JPH06126900A - Laminated polyphenylene sulfide film - Google Patents

Abstract

PURPOSE:To provide a film having excellent adhesive properties and balanced mechanical properties and heat resistance. CONSTITUTION:A laminated polyphenylene sulfide film is obtained by laminating a surface layer made of thermoplastic resin film containing 0.01-30 pts.wt. of polyalkylene glycol to 100 pts.wt. of thermoplastic resin at least one side of a central part of a biaxially oriented polyphenylene sulfide film.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a laminated polyphenylene sulfide film. More specifically, it relates to a laminated polyphenylene sulfide film having excellent mechanical properties and heat resistance and excellent adhesiveness.

[0002]

2. Description of the Related Art Polyphenylene sulfide films, especially poly-p-phenylene sulfide films, are promising and proposed for application in various fields because of their excellent mechanical properties and heat resistance. For example, JP-A-57-1210
No. 52 discloses a non-oriented sheet of polyphenylene sulfide, and JP-A No. 54-142275 discloses a biaxially oriented film. The non-oriented sheet is
Although it has a high tear strength, it has the drawbacks that when it is exposed to high temperatures, its mechanical strength rapidly decreases and its long-term heat resistance is poor. On the other hand, the biaxially oriented film has the characteristics that mechanical properties other than the tear strength are significantly improved as compared with the non-oriented sheet, and the chemical resistance and the long-term heat resistance are extremely excellent. However, as it is expected from the structure and it is clear from the excellent chemical resistance and heat resistance, the surface is inactive, so the adhesiveness is poor, so for packaging,
In order to use it for electrical insulation, general industrial use, etc., it was necessary to impart adhesiveness.

Conventionally, as a method for improving the adhesiveness, a corona treatment has been disclosed (Japanese Patent Laid-Open No. 187327/1982), but although improvement is recognized as compared with untreated, it is still insufficient. It was

[0004]

The object of the present invention is to solve the above-mentioned drawbacks of the conventional polyphenylene sulfide film, to provide a film having excellent adhesiveness and balanced mechanical properties and heat resistance. Is.

[0005]

[Means for Solving the Problems] In order to achieve the above object, the present invention provides 0.01 to 30 parts based on 100 parts by weight of a thermoplastic resin on at least one side of a central part made of a biaxially oriented polyphenylene sulfide film. This is a laminated polyphenylene sulfide film in which a surface layer made of a thermoplastic resin composition containing parts by weight of polyalkylene glycol is laminated.

In the present invention, the surface layer is at least one side of the central portion of the biaxially oriented polyphenylene sulfide film and constitutes at least one surface of the laminated polyphenylene sulfide film of the present invention.

The surface layer is composed of a thermoplastic resin composition containing 0.01 to 30 parts by weight of polyalkylene glycol with respect to 100 parts by weight of the thermoplastic resin.

Examples of the thermoplastic resin in the present invention include polyesters, polyolefins, polyamides, polyphenylene sulfides, and polyether ether ketones. Among them, polyesters, especially ethylene terephthalate and ethylene-2,6-naphthalate, are mainly repeated. Unit polyester or p-
Polyphenylene sulfide containing phenylene sulfide as a main repeating unit is preferable. Here, the term “mainly repeating unit” means that the repeating unit is 70 mol% or more, preferably 85 mol% or more, more preferably 95 mol% or more.
In the case of other components that can be copolymerized, and are, for example, polyesters such as polyethylene terephthalate and polyethylene naphthalate, which are mol% or more, glycol components other than ethylene glycol, other than terephthalic acid or 2,6-naphthalenedicarboxylic acid. In the case of dicarboxylic acid component or hydroxycarboxylic acid component, or polyphenylene sulfide,

[Chemical 1]

[Chemical 2]

[Chemical 3]

[Chemical 4]

[Chemical 5]

[Chemical 6] Or a small amount of

[Chemical 7] There is no problem that such a trifunctional component as described above is copolymerized.

The polyphenylene sulfide is preferably a polyphenylene sulfide having an xylene extraction amount of 1.5% by weight or less. Here, the xylene extraction amount is 2
It refers to the ratio of the weight of the extract when extracted with xylene for 36 hours by a Soxhlet extractor immersed in an oil bath heated to 00 ° C. to the weight of the substance to be extracted before extraction.

In the present invention, the thermoplastic resin composition constituting the surface layer needs to contain polyalkylene glycol. The polyalkylene glycol is a high polymer composed of, for example, an oxyethylene unit, an oxybutylene unit, an oxyhexylene unit, or the like, or an oxyalkylene unit formed by mixing these units. A preferred polyalkylene glycol is polyethylene glycol. The molecular weight is preferably about 400 to 1,000,000, more preferably about 400 to 20,000.

The content of polyalkylene glycol is preferably 0.01 with respect to 100 parts by weight of the thermoplastic resin.
-30 parts by weight, more preferably 0.05-10 parts by weight,
It is more preferably 0.1 to 3 parts by weight. If the amount is less than 0.01 part by weight, the effect of improving the adhesiveness is not seen, which is not preferable. Also, the polyalkylene glycol content is 30
If the amount is more than parts by weight, the heat resistance decreases, which is not preferable. Polyalkylene glycol is preferably dissolved or dispersed in the thermoplastic resin composition,
Even when they are dispersed, it is particularly preferable that the major axis of the polyalkylene glycol portion is finely dispersed to 10 μm or less.

The thermoplastic resin composition of the present invention may be added in various amounts such as other polymers, inorganic or organic lubricants, colorants, ultraviolet absorbers, antioxidants, heat stabilizers, crystal nucleating agents, etc. It is acceptable to include a drug. In particular, the inorganic and organic inert particles are preferably used for controlling the slipperiness of the film. As inert particles,
Examples thereof include silica, alumina, calcium carbonate, barium sulfate, kaolin, calcium phosphate, titanium oxide, talc, zinc oxide, and crosslinked polystyrene particles. It is also possible to utilize particles that precipitate during the polymerization.

In the present invention, the biaxially oriented polyphenylene sulfide film constituting the central portion is poly-p-
It is composed of polyphenylene sulfide containing phenylene sulfide as a main component, and the polyphenylene sulfide accounts for 80% by weight or more, preferably 90% by weight or more, and more preferably 95% by weight or more. The remaining 20% by weight
If it is less than 1, preferably less than 10% by weight, and more preferably less than 5% by weight, it may contain the same additives, inert particles and the like as those described in the thermoplastic resin composition constituting the surface layer. Absent.

Further, the polyphenylene sulfide is
80 mol% or more, preferably 90 mol% or more, and more preferably 95 mol% or more of all repeating units are p-phenylene sulfide units. If less than 20 mol% of all repeating units,

[Chemical 8]

[Chemical 9]

[Chemical 10]

[Chemical 11]

[Chemical 12]

[Chemical 13] Or a small amount of

[Chemical 14] A trifunctional component such as the above may be copolymerized.

The polyphenylene sulfide constituting the central portion preferably has a xylene extraction amount of 1.5% by weight or less. The melt viscosity is preferably in the range of 100 to 50,000 poises at 300 ° C. and a shear rate of 200 sec ⁻¹ , and more preferably 500 to
It is in the range of 20000 poise.

In the present invention, the polyphenylene sulfide constituting the central portion needs to be biaxially oriented, and the degree of orientation measured from the two directions of Edge and End by the wide-angle X-ray diffraction method is It is also preferable that 0.1 is not less than 0.6 and the degree of orientation measured from the Through direction is not less than 0.7.

In the laminated polyphenylene sulfide film of the present invention, the surface layer made of the thermoplastic resin composition is preferably 0.01 to 5 μm, more preferably 0.05, from the viewpoint of the balance of adhesiveness, mechanical properties and heat resistance.
˜3 μm, and 0.5 to 1000 for the biaxially oriented polyphenylene sulfide film that constitutes the central part.
μm. Further, the laminated polyphenylene sulfide film has a heat shrinkage in the longitudinal direction of 10% or less, preferably 6% or less, when heat-treated at 230 ° C. for 10 minutes. Further, the surface of one surface layer of the laminated polyphenylene sulfide film of the present invention has a surface roughness of 0.0 from the viewpoint of workability and processability of the film.
The range of 05 μm or more and 0.10 μm is preferable, and 0.01
More preferably, it is not less than μm and not more than 0.07 μm.

Next, a method for producing the laminated poly-p-phenylene sulfide film of the present invention will be described.

The laminated polyphenylene sulfide film of the present invention comprises a biaxially oriented polyphenylene sulfide film forming a central portion and a thermoplastic resin composition forming a surface layer laminated on at least one side thereof.

The thermoplastic resin of the present invention can be produced by any method known in the art. For example, when the thermoplastic resin is polyethylene terephthalate or polyethylene naphthalate, terephthalic acid or 2,6-naphthalenedicarboxylic acid or its lower alkyl ester and ethylene glycol are esterified or transesterified in the presence of a catalyst to reduce the weight of the polymer. It is obtained as a united body and further polymerized under reduced pressure at high temperature. Polyethylene terephthalate and polyethylene naphthalate preferably have an intrinsic viscosity of 0.5 or more. When using inert particles other than the catalyst residue, they are added at any of these stages to obtain a composition comprising the resin.

When the thermoplastic resin is polyphenylene sulfide, it can be obtained by reacting alkali sulfide with p-dihalobenzene in a polar solvent at high temperature and high pressure. In particular, it is preferable to react sodium sulfide and p-dichlorobenzene in an amide-based polar solvent such as N-methyl-2-pyrrolidone. At this time, in order to adjust the degree of polymerization, it is most preferable to add a polymerization aid such as an alkali metal, a hydroxide or an alkali metal salt of a carboxylic acid and react at 230 ° C to 280 ° C. The pressure and the polymerization time in the polymerization system are appropriately determined depending on the kind and amount of the auxiliary agent used and the desired degree of polymerization. After completion of the polymerization, the system is gradually cooled to precipitate the polymer, and the slurry formed by pouring in water or a polar solvent is filtered with a filter, washed with water or an organic solvent, and dried to obtain a polyphenylene sulfide powder. be able to. When the inert particles are used, they can be added by any addition method at any of these steps, but the inert particles dispersed in the liquid are mixed with the above polyphenylene sulfide powder, and the particles are mixed with a Henschel mixer. After uniformly mixing by a high-speed stirring means, the resulting mixture is supplied to an extruder having at least one stage of vent holes, first melt-kneaded in the extruder, and then the liquid component is removed from the vent holes, A method of obtaining a polyphenylene sulfide composition in which inert particles are finely dispersed by extruding from a suitable die is preferable from the viewpoint of preventing generation and mixing of coarse particles. The liquid used to make the inert particles into a slurry has a boiling point of 1
80 ° C to 290 ° C is preferable, 180 ° C to 250
C is more preferred. Specifically, ethylene glycol,
N-methyl-2-pyrrolidone is preferred.

Polyalkylene glycol is added at any stage of the above thermoplastic resin production to obtain a thermoplastic resin composition. When the thermoplastic resin is polyethylene terephthalate or polyethylene naphthalate, it is preferable to mix at any stage until the end of polymerization, and when it is polyphenylene sulfide, it is preferable to mix after the end of polymerization.

On the other hand, the polyphenylene sulfide forming the central portion can be obtained by polymerization in the same manner as the polyphenylene sulfide forming the surface layer. In addition, inert particles and various additives are added by the same method.

As a method for laminating, a method by coating, laminating, coextrusion or the like is used, but a method by coating or coextrusion is preferable in order to make the surface layer mainly contributing to the adhesiveness as thin as possible. Further, in the present invention, lamination by coextrusion is preferable in terms of controlling the thickness of each layer of the laminated film. In lamination by coextrusion, the thermoplastic resin composition (hereinafter referred to as composition A) forming the surface layer and the polyphenylene sulfide (hereinafter referred to as composition B) forming the central portion are the polymer between the melt extrusion device and the die. It is merged and laminated in the flow path,
It is preferable that the layers are combined and laminated upstream of the die (for example, a manifold). That is, the composition A and the composition B, which are supplied to separate melt extruders and heated and melted at a temperature higher than the melting point of each composition, are melted by a confluent device provided between the extruder and the outlet of the die. Two or three layers are laminated and extruded from a slit-shaped mouthpiece outlet. The molten laminate is cooled to a temperature not higher than the glass transition point of the composition B on a rotary cooling drum to obtain a substantially amorphous laminated sheet. A known apparatus can be applied to the melt extrusion apparatus, but an extruder is preferable because it is simple. The merging device may have two layers (composition A / composition B) or three layers (composition A / composition B / composition A ', where composition A and composition A'are respectively It is a thermoplastic resin composition that forms the surface layer, and it is preferable that the two are the same) and has a function of laminating in a molten state.

Next, the amorphous laminated sheet is biaxially stretched at a temperature not lower than the glass transition temperature of the composition B to biaxially orient at least the central layer, and further heat-treated to form the laminated polyphenylene sulfide film of the present invention. Is obtained. The method for producing such a laminated polyphenylene sulfide film may be substantially the same as that for a single-layered polyphenylene sulfide film except for the constitution of the laminated components and the melt extrusion step, and the method disclosed in Japanese Examined Patent Publication No. 59-5099 can be applied. That is, in the range of 80 to 120 ° C, 2.0 to
It is stretched 5.0 times in the longitudinal direction and then 2.0 to 5.0 times in the longitudinal direction at 80 to 120 ° C. to obtain a biaxially stretched laminated film. Next, the biaxially stretched laminated film is heat-treated at 220 to 290 ° C. under a fixed length. Furthermore, if necessary, the shrinkage (relaxation) of the polyphenylene sulfide may be limited to 0% to 20% vertically and horizontally at a temperature equal to or lower than the melting point of the polyphenylene sulfide.

In the present invention, the handleability of the film,
As a method for appropriately controlling the surface roughness of the surface layer of the laminated polyphenylene sulfide film in order to improve the processability, (1) a method in which inert particles are present in the polymer of the composition A forming the surface layer ( 2) A method of controlling the surface roughness of the composition B by the method of the above (1) to indirectly form the surface of the composition A (3) A method of combining (1) and (2) and the like are also used. You can In electrical insulation applications and the like, composition B does not substantially contain inert particles, and in order to prevent dielectric breakdown, a method of forming a surface of a laminated film by adding inert particles to composition A is adopted. it can.

[0027]

[Physical property measuring method and effect evaluating method] The characteristic value measuring method and effect evaluating method of the present invention are as follows.

(1) Film thickness of the whole and each layer The cross section of the laminated film was determined by a scanning electron microscope.

(2) Strength and Elongation A Tensilon type tensile tester was used to measure a width of 10 mm and a test length of 50.
The breaking elongation and breaking strength of the mm sample were calculated and calculated as the average value of n = 5.

(3) Melt viscosity The melt viscosity was measured by the high flow tester method.

(4) Heat Shrinkage A film having a test length of 200 mm and a width of 10 mm was heated in a hot air oven at 230 ° C. for 10 minutes under no load, and the shrinkage was calculated from the length before and after heating.

(5) Melting point It was measured using a differential scanning calorimeter (DSC-2 type).

(6) Heat resistance At the initial stage of the sample film and at 180 ° C. in a hot air oven, 2
The tensile strength after aging for 000 hours is ASTM-D-6.
It measured according to 38-72 and calculated | required the intensity | strength after aging.

⊚: 70% or more of initial value ◯: 50 to less than 70% of initial value Δ: 30 to less than 50% of initial value ×: less than 30% of initial value

(7) Surface Roughness The surface layer was measured according to JIS-R-0601.

(8) Adhesiveness A film of width W (cm) is attached to a cellotape (Nichiban Co., Ltd.).
(Made by the company) is attached, and the peeling angle is 180 degrees, and it is continuously 200 mm.
The tension when peeling at a speed of / min was measured. When the tension at this time was T (g), the peeling force was calculated by the formula T / W (g / cm).

⊚: 10 g / cm or more ◯: 6 g / cm to less than 10 g / cm Δ: 4 g / cm to less than 6 g / cm ×: less than 4 g / cm

[0038]

EXAMPLES Next, the present invention will be described in detail with reference to examples.

Example 1 (1) Preparation of Polyphenylene Sulfide 100 mol of sodium sulfide nonahydrate in an autoclave,
Charge 45 mol of sodium acetate and 25 liter of N-methyl-2-pyrrolidone (hereinafter referred to as NMP),
While stirring, the temperature was gradually raised to 220 ° C. and the contained water was removed by distillation.

101 mol of p-dichlorobenzene and 0.2 mol of 1,2,4-trichlorobenzene were added to the system after dehydration together with 5 liter of NMP, and 17
Nitrogen was pressurized to 3 kg / cm ² at 0 ° C, and the temperature was raised to 2
Polymerization was carried out at 60 ° C. for 4 hours. After the completion of the polymerization, the mixture was cooled and the polymer was precipitated in distilled water, and a small block polymer was collected with a wire net having a 150 mesh opening.

The polymer was washed 5 times with distilled water at 90 ° C. and then dried at 120 ° C. under reduced pressure to obtain a melt viscosity of 3
A white granular polyphenylene sulfide having a poise of 800 and a melting point of 283 ° C. was obtained.

Next, polyphenylene sulfide 10k
50 g of spherical silica having a diameter of 0.5 μm was added to g, 32
The mixture was extruded into a gut-like shape at 0 ° C. with a 30 mmφ twin-screw extruder and pelletized.

(2) Production of thermoplastic resin composition comprising polyphenylene sulfide 10 kg of the white granular polyphenylene sulfide obtained in (1) was added with polyethylene glycol (molecular weight 400
0) 50 g was added and pelletized at 300 ° C. using a twin-screw kneader to obtain a polymer in pellet form.

(3) Film-forming Each of the spherical silica-containing polyphenylene sulfide obtained in (1) and (2) above and the thermoplastic resin composition comprising polyphenylene sulfide at 180 ° C.
After being dried for 3 hours under a reduced pressure of 1 mmHg, they were supplied to separate extruders, and in a molten state, a double-tube type laminating device on the upper part of the die was introduced so that the central portion became polyphenylene sulfide. It was discharged from a T-die type die and rapidly cooled by a cooling rotary drum to obtain a two-layer laminated sheet of a thermoplastic resin composition / polyphenylene sulfide consisting essentially of amorphous polyphenylene sulfide.

Next, the laminated sheet is caused to run in contact with a plurality of heating rolls having a surface temperature of 90 ° C., and it is longitudinally moved between the heating roll group and cooling rolls having different peripheral speeds of 30 ° C. in the longitudinal direction. It was stretched 7 times. This uniaxially stretched sheet was stretched 3.5 times in the direction orthogonal to the longitudinal direction at 100 ° C. using a tenter, and then heat treated at 260 ° C. for 10 seconds to give a total thickness of 2
5 μm, surface layer thickness 2 μm made of thermoplastic resin composition
A laminated film of the present invention was obtained. The composition of this film,
The evaluation results are shown in Tables 1 and 4.

Comparative Example 1 Polyphenylene sulfide containing spherical silica of Example 1 (1) was supplied to an extruder and discharged as a single layer from a T-die type die under the film forming conditions of Example 1 (3). Then, heat treatment was performed to obtain a biaxially oriented polyphenylene sulfide film. The structures and evaluation results of this film are shown in Tables 1 and 4.

Example 2, Example 3 and Comparative Example 2 A laminated polyphenylene sulfide film was obtained in the same manner as in Example 1 except that the addition amount of polyethylene glycol was changed. Details of the layer structure and evaluation results are shown in Table 1 and Table 4.
It was shown to.

Examples 4 to 6 Laminated polyphenylene sulfide films were obtained in the same manner as in Example 1, except that the thickness of the surface layer made of the thermoplastic resin composition and the total thickness were variously changed. The details of the configuration and the evaluation results are shown in Tables 2 and 4. Example 7 to Example 9 The same as in Example 1 except that the surface layer made of the thermoplastic resin composition was laminated on both surfaces. Film by the method,
Films having various three-layer constitutions (thermoplastic resin composition comprising polyphenylene sulfide / biaxially oriented polyphenylene sulfide / thermoplastic resin composition comprising polyphenylene sulfide) having different thickness constitutions were obtained. Details of the configuration and evaluation results are shown in Tables 2 and 4.

Examples 10 to 12 Laminated polyphenylene sulfide films were obtained in the same manner as in Example 1 except that the kind of polyalkylene glycol was changed. Details of the configuration and evaluation results are shown in Tables 3 and 4.
It was shown to.

Examples 13 and 14 Example 1 was repeated except that polyethylene terephthalate having an intrinsic viscosity of 0.6 and polyethylene naphthalate having an intrinsic viscosity of 0.6 were used as the thermoplastic resin constituting the surface layer.
A laminated film was obtained in the same manner as in. Details of the configuration and evaluation results are shown in Tables 3 and 4.

Example 15 A laminated film was obtained in the same manner as in Example 1 except that spherical calcium carbonate having an average diameter of 0.3 μ was used as the inert particles. Details of the configuration and evaluation results are shown in Tables 3 and 4.

[0052]

[Table 1]

[Table 2]

[Table 3]

[Table 4] As described above, the laminated polyphenylene sulfide film of the present invention eliminates the conventional defects, is excellent in adhesiveness, and has a balance of mechanical properties and heat resistance.

[0053]

EFFECT OF THE INVENTION The laminated polyphenylene sulfide film of the present invention is excellent in adhesiveness and has a good balance of mechanical properties and heat resistance due to the above-mentioned constitution. It can be widely used for industrial purposes, etc., and particularly when it is used for an adhesive tape, an exterior of an electric or electronic element, etc., its effect is more remarkably exhibited. Further, it can be used as a composite material by laminating it with another film, laminating it with paper, a fiber sheet, or glass cloth.

Claims (1)

[Claims] 1. A thermoplastic resin composition containing 0.01 to 30 parts by weight of a polyalkylene glycol with respect to 100 parts by weight of the thermoplastic resin on at least one side of a central portion made of a biaxially oriented polyphenylene sulfide film. A laminated polyphenylene sulfide film in which a surface layer is laminated.