JP3022626B2 - Polyester film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester film, and more particularly to a polyester film having excellent running properties and abrasion resistance and excellent transparency.

[0002]

2. Description of the Related Art Polyesters, especially polyethylene terephthalate, are widely used as fibers, films and other molded articles because of their excellent physical and chemical properties. However, contrary to its excellent properties, the workability due to poor processability in the molding process of obtaining the molded product, or poor slipperiness in handling the product itself,
It is also known that undesired troubles such as a decrease in product value occur.

Hitherto, as a method for lowering the friction coefficient of polyester, many methods have been proposed in which fine particles are present in the polyester. However, the affinity between the fine particles and the polyester is not sufficient, and the transparency and film resistance of the film are low. Neither abrasion was satisfactory.

[0004] This method will be further explained. As a means for improving the surface characteristics of polyester, a method of depositing a part or all of a catalyst or the like used in polyester synthesis in a reaction step (internal particle deposition method) calcium carbonate, oxidation Many methods of adding fine particles such as silicon during or after polymerization (external particle addition method) have been proposed.

[0005] However, the internal particle precipitation method is as follows.
Since the particles are a metal salt of the polyester component, etc., the affinity with the polyester is good to some extent, but since it is a method of generating particles during the reaction, control of the particle amount, particle diameter and prevention of generation of coarse particles, etc. Is difficult.

[0006] In one method, if the particle size and the amount of addition are appropriately selected, and fine particles from which coarse particles have been removed by classification or the like are added, the lubricity will be excellent.

However, in recent years, film processing steps
For example, as the processing speed of the printing process for packaging applications and the magnetic layer application / calendering process for magnetic media applications has increased, the abrasion resistance required for films has become increasingly severe. The disadvantage of causing troubles in process and product performance has become a problem.

As another problem, when fine particles are added, transparency, which is an important property of polyester, decreases as the amount of fine particles increases. When molded into film,
In particular, it is known that the transparency is significantly impaired due to the influence of the refractive index of the particles and the polyester and the generation of voids around the particles due to stretching. Regarding the refractive index of the particles, few particles have a refractive index close to that of polyester, especially polyethylene terephthalate, and there is a problem that even if there is a particle having a close refractive index, the lubricity is poor.

[0009] In recent years, especially in copying applications such as plate making, X-ray photography, micro film, electrophotography, and diazo photography, which require films having excellent lubricity and transparency, lubricity and transparency are high. It has become necessary to satisfy the irrational phenomenon of sex to a higher degree.
However, the situation has not been solved yet.

[0010]

DISCLOSURE OF THE INVENTION In view of the above-mentioned circumstances, the present inventors have improved the disadvantages of the method of adding external particles, and obtained a polyester film having excellent running properties, excellent abrasion resistance and excellent transparency. As a result of intensive studies, it has been found that the use of fine particles containing a silicone resin component and a metal oxide component as main components enables the obtained polyester film to have good properties, and has reached the present invention.

Accordingly, an object of the present invention is to provide a polyester film which is excellent in running properties and abrasion resistance and has good transparency.

[0012]

An object of the present invention In order to achieve the above object, according to a silicone resin component and the metal oxide component as the main component,
The silicone resin component is represented by the following formula R _X SiO _{2 -X / 2} [where R is a hydrocarbon group having 1 to 7 carbon atoms, and x is
It is a number from 0.5 to 2.8. Organosyn represented by]
Rusesquioxane having an average particle size of 0.01 to 5
It is achieved by a polyester film characterized by containing fine particles having a size of μm.

The polyester in the present invention is a polyester containing an aromatic dicarboxylic acid as a main acid component and an aliphatic glycol as a main glycol component. Such polyesters are substantially linear and have film forming properties, especially film forming by melt molding. As the aromatic dicarboxylic acid, for example, terephthalic acid, naphthalenedicarboxylic acid, isophthalic acid, diphenylethanedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenylsulfonedicarboxylic acid,
Examples include diphenyl ketone dicarboxylic acid and anthracene dicarboxylic acid. Examples of the aliphatic glycol include alkylene glycols having 2 to 10 carbon atoms such as ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, and decamethylene glycol.
Alternatively, an alicyclic diol such as cyclohexanedimethanol can be used.

In the present invention, polyesters containing alkylene terephthalate and / or alkylene naphthalate as a main component are preferred.

Among such polyesters, in particular, polyethylene terephthalate and polyethylene-2,6-naphthalate, for example, 80 mol% or more of all dicarboxylic acid components are terephthalic acid and / or 2,6-
Naphthalenedicarboxylic acid, 8 of all glycol components
A copolymer in which 0 mol% or more is ethylene glycol is preferred. In this case, 20 mol% or less of the total acid component can be the above-mentioned aromatic dicarboxylic acids other than terephthalic acid and / or 2,6-naphthalenedicarboxylic acid, and aliphatic dicarboxylic acids such as adipic acid and sebacic acid. acid;
An alicyclic dicarboxylic acid such as cyclohexane-1,4-dicarboxylic acid can be used. Further, 20 mol% or less of the total glycol component can be the above-mentioned glycol other than ethylene glycol, or an aromatic diol such as hydroquinone, resorcinol, 2,2-bis (4-hydroxyphenyl) propane; Aliphatic diols having an aromatic ring such as 4-dihydroxymethylbenzene; polyalkylene glycols (polyoxyalkylene glycols) such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol can also be used.

The polyester in the present invention includes:
Aromatic oxyacids such as, for example, hydroxybenzoic acid;
Also included are those in which a component derived from an oxycarboxylic acid such as an aliphatic oxyacid such as hydroxycaproic acid is copolymerized or bonded at 20 mol% or less based on the total amount of the dicarboxylic acid component and the oxycarboxylic acid component.

Further, in the polyester of the present invention, a tricarboxylic or polyfunctional polycarboxylic acid or a polyhydroxy compound such as trimellit in an amount in a substantially linear range, for example, an amount of 2 mol% or less based on the total acid component. Those obtained by copolymerizing an acid, pentaerythritol and the like are also included.

Further, the polyester in the present invention includes, for example, pigments, dyes, ultraviolet absorbers, heat stabilizers, light stabilizers,
Other additives such as an antioxidant and a light-shielding agent (for example, carbon black, titanium dioxide, etc.) can be contained as necessary.

The fine particles in the present invention are mainly composed of a silicone resin component and a metal oxide component, and are substantially composed of a silicon atom and a metal atom bonded via oxygen. For this reason, the fine particles in the present invention have both the characteristics of organic particles due to the hydrocarbon group bonded to the silicon element, and the characteristics of inorganic particles due to the metal oxide component, both due to the silicone resin component. At the same time, it can also have intermediate properties between the two.

[0020] As the silicone resin component, it is o Ruganoshirusesu key oxane component represented by the following formula (A) is preferably the plane of the flexibility of the particle.

R _x SiO _{2-x / 2} (A) wherein R is a hydrocarbon group having 1 to 7 carbon atoms, and x is a number of 0.5 to 2.8. ]

R in the above formula (A) is a hydrocarbon group having 1 to 7 carbon atoms, for example, an alkyl group having 1 to 7 carbon atoms,
A phenyl group or a tolyl group is preferred. 1-7 carbon atoms
May be linear or branched, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, n -Heptyl and the like.

Of these, R is preferably methyl and phenyl, more preferably methyl.

In the above formula (A), x is 0.5 to 2.8.
Is the number of For example, when x is 1 in the above formula (A), the above formula (A) is represented by the following formula (A) -1 RSiO _1.5 ... (A) -1 where R has the same definition as above. Can be represented by

The composition of the above formula (A) -1 has the following structural part in the three-dimensional polymer chain structure of the silicone resin component:

[0026]

Embedded image It is derived from.

Similarly, the three-dimensional polymer chain structure of the silicone resin component can have the following structural parts.

[0028]

Embedded image

Accordingly, a silicone resin component having a structure in which the four types of three-dimensional structures coexist in a state of being randomly bonded at an appropriate ratio according to the value of x in the above formula (A).

On the other hand, the metal oxide component is not particularly limited as long as it can bond to a silicon atom through oxygen, and examples thereof include titanium oxide, zirconium oxide, germanium oxide, aluminum oxide, tin oxide, and magnesium oxide. Are preferable, and may further contain components such as sodium oxide and potassium oxide which are alkali metal oxides. Among these, components of titanium oxide, zirconium oxide and aluminum oxide are particularly preferred from the viewpoint of the transparency of the film.

The method for producing the fine particles in the present invention is not particularly limited, but the following method is mentioned as a typical method.

An organosilicon compound is used as a silicone resin component, and an organometallic compound is used as a metal oxide component. These are mixed to prepare a mixed solution. Subsequently, a hydrolysis / condensation reaction is carried out by an interfacial reaction or a mixing reaction with an alkaline aqueous solution such as aqueous ammonia to generate particles.

Examples of the organosilicon compound include chlorosilanes such as dimethyldichlorosilane, methyltrichlorosilane and diphenyldichlorosilane, and alkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane and methyltriethoxysilane. . At the same time, tetramethoxysilane, tetraethoxysilane, H ₂ NCONHC
H ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ , H ₂ NCH ₂ CH ₂
CH ₂ Si (OCH ₂ CH ₃ ) ₃ , (CH ₃ ) ₂ NCH
₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ , H ₂ NCH
₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ CH ₂ ) ₂ NCH ₂ CH ₂ CH ₂ Si (OCH
_{3) 3, H 5 C 2} OCOCH 2 CH 2 NHCH 2 CH 2
CH ₂ Si (OCH ₃ ) ₃ , NH ₂ C ₆ H ₄ Si (OC
_{H 3) 3, C 6 H} 5 NHCH 2 CH 2 CH 2 Si (OC
An alkoxysilane such as H ₃ ) ₃ may coexist.

The organometallic compound includes, for example, a titanium compound such as tetrabutyltatinate and / or a hydrolysis / condensate thereof, a zirconium compound such as tetrabutylzirconate and / or a hydrolysis / condensation product thereof, Aluminum compounds such as aluminum ethylate, aluminum isopropylate, mono-sec-butoxyaluminum dipropylate, aluminum-sec-butyto, ethyl acetoacetate aluminum diisopropylate and / or their hydrolysis / condensation products, such as dibutyltin diacetate Tin compounds and the like can be mentioned.

The composition ratio of the silicone resin component to the metal oxide component is from 95: 5 to 1 depending on the flexibility and refractive index of the particles.
The region up to 0:90 is preferred.

In the present invention, the shape of the fine particles is easy to slide,
From the viewpoint of abrasion resistance, a spherical shape, a rugby ball shape, a cocoon shape, or the like is preferable.
Those in the range of -π / 6 are preferred.

[0037]

(Equation 1)

In order to sharpen the distribution of protrusions on the film surface, the fine particles preferably have a relative standard deviation of 0.7 or less, more preferably 0.5 or less, particularly preferably 0.3 or less.

[0039]

(Equation 2)

Here, di is the major axis (μ) of each fine particle.
a m), D _A is the number average of the major axis of the particle ([mu] m), and n is the number of particles.

The average particle size of the fine particles in the present invention is 0.0
It is necessary to be 1-5 μm, more preferably 0.05
２2 μm. If the average particle size is less than 0.01 μm, the film becomes less slippery when formed into a film. On the other hand, if the average particle size exceeds 5 μm, the transparency of the film is reduced due to the occurrence of voids, the scattering of the film surface due to the coarse projections, or the abrasion resistance of the film is deteriorated.

The amount of the fine particles added to the polyester is preferably 0.001 to 10% by weight, more preferably 0.002 to 2% by weight.

The timing and method for adding the fine particles to the polyester in the present invention are not particularly limited, but it is particularly preferable to add the fine particles at a stage during the polymerization reaction before the start of the polymerization from the viewpoint of the particle dispersibility. The addition of the particles in the precursor stage or the polycondensation stage of the polyester production is preferably carried out in the form of a slurry dispersed in ethylene glycol.

As a method of dispersing in a dispersion medium such as ethylene glycol, a high-speed disperser, a sand mill, a roll seal, or the like may be used.

At the time of dispersion, compounds containing phosphorus atoms such as phosphoric acid, phosphorous acid and sodium hexametaphosphate, compounds containing nitrogen atoms such as tetraethylammonium hydroxide and hydroxylamine, alkali compounds,
It is particularly preferable to use a dispersant such as a cationic, anionic, amphoteric or nonionic surfactant or the like because the dispersibility of the fine particles in the slurry and the polymer is further improved.

In the present invention, the polyester film containing the fine particle-containing polyester is used as it is, or another polyester (polyester containing no particles) is used.
It can be obtained by diluting with Other polyesters used for dilution include, for example, polyesters containing internally precipitated particles, calcium carbonate, silica, alumina, etc., produced by a conventional precipitation method or addition method.

The polyester film of the present invention can be prepared by, for example, melt-extruding a polyester at a temperature of melting point (Tm: ° C.) to (Tm + 70) ° C., quenching it, and having an intrinsic viscosity of 0.3.
An unstretched film of 5 to 0.9 dl / g was obtained, and the unstretched film was uniaxially (longitudinal or transverse) (Tg-1).
0) to (Tg + 70) ° C. (however, Tg: glass transition temperature of polyester) at a magnification of 2.5 to 5.0 times, and then in a direction perpendicular to the above-mentioned stretching direction (the first-stage stretching is the longitudinal direction). In the case, the second stretching is in the transverse direction).
It can be manufactured by stretching at a temperature of ~ (Tg + 70) ° C at a magnification of 2.5 to 5.0 times. In this case, the area stretching ratio is preferably 9 to 22 times, more preferably 12 to 22 times.
The stretching means may be either simultaneous biaxial stretching or sequential biaxial stretching.

Further, the biaxially oriented film is (Tg + 7
0) It can be heat-set at a temperature of from 0 ° C. to Tm (° C.).
For example, a polyethylene terephthalate film is preferably heat-set at 190 to 230 ° C. The heat fixing time is, for example, 1 to 60 seconds.

The thickness of the polyester film is 1 to 10
0 μm, further preferably 1 to 50 μm, particularly preferably 1 to 25 μm.

The polyester film of the present invention has various advantages such as excellent runnability, abrasion resistance and good film transparency, and can be used for various applications. In particular, it can be preferably used for magnetic tapes, stamping foils, gold and silver threads, transfer tapes and the like that require abrasion resistance in the calendering step, and is also preferably used for photographic and plate-making printing applications that require transparency. be able to.

[0051]

EXAMPLES The present invention will be further described below with reference to examples. In addition, the measurement of each characteristic value in the example followed the following method.

(A) Particle Size of Particles The average particle size was measured by an electron micrograph of the particles.
It is determined by the equivalent sphere diameter (μm) of the particle corresponding to the volume% point. The equivalent sphere diameter is the diameter of a sphere having the same volume as a particle.

(B) Composition Ratio of Particles The composition ratio of the metal oxide in the fine particles is determined by quantifying each component by ICP (inductively coupled plasma) emission spectroscopy to determine the ratio (weight ratio) .

(C) Abrasion The abrasion of the running surface of the film is evaluated using a five-stage mini super calender. The calender is a 5-stage calender consisting of nylon rolls and steel rolls.
The film is run at 0 ° C., at a linear pressure applied to the film of 200 kg / cm, and at a film speed of 50 m / min. The running film is evaluated for the sharpness of the film by the dirt adhering to the top roller of the calendar when the running film runs for a total length of 6000 m. <Four-step judgment> ◎ Nylon roll dirt at all ○ Nylon roll dirt almost none △ Nylon roll gets dirty × Nylon roll gets very dirty

(D) Haze According to JIS-K674, a film haze is determined by an integrating sphere HTR meter.

[0056]

EXAMPLE 1 Porimechirushiru an average particle size of 1.0μm Seth
· The dioxane component and an oxide of titanium component particles _{(CH 3 SiO 1.5 · TiO 2} , the composition ratio CH ₃ SiO _1.5:
TiO ₂ = 75: 25, volume shape factor 0.48) to 0.
After drying a polyethylene terephthalate having an intrinsic viscosity (orthochlorophenol, 35 ° C.) of 0.60 dl / g containing 05% by weight, it was melt-extruded at 290 ° C. and quenched and solidified by a casting drum to obtain an unstretched film.
Subsequently, after preheating to 70 ° C. with a heating roller, the film was stretched 3.4 times in the longitudinal direction while heating with an infrared heater. Subsequently, the film was stretched in the transverse direction at 95 ° C. by 3.6 times, and then heat-treated at 200 ° C. to obtain a film having a thickness of 15 μm.

The properties of this film are shown in Table 1. The film had good abrasion resistance and transparency.

[0058]

Examples 2 to 6 Constituent components and component ratio of fine particles(weight
ratio), Average particle size(Μm),Content(Addition amount: wt%)
Was changed in various ways as shown in Table 1, except that
In the same manner, biaxially oriented polyethylene terephthalate
I got Irum. Table 1 shows the results.
Both abrasion and transparency were good.

[0059]

Comparative Examples 1 and 2 A biaxially oriented film of polyethylene terephthalate was obtained in the same manner as in Example 1, except that the fine particles were silica or composite particles of silica and titania. The results are shown in Table 1, and all were inferior to those of the present invention in abrasion resistance and transparency.

[0060]

[Table 1]

[0061]

According to the present invention, it is possible to provide a polyester film having excellent running properties and abrasion resistance and excellent film transparency.

──────────────────────────────────────────────────続 き Continuation of front page (51) Int.Cl. ⁷ identification symbol FI // (C08L 67/02 83:04) (58) Investigated field (Int.Cl. ⁷ , DB name) C08J 5/18 C08L 67/02

Claims (4)

(57) [Claims] 1. A silicone resin component and a metal oxide component as main components, wherein the silicone resin component has the following formula: R _X SiO _{2 -X / 2} [where R is a hydrocarbon group having 1 to 7 carbon atoms. Yes, x is
It is a number from 0.5 to 2.8. Organosyn represented by]
Rusesquioxane having an average particle size of 0.01 to 5
A polyester film containing fine particles of μm. 2. A Metal oxide component oxides of titanium, at least polyester film of claim 1 wherein the one component selected from the group of zirconium oxide and aluminum oxide. 3. The composition of a silicone resin component and a metal oxide component.
The composition according to claim 1, wherein the composition ratio is 95: 5 to 10:90.
Ester film. 4. The content of the fine particles in the polyester is as follows:
2. The polyester according to claim 1, wherein the amount is 0.001 to 10% by weight.
Telfilm.