CN100469814C - Polyester resin compositions, catalyst for polyester production, polyester film, and magnetic recording medium - Google Patents

Abstract

A practical polyester which is provided with substantially no antimony compound as a polycondensation catalyst. (I) One of the polyester resin compositions has an antimony content of 30 ppm by weight or lower, a titanium content of 0.5 to 50 ppm by weight, and a phosphorus content of 0.1 to 100 ppm by weight and has titanium-containing particles having a diameter of 1 m or larger in terms of equivalent-circle diameter, the number of the particles being less than 100 per 0.02 mg. (II) The other polyester resin composition has an antimony content of 30 ppm by weight or lower, a titanium content of 0.5 to 50 ppm by weight, and a phosphorus content of 0.1 to 100 ppm by weight and contains 0.1 to 5 wt.% organic polymer particles which have an average particle diameter as measured by the dynamic light scattering method of 0.05 to 3 m and in which the number of coarse particles having a particle diameter at least two times the average particle diameter account for up to 0.01% of the number of all particles.

Description

Polyester and resin composition, catalyst for polyester production, polyester film and magnetic recording media

Technical field

The present invention relates to polyester and resin composition, catalyst for polyester production, polyester film and magnetic recording media.

Background of invention

Polyester, particularly polyethylene terephthalate the mechanical characteristics of crystallinity, intensity etc., chemical resistant properties, thermal property, electrical characteristic, transparent aspect excellence, use in various industry purposes such as film, fiber, bottle, extrusion molding article, its demand constantly increases.Wherein in thin film application, it has excellent mechanical characteristics and economy, and therefore use with, agricultural usefulness, packaging, electrical condenser at magnetic recording, building materials are used etc. has in the field of a large amount of needs uses.

For example polyethylene terephthalate still in the business method of general manufacturing high-molecular weight polymer, is extensive use of the antimony compounds as polycondensation catalyst by terephthalic acid or its ester formation property derivative and ethylene glycol manufacturing.

But be to use the antimony compounds to have following several problems.

For example, the antimony compounds is part generating gasification when the polymer melt moulding, becomes separated in flight, and piles up its residue at the die orifice periphery.If so, will cause film surface and produce defective.

In addition, the antimony compounds forms bigger particulate state easily in polymkeric substance, becomes to make the film filter press liter, and perhaps the reason of film surface generation defective when making film becomes the reason that causes film breaks under serious situation.

In addition, the use of antimony compounds will destroy the particulate stability of adding in the polymkeric substance, cause that particle builds up, and be to cause the surface to produce the reason that grade such as thick projection reduces, perhaps with above-mentioned the same, the filter that becomes strainer presses a reason that rises and cause operability to reduce.

Therefore, wish to use antimony content few, perhaps not stibiated polyester.

For example, when seeking antimony compounds compound in addition as polycondensation catalyst, known have the germanium compounds, but because germanium compounds price is very high, general having difficulties.

As the compound except antimony compounds, germanium compounds, also known use titanium compound.

For example, open to disclose in the 2002-187942 communique the spy and use the mixture of the water, organic solvent or these materials that contain basic cpd that titanium compound is handled, it is added into method in the polyester operation.

In addition, open in the 2000-119383 communique, disclose the catalyst for polymerization of polyester of average primary particle diameter at 100nm or the titanium dioxide below it the spy.

In addition, open the polymer blend that discloses employing high purity dicarboxylic acid composition and titanium compound formation in the 2000-17065 communique the spy.

In addition, open to disclose in the flat 10-316749 communique the spy and use organic titanic compound and organo-tin compound mixes, heat treated forms resultant manufacture method as the vibrin of catalyzer.

In addition, open the process for producing polyester that discloses the manganic compound that used specified quantitative and alkali metal compound, phosphorus compound, organic titanic compound in the clear 63-278927 communique the spy.

In addition, open the method that discloses in the clear 54-43294 communique by zn cpds, cobalt compound and aromatic series polyvalent carboxylic acid and tetraalkyl titanate manufacturing polyester the spy.

In addition, open in the transesterification reaction that discloses the manganic compound that adopting specified quantitative and cobalt compound in the clear 54-37196 communique the spy and use reactant to carry out the polymeric process for producing polyester as catalyzer by aromatic series polyvalent carboxylic acid and tetraalkyl titanate.

In addition, open in the clear 51-81896 communique the spy and to disclose the use titanium oxide, add the method for the cobalt salt of tellurium compound, cobalt compound, phosphorus compound as catalyzer.

In addition, open in the clear 51-81895 communique, disclose the use titanium oxide, add the method for the cobalt salt of bismuth compound, cobalt compound, phosphorus compound as catalyzer the spy.

In addition, open in the clear 51-66395 communique the spy and to disclose the use titanium oxide, add the method for nickel compound as catalyzer.

In addition, opening the catalyzer that discloses in the flat 7-292087 communique by using titanium the spy makes metal separate out granule content in specified quantitative or polyester below it and manufacture method thereof.

But in these technology, rotten or aggegation take place in titanium compound (catalyst for polymerization of polyester) in the polyester reaction, form foreign matter, even the content that for example reduces foreign matter can not suppress the formation of big particle, the magnetic recording media of for example special smooth-flat-surface of demand with film etc. in, its effect deficiency.

And, with in the film etc., be to improve the slipperiness of film or the superficiality of film at magnetic recording media, generally make and wherein contain particle.For example open the organic polymer particle that discloses preferred use and polyester affinity excellence in the clear 59-217755 communique the spy.But, still not enough aspect the thick projection of film surface.

In addition, when using titanium compound to use as polycondensation catalyst, the polyester of gained himself yellow, and it is unstable that melting heat stability also becomes, and exists the generation film breaks, causes the problem of productivity deterioration etc.

For eliminating the xanchromatic problem, generally come the inhibition zone yellow, but because cobalt compound damages the thermostability of polyester, so melting heat stability becomes unstable more, but also cause productivity to become bad by in polyester, adding cobalt compound.

In addition, as the method for eliminating tone, thermotolerance problem in the titanium class catalyzer, the composite oxides that use titanium and the silicon formation method as catalyzer in disclose No. 95/18839 brochure, the world is disclosed.

In addition, open the titanium compound catalyst that discloses in 2001-89557 number by the titanium halide hydrolysis is formed the spy.

But, particularly in optical applications of for example film that just has problems of the small difference of tone etc., the improvement deficiency of tone.In addition, tone is adjusted agent self bad dispersibility, will produce foreign matter or disperses etc., still has problems eventually.

The object of the present invention is to provide do not use in fact the antimony compounds as polycondensation catalyst, can be in the polyester of practicality.

Disclosure of an invention

The present invention is made of following.

(1) a kind of polyester and resin composition, wherein the content of antimony element in weight basis at 30ppm or below it, titanium elements contains 0.5～50ppm in weight basis, phosphoric contains 0.1～100ppm in weight basis, and the circular diameter of equal value that contains titanium elements is at 1 micron or particulate 100 a/0.02mg of number density less than more than it.

(2) as above-mentioned (1) described polyester and resin composition, wherein use titanium compound as polymerizing catalyst.

(3) as above-mentioned (1) or (2) described polyester and resin composition, wherein contain titanium oxide.

(4), wherein contain the composite oxides of titanium and silicon as above-mentioned (3) described polyester and resin composition.

(5) as each described polyester and resin composition of above-mentioned (1)～(4), wherein contain titanium compound, and this titanium compound has at least a kind of substituting group selecting from alkoxyl group, phenoxy group, acidylate base, amino and hydroxyl.

(6) as above-mentioned (5) described polyester and resin composition, wherein the alkoxyl group of titanium compound is at least a kind of functional group who selects from beta-diketon class functional group, hydroxycarboxylic acid functional group and ketone ester class functional group.

(7) as above-mentioned (5) described polyester and resin composition, wherein the acidylate base of titanium compound is polyvalent carboxylic acid's class functional group or nitrogenous polyvalent carboxylic acid's class functional group.

(8) as above-mentioned (5) described polyester and resin composition, wherein titanium compound has aliphatics alkoxyl group or aliphatics acidylate base.

(9) as each described polyester and resin composition of above-mentioned (1)～(8), wherein contain at least a Phosphorus compound of from phosphoric acid class, phosphorous acid class, phosphonic acid based, phospho acid class, phosphinoxides, phosphonous acid class, phosphinous acid class and phosphine class, selecting.

(10) as above-mentioned (9) described polyester and resin composition, wherein contain phosphoric acid and/or phosphate compound.

(11) as above-mentioned (9) described polyester and resin composition, wherein contain phosphinic acid compounds and/or phosphonate compound.

(12) as above-mentioned (11) described polyester and resin composition, wherein Phosphorus compound is the diethyl phosphonyl ethyl acetate.

(13) as each described polyester and resin composition of above-mentioned (1)～(12), wherein relative phosphoric, the mol ratio of titanium elements (Ti/P) is 0.1～20.

(14) as each described polyester and resin composition of above-mentioned (1)～(13),, contain the alkali earth metal of 5～100ppm wherein in weight basis.

(15) as above-mentioned (14) described polyester and resin composition,, contain the magnesium elements of 15～60ppm wherein in weight basis.

(16) as each described polyester and resin composition of above-mentioned (1)～(15), wherein the volume specific resistance during fusion is 1 * 10 ⁶～1 * 10 ⁹Ω cm.

(17) a kind of polyester film, it contains as each described polyester and resin composition of above-mentioned (1)～(16).

(18) laminated polyester film that forms by multilayer laminated polyester, wherein at least 1 layer of employing such as each described polyester and resin composition of above-mentioned (1)～(16).

(19) magnetic recording media that adopts above-mentioned (18) described laminated polyester film to form.

(above (1)～(19) are called " I organizes the present invention ").

(20) a kind of polyester and resin composition, wherein the content of antimony element in weight basis at 30ppm or below it, titanium elements contains 0.5～50ppm in weight basis, phosphoric contains 0.1～100ppm in weight basis, and the organic polymer particle that contains 0.1～5 weight %, the median size that this particle is gone out by dynamic light scattering determination is 0.05～3 micron, is that the individual percentage of 2 times or big particle more than it is 0.01% or below it with respect to whole particle number average particle diameters.

(21) as above-mentioned (20) described polyester and resin composition, wherein use titanium compound as polymerizing catalyst.

(22) as above-mentioned (20) or (21) described polyester and resin composition, wherein contain titanium oxide.

(23), wherein contain the composite oxides of titanium and silicon as above-mentioned (22) described polyester and resin composition.

(24) as each described polyester and resin composition of above-mentioned (20)～(23), wherein contain titanium compound, and this titanium compound has at least a kind of substituting group selecting from the functional group with 6 expressions of following formula 1～formula.

(formula 1)

(formula 2)

(formula 4)

(formula 5)

---OH (formula 6)

(in formula 1～formula 6, R ₁～R ₉Expression hydrogen or carbonatoms are 1～30 alkyl.)

(25) as above-mentioned (24) described polyester and resin composition, the R of its Chinese style 1～formula 6 ₁～R ₉In at least one is that to have alkoxyl group, hydroxyl, carbonyl, ethanoyl, carboxyl, ester group or amino carbonatoms be 1～30 alkyl.

(26) as above-mentioned (25) described polyester and resin composition, the R of its Chinese style 1～formula 3 ₁～R ₆In at least one is that carbonatoms with hydroxyl, carbonyl, ethanoyl, carboxyl or ester group is 1～30 alkyl.

(27) as above-mentioned (25) described polyester and resin composition, the R of its Chinese style 1 ₁～R ₃In at least one is that carbonatoms with carboxyl or ester group is 1～30 alkyl.

(28) as above-mentioned (25) described polyester and resin composition, the R of its Chinese style 4 ₇It for carbonatoms 1～30 alkyl.

(29) as above-mentioned (28) described polyester and resin composition, the R of its Chinese style 4 ₇It for carbonatoms 1～30 alkyl with hydroxyl, carbonyl, ethanoyl, carboxyl or ester group.

(30), wherein contain at least a kind of Phosphorus compound from phosphoric acid class, phosphorous acid class, phosphonic acid based, phospho acid class, phosphinoxides, phosphonous acid class, phosphinous acid class and phosphine class, selecting as each described polyester and resin composition of above-mentioned (20)～(29).

(31) as above-mentioned (30) described polyester and resin composition, wherein contain phosphoric acid and/or phosphate compound.

(32) as above-mentioned (30) described polyester and resin composition, wherein contain phosphinic acid compounds and/or phosphonate compound.

(33) as above-mentioned (32) described polyester and resin composition, wherein Phosphorus compound is a diethyl phosphonyl vinegar ethyl ester.

(34) as each described polyester and resin composition of above-mentioned (20)～(33), wherein relative phosphoric, the mol ratio of titanium elements (Ti/P) is 0.1～20.

(35) as each described polyester and resin composition of above-mentioned (20)～(34),, contain the alkali earth metal of 5～100ppm wherein in weight basis.

(36) as above-mentioned (35) described polyester and resin composition,, contain the magnesium elements of 15～60ppm wherein in weight basis.

(37) as each described polyester and resin composition of above-mentioned (20)～(36), wherein organic polymer particulate degree of crosslinking is 50% or more than it.

(38) as each described polyester and resin composition of above-mentioned (20)～(37), wherein the organic polymer particle is the multipolymer of vinyl benzene-Vinylstyrene.

(39) as each described polyester and resin composition of above-mentioned (20)～(38), wherein relative organic polymer particle contains the water-soluble polymer of 0.1～5 weight %.

(40) as above-mentioned (39) described polyester and resin composition, wherein water-soluble polymer has the pyrrolidone residue.

(41) as each described polyester and resin composition of above-mentioned (20)～(40), wherein the volume specific resistance during fusion is 1 * 10 ⁶～1 * 10 ⁹Ω cm.

(42) a kind of polyester film, it contains as each described polyester and resin composition of above-mentioned (20)～(41).

(43) laminated polyester film that forms by multilayer laminated polyester, wherein at least 1 layer of employing such as each described polyester and resin composition of above-mentioned (20)～(41).

(44) magnetic recording media that adopts above-mentioned (43) described laminated polyester film to form.

(above (20)～(44) are called " II organizes the present invention ").

(45) a kind of manufacturing polyester catalyzer, it contains a kind of reaction product, this reaction product is a kind of compound of selecting from compound shown in following general formula 7 or 8, with contain at least a kind of atom from nitrogen-atoms, sulphur atom and Sauerstoffatom, selecting as foreign atom, can carry out the reaction product of 2 or 2 above coordinate coordination compoundes at least.

Ti (OR) ₄(formula 7)

Ti (OH) _m(OR) _4-m(formula 8)

(R: carbonatoms is 2～10 organic group (can be identical or different mutually), the integer of m:1～4)

(46) as above-mentioned (45) described catalyst for polyester production, wherein organic group R is an alkyl.

(47) as above-mentioned (45) or (46) described catalyst for polyester production, the compound of its formula of 7 or 8 expressions is four alkoxy titanium compounds or titanium chelate.

(48) as each described catalyst for polyester production of above-mentioned (45)～(47), wherein coordination compound is at least a kind of compound selecting from metal-free phthalocyanine, indanthrone, anthraquinone and methine dyes.

(49) use the polyester and resin composition that produces as each described catalyst for polyester production of above-mentioned (45)～(48).

(50) contain the polyester film of above-mentioned (49) described polymer blend.

(51) laminated polyester film that forms by multilayer laminated polyester, wherein at least 1 layer of employing such as above-mentioned (49) described polyester and resin composition.

(52) magnetic recording media that adopts above-mentioned (51) described laminated polyester film to form.

(above (45)～(52) are called " III organizes the present invention ").

The present invention by I～III group can provide a kind of like this polyester, and it does not use the antimony compounds as polycondensation catalyst in fact, and its oilness and thermostability etc. are excellent, can be suitable for purposes such as magnetic recording media in practicality.

(III organizes the present invention)

In addition, further, can provide the polyester that presents good tone by the present invention of III group.

The optimised form that carries out an invention

(the present invention of the I～III group)

The polymkeric substance of polyester for synthesizing by dicarboxylic acid or its ester formation property derivative and glycol or its ester formation property derivative.

Example as dicarboxylic acid, for example can enumerate, terephthalic acid, m-phthalic acid, phthalic acid, 1,4-naphthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, 4,4 '-phenylbenzene dioctyl phthalate, 4,4 '-diphenyl ether dioctyl phthalate, 4, the ester ring type dicarboxylic acid of the aliphatic dicarboxylic acid of the aromatic dicarboxylic acid of 4 '-sulfobenzide dioctyl phthalate, 5-sulfoisophthalic acid sodium etc., dimeracid, hexanodioic acid, sebacic acid etc., cyclohexane cyclohexanedimethanodibasic etc. etc. also can use these ester to form the property derivative.

In addition, as glycol, can make spent glycol, 1, ammediol, 1, the 2-propylene glycol, neopentyl glycol, 1,3 butylene glycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4 cyclohexane dimethanol, glycol ether, triglycol, polyalkylene glycol, 2, the aliphatics of the affixture of 2-two (4 '-beta-hydroxy ethoxyl phenenyl) propane, bisphenol-A epoxy ethane etc., alicyclic, aromatic diol etc.

These compositions can distinguish only use a kind of, perhaps with 2 kinds or more than it and use.

In addition, also can and use hydroxycarboxylic acid or its ester to form the property derivative to Para Hydroxy Benzoic Acid etc.

As polyester, for example can exemplify out, polyethylene terephthalate, polybutylene terephthalate, poly terephthalic acid cyclohexanedimethyleterephthalate ester, poly terephthalic acid trimethylene ester) (being also referred to as Poly(Trimethylene Terephthalate)), PEN, polyethylene-1, two (the 2-chloro phenoxy group) ethane-4 of 2-, 4 '-dicarboxylic ester etc., wherein polyethylene terephthalate and mainly to contain the unitary polyester copolymer of ethylene glycol terephthalate be suitable aspect versatility.As the copolymer composition of this multipolymer, can from above-mentioned dicarboxylic acid of enumerating or glycol, select suitably.

Catalyzer described in the present invention refers in the polyreaction of polyester and can promote following (the 1)～total overall reaction of (3) and the material of a part of primitive reaction in fact.

(1) as the esterification of the reaction of dicarboxylic acid composition and diol component

(2) form the transesterification reaction of the reaction of property derivative composition and diol component as the ester of dicarboxylic acid

(3) esterification or transesterification reaction are finished in fact, and the polyethylene terephthalate oligopolymer of gained takes off two alcoholization reactions, and the polycondensation of height polymeric takes place.

In addition, in the matting agent of fiber etc., the catalyst action that above-mentioned relatively reaction does not have essence as the normally used titan oxide particles of inorganic particle, different with the titanium compound of the following stated of using as catalyzer among the present invention.

(I, II organizes the present invention)

At I, II organizes in the polyester and resin composition of the present invention, importantly antimony element content in weight basis at 30ppm or below it.Like this, situations such as the obstruction of die orifice pollution or strainer, production of foreign matters are less during forming process, and can obtain comparatively cheap polymkeric substance.This content does not more preferably contain antimony in fact preferably at 10ppm or below it.

In addition, at I, II organizes in the polyester and resin composition of the present invention, importantly contains titanium elements.This titanium elements derives from the titanium compound that uses as catalyst for polymerization.That is, at I, II organizes in the polyester and resin composition of the present invention, preferably titanium compound is used as polymerizing catalyst.

Importantly above-mentioned titanium elements is with respect to the content of resin combination, and promptly the titanium elements conversion amount of the titanium compound that uses as polymerizing catalyst is 0.5～50ppm in weight basis, is preferably 1～30ppm, more preferably 3～20ppm.By in this scope, polymerization activity improves, and the thermostability of the polymkeric substance of gained and tone are also good.When titanium elements contain quantity not sufficient 0.5ppm the time, polymerization activity is with deficiency.On the other hand, when it surpasses 50ppm, cause foreign matter by titanium catalyst easily, and also variation of the thermotolerance of the polyester of gained.

In addition,, can enumerate titanium oxide, from polymerization activity with suppress the viewpoint that foreign matter forms, the composite oxides or the ultrafine particle titanium oxide of special preferably titanium and silicon as one of preferred example of titanium compound.In addition, the composite oxides of titanium and silicon also can contain other metallic element.

The titanium oxide acquisition that for example can be hydrolyzed by alkoxide to titanium.

Composite oxides for example except titanium alkyl oxide as main raw material, also can with a small amount of other metal alkoxide or coexistence of multivalence alkylol cpd such as silicon or zirconium, can pass through coprecipitation method, portion water solution, synthetic acquisitions such as coordination chemistry sol-gel method.At this, described coprecipitation method refers to the solution that makes the regulation composition that contains composition more than 2 kinds or 2 kinds, makes this composition that the method for hydrolysis reaction directly take place.In addition, so-called portion water solution, refer to the composition that makes a side in advance form hydrolysis state, to wherein adding the opposing party's composition, further be hydrolyzed the reaction method.And so-called coordination chemistry sol-gel method refers to and for example makes alkyl titanium oxide raw material and intramolecularly have a plurality of functional groups' coexistences such as multivalence alkylol cpd, makes and is pre-formed reactant between the two, the method that the speed of after this hydrolysis reaction is controlled.The synthetic method of this compound for example is documented in u'eno etc. and " uses the preparation of catalysts of metal alkoxide ", and 353 page of the 16th row of the 321st page of the 1st row-Di is in ア イ ピ-シ-(distribution on August 10th, 1993) etc.

The molecular weight of the ultrafine particle titanium oxide that uses as polymerizing catalyst is during less than 100000 (g/mol), sees it is preferred from catalyst activity, the viewpoint that suppresses foreign matter.The molecular weight of ultrafine particle titanium oxide is 500～100000 (g/mol) more preferably, more preferably 1000～50000 (g/mol), more preferably 1500～20000 (g/mol).

In addition, as the titanium compound that polymerizing catalyst uses, preferably it has at least a kind of substituting group selecting from alkoxyl group, phenoxy group, acidylate base, amino and hydroxyl.

As alkoxyl group, for example can enumerate, four alkoxyl groups of tetraethoxy, four propoxy-, tetraisopropoxide, four butoxy, four-2-ethyl hexyl oxy etc., in addition, as organic group by Sauerstoffatom and titanium atom bonded broad sense alkoxyl group, can enumerate the beta-diketon class functional group's, lactic acid, oxysuccinic acid, tartrate, Whitfield's ointment, citric acid etc. of methyl ethyl diketone etc. hydroxyl polyvalent carboxylic acid class functional group, the ketone ester class functional group of methyl acetoacetate, methyl aceto acetate etc. particularly sees the preferred aliphat alkoxyl group from the viewpoint that suppresses foreign matter formation.

As phenoxy group, can exemplify out for example phenoxy group, cresylol oxygen base etc.

As the acidylate base; for example can exemplify out; lactate; four acidylate bases of stearate etc.; phthalic acid; trimellitic acid; trimesic acid; 1; 2; the 3-benzene tricarboxylic acid; pyromellitic acid; oxalic acid; propanedioic acid; succsinic acid; pentanedioic acid; hexanodioic acid; sebacic acid; toxilic acid; fumaric acid; polyvalent carboxylic acid's class functional group of the acid anhydrides of cyclohexane cyclohexanedimethanodibasic or these materials etc.; ethylene diaminetetraacetic acid; the nitrotrimethylolmethane propionic acid; the carboxylic acid iminodiethanoic acid; carboxyl methyl-imino dipropionic acid; diethylene triaminepentaacetic acid(DTPA); triethylene tetramino six acetate; iminodiethanoic acid; the imino-diacetic propionic acid; the hydroxyethyl iminodiethanoic acid; hydroxyethyl imino-diacetic propionic acid; nitrogenous polyvalent carboxylic acid's class functional group of methoxy ethyl iminodiethanoic acid etc.; from suppressing the viewpoint that foreign matter forms, special preferred aliphat acidylate base.

As amino, can enumerate for example aniline, phenyl amine, diphenylamine etc.

In addition, also can use and contain 2 kinds of above-mentioned these substituent diisopropoxy bis-acetylacetonate or isopropoxy trolamine etc.

In these titanium compounds, from suppressing the viewpoint that foreign matter forms, preferred especially four alkoxy titanium compounds or acidylate titanium compound.

In addition, suppress the viewpoint that foreign matter forms from what is called, the titanium compound as polymerizing catalyst uses preferably has from a kind of substituting group to select the represented functional group of following formula 1-6 at least.

(formula 1)

(formula 2)

(formula 4)

(formula 5)

---OH (formula 6)

Wherein, in formula 1～formula 6, R ₁～R ₉Expression hydrogen or carbonatoms are 1～30 alkyl.

In addition, preferably at the R of formula 1～formula 6 ₁～R ₉In at least one is that to have alkoxyl group, hydroxyl, carbonyl, ethanoyl, carboxyl, ester group or amino carbonatoms be 1～30 alkyl.

In addition, preferably at the R of formula 1～formula 3 ₁～R ₆In at least one is that carbonatoms with hydroxyl, carbonyl, ethanoyl, carboxyl or ester group is 1～30 alkyl.

In addition, the R of preferred formula 1 ₁～R ₃In at least one is that carbonatoms with carboxyl or ester group is 1～30 alkyl.

In addition, the R of preferred formula 4 ₇It for carbonatoms 1～30 alkyl.

In addition, the R of preferred formula 4 ₇It for carbonatoms 1～30 alkyl with hydroxyl, carbonyl, ethanoyl, carboxyl or ester group.

As the functional group of formula 1, can enumerate the functional group that the hydroxyl polyvalent carboxylic acid compounds by the alkoxyl group of oxyethyl group, propoxy-, isopropoxy, butoxy, 2-ethyl hexyl oxy etc., lactic acid, oxysuccinic acid, tartrate, citric acid etc. forms.

As the functional group of formula 2, can enumerate the functional group that the ketone ester compounds by the beta-diketone compounds of Acetyl Acetone etc., ethanoyl methyl acetate, ethanoyl ethyl acetate etc. forms.

As the functional group of formula 3, can enumerate the functional group who forms by phenoxy group, cresylol oxygen base, Whitfield's ointment etc.

Functional group as formula 4; can enumerate lactate; the acidylate base of stearate etc.; phthalic acid; trimellitic acid; trimesic acid; 1; 2, the 3-benzene tricarboxylic acid; pyromellitic acid; oxalic acid; propanedioic acid; succsinic acid; pentanedioic acid; hexanodioic acid; sebacic acid; toxilic acid; fumaric acid; polyvalent carboxylic acid's compounds of the acid anhydrides of cyclohexane cyclohexanedimethanodibasic or these materials etc.; ethylene diaminetetraacetic acid; the nitrotrimethylolmethane propionic acid; the carboxylic acid iminodiethanoic acid; carboxyl methyl-imino dipropionic acid; diethylene triaminepentaacetic acid(DTPA); triethylene tetramino six acetate; iminodiethanoic acid; the imino-diacetic propionic acid; the hydroxyethyl iminodiethanoic acid; hydroxyethyl imino-diacetic propionic acid; the functional group that the nitrogenous polyvalent carboxylic acid of methoxy ethyl iminodiethanoic acid etc. forms.

As the functional group of formula 5, can enumerate the functional group who forms by aniline, phenyl amine, diphenylamine etc.

Wherein, from the thermostability of polymkeric substance and the viewpoint of tone, preferably comprise the substituting group of formula 1 and/or formula 4.

In addition, as titanium compound, can enumerate the substituent diisopropoxy diacetyl acetate titanium that contains the above formula 1～formula 6 of above-mentioned 2 kinds or its or trolamine titanium isopropoxide etc.

In addition, I, II organize polyester and resin composition of the present invention and importantly contain phosphoric.In the process of making polyester, be the activity of control catalyst, improve the thermotolerance of gained polyester, as auxiliary agent, use Phosphorus compound, the phosphoric that uses in the polyester and resin composition comes from used Phosphorus compound.

Importantly be the content of above-mentioned phosphoric with respect to resin combination, that is, the phosphoric conversion amount of used Phosphorus compound is 0.1～100ppm in weight basis.When not enough 0.1ppm, forming of the foreign matter that caused by catalyzer taken place easily, in addition, the color harmony thermotolerance of gained polyester is variation also.On the other hand, when it surpasses 100ppm, forming of the foreign matter that caused by catalyzer taken place easily also, in addition, the time of polyreaction also extends, and makes the productivity of vibrin reduce.When throwing or system during film from the thermostability of polyester and the viewpoint of tone, the content of phosphoric is preferably 1-80ppm, 3-50ppm more preferably, more preferably 3-35ppm is more preferably 3-20ppm.

As this Phosphorus compound, form, improve the viewpoint of tone from thermostability, inhibition foreign matter, it is preferably at least a kind of Phosphorus compound selecting from phosphoric acid class, phosphorous acid class, phosphonic acid based, phospho acid class, phosphinoxides, phosphonous acid class, phosphinous acid class and phosphine class, wherein, be preferably phosphoric acid class, phosphonic acid based especially based on same viewpoint.

As the phosphoric acid class, for example can enumerate the phosphate compound of phosphoric acid, trimethyl phosphite 99, triethyl phosphate, triphenylphosphate etc. etc.In the phosphoric acid class, from thermostability, suppress the viewpoint that foreign matter forms, improves tone, preferably phosphoric acid and phosphate compound, that is, I, II organize polyester and resin composition of the present invention and preferably contain phosphoric acid and/or phosphate compound.In addition, in the present invention, described " and/or " expression can only use any in the two, also can and use the two.

As the phosphorous acid class, for example can exemplify out phosphorous acid, trimethyl phosphite, triethyl-phosphite, triphenyl phosphite etc.

In phosphonic acid based, from thermostability, suppress the viewpoint that foreign matter forms, improves tone, preferred phosphonic acids and phosphonate compound, that is, I, II organize polyester and resin composition of the present invention and preferably contain phosphonic acids and/or phosphonate compound.

As phosphinic acid compounds, for example can exemplify out, methyl-phosphorous acid, ethylphosphonic acid, propyl phosphonous acid, the sec.-propyl phosphonic acids, the butyl phosphonic acids, phenyl-phosphonic acid, benzylphosphonic acid, the tolyl phosphonic acids, the xylyl phosphonic acids, the xenyl phosphonic acids, the naphthyl phosphonic acids, the anthryl phosphonic acids, 2-carboxyl phenyl phosphonic acids, 3-carboxyl phenyl phosphonic acids, 4-carboxyl phenyl phosphonic acids, 2,3-dicarboxyl phenyl-phosphonic acid, 2,4-dicarboxyl phenyl-phosphonic acid, 2,5-dicarboxyl phenyl-phosphonic acid, 2,6-dicarboxyl phenyl-phosphonic acid, 3,4-dicarboxyl phenyl-phosphonic acid, 3,5-dicarboxyl phenyl-phosphonic acid, 2,3,4-three carboxyl phenyl-phosphonic acids, 2,3,5-three carboxyl phenyl-phosphonic acids, 2,3,6-three carboxyl phenyl-phosphonic acids, 2,4,5-three carboxyl phenyl-phosphonic acids, 2,4,6-three carboxyl phenyl-phosphonic acids etc.

In addition; as phosphonate compound; for example can exemplify out; dimethyl methyl phosphonate; the methyl-phosphorous acid diethyl ester; the ethylphosphonic acid dimethyl ester; diethyl ethylphosphate; the phenyl-phosphonic acid dimethyl ester; the phenyl-phosphonic acid diethyl ester; the phenyl-phosphonic acid diphenyl; the benzylphosphonic acid dimethyl ester; the benzylphosphonic acid diethyl ester; the benzylphosphonic acid diphenyl; (3; 5-di-tert-butyl-4-hydroxyl benzyl phosphinic acid ethyl ester) lithium; (3; 5-di-tert-butyl-4-hydroxyl benzyl phosphinic acid ethyl ester) sodium; two (3; 5-di-tert-butyl-4-hydroxyl benzyl phosphinic acid ethyl ester) magnesium; two (3,5-di-tert-butyl-4-hydroxyl benzyl phosphinic acid ethyl ester) calcium; diethyl phosphonyl acetate; the diethyl phosphonyl methyl acetate; diethyl phosphonyl ethyl acetate etc.Particularly the diethyl phosphonyl ethyl acetate sees it is preferred from the viewpoint that thermostability, inhibition foreign matter formed, improved tone.

As the phospho acid class, can enumerate Hypophosporous Acid, 50, sodium hypophosphite, the methyl phospho acid, the ethyl phospho acid, the propyl group phospho acid, the sec.-propyl phospho acid, the butyl phospho acid, phenyl phosphinic acid, the tolyl phospho acid, the xylyl phospho acid, the xenyl phospho acid, diphenyl phosphonic acid, the dimethyl phospho acid, the diethyl phospho acid, the dipropyl phospho acid, the di-isopropyl phospho acid, the dibutyl phospho acid, the xylyl phospho acid, two (xylyl) phospho acid, the dibiphenylyl phospho acid, the naphthyl phospho acid, the anthryl phospho acid, 2-carboxyl phenyl phospho acid, 3-carboxyl phenyl phospho acid, 4-carboxyl phenyl phospho acid, 2,3-dicarboxyl phenyl phosphinic acid, 2,4-dicarboxyl phenyl phosphinic acid, 2,5-dicarboxyl phenyl phosphinic acid, 2,6-dicarboxyl phenyl phosphinic acid, 3,4-dicarboxyl phenyl phosphinic acid, 3,5-dicarboxyl phenyl phosphinic acid, 2,3,4-three carboxyl phenyl phosphinic acids, 2,3,5-three carboxyl phenyl phosphinic acids, 2,3,6-three carboxyl phenyl phosphinic acids, 2,4,5-three carboxyl phenyl phosphinic acids, 2,4,6-three carboxyl phenyl phosphinic acids, two (2-carboxyl phenyl) phospho acid, two (3-carboxyl phenyl) phospho acid, two (4-carboxyl phenyl) phospho acid, two (2,3-dicarboxyl phenyl) phospho acid, two (2,4-dicarboxyl phenyl) phospho acid, two (2,5-dicarboxyl phenyl) phospho acid, two (2,6-dicarboxyl phenyl) phospho acid, two (3, the 4-dicarboxyl) phenyl phosphinic acid, two (3,5-dicarboxyl phenyl) phospho acid, two (2,3,4-three carboxyl phenyl) phospho acid, two (2,3,5-three carboxyl phenyl) phospho acid, two (2,3,6-three carboxyl phenyl) phospho acid, two (2,4,5-three carboxyl phenyl) phospho acid, two (2,4,6-three carboxyl phenyl) phospho acid, methyl phospho acid methyl esters, dimethyl phospho acid methyl esters, the methyl phosphinicacid ethyl ester, the dimethyl phosphinicacid ethyl ester, ethyl phospho acid methyl esters, diethyl phospho acid methyl esters, the ethyl phosphinicacid ethyl ester, the diethyl phosphinicacid ethyl ester, the phenyl phosphinic acid methyl esters, the phenyl phosphinic acid ethyl ester, the phenyl phosphinic acid phenylester, the diphenyl phosphonic acid methyl esters, the diphenyl phosphonic acid ethyl ester, the diphenyl phosphonic acid phenylester, benzyl phospho acid methyl esters, the benzyl phosphinicacid ethyl ester, benzyl phospho acid phenylester, dibenzyl phospho acid methyl esters, the dibenzyl phosphinicacid ethyl ester, dibenzyl phospho acid phenylester etc.

As phosphinoxides, can exemplify out trimethylammonium phosphine oxide, triethyl phosphine oxide, tripropyl phosphine oxide, triisopropyl phosphine oxide, tributylphosphine oxide, triphenylphosphine oxide etc.

As the phosphonous acid class, can enumerate methyl phosphonous acid, ethyl phosphonous acid, propyl group phosphonous acid, sec.-propyl phosphonous acid, butyl phosphonous acid, phenyl-phosphonite etc.

As the phosphinous acid class, but methyl phosphinous acid, ethyl phosphinous acid, propyl group phosphinous acid, sec.-propyl phosphinous acid, butyl phosphinous acid, phenyl phosphinous acid, dimethyl phosphinous acid, diethyl phosphinous acid, dipropyl phosphinous acid, di-isopropyl phosphinous acid, dibutyl phosphinous acid, phenylbenzene phosphinous acid etc.

As the phosphine class, can enumerate methylphosphine, dimethyl phosphine, trimethyl-phosphine, ethyl phosphine, diethyl phosphine, triethyl phosphine, Phenylphosphine, diphenylphosphine, triphenylphosphine etc.

For these Phosphorus compounds, can use wherein a kind separately, also can be also with 2 kinds or more than it.

As the mol ratio (Ti/P) of titanium elements with respect to phosphoric, when it was 0.1～20, it is good that the thermostability of polyester and tone become, therefore preferred.More preferably Ti/P is 0.2～10, more preferably 0.3～5.

When polymerization, the volume specific resistance viewpoint during from the formation that suppresses foreign matter, polymerization activity, vibrin fusion preferably makes it contain alkali earth metal.As its content, in weight basis, be preferably 5～100ppm, more preferably 10～80ppm, more preferably 15～60ppm.By making it, can suppress to contain the formation of the foreign matter of titanium elements at 100ppm or below it.

In alkali earth metal, preferred calcium, magnesium, the viewpoint of the volume specific resistance during from the formation that suppresses foreign matter, vibrin fusion is preferably magnesium especially, and the compound as adding can use its muriate or carboxylate salt.From identical viewpoint, can especially preferably use magnesium acetate.

In addition, I, II organize polyester and resin composition of the present invention and preferably contain manganese element.This manganese element is to be got by the manganic compound that adds in polyester and resin composition until the random time point of finishing to polyester.

Manganese element is with respect to the content of polyester and resin composition, that is, the manganese element conversion amount of used manganic compound is preferably 1～400ppm in weight basis.In addition, manganese element is preferably 0.1～200 with respect to the molar ratio (Mn/P) of phosphoric.By such modulation, can suppress polymerization activity and reduce.The tone of the polymkeric substance of gained also becomes well thus, and is therefore preferred.As manganic compound, can exemplify out Manganous chloride tetrahydrate, Manganese dibromide, manganous nitrate, manganous carbonate, etheric acid manganese, manganous acetate four water salt, manganous acetate two water salt etc.

In addition, at I, II organizes in the polyester and resin composition of the present invention, can add cobalt compound at the random time point place of manufacturing processed.That is, preferably also make it contain cobalt compound, make the polymkeric substance tone of gained good.As cobalt compound, for example can exemplify out cobalt chloride, Xiao Suangu, cobaltous carbonate, etheric acid cobalt, cobalt naphthenate, cobaltous acetate four water salt etc.

In addition, from improving the color harmony thermotolerance aspect of polyester, preferably also make it contain alkali metal compound, aluminum compound, zn cpds, tin compound etc.

(I organizes the present invention)

Organize polyester and resin composition of the present invention for I, the circular diameter of equal value that importantly contains titanium elements is 100 of 1 micron or the every 0.02mg polyester and resin composition of particulate number density less thaies more than it.Circular diameter of equal value described herein refers to the diameter that circle had that equates with the particle projection area.

This particle that contains titanium elements is a form as above-mentioned foreign matter, and above-mentioned number density exists surface roughness chap, the perhaps transparent impaired situation of film when forming polyester film under 100 or situation more than it.As above-mentioned number density, preferably 80/0.02mg of its less than, more preferably 50/0.02mg of less than.For the particle that suppresses to contain titanium elements is the formation of foreign matter, can suppresses the hydrolysis of titanium compound in polyreaction used as catalyst for polymerization etc. and get final product.

(II organizes the present invention)

II organizes polyester and resin composition of the present invention and importantly contains the organic polymer particle.Even the organic polymer particle is made at polyester under the situation of film etc., at the particle that is used for giving good crimp tendency, slipperiness, also with the affinity height of polyester, in addition, particle shape is homogeneous relatively also.

As organic polymer particulate size, be necessary for 0.05～3 micron according to the median size of dynamic light scattering determination, more preferably 0.1～2 micron, more preferably 0.3～1 micron.When median size surpasses 3 microns, when adopting strainer to filter, blockage phenomenon easily, and during 0.05 micron of less than, form film after, can not obtain to give the effect of good crimp tendency.

In addition, the organic polymer particle relatively median size of its whole particle numbers is that the ratio of 2 times or its above thick number must be 0.01% or below it, is preferably 0.005% or below it, more preferably 0.001% or below it.The ratio of big particle surpasses at 0.01% o'clock, and the thick projection on the film surface is more, when being used for magnetic recording media, produces situations such as record omission.

In addition,, be necessary for 0.1～5 weight %, be preferably 0.5～3 weight %, more preferably 1～2 weight % with respect to polyester and resin composition as organic polymer particulate content.When particulate contains quantity not sufficient 0.1 weight %, when making film, the slipperiness deficiency, on the other hand, when surpassing 5 weight %, the rugosity of film surface is too high, diminishes smoothness.

As organic polymer particulate material, can enumerate crosslinked polystyrene, polysiloxane, melamine/formaldehyde multipolymer, benzo guanamine, heat-curable epoxy resin, cross-linked polyester etc.Wherein, preferred crosslinked polystyrene, more specifically, from the particle thermotolerance and with the affinity viewpoint of polyester, be preferably vinyl benzene-divinyl benzene copolymer.

In addition, from the thermotolerance viewpoint, the degree of crosslinking of preferred organic polymeric particles is 50% or more than it, and more preferably 65% or more than it, more preferably 80% or more than it.In the degree of crosslinking of this so-called organic granular, be that cross-linkable monomer is with respect to whole monomeric weight add-on ratios.As cross-linkable monomer, can preferably use with the non-conjugated divinyl compound of Vinylstyrene as representative, be the having more than 2 or 2 of multivalence acrylic compound etc. of representative perhaps, be preferably the compound of 2 copolymerizable pair of keys with trimethylolpropane trimethacrylate, Viscoat 295.

As the organic polymer coating of particles, from giving film slipperiness effect viewpoint, be preferably spherical, be preferably the proper sphere shape especially.In addition, as its structure, also can be composite particles (core/shell mould), hollow particle etc.Also can carry out the surface treatment of silane coupling agent, the processing of titanic acid ester coupler etc. in addition to it.

In addition, when II organizes polyester and resin composition of the present invention and contains water-soluble polymer, be preferred aspect dispersed improving the organic polymer particulate.

The content of water-soluble polymer is preferably 0.1～5 weight % with respect to the organic polymer particle, 0.4～3 weight % more preferably, 0.8～2 weight % more preferably, when it is that 0.1 weight % or its are when above, organic polymer particulate dispersiveness will become good, and when 5 weight % or its are following, can prevent that it from becoming the reason of the thick projection of film surface.

As this water-soluble polymer, can adopt Polyvinylpyrolidone (PVP), polyvinyl alcohol, carboxymethyl cellulose etc., particularly from improving the viewpoint of organic polymer dispersiveness, the polymer that Polyvinylpyrolidone (PVP) etc. have the pyrrolidone residue is preferred.

By water-soluble polymer being added in the organic polymer particle slurry in advance, particle is carried out surface treatment, its melting mixing in polyester, can be obtained good dispersiveness, therefore preferred.

(III organizes the present invention)

The catalyst for polyester production of the present invention of III group contains a kind of reaction product, this reaction product be at least a kind of atom from nitrogen-atoms, sulphur atom and Sauerstoffatom, selecting of a kind of compound (hereinafter referred to as compound α) of from compound shown in following general formula 7 or 8, selecting and containing as foreign atom, can carry out the reaction product of 2 or 2 above coordinate coordination compoundes (hereinafter referred to as compound β) at least.

Ti (OR) ₄(formula 7)

Ti (OH) _m(OR) _4-m(formula 8)

In formula 7,8, R is that carbonatoms is 2～10 organic group, can be identical or different between organic radical R is mutual.M is 1～4 integer in addition.In addition, R is that the situation of alkyl is also preferred.

Organize in the catalyst for polyester production of the present invention at III, importantly compound α and compound β formation is the reaction product of ligand with compound β.

Compound α has activity with respect to polycondensation, bears so-called effect as polymerizing catalyst.On the other hand, compound β bears as the effect that improves the tone of gained polyester.Use as catalyzer by the reaction product that compound α and compound β are formed, can make the color harmony excellent heat resistance, and improve the production performance of polyester.At this, this reaction product is that coordination has coordination compound β on compound α, and is that the situation that purpose directly is added on coordination compound β on the polyester is visibly different to improve tone.By forming reaction product, the problem that produces in the time of can preventing from directly to be added on coordination compound β on the polyester, i.e. bad dispersibility, and disperse to reaction system, cause the productivity variation.

In addition, compound α also is preferably four alkoxy titanium compounds or titanate compound.

As four alkoxy titanium compounds, for example can exemplify out four alkoxy titanium compounds of tetra isopropyl titanate, tetrabutyl titanate ester, four (2-ethylhexyl) titanic acid ester, tetramethyl-titanic acid ester etc. etc., wherein preferred tetrabutyl titanate ester.

As the titanium chelate compound, can exemplify out etheric acid titanium, tetrem ethyl acetoacetic acid titanium, ethohexadiol titanium, lactic acid titanium, ethyl acetoacetic acid titanium, citric acid titanium, titanium peroxide citric acid titanium ammonium etc.Wherein, preferably with the good etheric acid titanium of coordination compound beta response, citric acid titanium, titanium peroxide citric acid titanium ammonium etc.

As coordination compound β, be preferably at least a kind of compound from indanthrone, anthraquinone, methine dyes and metal-free phthalocyanine, selecting, as indanthrone, preferred employing for example has the material as the A structural formula, preferably adopt as anthraquinone to have for example material of B, C, D, E, F structural formula, as methine dyes, preferred employing for example has the material as the G structural formula, as metal-free phthalocyanine, preferred employing for example has the material as the H structural formula.

For the mol ratio of compound α in the reaction product and coordination compound β, preferred 0.001≤(molar weight of molar weight/α of β)≤1.By making it 0.001 or more than it, because coordination compound β, its favorable dispersity can suppress to disperse to reaction system, also obtains good color tone in addition and improves and the coordination effect.And, can suppress polymkeric substance and produce excessive blueness by being 1 or below it.

The reaction product of compound α and coordination compound β, can be by for example coordination compound β being dissolved in the solvent, add compound α, make reaction system be in 0～200 ℃ and kept 10 minutes or time that it is above, preferably be in normal temperature～150 ℃, more preferably be in 40～150 ℃ and keep time of 30 minutes～2 hours, obtain by heating.In addition, compound α and coordination compound β are mixed, do not carry out special heat treated and be added in the pet reaction system, but also formation reaction product.

As solvent, can make spent glycol, propylene glycol, tetramethylene glycol, acetate etc., preferably the high solvent of affinity in the raw material of polyester.

The reaction product of compound α and coordination compound β is carried out recrystallization after separating by employing vaporizer, centrifuge separator or filtration method etc., and purifying can use this purifying thing as catalyzer.

III organizes polyester and resin composition of the present invention and uses III to organize catalyst for polyester production of the present invention to make.

Organize polyester and resin composition of the present invention with respect to III, the addition that III organizes catalyst for polyester production of the present invention is scaled titanium elements, is preferably 1～30ppm in weight basis.By making it at 1ppm or more than it, can obtain enough catalytic activitys, by making it, can keep good polymkeric substance color harmony thermotolerance at 30ppm or below it, also can suppress the foreign matter that catalyzer causes.

In addition, in esterification or transesterification reaction, can use various catalyzer.For example can use the acetate of lime acetate, magnesium acetate, lithium acetate etc. etc.

In addition, organize in the polyester and resin composition of the present invention the also preferred phosphorus compound that adds as the tone activator at III.

As this phosphorus compound, can enumerate the phosphonic acid based of the phosphorous acid class, phenyl-phosphonic acid, phenyl-phosphonic acid dimethyl esters, benzylphosphonic acid dimethyl esters, methyl-phosphorous acid dimethyl esters, methyl-phosphorous acid two proyl esters, diethyl phosphonoacetic acid ethyl ester etc. of the phosphoric acid class, phosphorous acid, dimethylphosphite, trimethyl phosphite etc. of phosphoric acid, monomethyl phosphoric acid, single ethyl phosphonic acid, trimethylammonium phosphoric acid etc., and the phospho acid class of diphenyl phosphonic acid etc. etc.

This phosphorus compound by being scaled phosphoric, is preferably 1～50ppm in weight basis, more preferably 5～20ppm with respect to the addition of polyester and resin composition.By making it,, can suppress because the colour-change that titanium causes by making it at 20ppm or below it, can be kept the polymerization activity that III organizes catalyst for polyester production of the present invention preferably at 5ppm or more than it at 1ppm or more than it.

In addition, organize the also preferred alkaline earth metal compound that adds in the polyester and resin composition of the present invention at III.Alkaline earth metal compound is with respect to the addition of polyester and resin composition, and the weight conversion in the alkali earth metal total amount is preferably 0～80ppm, more preferably 1～60ppm.By making it in this scope, can make that the productivity of polyester and resin composition is good, and can keep thermotolerance.

(the I～III organizes the present invention)

The polyester and resin composition of the present invention of the I～III group also can further comprise the pigment of titanium oxide, silicon oxide, lime carbonate, silicon nitride, clay, talcum, kaolin, carbon black etc., painted inhibitor, antioxidant, static inhibitor, nucleating agent, inorganic particle, organic granular, subtract viscosity agent, thermo-stabilizer, lubricant, infrared absorbent, UV light absorber etc.

Volume specific resistance when preferred the I～III organizes polyester and resin composition fusion of the present invention is 1 * 10 ⁶～1 * 10 ⁹Ω cm, more preferably 1 * 10 ⁷～5 * 10 ⁸Ω cm.Thus, in the static applying method, the adaptation between film and the cast drum is good, is difficult to enter air, can form the film of surface smoothing and thickness homogeneity excellence, perhaps can improve film speed.Volume specific resistance during fusion can be controlled with respect to the content of vibrin by adjusting alkali earth metal and phosphoric.For example, if increase the amount of alkali earth metal, reduce the content of phosphoric, then volume specific resistance tends to reduce, and on the contrary, if reduce alkali earth metal, increases the amount of phosphoric, and then volume specific resistance tends to increase.

As the manufacture method of polyester, for example polyethylene terephthalate can be made according to common following arbitrary method.

(1) with terephthalic acid and ethylene glycol as raw material, obtain oligopolymer by direct esterification, the further polycondensation after thus obtains the method for high molecular polymer.

(2) with terephthalic acid dimethyl esters and ethylene glycol as raw material, obtain oligopolymer by transesterification reaction, the further polycondensation after thus obtains the method for high molecular polymer.

In these reactions, can adopt the polymerization process of intermittent type, semibatch or continous way etc. to obtain.

The esterification of above-mentioned (1) also can be reacted under the condition of catalyst-free, but also can add above-mentioned titanium compound as catalyzer.In this case, titanium compound can add after just adding raw material, also can be added in the reaction system with raw material.

In addition,, can use the compound of manganese, calcium, magnesium, zinc, lithium etc. or above-mentioned titanium compound, reaction is carried out as catalyzer for the transesterification reaction of above-mentioned (2).

Use under the situation of catalyzer in these reactions, therefore phosphorus compound drops into after in fact these reactions finish because the catalyzer that uses in the reaction is played a part deactivation again.

Any stage in a succession of reaction of above-mentioned (1) or (2); preferably in (1), pass through esterification; (2) after obtaining oligopolymer by transesterification reaction in; after adding the organic polymer particle or various additive among the present invention of II group; interpolation is carried out polycondensation as the titanium compound of polycondensation catalyst, can obtain the high molecular polyethylene terephthalate.

In the esterification operation, owing to can obtain the less polyester and resin composition of side reaction product, therefore also preferably add a small amount of basic cpd.As this basic cpd, can enumerate the tertiary amine of triethylamine, tributylamine, benzyl methylamine etc., the quaternary ammonium compound of tetraethyl ammonium hydroxide, tetrabutylammonium, benzyltrimethyl ammonium hydroxide etc. in addition, also can be enumerated sodium hydroxide, sodium hydroxide, potassium acetate, sodium acetate etc.

In polycondensation step,, also can add stablizer for preventing the side reaction of polyester generation thermolysis etc.As stablizer, can enumerate [(3,5-two (1, the 1-dimethyl ethyl)-and the 4-hydroxy phenyl) methyl] the phosphonic acids diethyl ester, four { methylene radical-3-(dodecyl sulfo-) propionic ester } methane, four { methylene radical-(3,5-tertiary butyl-4-hydroxy hydrogenated cinnamate) } methane, three (dodecyl) phosphoric acid ester, three (2,4-dibutyl phenyl) phosphide, four { methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester } methane, two (2,6-di-t-butyl-4-aminomethyl phenyl) tetramethylolmethane-two-phosphorous acid ester etc., these materials can use separately, also can or be used in combination more than it 2 kinds.

As the addition of stablizer, with respect to the polyester and resin composition of gained, be preferably 0.03～2 weight %, more preferably 0.05～1.9 weight %.By making it, can obtain to improve the actual effect of oxidative stability at 0.03 weight % or more than it.And by being 2 weight % or below it, can preventing to hinder polycondensation.

(III organizes the present invention)

But, after being pre-mixed III to organize catalyst for polyester production of the present invention, adding under the situation of stablizer, addition also is preferably 0.003～1 weight %.Specially suitable is [[3,5-two (1, the 1-dimethyl ethyl)-and the 4-hydroxy phenyl] methyl] phosphonic acids diethyl ester, two (2,6-di-t-butyl-4-aminomethyl phenyl) tetramethylolmethane-two-phosphorous acid ester and III organize the combination of catalyst for polyester production of the present invention, by adding 0.003～0.1 weight %, can obtain the polyester and resin composition of thermotolerance, foreign matter, tone aspect excellence.

(the present invention of the I～III group)

Because phosphorus compound makes aforesaid esterification, the catalyzer deactivation that uses in the transesterification reaction, but also inhibition is as the activity of the titanium compound of polymerizing catalyst, therefore after esterification or transesterification reaction are finished, preferably begin preceding adding in polycondensation, but in this case, for preventing that titanium compound from contacting with phosphorus compound, make catalyst deactivation, the preferred method of putting in the differential responses groove that adopts, even or in same reactive tank, the making time of titanium compound and phosphorus compound is differed 1-15 minute method, perhaps separate the method that drops into the position.

The titanium compound and the phosphorus compound that use in the I～III group the present invention can be added directly in the reaction system of polyester, but in advance with its solvent with the diol component that contains formation polyester such as ethylene glycol or propylene glycol, make solution or slurry, after the low boiling point component of the alcohol that titanium compound or phosphorus compound are used when synthetic etc. is removed as required, when being added in the reaction system, since can further suppress production of foreign matters in the polymkeric substance, therefore preferred.

In addition, also titanium compound and phosphorus compound can be reacted the product that obtains in advance uses as catalyzer.As this method, for example be

(1) mixed with titanium compound in solvent, part or all is dissolved in the solvent to make it, to the stoste of this mixing solutions dropping phosphorus compound, perhaps phosphorus compound is dissolved in dilution back dropping in the solvent.

(2) have under the situation of complex compound of part using in coordination on the titanium compound, the ligand compound of titanium compound or hydroxycarboxylic acid compounds or polyvalent carboxylic acid's compounds etc. is mixed in solvent, part or all is dissolved in the solvent to make it, become the opposing party's who forms complex compound coordination compound or titanium compound stoste to this mixed solution and dripping, perhaps it is dissolved in that the dilution back drips in the solvent.After this further drip the stoste of phosphorus compound, perhaps phosphorus compound is dissolved in dilution back dropping in the solvent.

As the reaction conditions of above-mentioned (1), (2), preferably under 0～200 ℃, reacted 1 minute or the time more than it, more preferably 20～100 ℃ of times of reacting 2 minutes～100 minutes down.In addition, reaction pressure is at this moment had no particular limits, can be normal pressure.In addition, as solvent as used herein, can select from part or all titanium compound, phosphorus compound or contain the solvent of coordination compound of carbonyl of solubilized.Preferably from water, methyl alcohol, ethanol is selected in ethylene glycol, propylene glycol, butyleneglycol, benzene, the dimethylbenzene.

(the present invention of II group)

The organic polymer particle that uses in the present invention of II group for example can be by letex polymerization, and emulsifier-free emulsion polymerization, crystal seed letex polymerization, suspension polymerization, dispersion polymerization, 2 stage inflated polymers etc. are made.

The preferably coverlet dispersion in polyester of organic polymer particle.The polymkeric substance of this state can be by carrying out the melting mixing acquisition to organic polymer particle and polymkeric substance, particularly, for example the organic polymer particle can be made water and/or boiling point slurry at 200 ℃ or organic compound below it, be added in the polyester with slurry form, the water and/or the boiling point that adopt the elbow type shaper to remove in the slurry are 200 ℃ or its following organic compound, carry out melting mixing simultaneously and obtain.

As boiling point is 200 ℃ or organic compound below it, for example can exemplify out the hydrocarbon compound of the alcohols of methyl alcohol, ethanol, ethylene glycol etc., benzene, toluene etc., ester class, ketone, amine etc.From viewpoints such as operability, removing property, preferably the medium of water as slurry used.

In addition, in organic polymer particulate slurry, contain the nonionic class tensio-active agent etc. of the anionic species tensio-active agent, polyoxyethylene nonylplenyl ether, polyethylene glycol mono stearate etc. of the Sodium dodecylbenzene sulfonate that in the organic polymer particulate is made, uses, Sodium Lauryl Sulphate BP/USP etc.

The elbow type shaper is the melt molding machine that is provided with at least 1 elbow mouth, for example can be extrusion shaping machine, also can be Jet forming machine.Anhydrate and/or elbow mouth that boiling point is used at 200 ℃ or organic compound below it being used for removing, at least one is held under reduced pressure, preferably should the decompression degree remain on 13Kpa or below it, 7Kpa or below it more preferably, more preferably 4Kpa or below it.

The I～III organizes polyester film of the present invention and can contain and correspond respectively to the I～III and organize polyester and resin composition of the present invention.

In addition, the I～III organizes laminated polyester film of the present invention, and use corresponds respectively to the I～III and organizes polyester and resin composition of the present invention in its at least 1 layer, and is formed by multilayer laminated polyester.Stepped construction by the layer by the layer that uses polyester and resin composition of the present invention and other polyester and resin compositions of use forms can form the laminate film that has each layer characteristic simultaneously.

In the layer of the use polyester and resin composition of the present invention in polyester film of the present invention or laminated polyester film of the present invention, can use polyester and resin composition of the present invention separately, also can in other polyester and resin compositions, mix 1 weight % or more than it polyester and resin composition of the present invention use.From productivity and the stable on heating viewpoint that improves other kinds, it also is preferred mixing the form of using.

(I, II organizes the present invention)

As mentioned above, at I, II organizes the content of antimony element in the polyester and resin composition of the present invention at 30ppm or below it, therefore when making stacked polyester film, even the contained antimony element of the polyester that matches with lamination in weight basis above 30ppm, as laminate film integral body, still can suppress the antimony usage quantity lower, be preferred when making laminated polyester film therefore.

In addition, I, II organize laminated polyester film of the present invention and for example are preferred in the magnetic recording media, but when this situation etc., and preferably by I, II organizes the layer that polyester and resin composition of the present invention forms and constitutes its at least 1 surface.By using I, II organizes polyester and resin composition of the present invention, can make thick projection or hinder lessly etc. to form the also excellent film of superficiality excellence, slipperiness, thereby satisfy in the magnetic recording media strict demand to the film surface characteristic.

Below, be that example describes to the manufacturing process of polyester film with the film-forming method that melt extrudes.

At first prepare polyester and resin composition, in hot blast or under the decompression, carry out drying in advance as required, and provide to single shaft or twin shaft and melt extrude machine.

In forcing machine, be heated to fusing point or the fusion more than it resin make its extrusion capacity homogenization by toothed gear pump etc., by strainer etc. with foreign matter or sex change resin filter.Resin after the moulding, is spued it in the mould of T pattern mouth etc.

Making under the situation of laminate film, for example can use the above forcing machine of 2 or its, use have giving of rectangle laminated section send sleeve pipe or initial mixing tank, multiple manifold mould etc. general never the vibrin sent of homogeneous turbulence road carry out stacked method etc.As initial mixing tank, can enumerate pipe mixing tank, square mixer etc., but, preferably use square mixer from stacked homogeneity viewpoint.

Sheet with stepped construction that spues from mould in this way or single-iris are extruded on the cooling body of cast drum etc., and cooling curing forms casting film.When on cooling body, extruding, preferably use the electrode of thread, banded, needle-like or blade-like etc., make it closely contact (applying the static foundry goods) with cooling body, make its quick cooling curing by electrostatic force.

Because casting film is tensile film not, can carry out biaxial stretch-formedly according to purposes, make the polyester film of orientation.So-called biaxial stretch-formed referring on vertical and horizontal stretches.Stretching can be one by one biaxial stretch-formed, also can be the stretching on both direction simultaneously.In addition, also can vertically and/or transversely stretch once more.

At this, so-called stretching in the vertical refers to the stretching that the molecular orientation of giving the film length direction is used, and for example the roll surface speed difference by roller applies.This stretching can be implemented in 1 stage, also can divide a plurality of stages to carry out by using a plurality of rollers right.As the tensile multiplying power, be preferably 2～15 times, more preferably 2.5～7 times, more preferably 5 times or below it.

In addition, on the film surface behind the longitudinal stretching for example, adopt the coating technique of intaglio plate coating machine or metal bar etc. to apply coating, can give easy tack coat, easily sliding layer, granular layer etc.In addition, coating can be coated with the coating of also can rolling off the production line online except can also implementing before stretching or after stretching implementing between longitudinal stretching and the cross directional stretch.

In addition, so-called stretching transversely refers to and is used to give the stretching that is orientated on the thin-film width direction, for example adopts tenter machine by clamp the two ends of film to be controlled, and carries simultaneously, stretches on width.Be preferably 2～10 times as the tensile multiplying power, more preferably at 5 times or below it.

In addition, biaxial stretch-formed can the conveying simultaneously by in tenter machine the film two ends being controlled with clamp stretches simultaneously to vertical and horizontal and implements simultaneously.

For giving its planarity, dimensional stability, preferably in tenter machine, wait and carry out the thermal treatment of draft temperature～fusing point having carried out biaxial stretch-formed film thus, after the thermal treatment, slowly cool off equably, be cooled to room temperature after, with its coiling.As thermal treatment temp,, be preferably 120 ℃～240 ℃ from viewpoints such as planarity, dimensional stabilitys.

Because I～III organizes polyester film of the present invention and contains foreign matter hardly, so its surface excellence.The surface average roughness Ra of this film is preferably 0.5～30nm, more preferably 1～20nm, more preferably 1～10nm.

I～III organizes polyester film of the present invention and laminated polyester film, and the mean roughness of its film surface is less, can use with basement membrane as magnetic recording media suitably.That is, I～III organizes magnetic recording media of the present invention and is to use respectively corresponding I～III to organize that laminated polyester film of the present invention or polyester film form.Can use with magnetic recording media or digital recording band as the higher computer data record of recording density especially suitably.

(III organizes the present invention)

In addition, because the present invention of III group demonstrates good color tone (b value), and few foreign, melting heat excellent in stability, so can be used for the purposes of fiber applications, wrapping material, optical material etc. suitably.

Embodiment

Followingly the present invention is further elaborated according to embodiment.

(measuring method)

(embodiment 1～14, comparative example 1～5)

(1.1) content of the titanium elements in the polyester and resin composition, phosphoric, antimony element etc.

With the fusion of 8g polyester and resin composition, be shaped to tabularly, fluorescent X-ray device 3270 models of using the motor of science society as the fluorescent X-ray device to make are measured the intensity of fluorescent X-ray.This value and the detection line that adopts the known sample of content to produce are in advance contrasted, can converse the content of various elements.

(1.2) number of the thick foreign matter in the polyester and resin composition (a particulate number density that contains titanium elements)

According to following order, carry out the preparation and the mensuration of sample.

(1.2.1) make preparation

Adopt dilute hydrochloric acid to clean the polyester fragment, after this adopt Purified Water to clean, on slide glass, place the sample that 0.2mg takes from above-mentioned polyester fragment then, under 280 ℃, carry out fusion, place cover glass thereon so that it is clamped.Sample becomes tensile state between slide glass and cover glass, and covering slide and slide glass are peeled off mutually under 280 ℃ heated condition.It is cooled to room temperature, produces the preparation that on cover glass, is formed with polymeric film.Polymeric film on the preparation adopts sharp keen razor to be cut into 10 row * 10 row, produces and amounts to 100 components.

(1.2.2) adopt opticmicroscope that particle is measured

As opticmicroscope, the Metaloplan that uses Leitz society to make.The object lens of opticmicroscope are set at 32 times, adopt the dark-field method to detect, and monitor obtains its image in the high visual field of image analysis apparatus.At this moment, because object lens are high magnification, the depth of focus is less, when therefore on the face of upside, focusing, observation be the part of the about 1 micron degree in upside top layer.

Opticmicroscope is connected on the high visual field personal images analytical system " PIAS-IV " of ピ ア ス (Co., Ltd.) manufacturing.Observation multiplying power on watch-dog is set at 1560 times.The image of input is a black white image, carry out binaryzation by image and can carry out the briliancy conversion input, its setting means is, when under putting the condition of sample, observing in advance as blank value, the light and shade of aperture etc. of regulating opticmicroscope is so that briliancy mean value is adjusted into 183, other brightness value of indicated concentration level is set at 160 putting under the state of sample.

The circular diameter of equal value of the dash area that the image that binaryzation is obtained is suitable with this particle is as grain diameter, and the count particles particle diameter is read this particle position 1 micron or particle number more than it from component.

(1.2.3) affirmation that has or not of titanium elements

Implement the plasma ashing of polymer thin membrane portions handles for the preparation after observing in above-mentioned (1.2.2), further carry out the carbon evaporation, adopt the component of opticmicroscope, determine whether this particle contains titanium elements in 1 micron of observation on the SEM-XMA or the existence of the particle that is counted more than it.

With gained thus contain titanium elements, 1 micron or particle number more than it convert with respect to every 0.02mg polymkeric substance, with the numerical value that converses as a particle number density.

(1.3) volume specific resistance during the resin combination fusion

After resin combination carried out drying under reduced pressure, with its internal diameter of packing into is in the developmental tube of 50mm, under nitrogen atmosphere in thin film fabrication temperature (280 ℃) down after the fusion, in molten resin, insert a pair of copper electrode, apply volts DS, obtain the volume specific resistance [ρ] of molten resin according to following formula.Unit is Ω cm.

[ρ]＝(V×S)/(I×D)

At this, V for apply voltage (V), S is electrode area (cm ²), I is that current value, D are electrode distance (cm).

(1.4) casting surface

Slice surfaces to cast is injected 10m ²Or its above light, with the naked eye see this reflected light, whether there is the concave-convex surface in hole etc. to judge by identification.As determinating reference, will cannot see concavo-convex situation fully on the surface as zero, concavo-convex with existing on the surperficial part, 0.1 micron of its degree of depth less than, more shallow, by situation about stretch disappearing as △, with whole surface soil all see concavo-convex situation as *.

(1.5) surface roughness Ra

Measure according to JIS-B0601.

The differential meter of the high precision film ET-10 that uses little slope institute (Co., Ltd.) to make measures, and its contact pilotage front-end radius is 0.5 micron, and pin is pressed and is 5mg, and measured length is 1 micron, and holding back is 0.08 micron.

(1.6) leakage characteristics

The leakage number is to adopt commercially available Hi8 to measure with VTR, provides the signal of 4.4MHz from the TV test signal generator, uses the lost count device to obtain regenerated signal to decay to-16dB or more than it, length is 15 microseconds or its above leakage number.Carry out the regeneration/operating winding of 100 3 fens clock times under 25 ℃, 65%RH repeatedly, the leakage number that produces during with regeneration in 3 minutes is scaled the number of per 1 minute clock time, and judges according to following benchmark.

0～15/minute: excellent (qualified)

16～30/minute: good (qualified)

31 or its be above/minute: not good (defective)

(embodiment 15～19, reference example 1～3, comparative example 6,7)

(2.1) content of the titanium elements in the polyester, phosphoric, antimony element etc. is measured according to above-mentioned (1.1) the same mode.

(2.2) organic polymer particulate median size

The PAR-III that uses big Zhong Dianzishe to make is measured by dynamic light scattering method.

(2.3) in the organic polymer particle be the individual percentage of 2 times of median sizes or its above big particle

(2.3.1) mensuration in slurry

As medium, is that the slurry of 20 weight %s use 1000 times pure water dilute with the organic polymer particle with water, and the FPIA-2100 that uses Sysmex society to make is determined as the number of 2 times of median sizes or its above big particle.The gross weight of the sample size count particles of using when measuring (is about 1g/cm with it divided by organic polymer particulate density in each embodiment etc. ³), obtain the total particle number, with above-mentioned big particle number divided by the value of total particle number gained as being the individual percentage of 2 times of median sizes or the big particle more than it in the organic polymer particle.

(2.3.2) mensuration in resin combination

Contain interpolation 10mL o-Chlorophenic acid in the organic polymer particulate resin combination to 0.1g, after stirring 30 minutes under 100 ℃ or making its dissolving more than it simultaneously, at room temperature place until reaching normal temperature.After this, adopt methylene dichloride to be diluted to 5 times or more than it, the FPIA-2100 that uses Sysmex society to make is determined as the number of 2 times of median sizes or its above big particle.Following calculating is carried out according to the mode the same with above-mentioned (2.3.1).

(2.4) intrinsic viscosity of polymkeric substance ([η] (dL/g))

O-Chlorophenic acid as solvent, is measured under 25 ℃.

(2.5) pollution of cast drum, preheat roll

Before beginning, fully cleans the system film pouring into a mould drum, preheat roll and periphery thereof, visual observations begins preceding pollution condition after 48 hours from the system film respectively, it is evaluated as: with the conduct " ◎ " that does not change before the system film, almost can not find the conduct " zero " of pollution condition quickly, can confirm to occur pollutent situation as thin as a wafer, but continue to use the conduct " △ " of no problem, adhere to pollutent than heavy back, the conduct " * " that need clean or exchange.

(2.6) the surperficial thick protrusions number of film

With 100cm ²The mensuration face of 2 films of same embodiment or comparative example overlaps each other, under the condition that applies voltage 5.4kV by the electrostatic force close attachment after, judge thick projection from the Newton's rings that between 2 films, produces by the interference of light of thick projection.Light source uses the light source that the 564nm bandpass filter is set on halogen lamp.This Newton's rings reflects the height of thick projection, and the rising height of dual ring or its above thick projection from optical wavelength, be we can say at 0.5 micron or more than it.

(2.7) hinder on the surface of film

After will beginning to carry out cross directional stretch, thermal treatment to the 48th hour biaxially oriented film with tenter machine from continuous system film, the sampling width be that 165cm, length are the film of 20m, to see through light visual observations film, calculates certifiable surface and hinders number.The surface is hindered number and is " * " at 10 or short-life average evaluation more than it respectively, it is 3～9, certain degree ground, surface worsens, but spendable average evaluation is " △ ", it is 1～2, almost do not hinder, the good average evaluation of superficiality is " zero ", does not find that the average evaluation of hindering is " ◎ ".

(embodiment 20～30, comparative example 8～12)

(3.1) the carboxyl terminal base unit weight (COOH) of polyester

Method " Ana1.Chim.Acta, 22, the 363 (1960) " according to Maurice etc. is carried out.

(3.2) intrinsic viscosity of polymkeric substance ([η] (dL/g))

O-Chlorophenic acid as solvent, is measured under 25 ℃.

(3.3) content of the titanium elements in the polyester and resin composition, phosphoric and antimony element etc.

Measure according to the method the same with above-mentioned (1.1).

(3.4) content of the alkali metal in the polyester and resin composition

Atom light absorption method by the flame mode is measured.With the 8g polyester and resin composition as sample, flame uses acetylene-AIR MIXTURES, light source uses the hollow cathode lamp, and the polarisation ゼ-マ Application atom extinction photometer model 180-80 that makes in the Hitachi goes up the absorbancy of measuring in the spectrum corresponding with element.With this value and the detection line contrast of making in advance, converse the content of element.

(3.5) foreign matter number

Adopt dilute hydrochloric acid to clean the polyester fragment, after this adopt Purified Water to clean, gather 10mg, it is dissolved being heated on 260 ℃ the preparation from above-mentioned polyester fragment.Can observe roughly 500 visuals field from this preparation, but only observe 10 visuals field wherein, number goes out maximum diameter at 1 micron or foreign matter number more than it.

(3.6) fusion resistivity

2 copper coins as electrode, are clipped teflon (registered trademark) distance piece betwixt, and producing the copper coin area is 22cm ², the copper coin spacing is the electrode of 9mm.This electrode is settled down in 290 ℃ of following fused polymkeric substance, when between electrode, applying the voltage of 5000V, calculates resistance value from the magnitude of current of this moment.

(3.7) thermostability of resin combination (%BB)

The 8g resin combination is packed in the test tube, in nitrogen atmosphere, 0.1MPa add depress, under 300 ℃, carry out 10 minutes (t ₀), the thermal treatment of 6 hours (t), measure different intrinsic viscosities [η] constantly _T0, [η] _t, calculate according to following formula.

％BB _t＝(1/[η] _t ^(1/0.75)-1/[η] _t0 ^(1/0.75))

(3.8) tone of resin combination

The colour-difference meter (SM-3CH of SM color computer form) that uses ス ガ trier Co., Ltd. to make, optical condition is 45 ° of incidents, vertically accepts light, use C light as light source, the resin combination fragment is measured, measure the hunter value (L, a, b) in 2 ° of visuals field, with it as tone.

(3.9) static applies casting performance

Apply the volts DS of 6kv between electrode that is provided with on the film top that melt extrudes and the rotation cooling body, when pouring speed is risen, judge according to the pouring speed of following benchmark when generation applies the deviation situation.B or be qualified more than it.

60m/min< S

50-60m/min A

40-50m/min B

30-40m/min C

<30m/min D

(3.9) thick protrusions number H1, the H2 of film

According to implement (2.6) the same method, observe by Newton's rings.The number that will manifest the thick projection of monocyclic Newton's rings is counted H1, and the number that will manifest the thick projection of dual ring is counted H2.

In addition, under the situation that the said determination area is difficult to measure, can change the mensuration area aptly, be scaled 100cm again ²Data.(for example making and measuring area is 1cm ², 50 visuals field are measured, be scaled 100cm again ²Data).

In addition, also be difficult in the above described manner under the situation about measuring, using the 3 dimension roughness gauges (SE-3AK that little slope institute makes; Under the following conditions the thin-film width direction is scanned, carry out 50 times and measure.The stylus tip radius is 2 microns, the contact pilotage load is 0.07g, measuring area is that width 0.5mm * length 15mm (spacing 0.1mm), cutoff value are 0.08mm), measure highly is 0.28 micron or its above projection number and highly 0.56 micron or projection number more than it, by being scaled 100cm ²Data, obtain H1, H2 gets final product.In addition, can be as required, and detect known film surface projection number measuring method such as formula SEM with atomic force microscope (AFM) and 4.

[catalyst A: citric acid chelated titanium compound]

In having the 3L flask of stirrer, condenser and thermometer, add warm water (371g), to the monohydrate that wherein dissolves citric acid (532g, 2.52 moles).Stir on one side this solution, from addition funnel to this solution slowly add tetraisopropoxy titanium (288g, 1.00 mole) on one side.To this mixture heating up 1 hour, make its backflow, generate turbid solution, after this, under reduced pressure the mixture of isopropanol is removed in distillation.The solution that will comprise resultant is cooled to and is lower than 70 ℃ temperature, and this solution is stirred, and is slowly added simultaneously NaOH (380g, the 3.04 moles) aqueous solution of 32 weight % by addition funnel.Product to gained filters, and after this mixes with ethylene glycol (504g, 80 moles), and under reduced pressure isopropanol is removed in heating, obtains muddy a little faint yellow product (content of titanium elements is 3.85 weight %).Adopt ethylene glycol that it is diluted, obtaining titanium compound is the ethylene glycol solution of 1 weight %.With this citric acid chelated titanium compound as catalyst A.

[catalyst B: lactic acid chelated titanium compound]

Use has the 2L flask of stirrer, condenser and thermometer, drips ethylene glycol (218g, 3.51 moles) from addition funnel to the tetraisopropoxy titanium that is stirring (285g, 1.00 moles).Interpolation speed is adjusted, made reaction heat that the material in the flask is heated to 50 ℃.This reaction mixture was stirred 15 minutes, in this reaction flask, add DL-Lactic acid ammonium salt (252g, the 2.00 moles) aqueous solution of 85 weight %, obtain transparent faint yellow product (content of titanium elements is 6.54 weight %).Adopt ethylene glycol that it is diluted, obtaining titanium compound is the ethylene glycol solution of 1 weight %.With this lactic acid chelated titanium compound as catalyst B.

[catalyzer C: titanium alkyl oxide]

Use has the 2L flask of stirrer, condenser and thermometer, drips ethylene glycol (496g, 8.00 moles) from addition funnel to the tetraisopropoxy titanium that is stirring (285g, 1.00 moles).Interpolation speed is adjusted, made reaction heat that the material in the flask is heated to 50 ℃.Slowly add NaOH (125g, the 1.00 moles) aqueous solution of 32 weight % from addition funnel, obtain yellow transparent liquid (content of titanium elements is 4.44 weight %).Adopt ethylene glycol that it is diluted, obtaining titanium compound is the ethylene glycol solution of 1 weight %.With this titanium alkyl oxide as catalyzer C.

[embodiment 1]

(the ethylene glycol slurry of colloidal silica particle)

The saturated ammoniacal liquor that in the ethylene glycol of 40 weight parts, mixes 4 weight parts, stir on one side, on one side to the tetraamyl-silicane of wherein adding 4 weight parts, the acquisition median size is 0.1 micron a colloidal silica.After this, add the ethylene glycol of 100 weight parts,, ethylene glycol and water are distillated, obtain the ethylene glycol slurry of colloidal silica by heating.

(manufacturing of pet resin composition)

Pack in advance terephthalic acid two (hydroxyethyl) ester of about 120 weight parts, in temperature remains on esterification groove under 250 ℃, supply with continuously the ethylene glycol slurry of terephthalic acid of the ethylene glycol formation of the highly purified terephthalic acid of 100 weight parts and 43 weight parts with 4 hours time, after finishing supply, further use to distillate water on one side in 1 hour, Yi Bian carry out esterification.After this, the esterification reaction product with 120 weight parts is transferred in the polycondensation groove.

After this,, after this, further add 4 water salt of 0.03 weight part magnesium acetate with the diethyl phosphonyl ethyl acetate of adding 0.01 weight part in the above-mentioned polycondensation groove of esterification reaction product is arranged to handover, and above-mentioned catalyzer C, make that titanium elements content is 5ppm.After this, add the ethylene glycol slurry of above-mentioned colloidal silica, making its granule density in polymkeric substance is 0.1%.

After this, oligopolymer is stirred on the limit, and the limit slowly is warming up to 285 ℃ with reaction system from 250 ℃, simultaneously pressure is dropped to 100Pa.Time point forming the regulation mixing torque with the reaction system nitrogen purge, returns back to normal pressure, and polycondensation is stopped.

The resin combination of gained spues in cold water and is rope form, cuts off immediately and makes partical.

The volume specific resistance of (250 ℃) is 80M Ω cm (8 * 10 during particle fusion ⁷Ω cm)

(the system film of polyester film)

Particle to above-mentioned pet resin composition in the drying under reduced pressure machine carries out drying, provides it to forcing machine.

In forcing machine, under 280 ℃, the pet resin composition is formed molten state, after toothed gear pump and strainer, supply with the T mould, after being shaped to sheet, apply static by wire electrode, simultaneously on surface temperature remains 20 ℃ cast drum, carry out quick cooling curing.

The employing surface temperature is that 90 ℃ roller group heats this casting film, stretches 3.0 times in the vertical.

After this, film is directed in the tenter machine, in 100 ℃ hot blast, after the preheating, stretches 3.3 times in the horizontal.After this directly in tenter machine, heat-treat with 200 ℃ hot blast, slowly be cooled to room temperature after, reel.The thickness of gained film is 10 microns.

(manufacturing of magnetic recording media)

Magnetic coating and the hard coat below coating on the film surface, formed.

(magnetic coating)

Ferrous metal ferromagnetism powder 100 weight parts

Vinylchlorid/vinyl acetate copolymer 10 weight parts

Polyurethane elastomer 10 weight parts

Polymeric polyisocyanate 5 weight parts

Lecithin 1 weight part

Methyl ethyl ketone 75 weight parts

Methyl iso-butyl ketone (MIBK) 75 weight parts

Toluene 75 weight parts

Carbon black 2 weight parts

Lauric acid 1.5 weight parts

(hard coating)

Carbon black 100 weight parts

Polyester polyurethane resin 100 weight parts

Methyl ethyl ketone 500 weight parts

Toluene 500 weight parts

Further by test with small-sized calendering device (steel rider/nylon roller) after carrying out the calendering processing under 70 ℃, the line pressure of 2000N/cm, under 70 ℃, carry out 48 hours curing.After this, will put in order band and be cut to the 8mm width, be assembled in the box, make tape.

[embodiment 2～4]

(embodiment 2 adopts the magnesium acetate four water salt the same with embodiment 1 except the kind of the kind that changes titanium catalyst or its addition, alkaline earth metal compound.Be 1 water salt of lime acetate among the embodiment 4) or the addition of its addition, diethyl phosphonoacetic acid ethyl ester beyond, obtain pet resin composition, film and tape according to the mode the same with embodiment 1.

[comparative example 1]

Count the 60ppm except the addition with titanium catalyst changes to the weight basis that is scaled titanium elements, obtain vibrin, film and tape according to the mode the same with embodiment 1.

Because the amount of titanium elements surpasses 50ppm, so the foreign particles amount that produces in the resin is more, making the tape time-frequency living leakage phenomena that takes place frequently.

[comparative example 2]

Except changing to the weight basis that is scaled titanium elements, the addition with titanium catalyst counts the 0.2ppm, attempt to obtain pet resin composition etc. according to the mode the same with embodiment 1, but can not obtain to have can the film forming polymerization degree resin.

[comparative example 3]

As catalyst for polymerization, C replaces with ANTIMONY TRIOXIDE SB 203 99.8 PCT with catalyzer, its addition is scaled the weight basis of antimony element and counts 200ppm, and does not use four water salt of magnesium acetate, obtains the pet resin composition according to the mode the same with embodiment 1 in addition.

Attempt to adopt this resin combination according to the mode system film the same, but its casting performance is not good, and hole shape defective takes place on the surface of gained film with embodiment 1.This film is unworthy being used to be processed into tape.

[embodiment 5]

(using the resin combination of titanium catalyst)

Except not adding colloidal silica, obtain the pet resin composition according to the mode the same with embodiment 2.

(having used the resin combination of antimony catalyst)

The vibrin that uses comparative example 3 to obtain.

(the system film of laminated polyester film)

Above-mentioned 2 kinds of pet resin compositions are supplied with different forcing machines respectively, extrude, supplying with on the sleeve pipe stacked 2 layers, supply with the T mould, after being shaped to sheet, apply static by wire electrode on one side, in surface temperature be incubated in 20 ℃ cast drum on quick cooling curing on one side.

The employing surface temperature is that 90 ℃ roller group heats this casting film, stretches 3.0 times in the vertical.

After this, film is directed in the tenter machine, in 100 ℃ hot blast, after the preheating, stretches 3.3 times in the horizontal.After this directly in tenter machine, heat-treat with 200 ℃ hot blast, slowly be cooled to room temperature after, reel.The stacked ratio of gained film is 90 weight % for the resin that uses titanium catalyst, and using the resin of antimony catalyst is 10 weight %.

Relative this stacked film as coated face, is coated with magnetic substance according to the mode the same with embodiment 1 with the resin side of use titanium catalyst, makes tape.

[embodiment 6]

Except phosphorus compound is replaced with trimethylammonium phosphoric acid by diethyl phosphonoacetic acid ethyl ester, its addition is counted beyond the 10ppm with the weight basis that is scaled phosphoric, make polyester and resin composition, film and tape according to the mode the same with embodiment 1.

[embodiment 7]

Except phosphorus compound is replaced with phosphoric acid by diethyl phosphonoacetic acid ethyl ester, its addition is counted beyond the 10ppm with the weight basis that is scaled phosphoric, make polyester and resin composition, film and tape according to the mode the same with embodiment 1.

[embodiment 8]

Except the addition that makes catalyzer C is counted the 35ppm with the weight basis that is scaled titanium elements, make polyester and resin composition, film and tape according to the mode the same with embodiment 1.

[embodiment 9-12]

Except before polycondensation, add beyond the magnesium acetate four water salt with different addition, make polyester and resin composition, film and tape according to the mode the same with embodiment 3.

[embodiment 13,14, comparative example 4]

Except the addition of change diethyl phosphonoacetic acid ethyl ester, make polyester and resin composition, film and tape according to the mode the same with embodiment 2.

[comparative example 5]

Except the addition of change diethyl phosphonoacetic acid ethyl ester, attempt to carry out the polymerization of vibrin according to the mode the same with embodiment 2.But polymerization velocity is extremely slow, can not obtain to have can the film forming polymerization degree resin.

The evaluation result of embodiment 1-14 and comparative example 1-5 is shown in table 1-1, in 2.

In addition, in the table, the amount of each element of embodiment 5 is the value of whole relatively film.In addition, the film characteristics among the embodiment 5 is the characteristic that the face of the resin combination side of using titanium catalyst is estimated.

Table 1-1 vibrin characteristic

	Titanium elements amount (ppm)	The titanium catalyst kind	The alkali earth metal amount (kind/ppm)	Phosphoric amount (ppm)	Antimony element amount (ppm)
						Embodiment 1	5	C	Mg/30	10	0
Embodiment 2	15	B	Mg/30	10	0
						Embodiment 3	5	A	Do not have	10	0
Embodiment 4	2	A	Ca/100	35	0
						Embodiment 5	13.5	B	Mg/27	10	20
Embodiment 6	5	C	Mg/30	10	0
						Embodiment 7	5	C	Mg/30	10	0
Embodiment 8	35	C	Mg/30	10	0
						Embodiment 9	5	A	Mg/15	10	0
Embodiment 10	5	A	Mg/60	10	0
						Embodiment 11	5	A	Mg/70	10	0
Embodiment 12	5	A	Mg/100	10	0
						Embodiment 13	15	B	Mg/30	1	0
Embodiment 14	15	B	Mg/30	80	0
						Comparative example 1	60	C	Mg/30	10	0
Comparative example 2	0.2	C	Mg/30	10	0
						Comparative example 3	0		Do not have	10	200
Comparative example 4	15	B	Mg/30	0	0
						Comparative example 5	15	B	Mg/30	120	0

Table 1-2

[embodiment 15]

(manufacturing of pet resin composition)

Pack in advance terephthalic acid two (hydroxyethyl) ester of about 120 weight parts remains on 250 ℃, pressure in temperature and remains on 1.2 * 10 ⁵In the esterification groove under the Pa, supply with the ethylene glycol slurry of the terephthalic acid that the ethylene glycol of the highly purified terephthalic acid of 100 weight parts and 43 weight parts forms continuously with 4 hours time, supply with the back and further use and carried out esterification in 1 hour finishing.After this, the esterification reaction product with 120 weight parts is transferred in the polycondensation groove.

After this; to handover the ethylene glycol solution that adds triethyl phosphine acyl acetic acid ester in the above-mentioned polycondensation groove of esterification reaction product is arranged; it is converted with phosphoric count 10ppm; after 10 minutes; add the ethylene glycol solution of magnesium acetate 4 water salt; make the polymkeric substance of its relative gained count 39ppm with the magnesium elements conversion, also add the ethylene glycol solution of the % citric acid chelated titanium compound (catalyst A) of 1 weight, making the polymkeric substance of its relative gained is 5ppm in titanium atom conversion content.

After this, stir oligopolymer, reaction system slowly is warming up to 285 ℃ from 250 ℃, simultaneously pressure is dropped to 40Pa with the revolution of 30rpm.The time that heat up, step-down reaches outlet temperature, resulting pressure is altogether 60 minutes.Time point forming the regulation mixing torque with the reaction system nitrogen purge, makes it return back to normal pressure, and polycondensation is stopped.Beginning to the time that reaches the regulation mixing torque is 3 hours from reducing pressure.

The resin combination of gained spues in cold water and is rope form, cuts off immediately and makes partical.

The intrinsic viscosity of resulting polymers is 0.65.In addition, by measuring, determine in the resin combination that the content from the titanium elements of titanium catalyst is 5ppm, the content of phosphoric is 10ppm, and the content of antimony element is 0ppm.

(the organic polymer particulate is made and is added)

The organic polymer particle is made in the crystal seed emulsion polymerization.At this moment, obtain the extremely narrow seed particles of size-grade distribution by multistage crystal seed emulsification.After this adopt this seed particles to carry out the crystal seed letex polymerization.After this, by with 2 times of median size serving as the strainer that absolute Port-Le society that filters precision makes, carry out the circulating filtration of 20 paths, obtaining median size is 0.3 micron, and degree of crosslinking is 80%, the branch rate of big particle is vinyl benzene-divinyl benzene copolymer organic polymer particulate water slurry of 0.001%.

Above-mentioned particle forms molten state in the curved head type biaxial extruder, to wherein adding organic polymeric particles, make that its containing ratio in final resin combination is 2 weight %.

After adding organic polymeric particles, make curved mouthful of forcing machine to remain under the vacuum tightness of 1K Pa, at 280 ℃ resin combination is melt extruded simultaneously, cut, obtain to contain the particle of organic polymer particulate pet resin composition.The intrinsic viscosity of resulting polymers is 0.60.

(the system film of laminated polyester film)

20 weight parts are added with the resin combination that above-mentioned organic polymer particulate resin combination and 80 weight parts add before the particle carry out drying respectively, and be fed into respectively in the different single shaft forcing machines, behind interflow on the T mould, carry out 2 folded layer by layer with the stacked ratio of 5:1, under 290 ℃, melt extrude, form sheet, under 120 ℃ draft temperature, the sheet of gained is carried out biaxial stretch-formedly, obtain thickness and be 6 microns laminate film.Estimate the characteristic of this laminate film, the result is that film surface is good.

[embodiment 16]

In the process of making the pet resin composition, the highly purified terephthalic acid of 100 weight parts is replaced with the high purity terephthalic acid of 95 weight parts and the 5-sulfoisophthalic acid sodium of 5 weight parts, the addition of catalyst A is changed to the Ti element be scaled 10ppm.In addition, in organic polymer particulate water slurry, add the Polyvinylpyrolidone (PVP) of 1 weight %, stirred at normal temperatures 3 hours, the organic polymer particle is carried out surface treatment with respect to the organic polymer particle.In addition, obtain polyester and resin composition and film according to the method the same with embodiment 15.

[embodiment 17]

Except using 0.5 micron polysiloxane, obtain polyester and resin composition and film according to the method the same with embodiment 15 as the organic polymer particle.

[embodiment 18]

Replace catalyst A with catalyst B, make the addition of triethyl phosphonium mesitoyl acetate be scaled 20ppm with phosphoric, in addition, as the organic polymer particle, the median size that makes vinyl benzene-Vinylstyrene is 0.8 micron, and the branch rate of big particle is 0.005%.In addition, obtain polyester and resin composition and film according to the method the same with embodiment 15.

[embodiment 19]

Replace catalyst A with catalyzer C, make the addition of triethyl phosphonium mesitoyl acetate be scaled 40ppm with phosphoric, in addition, as the organic polymer particle, the median size that makes vinyl benzene-Vinylstyrene is 2.7 microns, and the branch rate of big particle is 0.01%.In addition, obtain polyester and resin composition and film according to the method the same with embodiment 15.

[comparative example 6]

Add ANTIMONY TRIOXIDE SB 203 99.8 PCT to replace catalyst A, make its relative resulting polymers, convert with antimony element and count 200ppm, in addition, according to method acquisition polyester and resin composition and the film the same with embodiment 15.Although polymerisation reactivity is good, cast is bulging when the system film, preheat roll is contaminated, and the wound of film surface and the surge of thick projection.

[reference example 1]

As the organic polymer particle, the branch rate that makes vinyl benzene-Vinylstyrene big particle is 0.02%.In addition, obtain polyester and resin composition and film according to the method the same with embodiment 15.The wound of film surface increases, and particularly the value of thick projection is up to 300/100cm ²

[reference example 2]

Make the addition of triethyl phosphonium mesitoyl acetate count 20ppm with phosphoric.In addition, as the organic polymer particle, the median size that makes vinyl benzene-Vinylstyrene is 5 microns, and the branch rate of big particle is 0.005%.In addition, obtain polyester and resin composition and film according to the method the same with embodiment 15.The wound of film surface increases, and particularly the value of thick projection is up to 250/100cm ²

[reference example 3]

Make the addition of triethyl phosphonium mesitoyl acetate count 60ppm with the phosphoric conversion.In addition, attempt to make polyester and resin composition according to the method the same with embodiment 15.But, can not carry out mixing processing to particle, in addition, can not obtain to have can the film forming polymerization degree resin combination.

[comparative example 7]

Count the 100ppm except making the addition of catalyst A convert, according to method acquisition polyester and resin composition and the film the same with embodiment 15 with titanium elements.The value of the thick projection of film is up to 200/100cm ²

The evaluation result of embodiment 15-19, reference example 1-3, comparative example 6,7 has been shown in table 2-1～3.

Table 2-1

Table 2-2

Table 2-3

[embodiment 20]

(preparation of catalysts)

In 94.95 weight part ethylene glycol, add the compound that 0.05 weight part is represented as the said structure formula D of coordination compound β,, make its dissolving 150 ℃ of heating 30 minutes down.In this ethylene glycol solution, add the aqueous isopropanol (concentration with titanium elements convert count 10 weight %s) of 5 weight parts, under 150 ℃, carry out 1 hour dissolving, obtain catalyst pulp as the etheric acid titanium of compound α.With respect to slurry, the content of titanium elements is 5000ppm.

(manufacturing of vibrin combination)

With the reactant of esterification of the terephthalic acid of 86 weight parts and 39 weight part ethylene glycol as storing composition, ethylene glycol to terephthalic acid that wherein adds 86 weight parts and 39 weight parts, esterification is carried out in continuation under 250 ℃, from reactivity reach 97% or reactant of esterification more than it reactant suitable with 86 weight part terephthalic acids moved to the polycondensation vessel, after this, add above-mentioned catalyzer of 0.1 weight part and 0.004 weight part methyl-phosphorous acid dimethyl esters, and move in the polycondensation groove.After this, on one side heat temperature raising, on one side reaction system is slowly reduced pressure, under the decompression of 133Pa, under 285 ℃ according to usual method polyase 13 hour under the constant stirring velocity, obtain intrinsic viscosity and be 0.630 polymer blend I.

[embodiment 21-23]

Except to the addition in the catalyst preparation according to the changing of table 3-1 record, according to the mode the same with embodiment 20, acquisition catalyzer and intrinsic viscosity are 0.64,0.63,0.64 polyester and resin composition II, III and IV.

[embodiment 24]

(preparation of catalysts)

In 94.975 weight part ethylene glycol, add the compound that 0.025 weight part is represented as the said structure formula D of coordination compound β,, make its dissolving 150 ℃ of heating 30 minutes down.In this ethylene glycol solution, add the aqueous isopropanol (concentration with titanium elements convert count 10 weight %s) of 5 weight parts, under 150 ℃, carry out 1 hour dissolving, obtain catalyst pulp as the tetrabutyl titanate ester of compound α.With respect to slurry, the content of titanium is 5000ppm.

(manufacturing of polyester and resin composition)

As catalyzer, add 0.1 weight part above-mentioned substance and add 0.004 weight part methyl-phosphorous acid dimethyl esters to replace, the methyl-phosphorous acid dipropyl of also adding 0.005 weight part, in addition, according to the method the same, obtain intrinsic viscosity and be 0.630 polyester and resin composition V with embodiment 20.

[embodiment 25]

In 94.7 weight part ethylene glycol, mixing the compound that the said structure formula D of 0.3 weight part as coordination compound β represents under 25 ℃, in this ethylene glycol solution, add the aqueous isopropanol (concentration with titanium elements convert count 10 weight %s) of 5 weight parts as the citric acid titanium chelate of compound α, mix at normal temperatures, obtain catalyst pulp.With respect to slurry, the content of titanium is 5000ppm.

(manufacturing of polyester)

As catalyzer; add 0.16 weight part above-mentioned substance and add 0.004 weight part methyl-phosphorous acid dimethyl esters to replace; also add the diethyl phosphonyl ethyl acetate of 0.004 weight part; further add the magnesium acetate four water salt of 0.03 weight part; in addition; according to the method the same, obtain intrinsic viscosity and be 0.63 polyester and resin composition VI with embodiment 20.

[embodiment 26]

Except using titanium to cross the oxo ammonium citrate aqueous solution, according to the method the same with embodiment 25, the acquisition intrinsic viscosity is 0.64 polyester and resin composition VII.

[comparative example 8]

With the reactant of esterification of the terephthalic acid of 86 weight parts and 39 weight part ethylene glycol as storing composition, ethylene glycol to terephthalic acid that wherein adds 86 weight parts and 39 weight parts, esterification is carried out in continuation under 250 ℃, from reactivity reach 97% or reactant of esterification more than it reactant suitable with 86 weight part terephthalic acids moved to the polycondensation vessel, after this, add 0.0035 weight part tetrabutyl titanate ester, 0.005 weight part methyl-phosphorous acid two propynyl esters, and move in the polycondensation groove.After this, on one side heat temperature raising, on one side reaction system is slowly reduced pressure, under the decompression of 133Pa and under 285 ℃ according to usual method polyase 13 hour under the constant stirring velocity, obtain intrinsic viscosity and be 0.630 polymer blend VIII.

[comparative example 9]

Except not adding methyl-phosphorous acid two propynyl esters,, obtain intrinsic viscosity and be the fragment of 0.63 pet resin composition I X according to the method the same with comparative example 8.

[comparative example 10]

Except adding 0.012 weight part ANTIMONY TRIOXIDE SB 203 99.8 PCT to replace 0.0035 weight part tetrabutyl titanate ester and 0.005 weight part methyl-phosphorous acid, two propynyl esters, according to the method the same, obtain intrinsic viscosity and be the fragment of 0.63 pet resin composition X with comparative example 8.

Table 3-1 has illustrated the evaluation result of embodiment 20～26 and comparative example 8～10 in 2.

Table 3-1

Table 3-2

[embodiment 27]

With above-mentioned polyester and resin composition V thorough drying, offer forcing machine, on the cast drum, melt extrude, apply static to pouring into a mould on the drum on one side,, cool off fast Yi Bian make its tight contact, after making the non-stretched film of individual layer, respectively 3.5 times of 90 ℃ of following longitudinal stretchings, 3.5 times of 105 ℃ of following cross directional stretchs, acquisition thickness is 10 microns polyester film with it.The system film is good.The thick projection of the film of gained is less thus, and tone is good.

[embodiment 28]

After above-mentioned polyester and resin composition III thorough drying, offer in the main stor(e)y forcing machine of stacked film forming apparatus.In addition, after with above-mentioned polyester and resin composition IV drying, offer secondary layer forcing machine, melt extrude at the cast drum from double-deck mould, to pour into a mould drum on apply static on one side, make its tight contact on one side, cool off fast, make main stor(e)y/secondary layer thickness than the double-deck non-stretched film that is 6/1.After this, respectively 3.5 times of 90 ℃ of following longitudinal stretchings, 3.5 times of 105 ℃ of following cross directional stretchs, obtaining thickness is the laminated polyester film of 8 microns (secondary layer thickness is 1.33 microns) to this non-stretched film.The system film is good.The thick projection of the film of gained is less thus, and tone is good.

[embodiment 29]

Except with above-mentioned polyester and resin composition III as main stor(e)y, as beyond the secondary layer, according to the method the same with embodiment 28, acquisition thickness is the laminated polyester film of 8 microns (secondary layer thickness is 1.33 microns) with above-mentioned polyester and resin composition V.The system film is good.The thick projection of the film of gained is less thus, and tone is good.

[embodiment 30]

Except using above-mentioned polyester and resin composition VI,, obtain thickness and be 10 microns polyester film according to the method the same with embodiment 27.The system film is good.The thick projection of the film of gained is less thus, and tone is good.

[comparative example 11]

Except using above-mentioned polyester and resin composition IX,, obtain thickness and be 10 microns polyester film according to the method the same with embodiment 27.This film applies at static and does not have problems aspect the cast property.The thick projection of the film of gained is less thus, but tonal difference, poor heat stability in addition, and productivity is poor.

[comparative example 12]

Except using above-mentioned polyester and resin composition X as main stor(e)y, as beyond the secondary layer, according to the method the same with embodiment 28, acquisition thickness is the laminated polyester film of 8 microns (secondary layer thickness is 1.33 microns) with above-mentioned polyester and resin composition IX.This film applies at static and does not have problems aspect the cast property.The thick projection of the film of gained is more thus, tonal difference, and poor heat stability in addition, productivity is poor.

Table 4-1 has illustrated the evaluation result of embodiment 27～30, comparative example 11,12 in 2.

Table 4-1

Table 4-2

Claims (19)

1. polyester and resin composition, wherein the content of antimony element in weight basis at 30ppm or below it, titanium elements contains 0.5～50ppm in weight basis, phosphoric contains 0.1～100ppm in weight basis, and the circular diameter of equal value that contains titanium elements is at 1 micron or particulate 100 a/0.02mg of number density less than more than it.

2. polyester and resin composition as claimed in claim 1 wherein uses titanium compound as polymerizing catalyst.

3. polyester and resin composition as claimed in claim 1 wherein contains titanium oxide.

4. polyester and resin composition as claimed in claim 3 wherein contains the composite oxides of titanium and silicon.

5. polyester and resin composition as claimed in claim 1 wherein contains titanium compound, and this titanium compound has at least a kind of substituting group selecting from alkoxyl group, phenoxy group, acidylate base, amino and hydroxyl.

6. polyester and resin composition as claimed in claim 5, the wherein at least a kind functional group of the alkoxyl group of titanium compound for from beta-diketon class functional group, hydroxycarboxylic acid functional group and ketone ester class functional group, selecting.

7. polyester and resin composition as claimed in claim 5, wherein the acidylate base of titanium compound is polyvalent carboxylic acid's class functional group or nitrogenous polyvalent carboxylic acid's class functional group.

8. polyester and resin composition as claimed in claim 5, wherein titanium compound has aliphatics alkoxyl group or aliphatics acidylate base.

9. polyester and resin composition as claimed in claim 1 wherein contains at least a Phosphorus compound of selecting from phosphoric acid class, phosphorous acid class, phosphonic acid based, phospho acid class, phosphinoxides, phosphonous acid class, phosphinous acid class and phosphine class.

10. polyester and resin composition as claimed in claim 9 wherein contains phosphoric acid and/or phosphate compound.

11. polyester and resin composition as claimed in claim 9 wherein contains phosphinic acid compounds and/or phosphonate compound.

12. polyester and resin composition as claimed in claim 11, wherein Phosphorus compound is the diethyl phosphonyl ethyl acetate.

13. polyester and resin composition as claimed in claim 1, wherein titanium elements is 0.1～20 with respect to the mol ratio (Ti/P) of phosphoric.

14. polyester and resin composition as claimed in claim 1 wherein in weight basis, contains the alkali earth metal of 5～100ppm.

15. polyester and resin composition as claimed in claim 14 wherein in weight basis, contains the magnesium elements of 15～60ppm.

16. polyester and resin composition as claimed in claim 1, wherein the volume specific resistance during fusion is 1 * 10 ⁶～1 * 10 ⁹Ω cm.

17. a polyester film, it contains polyester and resin composition as claimed in claim 1.

18. by the laminated polyester film that multilayer laminated polyester forms, wherein at least 1 layer is adopted polyester and resin composition as claimed in claim 1.

19. the magnetic recording media that adopts the described laminated polyester film of claim 18 to form.