JP3289362B2 - Laminated film for drawing - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to heat resistance and drawability.
Laminated film for drawing with excellent and good shape retention
It is about.

[0002]

2. Description of the Related Art A thermoplastic polyester resin, especially a polyethylene tetphthalate resin, is widely used for various films and tapes since a film having extremely excellent strength and rigidity can be obtained by stretching. However, unstretched or stretched thermoplastic polyester resin films having a low draw ratio of 2 times or less are not very attractive in terms of strength, and their applications are extremely limited.

[0003]

As an application of such an unstretched or low-stretched stretched film, there is a drawing film called vacuum forming or pressure forming, but in the case of a thermoplastic polyester resin, there is a conventional method. It was not always suitable for drawing. That is, in the case of polybutylene terephthalate, a high stress is required at the time of drawing, it is difficult to perform drawing in a shape faithful to the mold, and the heat resistance is insufficient for some applications. On the other hand, in the case of the polyethylene terephthalate resin, even if the drawability is good, post-deformation due to residual stress or post-crystallization after drawing tends to occur, and the shape retention is difficult.

[0004] Further, a film made of a thermoplastic polyester resin can be used not only as a single unit for drawing but also for lamination, but in that case, it also has considerable disadvantages. That is, in recent years, practical examples of subjecting a thermoplastic resin sheet to drawing are increasing, and various products are mass-produced by stamping molding in which, for example, a sheet of a polypropylene resin or a nylon resin is heated and softened and then pressed. However, such a thermoplastic resin sheet for drawing often contains an inorganic filler or a fibrous reinforcing material, and it is difficult to obtain a good appearance. In addition, there is often a difficulty in production due to the fact that the material is greatly deformed by its own weight during heating and softening and loses its shape so that it cannot be put into the drawing process.

For this reason, the surface layer of the thermoplastic resin sheet or the intermediate layer between the surface layer and the like has a good appearance, has high heat resistance, and has an appropriate tensile strength to prevent the entire sheet from deforming under its own weight when softened by heating. In addition, it is effective to laminate and use a drawing film which has good drawing workability and hardly causes post-deformation. Therefore, for such a purpose, in a sheet using polypropylene as a part of a laminate,
Although it is conceivable to use a polyethylene terephthalate resin film having a high melting point, it cannot be used sufficiently because of insufficient drawability as described above. on the other hand,
Even when a polybutylene terephthalate resin film is used, heat resistance is insufficient at a temperature at which the polypropylene is sufficiently softened. Therefore, the use of a thermoplastic polyester resin for such a purpose is very restrictive.

Accordingly, it is suitable for use as a part of a laminate containing a thermoplastic polyester resin material for drawing, which is excellent in heat resistance and drawability and has good shape retention, particularly, a polypropylene resin. In fact, thermoplastic polyester resin films have not been obtained industrially.

[0007]

Means for Solving the Problems The present inventors have overcome the above-mentioned drawbacks of the conventional thermoplastic polyester resin material, and have excellent heat resistance, drawability, and good shape retention. As a result of intensive studies to provide a resinous film, such a purpose can be satisfied by using a composition in which a polyethylene terephthalate resin, a polybutylene terephthalate resin, an ethylene-based ionomer resin, and an inorganic filler and the like are blended as necessary. This has led to the present invention.

That is, the gist of the present invention is that (A) polyethylene terephthalate resin: 40 to 80% by weight, (B)
Polybutylene terephthalate resin: 10 to 40% by weight,
(C) an ethylene ionomer resin: 2 to 20% by weight,
(D) Thermoplastic polyester comprising 0 to 5% by weight of inorganic filler and (E) 0 to 0.5% by weight of phosphorus-containing compound
A layer made of a resin composition and a polypropylene resin layer.
Existing in laminated films for drawing.

Hereinafter, the present invention will be described specifically. The thermoplastic polyester resin used in the present invention is terephthalic acid, or a polyalkylene terephthalate obtained by a polycondensation reaction of a dialkyl ester thereof with an aliphatic glycol or a copolymer mainly containing these, and the aliphatic glycol is used. When ethylene glycol is the main component, it is called polyethylene terephthalate resin, and when it is mainly composed of tetramethylene glycol, it is called polybutylene terephthalate resin.

Examples of the aliphatic glycols include ethylene glycol, propylene glycol, tetramethylene glycol, and the like. In addition to these aliphatic glycols, other diols or polyhydric alcohols such as aliphatic glycols can be used. Cyclohexanediol, cyclohexanedimethanol, xylylene glycol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis ( 4-hydroxyethoxyphenyl) propane, 2,2-bis (4-hydroxyethoxy-3,5-dibromophenyl) propane,
Glycerin, pentaerythritol and the like may be used as a mixture.

In addition to terephthalic acid or its dialkyl ester, other dibasic acids, polybasic acids or their alkyl esters, such as phthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, etc. , Adipic acid, sebacic acid, trimesic acid, trimellitic acid, alkyl esters thereof, and the like may be used as a mixture.

Such a thermoplastic polyester resin is used as a polymerization catalyst in Sb ₂ O ₃ , GeO ₂ , or Ti.
(OBu) ₄ etc. in the order of several hundred ppm, usually 50
Although it is often contained in the range of about 500 ppm, mixing of the polyethylene terephthalate resin and the polybutylene terephthalate resin, and in order to obtain a stable property by suppressing the transesterification reaction at the time of melt heat processing, the polymerization catalyst Residue in the resin is 50 ppm or less, more preferably 20 p
pm or less is preferred.

The ethylene ionomer resin used in the present invention includes an α-olefin containing ethylene and an α, β-olefin.
An ionic copolymer obtained by adding a metal ion having a valence of 1 to 3 to a copolymer with an unsaturated carboxylic acid. Here, typical examples of the α, β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, and itaconic acid.
In addition, typical examples of metal ions having a valence of 1 to 3 include:
Na ⁺ , K ⁺ , Ca ⁺⁺ , Zn ⁺⁺ , Al ^{+++ and the} like. These ethylene ionomer resins, for example,
Commercially available from DuPont under the trademark Surlyn.

The inorganic filler particles used in the present invention are not particularly limited, and any one can be selected from those conventionally used as a resin filler. Specifically, silica-alumina-based clay minerals (hydrated aluminum silicates) represented by clay, kaolin, calcined kaolin, and silica represented by talc-
Magnesium, calcium silicate, silica,
Alumina, calcium carbonate and the like can be mentioned. Among them, talc, kaolin and calcined kaolin are particularly preferable in terms of easy dispersibility and shape retention. In particular, when talc is used, the heat resistance of the obtained film is improved.

When these inorganic filler particles are surface-treated with a well-known surface treatment agent such as a silane treatment agent or a titanium-based treatment agent, good dispersibility can be obtained and at the same time, the obtained film The properties are also improved.
The phosphorus-containing compound used in the present invention suppresses the transesterification reaction between the polyethylene terephthalate resin and the polybutylene terephthalate resin, stabilizes the properties of the obtained film, and further improves the heat resistance. Is a phosphorus-containing derivative such as an organic phosphate, and includes, for example, phosphite, hypophosphite, metaphosphoric acid, allylphosphinic acid, allylphosphonic acid and the like. Particularly preferred phosphorus-containing compounds include, for example, triphenyl phosphite, tributyl phosphite, triisopropyl phosphite, or organic phosphites represented by the following general formula (manufactured by Ciba Geigy,
Trade name Irgafos PEP-Q).

[0016]

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Further, organic phosphoric acid esters can also be suitably used.

[0018]

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(R is an alkyl group having 1 to 30 carbon atoms; n is an integer of 1 to 3).
Among them, those containing a higher aliphatic group as the R group are preferable because they have little loss due to evaporation and scattering during thermal processing at a high temperature. Such organic phosphates include, for example,

[0020]

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(Product name mark AX7, manufactured by Asahi Denka Co., Ltd.)
1) and the like. For the polypropylene resin used as a laminate including the film of the present invention, the type and filler, additives, thickness and the like are not particularly limited, for example, as a sheet for stamping molding,
You may use the sheet marketed under the name of Azdel (trade name, manufactured by Ube Industries, Ltd.) and X sheet (trade name, manufactured by Idemitsu Petrochemical Co., Ltd.).

The composition of the thermoplastic polyester resin composition of the present invention is as follows. That is, the polyethylene terephthalate resin is 40 to 80% by weight, preferably 5% by weight.
0-80% by weight, polybutylene terephthalate resin is 1
0 to 50% by weight, preferably 20 to 40% by weight, and the ethylene ionomer resin is 2 to 20% by weight, preferably 5 to 20% by weight.
-15% by weight, inorganic fillers are 0-5% by weight, preferably 0.05-1% by weight, and phosphorus-containing compounds are 0-0.5% by weight, preferably 0.05-0.2% by weight.

The compounding of each resin and the inorganic filler is performed by a method well known to those skilled in the art, and examples thereof include a method using a Banbury mixer, a super mixer, and an extruder. There is no particular limitation on the method of processing such a resin composition into a film, and a general film forming method such as a T-die method or a tubular method can be applied.
There are no particular restrictions on the film-forming conditions or thickness of the film, but in order to be subjected to drawing, it is not preferable to perform stretching at a high magnification, and unstretched or stretched films with a low magnification of 2 or less are effective. .

The thermoplastic polyester resin composition of the present invention may contain, in addition to the above-mentioned components, various additives known to those skilled in the art, for example, an antioxidant such as hindered phenol,
It may contain a weather resistance improver such as a triazine compound, a coloring agent such as a pigment or a dye, an antistatic agent, a lubricant, and the like.
It is also possible to mix other resins within a range that does not impair the effects of the present invention.

[0025]

The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples.

Examples 1-4 Comparative Examples 1-5 Commercially available polyethylene terephthalate resin (Nihon Unipet Co., Ltd.)
Commercially available polybutylene terephthalate resin (Novadur 502 manufactured by Mitsubishi Kasei Co., Ltd.)
0, Novadur is a registered trademark), commercially available ethylene ionomer resin (manufactured by Du Pont-Mitsui Co., Ltd., trade name Himilan 1707), and commercially available talc (manufactured by Shiraishi Calcium Co., Ltd., trade name Micron White 5000A), commercially available organic Using a phosphate ester (trade name AX71, manufactured by Asahi Denka Co., Ltd.), the mixture was mixed with the composition shown in Table 1, and then melt-mixed with a vented extruder having a cylinder diameter of 40 mm to obtain pellets. The obtained pellets were dried in a 120 ° C. hot air drier for 5 hours, and then a 50 μm thick film was formed at a cylinder temperature of 260 ° C. and a roll temperature of 80 ° C. using a T-die film forming machine having a cylinder diameter of 40 mmφ. did. Using the obtained film, the tensile strength at 150 ° C. and 200 ° C. corresponding to the drawing and the residual tension after cooling corresponding to the post-deformation after the drawing were measured. The results are shown in Table 2. In addition, the obtained film is made of 40% glass fiber.
A commercially available polypropylene sheet having a thickness of 3.8 mm (P403B, manufactured by Idemitsu Petrochemical Co., Ltd.); and
Commercially available polypropylene resin (Diapolymer Co., Ltd.,
1mm thick using Mitsubishi Polypro 4500J)
And a commercially available dry laminating adhesive (manufactured by Dainippon Seika Co., Ltd., trade name: Seikabond A158), and then heated with a hot air dryer at 220 ° C. With a small press molding machine with a force of 1t,
A dish-shaped molded product having a depth of 20 mm, a diameter of 100 mm, and a bottom corner 10R was formed, and the appearance of the obtained molded product was visually observed. The results are shown in Table 2.

[Test method] Heat resistance A film is stretched on a ring-shaped jig having an inner diameter of 100φ, and its periphery is fixed.
Load 150 through metal needle indenter with tip diameter 1mmφ
g, and the oil bath was heated at a rate of 50 ° C./hour,
The temperature at which the needle-shaped indenter penetrated the film was defined as the heat-resistant temperature.

Using an Instron type universal tester equipped with a thermostatic chamber, the film is set at a predetermined temperature, and a tensile test is performed on the film in accordance with JIS K-7127. It was measured as tensile strength.

Residual tension Using an Instron universal tester equipped with a thermostat, 200
In a 10 ° C atmosphere, a tensile test is performed on the film in accordance with JIS K-7127. When the displacement reaches 10%, the test is stopped while the displacement is fixed, and the constant temperature bath is removed. After standing for 30 minutes, the tension of the film was measured and defined as the residual tension.

Appearance of Pressed Product The corners of a molded product which was bonded to a glass fiber-filled polypropylene sheet and drawn were observed, and the glass fiber (abbreviated as GF) in the polypropylene sheet was a thermoplastic polyester resin film. It was visually observed whether or not it had broken through. Further, the molded article which had been laminated with a polypropylene sheet containing no glass fiber and which had been subjected to drawing was allowed to stand in a normal temperature atmosphere, and the radii of the corners after 1 hour and 24 hours were measured.

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

As shown in the examples, since the drawing film made of the thermoplastic polyester resin composition of the present invention has the same strength at 150 ° C. and 200 ° C. and low tensile strength, the drawing process is easy. It has a wide processing temperature range, and has a tension that does not cause harmful deformation during heating. In addition, since heat resistance is high and strength is excellent even during high-temperature drawing, breakage due to glass fibers or the like hardly occurs. Furthermore, since the residual stress is low, there is little return deformation after drawing, and the shape retention is excellent.

Such characteristics are remarkably exhibited when drawing is performed by laminating with a polypropylene resin. The drawing is easy, the corner portion is hardly broken, and the post deformation of the corner portion is reduced.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-61-184447 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 67/00-67/02

Claims (1)

(57) [Claims] (A) Polyethylene terephthalate resin: 40 to 80% by weight, (B) polybutylene terephthalate resin: 10 to 40% by weight, (C) ethylene ionomer resin: 2 to 20% by weight, (D) inorganic Filler: 0
To 5% by weight and (E) a phosphorus-containing compound: a layer comprising a thermoplastic polyester resin composition comprising 0 to 0.5% by weight.
Laminate for drawing including a polypropylene and a polypropylene resin layer
M