JP3206223B2 - Polyester composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

This invention relates to polyester compositions. More specifically, it contains specific silicone particles,
The present invention relates to a polyester composition suitable for obtaining a film excellent in slipperiness and abrasion resistance, particularly, abrasion resistance of particles in a calendar treatment.

[0002]

2. Description of the Related Art In general, polyesters such as polyethylene terephthalate have excellent mechanical properties and chemical properties, and are widely used as molded articles such as films and fibers.

When these polyesters are processed into molded products and used, their slipperiness and abrasion resistance have a great influence on the manufacturing process, the workability in the processing steps in various applications, and the product quality.

In particular, when these properties are insufficient when used as a base film of a magnetic tape, shavings mainly composed of particles contained in the film are liable to be generated in various steps of magnetic tape production. As a result, coating omission occurs in the step of applying the magnetic layer, which causes a drop out of magnetic recording. In addition, the magnetic surface and the non-magnetic surface rub against each other during winding after the magnetic agent application / calendering process, causing scratches on the magnetic surface,
There is a disadvantage that image quality is deteriorated such as dropout when used as a product.

[0005] Among the various manufacturing processes, the calendering process performed for the purpose of smoothing the film surface after the application of the magnetic agent is performed by compressing the film between two rolls. This is a process in which shaving powder is particularly likely to be generated due to various stresses caused by the above.

Hitherto, many methods for improving the slipperiness of a film have been proposed in which inorganic particles such as titanium dioxide, calcium carbonate and silicon dioxide are contained in polyester. However, since these inorganic particles have low affinity for polyester, they easily fall off and become shavings when used in a film or fiber manufacturing process or as a product, causing the above-described problem.

As methods for improving the affinity between particles and polyester and preventing the particles from falling off, surface treatment of inorganic particles and use of organic particles have been proposed. Examples of the surface treatment of the inorganic particles include, for example, surface treatment with a polyacrylic acid-based polymer described in JP-A-63-128031 and JP-A-62-235.
No. 353, JP-A-63-234039, surface treatment with a phosphorus compound, JP-A-62-223239, JP-A-63-321345, surface treatment with a coupling agent, JP-A-63-304038. JP-A-63-280763 discloses a surface treatment with a silane compound.
Japanese Patent Application Laid-Open Publication No. H11-15083 proposes surface treatment by glycolatation, but it is difficult to obtain a sufficient affinity even if these methods are employed, and none of them has sufficient abrasion resistance. Also, various organic particles have been proposed, for example,
JP-A-49-117550 (polyethylene terephthalate particles, poly-1,4-bis (hydroxymethyl) cyclohexane terephthalate particles);
174254 (melamine / formaldehyde copolymer particles, phenol / formaldehyde copolymer particles, etc.) and JP-A-2-189359 (vinyl compound / divinylbenzene copolymer particles, dicarboxylic acid / acrylate copolymer particles, etc.) ), But even these organic particles have insufficient abrasion resistance in applications requiring high abrasion resistance.

Further, regarding silicone particles, Japanese Patent Publication No. Hei 4-30974, Japanese Patent Publication No. Hei 5-18327,
Although many proposals such as 04959 have been made, there is still no such thing that gives a sufficient improvement effect.

[0009]

The inventors of the present invention have conducted intensive studies on such a problem, and as a result, by using silicone particles having a specific composition, the abrasion resistance, particularly the calendering treatment, has been maintained while maintaining the lubricity of the film. It has been found that the abrasion resistance of the particles can be greatly improved.

[0010]

SUMMARY OF THE INVENTION The object of the present invention is that the average particle diameter defined by the formula (5) is 0.01 to 2;
A polyester composition characterized by containing 0.01 to 5% by weight of silicone particles having a particle size of substantially the polysiloxane represented by the formula (1) and having a composition of μm.

(R1) ₁ (R2) _m (R3) _n SiO _x (1) wherein R1 is a methyl group, R2 is an amino group, an acryloyloxy group, a methacryloyloxy group, an epoxy group, a mercapto A group selected from the group consisting of a group, a chlorine atom or a monovalent organic group having at least one of those functional groups, R3 is an alkyl group having 2 or more carbon atoms, an alkenyl group, a phenyl group, a benzyl group; , A phenethyl group, a fluoroalkyl group, or a monovalent organic group having at least one of these groups, wherein x, l, m, and n are the following formulas (2) to Satisfies (4).

1.0 <x <1.5 (2) 1 + m + n = 2 × (2-x) (3) 0 ≦ l, m, n (4)]

Embedded image Achieved by

The polyester used in the present invention is produced from a dicarboxylic acid having an aromatic dicarboxylic acid as a main acid component and / or an ester-forming derivative thereof, and glycol. Examples of the aromatic dicarboxylic acid in the present invention include terephthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, and isophthalic acid. Examples of the glycol component in the present invention include aliphatic glycols such as ethylene glycol, butanediol, tetramethylene glycol, and hexamethylene glycol, and alicyclic diols such as cyclohexanedimethanol. As the polyester in the present invention, for example, those containing alkylene terephthalate or alkylene naphthalate as a main component are preferable. Also,
These polyesters may be homopolyesters or copolyesters. Examples of the copolymer component include aliphatic dicarboxylic acids such as adipic acid and sebacic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid and hexahydroisophthalic acid, polyethyne glycol, polypropylene glycol, and 5-sodium sulfoisophthalic acid. And the like. The silicone particles in the present invention preferably have a siloxane component having an organic group other than a methyl group.

The silicone particles may contain a small amount of other organic polymer or inorganic component in addition to the polysiloxane within a range that does not impair the effects of the present invention.

For example, organic polymers such as polyamide, polyester, polystyrene, polyacrylic acid, epoxy resin, and phenol resin may be copolymerized in a small amount or may be physically mixed. Further, inorganic components such as silica, alumina, titania, calcium carbonate, and carbon, and components added to ordinary polymers such as pigments, dyes, and antioxidants may be mixed in a usual range.

In the formula (1), R1, R2 and R3 are all groups bonded to Si atoms, and l, m and n each represent the number of each organic group bonded per Si atom. ing. R2 and R3 each represent a siloxane component having an organic group other than a methyl group contained in the silicone particles, and R2 represents an amino group, an acryloyloxy group, a methacryloyloxy group, an epoxy group, a mercapto group, a chlorine atom or a functional group thereof. R3 represents an alkyl group having 2 or more carbon atoms, an alkenyl group, a phenyl group, a benzyl group, a phenethyl group, a fluoroalkyl group, or at least one of these groups. It is a group selected from monovalent organic groups having two groups.

R2 is further preferably the following: That, R2 is Z (CH ₂₎ p, Z is

Embedded image From a selected group, R4 is, -H, -CH ₂ CH ₂
A group selected from NH ₂ or a phenyl group;
Is a group selected from —H and —CH ₃ , and p is 2 or 3.

As a specific example of R2,

Embedded image And the like.

As a specific example of R3,

Embedded image And the like. Each of R2 and R3 may be composed of only the same kind of organic group, or a plurality of different components may be contained.

All organic groups of R2 and R3, ie, R
1, the molar ratio to R2 and R3, ie (m +
n) / (l + m + n) is preferably larger than 0.01, particularly preferably larger than 0.05. Also R2
It is particularly preferable that at least R2 of R3 and R3 be contained.

X in the formula (1) corresponds to the average number of oxygen atoms directly bonded to one Si atom in the siloxane structure of the silicone particles. The number of oxygen atoms directly bonded to one Si atom is three, that is, a siloxane structure as shown in the formula (8). That is, in this case, the silicone particles have a crosslinked structure formed by all Si atoms. When x is smaller than 1.5, the silicone particles have the structure of the formula (9) together with the formula (8), that is, silicone particles having a small crosslinked structure.

[0022]

Embedded image (R and R 'represent R1, R2 or R3 in the formula (1).)

In the present invention, it is necessary that 1.0 <x <1.5, and preferably 1.1 ≦ x ≦ 1.4. When x is 1.5, the abrasion resistance of the calendar deteriorates, which is not preferable. Although the reason for this is not clear, it is presumed that when x is less than 1.5, the elastic modulus of the particles becomes low and the particles are deformed when subjected to an external force to disperse the force.

In the present invention, when a plurality of types of siloxane components are contained, it is preferable that the components are substantially uniformly distributed. Substantially uniform means that each siloxane component is distributed in approximately equal amounts throughout the particle. For example, the center of the particle is (R1Si
O _1.3 ) only and the outer shell is made of (R2SiO _1.3 ) or (R3
Substantially uniform particles as compared with particles composed only of SiO _1.3 ) can further exert the effects aimed at by the present invention. However, it is not necessary to be a completely random copolymer at the molecular level, and even a block copolymer is substantially uniform.

The following method can be used as a method for confirming that it is substantially uniform. That is, the particles are treated with an aqueous alkaline solution and gradually dissolved from the surface. If a plurality of solutions having different dissolution amounts are collected while changing the dissolution time, and the composition of each solution is analyzed, the distribution state of the organic groups in each particle layer can be known.

The method for obtaining the silicone particles in the present invention is not particularly limited, and examples thereof include the following methods.

A silane compound or polysiloxane can be used as a compound as a raw material for producing particles.

Specific examples thereof include trimethylsilanol, trimethylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylacetoxysilane, trimethyl (dimethylamino) silane and trimethyl (methylethylketoximo) silane as silane compounds corresponding to R1. , Trimethylsilane, silylethylsilanol, dimethylethylchlorosilane, dimethyl-t-butylchlorosilane, simethylvinylchlorosilane, dimethylallylmethoxysilane, dimethylphenylchlorosilane, methyltrimethoxysilane, methyldimethoxyethoxysilane, methyltriethoxy Silane, methyltripropoxysilane, methyltributoxysilane, methylmethoxydibutoxysilane, dimethylsilanediol, dimethyl Chlorosilane, dimethylchloromethoxysilane, dimethylchlorosilane, dimethyldimethoxysilane, dimethyldiacetoxysilane, dimethylbis (dimethylamino) silane, dimethylbis (methylethylketoximo) silane, methylethyldichlorosilane, methyl-t-butyldichloro Silane, methylvinyldichlorosilane, methylallyldichlorosilane, methylphenyldichlorosilane, methylsilanetriol, methyltrichlorosilane, methyldichlorosilanol, methylchlorosilanediol, methyldichloromethoxysilane, methyldichlorosilane, methyl Trimethyloxysilane, methyltriacetoxysilane and the like can be mentioned.

As the polysiloxane corresponding to R1, for example,

Embedded image And the like.

As the silane compound corresponding to R2, 3
-Aminopropyltriethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3
-Anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane,
3-glycidoxypropyltrimethoxysilane, 2-
(3,4-epoxycyclohexylethyl) trimethoxysilane, 4-aminobutyldimethylmethoxysilane,
Examples thereof include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane and 3-aminopropylmethyldiethoxysilane.

Examples of the polysiloxane corresponding to R2 include a modified silicone oil which is a copolymer containing an organic group corresponding to R2.

For example,

Embedded image And the like.

As the compound corresponding to R3, ethyltrimethoxysilane, ethyltrichlorosilane, n-hexyltrimethoxysilane, cyclohexyltriethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, benzyltrimethoxysilane, phenethyltrimethoxysilane Examples thereof include silane and 3,3,3-trifluoropropyltrimethoxysilane.

Further, as the polysiloxane of R3,

Embedded image Alternatively, a modified silicone oil containing an organic group corresponding to R3 can be used.

The silicone particles according to the present invention may be any one of the above R
A silane compound or polysiloxane corresponding to 1, R2, R3 is mixed or condensed at a ratio within the range of the above formula (2), for example, sodium hydroxide, potassium hydroxide, barium hydroxide, hydrogen carbonate Inorganic or organic alkali compounds such as sodium, potassium carbonate, sodium methoxide, potassium butoxide, diazabicycloundecene, and tetramethylammonium hydroxide; titanium compounds such as tetramethoxytitanium, tetrabutoxytitanium, and orthotitanate stearate; Dibutyltin oxide, dibutyltin dilaurate, heated in the presence or absence of a tin compound such as tributyltin acetate, and equilibrated, or partially hydrolyzed in the presence of water amine, Choose from amides and nitriles That one or more of the mixed solvent, condensed in the presence the condensation catalyst, the formula (1) to
Silicone particles corresponding to (7) are produced.

The particles thus obtained were uniformly dispersed throughout the particles. Silicone fine particles containing an organic group other than a methyl group. In general, when various kinds of fine particles are used, their surface properties and interaction with other substances are very important.

The particles obtained by such a method are as follows:
Surface properties and interactivity with other substances are always stable, and the surface is constantly renewed due to dissolution, abrasion, destruction, etc. of fine particles during reaction or mixing with other substances, and during use. Since it has a certain physical property, it is considered that the silane compound having another organic group is more preferable than the silane compound having a surface treatment.

Next, specific examples of the composition of the thus-produced silicone particles are shown, but these are only a few examples of the present invention.

[0039]

Embedded image The average particle diameter of the silicone particles in the present invention is expressed by the formula (5).
Is 0.01 to 2 μm, and preferably 0.05 to 1 μm. If the average particle diameter is less than 0.01 μm, the lubricity becomes insufficient when molded into a film or the like, while if it exceeds 2 μm, the flatness of the surface deteriorates, which is not preferable.

The content of the silicone particles in the present invention relative to the polyester composition is from 0.01 to 2% by weight, preferably from 0.02 to 1% by weight. If the content is less than 0.01% by weight, the lubricity when molded into a film or the like becomes insufficient, while if it exceeds 2% by weight, the flatness of the surface deteriorates, which is not preferable.

In the silicone particles of the present invention, the relative standard deviation of the particle diameter defined by the formula (6) is 0.5 or less. This is preferable in that coarse projections are not formed and dropping out hardly occurs. The relative standard deviation is 0.
It is more preferably 3 or less, particularly preferably 0.2 or less.

[0042]

Embedded image The strength (S ₁₀ ) of the silicone particles according to the present invention when the particles are deformed by 10% preferably satisfies the following expression (7). 0.1 ≦ S ₁₀ ≦ 10 (unit: kgf / mm ² ) (7)

[0043] Here, S ₁₀ is an index representing the deformation behavior due to an external force of a particle is measured by the following method. That is, as shown in FIG. 1, first, particles are dispersed on the lower external indenter [11], and one particle [13] is fixed between the upper external indenter [12] and the lower external indenter. Then, a load force is applied at a constant increase rate, the deformation amount and the load force of the particles are measured, and the equation (1) is obtained from the load P (kgf) when the particles are deformed by 10%.
In accordance 0), to calculate the S _10. S = 2.8 P / πd ² (kgf / mm ² ) (10) Here, d indicates the particle diameter (mm). If the particle size is small and direct measurement is difficult, the measurement should be made with the same particle composition and large particle size instead.

The method and timing for adding the silicone particles to the polyester may be determined by a conventionally known method, for example, a method of adding a powder or a glycol slurry to a polyester reaction system, or a method of adding a powder or a slurry. It is possible to adopt a method of kneading the polyester with the above.

When silicone particles are added as a slurry to a reaction system or a polymer, an anion such as sodium dodecylbenzenesulfonate or sodium lauryl sulfate is added to the slurry in order to improve the dispersibility of the particles in the slurry and the polymer. Nonionic surfactants such as polysurfactants, polyoxyethylene nonylphenyl ether and polyethylylene glycol monostearate, or water-soluble polymers such as polyvinylpyrrolidone, polyvinyl alcohol and carboxymethyl cellulose may be added.

With respect to the heat resistance of the silicone particles in the present invention, the particles having a heat decomposition temperature of 350 ° C. or higher in an inert gas stream by a thermobalance at a temperature of 350 ° C. or more are used when producing the polyester composition. It is preferable because there is no problem such as agglomeration at the time of melt molding or at the time of recovery and reuse of the molded product, which impairs the surface uniformity and abrasion resistance of the film or fiber.

The polyester composition of the present invention contains a metal compound catalyst such as lithium, sodium, calcium, magnesium, manganese, zinc, antimony, germanium, titanium or the like, which is usually used in the production of polyester, as a catalyst or a coloring inhibitor. A known additive such as a phosphorus compound may be contained.

In the case where a molded article such as a film made of the polyester composition of the present invention is required to have a particularly high degree of slipperiness, other particles may be contained in addition to the silicone particles. Other particles include inorganic particles such as silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, and calcium carbonate, in a polyester polymerization reaction system in which at least one of an alkali metal and an alkaline earth metal and phosphorus are part of a component. Precipitated particles, that is, internal particles, and organic particles such as crosslinked polymer particles can be used. Further, the polyester composition of the present invention may contain a plurality of types of silicone particles at the same time.

When the polyester composition of the present invention is used as a film, it can be applied to either a single-layer film or a laminated film. From the viewpoint of surface flatness, at least one film composed of the polyester composition of the present invention is required. Films laminated to layers are preferred.

The laminated film mentioned here has a structure of at least two layers in the thickness direction of the film, and a film having a structure of three or more layers is also included in this category. Further, it is preferable that at least the outermost layer portion on one side is made of the polyester composition of the present invention since the desired effects of the present invention can be sufficiently exhibited. A laminated film having the polyester film of the present invention on both sides is particularly preferred.

As the form of the laminated film, various types are possible. For example, in the case of a two-layer laminated film, a layer (X layer) containing the polymer particles of the present invention and another layer (Y layer)
And a layered structure in which a coating layer (for example, an easily adhesive layer) is provided on the surface of the X layer, a laminated structure in which a coating layer (for example, an easily adhesive layer) is provided on the surface of the Y layer,
A laminated structure in which a back coat layer is provided on the surface of the Y layer can be employed. In the case of a three-layer laminated film, a three-layer laminated structure of simply X layer / Y layer / X layer, a laminated structure in which a coating layer is provided on the surface of one X layer of the three-layer laminated structure, and an X layer on both sides It is possible to adopt a laminated structure in which a coating layer is provided on the surface (on both sides of the laminated film). In this case, the thickness of the X layer is preferably 0.1 to 2.0 μm, and the thickness of the coating layer is preferably about 0.01 to 1 μm. In the case of a laminated film of four or more layers, basically, the number of Y layers (intermediate layers) in the above-mentioned three-layer laminated film only increases, so the positional relationship between the X layer and the coating layer is the case of the three-layer laminated film. Is the same as

In the case of adopting such a laminated film form, assuming that the thickness of the laminated film layer containing the silicone particles of the present invention is t (μm), the average particle diameter D (μm) of the silicone particles of the present invention is And the following relationship is preferably established. 0.1 ≦ t / D ≦ 100

A method for producing such a composite film will be specifically described. First, the polyester pellets are mixed at a predetermined ratio, dried, and then supplied to a known melt laminating extruder, extruded from a slit die into a sheet,
It is cooled and solidified on a casting roll to make an unstretched film. That is, two or three or more extruders,
The sheets are laminated using a manifold or a confluence block (for example, a confluence block having a square confluence part) having two or more layers, extruding two or more layers of sheets from a die, and cooling with a casting roll to produce an unstretched film. In this case, installing a static mixer and a gear pump in the polymer flow path, or lowering the melting temperature of the extruder that extrudes the polymer on the outermost layer stacking part side by 5 to 10 ° C. lower than the base layer part side,
This is effective for improving the uniformity of the film thickness.

Next, the unstretched film is biaxially stretched and biaxially oriented. As the stretching method, a sequential biaxial stretching method or a simultaneous biaxial stretching method can be used. Here, the longitudinal stretching is divided into three or more stages using a sequential biaxial stretching method in which stretching in the longitudinal direction is performed first and then in the width direction, and the total longitudinal stretching ratio is 3.5 to 6.5 times. The method used is particularly preferred. The stretching temperature in the longitudinal direction varies depending on the type of polyester and cannot be unconditionally determined.
It is effective that the temperature is set to 130 ° C. and higher than the second and subsequent stages. The longitudinal stretching speed is 5000-50,000%
/ Min range is preferred. As a stretching method in the width direction, a method using a stenter is generally used. Stretch ratio is 3.0
A range of up to 5.0 times is appropriate. The stretching speed in the width direction is 1
2,000 to 20,000% / min, and the temperature is preferably in the range of 80 to 160 ° C. Next, this stretched film is heat-treated. The heat treatment temperature in this case is 170 to 220 ° C., particularly 1
The temperature is preferably from 80 to 200 ° C. and the time is preferably from 0.2 to 20 seconds.

As the surface roughness of the film, a surface roughness parameter Rt / Ra, which is a ratio of the center line average roughness Ra to the maximum height Rt, is preferably 40 or less, more preferably 30 or less.
In particular, it is preferably 20 or less from the viewpoint that the wear resistance becomes good.

Further, regarding the distribution of the surface protrusion height of the film, the one having a height of 20 nm or more is defined as the protrusion height, and when the relative standard deviation is 1.0 or less,
This is preferable because the uniformity of the height of the projections and the sharpness can be improved.

The method for measuring physical properties and the method for evaluating effects in the present invention are as follows.

A. Particle Properties (1) Average Particle Size and Relative Standard Deviation Photographing the particles in the polymer or film at 20000 magnifications with an electron microscope, measuring the equivalent circle diameter of the particles, and defining by the formulas (5) and (6) Average particle diameter and relative standard deviation were determined.

[0059] (2) S ₁₀ Shimadzu Corp. of micro compression tester (MCTM-20
Load rate; 0.0145 gf / g using
The amount of deformation was measured by applying a load of 0 to 1 gf. Then, based on the load P (kgf) when the particles were deformed by 10%, S ₁₀ (this measurement was taken as a total of 10
Once performed, the average value of 10 times was the S _10. ) Was calculated.

B. Polymer properties (1) Intrinsic viscosity Measured at 25 ° C using o-chlorophenol as a solvent.

C. Film Characteristics (1) Surface Roughness Parameters Ra, Rt Measured using a high-precision thin film step measuring device ET-10 manufactured by Kosaka Laboratory. Ra is the center line average roughness, Rt is the maximum height, and represents the distance between the maximum peak and the deepest valley of the roughness curve. The measurement conditions are as follows, and the average value of 20 measurements was taken as the value.・ Stylus tip radius: 0.5 μm ・ Stylus load: 5 mg ・ Measurement length: 1 mm ・ Cutoff value: 0.08 mm For details of the definition of each parameter, refer to “Measurement of Surface Roughness” by Jiro Nara. Evaluation method ”(General Technology Center, 1
983).

(2) Lamination Thickness When the particles most contained in the film are silicone particles, they are etched from the surface by XPS (X-ray photoelectron spectroscopy), IR (infrared spectroscopy) or a confocal microscope. The depth profile of the particle concentration is measured. In the surface layer of the film laminated on one side, the particle concentration is low due to the interface of the surface, and the particle concentration increases as the distance from the surface increases.

In the case of the film laminated on one side according to the present invention, the particle concentration starts to decrease again after reaching the maximum value once at the depth [I]. Based on this concentration distribution curve, a depth [II] (here, II> I) at which the particle concentration becomes 1/2 of the maximum particle concentration.
Was taken as the lamination thickness. Further, with respect to the other laminated films, the same analysis was performed from the point where the particle concentration appeared, and the results were obtained. Further, when inorganic particles and the like are contained, the secondary ion mass spectrometer (SIMS) is used to determine the concentration ratio of the element resulting from the highest concentration of particles in the film to the carbon element of the polyester. (M ⁺ / C ⁺ ) is the particle concentration, and the depth (thickness) from the surface of the polyester X layer
Perform direction analysis. Then, the lamination thickness can be obtained from the same method as described above. In addition, it can also be obtained by observing a cross section of a film or using a thin film step measuring device.

(3) Slipperiness A film was slit to a width of 1/2 inch, and a tape running tester TBT-300 type [manufactured by Yokohama System Laboratory Co., Ltd.]
Was used, and the vehicle was run in a 20 ° C., 60% RH atmosphere, and the initial friction coefficient μk was determined by the following equation. The guide diameter is 6
mmφ, and the guide material is SUS27 (surface roughness of 0.
2S), winding angle is 180 °, running speed is 3.3cm
/ Sec. μk = 0.733 × log (T ₁ / T ₂ ) T ₁ : Outgoing side tension T ₂ : Incoming side tension If the above μk is 0.35 or less, the sliding property is good. Here, when μk is larger than 0.35, the slipperiness when processing a film or as a product is extremely deteriorated.

(4) Abrasion resistance 1 A tape-like roll obtained by slitting a film to 1/2 inch was wound around a stainless steel SUS-304 guide roll at an angle of 60 °, a speed of 250 m / min, and a tension of 95 g at 50 g.
It was rubbed over 0 m and ranked according to the amount of white powder generated on the guide roll surface as follows. A and B grades were accepted. Class A: No white powder is generated. Class B: Small amount of white powder is generated. C class: White powder is generated in a large amount. Class D: Large amount of white powder is generated.

(5) Abrasion resistance 2 (calendar shaving) The tape coated with the magnetic layer was heated to a temperature of 70 using a small test calender (styrene, nylon roll, five-stage type, nylon roll in contact with the base film surface). Calendering is performed at a linear pressure of 200 kg / cm. After the above treatment is continued for a total of 10,000 m, white powder adhering to the nylon roll generated by this treatment is observed, and the following ranking is performed. The first and second grades were accepted. Class A: Almost no white powder adheres. Class B: White powder slightly adheres, but does not lead to troubles in processing steps and product performance. Class C: A large amount of white powder adhered, causing troubles in the processing process and product performance, making it unusable.

[0067]

The present invention will be described in more detail with reference to the following examples. Example 1 Silicone particles were produced as follows. As a raw material corresponding to R1, 68.1 g of methyltrimethoxysilane
(0.5 mol), and 1,1,3,3,5,5,7,
59.2 g of 7-octamethylcyclotetrasiloxane
(0.2 mol), and as a raw material corresponding to R2, γ
Using-(2-aminomethyl) aminopropyltrimethoxysilane 22.1 (0.1 mol), a 200 ml four-necked round bottom flask was charged and mixed. 0.2 g of KOH (grain)
, And stirred at 90 to 105 ° C for 3 hours (300 rpm
m) Treated (equilibration). 100 g of this equilibrated mixture was placed in 2 liters of acetonitrile and 38 ml of H ₂ O in a 3 liter four-necked round bottom flask, and heated to 45 to 50 ° C.
Stirring yielded a homogeneous solution. NKOH / M
25 ml of MeOH solution was added and the mixture was treated at the same temperature for 3 hours. After cooling, the mixture was filtered, washed with about 100 ml of MeOH and about 200 ml of distilled water, and diluted with water to obtain silicone particles having a slurry concentration of 20% by weight. A part of the silicone particles is taken, and a 4% NaOH / heavy water (D ₂ O) solution is used at 50 ° C.
For 6 hours to dissolve. As a result of analyzing this solution by ¹ H-NMR, it was found that the CH ₃ group component was 1.30 and H ₂ NCH ₂
The ratio of CH ₂ NH (CH ₂ ) ₃ group components was 0.10. As a result of measuring the particles with a scanning electron microscope, the average particle diameter was 0.5 μm and the relative standard deviation was 0.15.

Silicon particles obtained by dissolving undried polyethylene terephthalate chips having an intrinsic viscosity of 0.660 dl / g in a molten state using a vent-type twin-screw extruder and dispersing them as a 20% by weight aqueous slurry (Table 1). 1
(Shown below) is added so as to be 0.3% by weight in the polyester composition. The vent port was maintained at a vacuum of 10 Torr, and was melt-extruded at a resin temperature of 280 ° C. to obtain a polyethylene terephthalate composition (I) containing silicone particles.
I got The intrinsic viscosity of the obtained polymer is 0.620 dl
/ G. From the observation of the particles in the polymer, the average particle size and relative standard deviation of the silicone particles were 0.5 μm each,
0.15.

The polyethylene terephthalate composition (I) was melt-extruded at 290 ° C. to form an unstretched film by using an electrostatic application casting method. Then, in the longitudinal direction
The film was stretched 3.6 times in the width direction and then heat-treated at 200 ° C. for 5 seconds under a constant length to obtain a film having a thickness of 10 μm. As shown in Table 1, the film had Ra = 0.014, the slipperiness was μk = 0.23, and the abrasion resistance 1 or 2 was Class A, which was good.

Example 2 Using the silicone particles having the composition shown in Table 1, a polyethylene terephthalate composition was obtained in the same manner as in Example 1, and a film was obtained. The resulting film exhibited good slipperiness and abrasion resistance as shown in Table 1.

Example 3 A polyester composition was obtained in the same manner as in Example 1 except that the polyester was changed to polyethylene-2,6-naphthalate using silicone particles having the composition shown in Table 1, and a film was obtained. The resulting film exhibited good slipperiness and abrasion resistance as shown in Table 1.

Example 4 A polyethylene terephthalate composition (II) was obtained in the same manner as in Example 1 except that silicone particles having the composition shown in Table 1 were used.

On the other hand, 100 parts by weight of dimethyl terephthalate, 70 parts by weight of ethylene glycol, 0.06 parts by weight of magnesium acetate as a transesterification catalyst, 0.03 parts by weight of antimony trioxide as a polymerization catalyst, and 0,3 parts of trimethyl phosphate as a heat stabilizer. 0.03 parts by weight,
Polyethylene terephthalate (III) having an intrinsic viscosity of 0.650 dl / g was obtained by an ordinary method. Next, the polyethylene terephthalate composition (II) was melt-extruded at 290 ° C. on the polyethylene terephthalate (III) to form a laminated unstretched film using an electrostatic application casting method.

The unstretched film was divided into three stages in the longitudinal direction, and 1.2 times at 123 ° C., 1.45 times at 126 ° C.,
Each was stretched 2.3 times at 14 ° C. This uniaxial film is stretched 3.5 times in the width direction at 111 ° C. using a stenter, and is heat-treated at 200 ° C. for 5 seconds under a constant length to have a thickness of 10.
A film having a thickness of 0 μm (lamination thickness: 1.0 μm) was obtained. Table 1
As shown in the figure, the content of the silicone particles in the laminated portion of the obtained film was 0.5% by weight, and the film characteristics were Ra = 0.014, μk = 0.23, and abrasion resistance A
The grade was good.

Comparative Examples 1 to 3 Polymers and films were obtained in the same manner as in Example 1 except that the composition of the silicone particles or particles other than the silicone particles were used. As shown in Table 2, the obtained film had sufficient lubricity but insufficient abrasion resistance.

[0076]

[Table 1]

[Table 2]

[0077]

Since the thermoplastic polyester composition of the present invention contains silicone particles of a specific composition,
It is excellent in affinity between the particles and polyester, and when formed into a film or fiber, the particles are hardly dropped off, and in particular, the abrasion resistance in the calendering step is good. Therefore,
It is possible to solve the problem caused by the falling off of particles, which has been a problem when other conventional particles are added, and it is particularly possible to suitably use the product as a product such as a magnetic tape.

[Brief description of the drawings]

FIG. 1 is a schematic longitudinal sectional view showing a method for measuring the strength (S ₁₀ ) of particles in the present invention.

[Explanation of symbols]

 [11] Lower press indenter [12] Upper press indenter [13] Fine particles

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 67/00-67/04

Claims (4)

(57) [Claims] An average particle size defined by the formula (5) is 0.0
0.01 to 5% by weight of silicone particles having a composition of substantially 1 to 2 μm and having a composition substantially represented by the polysiloxane of the formula (1)
A polyester composition characterized by containing: (R1) ₁ (R2) _m (R3) _n SiO _x (1) [where R1 is a methyl group, R2 is an amino group, an acryloyloxy group, a methacryloyloxy group, an epoxy group, a mercapto group, a chlorine atom] Or a group selected from the group consisting of monovalent organic groups having at least one of those functional groups, R3 represents an alkyl group having 2 or more carbon atoms, an alkenyl group, a phenyl group, a benzyl group, a phenethyl group, A fluoroalkyl group or a group selected from the group consisting of monovalent organic groups having at least one of these groups, wherein x, l,
m and n satisfy the following expressions (2) to (4). 1.0 <x <1.5 (2) 1 + m + n = 2 × (2-x) (3) 0 ≦ l, m, n (4)] 2. In the formula (1), R2 is Z (CH ₂ ) p
And Z is: From a selected group, R4 is, -H, a group selected from -CH ₂ CH ₂ NH ₂ or phenyl group, R5 is, -H, a group selected from -CH _3, p The polyester composition according to claim 1, wherein is 2 or 3. 3. The polyester composition according to claim 1, wherein the relative standard deviation of the particle size of the silicone particles defined by the formula (6) is 0.5 or less. Embedded image 4. The polyester composition according to claim 1, wherein the strength (S ₁₀ ) when the silicone particles deform the particles by 10% satisfies the following formula (7). 0.1 ≦ S ₁₀ ≦ 10 (unit: kgf / mm ² ) (7)