JPH09239813A - Apparatus and method for producing film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stably produce an excellent film free from a pit like surface defect for a long time in such a state that an oligomer present in a polymer is not bonded to the surface of a drum or roll during the production of the film. SOLUTION: A film producing drum or roll having a chromium plating film containing a silicon atom so that a silicon atom/chromium atom ratio becomes 10<-4> or more as a strength ratio of SIMS with respect to a chromium atom provided in the outer peripheral surface thereof is used in a film producing apparatus. Otherise, a film producing drum or roll having a chromium plating film containing a carbon atom so as to become carbon atom > oxygen atom as strength of SIMS with respect to an oxygen atom provided to the outer peripheral surface thereof is used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film manufacturing method and a film manufacturing apparatus, and more particularly, to an excellent film which does not suffer from defects such as adhesion of oligomers existing in a polymer and scratches on the film surface caused by the adhesion. TECHNICAL FIELD The present invention relates to a method for manufacturing a metal and a manufacturing apparatus thereof.

[0002]

2. Description of the Related Art Conventionally, when a molten polymer is extruded from a die and then stretched to form a film, the molten polymer extruded from the die is called a casting drum in order to obtain good flatness of the film. It is used as an industrial method in which the film is preheated to a predetermined temperature while running in contact with a roll, stretched and cooled, and the metal surface is hard chrome plated on such a casting drum or roll. I used the one coated with. However, in the conventional method, the oligomer (low polymer) present in the polymer is deposited on the surface during film production, adheres to the surface of the casting drum or roll described above, and the adhered matter is transferred onto the film, Scratches and digging scratches will occur due to this deposit,
This is a surface defect of the film, which is a problem in that a recording dropout occurs in magnetic recording applications, and an optical defect occurs in optical applications. Conventionally, trial and error has been added to avoid this, but there is no fundamentally good method, and it is said that the surface of the casting drum or roll is regularly polished and washed to remove deposits and produce. The method is general, and it is impossible to carry out production for a long time by this method, and there is a drawback that productivity is lowered.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art. Specifically, the oligomer (low polymer) present in the polymer is cast during film production. It is an object of the present invention to provide a film manufacturing method and a film manufacturing apparatus capable of manufacturing a film for a long time without being attached to the surface of a drum or a roll.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that if the outer peripheral surface of a drum or roll contacting the film during the production of the film is made of a specific material. The present invention has been accomplished by solving the above problems and finding that a film having no surface defects as described above can be produced.

That is, a drum or roll for producing a film having a chromium plating film containing silicon atoms / chromium atoms in a SIMS intensity ratio of silicon atoms / chromium atoms of 10 ⁻⁴ or more on the outer peripheral surface is used. A film production apparatus characterized by using a drum or roll for film production having a chromium plating film on the outer peripheral surface so that carbon atoms with respect to oxygen atoms are contained in the SIMS strength as carbon atoms> oxygen atoms A film production apparatus characterized in that, further, the method for producing a film of the present invention, a molten polymer is extruded from a spinneret, then, when forming the film by stretching, of the drum or roll in contact with the film. Simulate at least one silicon atom with respect to chromium atom
A method for producing a film, which comprises using a drum or roll for producing a film having a chromium plating film containing ^10-4 or more of silicon atoms / chromium atoms as the strength ratio of S on the outer peripheral surface, or a molten polymer. When extruded from a die and then stretched to form a film, at least one drum or roll in contact with the film contains a carbon atom with respect to an oxygen atom such that carbon atom> oxygen atom as SIMS strength. The method for producing a film is characterized by using a film-producing drum or roll having a chromium plating film on the outer peripheral surface thereof.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The molten polymer in the present invention means a thermoplastic resin which is plastically fluidized by heating to a temperature above its melting point to bring it into a molten state, and such a thermoplastic resin is not particularly limited. Typical examples thereof include polyesters, polyamides, polyolefins, polystyrenes, polycarbonates, polyacrylonitriles, polyvinyl alcohols, polyphenylene sulfides, polyacetals, polyethers, and copolymers thereof. Further, two or more kinds of these thermoplastic resins may be blended.

Of these, polyesters, polyamides, polyolefins and their copolymers are preferable, and polyesters and their copolymers are more preferable.

The term "polyester" as used herein refers to a polyester containing an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid or an alicyclic dicarboxylic acid and a diol as main constituent components. As the aromatic dicarboxylic acid component, for example, terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid,
1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid,
4,4′-diphenyl ether dicarboxylic acid, 4,4 ′
-Diphenyl sulfone dicarboxylic acid and the like can be mentioned, among which terephthalic acid, isophthalic acid,
2,6-naphthalenedicarboxylic acid and the like can be mentioned. Examples of the aliphatic dicarboxylic acid component include adipic acid, suberic acid, sebacic acid, dodecanedioic acid and the like. Moreover, as an alicyclic dicarboxylic acid component, 1,4-cyclohexane dicarboxylic acid etc. can be mentioned, for example. One of these acid components may be used alone, two or more of them may be used in combination, and an oxy acid such as hydroxybenzoic acid may be partially copolymerized. Examples of the diol component include ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, polyalkylene glycol, 2,2'-bis (4 ' Examples include -β-hydroxyethoxyphenyl) propane and the like. Among them, ethylene glycol is preferably used.
These diol components may be used alone or in combination of two or more.

More specifically preferred polyesters are polyethylene terephthalate and polyethylene-
Mention may be made of 2,6-naphthalate and copolymers thereof. Further, these polyesters may be blended with other polymers.

In addition, such polyesters may optionally contain organic lubricants such as flame retardants, heat stabilizers, viscosity reducing agents, antioxidants, ultraviolet absorbers, antistatic agents, pigments, dyes, fatty acid esters, waxes and the like. Alternatively, an antifoaming agent such as polysiloxane can be blended.

Further, in order to impart slipperiness depending on the use, for example, clay, mica, titanium oxide, calcium carbonate, kaolin, talc, wet silica, dry silica, calcium phosphate, aluminum oxide, zirconium oxide, etc. Particles such as inorganic particles, organic particles having acrylic acid, styrene, divinylbenzene or the like as a constituent component, and internal particles using a catalyst during polyester synthesis may be blended.

In order to obtain the effects of the present invention better, the concentration of carboxyl end groups in the polyester is
It is preferably in the range of 15 equivalents / ton or more and 65 equivalents / ton or more.

In the present invention, when a molten polymer is extruded from a die and then stretched to form a film, the molten polymer extruded from the die is cooled by a cooling drum called a casting drum in order to obtain a surface property of the film. After that, the film is produced by a method of preheating to a predetermined temperature while running the film in contact with a roll, stretching, and cooling. At this time, at least one drum or roll in contact with the film contains silicon for chromium atoms relative to chromium atoms. A drum or roll having a chromium plating film containing silicon atoms / chromium atoms of 10 ⁻⁴ or more in terms of SIMS intensity ratio on the outer peripheral surface, or at least 1
It is necessary that the film-forming drum or roll has a chromium plating film on the outer peripheral surface containing carbon atoms more than the number of oxygen atoms so that the SIMS strength is such that carbon atoms> oxygen atoms. . The preferable range of silicon atom / chromium atom is 5 × 10 ^{−4 in} terms of SIMS intensity ratio of silicon atom to chromium atom.
It is not less than 10 ⁻¹ . The absolute intensity of the SIMS of carbon atom and oxygen atom referred to here is 1 each.
It is preferably not less than ⁰ cps and not more than 10 ¹⁰ cps.

This makes it possible to produce a film for a long time in a state where the catalyst or additives in the polymer and the deterioration products of the polymer do not adhere to the surface of the drum or roll which comes into contact with the molten polymer during the production of the film. .
Note that the SIMS intensity ratio here means SIMS (Secondary I) as described in the section of characteristic evaluation.
On Mass Spectrometry) means an average secondary ion intensity ratio between a depth of 100 nm and 2000 nm from the surface layer.

The surface roughness of the chromium plating film portion is preferably 1 S or less, more preferably 0.6 S or less, and further preferably in the range of 0.05 to 0.4 S. 1S means that the Rmax value specified in JIS-B-0601 surface roughness measurement is 1 μm. The surface roughness can be measured using a commercially available surface roughness meter with a sample length of 1 to 10 mm and a cutoff of 0.1 to 1 mm. In the case where the sample is too large to fit on the surface roughness meter or the like, it is also possible to substitute for this by measuring a sample piece treated in the same manner as the sample.

Further, it is preferable that the chromium plating film has a chromium plating film containing 0.5 to 5% of carbon atoms with respect to chromium atoms as the number of atoms.

The surface film of the present invention can be obtained, for example, by a method of adding a silicon compound such as hexafluorosilicic acid to a chromic acid plating bath. In addition, formic acid,
It is preferable to add an organic substance such as oxalic acid, because the above-mentioned carbon is contained. The structure of the obtained plating film is changed by subsequent heat treatment. The crystal structure is X
Although it can be confirmed by line diffraction, it is in a so-called amorphous state in which a clear crystal structure is not shown at about 380 ° C. or lower, and a crystal structure comes to be displayed at higher than about 380 ° C. In the present invention, the structural change due to this heat treatment may be either an amorphous or a crystalline structure, but in order to prevent scratches on the plated surface during use, the harder the surface, the better the durability. The surface hardness is preferably a hard Vickers hardness of 1000 or more.

If the plating film thickness is too thin, it is affected by the softness of the underlying metal, and conversely, if the plating film thickness is too thick, cracks easily occur due to heat or stress strain, resulting in defects. Is preferably 0.1 μm or more and 15 μm or less, more preferably 0.5 μm or more and 1
It is preferably 0 μm or less.

The underlying metal on which the plating film is placed is not particularly limited, but usually SUS or carbon steel is preferably used.

Further, in the present invention, it is preferable that the surface of the drum or roll on which the plating film is placed has a width of 1 to 20 μm and a length of 50 μm or more in the range of 0 to 100 cracks / 10 mm ² . The crack here is
It means a crack that can be seen on the surface, and the magnification is 10
It can be observed with a microscope of 0 to 200 times. When there is one crack, the length can be measured as it is, but when it becomes terrible, this crack exists in this visual field like a hexagonal pattern. In such a case, the distance between the intersections is defined as the length of one crack. The presence of cracks is not preferable because when the film comes into contact with the film, the film is scraped at the cracked portion and piles up on the surface of the drum or roll, resulting in transfer to the film surface, scratches, and dents.
Furthermore, it contacts with the base metal through the cracks and reacts with them to lead to the precipitation of metal antimony and the precipitation of oligomers, which similarly causes defects on the film surface, which is not preferable.

[0021]

[Characteristics measurement method]

(1) Ion intensity ratio of SIMS Secondary ion mass spectrometer A-DI manufactured by ATOMIKA, Germany
Using DA3000, the primary ion O ₂ was 40 × 40 at an ion energy of 12 kev and a primary ion current of 500 nA.
Metal analysis is performed from the surface layer to a depth of 2500 nm in the μm region to obtain secondary ion intensities Cr ⁺ and Si ⁺ (cps),
The average (100 nm to 2000 nm) was taken from the surface layer, and the ratio (Si ⁺ / Cr ⁺ ) was determined.

Further, using the same apparatus, the primary ions Cs ⁺
The ion energy is 12 kev and the primary ion current is 100
2500 nm from the surface layer in the 200 x 200 μm region with nA
Of the secondary ion intensity O ⁻ , C ⁻ (c
ps) was obtained, and the respective intensities from 100 nm to 5000 nm were compared from the surface layer.

(2) Intrinsic viscosity [η] After the sample was dried at 120 ° C. for 3 hours, 0.1 g ± 0.0
005 g was weighed and dissolved in o-chlorophenol by stirring at 160 ° C. for 15 minutes. After cooling, the viscosity at 20 ° C. was measured with a Yamatrabotic AVM-10S type automatic viscosity meter.

(3) Carboxyl terminal concentration [Method of Maurice et al. [Anal. Chim. Act
a. , 22, 363 (1960)].

(4) Evaluation of cracks on the surface of the drum or roll The surface of the drum or roll was observed with a dark field microscope of 100 to 200 times at an arbitrary position within a range of 10 mm ² , and the width was 1-2.
A crack (crack) having a length of 0 μm and a length of 50 μm or more was observed and measured.

(5) Drum or Roll Surface Hardness The hard Vickers hardness was measured according to the usual method and used as the surface hardness.

(6) Evaluation of Adhesion of Oligomer When actually manufacturing a film, it was visually judged whether or not white powder adhered to the roll surface. When white powder was accumulated and defects such as scratches and digs were generated on the film surface, the film formation was stopped, and it was judged that the longer the time, the better the film formation stability.

(7) Surface roughness According to JIS-B-0601, using a contact surface roughness meter manufactured by Tokyo Seimitsu Co., Ltd., measuring length 4 mm, cutoff 0.25 m
Rmax was measured in m.

[0029]

EXAMPLES The present invention will now be described in more detail with reference to examples.

Example 1 Polyethylene terephthalate (Intrinsic viscosity [η] = 0.6
18, pellets having a carboxyl terminal group concentration of 41.6 equivalent / ton and a melting point of 256 ° C.) were melted at 275 ° C., extruded from a T die and rapidly cooled by a casting drum cooled to 25 ° C. to obtain an amorphous sheet. After that, 4 metal rolls (N
O. 1 to NO. 4) was heated to 90 ° C. and stretched 3.8 times in the longitudinal direction between the silicon roll (NO. 5) and the ceramic roll (NO. 6), and then 6 metal rolls (NO. 7 to 12). ), And the uniaxially stretched film was obtained. Next, both sides of the obtained uniaxially stretched film are held with clips, heated with hot air and stretched 4.5 times in the width direction at 95 ° C., and heat fixed at 120 ° C. for 2 seconds to biaxially stretch with a thickness of 8.6 μm. A polyethylene terephthalate film was obtained.

The NO. 1 to NO. 4 rolls are hard chrome plated, NO. 7-NO. No. 12 has a surface roughness of 0.3 S, and the chromium atom and the silicon atom in SIMS and the carbon atom and the oxygen atom are Si ⁺ / Cr ⁺ = 10 ⁻³ , C ⁻ > O ⁻ (C.
^- = 5 × 10 ⁴ cps, O ⁻ = 3 × 10 ³ cps) A roll having a chrome-plated film (surface hard Vickers hardness = 1300) was used. In addition, this plating has a thickness of 8 in a chromic acid, formic acid, or hexafluorosilicic acid bath.
It was formed by forming a plated film of μm and baking at 310 ° C. Further, the surface of this roll was observed under a microscope at a magnification of 150 times, but no crack was observed.

It is very stable during the production of the film,
O. 7-NO. It was possible to form a film for 85 hours without deposits that seemed to be oligomers in No. 12. After film formation, N
O. 7-NO. When the surface of No. 12 was observed, neither adhesion of oligomers nor cracks were observed.

Example 2 Polyethylene terephthalate (Intrinsic viscosity [η] = 0.6
No. 21, pellets having a carboxyl end group concentration of 40.5 equivalent / ton and a melting point of 256 ° C.) were melted at 275 ° C., extruded from a T die and rapidly cooled by a casting drum cooled to 25 ° C. to obtain an amorphous sheet. After that, 4 metal rolls (N
O. 1 to NO. 4) was heated to 90 ° C. and stretched 3.6 times in the longitudinal direction between the silicon roll (NO. 5) and the ceramic roll (NO. 6), and then 6 metal rolls (NO. 7 to 12). ), And the uniaxially stretched film was obtained. Then, both sides of the obtained uniaxially stretched film were gripped with clips, heated with hot air, stretched 4.5 times in the width direction at 95 ° C., and heat-set at 120 ° C. for 2 seconds, and then four metal rolls (NO. 13 to NO. 16) and heated to 140 ° C., and further 5 metal rolls (NO. 17 to NO. 21)
Again by 1.15 times in the longitudinal direction using
It heat-processed at 2 degreeC for 2 seconds, and the 4.5-micrometer-thick biaxially-stretched polyethylene terephthalate film was obtained.

The NO. 1 to NO. 4 rolls are hard chrome plated, NO. 7-NO. 12 and NO. 17-N
O. No. 21 has a surface roughness of 0.3 S, and has a chromium and silicon element in SIMS and a carbon atom and an oxygen atom of Si ⁺ / C.
r ⁺ = 2 × 10 ⁻³ , C ⁻ > O ⁻ (C ⁻ = 6 × 10 ⁴ c
ps, O ⁻ = 1 × 10 ³ cps) with a chrome-plated film (hard surface Vickers hardness = 1)
350) was used. The plating was prepared by forming a plating film having a thickness of 8 μm in a bath of chromic acid, formic acid, and hexafluorosilicic acid, and baking it at 310 ° C. Also, the surface of this roll was observed under a microscope at a magnification of 150 times.
No crack was observed.

It is very stable during the production of the film,
O. 7-NO. 12 and NO. 17-NO. It was possible to form a film for 95 hours without deposits that appeared to be oligomers in No. 21. After completion of film formation, NO. 7-NO. 12 and NO. 17-NO. When the surface of No. 21 was observed, neither adhesion of oligomers nor cracks were observed.

Example 3 Polyethylene-2,6-naphthalate (intrinsic viscosity [η]
= 0.625, carboxyl end group concentration 33.6 equivalents /
Ton, melting point 275 ° C.) at 291 ° C.,
It was extruded from a T-die and rapidly cooled with a casting drum cooled to 25 ° C. to obtain an amorphous sheet. After that, it is heated to 130 ° C. using four metal rolls (NO.1 to NO.4) and stretched 3.8 times in the longitudinal direction between the silicon roll (NO.5) and the ceramic roll (NO.6). After that, it was cooled with 6 metal rolls (NO. 7 to 12) to obtain a uniaxially stretched film. Next, the both sides of the obtained uniaxially stretched film are held by clips, heated with hot air and stretched 4.5 times in the width direction at 135 ° C., and heat fixed at 160 ° C. for 2 seconds, and biaxially stretched with a thickness of 8.5 μm. A polyethylene-2,6-naphthalate film was obtained.

Here, the NO. 1 to NO. The same 12 rolls as in Example 1 were used. It is very stable during the production of the film, and the NO. 7-NO. It was possible to form a film for 103 hours without deposits that seemed to be an oligomer in 12. After completion of film formation, NO. 7-NO. When the surface of No. 12 was observed, neither adhesion of oligomers nor cracks were observed.

Comparative Example 1 No. 1 was used as the roll of the prior art. 7-NO. Example 1 except that hard chrome plating with a surface roughness of 1.1S was used for 12
A biaxially stretched polyethylene terephthalate film was obtained in the same manner as above, but oligomers adhered to the roll like white powder in 22 hours, and many feather-like scratches were generated on the film surface, so film formation was stopped and the roll was washed. did.

Comparative Example 2 NO. 7-NO. A biaxially stretched polyethylene terephthalate film was obtained in the same manner as in Example 1 except that the surface roughness of No. 12 was 1.1 S. However, the oligomer adhered like white powder on the roll in 49 hours, and the film surface had feathers. Since many scratches were generated, the film formation was stopped and the roll was washed.

Comparative Example 3 No. 1 was used as the roll of the prior art. 17-NO. A biaxially stretched polyethylene terephthalate film was obtained in the same manner as in Example 1 except that hard chrome plating having a surface roughness of 1.1S was used for No. 21, but the oligomer adhered to the roll like white powder in 20 hours, and the film was obtained. 24 digging scratches on the surface
Since the film broke in a certain time, film formation was stopped and the roll was washed.

[0041]

Since the present invention has the above-mentioned structure, it has the following effects. That is, since it is possible to produce a film for a long time in a state where the oligomers present in the polymer do not adhere to the surface of the drum or roll during the production of the film, it is possible to stabilize an excellent film having no dented surface defects. Can be manufactured. Therefore, it is excellent as a manufacturing method and a manufacturing apparatus of a film for base recording such as magnetic recording, particularly 8 mm, DVC (digital video cassette) and optical.

Claims (8)

[Claims] 1. A silicon atom / chromium atom ratio of silicon atom / chromium atom is 1 in terms of SIMS intensity ratio on the outer peripheral surface.
A film production apparatus comprising a film production drum or roll having a chrome plating film containing ^0-4 or more. 2. A carbon atom on the outer peripheral surface of which is S with respect to oxygen
A film manufacturing apparatus comprising a film manufacturing drum or roll having a chrome-plated coating containing carbon atoms> oxygen atoms as the IMS strength. 3. The surface roughness of the chromium plating film portion is 1S.
It is the following, The film manufacturing apparatus of Claim 1 or Claim 2 characterized by the following. 4. The width 1 existing on the surface of the chrome-plated coating part.
~ 20μm, and 0 ~ 1 cracks with a length of 50μm or more
It is the range of 00 pieces / 10mm < ² >, The film manufacturing apparatus in any one of Claims 1-3 characterized by the above-mentioned. 5. When a molten polymer is extruded from a die and then stretched to form a film, at least one drum or roll in contact with the film has a silicon atom relative to a chromium atom as a SIMS intensity ratio of silicon atom. / A method for producing a film, which comprises using a film-producing drum or roll having a chromium plating film containing 10 ⁻⁴ or more of chromium atoms on its outer peripheral surface. 6. When a molten polymer is extruded from a spinneret and then stretched to form a film, at least one drum or roll in contact with the film has a carbon atom as an SIMS strength as a carbon atom with respect to an oxygen atom. A method for producing a film, which comprises using a film-producing drum or roll having a chromium plating film contained so as to become oxygen atoms on the outer peripheral surface. 7. The production of a film according to claim 5 or 6, wherein the molten polymer is at least one selected from polyester, polyamide, polyolefin, copolymers thereof and alloys. Method. 8. The polyester is at least one selected from polyethylene terephthalate, polyethylene-2,6-naphthalate and copolymers and composites thereof.
It is more than 1 type, The manufacturing method of the film in any one of Claims 5-7.