JP3070797B2 - Laminated polyphenylene sulfide 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 laminated polyphenylene sulfide film. More specifically, the present invention relates to a laminated polyphenylene sulfide film having good mechanical properties and heat resistance and excellent adhesion.

[0002]

2. Description of the Related Art Polyphenylene sulfide films, in particular, poly-p-phenylene sulfide films have been proposed and expected to be applied to 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 drawback that when it is exposed to high temperatures, its mechanical strength is rapidly reduced and its long-term heat resistance is poor. On the other hand, the biaxially oriented film has features that the mechanical properties other than the tear strength are greatly improved as compared with the non-oriented sheet, and the chemical resistance and the long-term heat resistance are extremely excellent. However, as expected from the structure, it is clear from the fact that it has excellent chemical resistance and heat resistance.
For use in applications such as electrical insulation and general industrial use, it was necessary to impart adhesiveness.

Conventionally, as a method for improving the adhesiveness, a corona treatment (Japanese Patent Application Laid-Open No. 57-187327) has been disclosed. However, although improvement has been recognized as compared with untreated, it is still insufficient. Was.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks of the conventional polyphenylene sulfide film, and to provide a film having excellent adhesiveness and balanced mechanical properties and heat resistance. It is.

[0005]

SUMMARY OF THE INVENTION In order to achieve the above-mentioned object, the present invention provides a method for manufacturing a biaxially oriented polyphenylene sulfide film on at least one side of a center portion of a thermoplastic resin. The laminated polyphenylene sulfide film has a surface layer made of a thermoplastic resin composition containing parts by weight of a polyalkylene glycol.

[0006] In the present invention, the surface layer is at least one side of a central portion made of a biaxially oriented polyphenylene sulfide film and forms 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 a polyalkylene glycol based on 100 parts by weight of the thermoplastic resin.

In the present invention, examples of the thermoplastic resin include polyesters, polyolefins, polyamides, polyphenylene sulfides, polyether ether ketones, etc. Among them, polyesters, among them, ethylene terephthalate and ethylene-2,6-naphthalate are mainly used. Polyester as a unit, or p-
Polyphenylene sulfide having phenylene sulfide as a main repeating unit is preferred. Here, the term "main repeating unit" means that the repeating unit is 70 mol% or more, preferably 85 mol% or more, and more preferably 95 mol% or more.
Mol% or more, and other copolymerizable components, for example, in the case of polyesters such as polyethylene terephthalate and polyethylene naphthalate, glycol components other than ethylene glycol, other than terephthalic acid or 2,6-naphthalenedicarboxylic acid The dicarboxylic acid component, or the hydroxycarboxylic acid component, or in the case of polyphenylene sulfide,

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Embedded image It is no problem that the trifunctional component 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 to the weight of the extract before extraction when extracted with xylene for 36 hours using a Soxhlet extractor immersed in an oil bath heated to 00 ° C.

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

The content of the polyalkylene glycol is preferably 0.01 to 100 parts by weight of the thermoplastic resin.
To 30 parts by weight, more preferably 0.05 to 10 parts by weight,
More preferably, it is 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 obtained, which is not preferable. Further, when the polyalkylene glycol content is 30
If the amount exceeds the weight part, heat resistance is undesirably reduced. The polyalkylene glycol is preferably dissolved or dispersed in the thermoplastic resin composition,
Even when 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 contain a small amount of various additives such as other polymers, inorganic or organic lubricants, coloring agents, ultraviolet absorbers, antioxidants, heat stabilizers, and crystal nucleating agents in a small amount. Agents may be included. In particular, inorganic and organic inert particles are preferably used for controlling the slip property of the film. As inert particles,
Examples include silica, alumina, calcium carbonate, barium sulfate, kaolin, calcium phosphate, titanium oxide, talc, zinc oxide, and crosslinked polystyrene particles. In addition, particles precipitated during polymerization can be used.

In the present invention, the biaxially oriented polyphenylene sulfide film constituting the central portion is a poly-p-polyphenylene sulfide film.
It is composed of polyphenylene sulfide containing phenylene sulfide as a main component, wherein 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 10% by weight, preferably less than 10% by weight, and more preferably less than 5% by weight, the same additives, inert particles and the like as described for the thermoplastic resin composition constituting the surface layer may be contained. Absent.

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

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The polyphenylene sulfide constituting the central portion preferably has an xylene extraction amount of 1.5% by weight or less. Further, the melt viscosity is preferably in the range of 100 to 50,000 poise at 300 ° C. and a shear rate of 200 sec ⁻¹ , more preferably 500 to 50,000 poise.
It is in the range of 20,000 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 a wide-angle X-ray diffraction method is one of those. Also, it is preferable that the degree of orientation is 0.1 or more and 0.6 or less and the degree of orientation measured from the through direction is 0.7 or more.

In the laminated polyphenylene sulfide film of the present invention, the surface layer composed of the thermoplastic resin composition is preferably 0.01 to 5 μm, more preferably 0.05, from the balance of adhesiveness, mechanical properties and heat resistance.
３3 μm, and 0.5 to 1000 for the biaxially oriented polyphenylene sulfide film constituting the central portion.
μm. The laminated polyphenylene sulfide film has a heat shrinkage in the longitudinal direction when heat-treated at 230 ° C. for 10 minutes is preferably 10% or less, more preferably 6% or less. 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 workability of the film.
It is preferably in the range of from 0.05 μm to 0.10 μm,
It is more preferably at least μm and at most 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 is obtained by laminating a thermoplastic resin composition constituting a surface layer on at least one side of a biaxially oriented polyphenylene sulfide film constituting a central portion.

The production of the thermoplastic resin of the present invention can employ 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 a lower alkyl ester thereof and ethylene glycol are subjected to esterification or transesterification in the presence of a catalyst to reduce the polymerization rate. It is obtained by performing polymerization at high temperature under reduced pressure. As polyethylene terephthalate and polyethylene naphthalate, those having an intrinsic viscosity of 0.5 or more are preferable. 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 an alkali sulfide with p-dihalobenzene in a polar solvent at high temperature and high pressure. In particular, it is preferable to react sodium sulfide with p-dichlorobenzene in an amide 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 to 280 ° C. The pressure and the polymerization time in the polymerization system are appropriately determined depending on the type and amount of the auxiliary agent used and the desired degree of polymerization. After the polymerization is completed, the system is gradually cooled to precipitate the polymer, and the slurry formed by pouring the polymer into water or a polar solvent is filtered through 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 stages.However, the inert particles dispersed in the liquid are mixed with the polyphenylene sulfide powder, and a mixture such as a Henschel mixer is used. After uniformly mixing by high-speed stirring means, the obtained mixture is supplied to at least an extruder having a one-stage vent hole, first melt-kneaded in the extruder, and then the liquid component is removed from the vent hole, A method of extruding from an appropriate die to obtain a polyphenylene sulfide composition in which inert particles are finely dispersed is preferable from the viewpoint of preventing generation and mixing of coarse particles. The liquid used for slurrying inert particles has a boiling point of 1
80 ° C to 290 ° C, preferably 180 ° C to 250 ° C
C is more preferred. Specifically, ethylene glycol,
N-methyl-2-pyrrolidone is preferred.

The polyalkylene glycol is added at an optional stage in the production of the above-mentioned thermoplastic resin 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 polymerization is completed, and when the thermoplastic resin is polyphenylene sulfide, it is preferable to mix after the polymerization is completed.

On the other hand, the polyphenylene sulfide constituting the central portion is obtained by polymerizing in the same manner as the polyphenylene sulfide constituting the surface layer. In addition, inert particles and various additives are added in the same manner.

As a method of laminating, a method of coating, laminating, co-extrusion and the like are used, and a method of coating and co-extrusion is preferable in order to make the surface layer mainly contributing to adhesiveness as thin as possible. Further, in the present invention, lamination by co-extrusion is preferred in terms of controlling the thickness of each layer of the laminated film. In lamination by co-extrusion, a thermoplastic resin composition (hereinafter, referred to as composition A) forming a surface layer and polyphenylene sulfide (hereinafter, referred to as composition B) constituting a central portion are formed of a polymer between a melt extruder and a die. It is merged and laminated in the channel,
It is preferable that the layers are merged 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 to the melting points of the individual compositions or higher, are melted by a joining device provided between the extruder and the die outlet. It is laminated in two or three layers and extruded from a slit-shaped die outlet. The melted laminate is cooled below the glass transition point of the composition B on a rotating cooling drum to obtain a substantially amorphous laminated sheet. As the melt extrusion device, a known device can be applied, but an extruder is simple and preferable. The merging apparatus is composed of two layers (composition A / composition B) or three layers (composition A / composition B / composition A ′, wherein composition A and composition A ′ are respectively It is a thermoplastic resin composition that forms a surface layer, and has a function of being laminated in a molten state on two preferably identical ones.

Next, the amorphous laminated sheet is biaxially stretched at a temperature equal to or higher than the glass transition temperature of the composition B, at least the central layer is biaxially oriented, and further heat-treated to obtain 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-layer polyphenylene sulfide film except for the constitution of the laminated components and the melt extrusion step, and the method disclosed in JP-B-59-5099 can be applied. That is, in the range of 80 to 120 ° C., 2.0 to
The film is stretched 5.0 times in the longitudinal direction, and then stretched 2.0 to 5.0 times in the direction perpendicular to the longitudinal direction in the range of 80 to 120 ° C. to obtain a biaxially stretched laminated film. Next, the biaxially stretched laminated film is heat-treated at a constant length at 220 to 290 ° C. Further, if necessary, the material may be subjected to limited shrinkage (relaxation) in the range of 0 to 20% in each of the vertical and horizontal directions at a temperature lower than the melting point of 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 a polymer of the composition A forming the surface layer ( 2) A method of controlling the surface roughness of the composition B by the method (1) and indirectly forming the surface of the composition A. (3) A method of combining (1) and (2), etc. Can be. In applications such as electrical insulation, in order to prevent dielectric breakdown, composition B contains substantially no inert particles, and a method of adding inert particles to composition A to form the surface of the laminated film is employed. it can.

[0027]

[Method for measuring physical properties and method for evaluating effects] The method for measuring characteristic values and the method for evaluating effects according to 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, elongation A tensile tester with a width of 10 mm and a test length of 50 was used.
The elongation at break and the breaking strength of the mm sample were determined and calculated as the average value of n = 5.

(3) Melt viscosity The melt viscosity was measured by a Koka type flow tester method.

(4) Thermal 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 Measured using a differential scanning calorimeter (DSC-2).

(6) Heat resistance Initial temperature of the sample film and 2 hours at 180 ° C. in a hot air oven
ASTM-D-6 tensile strength after aging for 2,000 hours
The strength after aging was determined according to 38-72.

◎: 70% or more of the initial value ：: 50 to less than 70% of the initial value Δ: 30 to less than 50% of the initial value ×: Less than 30% of the initial value

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

(8) Adhesiveness Cellotape (Nichiban Co., Ltd.) was applied to a film having a width of W (cm).
200mm continuously at 180 °
The tension at the time of peeling at a speed of / min was measured. Assuming that the tension at this time was T (g), the peel force was determined 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]

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

Example 1 (1) Production of polyphenylene sulfide 100 mol of sodium sulfide nonahydrate was placed in an autoclave.
45 mol of sodium acetate and 25 liters of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) were charged,
While stirring, the temperature was gradually raised to 220 ° C. to remove the contained water by distillation.

Into the dehydrated system, 101 mol of p-dichlorobenzene and 0.2 mol of 1,2,4-trichlorobenzene were added together with 5 liters of NMP.
At 0 ° C., pressurize and fill with nitrogen to 3 kg / cm ² , raise the temperature,
Polymerization was performed at 60 ° C. for 4 hours. After the completion of the polymerization, the mixture was cooled, the polymer was precipitated in distilled water, and a small block polymer was collected by a wire mesh having a 150 mesh opening.

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

Next, polyphenylene sulfide 10k
g of 50 g of spherical silica having a diameter of 0.5 μm,
It was extruded at 0 ° C. into a gut shape by a 30 mmφ twin screw extruder and pelletized.

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

(3) Film Formation Polyphenylene sulfide containing the spherical silica obtained in the above (1) and (2) and a thermoplastic resin composition comprising polyphenylene sulfide were each heated to 180 ° C.
After drying under reduced pressure of 1 mmHg for 3 hours, the mixture was supplied to a separate extruder, and in a molten state, guided by a double-tube type laminating apparatus above the die so that the central portion became polyphenylene sulfide. The mixture was discharged from a T-die 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 brought into contact with a plurality of heating rolls having a surface temperature of 90 ° C. and run in a longitudinal direction between the heating rolls and a cooling roll having a different peripheral speed of 30 ° C. provided next to the heating rolls. The film was stretched 7 times. This uniaxially stretched sheet is stretched 3.5 times at 100 ° C. in a direction perpendicular to the longitudinal direction using a tenter, and then heat-treated at 260 ° C. for 10 seconds to obtain a total thickness of 2
5 μm, thickness of surface layer made of thermoplastic resin composition 2 μm
Of the present invention was obtained. The composition of this film,
The evaluation results are shown in Tables 1 and 4.

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

Example 2, Example 3, Comparative Example 2 A laminated polyphenylene sulfide film was obtained in the same manner as in Example 1 except that the amount of polyethylene glycol was changed. Tables 1 and 4 show the details of the layer structure and the evaluation results.
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 structure and the evaluation results are shown in Tables 2 and 4. Examples 7 to 9 The same as Example 1 except that a surface layer made of a thermoplastic resin composition was laminated on both surfaces. Film by the method,
Films of various three-layer constitutions having different thickness constitutions (thermoplastic resin composition composed of polyphenylene sulfide / biaxially oriented polyphenylene sulfide / thermoplastic resin composition composed of polyphenylene sulfide) were obtained. Tables 2 and 4 show the details of the configuration and the evaluation results.

Examples 10 to 12 A laminated polyphenylene sulfide film was obtained in the same manner as in Example 1 except that the kind of the polyalkylene glycol was changed. Tables 3 and 4 show the details of the configuration and the evaluation results.
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 described above. Tables 3 and 4 show the details of the configuration and the evaluation results.

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 μm was used as inert particles. Tables 3 and 4 show the details of the configuration and the evaluation results.

[0052]

[Table 1]

[Table 2]

[Table 3]

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

[0053]

The laminated polyphenylene sulfide film of the present invention is excellent in adhesiveness and balanced in mechanical properties and heat resistance due to the above-mentioned constitution, so that it can be used for packaging, electrical insulation, and the like. It can be widely used for industrial purposes and the like, and its effects are more remarkably exhibited when it is used for, for example, an adhesive tape, an exterior of electric and electronic elements, and the like. Further, it can be used as a composite material by lamination with another film or lamination with paper, fiber sheet or glass cloth.

Continuation of front page (56) References JP-A-2-310049 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 C08J 7/04

Claims (1)

(57) [Claims] 1. A thermoplastic resin composition comprising, on at least one side of a central portion comprising a biaxially oriented polyphenylene sulfide film, 0.01 to 30 parts by weight of a polyalkylene glycol with respect to 100 parts by weight of a thermoplastic resin. A laminated polyphenylene sulfide film having a surface layer laminated.