JPH061908A - Antiblocking Agent Dispersion and Saturated Polyester Composition Comprising the Dispersion - Google Patents

Abstract

(57) [Summary] [Structure] Calcium carbonate having 0.01 to 5 mg of fatty acid or its derivative adsorbed per 1 m ^{2 of} calcium carbonate surface measured by nitrogen adsorption method (BET method) and 1 m of calcium carbonate surface. 0.01 to 5 mg of α, β monoethylenically unsaturated carboxylic acid polymer or copolymer per ² alkali metal salt, ammonium salt, amine salt, and α, β
It is selected from the group consisting of an alkali metal salt, an ammonium salt, and an amine salt of a copolymer of a monoethylenically unsaturated carboxylic acid and the α, β monoethylenically unsaturated carboxylic acid and a monomer having a polymerizable property. A dispersion of an antiblocking agent, which comprises at least one kind and glycol. [Effect] It has excellent dispersibility and dispersion stability in glycol, has an excellent anti-blocking effect on polyester, and imparts good physical properties such as surface smoothness, running property, abrasion resistance, and transparency. .

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a dispersion of an antiblocking agent comprising calcium carbonate, and a saturated polyester composition prepared using the dispersion of the antiblocking agent. It has excellent dispersibility in glycol, which is the raw material of the composition, and dispersion stability, and also has excellent ability to prevent blocking of a saturated polyester composition, such as a polyester film, good running properties, abrasion resistance, and transparency. An object of the present invention is to provide a dispersion of an antiblocking agent, which can impart good physical properties such as properties to a polyester composition, and a saturated polyester composition prepared using the antiblocking agent.

[0002]

2. Description of the Related Art Saturated polyesters produced industrially today, especially polyethylene terephthalate (hereinafter referred to as P
Abbreviated as ET. ) Has excellent physical and chemical properties, and is widely used as fibers, films, and other molded articles. For example, in the film field, it is used for magnetic tapes such as audio tapes and video tapes, for capacitors, for photography, for packaging, and for OHP.

In a polyester film, its slipperiness and abrasion resistance are major factors that affect the workability of the film manufacturing process and the processing process in each application, and further the quality of the product. When these slipperiness and abrasion resistance are insufficient, for example, when the magnetic layer is applied to the polyester film surface and used as a magnetic tape, the friction between the coating roll and the film surface during the application of the magnetic layer is severe, and This causes severe abrasion of the film surface, and in extreme cases, wrinkles, scratches, etc. occur on the film surface. In addition, even after slitting the film after coating the magnetic layer and processing it into audio, video, computer tape, etc., many guide parts, playback heads, etc. when pulling out from the reel or cassette, winding up and other operations Wear occurs between the and
As a result of generation of distortion and further deposition of white powdery substances due to abrasion of the surface of the polyester film, etc., this often becomes a major cause of loss of magnetic recording signals, that is, dropout.

Conventionally, as a method for lowering the friction coefficient of polyester, many methods have been proposed in which fine particles are contained in the polyester to give fine and appropriate irregularities to the surface of the molded article to improve the surface smoothness of the molded article. Has been
The affinity between the fine particles and polyester was not sufficient, and neither the transparency of the film nor the abrasion resistance was satisfactory. To further explain this method, as means for improving the surface characteristics of polyester, conventionally, a method of precipitating a part or all of a catalyst used during polyester synthesis in a reaction step (internal particle precipitation method), calcium carbonate, dioxide Many methods of adding fine particles such as silicon during or after the polymerization (external particle addition method) have been proposed. The particles forming the irregularities on the surface of these polyester films generally have a greater effect of improving the slipperiness as their size increases,
In precision applications such as magnetic tapes, especially for video, the large particles themselves can cause defects such as dropouts, so the surface irregularities of the film must be as fine as possible. At present, there is a demand for satisfying the characteristics at the same time.

However, the internal particle precipitation method of (1) has a good affinity with polyester to some extent because the particles are metal salts of the polyester component, but on the other hand, it is a method of forming particles during the reaction. It is difficult to control the amount of particles and the particle size and prevent the formation of coarse particles. On the other hand, if the amount of addition of the particle size and the like are appropriately selected and fine particles obtained by removing coarse particles by classification etc. are added, the method becomes excellent in terms of slipperiness. However, since the affinity between the inorganic fine particles and the polyester, which is the organic component, is not sufficient, peeling occurs at the boundary between the particles and the polyester during stretching, and voids are generated. When the voids are present in the polyester, the particles are easily detached from the polyester film due to damage to the polyester film due to contact between the polyester film or the polyester film and other substrate, and for example, in the magnetic tape film as described above. This may cause white powder and dropout.
Also, since there are large voids around the particles, the transparency of the polyester film is impaired. Therefore, the lack of affinity between the inorganic particles and polyester is a problem to be solved in terms of abrasion resistance and transparency.

For improving the affinity between the inorganic particles and the polyester, for example, surface treatment by a coupling reaction between a silane compound or a titanate compound and the inorganic particles has been proposed, but the treatment process is complicated,
There were various problems such as the effect being less than expected. Also,
In order to improve the dispersibility of these inorganic compounds in the polyester, a glycol slurry of fine particles of the inorganic compound is prepared and added to the production process of the polyester. It can not be said that the stability is good, and when the glycol in which the inorganic compound is suspended is stored for a long period of time, the inorganic compound precipitates and precipitates, a hard hard cake is formed, and redispersion becomes difficult. There is also a drawback that the inorganic compound is aggregated during the production of the inside or the polyester. The presence of agglomerated coarse particles in the polymer causes yarn breakage during spinning, and causes coarse protrusions, fish eyes, etc. in the film. Especially when used in magnetic tape films, dropout and S / The development of fine particles that do not generate agglomerated coarse particles is awaited because it causes a decrease in N ratio.

Among the fine particles used for these polyesters, calcium carbonate is used in various fields as a filler for papermaking, paints, rubbers, plastics, etc., because limestone, which is a raw material thereof, is abundantly produced in Japan. ing. This calcium carbonate is generally roughly classified into two types, heavy calcium carbonate and precipitated calcium carbonate (synthetic calcium carbonate). These calcium carbonates are relatively low in hardness as compared with other fine particles used for polyester, and are easy to be made finer, so that they are often used favorably. This method is often adopted. A method in which calcite-type precipitated calcium carbonate having both specific dispersibility and specific particle size and having been surface-treated with a specific surface-treating agent is dispersed in glycol, and wet-pulverized under specific conditions before use. (JP-A-64-424
0). A vaterite-type calcium carbonate surface-treated with a specific surface-treating agent (JP-A-4-31319) and a method using a vaterite-type calcium carbonate prepared by a specific method (JP-A-4-31456).

However, when the above-mentioned calcium carbonate is used for polyester, it has the following drawbacks. In the case of using a calcite-type precipitated calcium carbonate having a dispersibility of a specific particle size or a specific dispersity as a raw material and performing wet pulverization within a specific pulverization condition range, coarse particles, ultrafine particles, etc. Does not contain a large amount of unnecessary particles,
It is possible to obtain a sharp calcium carbonate in which the particle size of each individual particle is relatively uniform. Therefore, although the calcium carbonate prepared by this method has sufficient physical properties as an anti-blocking agent for polyester films for standard grade video tapes, the anti-blocking agent prepared by this method can be stored for a long time. If so, there is a tendency that some fine particles agglomerate, when a large amount of a surface treatment agent for preventing this partial agglomeration is used, fisheyes in the film increase, and the film physical properties tend to decrease, Not preferable.

In the case of, the vaterite type calcium carbonate prepared by this method has very good dispersibility in glycol,
Since no media such as glass beads used in a wet crusher is mixed and the affinity with polyester is better than that of conventionally used calcium carbonate, it is suitable for high-grade video tapes currently on the market. It is suitable as an antiblocking agent for polyester films, and its practical use is being studied in various fields.

However, since vaterite-type calcium carbonate is originally inferior in heat resistance as compared with calcite-type calcium carbonate and aragonite-type calcium carbonate, which are other crystal forms of calcium carbonate, it is partially contained during polyester production. Aggregation is likely to occur, and in order to maintain good dispersibility in glycol of vaterite-type calcium carbonate prepared by this method in the polyester composition, a special polymerization technique or dispersion technique is required. Point improvements were requested. Also, in recent years, some high-definition broadcasts have started, and in response to this, the performance of electric and electronic devices is becoming higher and higher, and the traveling speed such as film rewinding is further increased. The abrasion damage of the tape on the pin portion is likely to be large, and the resulting white powder etc. may disturb the image or significantly reduce the dubbing property. Physical properties, in particular, a polyester film having abrasion resistance during high-speed running is required from all directions, and compared with polyester films for high-grade video tapes that are currently on the market, several times better running property, transparency, There is a demand for a polyester film having surface smoothness and the like.

[0011]

In view of the above situation, the present invention has excellent dispersibility and dispersion stability in a glycol which is a raw material of a saturated polyester composition, and a saturated polyester composition such as a polyester film. A dispersion of an anti-blocking agent, which has an excellent ability to prevent blocking, and can impart good physical properties such as good surface smoothness, running property, abrasion resistance, and transparency to a polyester composition, and the anti-blocking property. The present invention provides a saturated polyester composition having good physical properties prepared by using the agent.

[0012]

As a result of intensive studies to solve the above problems, the present inventors have found that calcium carbonate having a specific amount of a fatty acid or a derivative thereof adsorbed thereon and a specific polymer and / or copolymer. A specific amount of dispersant consisting of, and a glycol dispersion of calcium carbonate consisting of glycol is a very good antiblocking agent that achieves the intended purpose, and a fatty acid or its derivative alone or the above-mentioned specific polymer and It was found that it is an anti-blocking agent that cannot be obtained at all by a glycol dispersion of calcium carbonate in which a specific amount of a dispersant composed of a copolymer is added to calcium carbonate alone, and the anti-blocking agent is added in a specific amount. The inventors have found that the prepared polyester composition has extremely good physical properties and completed the present invention.

That is, the first aspect of the present invention is the nitrogen adsorption method (BE
Calcium carbonate to which 0.01 to 5 mg of fatty acid or its derivative was adsorbed per 1 m ^{2 of} calcium carbonate surface measured by T method), and 0.01 to 5 mg of α, β monoethylene per 1 m ^{2 of} calcium carbonate surface Of an unsaturated metal carboxylic acid polymer or copolymer, an alkali metal salt, an ammonium salt, an amine salt, and an α, β monoethylenically unsaturated carboxylic acid, and the α, β monoethylenically unsaturated carboxylic acid An alkali metal salt of a copolymer with a monomer having
An ammonium salt, at least one selected from the group consisting of amine salts, and a dispersion of an anti-blocking agent, which comprises a glycol,

The second aspect of the present invention is the nitrogen adsorption method (BET method).
Per m ^{2 of} calcium carbonate surface measured by
Calcium carbonate adsorbed with 01 to 5 mg of fatty acid or its derivative and 0.01 per 1 m ^{2 of} calcium carbonate surface
To 5 mg of an α, β monoethylenically unsaturated carboxylic acid polymer or copolymer, an alkali metal salt, an ammonium salt, an amine salt, and an α, β monoethylenically unsaturated carboxylic acid, and the α, β monoethylene Of an antiblocking agent consisting of at least one selected from the group consisting of alkali metal salts, ammonium salts and amine salts of a copolymer of a polymerizable unsaturated carboxylic acid and a polymerizable monomer, and glycol. The saturated polyester composition is characterized by containing 0.005 wt% to 10 parts by weight with respect to 100 parts by weight of polyester as calcium carbonate.

Regarding the calcium carbonate used in the present invention, there are no particular restrictions on the production method, crystal form, etc., but as blocking inhibitors for polyester films used in high-grade industrial applications, the following (a) to (g) can be used. Spherical, rugby ball-shaped ellipsoidal spheres, goose-shaped ellipsoidal spheres, and vaterite-type calcium carbonate having a plate-like morphology, which satisfy both requirements of (1), are preferable. (A) 0.05 μm ≦ DS1 ≦ 2.0 μm (b) 0.04 μm ≦ DS2 ≦ 2.0 μm (c) 1.0 ≦ DS1 / DS2 ≦ 20 (d) DP3 / DS1 ≦ 1.25 (e) 1 0.0 ≦ DP2 / DP4 ≦ 2.5 (f) 1.0 ≦ DP1 / DP5 ≦ 4.0 (g) (DP2-DP4) /DP3≦1.0 However, DS1: by scanning electron microscope (SEM) Major particle average particle diameter (μm) of primary particles examined DS2: Minor particle average particle diameter (μm) of primary particles examined by the above-mentioned microscope DP1: Light transmission type particle size distribution measuring instrument (Shimadzu SA-
In the particle size distribution measured using CP3), the particle size when the cumulative total weight is 10% calculated from the large particle size side (μ
m) DP2: in the particle size distribution measured using the above measuring machine, the particle size at the time of cumulative weight of 25% calculated from the large particle size side (μm) DP3: in the particle size distribution measured using the above measuring machine, Particle diameter at the time of cumulative weight 50% calculated from the particle diameter side (μm) DP4: Particle diameter at the time of cumulative weight 75% calculated from the large particle diameter side in the particle size distribution measured using the above measuring device (μm) ) DP5: Particle size (μm) at the time of cumulative weight of 90% calculated from the large particle size side in the particle size distribution measured using the above measuring machine.

As a method for producing vaterite-type calcium carbonate which is preferably used in the present invention and has good dispersibility, there are disclosed in JP-A-4-31315, JP-A-4-31316, and Japanese Patent Application No. 3-313.
81532, Japanese Patent Application No. 3-348090, Japanese Patent Application No. 4-12
A method such as 1245 can be exemplified.

Examples of the fatty acid or its derivative used in the present invention include fatty acids, fatty acid metal soaps, fatty acid amides, fatty acid esters, higher alcohols, etc. One or more of these fatty acids or their derivatives may be used.

The calcium carbonate used in the present invention has fine irregularities on its surface, and in particular, vaterite-type calcium carbonate generally has many fine pores with a diameter of less than 200 angstroms on the surface of the calcium carbonate. In order to sufficiently adsorb a fatty acid or its derivative inside the irregularities or pores of the particle surface, among the above fatty acids or its derivatives, caprylic acid, capric acid, lauric acid, palmitic acid, stearic acid, hydroxyphenylstearic acid, It is preferable to use a carboxylic acid of a fatty acid derivative represented by oleic acid and the like, and a fatty acid derivative represented by a derivative of an alkylamino acid such as oleoyl sarcosine and lauroyl sarcosine, and more preferably a fatty acid having 6 to 30 carbon atoms, It is preferable to use a carboxylic acid which is a fatty acid derivative.

The method for adsorbing these fatty acids or their derivatives on the surface of calcium carbonate may be either a wet method or a dry method, and there is no particular limitation on the method, but water that becomes a solvent for the fatty acids or their derivatives used, Alternatively, a wet method in which the fatty acid or its derivative is added to a dispersion liquid obtained by dispersing calcium carbonate in an organic solvent such as alcohol, acetone, xylene, hexane, petroleum ether or the like is preferable. The amount of fatty acid or its derivative adsorbed on the surface of calcium carbonate is suitably 0.01 to 5 mg per 1 m ^{2 of the} surface of calcium carbonate measured by the nitrogen adsorption method (BET method), preferably 0.05 to 4 mg, More preferably 0.1
~ 3 mg.

Polymers or copolymers that can be used as the dispersant in the present invention include α, β monoethylenically unsaturated carboxylic acids represented by acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid and the like. Polymers or copolymers, which are polymerizable with these alkali metal salts, ammonium salts, amine salts, and the α, β monoethylenically unsaturated carboxylic acid, and the α, β monoethylenically unsaturated carboxylic acid. Alkali metal salt of copolymer with monomer,
Any ammonium salt or amine salt may be used, and one or more of these may be used. The molecular weight of the alkali metal, ammonium or amine salt of the polymer or copolymer is 500 to 5
0000 is preferable, and the degree of neutralization with an alkali metal, ammonium, or amine is preferably such that 5% or more of all carboxyl groups in the polymer or copolymer are neutralized with the above substance, and more preferably 20% or more. .

In the above-mentioned copolymer, as the monomer polymerizable with α, β monoethylenically unsaturated carboxylic acid, the following monomers (A) to (SA) can be exemplified as preferable ones. (A) Acrylic acid alkyl ester and methacrylic acid alkyl ester (A) Alkoxy group-containing acrylate and methacrylate (C) Cyclohexyl group-containing acrylate and methacrylate (D) α, β monoethylenically unsaturated hydroxy ester (E) Polyalkylene Glycol Monoacrylate and monomethacrylate (F) Vinyl ester (K) Vinyl aromatic (K) Unsaturated nitrile (K) Unsaturated dicarboxylic acid ester (Co) Vinyl ether (SA) Conjugated diene, chain olefin, cyclic olefin The copolymerization ratio of the α, β monoethylenically unsaturated carboxylic acid in the copolymer of the monomer and the α, β monoethylenically unsaturated carboxylic acid is preferably 50% by weight or more, 70
It is more preferably at least wt%.

Alkali metal salts, ammonium salts, amine salts of polymers or copolymers of α, β monoethylenically unsaturated carboxylic acids, or α, β monoethylenically unsaturated carboxylic acids, and the α, β monoethylene The amount of at least one selected from the group consisting of alkali metal salts, ammonium salts, and amine salts of a copolymer of a polymerizable unsaturated carboxylic acid and a monomer having polymerizability is the nitrogen adsorption method (BET
0.01-5 mg per 1 m ^{2 of the} surface of calcium carbonate measured by the method) is suitable, and preferably 0.05-4.
mg, more preferably 0.1 to 3 mg.

The anti-blocking agent dispersion comprising calcium carbonate of the present invention can be prepared only by using the above-mentioned specific amount of the fatty acid or its derivative and a specific amount of the dispersing agent comprising the polymer or copolymer of the specific composition. The object of the present invention can be achieved. That is, when a fatty acid or a derivative thereof is used alone, even if the vaterite-type calcium carbonate having good dispersibility (a) to (g) described above is used as the calcium carbonate, a glycol dispersion of the obtained calcium carbonate is obtained. The state of dispersion of calcium carbonate in the body becomes extremely poor, and as a result, precipitation occurs in glycol, which cannot be a good antiblocking agent for polyester compositions such as polyester films. Further, when a dispersant consisting of a polymer or copolymer of the above specific composition is used alone, the viscosity of the resulting glycol dispersion of calcium carbonate and the dispersion state of calcium carbonate are relatively good, but fatty acids Or, as compared with the case where a derivative thereof is used in combination, the viscosity of the glycol dispersion prepared becomes unfavorably high, the viscosity stability over time, the dispersibility in glycol is poor, and when used as an antiblocking agent for the polyester film, This results in poor wear resistance.

Further, even if the dispersant comprising the polymer or copolymer having the above specific composition is used in the amount specified in the present invention, the amount of the fatty acid or its derivative per m ^{2 on the} surface of calcium carbonate is less than 0.01 mg. In the case of, the effect of adding a fatty acid or its derivative can hardly be confirmed, which is not preferable, and when it exceeds 5 mg, calcium carbonate in the obtained glycol tends to aggregate, which is not preferable as an antiblocking agent. On the contrary, even if the fatty acid or the derivative thereof is used in the amount specified in the present invention, the amount of the dispersant comprising the polymer or copolymer having the above-mentioned specific composition per 1 m ^{2 on the} surface of calcium carbonate is 0.
If it is less than 01 mg, it is not preferable because the aggregate of calcium carbonate in the obtained glycol cannot be dispersed.
If the amount exceeds 5 mg, not only the calcium carbonate in the resulting glycol tends to agglomerate slightly, but when it is used as an antiblocking agent for polyester films, the fish eye caused by the polymer or copolymer is a film. It occurs inside and is not preferable.

The following is an example of the method for preparing the dispersion of the antiblocking agent of the present invention. By a conventional method, a calcium carbonate suspension is prepared by a carbon dioxide method in an aqueous system and / or an alcohol system, and the solvent of the obtained calcium carbonate suspension is changed to water and / or an organic solvent, if necessary. A specific amount of fatty acid or its derivative is added to the obtained calcium carbonate solvent suspension, and if necessary, heated and stirred to adsorb the fatty acid or its derivative on the surface of calcium carbonate. The adsorption referred to in the present invention includes both physical adsorption and chemical adsorption due to a chemical reaction between the surface of calcium carbonate and a fatty acid or its derivative. The solvent suspension of calcium carbonate having the fatty acid or its derivative adsorbed on the surface prepared as described above is concentrated and dried to obtain calcium carbonate powder. The calcium carbonate powder is put into a glycol such as ethylene glycol, a dispersant composed of the above-mentioned polymer or copolymer is added, and the glycol suspension of the calcium carbonate is vigorously stirred to give A dispersion of the inventive calcium carbonate antiblocking agent is prepared.

In the present invention, in order to make the dispersion state of calcium carbonate in glycol extremely good,
In the above method, the solvent suspension of calcium carbonate is not concentrated and dried, and a glycol such as ethylene glycol is added to the solvent suspension of calcium carbonate, and further the above-mentioned polymer or copolymer is used. After adding the dispersant,
It is preferable to concentrate under reduced pressure to prepare a dispersion of the anti-blocking agent of calcium carbonate of the present invention.

Next, the saturated polyester composition of the present invention will be described in detail. The saturated polyester composition of the present invention contains 0.005 to 10 parts by weight, preferably 0.05 to 10 parts by weight of the dispersion of the anti-blocking agent comprising calcium carbonate of the present invention as calcium carbonate, based on 100 parts by weight of the saturated polyester. It is prepared by blending 5 parts by weight, more preferably 0.1 to 3 parts by weight. If the blending amount is less than 0.005% by weight, the effect of improving slipperiness and abrasion resistance is insufficient. On the other hand, if the blending amount exceeds 10% by weight, the film surface is excessively roughened in the field of film and the like. This causes problems such as deterioration in sharpness.

The saturated polyester in the present invention is a polyester containing an aromatic dicarboxylic acid as a main acid component and a fatty acid glycol as a main glycol component.
Such polyesters are substantially linear and have film forming properties, especially film forming properties by melt molding. Examples of the aromatic dicarboxylic acid include terephthalic acid, naphthalene dicarboxylic acid, isophthalic acid, diphenylethane dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl ketone dicarboxylic acid, and anthracene dicarboxylic acid. They can be used alone or in combination of two or more. Examples of the fatty acid glycol include polymethylene glycol having 2 to 10 carbon atoms such as ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol and decamethylene glycol, and alicyclic diols such as cyclohexadimethanol. Etc. can be mentioned, and these are used individually or in combination of 2 or more types.

In the present invention, as the saturated polyester, for example, one having alkylene terephthalate and / or alkylene naphthalate as a main constituent is preferably used. Among such polyesters, not only polyethylene terephthalate and polyethylene-2,6-naphthalate but also, for example, 80 mol% or more of all dicarboxylic acid components are terephthalic acid and / or 2,6-naphthalene dicarboxylic acid, and all glycol components are used. Of 80
Copolymers in which more than mol% is ethylene glycol are preferred. 20 mol% or less of the total acid component can be the above-mentioned aromatic dicarboxylic acids other than terephthalic acid and / or naphthalenedicarboxylic acid, for example adipic acid,
It can be a fatty acid dicarboxylic acid such as sebacic acid; an alicyclic dicarboxylic acid such as cyclohexane-1,4-dicarboxylic acid. Also up to 20 mol% of the total glycol component can be the above glycols other than ethylene glycol, or for example hydroquinone, 2,
Aromatic diols such as 2-bis (4-hydroxyphenyl) propane; fatty acid diols containing aromatics such as 1,4-dihydroxymethylbenzene, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol ( It can also be a polyoxyalkylene glycol).

In the polyester of the present invention, a component derived from an oxycarboxylic acid such as an aromatic oxyacid such as hydroxybenzoic acid; a fatty acid oxyacid such as ω-hydroxycapric acid, a dicarboxylic acid component and an oxycarboxylic acid. Those containing 20% by mole or less of the total amount of components which are copolymerized or bonded are also included. Furthermore, in the polyester of the present invention, a tricarboxylic or polyfunctional polycarboxylic acid or polyhydroxy compound such as trimellitic acid or penta is used in an amount in a substantially linear range, for example, an amount of 2 mol% or less based on the total acid content. A copolymer of erythritol and the like is also included. Furthermore, in the polyester in the present invention,
For example, additives such as pigments, dyes, ultraviolet absorbers, light stabilizers, antioxidants, light-shielding agents (for example, carbon black, titanium dioxide, etc.) can be contained as necessary. The saturated polyester composition of the present invention is a glycol dispersion of an anti-blocking agent comprising the calcium carbonate of the present invention, together with glycol as a raw material of polyester,
This can be achieved by the method for producing a saturated polyester added to the reaction system. The timing of addition to the reaction system is arbitrary, but it is preferably from before the transesterification reaction to before the start of reduced pressure in the polycondensation reaction. In addition to the production method of adding to such a reaction system, it may be directly kneaded into the molten polyester.

[0031]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Preparation Method of Calcium Carbonate Used in Examples and Comparative Examples Granular quicklime (reagent special grade) having an activity of 82 was crushed with a dry crusher (Coloplex, manufactured by Alpine Co.), and the obtained quicklime powder was added to methanol. After throwing in and removing coarse particles using a 200-mesh sieve, a methanol suspension of quick lime having a solid content concentration of 20% as quick lime was prepared. The methanol suspension is wet-milled (Dyno Mill PILOT
Type, manufactured by WAB Co., Ltd.) to prepare a methanol suspension dispersion of quicklime. Methanol was added to this methanol suspension dispersion of quicklime, diluted so that the quicklime concentration became 3.90% by weight, and 6.4 times equivalent mol of water was added to quicklime to add methanol and quicklime. A mixed system of water and water was prepared. After adjusting the mixed system containing 200 g of quick lime to 43 ° C., carbon dioxide gas was introduced into the mixed system under stirring conditions to start the carbonation reaction. afterwards,
When the pH in the system reached 7.0, the rate of carbon dioxide conduction was stopped. After that, the carbonation reaction is advanced by the carbon dioxide gas remaining in the carbonation reaction system, and a small amount of carbon dioxide gas is intermittently conducted into the system, and after the electric conductivity in the carbonation system reaches the maximum point, 30 After a minute, the pH of the system was made to reach 6.8.
After that, the pH in the system started to rise slightly, so a very small amount of carbon dioxide was intermittently conducted into the system, and the pH in the system was adjusted to 6.8 ± 0.2.
For 15 minutes to obtain a rugby ball-shaped elliptic sphere vaterite type calcium carbonate methanol-water suspension.
The specific surface area of this vaterite-type calcium carbonate by the nitrogen adsorption method was measured by the surface area measuring device SA-1 manufactured by Shibata Scientific Instruments
As a result of measurement using 000, it was 22.5 m ² / g. A scanning electron microscope and a particle size distribution measuring instrument (SA-CP3 manufactured by Shimadzu Corporation) of this vaterite type calcium carbonate.
Table 1 shows the physical properties measured by using the (type).

Example 1 A rugby ball-shaped ellipsoidal sphere vaterite type calcium carbonate in a methanol-water suspension prepared by the above-mentioned method was used.
After heating to 5 ° C., 0.2 mg of stearic acid as a fatty acid was added per 1 m ^{2 of} surface area of the vaterite-type calcium carbonate particles, and the mixture was stirred for 10 minutes, after which ethylene glycol containing sodium polyacrylate was added to the vaterite-type carbonic acid. A methanol-ethylene glycol-water suspension of calcium was prepared. The addition amount of sodium polyacrylate is 0.5 mg per 1 m ^{2 of} surface area of vaterite-type calcium carbonate particles.
And The suspension was concentrated under reduced pressure using an evaporator to remove methanol and water to obtain an ethylene glycol dispersion of an antiblocking agent having a calcium carbonate solid content concentration of 30% by weight. Table 2 shows the polymers or copolymers, fatty acids or derivatives thereof used in this example, and their amounts used. The ethylene glycol dispersion of the anti-blocking agent obtained in this example was diluted with ethylene glycol to prepare 200 cc of ethylene glycol dispersion having a calcium carbonate solid content concentration of 5% by weight. The dispersion left for 7 days was subjected to pressure filtration under a condition of ² kg / cm ² using a 3.0 μm membrane filter, and the filter passing amount 60 seconds after the start of filtration was measured. The measurement results are shown in Table 3. From the results in Table 3, the ethylene glycol dispersion of the antiblocking agent prepared in this example was
It can be confirmed that it has good dispersibility and dispersion stability both immediately after preparation and 7 days after preparation.

Examples 2-9 Polymers or copolymers, fatty acids or derivatives thereof, except that the amount of each used was changed as shown in Table 2, except that calcium carbonate was added in the same manner as in Example 1. Solid content is 30
An ethylene glycol dispersion of wt% antiblock was obtained. In addition, the amount of the dispersion obtained in this example passing through the filter was measured by the same method as in Example 1. The measurement results are shown in Table 3. From the results of Table 3, it can be confirmed that the ethylene glycol dispersion of the anti-blocking agent prepared in this example has good dispersibility and dispersion stability immediately after the preparation and 7 days after the preparation.

Comparative Examples 1 to 6 The solid content concentration of calcium carbonate was the same as in Example 1 except that the amounts of the polymer or copolymer and the fatty acid used were changed as shown in Table 2. To obtain an ethylene glycol dispersion having an antiblocking agent of 30% by weight. In addition, the amount of the dispersion obtained in this Comparative Example passing through the filter was measured by the same method as in Example 1. Table 3 shows the measurement results
Shown in. From the results in Table 3, the ethylene glycol dispersions of the antiblocking agents prepared in Comparative Examples 1, 3, and 6 were
Immediately after the preparation and 7 days after the preparation, it was confirmed that the dispersibility was poor, and the ethylene glycol dispersions of the anti-blocking agents prepared in Comparative Examples 2, 4, and 5 had poor filter passing properties after 7 days of the preparation. It can be confirmed that the dispersion stability is inferior.

Examples 10 to 18 and Comparative Examples 7 to 12 Polyethylene was prepared by adding the ethylene glycol dispersion of the calcium carbonate antiblocking agent obtained in Examples 1 to 9 and Comparative Examples 1 to 6 before the polyesterification reaction. Reaction, and an intrinsic viscosity of 0.4% by weight as calcium carbonate (orthochlorophenol, 35 ° C) 0.6
A polyester composition consisting of 5 dl / g polyethylene terephthalate was prepared. The polyethylene terephthalate was dried at 160 ° C and then melt extruded at 290 ° C.
An unstretched film was obtained by rapid cooling and solidification on a casting drum kept at 0 ° C. Subsequently, the unstretched film was preheated to 70 ° C. with a heating roller and then stretched 4.5 times in the machine direction while being heated with an infrared heater. Then 9
It was stretched 5.5 times in the transverse direction at a temperature of 0 ° C. and then heat treated at 200 ° C. to obtain a biaxially oriented film having a thickness of 10 μm. The quality of the polyester films obtained in the examples and comparative examples was evaluated by the method shown below, and the results are shown in Table 4.
Shown in. From the results in Table 4, the polyester film obtained from the polyester composition of this example has no coarse projections, good slipperiness, and high-speed abrasion compared with the film obtained from the polyester composition of Comparative Example. It can be confirmed that the property (high-speed wear resistance) is remarkably excellent.

Film physical properties I: film surface roughness (R
a) It is a value defined by JIS-B0601 as the center line average roughness (Ra), and in the present invention, it is measured using a stylus surface roughness meter (SURFCORDER SF -30C) of Kosaka Laboratory Ltd. The measurement conditions are as follows. (A) Stylus tip radius: 2 μm (b) Measuring pressure: 30 mg (c) Cut-off: 0.25 mm (d) Measuring length: 0.5 mm (e) Repeatedly measuring 5 times for the same sample, the largest value Except one, the average value of the remaining four data is shown.

Film Physical Properties II: Number of Coarse Protrusions Aluminum was vapor-deposited on the surface of the film and measured using a two-beam interference microscope. The measurement wavelength is 0.52 μm and 3
The number of interference fringes of the following or more is converted and shown per 10 cm ² .

Film Physical Properties III: Sliding Property The static friction coefficient of the film was measured by the ASTM-1894B method.

Physical properties of film IV: High-speed shaving property A film is slit into a tape shape of 10 inches and a single blade is vertically pressed against the film, and the film is run for 2000 m while being pushed 0.5 mm (running tension: 1000 g, running speed 200 m / Minutes). At this time, the amount of white powder of the scraped material on the surface of the film attached to the tip of the single blade was visually observed and measured in the following 5 steps. <5-level judgment> ⊚: There is almost no stain on the cutting edge. ◯: A small amount of white powder adheres to the tip of the cutting edge. Δ: White powder adheres to the tip of the blade and accumulates. X: White powder accumulated on the tip of the blade adheres to the entire surface of the blade. XX: White powder stains are accumulated on the entire surface of the blade.

Film Physical Properties V: Transparency The film turbidity was measured according to JIS K6741. The criteria are ◯ for good ones, △ for slightly inferior ones, and × for bad ones.
Display with.

[0041]

[Table 1]

[0042]

[Table 2]

The amount of the polymer, copolymer, fatty acid or derivative thereof used is expressed in mg per 1 m ^{2 of} calcium carbonate surface area. Copolymer A: acrylic acid and maleic acid weight ratio 80: 2
Sodium salt of 0 copolymer Copolymer B: A copolymer of acrylic acid and polyethylene glycol monomethacrylate in a weight ratio of 90:10, in which 95% of all carboxylic acids are neutralized with sodium.

[0044]

[Table 3]

[0045]

[Table 4]

[0046]

INDUSTRIAL APPLICABILITY As described above, the dispersion of the present invention has excellent dispersibility and dispersion stability in glycol, and has an excellent ability to prevent blocking of the polyester film,
Provided is a polyester composition which imparts good physical properties such as good surface smoothness, running property, abrasion resistance and transparency.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C08K 9/04 KKG 7242-4J

Claims (6)

[Claims] 1. A nitrogen adsorption method and a fatty acid or calcium carbonate having adsorbed the derivatives of 1 m ² per 0.01~5mg the measured calcium carbonate surface by (BET method), 1 m ² per 0 calcium carbonate surface. 01-5mg of α, β
Alkali metal salt, ammonium salt, amine salt of polymer or copolymer of monoethylenically unsaturated carboxylic acid, and α, β monoethylenically unsaturated carboxylic acid, and α, β monoethylenically unsaturated carboxylic acid A dispersion of an antiblocking agent, which comprises at least one selected from the group consisting of an alkali metal salt, an ammonium salt and an amine salt of a copolymer of a polymerizable monomer, and glycol. 2. Calcium carbonate is the following (a) to (g)
Spherical, rugby ball-shaped ellipsoidal sphere,
The dispersion according to claim 1, which is a vaterite-type calcium carbonate having a goose-like ellipsoidal sphere or a plate-like morphology. (A) 0.05 μm ≦ DS1 ≦ 2.0 μm (b) 0.04 μm ≦ DS2 ≦ 2.0 μm (c) 1.0 ≦ DS1 / DS2 ≦ 20 (d) DP3 / DS1 ≦ 1.25 (e) 1 0.0 ≦ DP2 / DP4 ≦ 2.5 (f) 1.0 ≦ DP1 / DP5 ≦ 4.0 (g) (DP2-DP4) /DP3≦1.0 However, DS1: by scanning electron microscope (SEM) Major particle average particle diameter (μm) of primary particles examined DS2: Minor particle average particle diameter (μm) of primary particles examined by the above-mentioned microscope DP1: Light transmission type particle size distribution measuring instrument (Shimadzu SA-
In the particle size distribution measured using CP3), the particle size when the cumulative total weight is 10% calculated from the large particle size side (μ
m) DP2: in the particle size distribution measured using the above measuring machine, the particle size at the time of cumulative weight of 25% calculated from the large particle size side (μm) DP3: in the particle size distribution measured using the above measuring machine, Particle diameter at the time of cumulative weight 50% calculated from the particle diameter side (μm) DP4: Particle diameter at the time of cumulative weight 75% calculated from the large particle diameter side in the particle size distribution measured using the above measuring device (μm) ) DP5: Particle size (μm) at the time of cumulative weight of 90% calculated from the large particle size side in the particle size distribution measured using the above measuring machine. 3. The dispersion according to claim 1, wherein the monomer polymerizable with the α, β monoethylenically unsaturated carboxylic acid is at least one selected from the following. (A) Acrylic acid alkyl ester and methacrylic acid alkyl ester (A) Alkoxy group-containing acrylate and methacrylate (C) Cyclohexyl group-containing acrylate and methacrylate (D) α, β monoethylenically unsaturated hydroxy ester (E) Polyalkylene Glycol Monoacrylate and monomethacrylate (F) Vinyl ester (K) Vinyl aromatic (K) Unsaturated nitrile (K) Unsaturated dicarboxylic acid ester (Co) Vinyl ether (SA) Conjugated diene, chain olefin, cyclic olefin. Wherein the nitrogen adsorption method and a fatty acid or calcium carbonate having adsorbed the derivatives of 1 m ² per 0.01~5mg the measured calcium carbonate surface by (BET method), 1 m ² per 0 calcium carbonate surface. 01-5mg of α, β
Alkali metal salt, ammonium salt, amine salt of polymer or copolymer of monoethylenically unsaturated carboxylic acid, and α, β monoethylenically unsaturated carboxylic acid, and α, β monoethylenically unsaturated carboxylic acid Polyester 100 using calcium carbonate as a dispersion of an antiblocking agent consisting of at least one selected from the group consisting of alkali metal salts, ammonium salts and amine salts of a copolymer of a polymerizable monomer, and glycol. 0 to parts by weight.
A saturated polyester composition comprising 005% by weight to 10 parts by weight. 5. Calcium carbonate is the following (a) to (g)
Spherical, rugby ball-shaped ellipsoidal sphere,
The composition according to claim 4, which is a vaterite-type calcium carbonate having a gob-like elliptical sphere or a plate-like form. (A) 0.05 μm ≦ DS1 ≦ 2.0 μm (b) 0.04 μm ≦ DS2 ≦ 2.0 μm (c) 1.0 ≦ DS1 / DS2 ≦ 20 (d) DP3 / DS1 ≦ 1.25 (e) 1 0.0 ≦ DP2 / DP4 ≦ 2.5 (f) 1.0 ≦ DP1 / DP5 ≦ 4.0 (g) (DP2-DP4) /DP3≦1.0 However, DS1: by scanning electron microscope (SEM) Major particle average particle diameter (μm) of primary particles examined DS2: Minor particle average particle diameter (μm) of primary particles examined by the above-mentioned microscope DP1: Light transmission type particle size distribution measuring instrument (Shimadzu SA-
In the particle size distribution measured using CP3), the particle size when the cumulative total weight is 10% calculated from the large particle size side (μ
m) DP2: in the particle size distribution measured using the above measuring machine, the particle size at the time of cumulative weight of 25% calculated from the large particle size side (μm) DP3: in the particle size distribution measured using the above measuring machine, Particle diameter at the time of cumulative weight 50% calculated from the particle diameter side (μm) DP4: Particle diameter at the time of cumulative weight 75% calculated from the large particle diameter side in the particle size distribution measured using the above measuring device (μm) ) DP5: Particle size (μm) at the time of cumulative weight of 90% calculated from the large particle size side in the particle size distribution measured using the above measuring machine. 6. The composition according to claim 4, wherein the monomer polymerizable with α, β monoethylenically unsaturated carboxylic acid is at least one selected from the following. (A) Acrylic acid alkyl ester and methacrylic acid alkyl ester (A) Alkoxy group-containing acrylate and methacrylate (C) Cyclohexyl group-containing acrylate and methacrylate (D) α, β monoethylenically unsaturated hydroxy ester (E) Polyalkylene Glycol Monoacrylate and monomethacrylate (F) Vinyl ester (K) Vinyl aromatic (K) Unsaturated nitrile (K) Unsaturated dicarboxylic acid ester (Co) Vinyl ether (SA) Conjugated diene, chain olefin, cyclic olefin.