CN1898306A - Ethylene copolymer modified oriented polyester films, tapes, fibers and nonwoven textiles - Google Patents
Ethylene copolymer modified oriented polyester films, tapes, fibers and nonwoven textiles Download PDFInfo
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- CN1898306A CN1898306A CN 200480038109 CN200480038109A CN1898306A CN 1898306 A CN1898306 A CN 1898306A CN 200480038109 CN200480038109 CN 200480038109 CN 200480038109 A CN200480038109 A CN 200480038109A CN 1898306 A CN1898306 A CN 1898306A
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Abstract
Disclosed are films, tapes, and melt-spun fibers prepared from compositions comprising (a) at least one polyester polymer; and (b) from about 1 to 30 weight % of at least one ethylene copolymer such as ethylene/vinyl acetate dipolymers, ethylene/vinyl acetate terpolymers, ethylene/alkyl (meth)acrylate dipolymers, ethylene/alkyl (meth)acrylate terpolymers, functionalized ethylene copolymers, ethylene/acid copolymers, and salts thereof. The films, tapes and fibers exhibit improved tensile properties such as tensile strength and elongation at break compared to nonmodified polyester compositions. Also disclosed are textiles and articles prepared from the fibers described.
Description
Technical field
The present invention relates to comprise with ethylene copolymer-modified polyester blend or by film, band and fiber, also relate to and comprise melt spun fibre that contains described modified poly ester or the nonwoven textiles for preparing with the melt spun fibre that contains described modified poly ester with ethylene copolymer-modified polyester blend preparation.
Background technology
The oriented film that comprises polyester can adopt the molten polymer preparation by multiple methods known in the art (for example, cast film is extruded or blown film is extruded).Film can utilize stretching device pass through thermal stretch in the vertical and annealing and in one direction the orientation.Film also can utilize suitable stretching device to go up orientation at both direction (vertical and horizontal).The polyester film of orientation can be used in the multiple packaging application.
Equally, variously be with the available polyester film preparation of extruding.Flat film can be expressed in the cooling bath or quenching on the cooling roller.Perhaps, tubular blown film can be extruded by annular die and film is air quenched.Film with quenching is cut into band with the cutter groove subsequently.These bands are made their elongations (being uniaxial orientation) several times to original length by the elongation band anneal that stretching device thermal stretch in the vertical also will have controlled width (for example about 1cm is to about 5cm).Polyester belt can be used in the multiple application.For example, these bands can be applied with various suitable tackiness agents and prepare adhesive tape.
The fiber that comprises polyester can directly adopt molten polymer to prepare by multiple methods known in the art, and described method comprises melt-spinning, centrifugal spinning and meltblown.Melt-spun or meltblown fibers can use in being applicable to the nonwoven textiles of multiple application, and described application examples is as being carpet backing fabric, agricultural cloth and geotextile.
Trevira can be used for cord or rope or is used to prepare the carpet yarn.Polyester yarn also can be woven or knitted into the fabric that is used for multiple application, for example oilcloth, liner, flag, bagging, carpet backing fabric, agricultural cloth and geotextile.
Need provide and have oriented polyester films, band and the fiber that improves mechanical property (for example tensile failure load, intensity (tensile failure stress) and elongation at break).
Be the cost of the slit film tapes that reduce to use elongation, need to reduce the fiber number (width constant but thickness attenuation) of band and/or increase (the CaCO for example of inert filler in the polyester formulations
3) amount.
The polymer blend that adopts conventional being used to prepare film and fiber is difficult to reach above-mentioned target.The higher elongation and the fiber number of reduction can cause unacceptable physicals loss.Also expectation overcomes polyester belt undesirable fibrillation effect under high elongation rate.
Trevira with mechanical property of improvement makes by a small amount of additive is added in the polyester.For example referring to EP 80274B1, EP 35796B1, EP 41327B1, EP47464B2, US 6,165,610 and Journal of Applied Polymer Science, 1986,31 (8), 2753-68.
Summary of the invention
The present invention relates to comprise composition or with the film of said composition preparation, described composition comprises following component or with following component preparation: (a) at least a polyester polymers and (b) at least a ethylene/alkyl acrylate copolymer of 1-30% weight.
Detailed Description Of The Invention
The present invention relates to have required mechanical property (for example tensile failure load, intensity (tensile failure stress) and elongation at break (%)) elongation polyester film or band or have intensity and the melt spun polyester fiber of elongation at break (%).These raisings are that (polyester formulations can be chosen wantonly and comprise other and be selected from weighting agent (CaCO for example by the polyester formulations that ethylene copolymer (for example Ethylene/vinyl acetate binary polymers, Ethylene/vinyl acetate ter-polymers, ethene/(methyl) alkyl acrylate binary polymer, ethene/(methyl) alkyl acrylate ter-polymers, functional ethylene copolymers, ethylene/acid copolymers and its salt) adding of a small amount of percentage ratio (about 1 to about 30% weight, perhaps 1 to about 15% weight) is used to prepare film and fiber
3) and the material of additive (for example UV stablizer, pigment etc.)) in and realize.Thereby the processing characteristics of vibrin can be improved by the melt strength with ethylene copolymer and polyester blend raising molten polyester resin.These blends can provide the stretchiness of the film of the improvement that is higher than normal polyester film and fiber and fiber and the stretchiness of prepared band improve (be that blend can stretch, and do not have or reduced the fibrillation effect of band) in manufacturing processed under the stretch ratio that improves.
Preferred embodiment relates to that a kind of usefulness comprises the composition of following component or by the film with the preparation of compositions of following component preparation: (a) at least a polyester polymers and (b) at least a ethylene/alkyl acrylate copolymer of 1-30% weight.This ethylene/alkyl acrylate copolymer can comprise at least a e/x/y copolymer of 1-30% weight, and wherein E comprises ethene; X is for being selected from the monomer of vinyl-acetic ester and (methyl) alkyl acrylate; Y is selected from following comonomer for one or more: carbon monoxide; Sulfurous gas; Vinyl cyanide; Maleic anhydride; Maleic acid diester; (methyl) vinylformic acid, toxilic acid, toxilic acid monoesters, methylene-succinic acid, fumaric acid, fumaric monoalkylester and its salt; Glycidyl acrylate, glycidyl methacrylate and glycidyl vinyl ether; Wherein X accounts for the 0-50% of described e/x/y copolymer weight, and Y accounts for the 0-35% of described e/x/y copolymer weight, and wherein the weight percentage of X and Y can not be 0, and surplus is E.
The present invention also provides a kind of slit film tapes (slit film tape) of this film preparation of usefulness.
The present invention also provides a kind of melt spun fibre that comprises composition or prepare with said composition, described composition comprises following component: (a) at least a polyester polymers and (b) at least a e/x/y copolymer of 1-15% weight, wherein E, X and Y can be as mentioned above.
A preferred embodiment also relates to a kind of melt spun fibre that comprises composition or prepare with said composition, and described composition comprises following component: (a) at least a polyester polymers and (b) at least a aforesaid ethylene/alkyl acrylate copolymer of 1-15% weight.
The nonwoven textiles that comprises aforesaid melt spun fibre or prepare with aforesaid melt spun fibre also is provided.
The present invention also provides film, slit film tapes, fiber (for example melt spun fibre) and nonwoven textiles, and wherein aforesaid composition also comprises at least a other component that is selected from weighting agent, matting agent, heat and ultra-violet stabilizer, UV light absorber, static inhibitor, chain terminator, white dyes, pigment and other additives of (c) 0.01-20% weight.
Thermoplastic compounds is a flowable polymer matter under pressurized, heated.Melting index (MI) is that polymkeric substance flows through specific mass rate capillaceous under the temperature and pressure condition of control.The melting index that this paper reported uses the 2160g load to measure according to ASTM 1238 under 190 ℃, and the MI value unit that is wherein reported is gram/10 minutes.
As noted before, film of the present invention, band and fiber are by the preparation of compositions that comprises with ethylene copolymer-modified vibrin.
Various polyester resins comprise the polymkeric substance by various glycol and various diacid (or derivatives thereof) condensation generation that is suitable for forming film or fiber.It should be noted that the various polyester that comprise aromatic dicarboxylic acid as main acid constituents.The example has polyethylene terephthalate, polybutylene terephthalate, poly terephthalic acid hexamethylene dimethyl ester and polyethylene glycol 2.These polyester also can be and other alcohol or multipolymers of other dicarboxylic acid (for example m-phthalic acid or isophthalic acid ester 5-sodium sulfonate) copolymerization as the 3rd component.Also can use the mixture of two or more these polyester.Term used herein " polyester " typically refers to any or all above-described polymkeric substance.Particularly preferred polyester is polyethylene terephthalate (being abbreviated as PET).Various polyester and its preparation method are known in the art.The preferred service performance viscosity of this paper (IV) is the polyester of 0.5-1.1 (using 8% ortho chloro phenol measured in solution down at 25 ℃).
Ethylene copolymer as polyester modification thing as described herein comprises Ethylene/vinyl acetate binary polymer, Ethylene/vinyl acetate ter-polymers, ethene/(methyl) alkyl acrylate binary polymer, ethene/(methyl) alkyl acrylate ter-polymers, functional ethylene copolymers, ethylene/acid copolymers and its salt.
As noted before, these ethylene copolymers may be defined as e/x/y copolymer, and wherein E comprises ethene, and X is for being selected from the comonomer of vinyl-acetic ester, (methyl) alkyl acrylate; Y is one or more other comonomers.
Term " Ethylene/vinyl acetate binary polymer " comprises the multipolymer that is closed generation by ethene and vinyl acetate copolymerization.
Term " Ethylene/vinyl acetate ter-polymers " comprises the multipolymer that is produced by ethene, vinyl-acetic ester and other comonomer copolymerizations.
In principle, the monomeric relative consumption of vinyl acetate copolymerization that adds in the ethylene can be in wide variation, from weight percent seldom count to up to the multipolymer gross weight 40% or higher.
Term " (methyl) vinylformic acid " and abbreviation " (M) AA " are meant methacrylic acid and/or vinylformic acid.Similarly, term " (methyl) acrylate " and " (methyl) alkyl acrylate " are meant methacrylic acid and/or acrylic acid ester, and preferred wherein said moieties comprises 1-6 carbon atom.The example of alkyl acrylate comprises methyl acrylate (being abbreviated as MA), ethyl propenoate (being abbreviated as EA) and butyl acrylate (being abbreviated as BA).
Term " ethene/(methyl) alkyl acrylate binary polymer " comprises by ethene and (methyl) alkyl acrylate copolymer and closes the multipolymer of generation.
Term " ethene/(methyl) alkyl acrylate ter-polymers " comprises the multipolymer that is produced by ethene, (methyl) alkyl acrylate and other comonomer copolymerizations.
The relative consumption that adds the alkyl acrylate comonomer in the ethylene/alkyl acrylate copolymer can be in wide variation, from weight percent seldom count to up to the multipolymer gross weight 40% or higher.Equally, the selection of alkyl also can be in principle from the alkyl (have or do not have significant branching) of simple methyl up to 6 carbon atoms.It is the factor that how to play polar polymer component and degree size thereof in thermoplastic compounds that the relative consumption of the alkyl in the alkyl acrylate comonomer and selection can be counted as the multipolymer of determining gained.
Alkyl in the preferred alkyl acrylate comonomer has 1-4 carbon atom, and the concentration of alkyl acrylate comonomer accounts for the 5-30% of this ter-polymers weight, preferred 10-25%.Most preferably the alkyl in the alkyl acrylate comonomer is a methyl.
Except the X comonomer works to the polarity of polymer composition, the relative consumption of the Y comonomer in the ethylene copolymer and select to be counted as and determine that the gained multipolymer is the factor that how to play polar polymer component and degree size thereof in thermoplastic compounds.As noted before, the Y comonomer also can provide functionality (to form functional ethylene copolymers) to ethylene copolymer except the integral polarity to multipolymer works.
Available Y can be acrylic or methacrylic acid.In the context of the present invention, alkene (for example ethene) is called ethylene/acid copolymers with the multipolymer of unsaturated carboxylic acid (for example acrylic or methacrylic acid).For example, " ethene/(methyl) vinylformic acid (being abbreviated as E/ (M) AA) " is meant its polymers of ethene (being abbreviated as E)/vinylformic acid (being abbreviated as AA) and/or methacrylic acid (being abbreviated as MAA).The available ethylene/acid copolymers comprises having about 2 to (M) AA of about 30% weight E/ (M) AA binary polymer among the present invention.In the context of the present invention, these multipolymers may be defined as e/x/y copolymer, and wherein the weight percentage of X is 0, and Y is that weight percentage is about 2 to about 30% acrylic or methacrylic acid, and surplus is an ethene.
Ethylene/acid copolymers also can be the ter-polymers that comprises other comonomers that are selected from (methyl) alkyl acrylate.When alhpa olefin was ethene, these sour ter-polymers can be described as e/x/y copolymer, and wherein E is an ethene, and X is selected from vinylformic acid C
1-C
8Alkyl ester or methacrylic acid C
1-C
8Alkyl ester, and Y is acrylic or methacrylic acid.X and Y percentage ratio on a large scale exist.X account for usually this terpolymer up to about 50% weight, Y account for usually this polymkeric substance up to about 35% weight.These ethylene acid ter-polymers for example comprise ethene/(methyl) n-butyl acrylate/(methyl) vinylformic acid ter-polymers, ethene/(methyl) isobutyl acrylate/(methyl) vinylformic acid ter-polymers, ethene/(methyl) methyl acrylate/(methyl) vinylformic acid ter-polymers and ethene/(methyl) ethyl propenoate/(methyl) vinylformic acid ter-polymers.
Ethylene/acid copolymers to small part as mentioned above can be neutralized into metal-salt.Use the part acidic-group at least a basic metal, transition metal or alkaline earth metal cation (for example lithium, sodium, potassium, magnesium, calcium or zinc) or the described cationic combination neutralized copolymer to cause thermoplastic resin to show the enhanced performance.These neutral acid copolymers are commonly referred to as ionomer resin (" ionomer ").
Useful ionomer can comprise those apparatus 2 ionomers to the preparation of E/ (M) the AA binary polymers of about 30% weight (M) AA of having an appointment among the present invention.In the context of the present invention, these multipolymers may be defined as e/x/y copolymer, wherein the weight percentage of X is 0, Y is that weight percentage is the about 2 acrylic or methacrylic acid to about 30% weight, surplus is an ethene, and described multipolymer is neutralized by at least a basic metal, alkaline-earth metal or transition-metal cation to small part.Various positively charged ions are selected from lithium
*, sodium
*, potassium, magnesium
*, calcium, barium, lead, tin or zinc
*(
*Refer to preferred cation) or described cationic combination.
Various ionomer resins by E.I.du Pont de Nemours and Company (DuPont), Wilmington, Delaware with trade mark " Surlyn
" sell or by ExxonCorporation with trade mark " Escor
" and trade mark " lotek " sale.
Term used herein " functional ethylene copolymers " expression add can with the ethylene copolymer of the reactive functional groups (for example acid anhydrides and epoxide) of other component reaction (for example passing through covalent bonding).
What also be suitable as the Y component that is used for e/x/y copolymer of the present invention is maleic acid diester or monoesters (toxilic acid half ester), and it comprises C
1-C
4The ester of alcohol (as methyl alcohol, ethanol, n-propyl alcohol, Virahol and propyl carbinol).Optimal ethylene/maleate copolymer comprises maleic anhydride.Also optimal ethylene/maleate copolymer comprises the toxilic acid half ester.
Maleic anhydride grafted ethene multipolymer (toxilic acid esterification polyethylene) is ethylene copolymer (for example polyethylene) known those multipolymers of handling as the maleic anhydride of compatilizer (compatiblizer) in this area.Grafting e/x/y copolymer as herein described comprises such multipolymer, and wherein a part of E component comprises alhpa olefin (for example butylene, hexene or nonene) except ethene to improve the density of multipolymer.The example of maleic anhydride modified linear high-density polyethylene is with trade mark Polybond
3009 sell the product that can buy from Crompton company.Similarly the polyolefine of toxilic acid esterification is with trade mark Fusabond
Sale can be buied from DuPont.Preferred grafting e/x/y copolymer is adding about 0.3 those multipolymers to the maleic anhydride of about 2% weight.
The ethylene copolymer that comprises reactive functional groups (for example maleic anhydride) also can easily obtain by the high-pressure free radical method.The high pressure method that is applicable to the described multipolymer of preparation is for example at United States Patent (USP) 4,351, and is open in 93.This method has been eliminated the second step grafting that tradition is used to produce maleic anhydride-functionalized polymeric.In addition, for grafting, use this method to be easy to obtain maleic anhydride add-on greater than 2% weight.Be to comprise about 3% weight those multipolymers preferably to the functionalized comonomer of about 15% weight with ethene with by the multipolymer that the functionalized comonomer that this method prepares prepares.It should be noted that following multipolymer: ethene/maleic anhydride (E/MAH) or ethene/toxilic acid monoesters (also being called ethene/toxilic acid monoesters or E/MAME) multipolymer, it is directly synthetic in autoclave.
The Y that is fit to also can be the epoxy-functional ethylene comonomer, for example glycidyl acrylate, glycidyl methacrylate or glycidyl Vinyl Ether (being the various comonomers that contain derived from the part of 2).
Preferred epoxy-functional multipolymer can represent that wherein E is the copolymer unit-(CH of derived from ethylene with formula E/X/Y
2CH
2)-; X is copolymer unit-(CH
2CR
1R
2)-, be R wherein
1Be hydrogen or methyl, R
2Be alkoxy carbonyl (for example X derived from propylene acid alkyl ester, alkyl methacrylate) or acetoxyl group with 1-10 carbon atom; Y is copolymer unit-(CH
2CR
3R
4)-, be R wherein
3Be hydrogen or methyl, R
4Be glycidoxypropyl carbonyl or glycidoxypropyl (for example Y derived from propylene acid glycidyl ester, glycidyl methacrylate or glycidyl vinyl ether).
Preferred e/x/y copolymer is following multipolymer, and wherein X accounts for the 5-50% of described e/x/y copolymer weight, and Y accounts for the 0.3-15% of described multipolymer weight, and surplus is E.
The comonomer that more preferably contains the Racemic glycidol base section (for example, glycidyl acrylate or glycidyl methacrylate) account for this epoxy-functional ethylene copolymer gross weight about 0.3 (or about 0.5) % weight to about 8 (or about 10 or about 12) % weight, alkyl acrylate account for this epoxy-functional ethylene copolymer gross weight about 5 to about 40 (preferred about 20 to about 40 or about 25 to about 35) % weight.
It should be noted that multipolymer, for example ethylene/methyl acrylate/glycidyl methacrylate (E/MA/GMA), ethylene/ethyl acrylate/glycidyl methacrylate (E/EA/GMA) and the positive butyl ester/glycidyl methacrylate of ethylene/acrylic acid (E/n-BA/GMA).
Also preferably with ring-containing oxide monomer (more preferably containing the glycidyl monomer) by monomeric concurrent reaction join the reaction multipolymer in and it is not grafted on the polymkeric substance by graft polymerization reaction.
The Y that is fit to also can be comonomer, for example two or more combination of carbon monoxide, sulfurous gas, vinyl cyanide or its.It should be noted that ter-polymers, for example ethylene/methyl acrylate/carbon monoxide (E/MA/CO), ethylene/ethyl acrylate/carbon monoxide (E/EA/CO) and the positive butyl ester/carbon monoxide of ethylene/acrylic acid (E/n-BA/CO) and Ethylene/vinyl acetate/carbon monoxide (E/VA/CO).
Term " ethylene/alkyl acrylate copolymer " comprises its polymers of ethene and alkyl acrylate, and wherein this moieties comprises 1-6 carbon atom.The example of alkyl acrylate comprises methyl acrylate, ethyl propenoate and butyl acrylate." ethylene/methyl acrylate (being abbreviated as EMA) " is meant the multipolymer of ethene (being abbreviated as E) and methyl acrylate (being abbreviated as MA)." ethylene/ethyl acrylate (being abbreviated as EEA) " is meant the multipolymer of ethene (being abbreviated as E) and ethyl propenoate (being abbreviated as EA)." ethylene/butyl acrylate (being abbreviated as EBA) " is meant the multipolymer of ethene (being abbreviated as E) and butyl acrylate (being abbreviated as BA).
But the relative consumption wide variation that adds the alkyl acrylate comonomer in the ethylene/alkyl acrylate copolymer, from weight percent seldom count to up to the multipolymer gross weight 40% or higher.Equally, the selection of alkyl also can be in principle from the alkyl (have or do not have significant branching) of simple methyl up to 6 carbon atoms.The relative consumption of the alkyl in the alkyl acrylate comonomer and selection can be counted as determines that the gained ethylene copolymer is the factor that how to play polar polymer component and degree size thereof in thermoplastic compounds.
Alkyl in the preferred alkyl acrylate comonomer can have 1-4 carbon atom, and the concentration of alkyl acrylate comonomer can account for the 5-40% weight (perhaps 30% weight) of ethylene/alkyl acrylate copolymer, preferred 10-35% weight (perhaps 25% weight).Most preferably the alkyl in the alkyl acrylate comonomer is a methyl.
Ethylene/alkyl acrylate copolymer can utilize autoclave or tubular reactor to prepare by the method for knowing in the polymer arts.Copolymerization can be used as successive processes to carry out in autoclave: with ethene, alkyl acrylate and optional solvent (for example methyl alcohol) (referring to United States Patent (USP) 5,028,674) supply in the agitated autoclave of United States Patent (USP) 2,897, the 183 disclosed types that contain initiator.Add speed and can be depending on various variablees, for example the monomer concentration in the reaction mixture of polymeric reaction temperature, pressure, the alkyl acrylate monomer that is adopted and needs acquisition target copolymer compositions.Under some situations, may need to use telogen (for example propane) to control molecular weight.Reaction mixture is shifted out from autoclave continuously.After reaction mixture leaves reaction vessel, multipolymer to be separated from unreacted monomer and solvent (if using solvent) by ordinary method, described ordinary method for example is to evaporate not polymeric material and solvent under the high temperature that reduces pressure.
Known to common in this area, the ethylene/alkyl acrylate copolymer of tubular reactor produced can be different from the ethylene/alkyl acrylate of more conventional autoclave preparation.Therefore, term or phrase " tubular reactor produced " ethylene/alkyl acrylate copolymer, for target of the present invention, be meant the ethylene copolymer for preparing under high pressure and high temperature in tubular reactor or similar reactor, the inherent differential responses kinetics of therein ethylene and alkyl acrylate comonomer obtains mitigation or part compensation by monomer importing of having a mind to along reaction glide path in tubular reactor.As generally known in the art, this tubular reactor copolyreaction technology can produce the multipolymer that has along the higher relative degree of irregularity of the main polymer chain comonomer of block distributed (more near), this can reduce existence of long chain branches and can prepare with than with same comonomer ratio, the multipolymer that in the high pressure stirred-tank reactor, prepares more high-melting-point be the multipolymer of feature.In general, the rigidity of the ethylene/alkyl acrylate copolymer of tubular reactor produced and elasticity are higher than the rigidity and the elasticity of the ethylene/acrylic acid alkyl copolymer of autoclave preparation.
Ethylene/alkyl acrylate with tubular reactor produced of this attribute can be available from DuPont.
The actual manufacturing of foregoing tubular reactor ethylene/alkyl acrylate copolymer is preferably carried out in the tubular reactor under the High Temperature High Pressure and under the condition that has other reactant comonomer to import along pipe, carries out and be not only in the High Temperature High Pressure tank reactor that stirs.Yet, similarly the ethylene/alkyl acrylate copolymer material can prepare in a series of autoclave reactors, and wherein the comonomer replacement realizes by a plurality of districts importing of reactant comonomer, as United States Patent (USP) 3,350,372,3,756,996 and 5,532,066 instruct, same, these materials with high melting point should be treated on an equal basis as target of the present invention.
Comparison for the multipolymer of the ethylene/alkyl acrylate copolymer that further illustrates and describe tubular reactor produced and the preparation of conventional autoclave, the EMA resin that following commercially available ethylene/methyl acrylate copolymer and fusing point data presentation thereof go out tubular reactor produced has the remarkable higher fusing point of EMA that the relatively high pressure still prepares, and this is owing to have very different MA distributions along polymer chain:
The multipolymer of autoclave preparation
Mp=76 ℃ of EMA-A1 (MA of 21.5% weight)
Mp=69 ℃ of EMA-A2 (MA of 24% weight)
Mp=80 ℃ of EMA-A3 (MA of 20% weight)
Mp=73 ℃ of EMA-A4 (MA of 24% weight).
The multipolymer of tubular reactor produced
Mp=88 ℃ of EMA-T1 (MA of 25% weight)
Mp=95 ℃ of EMA-T2 (MA of 20% weight).
About the other discussion of difference between ethylene/alkyl acrylate copolymer tubular reactor produced and autoclave preparation referring to Richard T.Chou, Mimi Y.Keating and LesterJ.Hughes, " High Flexibility EMA made from High Pressure TubularProcess (adopting the high flexible EMA of high pressure tubular prepared) ", Annual TechnicalConference-Society of Plastics Engineers (2002), 60
Th(the 2nd volume), 1832-1836).CODEN：ACPED4ISSN：0272-5223；AN 2002：572809；CAPLUS。
The specific examples of the ethylene/alkyl acrylate copolymer that is applicable to tubular reactor produced of the present invention that derives from DuPont is referring to Table A.
Table A
| Ethylene/alkyl acrylate copolymer | Alkyl acrylate % weight | Melt flow index (g/10min) |
| EMA EMA EMA EMA EMA EMA EMA EMA EMA EMA EEA EEA EEA EEA EBA EBA EBA EBA EBA EBA EBA | 25 25 9 14 18 24 9 20 13 30 12 16 15 15 7 7 17 17 27 17 35 | 0.4 0.6 2 2 2 2 6 8 9 3 1 1 6 7 1.1 1.1 1.5 1.8 4 7 1 |
But be applicable to the molecular weight noticeable change of ethylene/alkyl acrylate copolymer of the present invention, this numerical value by melt flow index is about 10 EMA to the maximum to be proved.The specific selection degree that is used for the ethylene/alkyl acrylate copolymer component of modified poly ester is subjected to the influence of balance factor, the stress strain curve (profile) (rate of extension and stretch ratio) of for example draft temperature of the melting index of properties-correcting agent and polyester, relevant ethylene/alkyl acrylate copolymer and polyester softening temperature separately and expection.Other factors that need to consider in the selection of ethylene/alkyl acrylate copolymer comprise the elastic recovery of the raising relevant with higher relative molecular weight multipolymer (the E/25% weight MA that for example has 0.7MI) and the relevant virtual rating that is easier to weighting agent (referring to following) blend with low-molecular weight copolymer (the E/20% weight MA that for example has 8MI) relatively more.
Being applicable to that composition of the present invention can be chosen wantonly also comprises weighting agent (CaCO for example
3) and other additives (for example matting agent is (as TiO
2), heat and ultraviolet ray (UV) stablizer, UV absorption agent, static inhibitor, chain terminator, white dyes, pigment etc.).These additives are known in polyester film and melt spun fibre field.The amount of these conventional ingredients in composition of the present invention can be 0.01-20% weight usually, preferred 0.1-15% weight.
Can this class conventional ingredient be chosen wantonly by any known method and join in the composition that comprises with ethylene copolymer-modified polyester.This adding can wait by for example dried mixture that mixes, extrudes various components, masterbatch technology by routine to be carried out.Typical masterbatch can comprise the CaCO of 75-90% weight
3Noticeable being to use comprises CaCO
3Masterbatch with ethylene copolymer-modified dose.
The mechanical property of film of the present invention, band and fiber (for example intensity, tensile failure load, elongation at break and fiber number) can be by regulating various parameters balance in addition, described parameter comprises
Resin formulation design (base resin, the additive (CaCO that is added
3, UV stablizer, pigment) content and type);
The amount of the ethylene copolymer that is adopted and type;
Processing units (quenching, cutting, stretching and annealing configuration); With
Processing conditions (extruder screw configuration, temperature curve and polymer output, stretching and annealing temperature and curve, linear velocity etc.).
In general, the manufacturing facility that is used to prepare film or fiber changes the limited in one's ability of equipment and processing conditions, therefore, and the ethylene copolymer-modified mechanical property that can significantly improve polyester film, band and the fiber of preparation of vibrin as herein described.
Thermoplastic compounds as herein described is suitable for preparing film and fiber by extruding processing.
The invention provides film with the preparation of compositions that comprises polyester and ethylene copolymer.This film can not be orientated, the single shaft direction is orientated (for example vertical) or biaxially oriented orientation (for example vertical and horizontal).
Described film is applicable to widely in the packaging application, comprises shrink film.As noted before, described film also is applicable to the preparation slit film tapes.
In fact, film of the present invention can prepare by any film well known by persons skilled in the art.With regard to purpose of the present invention, film can be the single or multiple lift polymeric film in principle, equally, film and membrane structure usually can by the whole bag of tricks (for example inflation film, mechanical stretching etc.) comprise orientation (single shaft or twin shaft) curtain coating, extrude, coextrusion etc.Usually the various additives of practice can be present in each thin film layer (comprise and be present in knitting layer etc.) in the art, and condition is the performance that their existence can not change film or membrane structure basically.Therefore, can be contemplated that the various additives of employing (for example antioxidant and thermo-stabilizer, ultraviolet (UV) photostabilizer, pigment and dyestuff, weighting agent, matting agent, slipproofing agent, softening agent, other processing aids etc.) have benefit.
Making film of the present invention with the above composition can carry out according to any currently known methods.For example, may utilize so-called " inflation film " or " flat-die " method to extrude described composition and prepare primary film.Inflation film is by polymer composition is extruded by annular die, and provides inflation film with the tubular film of gained with the airflow expanding and make.The cast flat film is to make by described composition is extruded by flat-die.The film that leaves mould includes the roller (cooling roller) of circulating fluid by at least one or cools off by water-bath provides cast film.The width of film of the present invention for example is about 60cm (2 feet).
But film of the present invention also behind quenching or cast film with its orientation.This method may further comprise the steps: the laminar flow of extruding molten polymer; The extrudate of quenching extrudate and orientation quenching at least one direction.Term used herein " quenching " thus describing extrudate is cooled to the following solid film material that obtains of its fusing point basically.
But described film uniaxial orientation, but preferably by on two orthogonal directions on the thin film planar, stretching diaxial orientation to obtain gratifying mechanical property and combination of physical properties.
The orientation of single shaft or biaxially oriented film and stretching device are known in the art and can be adjusted by those skilled in the art and make film of the present invention.The example of these type of apparatus and method for example comprises United States Patent (USP) 3,278,663,3,337,665,3,456,044,4,590,106,4,760,116,4,769,421,4,797,235 and 4,886,634 disclosed those apparatus and method.
Inflation film of the present invention can utilize double-membrane soaking extrusion method orientation, can carry out diaxial orientation simultaneously by following method, extrude primary tube, make its quenching subsequently, reheat, expanding by inherent air pressure causes horizontal orientation, and stretches with the speed that can cause portrait orientation by differential folder or delivery roll.
The working method (as the double-membrane soaking technology) of acquisition orientation inflation film is known in the art and it can be as 3,456, No. 044 described carrying out of United States Patent (USP) of Pahlke.More particularly, primary tube is melt extruded from annular die.The primary tube of extruding is cooled off fast so that crystallization is minimum.Then be heated to its orientation temperature (for example by means of water-bath).At the unitary oriented region of thin film fabrication, diode forms by expanding, and therefore (preferably taking place simultaneously) expansible temperature thin-film takes place in horizontal radial expansion and in vertically tractive or stretching on both direction; Rapid, the reduction suddenly at drawing point place thickness followed in the expansion of pipe.Tubular film flattens once more by nip rolls.Film is expanded again and make it carry out annealing steps (heat setting), during this step is carried out, be heated once more and adjust its shrinkage.
In one embodiment, film forms by extrusion method, and described extrusion method causes the polymer chain in the film to be arranged along extruding direction usually.Linear polymer has significant intensity on differently-oriented directivity after through the height uniaxial orientation, and intensity in the horizontal is less.This arrangement can extruded upward increase film strength of direction (corresponding to the length dimension of cutting the film yarn).Perhaps, film can form by blowing process known to those skilled in the art.
The preferred film of the present invention comprises:
The amount of the described alkyl acrylate in the preferred 1. wherein said ethylene/alkyl acrylate copolymers is about 5 films to about 40% weight (perhaps 30% weight).
Preferred 2. preferred 1 film, the amount of the described alkyl acrylate in the wherein said ethylene/alkyl acrylate copolymer are about 10 to about 35% weight (perhaps 25% weight).
Preferred 3. preferred 2 film, wherein said alkyl acrylate is selected from methyl acrylate, ethyl propenoate and butyl acrylate.
Preferred 4. preferred 3 film, wherein said alkyl acrylate are methyl acrylate.
Each film in preferred 5. preferred 1 to preferred 4, the amount of wherein said component (b) are 5 to 15% weight.
Each film in preferred 6. preferred 1 to preferred 5, described film further comprises
(c) at least a other component that is selected from weighting agent, matting agent, heat and ultra-violet stabilizer, UV light absorber, static inhibitor, chain terminator, white dyes, pigment and other additives of 0.01-20% weight.
Preferred 7. preferred 6 film, the amount of wherein said component (c) is a 0.1-15% weight.
Each film in preferred 8. preferred 1 to preferred 7, quenching prepares described film in the cooling bath by described composition is expressed into.
Each film in preferred 9. preferred 1 to preferred 7, quenching prepares described film on the cooling roller by described composition is expressed into.
Each film in preferred 10. preferred 1 to preferred 7, described film prepares by described composition is extruded for tubular blown film and with described film is air quenched by annular die.
Each film in preferred 11. preferred 1 to preferred 10, wherein said composition comprises the ethylene/alkyl acrylate copolymer of tubular reactor produced.
The present invention also provides the slit film tapes with film preparation of the present invention.Preferred band is those bands with preferred above-mentioned film preparation.
Elementary non-oriented film can cut into slit film tapes, and described slit film tapes is stretched before reeling.Slit film tapes can utilize cutting unit to prepare, described cutting unit comprises support, a plurality ofly is located substantially on conplane cutters, and each cutter comprises opposite cutting edge and opposite end, be used for that cutters are installed to the assembly structure of support and be connected to support and be configured to above the exposed cutting edge of blade feeding roller along downstream direction supply film.Described assembly structure be configured to by be essentially delegation, parallel and spaced apart relation is installed cutters, the installation of wherein said blade makes each blade expose one cutting edge to be used for cutting, and the cutting edge that wherein is close to blade spaced apart each other.
After film is cut into above-mentioned band, stretched operation will carry out in baking oven on the span of 3-6 rice (10-20 foot), and described baking oven for heating promotes stretched operation to the temperature of effective soften film.What usually take place is, film is cold when beginning to pass the passage of baking oven, and along with film passes baking oven, it is heated gradually and be softening.Constriction occurs on the constriction line (neckline) that is positioned at baking oven inlet certain distance.Multiple factor is depended in the position of necking down region, comprises the attribute and the thickness of rate of extension, oven temperature and thin-film material.The thickness of typical preliminary draft band for example can be about 120 microns and width and can be about 3cm and arrive about 15cm.After the stretching, the thickness of final band is that about 30-50 micron and width arrive about 5cm for about 1cm.Concerning specific end use, can prepare wideer or narrower band.
Stretch ratio generally can be about 2: 1 to about 16: 1, and the typical stretch ratio of some compositions is about 4: 1 to about 10: 1.The distance that longitudinal stretching took place can change according to employed technology.In short distance stretched, the distance that occurs in several inches of stretching was last, and other technologies comprise bigger distance.
As noted before, fiber also can be directly by the extrusion method preparation, and described extrusion method comprises centrifugal spinning, melt-spinning, spun-bond process and meltblown.
In centrifugal spinning, when quickening polymer melt, form fiber by the fast rotational source.The material of fusing of self-thermo furnace is sent in the rotary spinning machine, owing to centrifugal force is extruded material and is made fiber from the aperture of device for spinning side.
In melt-spinning, form the material fusion of fiber and extrude and directly solidify by cooling subsequently by spinning jet.Melt-spinning fiber can be extruded from spinning jet by different cross-sectional shapes (circle, trilobal, five leaf, octofoil etc.).Line drawing by with the motion Filament winding on the rotation roller group of moving under controlled temperature and the speed, realize.According to concrete melt spinning method and corresponding procedure of processing, product can be collected by the form of monofilament, yarn, tow or non-woven product (for example spunbonded type).The general reference of relevant melt-spinning fiber referring to
Fibers from Synthetic Polymers(synthetic polymeric fibers) .Rowland Hill compiles, Elsevier Publishing Co., NY, 1953.
Spun-bond process is the direct lapping that derives from the non-woven textile web of melt spun fibre.Continuous filament yarn is extruded, quickens (by roller or injector) and be layered on to form non-woven on the moving belt by spinning jet.The bonding place, fused fiber point of crossing that occurs in.
It is another kind of directly lapping method that fusion is sprayed, and wherein fiber is extruded by die tip, and logical superheated high-speed air drawing-down (and fracture) deposits to and forms fine (low-titer) fibrous woven net on moving belt or the screen cloth.
Spun-bond process (S) and fusion are sprayed (M) textile web and can further be come bonding and/or the formation decorative pattern by rolling after formation.The also available fiber of the present invention of multi-layer nonwoven product (for example SMS, SMMS, SMMMS) prepares.
The present invention also provides the melt spun fibre with above-mentioned preparation of compositions.Preferred melt spun fibre comprises:
The amount of the described alkyl acrylate in the preferred wherein said ethylene/alkyl acrylate copolymer of A. is about 5 fibers to about 40% weight (perhaps 30% weight).
The fiber of the preferred preferred A of B., the amount of the described alkyl acrylate in the wherein said ethylene/alkyl acrylate copolymer are about 10 to about 35% weight (perhaps 25% weight).
The fiber of the preferred preferred B of C., wherein said alkyl acrylate is selected from methyl acrylate, ethyl propenoate and butyl acrylate.
The fiber of the preferred preferred C of D., wherein said alkyl acrylate is a methyl acrylate.
The preferred preferred A of E. each fiber in the preferred D, wherein the amount of component (b) is a 5-10% weight.
The preferred preferred A of F. each fiber in the preferred E, described fiber also comprises
(c) at least a other component that is selected from weighting agent, matting agent, heat and ultra-violet stabilizer, UV light absorber, static inhibitor, chain terminator, white dyes, pigment and other additives of 0.01-15% weight.
The fiber of the preferred preferred F of G., wherein the amount of component (c) is a 0.1-5% weight.
The preferred preferred A of H. each fiber in the preferred G, wherein said composition comprises the ethylene/alkyl acrylate copolymer of tubular reactor produced.
Nonwoven textiles can prepare with aforesaid melt spun fibre.Preferred nonwoven textiles prepares with above-mentioned optimum fiber.
Woven or knitting textiles can prepare with aforesaid melt spun fibre.The preferred above-mentioned optimum fiber of woven or knitting used for textiles prepares.
Oriented film is used for packaging application widely.As mentioned above, film of the present invention also can be used for preparation and cuts the band fiber.
Fiber (comprise and cut the band fiber) by preparation described herein can be used for preparing flexible cord (cord), cord (twine) or rope (rope).Many fibers by for example twist, braiding, interlacing etc. combine and form flexible cord.Cord generally comprises the fiber of low quantity and diameter less than rope.The cross section of these flexible cords, cord or rope can be circular or flat roughly.Flexible cord and cord can be used for shoestring, the band rope of bag, the band rope of portfolio etc., and can be used in the packaging application.Rope can be used in wide industrial and the marine vessel applications.Flexible cord, cord and rope also further interlacing (for example by knitting) prepare the net with relative open architecture, for example fishing net, cargo net etc.
The band fiber of cutting of the present invention can be used as monfil and is used for carpet tufting, synthetic lawn, mat etc.They also can be used as the band rope.When using tackiness agent, it can be used as adhesive tape to use (for example being with rope) or use with jointing material in furniture.
Woven or knitting textiles can be with fiber or melt spun fibre preparation with aforesaid cutting.In general, woven fabric can have than knit goods structure more closely.By the polyester yarn of preparation described herein can be woven for being used for multiple application (strainer for example, oilcloth, canvas, the ship top, lid, canopy, tent, Emergency Ladder, shelter, flag, structure (for example roof) film, the machine band, leather trunk or packing material liner, the heavy duty bag, carpet backing fabric, book cover, footwear, the upholster that is used for furniture, Motor vehicles, ship, aircraft etc., clothes, agricultural cloth (is used to control breeding, weeds control, gardening, greenhouse and silage) and geotextile (be used for corrode control and Soil conservation)) fabric.Knit goods can be used for bagging (being used to carry huge material for example groceries, firewood etc.) and building and industrial net.
Use the woven fabric of modified poly ester composition as herein described to have lower tendency toward sliding, particularly to the load-carrying bag.
Supatex fabric of the present invention can be used for diaper and other are used for the article (for example adult incontinence products and lady's health product) of Personal hygiene; Medical clothes is cap, long gown, booties for example; Personal protective equipment comprises mouth mask etc.; For example coverlet, cover cap, blanket etc. are equipped in the healthy prevention; Packing material; Durable paper; Cleaning wiping cloth; Wrap; Flag; Carpet backing fabric; Geotextile; Agricultural cloth; Upholster; Clothes; Strainer; Liner; Be used for the heat of buildings and the building wrap or the roof film of moisture control.
To carpet backing fabric, the contraction of textiles for example preferably 45 ℃ of following shrinking percentages less than 2.5%.Weaving carpet backing fabric to provide intensity, dimensional stability and shape for carpet as the elementary base fabric of carpet usually.Its available band fiber of cutting of the present invention prepares.
Secondary carpet backing fabric can be used for providing substrate, and carpet yarn is anchored on the described substrate.Its available nonwoven material preparation.Melt spun fibre of the present invention can be used for preparing the non-woven substrate that can be used as secondary carpet backing fabric.
Geotextile can be used for the gravel of road and paving layer with the road improvement quality of getting off.Geotextile fabric is that the woven polyester of about 2.5mm brings manufacturing with width usually.The also available viscose non-woven material preparation that derives from melt spun fibre of geotextile.The shrinking percentage that the shrinking percentage of geotextile requires not resemble carpet backing fabric requires strictness.Yet endurable permeability is very important for geotextile.
Following examples only are used to illustrate, and should not think the restriction to category of the present invention.
Embodiment
Embodiment 1 and 2
Thereby the preparation plate is measured the tensile property of polymer blend and assess its stretchiness 180 ℃ (using this temperature stretching PET composition to make fiber, cut band or double orientating film usually) in industrial equipments.
Material therefor
PET-1:PET homopolymer, limiting viscosity (IV) are 1.0 (high viscosity), DEG:12000mg/kg, acid end group: 40mg/kg, with BGDQ available from AKZO.
EMA-1: ethylene/alkyl acrylate copolymer, the methyl acrylate of 24% weight, MI are 2g/10min (ASTM D-1238,190 ℃, loading is 2.16Kg).
Resin formulation:
Comparing embodiment C1:PET-1 (100%)
Embodiment 1:PET-1 (95%)+EMA-1 (5%)
Embodiment 2:PET-1 (90%)+EMA-1 (10%)
Plate uses following condition to make by compression moulding on the Collin press:
Preheating: under 270 ℃ and 10 bar pressures, carried out 4 minutes,
Heating: under 270 ℃ and 150 bar pressures, carried out 2 minutes,
Board size: 150 * 150 * 2mm.
Under 180 ℃, measure tensile property (every kind of blend is measured 20 times) according to ASTM 1708.
Table 1
| Embodiment | Tensile strength (Mpa) | Elongation at break (%) | |
| C1 | 100％PET-1 | 15.9 | 80 |
| 1 | 95％PET-1+5％EMA-1 | 252 | 269 |
| 2 | 90％PET-1+10％EMA-1 | 25.9 | 272 |
These test-results proofs add the mechanical property (for example tensile strength and elongation at break) that the 5-10% ethylene/alkyl acrylate copolymer has improved polymer blend in polyester.Based on these results, we are expected at and produce band, fiber or the double orientating film that can have highly reinforcing tensility in the production unit.
Embodiment 3 and 4
Film prepares with polymer blend.Band at high temperature stretches by the film cutting and with it.At room temperature assess its tensile property.
Material therefor
The PET-2:PET homopolymer, limiting viscosity is 0.58, with Crystar
Available from DuPont.
Resin formulation:
Comparing embodiment C2 and C3:PET-2 (100%)
Embodiment 3 and 4:PET-2 (95%)+EMA-1 (5%)
Sample is mixed in the 28mm twin screw extruder, extrude by coat hanger die, curtain coating quenching to the cooling roller obtains the film that thickness is the 5-6 mil.It is the band of 1/4th inches (6mm) that vertical this film of upward cutting obtains wide.These bands are stretched to 4 times and 6 times of original length being equipped with to remain on the tensile testing machine of baking oven under 75 ℃ with the speed of per minute 2,000%.At room temperature stretch with the speed of per minute 100% and measure tensile property, outcome record is in table 2.
Table 2
| Embodiment | Composition | Stretch | Tensile strength (MPa) | Elongation at break (%) |
| C2 | 100％PET-2 | 4 times | 310.3 | 79 |
| 3 | 95％PET-2+ 5％EMA-1 | 4 times | 333.2 | 95 |
| C2 | 100％PET-2 | 6 times | 488.7 | 21.8 |
| 4 | 95％PET-2+ 5％EMA-1 | 6 times | 496.3 | 28.7 |
These results be presented under the comparatively high temps stretch and at room temperature the mechanical property of testing film improve.
Claims (13)
1. one kind comprises composition or with the film of said composition preparation, wherein said composition comprises following component or prepares with following component: (a) at least a polyester polymers; (b) at least a e/x/y copolymer of 1-30% weight, wherein E comprises ethene; X is vinyl-acetic ester or (methyl) alkyl acrylate; Y is a carbon monoxide; Sulfurous gas; Vinyl cyanide; Maleic anhydride; Maleic acid diester; (methyl) vinylformic acid, toxilic acid, toxilic acid monoesters, methylene-succinic acid, fumaric acid, fumaric monoalkylester, its salt; Glycidyl acrylate; Glycidyl methacrylate; The glycidyl vinyl ether; Or its two or more combination; X accounts for the 0-50% of described e/x/y copolymer weight, and Y accounts for the 0-35% of described e/x/y copolymer weight; The weight percentage of X and Y can not be 0; Surplus is E, and preferably described at least a e/x/y copolymer is an ethylene/alkyl acrylate copolymer, and wherein alkyl acrylate accounts for about 5 to about 40% weight in described ethylene/alkyl acrylate copolymer, preferably accounts for about 10 to about 35% weight.
2. the film of claim 1, wherein said alkyl acrylate be methyl acrylate, ethyl propenoate, butyl acrylate or its two or more combination and be preferably methyl acrylate.
3. claim 1 or 2 film, wherein the amount of component (b) is a 5-10% weight.
4. claim 1,2 or 3 film, described film also comprises at least a weighting agent, matting agent, heat or ultra-violet stabilizer, UV light absorber, static inhibitor, chain terminator, white dyes, pigment or other additives of (c) 0.01-20% weight, preferred 0.1-15% weight or 5-10% weight.
5. claim 1,2,3 or 4 film, it is characterized in that described film prepares by following steps: (1) is expressed into described composition in the cooling bath or quenching on the cooling roller, or (2) are extruded described composition and are tubular blown film and described film is air quenched by annular die.
6. the film of claim 5, wherein said composition comprises the ethylene/alkyl acrylate copolymer of tubular reactor produced.
7. band, described band is by each film preparation in the cutting claim 1,2,3,4,5 or 6.
8. fiber, described fiber is by the band preparation of stretching claim 7.
9. a woven textiles or knitting textiles, described woven textiles or knitting textiles comprise the fiber of the band of claim 7 or claim 8 or with the band of claim 7 or the fiber production of claim 8.
10. fiber or melt spun fibre, described fiber or melt spun fibre comprise have claim 1, combination of features thing described in 2,3,4 or 5 or apparatus are had the right the preparation of combination of features thing described in requirement 1,2,3,4 or 5.
11. a woven textiles, nonwoven textiles or knitting textiles, described woven textiles, nonwoven textiles or knitting textiles comprise the fiber of claim 9 or melt spun fibre or with the fiber or the melt spun fibre preparation of claim 9.
12. goods, described goods comprise woven textiles, nonwoven textiles or the knitting textiles of claim 11 or with the woven textiles of claim 11, nonwoven textiles or the preparation of knitting textiles.
13. the goods of claim 12, wherein said goods are diaper, adult incontinence products, lady's health product, medical clothes, Personal protective equipment, healthy prevention equipment, packing material, durable paper, cleaning wiping cloth, wrap, flag, carpet backing fabric, geotextile, agricultural cloth, upholster, clothes, strainer, liner, the building wrap, roof film, oilcloth, canvas, the ship top, lid, canopy, tent, Emergency Ladder, shelter, flag, the building film, the machine band, leather trunk or packing material liner, sack cloth, book cover, footwear, the building net, the industry net, flexible cord, cord, rope, shoestring, the band rope, fishing net, cargo net, carpet tufting, synthetic lawn, band rope or adhesive tape.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US51336503P | 2003-10-21 | 2003-10-21 | |
| US60/513,365 | 2003-10-21 | ||
| US60/550,437 | 2004-03-05 |
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| CN104797654A (en) * | 2012-11-19 | 2015-07-22 | 三井化学株式会社 | Polyester resin composition, manufacturing method therefor, and camera module containing said polyester resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104350188A (en) * | 2012-05-04 | 2015-02-11 | 朗盛德国有限责任公司 | Thermoplastic fibres with reduced surface tension |
| CN104797654A (en) * | 2012-11-19 | 2015-07-22 | 三井化学株式会社 | Polyester resin composition, manufacturing method therefor, and camera module containing said polyester resin composition |
| CN104797654B (en) * | 2012-11-19 | 2016-08-24 | 三井化学株式会社 | Polyester and resin composition and manufacture method thereof, camera module containing this polyester and resin composition |
| CN105401243A (en) * | 2015-10-26 | 2016-03-16 | 安徽泛博纺织科技有限公司 | Automobile colored polyester filament for delaying strength loss of textiles, and preparation method thereof |
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| CN108395607B (en) * | 2017-02-08 | 2021-03-19 | 中国石油化工股份有限公司 | Ultraviolet-to-blue light conversion resin and preparation method and application thereof |
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