TWI711667B - Polyester composition for master batch, polyester composition for film, and polyester film - Google Patents

Abstract

The present invention is a polyester composition for master batch, which contains specific amounts of polyester, magnesium compound, alkali metal compound, specific phosphorus compound, and lubricant; the aforementioned polyester uses dicarboxylic acid components and glycol components as constituent components ; The polyester composition for masterbatch has a sufficiently low melt resistivity, excellent color tone and thermal stability. By mixing the polyester composition for the master batch, it is possible to provide a polyester film that has improved electrostatic adhesion to the cooling cylinder and improved film-forming properties, and is provided with optimal sliding properties and excellent quality.

Description

Polyester composition for master batch, polyester composition for film, and polyester film

The present invention relates to a polyester composition for a master batch, which is used to impart good electrostatic adhesion to a polyester film to improve film-forming properties, and to impart sliding properties and processability.

Polyester has excellent mechanical and chemical properties and is used in a wide range of fields such as films or sheets for packaging applications, tape applications, and optical applications. The polyester film is obtained by performing biaxial stretching after melt-extruding polyester. That is, the sheet material melted and extruded by the extruder is brought into close contact with the surface of the rotating cooling cylinder, and then wound (casting), and then the sheet material is guided to the stretching roll arranged at the rear stage of the cooling cylinder It is stretched longitudinally, and then stretched laterally using a tenter, and then heat-fixed. Here, in order to improve the uniformity of the film thickness and increase the casting speed, if the sheet that is melted and extruded from the extrusion die is cooled on the surface of the rotating cooling cylinder, the sheet must be Adhesively high enough. Therefore, as a method to improve the adhesion between the sheet and the surface of the rotating drum, the following so-called electrostatic adhesion casting method is often used: a linear electrode is placed between the extrusion die nozzle and the cooling rotating drum and a high voltage is applied , Make the surface of the uncured sheet material generate static electricity, make the sheet material electrostatically adhere to the surface of the cooling cylinder, and perform rapid cooling.

It is known that in the electrostatic adhesion casting method, in order to improve the electrostatic adhesion of the sheet to the cooling cylinder, it is effective to increase the amount of charge on the surface of the sheet. In order to increase the amount of charge, it is effective to make the raw material polyester Modification to reduce its melting resistivity. In addition, as a method for reducing the melt resistivity, the following operations are performed: in the production stage of the raw material polyester, an alkali metal or alkaline earth metal compound is added in the esterification or transesterification reaction (for example, refer to Patent Document 1).

As another method of reducing the melt resistivity, the following operations are also performed: adding a large amount of alkali metal or alkaline earth metal compounds to separately produce a masterbatch with a very low melt resistivity, and mixing it with the polyester that becomes the raw material of the film (such as , Refer to Patent Document 2). However, when a masterbatch is manufactured, a large amount of alkali metal or alkaline earth metal compound is added, which has the problem of easy generation of foreign matter, easy coloring, or reduced thermal stability. In addition, a sufficiently low melting resistivity cannot be obtained as a masterbatch, and a large amount of masterbatch must be mixed with the polyester of the film raw material, which is also disadvantageous in terms of cost.

Polyesters for films have the following problems: when the films are overlapped, the films are closely adhered to cause so-called blocking, or when the roll-shaped film is processed, defects such as damages due to poor sliding properties with guide rolls, etc. occur. In order to solve the problem of the operation of this kind of film, it is effective to make the polyester contain inert particles such as inorganic particles.

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2010-285527.

Patent Document 2: Japanese Patent Laid-Open No. 2008-201822.

The object of the present invention is to provide a polyester composition for master batch and a polyester film. The polyester composition for master batch has sufficiently low melt resistivity, excellent color tone and thermal stability, and the polyester film is mixed with The polyester composition for the master batch improves the electrostatic adhesion to the cooling cylinder and improves the film-forming properties, and is given the best sliding properties, and the quality is also excellent.

The inventors of the present invention conducted diligent studies, and as a result, found that the above-mentioned problems can be solved by the means shown below and completed the present invention.

That is, the present invention includes the following configurations.

[1] A polyester composition for a master batch, characterized by comprising polyester, a magnesium compound, an alkali metal compound, a phosphorus compound, and a lubricant; the polyester has a dicarboxylic acid component and a glycol component as constituent components, and The aforementioned phosphorous compound is selected from the group consisting of phosphoric acid trialkyl phosphate and the alkyl group of the alkyl ester having a carbon number of 2 to 4, and ethyl diethyl phosphoryl acetate At least one; and the aforementioned polyester composition for masterbatch meets the following requirements State (1) to (4).

(1) The polyester composition contains 400 ppm to 2,700 ppm of magnesium atoms, 40 ppm to 270 ppm of alkali metal atoms, and 200 ppm to 1,700 ppm of phosphorus atoms in terms of mass.

(2) The polyester composition contains 7,000 ppm to 20,000 ppm of lubricant with an average particle diameter of 0.5 μm to 3.0 μm.

(3) With respect to the dicarboxylic acid components constituting the polyester, the amount of magnesium atoms is set to m (mol%), the amount of alkali metal atoms is set to k (mol%), and the amount of phosphorus atoms is set to p (mol%) ), the formula I is satisfied.

2≦(m+k/2)/p≦3.5 (Formula I).

(4) The melting resistivity ρi satisfies 0.005×10 ⁸ Ω‧cm to 0.05×10 ⁸ Ω‧cm.

[2] The polyester composition for a master batch as described in [1], wherein the alkali metal is potassium.

[3] The polyester composition for a masterbatch as described in [1] or [2], wherein the aforementioned phosphorus compound is a trialkyl phosphate and the alkyl group of the alkyl ester is an alkyl group having 2 to 4 carbon atoms Phosphorus compounds.

[4] The polyester composition for a master batch as described in [1] or [2], wherein the phosphorus compound is triethyl phosphate.

[5] A polyester composition for a film comprising the polyester composition for a master batch as described in any one of [1] to [4].

[6] A polyester film composed of the polyester composition for a film as described in [5].

The polyester composition for master batch of the present invention is manufactured by adding a specific amount of magnesium compound, alkali metal compound, phosphorus compound and lubricant, and has a lower melting resistivity, so it can improve the film forming properties of the film using it. Furthermore, there are few foreign matter, color tone and thermal stability are also excellent, and the sliding property during film formation is also excellent, so it can be used in a wide range of applications such as packaging films and industrial films.

Fig. 1 is a graph showing the relationship between the amount of metal and the molten resistivity in Examples and Comparative Examples.

[Polyester composition for master batch]

The polyester composition for a masterbatch of the present invention is mixed with a polyester resin for a film raw material to become a polyester composition for a film.

The melt resistivity (ρi) of the polyester composition for the master batch of the present invention needs to be 0.005×10 ⁸ Ω‧cm to 0.05×10 ⁸ Ω‧cm. The melting resistivity can be measured by the method described in the section of the examples described later. In order to improve the film-forming properties of the polyester film, it is preferable that the melt resistivity of the polyester composition for the film is 0.1×10 ⁸ Ω‧cm to 0.3×10 ⁸ Ω‧cm, but if the masterbatch uses the polyester composition When the melt resistivity is higher than 0.05×10 ⁸ Ω‧cm, a large amount of masterbatch is required to improve the film-forming properties of the film polyester, so the efficiency of the masterbatch is low and the manufacturing cost increases And other issues. If the melt resistivity of the polyester composition for master batch is less than 0.005×10 ⁸ Ω‧cm, the amount of master batch added becomes too small, so segregation is likely to occur, and the melt resistivity of the film is uneven , The stability of the film is reduced. More preferably, the melt resistivity of the polyester composition for master batch is 0.005×10 ⁸ Ω‧cm to 0.025×10 ⁸ Ω‧cm.

In the polyester composition for a master batch of the present invention, a magnesium compound and an alkali metal compound are added in order to reduce the melt resistivity. In addition, it is presumed that these metal ion components react with unreacted dicarboxylic acid components or carbonyl end groups of oligomer components to form salts and become foreignized. However, in order to prevent these metal ions from foreignizing Disperse in polyester, and further improve thermal stability and add phosphorus compound. If the foreign matter aggregates, it may become a coarse defect (coarse particle) in the film obtained using the polyester composition for master batch.

As the magnesium compound used in the present invention, a known magnesium compound can be used. For example, lower fatty acid salts such as magnesium acetate, alkoxides such as magnesium methoxide, etc. may be mentioned, and any one of these may be used alone, or two or more of them may be used in combination. Particularly preferred is magnesium acetate.

The amount of magnesium atoms is 400 ppm to 2700 ppm relative to the polyester composition for master batch. If the atomic weight of magnesium is less than 400 ppm, the melt resistivity becomes high. In order to improve the film-forming properties of the polyester composition for film, a large amount of masterbatch is required. Therefore, the efficiency of the masterbatch is low and the manufacturing cost increases. Big question. If the atomic weight of magnesium exceeds 2700ppm, it is insoluble The amount of foreign matter (magnesium salt) generated increases, and the heat resistance is reduced and the coloration of the film becomes serious, so it is not good. The preferred amount of magnesium atoms is 450 ppm to 2500 ppm, and the more preferred amount of magnesium atoms is 450 ppm to 2000 ppm.

Examples of the alkali metal of the alkali metal compound used in the present invention include lithium, sodium, and potassium. In addition, as the alkali metal compound, for example, a lower fatty acid salt such as lithium acetate or potassium acetate, or an alkoxide such as potassium methoxide, etc. can be used alone or in combination. More than species. As an alkali metal, potassium is preferred because of its large effect of reducing the molten resistivity. As the alkali metal compound, acetate is preferred, and potassium acetate is particularly preferred.

The amount of alkali metal atoms is 40 ppm to 270 ppm relative to the polyester composition for master batch. If the atomic weight of the alkali metal is less than 40 ppm, the melt resistivity becomes high. In order to improve the film forming properties of the polyester composition for the film, a large amount of the polyester for the master batch is required, so the efficiency as a master batch is low And problems such as increased manufacturing costs. If the amount of alkali metal atoms exceeds 270 ppm, the heat resistance will decrease and the coloration of the film will become serious, which is not good. The preferred amount of alkali metal atoms is 45 ppm to 250 ppm, and the more preferred amount of alkali metal atoms is 45 ppm to 200 ppm.

Examples of phosphorus compounds that can be used in the present invention include phosphoric acid, phosphorous acid, hypophosphorous acid, phosphonic acid, phosphinic acid, and ester compounds of these. Examples include: phosphoric acid, trimethyl phosphate, tributyl phosphate, triphenyl phosphate, monomethyl phosphate, dimethyl phosphate, monobutyl phosphate, dibutyl phosphate, phosphorous Acid, trimethyl phosphite, tributyl phosphite, methylphosphonic acid, dimethyl methylphosphonate, dimethyl ethylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate , Diphenyl phenyl phosphonate, ethyl diethyl phosphinyl acetate, phosphinic acid, methyl phosphinic acid, dimethyl phosphinic acid, phenyl phosphinic acid, diphenyl phosphinic acid , Methyl dimethylphosphinate, methyl diphenylphosphinate. Among them, in order to highly express the effects of the present invention, the phosphorus compound is preferably selected from the group consisting of trialkyl phosphates and the alkyl group of the alkyl ester is a C 2 to 4 alkyl group, and At least one of the group consisting of ethyl diethyl phosphatidyl acetate. Among them, it is preferable to use a phosphoric acid triester having an alkyl group having a carbon number of 2 to 4. Specifically, triethyl phosphate, tripropyl phosphate, tributyl phosphate, etc. may be mentioned, and these may be used alone or in combination of two or more kinds. In particular, triethyl phosphate is preferable because it forms a complex with moderately strong interactions with magnesium ions to obtain a polyester composition with low melt resistivity, less foreign matter, and excellent color tone.

The amount of phosphorus atoms is 200 ppm to 1700 ppm relative to the polyester composition for master batch. If the phosphorus atomic weight is less than 200 ppm, the magnesium ions and alkali metal ions are stabilized, and the effect of dispersing in the polyester becomes low, and the amount of insoluble foreign matter generated increases. Furthermore, the effect of the foreignized magnesium to lower the melt resistivity disappears, and therefore the melt resistivity becomes higher relative to the amount of magnesium added. In addition, the heat resistance is reduced and the coloration of the film becomes serious, so it is not good. If the amount of phosphorus atoms exceeds 1700 ppm, excess phosphorus compounds interact with magnesium ions. Therefore, the charge of magnesium ions does not contribute to the effect of reducing the melting resistivity. Compared with the amount of magnesium added, the melting resistivity becomes higher, which is not good. More The preferred amount of phosphorus atoms is 220 ppm to 1000 ppm.

For the purpose of improving the handling characteristics of the film, a lubricant is added to the polyester composition for master batch of the present invention. The lubricant is one that is inert particles such as inorganic particles, and by adding the lubricant, irregularities are formed on the surface during film formation, thereby imparting migration, sliding, winding, and processability to the film.

Examples of lubricants used in the present invention include oxides, carbonates, silicates, sulfates, and aluminates of metals such as titanium, aluminum, silicon, calcium, magnesium, and barium. Examples include: titanium dioxide, alumina, aluminosilicate, silica, calcium oxide, calcium carbonate, barium sulfate, etc., and particles derived from natural talc, mica, kaolin, zeolite, etc., but are not limited In these.

The average particle size of the lubricant is 0.5 μm to 3.0 μm, more preferably 0.8 μm to 2.5 μm. If it is less than 0.5 μm, the effect of forming irregularities on the surface and imparting operability such as sliding properties and migration properties is reduced, which is not preferable. On the other hand, if it exceeds 3.0 μm, the quality of the film may be impaired due to the formation of coarse protrusions, which is not good. The average particle size of the lubricant is measured using a particle size distribution meter of the laser light scattering method as described in the section of the examples.

The amount of lubricant is 7000 ppm to 20000 ppm relative to the polyester composition for master batch on a mass basis. When it is mixed with the polyester resin for the film raw material to form the polyester composition for the film, the polyester composition for the master batch is added so that the amount of lubricant becomes a preferable amount. If the lubricant does not reach 7000ppm, Due to the addition of a large amount of polyester composition for master batches, the color tone and heat resistance deteriorate. In addition, due to its low efficiency as a masterbatch, it will increase the manufacturing cost. If the lubricant exceeds 20,000 ppm, the amount of metal in the polyester composition for film will decrease, and the melt resistivity will increase, and the film-forming properties will deteriorate, which is not good. In addition, agglomeration of the lubricant occurs during polymerization, which will increase the number of coarse defects (coarse particles) after blending and dilution, which is not good. The lower limit of the lubricant content is preferably 8000 ppm or more, more preferably 10000 ppm or more, and still more preferably 12000 ppm or more. The upper limit of the content is preferably 18000 ppm or less.

The content of magnesium atom, alkali metal atom, phosphorus atom, and lubricant in the polyester composition for master batch can be quantified by the method described in the following Examples. The addition period of the magnesium compound, alkali metal compound, and phosphorus compound to the polyester is not particularly limited. However, it is determined during the polymerization of the polyester, especially in the middle of the esterification (or transesterification) step, or esterification (or ester exchange). It is added between the end of the exchange) step and the start of the polycondensation step to prevent the acid component of the polyester from forming a salt with magnesium ions or alkali metal ions to form a salt, and it can be uniformly dispersed in the oligomer, so it is preferred . The period of time when the lubricant is added to the polyester is not particularly limited, but it is determined from the time when the polyester is polymerized, especially in the middle of the esterification (or transesterification) step, or the end of the esterification (or transesterification) step. It is preferably added between the beginning of the polycondensation step, which can be uniformly dispersed in the oligomer.

If these compounds are added during the polymerization of polyester, magnesium atoms and alkali metal atoms remain in the polyester composition while maintaining the added amount, but Phosphorus atoms are sometimes distilled out of the polymerization system under reduced pressure. Therefore, the relationship between the addition amount and the residual amount must be known in advance, and then the addition amount of the phosphorus compound must be determined. The lubricant remains in the polyester composition while maintaining the added amount.

When the polyester is a polyester with a dicarboxylic acid component and a diol component as constituent components, the amount of magnesium atoms relative to the dicarboxylic acid component is m (mol%), and the amount of alkali metal atoms is k( When the amount of phosphorus atom is set to p (mol%), the molar ratio of magnesium atom, alkali metal atom, and phosphorus atom satisfies the following formula I, thereby obtaining the effect of the present invention.

2≦(m+k/2)/p≦3.5 (Formula I)

It is considered that the phosphorus atom stabilizes the magnesium ion and the alkali metal ion without being foreignized. Magnesium ions are divalent, while alkali metal ions are monovalent. Therefore, the sum of the amounts of magnesium ions and alkali metal ions is expressed as (m+k/2) and divided by p to get the ratio "(M+k/2)/p" is the relative amount of magnesium ion and alkali metal ion with respect to phosphorus atom.

If the value of "(m+k/2)/p" exceeds 3.5, the amount of phosphorus atoms is relatively small compared to magnesium atoms and alkali metal atoms, which stabilizes magnesium ions and alkali metal ions and disperses them in The effect of polyester becomes lower and the amount of insoluble foreign matter (magnesium salt, alkali metal salt) is increased. Furthermore, the effect of reducing the molten resistivity of the foreignized magnesium disappears, so the molten resistivity becomes higher relative to the amount of magnesium added. In addition, the heat resistance is reduced and the coloration of the film becomes serious. If the value of "(m+k/2)/p" is less than 2, the amount of phosphorus atoms is relatively excessive relative to magnesium atoms and alkali metal atoms, and the excess phosphorus is combined The substance interacts with magnesium ions, so the charge of the magnesium ions does not contribute to the effect of reducing the melting resistivity, and the melting resistivity becomes higher relative to the amount of magnesium added. "(M+k/2)/p" is more preferably 2.3 or more and 3 or less, and still more preferably 2.5 or more and 3 or less.

"(M+k/2)/p" in formula I can also be calculated based on the content of each atom in the polyester composition for master batch.

As before, when the amount of magnesium atoms is set to m (mol%) and the amount of alkali metal atoms is set to k (mol%), the amount of metal (the total amount of magnesium atoms and alkali metal atoms) and the molten resistivity When the relationship satisfies the following formula II, it is considered that the added metal does not become foreignized and contributes to the reduction of the melt resistivity (ρi), and the polyester composition for master batch of the present invention satisfies the formula II.

R<1.2×10 ^-2 /(m+k/2) (Formula II)

(Here, R=ρi×10 ^-8 )

Magnesium compounds and alkali metal compounds have the effect of lowering the melting resistivity. In addition, magnesium ions are divalent, while alkali metal ions are monovalent. Therefore, the sum of the amounts of magnesium ions and alkali metal ions (m+k /2) is a factor that has a greater effect on the melting resistivity.

If the added metal is foreignized, the foreignized metal hardly contributes to the melting resistivity, so the molten resistivity becomes higher compared to the system without foreignization. Therefore, if it deviates from the situation of formula II, there is a possibility that the molten resistivity relative to the amount of added metal becomes higher, and the amount of metal that is foreignized becomes more. Generally speaking, it can be said that the amount of metal is in inverse proportion to the value of molten resistivity. Fig. 1 is a graph obtained by plotting the relationship between the amount of metal (m+k/2) and the value of melt resistivity (ρi) in Examples 1 to 9 and Comparative Examples 1 to 5 described later. In the figure, the examples are represented by "◇" and the comparative examples are represented by "●". According to the figure, the range in which the effect of the invention of this case can be obtained is the range below the curve. Since the curve is R=1.2×10 ^-2 /(m+k/2), the above formula II is derived.

The polyester of the present invention is a polyester having a dicarboxylic acid component and a diol component as constituent components. One type or two or more types of dicarboxylic acid components and diol components can be used. In addition to dicarboxylic acid, polyhydric carboxylic acid may be included, and polyhydric alcohol may be included in addition to diol. Alternatively, it may also contain units containing hydroxycarboxylic acid and cyclic ester.

The production of polyester can be carried out by previously known methods. For example, in the case of polyester composed of terephthalic acid and ethylene glycol, any of the following methods can be used: a method of polycondensation after esterification of terephthalic acid and ethylene glycol; or A method of polycondensation after transesterification of alkyl esters of terephthalic acid such as dimethyl terephthalate and ethylene glycol. In addition, the polymerization device can be a batch type or a continuous type.

As the catalyst, metal-containing polyester polycondensation catalysts such as antimony compounds, aluminum compounds, titanium compounds, tin compounds, and germanium compounds, which are well-known as polyester polymerization catalysts, can be used. Among them, it is preferable to use an aluminum compound that is excellent in foreign matter suppression or thermal stability.

The polyester composition for a masterbatch of the present invention contains a polymerization catalyst component. If an antimony compound is used, it is preferably used in the master batch polyester composition Contains 50ppm to 300ppm of antimony atom in mass conversion. In the case of using an aluminum compound, it is preferable that the polyester composition for a master batch contains 20 ppm to 100 ppm of aluminum atoms in terms of mass. In the case of using a titanium compound, it is preferable that the polyester composition for a master batch contains 5 ppm to 150 ppm of titanium atoms in terms of mass. When a tin compound is used, it is preferable to contain 50 ppm to 200 ppm of tin atoms in the polyester composition for master batches in terms of mass. When a germanium compound is used, it is preferable that the polyester composition for master batch contains 50 ppm to 200 ppm of germanium atoms in terms of mass. Among the polymerization catalysts of these metals, in the case of antimony compounds, aluminum compounds, titanium compounds, and tin compounds, they remain in the polyester composition while maintaining the added amount. However, in the case of germanium compounds, they may be reduced It is distilled out of the polymerization system under pressure, so it is preferable to adjust the addition amount so that the residual amount in the polyester composition falls within the above-mentioned range.

The polyester polymerization catalyst can be added to the reaction system at any stage of the polymerization reaction. For example, it can be added to the reaction system at any stage before the start of the esterification reaction or the transesterification reaction and in the middle of the reaction, immediately before the start of the polycondensation reaction, or in the middle of the polycondensation reaction.

Examples of the aforementioned dicarboxylic acids include: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decane dicarboxylic acid, decane Dioxane dicarboxylic acid, tetradecane dicarboxylic acid, hexadecane dicarboxylic acid, 1,3-cyclobutane dicarboxylic acid, 1,3-cyclopentane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid Carboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornane Saturated aliphatic dicarboxylic acids or ester-forming derivatives exemplified by dicarboxylic acids and dimer acids; unsaturated aliphatic exemplified by fumaric acid, maleic acid, and itaconic acid Dicarboxylic acids or their ester-forming derivatives; phthalic acid, isophthalic acid, terephthalic acid, 5-(alkali metal) sulfoisophthalic acid, diphthalic acid, 1,3 -Naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid Carboxylic acid, 4,4'-biphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 1,2-bis(phenoxy)ethane-p, p'-dicarboxylic acid, Par Examples of aromatic dicarboxylic acids such as pamoic acid and anthracene dicarboxylic acid or ester-forming derivatives thereof.

Examples of polycarboxylic acids other than these dicarboxylic acids include ethane tricarboxylic acid, propane tricarboxylic acid, butane tetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4 ,3',4'-Biphenyltetracarboxylic acid and ester-forming derivatives thereof.

Examples of the aforementioned glycols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, triethylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3- Cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexane Alkylenediethanol, 1,10-decanediol, 1,12-dodecanediol and other alkylene glycols, polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, etc. Illustrated aliphatic diols; Hydroquinone, 4,4'-dihydroxybisphenol, 1,4-bis(β-hydroxyethoxy)benzene, 1,4-bis(β-hydroxyethoxy) Phenyl) chrysene, Bis(p-hydroxyphenyl) ether, bis(p-hydroxyphenyl) sulfide, bis(p-hydroxyphenyl)methane, 1,2-bis(p-hydroxyphenyl)ethane, bisphenol A, bisphenol C, 2 , 5-naphthalenediol, diols obtained by adding ethylene oxide to these diols, and aromatic diols exemplified.

Examples of polyols other than these diols include trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerin, and hexanetriol.

Examples of the aforementioned hydroxycarboxylic acid include lactic acid, citric acid, malic acid, tartaric acid, glycolic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, 4-hydroxycyclohexane Alkyl carboxylic acids, or ester-forming derivatives of these, etc.

Examples of the cyclic ester include ε-caprolactone, β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, glycolide, lactide, and the like.

Examples of ester-forming derivatives of polybasic carboxylic acid or hydroxycarboxylic acid include these alkyl esters, chlorides, and acid anhydrides.

The polyester used in the present invention is preferably polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and poly(1,4-terephthalate). Cyclohexane dimethyl), polyethylene naphthalate, polybutylene naphthalate, polypropylene naphthalate and copolymers of these, particularly preferred Polyethylene terephthalate and its copolymers.

The polyester composition for masterbatch of the present invention may contain one or more of diethylene glycol inhibitors, fluorescent brighteners, dyes or pigments and other hue adjusters, ultraviolet inhibitors, Various additives such as infrared absorbing pigments, heat stabilizers, surfactants, and antioxidants. As diethylene glycol inhibitors, basic compounds such as alkylamine compounds or ammonium salt compounds can be used. As antioxidants, aromatic amine-based and phenol-based antioxidants can be used. As stabilizers, sulfur-based, Amine series stabilizer.

These additives may be added to the master batch polyester composition in a total ratio of preferably 10% by mass or less, and more preferably in a ratio of 5% by mass or less.

The hue (Co-b) of the polyester composition for masterbatch of the present invention in the form of particles is preferably 0-40, more preferably 0-30. The polyester composition for a master batch is mixed with the polyester resin for a film raw material to become a polyester composition for a film, and it is shape|molded into a film. Even if the color tone (Co-b) of the polyester composition for masterbatch is relatively high in particle form, there is no problem as long as the film raw material is diluted with polyester resin to make the color tone of the film in a preferable range. .

The inherent viscosity (IV) of the polyester composition for masterbatch of the present invention is preferably 0.3dl/g to 0.7dl/g. The polyester composition for a master batch is mixed with the polyester resin for a film raw material to become a polyester composition for a film, and it is shape|molded into a film. Even if the inherent viscosity (IV) of the polyester composition for masterbatch is relatively high or low in the form of particles, as long as the film raw material is diluted with polyester resin, the inherent viscosity (IV) of the film is relatively high. The best range is no problem.

[Polyester composition for film, polyester film]

The polyester composition for a film of the present invention is obtained by mixing the above-mentioned polyester composition for a master batch and a polyester resin (composition) for a film raw material in an arbitrary ratio. A known film forming method can be used to obtain a polyester film from the polyester composition for film of the present invention.

The polyester resin (composition) for the film raw material may or may not contain an alkali metal compound or alkaline earth metal compound for lowering the melt resistivity. If there is no alkali metal compound or alkaline earth metal compound and the polyester resin for the film raw material with high melt resistivity is mixed with the polyester composition for the master batch of the present invention, it can be equivalent to the general polyester composition for the film The above film-forming properties. If the polyester composition for the master batch of the present invention is mixed with the polyester composition for the film raw material already containing the alkali metal compound or the alkaline earth metal compound, the film-forming properties can be further improved.

The polyester that can be used in the polyester resin (composition) for the film raw material is the same as the polyester that can be used in the aforementioned polyester composition for the master batch. It is preferable that the polyester used for the polyester resin (composition) for the film raw material and the polyester used for the polyester composition for the master batch are polyesters containing the same constituents.

Preferably, the amount of magnesium atoms in the polyester composition for a film is 15 ppm to 150 ppm, the amount of alkali metals is 1.5 ppm to 15 ppm, and the amount of phosphorus atoms is 7 ppm to 80 ppm. Specifically, it is preferable to prepare a polyester composition for film containing 1% to 20% by mass of the polyester composition for master batch of the present invention, and more preferably to prepare a polyester composition 2 containing the master batch. A polyester composition for film with a mass% to 10 mass %. If the polyester group for master batch is mixed in such a way The finished product can obtain a film with an excellent balance of melt resistivity, color tone, and heat resistance. Regarding the color tone (Co-b) of the film, when measured by the method described in the section of the examples, it is preferably 0-6, more preferably 0-5.2, and still more preferably 0-5.

[Example]

Hereinafter, the present invention will be explained in more detail through examples, but the present invention is not limited to these examples. Furthermore, the measurement method of the main characteristic values is explained below.

(1) Intrinsic viscosity of polyester resin ‧ composition (IV)

A 6/4 (weight ratio) mixed solvent of phenol/1,1,2,2-tetrachloroethane was used to dissolve the polyester composition (polyester resin) and measured at a temperature of 30°C.

(2) Melting resistivity

Place two electrodes (stainless steel wire with a diameter of 0.6mm) on both ends of the polyester composition melted at 275°C and sandwiched between two quartz plates with a width of 2cm to form a shape with a width of 2cm and a thickness of 0.6mm. For a layer of a homogeneous molten polyester composition, the current (io) when a DC voltage of 120V is applied at a temperature of 280°C is measured, and this is substituted into the following formula to obtain the melting resistivity value ρi(Ω‧cm).

ρi(Ω‧cm)=(A/L)×(V/io)

[A: electrode area (cm ² ), L: distance between electrodes (cm), V: voltage (V)]

A (cm ² )=[width of molten polyester composition layer]×[thickness]=2(cm)×0.06(cm), V=120(V). L is the measured value excluding the diameter of the electrode, which is 1.3cm.

(3) Quantitative methods of aluminum, magnesium, potassium, lithium, and phosphorus

The polyester composition is heated to [melting point + 20°C] in a stainless steel circular ring with a thickness of 5mm and an inner diameter of 50mm to make a sample piece. The element content is determined by fluorescent X-ray analysis and expressed in ppm (Quality standard) said. In addition, for quantification, a calibration curve obtained from a sample whose amount of each element is known in advance is used.

(4) Hue (Co-b)

A color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., ZE-2000) was used to measure the color difference (L, a, b) of the particles or film of the polyester composition. The particles are put into a measuring cell (measuring cell) and measured by reflection method. The film was superimposed on 10 pieces and measured by the reflection method.

(5) Heat resistance

Put the polyester film made of the polyester composition for the mixed masterbatch into a glass ampoule, and after nitrogen replacement, the glass ampoule is sealed under a reduced pressure of 13.3kPa (nitrogen environment) and measured Intrinsic viscosity before and after heat treatment when heat treatment is performed at 300°C for 2 hours. Heat resistance is expressed by the decrease in inherent viscosity caused by heat treatment (△IV=[IV after heat treatment]-[IV before heat treatment]). Generally, the inherent viscosity decreases due to heat treatment, so the smaller the absolute value of ΔIV, the better the heat resistance.

(6) Number of gross defects

The measurement of the number of gross defects is based on the image analysis and measurement of the particles in the cast film obtained by observation using a phase-contrast optical microscope (manufactured by Nikon) and objective lens (manufactured by Nikon, magnification 10 times, aperture 0.5) The size and number of particles. The particles are mainly formed by agglomeration of lubricants, but also include those formed by agglomeration of foreign matter derived from magnesium ions and alkali metal ions. In the image analysis, the number of aggregated particles above 10μm is measured, and the field of view is changed 20 times. The total number of aggregated particles is calculated, and the number of aggregated particles above 10μm per 1 square mm of field of view is calculated. Number of gross defects. The number of gross defects less than 300 is judged as ○, and 300 or more is judged as ×.

(7) Average particle size of lubricant

Using a laser light scattering particle size distribution meter (Leeds & Northrup, Microtrac HRA model 9320-X100), the ethylene glycol slurry of the lubricant is diluted with water and the measurement is substantially performed in an aqueous system. The 50% diameter of the cumulative volume of the measurement result is defined as the average particle diameter.

(Reference example 1) Production of polyester resin (X) for film raw materials

0.54 parts by weight of terephthalic acid, ethylene glycol, and antimony trioxide were added to a stainless steel autoclave equipped with a stirrer, a distillation tower, and a pressure regulator. Furthermore, 0.3 mol% of triethylamine, which is a diethylene glycol inhibitor, is added to terephthalic acid, and the water produced by the esterification is successively removed at 240°C and 0.35 MPa gauge pressure for 2 hours.化反应。 Chemical reaction.

Then, the temperature of the system was raised to 280°C for 1 hour, during which the pressure of the system was slowly reduced to 150 Pa, and the polycondensation reaction was carried out under this condition for 1 hour to obtain the polyester resin (X) for the film material. The inherent viscosity of the obtained polyester resin was 0.62dl/g, and the melt resistivity was 3.2×10 ⁸ Ω·cm.

(Example 1)

(1) Preparation of silica slurry

Add 5 liters of ethylene glycol and 750 g of silica particles (manufactured by Fuji Silysia, Silysia 310) with an average particle size of 2.4 μm to a dispersion tank with a homogenizer, and stir and disperse at 8000 rpm for 2 hours. 150g/l slurry.

(2) Manufacturing of polyester composition for master batch

Terephthalic acid and ethylene glycol are added to a stainless steel autoclave equipped with a stirrer, distillation tower, and pressure regulator. The silicon dioxide slurry is added so that the theoretical amount of silica becomes 16,000 ppm relative to the theoretical amount of polyester, and triethylamine is added so that it becomes 0.3 mol% relative to terephthalic acid, and the esterification reaction is carried out according to the conventional method. , To obtain oligomers.

Next, basic aluminum acetate, magnesium acetate dihydrate, potassium acetate, and triphosphate were added so that aluminum atoms became 60 ppm, magnesium atoms became 1000 ppm, potassium atoms became 100 ppm, and phosphorus atoms became 660 ppm relative to the theoretical amount of polyester. For ethyl ester, the temperature of the system was raised to 280℃ in 1 hour, during which the pressure of the system was slowly reduced to 150Pa, and the polycondensation reaction was carried out for 80 minutes under this condition to obtain the polyester composition for master batch The particles of things. The physical properties of the obtained polyester composition are shown in Table 1. The aluminum atom, magnesium atom, and potassium atom remain the added amount and become the residual amount (content), but part of the phosphorus atom is distilled out of the polymerization system in the polycondensation reaction step, so the residual amount (content) decreases relative to the added amount (below The same is true in the example).

(3) Film making of polyester film

The particles of the polyester composition for the master batch produced above and the particles of the polyester resin (X) for the film raw material were mixed in a mass ratio of 5:95, and vacuum dried at 135°C for 10 hours. Then, it was quantitatively supplied to a twin-screw extruder, melt-extruded into a sheet at 280°C, and quenched and solidified on a metal roll maintained at a surface temperature of 20°C to obtain a cast film with a thickness of 1400 μm.

Next, the cast film is heated to 100° C. with a heated roll group and an infrared heater, and then a roll group with a peripheral speed difference is used to extend 3.5 times in the longitudinal direction to obtain a uniaxially aligned film. Then, stretch 4.0 times in the width direction at 120°C with a tenter, heat the film with an infrared heater at 260°C for 0.5 seconds while the film width is fixed, and then perform a 3% relaxation treatment at 200°C for 23 seconds , A biaxially aligned polyester film with a thickness of 100 μm was obtained. The characteristics of the obtained film are shown in Table 1. The number of gross defects is measured by cast film.

(Example 2)

In the polymerization method of Example 1, based on the theoretical amount relative to polyester, silicon dioxide becomes 8000ppm, aluminum atom becomes 30ppm, and magnesium atom Add silica slurry, basic aluminum acetate, magnesium acetate dihydrate, potassium acetate, and triethyl phosphate so that it becomes 500ppm, potassium atom becomes 50ppm, and phosphorus atom becomes 330ppm. Other than that, use the same as in Example 1. The method obtains the particles of the polyester composition for the master batch. The physical properties of the obtained polyester composition are shown in Table 1.

The obtained polyester composition for the master batch and the particles of the polyester resin (X) for the film raw material were mixed in a ratio of 10:90 by mass, and the polyester film was processed by the same method as in Example 1. Film making. The characteristics of the obtained film are shown in Table 1.

(Example 3)

In the polymerization method of Example 1, alkaline aluminum acetate and magnesium acetate dihydrate were added so that aluminum atoms became 80 ppm, magnesium atoms became 2500 ppm, potassium atoms became 250 ppm, and phosphorus atoms became 1650 ppm relative to the theoretical amount of polyester. Except this, potassium acetate, and triethyl phosphate were used in the same manner as in Example 1 to obtain pellets of the polyester composition for master batch. The physical properties of the obtained polyester composition are shown in Table 1.

The film forming method was the same as in Example 1 to obtain a film. The characteristics of the obtained film are shown in Table 1.

(Example 4)

In the polymerization method of Example 1, basic aluminum acetate, aluminum acetate and aluminum were added so that aluminum atoms became 60 ppm, magnesium atoms became 1000 ppm, potassium atoms became 250 ppm, and phosphorus atoms became 530 ppm relative to the theoretical amount of polyester. Except for magnesium acetate dihydrate, potassium acetate, and triethyl phosphate, the same method as in Example 1 was used to obtain pellets of the polyester composition for master batch. The physical properties of the obtained polyester composition are shown in Table 1.

The film forming method was the same as in Example 1 to obtain a film. The characteristics of the obtained film are shown in Table 1.

(Example 5)

In the polymerization method of Example 1, basic aluminum acetate and magnesium acetate dihydrate were added so that aluminum atoms became 60 ppm, magnesium atoms became 1000 ppm, potassium atoms became 100 ppm, and phosphorus atoms became 660 ppm relative to the theoretical amount of polyester. Except this, potassium acetate and tripropyl phosphate were used in the same manner as in Example 1 to obtain pellets of the polyester composition for master batch. The physical properties of the obtained polyester composition are shown in Table 1.

The film forming method was the same as in Example 1 to obtain a film. The characteristics of the obtained film are shown in Table 1.

(Example 6)

In the polymerization method of Example 1, alkaline aluminum acetate and magnesium acetate dihydrate were added so that aluminum atoms became 60 ppm, magnesium atoms became 1000 ppm, lithium atoms became 90 ppm, and phosphorus atoms became 660 ppm relative to the theoretical amount of polyester. Except for this compound, lithium acetate dihydrate, and triethyl phosphate, the same method as in Example 1 was used to obtain pellets of the polyester composition for master batch. The physical properties of the obtained polyester composition are shown in Table 1.

The film forming method was the same as in Example 1 to obtain a film. So The properties of the obtained film are shown in Table 1.

(Example 7)

In the polymerization method of Example 1, basic aluminum acetate and magnesium acetate dihydrate were added so that aluminum atoms became 60 ppm, magnesium atoms became 1000 ppm, potassium atoms became 100 ppm, and phosphorus atoms became 660 ppm relative to the theoretical amount of polyester. Except this, the same method as in Example 1 was used to obtain pellets of the polyester composition for master batches, except for potassium acetate and ethyl diethyl phosphatidyl acetate. The physical properties of the obtained polyester composition are shown in Table 1.

The film forming method was the same as in Example 1 to obtain a film. The characteristics of the obtained film are shown in Table 1.

(Example 8)

In the polymerization method of Example 1, silica was added in such a way that the theoretical amount relative to polyester was 12000ppm, aluminum atoms became 60ppm, magnesium atoms became 1000ppm, potassium atoms became 100ppm, and phosphorus atoms became 660ppm. Except for the slurry, basic aluminum acetate, magnesium acetate dihydrate, potassium acetate, and triethyl phosphate, the same method as in Example 1 was used to obtain pellets of the polyester composition for master batch. The physical properties of the obtained polyester composition are shown in Table 1.

The obtained polyester composition for the masterbatch and the particles of the polyester resin (X) for the film raw material were mixed in a mass ratio of 6.7: 93.3, and the polyester film was processed by the same method as in Example 1. Film making. The characteristics of the obtained film are shown in Table 1.

(Example 9)

In the polymerization method of Example 1, silicon dioxide was added in such a way that the theoretical amount relative to the polyester was 18000ppm, aluminum atoms became 60ppm, magnesium atoms became 1000ppm, potassium atoms became 100ppm, and phosphorus atoms became 660ppm. Except for the slurry, basic aluminum acetate, magnesium acetate dihydrate, potassium acetate, and triethyl phosphate, the same method as in Example 1 was used to obtain pellets of the polyester composition for master batch. The physical properties of the obtained polyester composition are shown in Table 1.

The obtained polyester composition for the master batch and the particles of the polyester resin (X) for the film raw material were mixed in a mass ratio of 4.4:95.6, and the polyester film was processed by the same method as in Example 1. Film making. The characteristics of the obtained film are shown in Table 1.

(Comparative example 1)

In the polymerization method of Example 1, basic aluminum acetate and magnesium acetate dihydrate were added so that aluminum atoms became 60 ppm, magnesium atoms became 1000 ppm, potassium atoms became 100 ppm, and phosphorus atoms became 400 ppm relative to the theoretical amount of polyester. Except this, potassium acetate, and triethyl phosphate were used in the same manner as in Example 1 to obtain pellets of the polyester composition for master batch. The physical properties of the obtained polyester composition are shown in Table 2.

The film forming method was the same as in Example 1 to obtain a film. The properties of the film obtained are shown in Table 2.

(Comparative example 2)

In the polymerization method of Example 1, basic aluminum acetate and magnesium acetate dihydrate were added so that aluminum atoms became 30 ppm, magnesium atoms became 500 ppm, potassium atoms became 50 ppm, and phosphorus atoms became 660 ppm relative to the theoretical amount of polyester. Except this, potassium acetate, and triethyl phosphate were used in the same manner as in Example 1 to obtain pellets of the polyester composition for master batch. The physical properties of the obtained polyester composition are shown in Table 2.

The film forming method was the same as in Example 1 to obtain a film. The properties of the film obtained are shown in Table 2.

(Comparative example 3)

In the polymerization method of Example 1, basic aluminum acetate and magnesium acetate dihydrate were added so that aluminum atoms became 60 ppm, magnesium atoms became 2000 ppm, potassium atoms became 50 ppm, and phosphorus atoms became 660 ppm relative to the theoretical amount of polyester. Except this, potassium acetate, and triethyl phosphate were used in the same manner as in Example 1 to obtain pellets of the polyester composition for master batch. The physical properties of the obtained polyester composition are shown in Table 2.

The film forming method was the same as in Example 1 to obtain a film. The properties of the film obtained are shown in Table 2.

(Comparative Example 4)

In the polymerization method of Example 1, basic acetic acid was added so that aluminum atoms became 60 ppm, magnesium atoms became 1000 ppm, potassium atoms became 1000 ppm, and phosphorus atoms became 660 ppm relative to the theoretical amount of polyester. Except for aluminum, magnesium acetate dihydrate, potassium acetate, and triethyl phosphate, the same method as in Example 1 was used to obtain pellets of the polyester composition for master batch. The physical properties of the obtained polyester composition are shown in Table 2.

The film forming method was the same as in Example 1 to obtain a film. The properties of the film obtained are shown in Table 2.

(Comparative Example 5)

In the polymerization method of Example 1, basic aluminum acetate and magnesium acetate dihydrate were added so that aluminum atoms became 60 ppm, magnesium atoms became 1000 ppm, potassium atoms became 100 ppm, and phosphorus atoms became 660 ppm relative to the theoretical amount of polyester. Except for this, potassium acetate and trimethyl phosphate were used in the same manner as in Example 1 to obtain pellets of the polyester composition for master batch. The physical properties of the obtained polyester composition are shown in Table 2.

The film forming method was the same as in Example 1 to obtain a film. The properties of the film obtained are shown in Table 2.

(Comparative Example 6)

In the polymerization method of Example 1, silicon dioxide was added in such a way that the theoretical amount relative to the polyester was 5000ppm, aluminum atoms became 60ppm, magnesium atoms became 1000ppm, potassium atoms became 100ppm, and phosphorus atoms became 660ppm. Except for the slurry, basic aluminum acetate, magnesium acetate dihydrate, potassium acetate, and trimethyl phosphate, the same method as in Example 1 was used to obtain pellets of the polyester composition for master batch. The physical properties of the obtained polyester composition are shown in Table 2.

The obtained polyester composition for the master batch and the particles of the polyester resin (X) for the film raw material were mixed in a ratio of 16:84 by mass ratio, and the polyester film was subjected to the same method as in Example 1. Film making. The properties of the film obtained are shown in Table 2.

(Comparative Example 7)

In the polymerization method of Example 1, silicon dioxide was added in such a way that the theoretical amount relative to polyester was 30000ppm, aluminum atoms became 60ppm, magnesium atoms became 1000ppm, potassium atoms became 100ppm, and phosphorus atoms became 660ppm. Except for the slurry, basic aluminum acetate, magnesium acetate dihydrate, potassium acetate, and trimethyl phosphate, the same method as in Example 1 was used to obtain pellets of the polyester composition for master batch. The physical properties of the obtained polyester composition are shown in Table 2.

The obtained polyester composition for the master batch and the particles of the polyester resin (X) for the film raw material were mixed in a mass ratio of 2.7: 97.3, and the polyester film was processed by the same method as in Example 1. Film making. The properties of the film obtained are shown in Table 2.

※TMPA；Trimethyl phosphate=磷酸三甲酯※TEPA；Triethyl phosphate=磷酸三乙酯※TPPA；Tripropyl phosphate=磷酸三丙酯※EDPA；Ethyl diethyl phosphonoacetate=乙基二乙基磷醯基乙酸酯 [Table 1]

※TMPA; Trimethyl phosphate=trimethyl phosphate ※TEPA; Triethyl phosphate=triethyl phosphate ※TPPA; Tripropyl phosphate=tripropyl phosphate ※EDPA; Ethyl diethyl phosphonoacetate=ethyl diethyl phosphonoacetate

※TMPA=磷酸三甲酯※TEPA=磷酸三乙酯※TPPA=磷酸三丙酯※EDPA=乙基二乙基磷醯基乙酸酯

※TMPA=Trimethyl Phosphate ※TEPA=Triethyl Phosphate ※TPPA=Tripropyl Phosphate ※EDPA=Ethyl Diethyl Phosphoryl Acetate

The polyester compositions for master batches of Examples 1 to 9 have low melt resistivity and few foreign matter, and the films obtained using them have excellent color tone and thermal stability. In addition, it is considered that by satisfying the above-mentioned formula II, the added metal does not become foreignized and contributes to the reduction of the melt resistivity (ρi). And the use of lithium as an alkali metal Compared with Example 6, in Example 1 using potassium, the melt resistivity became lower and the color tone was excellent. Compared with Example 7 using ethyl diethyl phosphatidyl acetate as the phosphorus compound, Examples 1 and 5 using trialkyl phosphate (the alkyl group has a carbon number of 2 to 4) have excellent color tone. Compared with Example 5 using tripropyl phosphate, in Example 1 using triethyl phosphate, the melt resistivity became lower.

The polyester composition for master batch of Comparative Example 1 has a relatively low content of phosphorus compounds (the ratio of (m+k/2)/p is large), and therefore has a poorer color tone than Example 1 with the same amount of magnesium. The obtained film has poor heat resistance. In Comparative Example 2, since the content of the phosphorus compound is relatively large (the ratio of (m+k/2)/p is small), it can be said that the melt resistivity is high and the film forming property is poor. In Comparative Example 3, since the total of the amount of magnesium and the amount of alkali metal is relatively large (the ratio of (m+k/2)/p is large), the color tone is poor. In Comparative Example 4, due to the high content of the potassium compound, the color tone was inferior compared with Example 1, and the heat resistance of the obtained film was inferior. In Comparative Example 5, the use of trimethyl phosphate as the phosphorus compound can be said to have high melting resistivity and poor film forming properties. In Comparative Example 6, since the amount of lubricant used as the master batch was small, a large amount of the master batch was added to the film, so the color tone of the film was poor. In Comparative Example 7, since the amount of lubricant used as the master batch was large, the addition amount of the master batch was small, and the melt resistivity as the film was low, and the film forming property was poor. In addition, since a large amount of lubricant is added during the polymerization of the masterbatch, the number of coarse defects is large.

(Industrial availability)

The polyester composition for master batch of the present invention has sufficiently low melting resistance With less foreign matter, excellent color tone and thermal stability, it is possible to produce the following polyester film by mixing it with the polyester used as the film material. The polyester film has improved film-forming properties and is given the best It has excellent sliding properties and excellent quality. Therefore, the film using the polyester composition for the master batch of the present invention can be used in a wide range of applications such as antistatic films, easily adhesive films, cards, dummy cans, agriculture, building materials, For cosmetic materials, wallpaper, OHP (overhead projector) film, printing, inkjet recording, sublimation transfer recording, laser beam printer recording, electronic photo recording, thermal transfer For printing and recording, for thermal transfer recording, for printed circuit board wiring, for membrane switches, near-infrared absorbing films for plasma displays, transparent conductive films for touch panels or electroluminescence, for masking films, for photo plate making, X-ray film, photo negative film, retardation film, polarizing film, polarizing film protection (Tri-Acetyl Cellulose), deflection plate or phase difference plate inspection protective film and / Or for isolation film, photosensitive resin film, field of vision expansion film, diffuser sheet, reflective film, anti-reflection film, UV protection, back polishing tape, etc.

Claims (6)

A polyester composition for master batches, comprising polyester, magnesium compounds, alkali metal compounds, phosphorus compounds, and lubricants; the aforementioned polyester has dicarboxylic acid components and glycol components as constituent components; the aforementioned phosphorus compounds are selected from phosphoric acid Trialkyl ester and the alkyl group of the alkyl ester is at least one of the group consisting of a phosphorus compound having an alkyl group of 2 to 4 carbon atoms and ethyl diethyl phosphatidyl acetate; and the aforementioned master batch is used The polyester composition satisfies the following (1) to (4): (1) The polyester composition contains 400 ppm to 2,700 ppm (but not including 400 ppm) of magnesium atoms, 40 ppm to 270 ppm of alkali metal atoms, and phosphorus atoms in terms of mass. 200ppm to 1,700ppm: (2) The polyester composition contains a lubricant with an average particle size of 0.5μm to 3.0μm, 7,000ppm to 20,000ppm: (3) Compared to the dicarboxylic acid component constituting the polyester, the magnesium atom When the amount is set to m (mol%), the amount of alkali metal atoms is set to k (mol%), and the amount of phosphorus atoms is set to p (mol%), the formula I is satisfied: 2≦(m+k/2)/p ≦3.5 (Formula I); (4) The melting resistivity ρi satisfies 0.005×10 ⁸ Ω. cm to 0.05×10 ⁸ Ω. cm. The polyester composition for a master batch according to claim 1, wherein the alkali metal is potassium. The polyester composition for a master batch as described in claim 1 or 2, wherein the phosphorus compound is a phosphorus compound having a trialkyl phosphate and the alkyl group of the alkyl ester is an alkyl group having 2 to 4 carbon atoms. The polyester composition for master batches according to claim 1 or 2, wherein the phosphorus compound is triethyl phosphate. A polyester composition for a film, comprising the polyester composition for a master batch as described in any one of claims 1 to 4. A polyester film composed of the polyester composition for a film as described in claim 5.

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