i) about 20 to about 60 mol% of a modifying glycol consisting of 2 to 20 carbon atoms and (ii) about 40 to about 80 mol% of a second modifying glycol consisting of 2 to 20 carbon atoms; mixing the compounded composition with a polyvinyl chloride resin to create a polyvinyl chloride composition; extruding the polyvinyl chloride composition through a die to produce pellets; and introducing the pellets into a calendering, extrusion or injection molding process to produce a polyvinyl chloride article.

[0087]

[0109] In some embodiments, the PVC compositions of the present disclosure are used to produce articles such as films, sheets, profiles, or injection-molded articles and components.

[0110] The compositions of this disclosure are useful as molded plastic parts or solid plastic objects. In some embodiments, films, sheets, profiles, and injection molded articles and parts can be produced using any extrusion process, including an extrusion process in which pellets are blended together (when using concentrated materials) or added directly to an extruder (when using fully formulated compositions). In some embodiments, films, profiles, and sheets can be produced using any calendering process.

[0088]

[0111] In some embodiments, the melt processing of the compositions of the present disclosure includes extrusion using any equipment known in the art, including, but not limited to, twin-screw extruders, single-screw extruders, high-strength batch mixers, Banbury mixers, Brabender mixers, roll mills, cone-kneaders, or planetary gear extruders. The shear energy during mixing depends on the combination of equipment, blade design, rotational speed (rpm), and mixing time. The shear energy should be sufficient to disperse the copolyester throughout the polyvinyl chloride resin.

[0089]

[0112] In some embodiments, the copolyester, polyvinyl chloride resin, and additives can be combined in any order during the process. In one embodiment, the copolyester is pre-mixed with the polyvinyl chloride resin. In another embodiment, the polyvinyl chloride resin is pre-mixed with the additive and then mixed with the copolyester.

[0090]

[0113] This disclosure also relates to products comprising films and / or sheets containing the polyvinyl chloride compositions described herein. In embodiments, the films and / or sheets of this disclosure may have any thickness that is apparent to those skilled in the art.

[0091]

[0114] This disclosure also relates to molded articles described herein. Any method known in the art can be used to form a polyvinyl chloride composition into a molded article. Examples of molded articles of this disclosure include, but are not limited to, injection-molded articles and extruded articles. Methods for producing molded articles include, but are not limited to, injection molding and extrusion.

[0092]

[0115] The polycarbonate, copolyester, and polyvinyl chloride resin compositions of this disclosure can be prepared into pellets using any of the standard procedures.

[0116] For example, the pellets of this disclosure can be produced as follows: In one embodiment, a twin-screw compounding line can be used to incorporate a polycarbonate / copolyester mixture and polyvinyl chloride resin. The polycarbonate, copolyester, and polyvinyl chloride resin are fed separately into the throat of an extruder and melted to produce a viscous thermoplastic material.

[0093]

[0117] In one embodiment, a loss-in-weight feeder can be used to add a polycarbonate / copolyester mixture and polyvinyl chloride resin. By twin-screw rotation, the polycarbonate / copolyester mixture and PVC are melted together. The mixture is then extruded through a die to produce multiple strands. The strands are fed into a water tank to cool the pellets. As soon as the strands leave the water tank, they are dried and fed into a dicer to be cut into pellets. Alternatively, the mixture can be extruded through a circular flat die with multiple openings to water. The flat die is equipped with a rotary cutter that thins the strands as they are extruded from the die to produce pellets. A continuous stream of water cools the pellets, which are then transported to a drying area, and then the pellets and water are separated, typically using a centrifuge.

[0094]

[0118] In one embodiment, a two-rotor continuous mixing mixer (such as a Farrell continuous mixer) can be used to incorporate a polycarbonate / copolyester blend and PVC. The polycarbonate / copolyester blend can be fed into the throat of the mixer together with the PVC and melted to produce a viscous thermoplastic material. The copolyester can be pre-blended with the polycarbonate and then added to the PVC, and this mixture can be fed into an extruder equipped with a loss-in-weight feeder. The output speed of the mixer is controlled by changing the area of ​​the discharge orifice. The molten material can be thinly sliced ​​into "lumps" and fed into the throat of a two-roll mill or a single-screw extruder. When the molten material is fed into a two-roll mill, the molten material can cover one of the rolls, and the slices can be fed into the throat of a single-screw extruder. The mixture is then extruded through a die to produce multiple strands. The strands can be fed into a water tank to cool the pellets. As soon as the strands leave the water tank, they are dried and fed into a dicer to cut them into pellets. Alternatively, the mixture can be extruded through a circular flat die with multiple openings to water. The flat die is equipped with a rotary cutter that slices the strands thinly as they are extruded from the die, producing pellets. A continuous stream of water cools the pellets, which are then transported to a drying area, typically a centrifuge, to separate the pellets from the water. When a "lump" is fed into a single-screw extruder, the mixture is extruded through a die to produce multiple strands. The strands can be sent to a water tank to cool the pellets. As soon as they leave the water tank, the strands are dried and sent to a dicer to cut them into pellets. Alternatively, the mixture can be extruded through a circular flat die with multiple openings to water. The flat die is equipped with a rotary cutter that slices the strands thinly as they are extruded from the die, producing pellets. A continuous stream of water cools the pellets, which are then transported to a drying area, typically a centrifuge, to separate the pellets from the water.

[0095]

[0119] In some embodiments, polycarbonate / copolyester admixtures and PVC resin can be incorporated into a plastic compounding line, such as a Banbury batch mixer. In these embodiments, the polycarbonate / copolyester admixture is pre-blended, mixed with PVC, and then fed into a Banbury high-strength mixer, where the ram is lowered to compress the mixture into the mixing chamber. Two rotary mixer blades melt the pellets, melting the copolyester / polycarbonate admixture and PVC. Once the desired temperature is reached, the door is opened at the bottom of the mixer, and the mixture is dripped into a two-roll mill. The ribbon from the two-roll mill can then be fed into a single-screw extruder. The mixture is then extruded through a die to produce multiple strands. The strands can be fed into a water tank to cool. As soon as they leave the water tank, the strands are dried and fed into a dicer to cut them into pellets. Alternatively, the mixture can be extruded through a circular flat die with multiple openings to water. The flat die is equipped with a rotary cutter that slices the strand as it is extruded from the die to produce pellets. A continuous stream of water cools the pellets and transports them to a drying area, typically a centrifuge, to separate the pellets from the water.

[0096]

[0120] This disclosure considers several different methods for producing plastic articles: extrusion for producing continuous flat sheets or profiles, injection molding for creating discontinuous articles, or extrusion for producing continuous films or sheets.

[0097]

[0121] Another embodiment of the present disclosure comprises the step of combining a copolyester / polycarbonate admixture with a PVC resin composition and using an extrusion process to produce a flat sheet or profile. In some embodiments, this can be achieved in several ways, for example, by adding the copolyester / polycarbonate admixture and the PVC resin composition separately to the throat of a uniscrew or twin-screw extruder. In another embodiment, the copolyester and polycarbonate admixture is compounded with the PVC resin composition and then added to the throat of a uniscrew or twin-screw extruder. In some embodiments, the compounded mixture is transported by a screw to the extruder barrel, compressed to melt the mixture, and the molten material is discharged from the end of the extruder. The molten material is then fed into a die to create a continuous flat sheet, or into a profile die to create a continuous shape. In embodiments using a flat sheet die, the molten material is extruded onto a series of metal rolls, typically three metal rolls, to cool the molten material and give the sheet a finish. The flat sheet is then transported as a continuous sheet to cool the sheet. The sheet can then be trimmed to the desired width, rolled up, cut into a sheet shape, or sawn. The flat sheet can also be formed into a shape by mechanical means to achieve the desired shape, and then cooled by spraying water through a water tank or by blowing air onto the profile. It can then be sawn or cut to the desired length.

[0098]

[0122] In embodiments using a profile die, the die is designed to produce an article of a desired shape. After leaving the die, it can then be cooled by spraying it with water through a water bath or by blowing air onto the profile. It can then be sawn or cut to the desired length.

[0099]

[0123] Another embodiment of the present disclosure comprises the step of producing an injection-molded article by combining a copolyester / polycarbonate blend with a PVC resin composition. This can be achieved in several ways by adding the above-mentioned copolyester / polycarbonate blend and PVC resin separately to the throat of a single-screw or twin-screw extruder. In another embodiment, the copolyester and polycarbonate blend is mixed with the PVC composition and then added to the throat of a single-screw or twin-screw extruder. In some embodiments, the blended mixture is transported by a screw to the extruder barrel, compressed to melt the mixture, and the molten material is discharged from the end of the extruder. When the pellet reaches the desired temperature, a gate is opened at the end of the extruder, and the molten plastic is fed by a screw into a heated mold to form an article of the desired shape. After filling the mold, a coolant is fed through the mold to cool it and the molten plastic. After the plastic has solidified, the mold is opened and the article is removed from the mold.

[0100]

[0124] For example, one embodiment of the present disclosure is a method for producing a polyvinyl chloride composition, comprising the steps of: extruding at least one polyvinyl chloride resin composition and at least one copolyester / polycarbonate admixture as described above to produce a viscous blend of thermoplastic materials; and introducing the blend of thermoplastic materials into a calendering, extrusion or injection molding process to produce a polyvinyl chloride article.

[0101]

[0125] Another embodiment of the present disclosure is a method for producing a polyvinyl chloride composition, comprising the steps of: formulating a miscible mixture of at least one polyvinyl chloride resin composition and at least one copolyester / polycarbonate admixture as described above to produce a viscous thermoplastic material; extruding the compound through a die to produce pellets; and introducing the pellets into a calendering, extrusion or injection molding process to produce a polyvinyl chloride article. In some embodiments, the polyvinyl chloride composition is rigid.

[0102]

[0126] Useful applications for these PVC compositions include numerous building and construction applications such as corner profiles, decking, fencing, railing, window profiles, and other interior and exterior applications.

[0103]

[0127] Other applications for these PVC compositions include appliances, electrical and electronic enclosures, signage enclosures, automotive applications, aircraft interiors, and other applications where rigid PVC formulations have been limited due to their lower tensile strength and modulus, as well as their flexural strength and modulus.

[0104]

[0128] For example, in some embodiments, the PVC articles of this disclosure are used in the following applications: buildings and construction, corner profiles, decking, fencing, railing, soffits, vinyl siding, cladding, window profiles, door frames, siding, fences, gutters, pipes, piping, electrical and electronic enclosures, electrical junction boxes, automotive interiors and exteriors, fixtures, office equipment, sign enclosures, medical devices, aircraft interiors, and other applications. In some embodiments, the polyvinyl chloride articles are rigid.

[0105]

[0129] The present disclosure can be further illustrated by the following embodiments, which are included for illustrative purposes only and should not be understood as limiting the scope of the present disclosure unless specifically indicated. [Examples]

[0106]

[0130] The following tables and figures summarize the experimental results of the examples and comparative examples of this disclosure. Examples:

[0107] [Table 1]

[0108]

[0131] Table 1 shows the control formulations used in all examples. All generated data were obtained using the control formulations, with additives incorporated at various part-per-100 parts PVC resin levels. All samples were melted and prepared by mixing 280 grams of compound in a Brabender Intelli-Torque mixer set to 190°C at a blade speed of 30 rpm. The samples were removed from the Brabender at 190°C and transferred to a Dr. Collin two-roll mill. The front roll temperature was set to 180°C and the back roll temperature to 175°C. The molten material was placed on the mill and the roll speed was set to 20 rpm. The material was removed from the mill once its temperature reached 175°C. The film was taken from the mill at a rate of 0.010 inches (250 microns) and allowed to cool.

[0109] [Table 2]

[0110]

[0132] Table 2 summarizes the sample compositions. The sample compositions were created by blending the control formulations in Table 1 with variable amounts of HDT 1, HDT 2, and HDT 3 as described, to create admixtures containing various amounts of polycarbonate from 0% to approximately 31% by weight.

[0111]

[0133] Amorphous copolyesters are commercially available from Eastman Chemical Company and have a glass transition temperature of approximately 116°C. Makrolon 2608, a polycarbonate, is a medium-viscosity amorphous bis-phenol A polycarbonate resin manufactured by Covestro, with a glass transition temperature of approximately 148°C.

[0112]

[0134] Makrolon 2658, a polycarbonate manufactured by Covestro, is a medium-viscosity amorphous bis-phenol A polycarbonate resin with a glass transition temperature of approximately 148°C, and was also used in several examples.

[0113] Example 1: DSC and HDT

[0135] Samples were prepared by adding HDT 1, HDT 2, and HDT 3 at 30, 40, 50, 60, and 80 phr. Additional samples were prepared by adding mixtures of HDT 2 and HDT 3 in ratios of 50 / 10, 30 / 30, and 10 / 50 (total 60 phr), and mixtures of HDT 2 and HDT 3 in ratios of 65 / 15, 40 / 40, and 15 / 65 (total 80 phr). Table 3 includes the results of differential scanning calorimetry (DSC) (ASTM D3418) and load-induced thermal distortion temperature (HDTUL) (ASTM D1637) at strains of 1% and 2%. The data show that the Tg values ​​of all compositions containing HDT 1, HDT 2, HDT 3, and mixtures of HDT 2 and HDT 3, determined by DSC, were higher than those of the control samples. The Tg values ​​determined by DSC were taken at the midpoint of the glass transition region. The data also shows that HDTUL was higher than the control formulation when determined by tensile DMA at strains of 1% and 2%.

[0114] [Table 3]

[0115] Example 2: Impact Characteristics

[0136] Samples were prepared by adding HDT 1, HDT 2, and HDT 3 at 30, 40, 50, 60, and 80 phr. Additional samples were prepared by adding mixtures of HDT 2 and HDT 3 in ratios of 50 / 10, 30 / 30, and 10 / 50 (total 60 phr), and mixtures of HDT 2 and HDT 3 in ratios of 65 / 15, 40 / 40, and 15 / 65 (total 80 phr). Table 4 summarizes the results of instrumented impact (ASTM D 3763). The data shows that all compositions containing HDT 1 alone were ductile, as determined by visual inspection of the impacted samples. The data also shows that compositions containing the polycarbonate Makrolon 2608 exhibited mostly ductile impact properties up to approximately 15% by weight load, as determined by visual inspection of the impacted samples. The data also shows that, despite its brittleness, a significant loss of impact strength was not observed until the polycarbonate's Makrolon 2608 content reached approximately 25%, as measured by average maximum load (kN), average energy at maximum load (J), average puncture energy (J), and average total energy (J).

[0116] [Table 4]

[0117] Example 3: Tensile properties

[0137] Samples were prepared by adding HDT 1, HDT 2, and HDT 3 at concentrations of 30, 40, 50, 60, and 80 phr. Additional samples were prepared by adding mixtures of HDT 2 and HDT 3 in ratios of 50 / 10, 30 / 30, and 10 / 50 (total 60 phr), and mixtures of HDT 2 and HDT 3 in ratios of 65 / 15, 40 / 40, and 15 / 65 (total 80 phr). Table 5 summarizes the tensile property data (ASTM D-638). Measurements were performed in the direction in which the film was peeled from the two-roll mill (longitudinal direction) and in the direction perpendicular to the direction in which the film was peeled from the mill (transverse direction). Using fracture strain (%) as a surrogate for impact strength, the longitudinal and transverse data generally reflected the instrumented impact data, and complete embrittlement was not observed until the polycarbonate's Makrolon 2608 content reached approximately 25%.

[0118] [Table 5]

[0119] Example 4: Processing Characteristics

[0138] Samples were prepared by adding HDT 1, HDT 2, and HDT 3 at 80 phr. Additional samples were prepared by adding mixtures of HDT 2 and HDT 3 at 65 / 15, 40 / 40, and 15 / 65 (total 80 phr). Additional samples were prepared by adding amorphous copolyester at 20, 40, 60, 80, and 100 phr. Figures 1 and 2 show viscosity data versus shear rate at 190°C determined by parallel plate rheometry. The data indicate that formulations containing polycarbonate tend to have lower melt viscosity than formulations containing PVC and amorphous copolyester.

[0120] Example 5: Glass transition temperature and miscibility

[0139] Samples were prepared by adding HDT 2 and HDT 3 to a control formulation at 30, 40, and 50 phr. Figures 3 and 4 show the storage modulus and tan delta charts for HDT 2 added at 30, 40, and 50 phr. Figures 5 and 6 show the storage modulus and tan delta charts for HDT 3 added at 30, 40, and 50 phr. All charts show a single aggregated glass transition temperature for all mixtures. The storage modulus chart shows a single steep downward slope, starting at approximately 90–95°C and ending at approximately 100°C. The tan delta chart shows a single peak in the range of approximately 95–100°C. These data suggest that a single miscible admixture of polymers, as opposed to an immiscible polymer admixture, would be expected to have two or more different glass transition temperatures.

[0121] Comparative Example 1: Tensile properties, impact properties, and compatibility of polycarbonates with 20, 40, and 60 phr

[0140] Samples were prepared by adding polycarbonate Makrolon 2658 at 20, 40, and 60 phr to a PVC control formulation. Table 6 summarizes the tensile property data and instrumented impact data. Figure 7 includes dynamic mechanical analysis (DMA) data. Polycarbonate Makrolon 2658 has a Tg of approximately 145°C, and polycarbonate is generally known to be a tough polymer. The data in Table 6 show that all test levels of polycarbonate Makrolon 2658 exhibit insufficient impact properties due to lower fracture strain (%) and brittle instrumented impact properties. Figure 7 shows that the blend of polycarbonate Makrolon 2658 and the PVC control formulation is inmiscible, as is evident from the two different glass transition temperatures (Tg) determined by the tan delta peaks. This data indicates that simply incorporating high-Tg thermoplastic materials into rigid PVC is insufficient to increase Tg and HDTUL while maintaining the impact properties of the blend. High-Tg thermoplastic materials must also be miscible and compatible.

[0122] [Table 6] The present invention includes the following embodiments. [1] A polyvinyl chloride composition comprising at least one polyvinyl chloride resin, at least one polycarbonate resin and at least one copolyester resin, wherein at least one copolyester resin is (a) (i) Approximately 90 to 100 mol% of terephthalic acid residues, (ii) Aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, present in amounts of approximately 0 to 10 mol% A dicarboxylic acid component containing, (b) (i) a residue of a first glycol consisting of 2 to 20 carbon atoms, in an amount of approximately 20 to 60 mol%, and (ii) Residues of a second glycol consisting of 2 to 20 carbon atoms, in an amount of approximately 40 to 80 mol% Glycol components containing A polyvinyl chloride composition comprising a dicarboxylic acid component and a glycol component, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the glycol component is 100 mol%. [2] The polyvinyl chloride composition according to [1], wherein the first glycol is present in an amount of 20 to 40 mol% and the second glycol is present in an amount of 60 to 80 mol%. [3] The polyvinyl chloride composition according to [1], wherein the first glycol is 1,4-cyclohexanedimethanol and the second glycol is ethylene glycol, or the first glycol is 2,2,4,4-tetramethyl-1,3-cyclobutanediol and the second glycol is 1,4-cyclohexanedimethanol. [4] The polyvinyl chloride composition according to [1], wherein the inherent viscosity of the copolyester is determined to be approximately 0.50 to approximately 0.80 dL / g at 25°C in a concentration of 0.25 g / 50 ml of phenol / tetrachloroethane in a 60 / 40 (weight / weight) solution. [5] The polyvinyl chloride composition according to [1], wherein the Tg of the copolyester is at least about 90°C or higher, or the Tg of the copolyester is at least about 100°C or higher. [6] The polyvinyl chloride composition according to [1], wherein the polycarbonate is present in an amount of approximately 1 to approximately 50 parts (phr) per 100 parts of polyvinyl chloride resin, and the copolyester is present in an amount of approximately 1 to approximately 100 parts (phr) per 100 parts of resin. [7] The polyvinyl chloride composition according to [1], wherein the copolyester is amorphous or the copolyester has a semi-crystallization time of about 5 minutes or more. [8] The polyvinyl chloride composition according to [1], wherein the polyvinyl chloride resin is a polyvinyl chloride resin, a chlorinated polyvinyl chloride resin, or an alloy thereof. [9] The polyvinyl chloride composition according to [1], wherein the polycarbonate resin is a bisphenol-based polycarbonate resin, or the polycarbonate resin is a bisphenol A-based polycarbonate resin.

[10] The polyvinyl chloride composition according to [1], wherein the copolyester has a viscosity range of about 100 to about 100,000 Pa·s (about 1,000 to about 1,000,000 poise) as measured at about 170 to about 230°C and a shear rate of 10¹ / s.

[11] The composition according to [1], wherein the ratio of polyvinyl chloride resin:copolyester based on weight fraction is greater than about 1, or the ratio of polyvinyl chloride resin:copolyester and polycarbonate based on weight fraction is greater than about 1.

[12] A method for producing a polyvinyl chloride composition, The step of producing a viscous thermoplastic material by compounding a miscible mixture of at least one polycarbonate resin and at least one amorphous copolyester resin, wherein at least one amorphous copolyester resin is (a) (i) Approximately 90 to 100 mol% of terephthalic acid residues, (ii) Aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, present in amounts of approximately 0 to 10 mol% A dicarboxylic acid component containing, (b) (i) a first glycol consisting of 2 to 20 carbon atoms in an amount of approximately 20 to 60 mol%, and (ii) A second glycol consisting of 2 to 20 carbon atoms, in an amount of approximately 40 to 80 mol% Glycol components containing The step includes a mixture containing a total mol% of the dicarboxylic acid component, where the total mol% of the glycol component is 100 mol%, and the step is to include a mixture containing a total mol% of the glycol component, A step of blending the compound with at least one polyvinyl chloride resin composition, The steps include introducing the blend into a calendering, extrusion, or injection molding process to produce polyvinyl chloride articles and Methods that include...

[13] The method according to

[12] , wherein a first glycol is present in an amount of 20-40 mol% and a second glycol is present in an amount of 60-80 mol%.

[14] The method according to

[12] , wherein the first glycol is 1,4-cyclohexanedimethanol and the second glycol is ethylene glycol, or the first glycol is 2,2,4,4-tetramethyl-1,3-cyclobutanediol and the second glycol is 1,4-cyclohexanedimethanol. A polyvinyl chloride article manufactured using the method described in

[15]

[12] , wherein the Tg and HDTUL (heat distortion temperature under load) are increased by at least 3°C. A polyvinyl chloride article manufactured using the method described in

[16]

[12] , wherein the polyvinyl chloride article has a maximum Tg of 110°C or a maximum HDTUL of 130°C.

[17] The polyvinyl chloride composition according to

[12] , further comprising at least one additive selected from the group consisting of processing aids, plasticizers, stabilizers, impact resistance modifiers, biocides, flame retardants, foaming agents, blowing agents, heat stabilizers, ultraviolet stabilizers, ultraviolet absorbers, minerals, pigments, dyes, colorants, fillers, fibers, waxes, fusion accelerators, antioxidants, antistatic agents, release agents, lubricants, additional resins, and heat distortion temperature modifiers.

[18] The polyvinyl chloride composition according to

[12] , wherein the polyvinyl chloride resin is a polyvinyl chloride resin, a chlorinated polyvinyl chloride resin, or an alloy thereof, and / or the polyvinyl chloride resin composition is rigid.

[19] The method according to

[12] , wherein the polycarbonate resin is a bisphenol-based polycarbonate resin, or the polycarbonate resin is a bisphenol A-based polycarbonate resin.

[20] The method according to

[12] , wherein the copolyester is present in an amount of about 1 to about 100 parts (phr) per 100 parts of resin relative to the content of PVC resin in the composition, or the polycarbonate is present in an amount of about 1 to about 50 parts (phr) per 100 parts of resin relative to the content of polyvinyl chloride resin in the composition.

Claims

1. A polyvinyl chloride composition comprising at least one polyvinyl chloride resin, at least one polycarbonate resin, and at least one amorphous copolyester resin, wherein the at least one amorphous copolyester resin is (a) (i) 90-100 mol% of terephthalic acid residues, and (ii) 0 to 10 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms. A dicarboxylic acid component containing, (b) (i) 20 to 60 mol% of a first glycol residue consisting of 2 to 20 carbon atoms, and (ii) 40–80 mol% of a second glycol residue consisting of 2–20 carbon atoms Glycol components containing It contains, with a total molar percentage of the dicarboxylic acid component being 100 mol%, and a total molar percentage of the glycol component being 100 mol%, The first glycol is 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and the second glycol is 1,4-cyclohexanedimethanol. A polyvinyl chloride composition wherein the polycarbonate resin is a bisphenol A-based polycarbonate resin having a melt flow of 3 to 80 g / 10 min at 300°C and a load of 3.8 kg (ASTM).

2. The polyvinyl chloride composition according to claim 1, wherein a first glycol is present in an amount of 20 to 40 mol%, and a second glycol is present in an amount of 60 to 80 mol%.

3. The polyvinyl chloride composition according to claim 1, wherein the inherent viscosity of the amorphous copolyester resin is 0.50 to 0.80 dL / g, determined at 25°C at a concentration of 0.25 g / 50 ml in 60 / 40 (weight / weight) phenol / tetrachloroethane.

4. The polyvinyl chloride composition according to claim 1, wherein the Tg of the amorphous copolyester resin is at least 90°C or at least 100°C.

5. The polyvinyl chloride composition according to claim 1, wherein the polycarbonate resin is present in an amount of 1 to 50 parts (phr) per 100 parts of polyvinyl chloride resin, and the amorphous copolyester resin is present in an amount of 1 to 100 parts (phr) per 100 parts of polyvinyl chloride resin.

6. The polyvinyl chloride composition according to claim 1, wherein the amorphous copolyester resin has a semi-crystallization time of 5 minutes or more.

7. The polyvinyl chloride composition according to claim 1, wherein the polyvinyl chloride resin is a polyvinyl chloride resin, a chlorinated polyvinyl chloride resin, or an alloy thereof.

8. The polyvinyl chloride composition according to claim 1, wherein the amorphous copolyester resin has a viscosity range of 100 to 100,000 Pa·s (1,000 to 1,000,000 poise) as measured at 170 to 230°C and a shear rate of 10 (1 / s).

9. The composition according to claim 1, wherein the ratio of polyvinyl chloride resin to amorphous copolyester resin based on weight fraction is greater than 1, or the ratio of polyvinyl chloride resin to amorphous copolyester resin and polycarbonate resin based on weight fraction is greater than 1.

10. A method for producing polyvinyl chloride articles, The step is to produce a viscous thermoplastic material by compounding a miscible mixture of at least one polycarbonate resin and at least one amorphous copolyester resin, wherein at least one amorphous copolyester resin is (a) (i) 90-100 mol% of terephthalic acid residues, and (ii) 0 to 10 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms. A dicarboxylic acid component containing, (b) (i) 20 to 60 mol% of a first glycol consisting of 2 to 20 carbon atoms, and (ii) A second glycol consisting of 2 to 20 carbon atoms, in an amount of 40 to 80 mol% Glycol components containing The step includes a mixture containing a total mol% of the dicarboxylic acid component, and a total mol% of the glycol component, A step of blending the compound with at least one polyvinyl chloride resin composition containing at least one polyvinyl chloride resin, The steps include introducing the blend into a calendering, extrusion, or injection molding process to produce polyvinyl chloride articles and Includes, The first glycol is 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and the second glycol is 1,4-cyclohexanedimethanol. The method wherein the polycarbonate resin is a bisphenol A-based polycarbonate resin having a melt flow of 3 to 80 g / 10 min at 300°C and a load of 3.8 kg (ASTM).

11. The method according to claim 10, wherein a first glycol is present in an amount of 20 to 40 mol%, and a second glycol is present in an amount of 60 to 80 mol%.

12. A method according to claim 10, wherein the Tg and HDTUL (heat distortion temperature under load) of a polyvinyl chloride article are increased by at least 3°C.

13. A method according to claim 10, wherein the polyvinyl chloride article has a maximum Tg of 110°C or a maximum HDTUL of 130°C.

14. The method according to claim 10, wherein the polyvinyl chloride resin composition further comprises at least one additive selected from the group consisting of processing aids, plasticizers, stabilizers, impact resistance modifiers, biocides, flame retardants, foaming agents, blowing agents, heat stabilizers, ultraviolet stabilizers, ultraviolet absorbers, minerals, pigments, dyes, colorants, fillers, fibers, waxes, fusion accelerators, antioxidants, antistatic agents, release agents, lubricants, additional resins, and heat distortion temperature modifiers.

15. The method according to claim 10, wherein the polyvinyl chloride resin is a polyvinyl chloride resin, a chlorinated polyvinyl chloride resin, or an alloy thereof, and / or the polyvinyl chloride resin composition is rigid.

16. The method according to claim 10, wherein the amorphous copolyester resin is present in an amount of 1 to 100 parts (phr) per 100 parts of polyvinyl chloride resin relative to the content of polyvinyl chloride resin in the composition, or the polycarbonate resin is present in an amount of 1 to 50 parts (phr) per 100 parts of polyvinyl chloride resin relative to the content of polyvinyl chloride resin in the composition.

Images