CN1510512A - Multi-layer photo picture substrate containing 1,4-oxane dimethonal - Google Patents
Multi-layer photo picture substrate containing 1,4-oxane dimethonal Download PDFInfo
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- CN1510512A CN1510512A CNA2003101209548A CN200310120954A CN1510512A CN 1510512 A CN1510512 A CN 1510512A CN A2003101209548 A CNA2003101209548 A CN A2003101209548A CN 200310120954 A CN200310120954 A CN 200310120954A CN 1510512 A CN1510512 A CN 1510512A
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Abstract
It is an object of the present invention to provide a proton-conducting membrane, excellent in resistance to heat, durability, dimensional stability and fuel barrier characteristics, and showing excellent proton conductivity at high temperature. It is another object of the present invention to provide a method for producing the same. It is still another object of the present invention to provide a fuel cell using the same. The present invention provides a proton-conducting membrane, comprising a carbon-containing compound and inorganic acid, characterized by a phase-separated structure containing a carbon-containing phase containing at least 80% by volume of the carbon-containing compound and inorganic phase containing at least 80% by volume of the inorganic acid, the inorganic phase forming the continuous ion-conducting paths. The present invention also provides a method for producing the above proton-conducting membrane, comprising steps of preparing a mixture of a carbon-containing compound (D) having one or more hydrolyzable silyl groups and inorganic acid (C), forming the above mixture into a film, and hydrolyzing/condensing the hydrolyzable silyl group contained in the mixture formed into the film, to form a three-dimensionally crosslinked silicon-oxygen structure (A). The present invention also provides a fuel cell which incorporates the above proton-conducting membrane.
Description
Technical field
The present invention relates to have the photograph polyester multilayer sheet base that improves performance.The multilayer tablet base comprises PET-base polyester material, wherein in ground floor, be derived from 1, the relation that has regulation between the monomeric unit content of 4-cyclohexanedimethanol (CHDM) and the 1,4 cyclohexane dimethanol content in other layer of multilayer tablet base, thereby the cutting-relevant performance of acquisition regulation.
Background technology
The photographic silver halide element is included in one or more layers photographic layer that is coated with on the carrier.Typically carrier comprises the sheet material of transparent or semitransparent film, claims that usually it is the sheet base.Other layer can be in turn laminated to the either side of sheet base as substrate layer or glue-line.The ordinary tablet sill that photograph component is used is cellulose triacetate (CTA) and gathers (ethylene glycol terephthalate) (PET).Just at the sheet base that has proposed recently to use poly-((ethylene naphthalate)) (PEN) to use as photograph component, this photograph component is intended being used in the swedged magazine, and this requires than film winding operation more closely in the past.
For all kinds of photographic films, CTA has the good fit of physical property usually.Yet its manufacture method involves high-caliber gaseous emission and it is that relative cost is high.On the other hand, the manufacture method of PET is eco-friendly.Aspect the transparency, dimensional stability, physical strength, thermal deformation resistant, poly-(ethylene glycol terephthalate) (PET) film demonstrates premium properties as photographic sheet substance.Yet, compare with CTA, the PET film is extremely tough and tensile, therefore be not to be suitable for very much the completion operation as rip cutting, cut-out and/or perforation procedure, and these operate in the manufacturing of photographic film or prepare in need.In addition, each step of the processing of taking a picture as splicing, otch and encapsulation (sleeving) in, these films are difficult to cut.Some consumption photographic film application in that necessary control is easily completed as the 35mm film, requires in the non--external process of concentrating or the consumption film of small test chamber processing especially, and this is that the PET material can not be used as one of reason of sheet base.The photographic film that the PET material is used for not requiring not dispersion processing so at present is x-ray film, cinefilm and graphic arts film for example.About back one class film, can more easily regulate processing, cut with control etc.The method of making polyester-Ji photographic sheet substance typically comprise the steps: with molten polyester resin vertically curtain coating to the curtain coating surface, to form continuous sheet, by stretching traction piece material vertically, by the sheet material that comes tentering sheet material, heat setting traction and tentering to cross along cross directional stretch, and heat of cooling setting sheet material, form the heat setting film stretched, as described in the U.S. Patent No. 4141735.U.S. Patent No. 5385704 and 5607826 discloses the method for improving the photographic material completion feature of using PET sheet base, comprising in the manufacture process of film, after the heat setting step, go tentering (detenter) step by what the film that tentering is crossed shrank 2-20% (preferred 10-18%) on Width, the planar birefringence of sheet base is reduced to is lower than 0.150.Also disclose the improvement of PET-base photographic film completion feature in U.S. Patent No. 6228569 and USSN09/223876, this proves by the dust that produced in the completion operating process and the reduction of chip.These disclosure of the Invention of back utilize the method for the high relatively heat-set temperature (＞220 ℃) in the film process for making, apply, this method is significantly improved the completion and the cutting characteristic of PET-base photograph carrier.Yet, even under the improvement situation of the completion that is proved, in each step of photograph processing technology, PET-base film still is difficult to cutting.
Another FAQs of PET film is that it tends at high temperature in magazine, occurs highly curling in storage process and can not fully reduce this in the photo processing procedure curling, and this can show in CTA-base photographic film usually.Authorize the U.S. Patent No. 5556739 of Nakanishi etc., authorizing the U.S. Patent No. 5387501 of Yajima etc. and authorizing the method that has proposed to solve back one problem in the U.S. Patent No. 5288601 of Greener etc., wherein the multilayer carrier comprises the polyester by sulfonate and other hydrophilic segment modification, wherein in wet processing, this polyester helps to recover to force at curling of film in storage process in magazine.Being reduced in occur curling another universal method of (following core (core-set)) tendency of polyester film base in the storage process is to anneal at elevated temperatures and/or by improving the glass transition temperature (Tg) of polyester.
The U.S. Patent No. 3326689 of authorizing Murayama discloses the glow discharge processing, is used for improving by polyester material, and preferably the sheet base of PEN made curls.In one case, polyester material comprises PET-section bar material, and wherein the diol component repetitive of 25mol% is derived from CHDM.The U.S. Patent No. 5294473 of authorizing Kawamoto discloses similarly has the PET polyester film base that improvement (reduction) is curled, and wherein the diol component repetitive of 25mol% is derived from CHDM.
The U.S. Patent No. 5925507 of authorizing Massa etc. discloses has the PET plate substrate material that core curls under the less tendency, and it comprises and contain 30wt%1 at least that the polyester of 4-cyclohexanedimethanol (CHDM) is with this polyester and the polycarbonate blending that contains bis-phenol.The U.S. Patent No. 4141735 of authorizing Schrader etc. discloses a kind of polyester film base that improved core down curls that has, and comprising using hot tempering, in one embodiment, uses poly-(terephthalic acid (TPA) 1,4 cyclohexane dimethanol ester).Therefore yet this polymkeric substance rapid crystallization makes its preparation difficulty of alignment films.Equally, the photograph that becomes opaque or fuzzy and can't be used for the requirement transparency of this polymkeric substance is used.
The use of high heat-set temperature also is used to improve the completion of PET-base photographic film in sheet base manufacture method.Yet, even under the situation that the completion that is proved is improved, PET-base film still is difficult to cutting in each step of photograph processing technology.The U.S. Patent No. 5034263 of authorizing Maier etc. discloses a kind of laminated film, it comprises poly-(ethylene glycol terephthalate) core and at least one lip-deep poly-(terephthalic acid (TPA) 1 at it, the 4-cyclohexanedimethanoester ester) finishing coat, make and use consumption film technology commonly used, make laminated film easily to cut and to bore a hole.Maier etc. address the CHDM component should comprise the diol component of 70mol% polyester at least.Yet, find that this laminated material is easy to delamination.
Also proposed the polyester of blend or copolymerization routine and other polyester composition (polymkeric substance or comonomer) and be used for PEN-base mylar, made the cutting performance that improves film, as disclosed in authorizing the U.S. Patent No. 6232054B1 of Okutu etc.Yet the common cost of PEN is significantly higher and than the more difficult manufacturing of PET, therefore is starved of the cutting that improves PET-base polyester support.
Outside photographic art, poly-(ethylene glycol terephthalate) is common commercial semicrystalline polyester (PEN) with poly-((ethylene naphthalate)) (PET), because the combination that they have desired properties causes them to be widely used in packaging applications.The oxygen barrier performance of these polyester height makes them valuable especially aspect the packing quick food of oxygen and other object and material.PEN has advantage with respect to PET, and this is because of its higher Tg and higher oxygen barrier performance, but as mentioned above, the PEN cost is significantly higher and more be difficult to processing than PET sometimes.
The toughness of PET and similar polyester and cutting difficulty are usually owing to the crystalline texture and the molecular orientation of film.Knownly can change or order about these factors vary, to reduce toughness and to improve the cutting performance of PET by prescription by improved process conditions.Usually, can reduce or eliminate fully the crystallinity of PET by adding suitable crystal modifier.Crystal modifier such as m-phthalic acid (IPA) and 1,4 cyclohexane dimethanol (CHDM) often are copolymerized in PET and the PEN polyester, the copolyesters that has better processing characteristics with formation.An amount of IPA slows down crystallization and improves the oxygen barrier performance.The amorphous copolyester that the IPA of high level interrupts crystallization and causes having the good barrier performance, but known these copolyesters of those skilled in the art have poor impact and other mechanical property.The addition of C HDM also slows down crystallization, but reduces the oxygen barrier performance.The CHDM of known high level forms a class amorphous copolyester, and these copolyesters in many application, comprise in big thickness sheet material, adhesive label, the medical package etc. being widely used in commerce.These copolyesters have good impact resistance and other mechanical property, but have lower oxygen barrier performance and have lower oxygen barrier performance than PET than the copolyesters of IPA-modification.
Amorphous copolyester is normally defined the copolyesters that is not demonstrated remarkable fusing point by differential scanning calorimetry.These copolyesters are typically based on terephthalic acid (TPA), m-phthalic acid, ethylene glycol, neopentyl glycol and 1,4 cyclohexane dimethanol.Known amorphous copolyester has the combination of desired properties, as good transparency and color, toughness, chemical resistance and processing easily.Therefore, known this copolyesters is used to make extrusion sheet, wrappage and medical device parts.For example, the U.S. Patent No. 5385773 and 5340907 of authorizing Yau etc. discloses the polyester of 1,4 cyclohexane dimethanol, and wherein the amount of glycol is the 10-95mol% of diol component and discloses the method for producing this multipolymer by esterification.The U.S. Patent No. 6183848B1 that authorizes Turner etc. discloses a kind of amorphous copolyester, and it comprises that different amounts is derived from the comonomer of 1,4 cyclohexane dimethanol, because improved gas barrier property, this amorphous copolyester is used to pack putrefactive goods.In one embodiment, the sheet material of copolyesters as biaxial orienting disclosed.Eastman ChemicalCompany sells film and the sheet material from the CHDM repetitive of containing by the manufacturing of various amorphous PET copolyesters with trade mark EASTAPAK and EASTAR copolyesters.
Many patent disclosures the multilayer tablet base.For example, the U.S. Patent No. 5034263 of authorizing Maier discloses the multilayer tablet base that contains the PET sandwich layer.The U.S. Patent No. 5387501 of authorizing Yajima discloses a kind of multilayer tablet base, and it comprises the PET that has CHDM at ground floor with in the second layer.The U.S. Patent No. 5759756 of authorizing Laney discloses a kind of sheet base that contains the CHDM-core that has.The WO01/34391 of Moskala, the U.S. Patent No. 5288601 of authorizing Greener and U.S. Patent No. 5556739 are the further examples that can contain the multilayer tablet base of CHDM.
Therefore, be desirable to provide PET sheet base with improvement physical property.Especially, wish that acquisition toughness is less and be suitable for completion operation, i.e. the PET sheet base of rip cutting, cut-out and perforation procedure (these processes are requirements) better in the preparation of these films.In addition, wish to obtain the PET sheet base that in each step of the processing of taking a picture such as splicing, otch and encapsulation, is easier to cut.In addition, hope can be consumed in the film that photographic sheet substance uses and process in the small test room environmental at some, uses PET as the sheet base.Wish that also this PET sheet base has other favourable performance such as dimensional stability and at high temperature, in magazine, in storage process, reduce and the tendency that higher degree curls takes place and/or in the photograph process, can reduce this curling than the highland.
Summary of the invention
The present invention relates to contain poly-(ethylene glycol terephthalate) photographic sheet substance of sandwich construction, what wherein have controlled quentity controlled variable in two-layer at least is derived from 1, the monomeric unit of 4-cyclohexanedimethanol (CHDM) makes the multilayer tablet base have the cutting of regulation-relevant performance.This can add/be blended in the PET material by the polyester polymers that will contain the CHDM monomeric unit and/or in right amount the CHDM monomeric unit is incorporated in the PET-main polymer chain realizes.
The further embodiment of the present invention relates to photograph component, and it comprises that one deck contains the emulsion layer of photothermographic silver halide and the PET multilayer tablet base of producing according to above-mentioned embodiment at least.
Multilayer tablet base of the present invention has the desired properties that uses in photograph component.These comprise favorable rigidity, low tear strength and improved cutting.In addition, the multilayer tablet base that is used for these films or other element also provides good dimensional stability, optical clarity and physical strength except having improved cutting.
In the present invention, the monomeric unit that is derived from 1,4 cyclohexane dimethanol (CHDM) is also referred to as " CHDM repetitive " or " CHDM-comonomer unit ".Other definition of term as used herein comprises following:
Term as used herein " terephthalic acid (TPA) " is meant and comprises synthetic equivalent such as dimethyl terephthalate (DMT).Be to be understood that " dicarboxylic acid " comprises the corresponding acid anhydrides of these acid, ester and acyl chlorides.About dibasic alcohol/diol component in the polyester material or acid constituents, mol percentage is meant that herein summation is 100mol% separately.
" pet polymer ", " PET resin ", " poly-(ethylene glycol terephthalate) resin " etc. are meant based on total acid constituents, contain 98mol% terephthalic acid (TPA) comonomer unit at least, with based on total diol component, contain the polyester of the ethylene glycol comonomer unit of 98mol% at least.It comprises based on total acid constituents, basically by 100mol% terephthalic acid (TPA) comonomer unit with based on total diol component, and the PET resin of forming by 100mol% ethylene glycol comonomer unit basically.
Term " modified PET polymkeric substance ", " modified PET resin " etc. are based on total acid constituents, contain the polyester of 70mol% terephthalic acid (TPA) comonomer unit at least, wherein said polyester is modified, make acid constituents have and have, or the consumption of TA and these two comonomer units of EG is all less than 98mol% less than 98mol% ethylene glycol (" EG ") comonomer unit less than 98mol% terephthalic acid (TPA) (" TA ") comonomer unit or diol component.With consumption greater than acid constituents and/or diol component 2mol% (comprising) greater than 5mol%, one or more comonomers outside use terephthalic acid (TPA) comonomer and/or the ethylene glycol comonomer are to the pet polymer modification of modification, or make it pet polymer copolymerization with modification, for example for cutting that improves the sheet base or the performance that changes the sheet base that is used in addition." modified PET resin " is not must need contain any ethylene glycol comonomer unit and it is not any acid constituents that must need contain outside the terephthalic acid (TPA) comonomer unit.
In a preferred embodiment, " pet polymer of modification " is based on total acid constituents, contain the terephthalic acid (TPA) comonomer unit of 80mol% at least, at least the polyester of the ethylene glycol of 60mol% (EG) comonomer unit, this polyester are further used the comonomer modification or the copolymerization with it of preferable amount greater than one or more other types of the acid constituents of 5mol% and/or diol component.
Term " PET of CHDM-modification " or " the PET polyester of CHDM-modification " are meant by comprising the modification-pet polymer of 2mol% (comprising 3.5mol% at least) CHDM comonomer unit modification at least.In a preferred embodiment, by comprising based on total diol component, 65mol%CHDM-comonomer unit at least is to the pet polymer modification of modification.
Similarly, term " polyester of CHDM-modification " is meant and comprises based on total diol component 2mol% (comprising 3.5mol% at least) CHDM-comonomer unit at least, but is not the polyester that must comprise the terephthalic acid component of any specific consumption.In one embodiment, the polyester of CHDM-modification comprises based on total diol component 65mol%CHDM-comonomer unit at least, but is not the terephthalic acid (TPA) comonomer unit that must comprise any specific consumption.
Term " PET of height-CHDM-modification " is meant the PET polyester of CHDM-modification, and wherein the content of CHDM-comonomer unit is equal to or greater than 95mol% (comprising 100mol%).It comprises " PCT " (poly terephthalic acid 1,4 cyclohexane dimethanol ester) and " PCTA ", and PCTA is three kinds of monomers: terephthalic acid (TPA), m-phthalic acid and 1, the multipolymer of 4-cyclohexanedimethanol, wherein, has the 1,4 cyclohexane dimethanol of 100mol% based on its diol component.
Term " polyester of height-CHDM-modification " is meant the polyester of CHDM-modification, and wherein the content of CHDM-comonomer unit is greater than 95mol% (comprising 100mol%), but is not the terephthalic acid (TPA) comonomer unit that must comprise any amount.
" PET-base polyester material " is a kind of those semi-crystalline materials that contains one or more polymkeric substance, and wherein the material of 70wt% is one or more polymkeric substance in pet polymer or the modified PET polymkeric substance at least.Randomly, this material also can comprise adjuvant such as silica beads, plastifier etc.
In the present invention, use PET-base polyester material to make the sheet base.In one embodiment, being preferably greater than 80wt%, is one or more polymkeric substance in pet polymer or the modified PET polymkeric substance more preferably greater than the PET-used in the present invention base polyester material of 90wt%.
As mentioned above, one aspect of the present invention relates to a kind of imageable element, and it is included in the photosensitive or temperature-sensitive imaging layer of one deck at least on the carrier, and wherein carrier comprises and contains two-layer at least biaxial stretch-formed hypocrystalline multilayer tablet base.
In one embodiment, main stor(e)y or the ground floor adjacent with the second layer, form by the first kind of PET-base polyester material that contains one or more vibrin, in this material, based on the total diol component in this material, be derived from 1, the total content of the repetitive of 4-cyclohexanedimethanol is 3.5mol% at least, what make an exception is based on the total diol component in this material in the adjacent second layer, be derived from 1, the content of the repetitive of 4-cyclohexanedimethanol is under 3.5 to 25mol% the situation, then ground floor can have less than 3.5mol% or not be derived from 1 at all, the repetitive of 4-cyclohexanedimethanol, that is ground floor can be made up of pet polymer.The second layer adjacent at least one side of ground floor is made up of the second kind of PET-base polyester material that contains one or more vibrin, in this material, based on the total diol component in this material, be derived from 1, the total content of the repetitive of 4-cyclohexanedimethanol is greater than the mol% in the ground floor, wherein based on diol component, in the content difference of described 1,4 cyclohexane dimethanol between two-layer less than 50mol%.At least the polyester material in the second layer is a those semi-crystalline materials.Typically gross thickness is that this base of 50-180 micron has the cutting index less than 4.2, wherein cuts index as shown in the formula 1 and 2 definition.
The multilayer tablet base can be by only two-layer, and the ground floor and the second layer are formed, or the sheet base can comprise three layers or multilayer.Under three layers multilayer tablet base situation, on ground floor one side relative with the second layer the 3rd layer, can comprise the third PET-base polyester material that contains one or more vibrin, in this material, based on the total diol component in this material, be derived from 1, the total content of the repetitive of 4-cyclohexanedimethanol is greater than the content in the ground floor, wherein between main stor(e)y and any adjacent layer 1, the content difference of 4-cyclohexanedimethanol is less than the 50mol% of total diol component, with the second layer wherein and the 3rd layer composition can be identical or different.Containing under three layers the multilayer tablet base situation, ground floor can be described as sandwich layer and the second layer and the 3rd layer can be called first and second skins or superficial layer.
As mentioned above, the thickness of ground floor can be greater than any other layer.Ground floor is preferably 0.30-0.95, more preferably 0.40-0.85 to the thickness ratio of whole base.Under two synusia base situations, this ratio is preferably 0.5-0.95.Similarly, the thickness of the second layer is preferably 0.05-0.70 to the ratio of whole basic thickness.
Term " main stor(e)y " is meant that this layer provides main stiffness and sometimes for the sheet base, but not necessarily, in the multilayer tablet base, this layer thickness is greater than other layer.In a special embodiment that comprises one deck or two-layer other layer, described main stor(e)y to the thickness of other layer sum in the multilayer tablet base than being 0.5-20.
In one embodiment of the invention, the second layer comprises first kind of PET-base polyester material, wherein based on the total diol component in this material, be derived from 1, the total content of the repetitive of 4-cyclohexanedimethanol is 3.5 to 25mol%, comprise more a spot of with main stor(e)y or do not have any 1,4 cyclohexane dimethanol, based on the total diol component in this material.With respect to next embodiment, this embodiment comprises the 1,4 cyclohexane dimethanol of relative low content in the second layer.
Another embodiment of sheet base of the present invention comprises the sheet base with main stor(e)y and skin or second layer, wherein main stor(e)y comprises first kind of PET-base polyester material, wherein based on the total diol component in this material, be derived from 1, total repetition unit of 4-cyclohexanedimethanol is 10mol% at least, comprise second kind of PET-base polyester material with the skin or the second layer, based on the total diol component in this material, it comprises greater than 60mol% and is derived from 1, the repetitive of 4-cyclohexanedimethanol, wherein the difference of the 1,4 cyclohexane dimethanol content between sandwich layer and any adjacent layer is less than the 50mol% of total diol component.This embodiment comprises the 1,4 cyclohexane dimethanol of relative high-load in the second layer.
Preferably, in such embodiments, the total diol component based in this material is derived from 1 in main stor(e)y, the content range of the repetitive of 4-cyclohexanedimethanol be the sheet base of 10-22mol% and described multilayer the cutting index (as shown in the formula 1 and 2 the definition) less than 3.5.
PET-base polyester material in ground floor can be the miscible blend of at least two kinds of polyester, the first kind of for example following polyester and the miscible blend of second kind of polyester, wherein first kind of polyester is pet polymer or modification-pet polymer, comprise with second kind of polyester and to be derived from 1, the repetitive of 4-cyclohexanedimethanol, make based on the total diol component in this polyester material, the content that is derived from total repetitive of 1,4 cyclohexane dimethanol in this polyester material is 3.5-25mol%.
Similarly, in one embodiment of the invention, PET-base polyester material in the second layer can be the miscible blend that contains at least two kinds of polyester, the first kind of for example following polyester and the miscible blend of second kind of polyester, first kind of PET polyester that polyester is height-CHDM-modification wherein, wherein the content of CHDM-comonomer unit is higher than 95mol%, comprise with second kind of polyester and to be derived from 1, the repetitive of 4-cyclohexanedimethanol, wherein based on the total diol component in this polyester material, the content that is derived from total repetitive of 1,4 cyclohexane dimethanol in this PET-base polyester material is 60-100mol%, preferred 65-100mol%.
Some instantiations of multilayer tablet base comprise that wherein ground floor is the polyester of CHDM-modification and the dibasic alcohol content that the second layer is based on it, contain 100mol%1, the situation of the polyester of 4-cyclohexanedimethanol.Similarly, under the situation of three-layer tablet base, sandwich layer can be that the polyester and the two outer layers of CHDM-modification can contain 100mol%1 by the dibasic alcohol content based on it, and the polyester of 4-cyclohexanedimethanol is formed.
According to another embodiment of the present invention, use suitable method of compounding, blend PET resin and the PET polyester that contains the CHDM-modification of enough content CHDM comonomers, use this blend then, with preparation conventional PET film employed those similar conditions under, prepare biaxial stretch-formed and film or sheet stock heat setting.Again in the embodiment, use the modification-PET resin that contains enough content CHDM comonomers in the present invention, with employed those the similar conditions of the conventional PET film of preparation under, prepare biaxial stretch-formed and film or sheet stock heat setting.
As mentioned above, in an embodiment of photograph multilayer tablet base of the present invention, can make main stor(e)y by the PET-base polyester material that contains one or more vibrin, wherein in this material, based on the total diol component in this material, the content that is derived from the repetitive of 1,4 cyclohexane dimethanol (CHDM) can be 3.5 to 25mol%, makes the cutting index (as shown in the formula 1 and 2 definition) of described multilayer tablet base less than 4.2.Preferably, in this case, the multilayer tablet base comprises based on the total diol component in this material, wherein is derived from 1, the content of the repetitive of 4-cyclohexanedimethanol is that the cutting index (as shown in the formula 1 and 2 definition) of 5 to 22mol% material and described multilayer tablet base is less than 3.5.Equally, preferably less than 25mol%, be more preferably less than 10mol%, most preferably total diol component of 0mol% is the aromatic diol component basically.
Under the blend situation, the main stor(e)y of multilayer tablet base of the present invention can comprise the polyester material that contains at least two kinds of polyester, wherein first kind of polyester is pet polymer or the modification-pet polymer with second kind of polyester blend, and second kind of polyester comprises and is derived from 1, the repetitive of 4-cyclohexanedimethanol, make that based on the total diol component in this polyester material the content that is derived from total repetitive of 1,4 cyclohexane dimethanol in this polyester material is 3.5 to 25mol%.In one embodiment, first kind of polyester can not contain the repetitive from 1,4 cyclohexane dimethanol, and/or second kind of polyester can be modification-PET polyester.In another embodiment, second kind of polyester can not contain the repetitive from terephthalic acid (TPA) or its ester.
The cutting index (as shown in the formula 1 and 2 definition) that preferably contains the multilayer tablet base of PET-base polyester material less than 3.5, is more preferably less than 3.0.
Preferably, at the ground floor at least and the second layer of multilayer tablet base according to the present invention, preferably the Tg of the polymkeric substance in the polyester material in all layers is less than 90 ℃.
In making goods of the present invention employed CHDM-modification-the PET polyester preferably has 100mol% dicarboxylic acid part and 100mol% dibasic alcohol part.Less than 30mol%, the dicarboxylic acid repetitive that preferably is not more than 20mol% can be from other conventional acid as being selected from succinic acid, glutaric acid, hexane diacid, azelaic acid, decanedioic acid, fumaric acid, maleic acid, itaconic acid, 1, those in 4-cyclohexane dicarboxylic acid, phthalic acid, m-phthalic acid and the naphthalenedicarboxylic acid.
Preferred CHDM-modification-diol component in the PET polyester contains 3.5 to 50mol%1, the repetitive of 4-cyclohexanedimethanol and 96.5-50mol% ethylene glycol.Diol component can randomly comprise less than 35mol%, preferably is not more than other conventional dibasic alcohol such as propylene glycol of 10mol%, 1, ammediol, 2,4-dimethyl-2-ethyl hexane-1, the 3-glycol, 2,2-dimethyl-1, ammediol, 2-ethyl-2-butyl-1, ammediol, 2-ethyl-2-isobutyl-1, ammediol, 1, ammediol, 1, the 4-butylene glycol, neopentyl glycol, 1, the 5-pentanediol, 1, the 6-hexanediol, 1, the 8-ethohexadiol, 2,2,4-trimethyl-1,6-hexanediol, thiodiethanol, 1, the 2-cyclohexanedimethanol, 1, the 3-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclo-butane glycol, various molecular weight polyethylene glycol etc.
In embodiments of the invention, the CHDM-modification of in the multilayer tablet base, using-the PET polyester comprises the copolyesters with dicarboxylic acid component and diol component, wherein the dicarboxylic acid component comprises from the repetitive of 80mol% terephthalic acid (TPA) (or its ester) at least, comprise less than 25mol% with diol component, preferred 3.5 to 25mol% from 1, the repetitive of 4-cyclohexanedimethanol and 96.5-75mol% be from another dibasic alcohol, preferably from the repetitive of ethylene glycol.
Comprising under the embodiment situation of blend, blend comprises at least two kinds of polyester, wherein with the polyester of at least a pet polymer and/or modification-pet polymer and CHDM-modification, preferred CHDM-modification-the PET polyester blend, make that in total blend the content of CHDM-comonomer unit is 3.5 to 25mol%, preferably, be more preferably less than 20mol% less than 22mol%.In the polyester of CHDM-modification, can use any above-mentioned acid constituents and except the CHDM component, also can use any above-mentioned diol component.
In one embodiment, with following structure represent to be used for one or more layers the preferred CHDM-modification at the sheet base of the present invention-PET:
In said structure (I), subscript x and y represent the mol% based on total diol component of comonomer.Can replace other acid or dibasic alcohol monomer by degree as mentioned above.
In one embodiment, the miscible blend in the ground floor of multilayer tablet base preferably includes the polymkeric substance of pet polymer and CHDM-modification, and its ratio is 95: 5-5: 95, more preferably 85: 15-10: 90.In the polymkeric substance of CHDM-modification, with respect to total diol component, the mol% of CHDM-comonomer is preferably 3.5-35mol%.Preferably, in the polymkeric substance of CHDM-modification, acid constituents is the terephthalic acid component of 80%-100%.
As mentioned above, in one embodiment of the invention, the second layer or the outer PET resin that comprises height-CHDM-modification wherein use suitable method of compounding, with the PET resin and the polyester blend that contains the CHDM-comonomer unit of capacity of described height-CHDM-modification.Then with preparation PET sheet base employed those similar conditions under, use the film of the biaxial stretch-formed and heat setting of this resins.In another embodiment of the present invention, with preparation PET sheet base employed those similar conditions under, use the modification that contains capacity CHDM comonomer-the PET resin, prepare biaxial stretch-formed and film heat setting.Typically, biaxial stretch-formed material causes that amorphous materials becomes hypocrystalline.In typical embodiment, crystallinity is at least 10%.
More particularly, in one embodiment of the invention, the second layer of photographic sheet substance of the present invention or one or more layers skin comprise the PET-base polyester material that contains one or more vibrin, wherein in this material, the total diol component based in this material is derived from 1, the content of the repetitive of 4-cyclohexanedimethanol (CHDM) adds up to 60-100mol%, preferred 65-95mol% makes the cutting index (as shown in the formula 1 and 2 definition) of described base less than 4.2, preferably less than 3.5.In this case, the second layer of sheet base or outer preferably including wherein based on the total diol component in this material, the content that is derived from the repetitive of 1,4 cyclohexane dimethanol (CHDM) is the material of 70-95mol%, with the cutting index of described base less than 4.2, preferably less than 3.5.Equally, preferred, be aromatics less than total glycol unit of 25mol%.
Under the blend situation, the second layer of an embodiment or skin comprise a kind of polyester material behind the present invention, it comprises first kind of polyester with second kind of polyester blend, first kind of pet polymer that polyester is height-CHDM-modification wherein, second kind of polyester comprises the repetitive that is derived from 1,4 cyclohexane dimethanol, makes based on the total diol component in this polyester, the content that is derived from total repetitive of 1,4 cyclohexane dimethanol in this polyester material is 65-100mol%.All polyester materials in blend must be miscible, that is, by the necessary optical clear of the film of described blend production, to satisfy strict optics requirement to the high grade of transparency and the low haze of photographic sheet substance.In the material in the second layer of this embodiment, based on the total diol component in this polyester, the content that is derived from the repetitive of 1,4 cyclohexane dimethanol is preferably greater than 70, more preferably greater than 75mol%.
The PET polyester of employed CHDM-modification preferably has 100mol% dicarboxylic acid part and 100mol% dibasic alcohol part in making goods of the present invention.Less than 20mol%, preferably being not more than 10mol% dicarboxylic acid repetitive can be from the acid of other routine as being selected from succinic acid, glutaric acid, hexane diacid, azelaic acid, decanedioic acid, fumaric acid, maleic acid, itaconic acid, 1, those in 4-cyclohexane dicarboxylic acid, phthalic acid, m-phthalic acid and the naphthalenedicarboxylic acid.
Preferably, diol component in the PET polyester of the CHDM-modification of using in one embodiment of the invention contains and comprises 65-100mol%1, the repetitive of 4-cyclohexanedimethanol and 5-35mol% ethylene glycol is wherein at the 1,4 cyclohexane dimethanol of outer internal memory at relative high-load.Diol component can randomly comprise less than 35mol%, preferably is not more than other conventional dibasic alcohol of 10mol%, as propylene glycol, 1, ammediol, 2,4-dimethyl-2-ethyl hexane-1,3-glycol, 2,2-dimethyl-1, ammediol, 2-ethyl-2-butyl-1, ammediol, 2-ethyl-2-isobutyl-1, ammediol, 1,3 butylene glycol, 1, the 4-butylene glycol, neopentyl glycol, 1, the 5-pentanediol, 1, the 6-hexanediol, 1, the 8-ethohexadiol, 2,2,4-trimethyl-1, the 6-hexanediol, thiodiethanol, 1, the 2-cyclohexanedimethanol, 1, the 3-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclo-butane glycol etc.
Another embodiment of the present invention comprises wherein one deck, the preferred second layer or skin are the sheet bases of being made by PET-base polyester material, described PET-base polyester material comprises one or more vibrin, wherein in this material, based on total diol component, be derived from 1, the content of the repetitive of 4-cyclohexanedimethanol is 65-100mol%, with based on total acid constituents, the content that is derived from the repetitive of the acid constituents except that terephthalic acid (TPA) or its ester is 3-30mol%, preferred 5-20, wherein the cutting index of sheet base is less than 4.6, preferably less than 4.2, be more preferably less than 3.5 and most preferably less than 2.0.
Acid constituents except that terephthalic acid (TPA) can be for example m-phthalic acid (IPA), dimethyl isophthalate, 1,4-cyclohexane dicarboxylic acid (1,4-CHDA), 1,4-cyclohexanediacetic, diphenyl-4,4-dicarboxylic acid, dimethyl-2,6-naphthalene dicarboxylic acids ester, succinic acid, glutaric acid, hexane diacid, azelaic acid, decanedioic acid, to benzene dicarboxylic acid (PPDA), naphthalene dicarboxylic acids (NDA) and composition thereof.The preferred m-phthalic acid of other acid constituents (IPA), 1, and the 4-cyclohexane dicarboxylic acid (1,4-CHDA), to benzene dicarboxylic acid (PPDA), naphthalene dicarboxylic acids (NDA) etc. and composition thereof.
As mentioned above, the multilayer tablet base is used for photograph component, and described photograph component is included in the silver halide of one deck at least imaging layer on the carrier that contains the multilayer tablet base.This photograph component can be photographic film or thermal development (photothermographic) film.
Except PET-basic unit of the present invention or multilayer tablet base, carrier can further comprise one or more layers take a picture upward acceptable glue-line, laying, tack coat, magnetospheres etc.
Glue-line is used for providing bounding force between polyester support and surperficial photographic emulsion, and it contains bonding agent such as gelatin, and this is hydrophobic very consumingly because of mylar in essence, and emulsion is hydrophilic colloid.If in the bonding deficiency of taking a picture between layer and the carrier, then produce several actual problems, as the layer delamination from the carrier of taking a picture at place, the cut edge of photographic material, this can produce the fractionlet of the emulsion layer of many fragmentations, thereby causes spot defects in the imaging region of photographic material.
Therefore, used or proposed various adhesive technologies and material, made between carrier film and hydrophilic colloid layer, to produce improved bonding.For example, can handle the photograph carrier with adhesive accelerant at first, described adhesive accelerant for example contains at least a resorcinol, catechol, 1,2,3,-thrihydroxy-benzene, 1-naphthols, 2,2, 4-dinitrophenol, 2,4,6-trinitrophenol, 4-chloro resorcinol, 2,4-orcin, 1,3-naphthalenediol, 1, the material of the sodium salt of 6-naphthalenediol, acrylic acid, Neville acid, phenmethylol, trichloroacetic acid, dichloroacetic acid, o-hydroxy benzotrifluoride, a hydroxybenzotrifluoride, adjacent fluorophenol, m fluorophenol, p-fluorophenol, chloral hydrate and parachlorometacresol.Also known and use polymkeric substance in being called as the structure of glue-line, be used to promote the bonding between carrier and the emulsion layer.In U.S. Patent No. 2627088,2968241,2764520,2864755,2864756,2972534,3057792,3071466,3072483,3143421,3145105,3145242,3360448,3376208,3462335,3475193,3501301,3944699,4087574,4098952,4363872,4394442,4689359,4857396; BrP No.788365,804005,891469; With the example that discloses the suitable polymers that is used for this purpose among the European patent No.035614.Usually these are included in the polymer of monomers that has polar group in the molecule; described polar group such as carboxyl; carbonyl; hydroxyl; sulfo group; amino; amide group epoxy or anhydride group; described monomer is acrylic acid for example; PAA; methacrylic acid; itaconic acid; crotonic acid; sorbic acid; itaconic anhydride; maleic anhydride; cinnamic acid; methyl vinyl ketone; hydroxy-ethyl acrylate; hydroxyethyl methylacrylate; methacrylic acid hydroxyl chloro propyl ester; the acrylic acid hydroxy butyl ester; vinyl sulfonic acid; vinylbenzenesulfonic acid potassium; acrylamide; the N-methyl nitrosourea; N methacrylamide; acryloyl morpholine; dimethylmethacryl amide; N tert butyl acrylamide; the diacetyl acrylamide; vinyl pyrrolidone; glycidyl acrylate or glycidyl methacrylate, or the multipolymer of above-mentioned monomer and other copolymerisable monomer.Other example is the polymkeric substance of acrylate such as ethyl acrylate or butyl acrylate, methacrylate such as methyl methacrylate or Jia Jibingxisuanyizhi for example, or the multipolymer of these monomers and other vinyl monomer, or the multipolymer of polycarboxylic acid such as itaconic acid, itaconic anhydride, maleic acid or maleic anhydride and vinyl monomer such as styrene, vinyl chloride, vinylidene chloride or butadiene; Or the tripolymer of these monomers and other ethylenically unsaturated monomers.The material that uses in adhesion promotion layer often comprises the multipolymer of chloride group such as vinylidene chloride.
The composition of PET-base polyester material that can contain the two-layer or multilayer of multilayer tablet base of the present invention by the conventional method manufacturing.Usually, polyester as well known to those skilled in the art comprises the reaction product of at least a dicarboxylic acid and at least a diol component.The dicarboxylic acid component can typically comprise terephthalic acid (TPA), m-phthalic acid, 1,4-cyclohexane dicarboxylic acid, 2, the residue of 6-naphthalene dicarboxylic acids and/or its potpourri.Same suitable be that its acid anhydrides, its acyl chlorides and its are rudimentary, C1-C8 Arrcostab for example.Can use dicarboxylic acid component's any isomeride or its potpourri.For example, can use 1, the cis of 4-cyclohexane dicarboxylic acid, trans or cis/trans potpourri.The example of suitable naphthalene dicarboxylic acids isomeride comprises 1,4-naphthalene dicarboxylic acids, 2,6-naphthalene dicarboxylic acids, 2,7-naphthalene dicarboxylic acids or its potpourri.
Can be enough to carry out under the temperature of esterification or transesterification by being included in, make the reaction of dicarboxylic acid component and diol component, with in the presence of catalyzer and inhibitor system, under absolute pressure less than 10mmHg, polycondensation product prepares polyester polymers used in the present invention less than 2 hours time method.The example of preferred catalyzer and inhibitor system is 0-75ppm Mn, 50-150ppm Zn, 5-200ppm Ge, 5-20ppmTi and 10-80ppm P, and all wt part is based on the weight of copolyesters.
In producing copolyesters, can use dimethyl terephthalate (DMT) (or other lower dialkyl ester of terephthalic acid (TPA)) or terephthalic acid (TPA).Therefore, " terephthalic acid component, monomer, repetitive or part " herein is meant and comprises acid or ester-formin.These materials are commercially available.Dibasic alcohol CHDM and ethylene glycol are also commercially available.According to the present invention, can use cis or trans-isomer or its potpourri of CHDM.
Usually, for example can use, produce copolyesters in the polyesterification step described in U.S. Patent No. 3305604 and 2901460.By using conventional polymerization known in the art, for example disclosed conventional polymerization in U.S. Patent No. 4093610 and 5681918 prepares amorphous or hypocrystalline copolyesters of the present invention.The example of available polycondensation method comprises introducing inert gas such as nitrogen, the fusion phase method that balance and reaction process are moved to the high molecular direction in making PET material of the present invention; Or more conventional be vacuum fusion phase polycondensation method under 240-300 ℃ or the commercial exercisable higher temperature in temperature range.Although and do not require, the adjuvant of routine can be joined in the copolyester material of the present invention with typical consumption.This adjuvant comprises pigment, colorant, stabilizing agent, antioxidant, extrusion aid, slip agent, carbon black, fire retardant and composition thereof.
Can use in the present invention comprise from the various modifications-PET polyester of the repetitive of CHDM can with trade mark EASTAPAK and EASTAR copolyesters be available commercially from Eastman Chemical Company (Kingsport, Tenn.), as
Http:// www.eastman.comDescribed in.
Photograph component of the present invention can have structure and the component shown in the Research Disclosure Item 37038, with can use known technology and composition, be included in described in the above Research Disclosure Item37038 that quotes as proof those, with image mode exposure photograph component and handle.
Can pass through curtain coating, biaxial stretch-formed and heat setting manufacturing multilayer tablet base.The method of making PET multilayer tablet base typically comprises the steps: coextrusion and at upper edge, curtain coating surface axial curtain coating molten sheet base, form continuous sheet, by this sheet material of stretching and drawing vertically, by along this sheet material of cross directional stretch tentering, the sheet material that heat setting traction and tentering are crossed, and cool off this heat setting sheet material, form the heat setting PET film that stretched, as authorizing described in the U.S. Patent No. 4141735 of Schrader etc.Perhaps, can use suitable machine, simultaneously at axial and cross directional stretch film.
In a special embodiment, the method that is prepared film by resin combination of the present invention comprises the steps:
(1) by two extruders of plasticating, resin is fed in branch manifold coextrusion sheet material-shaping die, and under melting condition with its curtain coating to cooling surface, to form continuous cast-sheet.The vibrin of preferred molten have the logarithmic viscosity number of 0.5-0.8dl/g and under 250-310 ℃ temperature curtain coating, simultaneously the curtain coating surface has 40-70 ℃ temperature.Adopt Ubbelohde glass viscosity meter, under 25 ℃, in the solvent mixture of phenol/chlorobenzene (60/40 weight), under the concentration of 0.25g/dl, measure logarithmic viscosity number (IV).
(2) remove continuous multi-layer sheet and being sent to the towing area from the curtain coating surface, this at first preheating it, then with the draw ratio of 2.0-4.0, at 80-110 ℃ temperature lower edge axial tension.Towing area typically comprises two cover pressure rollers, and first cover is the inlet of towing area, and second cover is the outlet of towing area.In order to realize the necessary draw ratio of the present invention, the outlet pressure roller is with the speed rotation bigger than the inlet pressure roller.Final stage at towing area is cooled to 25-40 ℃ with film.
(3) film is moved to the tentering district from towing area, this preheating it and with the draw ratio of 2.0-4.0, at 80-115 ℃ temperature lower edge cross directional stretch.The device that the tentering district typically is included in its edge's engagement (engage) film and stretches makes that final width is 2.0-4.0 a times of its initial width.
(4) then by film is maintained at least 200 ℃, but under the low-melting temperature than the resin that has minimum melting transition in the multi-layer sheet, preferably at least 200 ℃-240 ℃, tightly clamp the time that is enough to carry out heat setting when in the tentering district simultaneously, come the heat setting film.Than produce this as a result the longer time of required time can not damage film, but the longer time be unwanted because lengthening that should the district requires higher fund cost, do not realize additional advantage simultaneously.Typically in the time period of 0.1-15 second and preferred 0.1-10 second, finish the heat setting step.At last, under the situation of significantly not removing tentering, cool off film (device of clamping film edge can not allow film greater than 2% shrinkage factor).
For the dimensional stability of improving it and the following core tendency that reduces it, preferably at 50 ℃ until thermal treatment multilayer tablet base 1 hour-1000 hours under the temperature of Tg (H), wherein Tg (H) is the glass transition temperature that has the polyester material of maximum glass transition temperature in multifilm.
About cutting, common known cutting technique forms and expansion in conjunction with the crack in sheet stock cutting field.In order to form the crack, people need use cutting machine, causing in the lip-deep compression of sheet stock, up to material deformation and reach its breakaway poing.In case reach the breakaway poing of material, then will form the crack, this has just begun the second step-crack propagation of cutting.By further use cutting machine compression sheet stock, people can keep and finally finish cutting technique.At last, when the thickness of sheet material is crossed in crack propagation, finish cutting.
In order to estimate the cutting of given material, the behavior of people's needs assessment material in crack formation and extension phase process.If in crack formation and expansion process, the absorbed and the more mechanical energy that dissipates then illustrate more difficult cutting and will have lower cutting.Can use two kinds of code tests, estimate how much mechanical energy of absorbed in formation of described crack and spread step process.A kind of is that tension test (ASTM D882) and another kind are tear test (ASTM D1938).The crack that can use the former to estimate cutting process forms part and can use the latter to estimate the crack propagation part of cutting process.
Machinery and cutting performance according to following program appraisal mylar of the present invention:
Tensile property: can use tension test,, measure modulus and stretching toughness as in the test described in the ASTM D882.Tension test is included under the particular rate, adopts tension load tractive material sample to rupture up to it.Employed sample can have circle or square-section.Historical according to load and elongation, marking and drawing strain on the x-axle and on the y-axle, marking and drawing stress, obtain stress-strain curve.Modulus is defined as the slope of the initial straight line portion of stress-strain curve.Modulus is measuring of material stiffness.The stretching toughness is defined as at the area under breakaway poing under the whole stress-strain curve.The stretching toughness is the measuring of absorbed energy in stretcher strain.The two all is basic mechanical propertys of material for modulus and stretching toughness.
Tear strength: can use tear test,, measure tear resistance as in the test described in the ASTM D1938.This experimental measurement makes the power of tearing expansion in fracture mode II.The otch that employed sample has rectangular shape and has sharp-pointed length in the centre.Two arms that sample is separated are fixed in the conventional test machine such as Instron then.Move this clamp device with constant speed, the power under the steady state (SS) that otch that prolongation is pre-existing in and record are torn.
The cutting index: common known stretching toughness is represented the desired energy of created fractures, and the fracture toughness decision further expands this crack energy needed.Because typical cutting process comprises that the crack begins and this two aspect of crack propagation, so can be based on the size of these two stock parameter-definition cuttings.Can be by extension test evaluation stretching toughness.Can calculate fracture toughness G according to tear strength
c:
G
c＝2P
c/b????(1)
P wherein
cBe load when tearing crack growth and b be thickness of sample (referring to Rivlin, R.S. ﹠amp; Thomas, A.G., (1953), J.Polym.Sci., 10,291).
For the simplicity of practicality, according to cut the dimensionless group of index as giving a definition:
C＝0.5*Wt/W
tr+0.5*G
c/G
cr????(2)
Wherein C is the cutting index, W
tBe the stretching toughness, and G
cBe fracture toughness, and W
TrWith G
CrBe the respective performances of reference material, wherein select CTA as reference material of the present invention.The cutting index of plate substrate material commonly used such as PET, PEN and the CTA cutting performance actual with it coincide well.Usually, wish that C approaches 1 (CTA value).
Having above listed performance and the mylar by above-described method preparation may not break down so and may produce more neat cutting surface more in various cutting operations.In fact, film prepared in accordance with the present invention can advantageously match in excellence or beauty with CTA, and because the specific physical of CTA, CTA is the selection of sheet base in photographic industry for a long time.
Embodiment
By reference example, below the present invention will be described in more detail.Yet the present invention should not be limited to this.
Material:
Use among the following embodiment of following material preparation poly-(ethylene glycol terephthalate) (PET)-base carrier:
Polyester-1 (P-1): EASTAPAK PET polyester 7352 (Eastman Chemical Company, the trade mark of USA) is a kind of PET resin.
Polyester-2 (P-2): EASTAR copolyesters 15086 (Eastman Chemical Company, the trade mark of USA) is a kind of PET resin of CHDM-modification, and it comprises 1,4 cyclohexane dimethanol (CHDM) monomeric unit of the about 12mol% of diol component that accounts for it.
Polyester-3 (P-3): EASTAR copolyesters 6763 (Eastman Chemical Company, the trade mark of USA) is a kind of PET resin of CHDM-modification, and it comprises the CHDM monomeric unit of the about 31mol% of diol component that accounts for it.
Polyester-4 (P-4): EASTAR copolyesters 5445 (Eastman Chemical Company, the trade mark of USA) is a kind of PET resin of CHDM-modification, and it comprises the CHDM monomeric unit of the about 62mol% of diol component that accounts for it.
Polyester-5 (P-5): EASTAR A150 (Eastman Chemical Company, the trade mark of USA) be a kind of high-the PET resin of CHDM-modification, it comprises the m-phthalic acid of the total about 17mol% of acid constituents that accounts for it and accounts for the CHDM of its diol component 100mol%.
Polyester-6 (P-6): with EASTAPAK PET (Eastman Chemical Company, the trade mark of USA) and EASTAR copolyesters 6763 (Eastman Chemical Company, the trade mark of USA) mixes with 32: 68 weight ratio, drying is 24 hours under 66 ℃, melt kneading then, and the use double screw extrusion machine, under 277 ℃, extrude, thereby obtain containing the blend of the CHDM of the about 21mol% of diol component that accounts for it.
Polyester-7 (P-7): with EASTAR copolyesters 5445 (Eastman Chemical Company, the trade mark of USA) and EASTAR A150 (Eastman Chemical Company, the trade mark of USA) mixes with 77: 23 weight ratio, drying is 24 hours under 66 ℃, melt kneading then, and the use double screw extrusion machine, under 277 ℃, extrude, thereby obtain containing the blend of the CHDM of the about 70mol% of diol component that accounts for it.
Embodiment 1
Use P-4 and P-3 resin,, form two-layer film by melt coextrusion and biaxial stretch-formed.By two single screw extrusion machines, through sheet material-shaping coextrusion die head, at about 280 ℃ of following extrusion resins.The sheet material curtain coating on the cooling surface under about 60 ℃, is formed continuous two-layer cast-sheet.Remove sheet material from cooling surface after, under about 95 ℃, vertically and laterally, traction and tentering sheet material are to its about 3.4 times of initial size.The gained film is 70 micron thickness, and it has 1: 3.7 layer thickness ratio, and wherein P-3 constitutes thicker main stor(e)y in two-layer film.
Embodiment 2
Repeat the method for embodiment 1, different is to make P-2 resin and the coextrusion of P-1 resin, forms two-layer laminated material.At about 280 ℃ of following extruding polymerization resins.Under about 95 ℃, vertically and laterally, traction and this laminated material of tentering are to its about 3.4 times of initial size.The gained film is 70 micron thickness, and it has 1: 3.7 layer thickness ratio, and wherein P-1 constitutes thicker main stor(e)y in two-layer film.
Embodiment 3
Repeat the method for embodiment 1, different is to make P-5 resin and the coextrusion of P-4 resin, forms two-layer laminated material.At about 280 ℃ of following extruded polymers.Under about 102 ℃, vertically and laterally, traction and this laminated material of tentering are to its about 3.4 times of initial size.The gained film is 70 micron thickness, and it has 1: 3.7 layer thickness ratio, and wherein P-4 constitutes thicker main stor(e)y in two-layer film.
Embodiment 4
Repeat the method for embodiment 1, different is to make P-7 resin and the coextrusion of P-6 resin, forms three layers laminated material.At about 280 ℃ of following extruding polymerization resins.Under about 99 ℃, vertically and laterally, traction and this laminated material of tentering are to its about 3.4 times of initial size.The gained film is 70 micron thickness, and it has 1: 3.7 layer thickness ratio, and wherein P-6 constitutes thicker main stor(e)y in two-layer film.
Comparative Examples 1
Use melt to extrude and biaxial stretch-formed method, the P-1 resin is changed into film.Under about 280 ℃, by the sheet material-shaping coextrusion die head that in above embodiment, uses, extrusion resin, and curtain coating is on the cooling surface under about 60 ℃, forms to have the continuous cast-sheet of even composition.Under about 100 ℃, vertically and horizontal both direction, traction and this laminated material of tentering are to its about 3.4 times of initial size.
Comparative Examples 2
Comparative Examples 2 is conventional cellulose triacetate (CTA) films as conventional 35mm photograph component carrier.Make this film by solvent-casting method routinely.
Physical property evaluation: stretching toughness, tear resistance and the back processing of measuring the film for preparing according to following program in above embodiment are curled.
The stretching toughness: according to ASTM D882-80a, under the standard environment of 50%RH and 23 ℃, carry out all tests.Use the Sintech 2 mechanical test systems of band Testworks 4.5 version softwares, carry out tension test.Sample size be 1.5cm wide * 10.2cm long (gauge length).Crosshead speed is 5.1cm/min.To 5 samples of each film sample test.The stretching toughness of being reported is the following area at stress-strain curve.
Tear strength: according to ASTM D 1938, under the standard environment of 50%RH and 23 ℃, carry out all tear tests.Use the Sintech 2 mechanical test systems of band Testworks 4.5 version softwares, carry out tear test.Sample size be 2.5cm wide * 7.6cm is long.At first on sample,, use sharp scissors to make the long otch of 2.5cm, thereby obtain two different arms in the center of width.These two arms are placed on two planes of mechanical test frame-over against between the clip of (flat-faced) and stretch and open.Crosshead speed is 25cm/min.By thickness correction average peak load, report tear strength with film.
Following table 1 has been listed the critical nature of the prepared test film of the embodiment of the invention.Measure the cutting index according to following formula 2.
Table 1
| Embodiment No. | Polyester in outer | Polyester in the main stor(e)y | The stretching toughness | Tear strength | The cutting index |
| ?MPa | ?g/100□m | ||||
| ?1 | ?P-4 | ?P-3 | ?49 | ?17 | ?1.4 |
| ?2 | ?P-2 | ?P-1 | ?102 | ?34 | ?2.9 |
| ?3 | ?P-5 | ?P-4 | ?22 | ?7 | ?0.6 |
| ?4 | ?P-7 | ?P-6 | ?43 | ?26 | ?1.5 |
| Comparative Examples 1 | ?- | ?P-1 | ?131 | ?81 | ?4.5 |
| Comparative Examples 2 | ?- | ?CTA | ?23 | ?25 | ?1.0 |
As shown in table 1, think that the film sample of Comparative Examples 1 is because its height cutting index causes having poor cutting performance in various photograph process operations.On the contrary, think that the multifilm sample of embodiment 1-4 of the polyester material that contains the CHDM-modification has improved cutting performance, more approaching with the performance of the CTA film (Comparative Examples 2) of standard, because it is relatively low and more approach 1 to cut index accordingly.
Claims (9)
1. biaxial stretch-formed hypocrystalline multilayer tablet base, it comprises two-layer at least:
A) ground floor of first kind of PET-base polyester material, described PET-base polyester material comprises one or more vibrin;
B) second layer of the second kind PET-base polyester material adjacent with at least one side of ground floor, described PET-base polyester material comprises one or more vibrin, in this material, based on total diol component of material, the total content of repetitive that is derived from 1,4 cyclohexane dimethanol is greater than the corresponding content in the ground floor, wherein, based on total diol component, the difference of the content of the 1,4 cyclohexane dimethanol between the ground floor and the second layer is less than 50mol%;
Wherein based on the total diol component in this material, in first kind of PET-base polyester material, be derived from 1, the total content of the repetitive of 4-cyclohexanedimethanol is 3.5mol% at least, what make an exception is based on the total diol component in this material in the described second layer, be derived from 1, the content of the repetitive of 4-cyclohexanedimethanol is under 3.5 to 25mol% the situation, then ground floor is based on total diol component, can have less than 3.5mol%1,4-cyclohexanedimethanol or do not have 1,4 cyclohexane dimethanol;
Wherein at least a polyester material in the second layer is a those semi-crystalline materials;
The gross thickness of wherein said base is the 50-180 micron;
With the cutting index of wherein said multilayer tablet base less than 4.2.
2. the sheet base of claim 1, wherein the second layer comprises second kind of PET-base polyester material, wherein based on the total diol component in this material, be derived from 1, the total content of the repetitive of 4-cyclohexanedimethanol is that 3.5-25mol% and ground floor comprise first kind of PET-base polyester material, wherein based on the total diol component in this material, the total content that is derived from the repetitive of 1,4 cyclohexane dimethanol is 0-25mol%.
3. the sheet base of claim 1, wherein main stor(e)y or ground floor comprise first kind of PET-base polyester material, wherein based on the total diol component in this material, the content that is derived from the repetitive of 1,4 cyclohexane dimethanol is 10mol% at least; With
The skin or the second layer of second kind of PET-base polyester material comprise based on the total diol component in this material, greater than the repetitive that is derived from 1,4 cyclohexane dimethanol of 60mol%; Wherein based on the total diol component in this material, the difference of the content of the 1,4 cyclohexane dimethanol between main stor(e)y and skin is less than 50mol%.
4. the sheet base of claim 1, wherein the multilayer tablet base is by only two-layer, and the ground floor and the second layer are formed.
5. the sheet base of claim 1, it comprises at least three layers, relative with the second layer the 3rd layer on ground floor one side wherein, comprise the third PET-base polyester material that contains one or more vibrin, in this material, based on the total diol component in this material, the total content of repetitive that is derived from 1,4 cyclohexane dimethanol is greater than the content in the ground floor; With
Wherein based on the total diol component in this material, the difference of the content of the 1,4 cyclohexane dimethanol between ground floor and any adjacent layer is less than 50mol%,
Wherein the second layer can be identical or different with the 3rd layer composition.
6. the sheet base of claim 1, wherein ground floor is that total diol component that the CHDM-modification-PET polyester and the second layer are based on it contains 100mol%1, the height of 4-cyclohexanedimethanol-CHDM-modification-the PET polyester.
7. imageable element, it comprises the sheet base of one deck photosensitive layer at least or heat-sensitive layer and claim 1.
8. the imageable element of claim 21, wherein said ground floor than the more approaching described imaging layer of the described second layer and wherein the imaging layer comprise silver emulsion.
9. the imageable element of claim 21, wherein this element is the photographic film of 35-mm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32538698A JP3668622B2 (en) | 1998-11-16 | 1998-11-16 | Article inspection method and apparatus |
| JP10/325386 | 2002-12-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1510512A true CN1510512A (en) | 2004-07-07 |
Family
ID=18176261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2003101209548A Pending CN1510512A (en) | 1998-11-16 | 2003-12-19 | Multi-layer photo picture substrate containing 1,4-oxane dimethonal |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3668622B2 (en) |
| CN (1) | CN1510512A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231239A (en) * | 2014-09-01 | 2014-12-24 | 湖北鼎龙化学股份有限公司 | Polyester composition and manufacturing method thereof, bonding resin and color matching agent for electrostatic charge image development |
| CN114957946A (en) * | 2022-06-09 | 2022-08-30 | 吉林建筑大学 | Modified polylactic acid-based material and application thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4704735B2 (en) * | 2004-11-04 | 2011-06-22 | 株式会社島津製作所 | X-ray fluoroscope |
| CN101071109B (en) * | 2006-05-08 | 2010-05-12 | 清华大学 | Multi-segment linear trace imaging cargo safety inspection system |
| JP6826227B1 (en) * | 2020-07-21 | 2021-02-03 | トーヨーカネツ株式会社 | Automatic proper packing system |
| KR102551054B1 (en) * | 2021-08-05 | 2023-07-05 | 한국원자력연구원 | Apparatus and operating method for x-ray imaging |
-
1998
- 1998-11-16 JP JP32538698A patent/JP3668622B2/en not_active Expired - Fee Related
-
2003
- 2003-12-19 CN CNA2003101209548A patent/CN1510512A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231239A (en) * | 2014-09-01 | 2014-12-24 | 湖北鼎龙化学股份有限公司 | Polyester composition and manufacturing method thereof, bonding resin and color matching agent for electrostatic charge image development |
| CN114957946A (en) * | 2022-06-09 | 2022-08-30 | 吉林建筑大学 | Modified polylactic acid-based material and application thereof |
| CN114957946B (en) * | 2022-06-09 | 2024-01-30 | 吉林建筑大学 | Modified polylactic acid-based material and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000146869A (en) | 2000-05-26 |
| JP3668622B2 (en) | 2005-07-06 |
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