JPS62294526A - Thermoplastic resin film - Google Patents

Abstract

PURPOSE:To obtain a film which is superior in transparency and has favorable slipperiness, by a method wherein a film which is composed mainly of a composition where specific thermoplastic resin and thermosetting resin are mixed up with each other, possesses a protrusion on the surface and has gloss falling within a specific range. CONSTITUTION:The title film is composed mainly of a composition where 97-99.99wt% thermoplastic resin (A) and 3-0.01wt% thermosetting resin (B) having heat resistance at a temperature which is higher by 20 deg.C than the fusion point of the said thermoplastic resin or more and is 200 deg.C or more are mixed up with each other. This film is of a thermoplastic film possessing a protrusion on the surface and having gloss of 110-170. The most suitable polymer especially as the thermoplastic resin (A) is a polyolefin series polymer. This polymer is stable thermally and the same neither gels nor decomposes thermally nor hydrolyzes nor includes impurities such as oligomer, too. The thermosetting resin (B) is epoxy resin or phenolic resin or silicone resin and includes a derivative having various substituents also. The silicone resin is most desirable among resin in view of slipperiness and transparency.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a thermoplastic resin film with excellent transparency and good slip properties.

[Prior Art] Conventionally, in order to improve the smoothness of thermoplastic resin films by several hundred, films to which inorganic fillers such as →neuroids have been added, and films to which fatty acid amides such as oleic acid amide have been added have been rated at 7.0. .

[The problem that the invention seeks to solve, however, g! For products with a filler added, if inorganic filler is added until sufficient slipperiness is obtained, the transparency will inevitably deteriorate, and products with organic lubricants such as fatty acid amide will only give similar results, and It had a fatal drawback in that the slipperiness decreased rapidly at high temperatures (approximately 80° C. or higher).

The present invention solves the above problems and provides a thermoplastic resin film that has excellent slip properties and good transparency.

[Means for solving the problems] The present invention provides thermoplastic resins (A>97 to 99.99 wt%
and a thermosetting resin (B) 3 whose heat resistance is 20'C higher than the melting point of the thermoplastic resin and 200°C or higher.
~0. The film is mainly composed of a composition mixed with 1t% of O, and the film has protrusions on the surface, and is made of a thermoplastic 1mm thick film with a cross diameter of 110 to 170%.
It is a characteristic of J.

The thermoplastic resin (A> in the present invention) refers to polyolefins such as polypropylene, polyethylene, 4-methylpentene-1-polymer, and copolymers thereof, polyethylene terephthalate, polybutylene terephthalate, polyhexene terephthalate-1 to , and polyesters such as copolymers thereof, nylon 6, nylon 66,
Polymers such as nylon 11, nylon 12, nylon 610, polymethaxylylene adipamide, polyhexamethylene terephthalamide/isophthalamide, and polyamides such as copolymers thereof, and these polymers alone or in blends. The most suitable polymer for the thermoplastic resin (A>) is a polyolefin polymer. It is an easy-to-handle polymer that does not contain any oligomeric impurities, and has various excellent features such as being a general-purpose polymer and being inexpensive.

Among polyolefins, polypropylene and copolymers thereof are particularly preferred. This is because it has excellent toughness, ease of film formation, transparency, and heat resistance.

The polypropylene has an isotactic index II (measured by boiling 111 in-heptane extraction method) of preferably 90% or more, more preferably 95% or more, and an intrinsic viscosity [η] (135°C, Te) to lauan solution. Measurement) Preferably, the range is 1.2 to 2.5 dQ/CI. In addition to propylene, comonomers such as ethylene, butene, and pentene may be randomly or block copolymerized, but the propylene component is preferably 90% or more.

The thermosetting resin (B) includes epoxy resin, phenol resin, urea resin, silicone resin, etc., and also includes derivatives having various substituents. Among the above resins, silicone resins are most preferred in terms of flexibility and transparency.

In addition, the heat resistance of the thermosetting resin (B) is different from that of thermoplastic resin (Si1 resin).
At a temperature 20°C higher than the melting point of A) and 200°C
The above is all you need to do. In addition, the thermoplastic resin (A>
The temperature is preferably 20°C higher than the melting point of , and preferably 250°C or higher.

When the film of the present invention is an unstretched film, slipperiness,
From the viewpoint of transparency, the amount of resin (B) added is 0°3~3wt%.
The content is preferably 0.5 to 2 wt%, and more preferably 0.5 to 2 wt%.

In addition, when the film is a stretched film, the resin (B)
The slippage becomes even more noticeable. That is, resin (B
) protrudes from the film surface during stretching, and sufficient slipperiness can be obtained with a small amount of addition. - When forming an axially stretched film, the amount of resin (B) added is 0.03 to 1. Q
It is preferably 0.08 to 0.5 wt%, more preferably 0.08 to 0.5 wt%. In addition, when making a biaxially stretched film, resin (B)
The addition t11 is preferably 0.01 to Q, 5 wt%,
More preferably, it is 0.05 to 0.2 wt%.

In the case of a multilayer 2111 stretched film, when the melting point of the layer to which resin (B) is added is lower than the melting point J: of the other layers, ! Nitoe! ;U', in a two-layer film of hoshiboria[]pyrene (referred to as PP) and PP copolymer, when resin (B) is used as a slipperiness improver for the copolymer layer, in the stretching process. Since the PP copolymer layer is in a molten or semi-molten state, the resin (B) 1 is difficult to protrude onto the film surface. Therefore, the amount of resin (B) added should be 0.1 to 2.
It is preferably 5 wt%, more preferably 0.3 to 2 wt%.

Although the film of the present invention has protrusions made of a thermosetting resin on the film surface, the reduction in gloss is smaller than that of the conventional Zuperi [with a raw meat finisher added].

Sufficient slipperiness and transparency are achieved when the cross is between 110 and 170. Cross or 110 end) 1'11 (but the transparency is poor, and if it exceeds 170, the smearability will be poor.

The most preferred cross range is thermoplastic) Mu・1 fat (A)
Depends on the type. For example, for polypropylene, 110 to 150 is preferable, and for polyethylene terephthalate 1, 130 to 170 is preferable. The preferred size and number of protrusions on the film surface is 2 to 30 μm.
, height is 0.1-1μ, 0.08-8 pieces/I'n
m, more preferably 0.15 to 4 pieces/mm.

In the present invention, better effects can be obtained by using a stretched film, but in order to improve the slip properties even more effectively, biaxial stretching is used, and the stretching ratio is preferably 30 times or more, and Preferably it is 40 times or more.

The size and number of protrusions on the film surface depend on the average particle size, particle size distribution, and dispersion state of the resin (B). That is, if the particle size is large or the dispersion is poor, large protrusions will be formed on the film surface, and if the particle size is small, small protrusions will be formed.

As the size and height of the film surface protrusions increases, transparency tends to deteriorate, while as they decrease, slipperiness tends to deteriorate. The resin (B) to be mixed is spherical and has an average diameter of 0.5 to 10
μ is preferable, and 95% or more of its distribution is 0.1 to 15 μ
Particularly preferred are those. In the case of an unstretched film, the average diameter is particularly preferably 2 to 10 μm. In the case of stretched films, an average diameter of 0°5 to 3μ is particularly preferred. Further, in the case of a laminated film having layers having different melting points, an average diameter of 1.5 to 8 μm is particularly preferable.

The film of the present invention is mainly composed of a composition in which the above-mentioned thermoplastic resin (A>) and a thermosetting resin (B) are mixed, and the known additives and the like are added to the extent that the object of the present invention is not impaired. They may be mixed.

In order to further improve the transparency of the film of the present invention while maintaining its slipperiness, thermoplastic resin, resin (B)
Most preferably, the mixed film layer is a film laminated on at least one side of a thermoplastic resin film. That is, by forming a laminated film, the film thickness of the present invention can be reduced, and transparency can be improved without deterioration of slipperiness.

The film thickness of the present invention is not particularly limited, but is 3 to 100 μm.
, preferably 5 to 60 μm, and in the case of a laminated film, the film layer thickness of the present invention is preferably 0.5 to 8 μm,
More preferably, the thickness is 1 to 5μ.

Next, a method for manufacturing the film of the present invention will be explained.

The thermoplastic resin is 97 to 99.99 wt%, the heat resistance is 20 °C higher than the melting point of the thermoplastic resin, and 20
Mix 3 to 0.01 wt% of thermosetting resin (B) at a temperature of 0°C or higher, and discharge it from a slit-shaped nozzle at a polymer temperature of 180 to below the heat-resistant temperature of resin (B) or 300°C or less, and Cast on a cooling drum at a temperature of 20 to 9°C to cool and solidify. In the case of forming a stretched film, it is further carried out as follows.

- In the case of an axially stretched film, stretching may be performed in only one direction, and in the case of a biaxially stretched film, stretching may be performed in both directions. After heating the cast film to 80 to 150°C, it is stretched 3 to 7 times in the longitudinal direction, and then stretched 4 to 12 times in the width direction at 80°C or below the melting point of the thermoplastic resin using a tenter-type stretching device. Stretch to. After stretching, the stretched film may be relaxed by 0 to 10% in the width direction and then heat treated for 3 to 10 seconds at 120° C. to a temperature below the melting point of the thermoplastic resin, if necessary. When making a laminated film, there are coextrusion method i'), a method of extrusion lamination of thermoplastic resin after -axial stretching or biaxial stretching, etc.
It doesn't hurt to do either one.

Roughly, the film of the present invention is subjected to corona discharge treatment or plasma treatment in air or under single or mixed gas such as carbon dioxide gas or nitrogen gas to improve surface adhesion, and then metal vapor deposition, printing, etc. are performed. good.

[Measurement method, evaluation method] The terms used in the present invention and the evaluation method of characteristics will be explained.

(1) Cross Measured at 60'-60' according to JIS 8471.

(2) Hayes Measured according to JIS-36782.

(3) Sharpness of the protrusions on the film surface, number J l5-8-
Measured at 0601 (3).

The surface of the film was measured under the following measurement conditions using S on a three-dimensional universal surface shape measuring instrument with an analyzer (manufactured by Koita Research Institute Co., Ltd.) 1 model 5E-3r.

Measurement length・・・・・・・・・・・・2mm Vertical magnification・
・・・・・・・・・・・・10000x horizontal magnification...
・・・・・・・・・・・・100 times feed speed・・・・
・・・・・・・・・Q, 1mm/eC cutoff (direct...
...0.25mm measurement interval...
・Number of 10 μ measurements・・・・・・・・・・・・25 Count the number of ridges of the corresponding size from the roughness curve obtained from the above-mentioned strip A1, and calculate the average number of ridges per 1 mm. Calculate.

(4) Slip coefficient Test fill 75 mm wide x 100 mm long at 20°C.

After conditioning the humidity at 65%R]-1 for more than 24 hours, use a slip tester (Kyoto Makinosha!
0101) to read the slip resistance 11L(q), and calculate the slip coefficient (Shizuma coefficient μs, dynamic friction coefficient μd) using the following formula. If the sample film is a laminated film, the lubricant-added layers are stacked on top of each other), 200 CI
The sliding speed was set to 150 m/min.

Slip coefficient = L/200 (5) Powder particle size E, average diameter The average diameter is an equivalent sphere equivalent value, and its measurement is performed using a Coulter Counter (TA-■ model) manufactured by Japan Fu4 Gakudenkai Co., Ltd. This was done using

(6) Using a heat-resistant differential scanning calorimeter, a 5n+c+ sample was heated to 300°C at a heating rate of 20°C/min, and the thermal decomposition onset temperature was measured.

(7) Melting point of thermoplastic resin Using a differential scanning calorimeter Model DSC-2 manufactured by Perkin-Elmer, a 5 mg sample was measured at 20
After raising the temperature to 280°C at a heating rate of °C/min and holding it for 5 minutes, it was cooled at a circumferential speed 1], and when the temperature was raised again, a so-called second-run melting curve was taken.

When there is one apex of the melting peak, the temperature at the apex of the peak is taken as the melting point.

When there are two or more apexes of melting peaks, the heat of fusion of each peak is determined, and the value calculated by the following formula is taken as the melting point.

Σ △l-11-1i- tWhen there are n melting peaks) However, △H1 is the heat of fusion of the i-th peak, and ↑mi is the i
Indicates the temperature at the top of the second peak.

Examples of curves with two melting peaks are shown in Figures 1 and 2.
As shown in the figure. In these figures, among the melting peaks, the melting peak on the low temperature side is Pl, and the melting peak on the high temperature side is P2. In addition, the apex of each melting peak, that is, the minimum point of the peak is designated as A and B, and the temperatures at these apex are Tm1 and Tm1, respectively.
Let it be m2.

Further, the peak heat of fusion on the low temperature side is 1''1, and the peak heat of fusion on the high temperature side is H2.

The method for determining the heat of fusion is shown by the first peak P1 in FIG. First, the absorption start point T1 and end point T2 are connected by a straight line (broken line C in FIG. 1) to form a baseline.

Peak +)? The intersection of the extrapolation line of the straight line part of the j half and the base line is d5, the intersection of the extrapolation line of the straight part of the second half of the peak and the base line is d6, and the area surrounded by the peak, extrapolation line, and base line (shaded area) Let the area be the heat of fusion H1.

Similarly, the heat of fusion H2 at the second peak P2 is determined.

However, as shown in FIG. 2, the end point T2 of the first peak P1
The starting point T3 of the second peak P2 becomes one point, connects T1 and T4, and if it deviates from the base line C, the intersection with the base line C perpendicularly below the point is set as T9, and the peak The linear portion of the latter half (the first half of the peak in the case of the second peak P2) is connected to %T9, and the area is determined by regarding this line as an extrapolation line.

[Example] Hereinafter, the present invention will be explained based on examples.

Examples 1 and 2 The average particle size, particle size division, and amount added are shown in Table 1 (
Direct silicone resin powder (temperature at the time of decomposition: 1/3oo')
c or more) and polypropylene powder ([η] = 2.0,
II=97%, melting point 162°C> were mixed in a Henschel mixer and extrusion granulated at 250'C before twin-screw extrusion. This granulation depth was processed using the T-die method at a polymer temperature of 250°C.
Extrusion, l! The mixture was cooled and solidified on a cooling drum kept at 10° C. to obtain an unstretched film with a thickness of 15 μm.

Examples 3 to 5 An unstretched film was made in the same manner as in Example 1 using a silicone resin having the average particle size and particle size distribution shown in Table 1, and the unstretched film was heated to 140°C and to 5
The film was stretched twice, immediately cooled to 40°C, then introduced into a tenter maintained at 160°C, and stretched 8 times in the width direction. The thickness of the film thus obtained was 15μ.

Comparative Examples 1 and 2 The amount of silicone resin added in Example 3 was reduced to 0.005 wt%.
(Comparative Example 1) and 4vt% (Comparative Example 2), but otherwise carried out in the same manner.

The film properties of Examples 1 to 5 and Comparative Examples 1 and 2 are shown in Table 1, and the PP films shown in the Examples all satisfy both the properties of slipperiness and transparency compared to the Comparative Examples. Ta. However, in Example 1, the slipperiness was slightly poor;
In Examples 4 and 5, the transparency was slightly lowered, but there was no practical problem. Comparative Example 1 had insufficient slip properties, and Comparative Example 2 had poor transparency.

Example 6.7 A silicone resin (decomposition initiation rate of 300°C or higher) with an average particle size and particle size distribution shown in Table 2 and an ethylene-propylene random copolymer (Edilene○Yibun 4,5W) were used.
t%, [η]=1.8. A mixture with a melting point of 136°C) was once extruded and granulated, and PP chips similar to those used in Example 1 were coextruded at 250°C using a two-layer die.
It was cooled and solidified on a cooling drum maintained at 40°C. The unstretched film was biaxially stretched in the same manner as in Example 3 to obtain a film having a total film thickness of 15 μm and a copolymer layer thickness of 3 μm.

Comparative Example 3 The amount of silicone resin added in Example 7 was reduced to 0.005 wt%.
Haku did the same thing.

Comparative Example 4 The same procedure was carried out except that instead of the silicone resin of Example 7, 1 wt % of thyroid 2/1/l with a particle size of 3 microns and 95% or more of 1 to 10 microns was added.

Comparative Example 5 A test was carried out in the same manner as in Example 3 except that 0.5 wt% of nylon-6 (melting point 220°C) was added instead of the silicone resin.

The film properties of Examples 6 and 7 and Comparative Example 3 are shown in Table 2, and the film properties of Comparative Examples 4 and 5 are shown in Table 3. The PP laminated film shown in the Example has smoothness and transparency compared to the Comparative Example. It satisfied both gender characteristics. Comparative Example 3 had insufficient slip properties, Comparative Example 5 had poor transparency, and Comparative Example 4 had insufficient slip properties and transparency.

[Effects of the Invention] The present invention provides a thermosetting resin having a heat resistance higher than the melting point of the thermoplastic resin and a temperature higher than 200°C.
Since the cross was mixed with 0.01 to 3 wt% to give a cross of 110 to 170, it is possible to maintain excellent slipperiness while maintaining transparency compared to conventional films.

[Brief explanation of the drawing]

FIG. 1 and FIG. 2 are explanatory diagrams each showing an outline of a melting spectrum measured by a differential scanning thermometer. Pl...first (low temperature side) melting peak P2...second
(High temperature side) Melting peak A...Apex B of the first melting peak...Apex C of the second melting peak...
...Black line D...Start point of the first melting peak m1...
Temperature at point A Tm2...Temperature at point B Hl...Heat of fusion at Pl

Claims (1)

[Claims] Thermoplastic resin (A) 97 to 99.99wt% and thermosetting resin (B) 3 to 0.01w with heat resistance at a temperature higher than 20°C than the melting point of the thermoplastic resin and 200°C or higher.
t%, the film has protrusions on the surface and has a cross of 110~
170 thermoplastic resin film.