JPS62292431A - Laminated film - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a laminated film using a biaxially oriented poly-p-phenylene sulfide film.

(Prior Art) As for conventional films, (1) the use of a biaxially oriented poly-p-phenylene sulfide film as an electrical insulating material is known from Japanese Patent Application Laid-Open No. 55-35459 and the like. It is also known to use (2) polynisdel film, (3) polyimide film, etc. for similar purposes.

Also known are printed wiring boards in which electrical circuits made of conductive paint, resistive paint, metal foil, etc. are formed on these films.

In addition, as a laminated film, (4) biaxially oriented poly-p
- A phenylene sulfide film is used as the center layer, and on both sides, polyethylene terephthalate, polyethylene 2.
A biaxially oriented polyester film made of 6-naphthalate, a wholly aromatic polyamide film, a non-aromatic polyimide film, etc., each having a thickness of 50% the thickness of the center layer.
It is disclosed in Japanese Patent Application Laid-Open No. 60-80125 that a film laminated in a range of less than
It is proposed in the publication No.

(Problems to be Solved by the Invention) However, the above conventional film has the following problems.

The film described in item (1) lacks impact resistance and, for example, when used as a slot liner or wedge for a motor,
It is easy for two or more layers to peel off (delamination) or tear inside the film.

The film in item (2) has poor heat resistance.

Although the film described in item (3) has high heat resistance, it has a high water absorption rate and requires moisture management during use, or it is difficult to manufacture thick films exceeding 125 μm, and automatic insertion of slot liners and wedges is difficult. The disadvantage is that it is difficult to

In the laminated film of item (4), by using a biaxially oriented polyester film as the surface layer, some improvement in impact resistance can be seen, but it is not sufficient.

The object of the present invention is to solve these problems and provide a film that has excellent heat resistance and impact resistance.

[Means for solving problems]

The present invention provides biaxially oriented poly-p-phenylene sulfide film, biaxially oriented polyester film and/or
an axially oriented poly-p-phenylene sulfide film,
This invention relates to a laminated film characterized by being laminated with an adhesive having a hardness index of 1 to 3,000.

In the present invention, a biaxially oriented poly-p-phenylene sulfide film (hereinafter sometimes abbreviated as PP5-BO) is a film obtained by melt-molding a resin composition containing poly-p-phenylene sulfide as a main component. It is a film formed into a sheet, biaxially stretched, and heat treated.

The degree of orientation of the film is determined by wide-angle X-ray diffraction to be 20=20 to 2.
The degree of orientation OF determined for one crystal peak is 0.07 to 0.50 in the End direction and Edge direction. Through
It is preferable that the angle is in the range of 0.60 to 1°OO in the gh direction.

Moreover, the thickness of the film is preferably in the range of 3 to 200 microns.

In the present invention, a resin composition containing poly-p-phenylene sulfide as a main component (hereinafter sometimes abbreviated as PPS-based composition) refers to a composition containing 90% by weight or more of poly-p-phenylene sulfide. To tell.

If the content m of PPS is less than 90% by weight, the crystallinity, thermal transition degree, etc. of the composition will be low, and the characteristics of the film made of the composition, such as heat resistance, dimensional stability, and mechanical properties, will be impaired.

The remaining less than 10% by weight of the composition may contain additives such as polymers other than PPS, inorganic or organic fillers, lubricants, colorants, ultraviolet absorbers, etc., as long as the purpose of the present invention is not impaired. No problem.

The melt viscosity of the resin composition is preferably in the range of 500 to 12,000 poise (more preferably 700 to 100 poise) at a temperature of 300° C. and a shear rate of 2001/SeC from the viewpoint of film formability.

The melt viscosity of the resin composition is finally 1q 2! I
II oriented poly-p-phenylene sulfide film,
Equal to melt viscosity.

In the present invention, poly-p-phenylene sulfide (hereinafter sometimes abbreviated as PPS) is a structure in which 70 mol% or more (preferably 85 mol% or more) of repeating units are represented by the structural formula ÷Q-5÷ It refers to a combination of units. If the content of such components is less than 70 mol%, the crystallinity, thermal transition temperature, etc. of the polymer will become low, impairing the heat resistance, dimensional stability, apogemechanical properties, etc. that are the characteristics of a film made of a resin composition containing PPS as a main component. .

Less than 30 mol% of repeating units, preferably 15 mol%
If the amount is less than 1, there is no problem even if a middle group containing a copolymerizable sulfide bond is included.

In the present invention, the biaxially oriented polyester film is
A film made of polyester that has been biaxially stretched and heat treated.

The thickness of the film preferably ranges from 3 to 250 microns.

Here, polyester refers to polyester containing aromatic dicarboxylic acid as the main acid component and alkylene glycol as the main glycol component.

Those containing polyethylene terephthalate, polyethylene 2.6 naphthalate, etc. as main components are preferred.

The polyester is coated with inorganic or line-specific fillers, lubricants,
Additives such as stabilizers, flame retardants, and other types of polymers, etc.
There is no problem in meeting a small number of people.

The first laminated film of the present invention has the above-mentioned PP5-SO<
Assuming the thickness is A micron) and 2IpI! This is a film in which an I-oriented polyester film (thickness: 8 microns) is laminated via an adhesive.

The thickness relationship of each layer constituting the laminated film is 0.1
≦A/B≦1.8 is preferable. More preferably 0.2≦
A/B≦1.5. When A/B is small, heat resistance tends to decrease, and conversely, when A/B is large, VIM resistance tends to decrease.

The second laminated film of the present invention is a film in which another PP5-BO (thickness: A' microns) is further laminated on the 2111Ill oriented polyester film side of the above laminated film via an adhesive.

The thickness relationship of each layer constituting the laminated film is 0.2
≦(A-1-A')/B≦3.6 is preferable.

More preferably 0.4≦(A+A')/[3≦2゜O
). When (A+A')/B is small, heat resistance tends to decrease, and when it is large, impact resistance tends to decrease.

Further, A/A' is preferably in the range of 0.5 to 2.0 in order to achieve the object of the present invention.

The total thickness of both the first and second laminated films is 1
A range of 0 to 500 microns is preferred.

The third laminated film of the present invention is PP5-BO (thickness: A).
This is a film in which PP5-BO (with a thickness of A-micron) and another PP5-BO (with a thickness of A-micron) are laminated via an adhesive.

The thickness ratio A/A' of each layer constituting the laminated film is:
A range of 173 to 3 is preferred.

The thickness of the entire laminated film is preferably in the range of 100 to 400 microns.

The hardness index of the adhesive layer constituting the laminated film of the present invention must be in the range of 1 to 3,000. Even if the hardness index is less than 1 or more than 3,000, the impact resistance of the laminated film decreases.

Here, the hardness index is the peel length expressed in millimeters per 60 seconds when the laminated film is kept at 180 ° C and a peel force of 80 g/cm is applied to both adhesive layers. , which is a measure of the hardness of the adhesive. Needless to say, the higher the hardness index, the softer the adhesive.
The smaller the size, the harder it will be.

The composition of the adhesive layer constituting the laminated film of the present invention is not particularly limited, but examples include polyurethane, epoxy, polyester, and silicone.

The thickness of the adhesive layer is preferably in the range of 1μ7n to 30μ. The ratio of the total thickness of the adhesive layer to the total thickness of the laminated film is preferably 3 to 10% when the film has a two-layer structure, and 4 to 15% when the film has a three-layer structure.

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

PPS used in the present invention is obtained by reacting an alkali sulfide and paradihalobenzene in a polar solvent at high temperature and high pressure. In particular, sodium sulfide and balajichlorobenzene are
- It is preferable to carry out the reaction in an amide-based high boiling point polar solvent such as methylpyrrolidone. In this case, in order to adjust the reaction temperature, it is most preferable to add a so-called polymerization aid such as a caustic alkali or an alkali metal carboxylic acid salt, and to carry out the reaction at 230 to 280°C. The pressure and time in the polymerization system are appropriately determined depending on the type and amount of auxiliary agent used, the desired degree of concentration, etc. 1 q of the powdered or granular polymer is washed with water and/or a solvent to separate by-product salts, polymerization aids, unreacted additives, and the like.

In order to form this polymer into a biaxially oriented film, the resin is melted using an extruder and cast onto a metal drum through a die and rapidly cooled to form a non-oriented, amorphous sheet. Then, the sheet is stretched to 21 Nl and heat treated by a well-known method. Stretching is carried out at 90 to 110'C in both the longitudinal direction and the width direction in a range of 3.0 to 4.5 times. Heat treatment in the range of 240°C - melting point, constant length or less than 15%! Perform 1 to 60 seconds under i11 contraction. Additionally, the film may be relaxed in one or two directions to improve its thermal dimensional stability.

As the 21Nl oriented polyester film used in the present invention, commercially available or well-known films such as 2q4A oriented polyethylene terephthalate film and 21111 oriented polyethylene 2.6 naphthalate film can be used.

Next, a method for manufacturing the adhesive used in the present invention will be described.

Although both solvent-free and solvent-based adhesives can be used, a curable solvent-based adhesive is preferable in view of the heat resistance of the adhesive and the workability of laminating the adhesive.

As an example, polyurethane adhesives will be described.

A commercially available polyurethane adhesive may be used, but from the viewpoint of heat resistance, it is necessary to use an isocyanate made by reacting caulking isocyanate (preferably aromatic isocyanate) with polypropylene glycol, polyester, etc.
A polyurethane adhesive made of a prepolymer and polypropylene glycol, polyester, polyol, etc. is preferred.

The prepolymer, polypropylene glycol, polyester, polyol, etc. are uniformly mixed in an organic solvent such as ethyl acetate or butyl acetate to form an adhesive solution. Further, it is permissible to add inorganic or organic additives such as flame retardants to the adhesive to an extent that does not impair adhesiveness.

Next, PPS-130 and a biaxially oriented polyester film are laminated via the adhesive.

It is preferable to perform a surface treatment such as corona discharge treatment, plasma treatment, primer coating treatment, etc. on one side of the PP5-BO film and on both sides of the biaxially oriented polyester film, either singly or in combination, so that the lamination is not laminated.

The laminating method is to apply an adhesive adjusted to a predetermined composition on one side of PP5-BO (or 2-layer oriented polyester film), dry it, and then use a heated roll or hot press to laminate the biaxially oriented polyester film ( or PP5-BO
). Next, apply an adhesive similar to the above and 1ii1 to one side of the biaxially oriented polyester film side (or another layer of PP5-BO) of the above two-layer structure of PP5-BO and 21Nl oriented polyester film. After that, the best method is to use a heated roll or hot press to bond another layer of PP5-BO (or 2 layers of 2+111 oriented PPS film and biaxially oriented polyester film) with the biaxially oriented polyester film as the core. This is common. Application methods include gravure roll method and reverse roll coater method.

Drying of the solvent after application varies depending on the type of solvent used, and conditions are usually selected at a temperature near the boiling point of the solvent so that the residual solvent is completely eliminated and the curing of the adhesive is not accelerated. The bonding conditions were a temperature of 50°C to 150'G, a linear pressure of 1
It is preferable to perform this in the range of ~50 to +3/cm.

Next, the adhesive is cured for 0.5 to 100 hours at a temperature of room temperature to 170°C, although it varies depending on the type, composition, and thickness of the adhesive.

[Application]

The laminated film of the present invention can be used as a general electrical insulating material, printed wiring boards, sheet keyboard boards,
Suitable for acoustic diaphragms, etc. It is particularly suitable for applications that require a high level of balance between heat resistance and Ml''l resistance, such as slot litchi and wedges for motors.

Next, methods for measuring characteristics and evaluation criteria used in describing the present invention will be described.

(1) A laminated film with a hardness index of 10TrLTn and a width is maintained at 180°C,
Peeling length per minute 7rLT when a peeling load of 80 Q/cm is applied to the film layers on both sides of the adhesive layer
rL/TrLin) was taken as the hardness index. A hot air oven was used to maintain the laminated film at 180°C.

(2) Impact resistance Measured using a Scotto type fir test chamber (manufactured by Toyo Baldwin). The sample is placed in the device and pressed and subjected to reciprocating motion, and is expressed as the number of times the film is rubbed until delamination occurs. In addition, the sample was measured in the longitudinal direction of the laminated film, and the compression cart was set to 0.5 ki.

<3) A heat-resistant sample was exposed in an oven at 18.0° C., and the sample was taken out every 240 hours to measure the tensile elongation rate, which was expressed as the time it took to reach the initial value of 172.

The tensile elongation rate was measured in accordance with ASTM D882-
Measured using 61T.

<4) Orientation degree of P P S -B O The stretching direction of the sample is aligned and the thickness is 1TrLTrL, the width is 1TrLTrL,
The film was molded into a strip with a length of 10 TrLTrL (each film was fixed using a 5% amyl acetate solution of collodion during molding), and X-rays were incident along the film surface of the film (in the edge and end directions). 1 - The photo was blocked. The X-ray generator is a D-3F type device manufactured by Rigaku Denki, and has a power of 40KV.
The X-ray source was Cu-K rays passed through a Ni filter at -20 mA.

The sample-film distance was 41 mTrL, a Kodak non-screen type film was used, and a multiple exposure method (15 minutes and 30 minutes) was employed. Next, on the plate photo (200
＞The intensity of the peak is φ=O° (on the equator line＞10', 20
The degree of blackening I is read by scanning the densitometer in the radial direction from the center of the photograph at 30° and 30°, and the degree of orientation (O
F> was defined as 0F=I(φ=30°)/I(φ=0°).

Here, ■ (φ=30') is the maximum intensity of the 30' scan, and I (φ=09) is the maximum intensity of the equatorial line scan. In addition,
I(φ-0°) is φ=00 and φ=1800, I(φ=3
0'), the average value of the intensity at φ=30° and φ=150° was used. The measurement conditions of the densitometer are as follows.

The device used was a Sukura Microdensitometer Model PDM-5 Type A manufactured by Roku Konishi Photo Industry, the measurement temperature range was O1O to 4.0D (minimum measurement area 4μ2 equivalent), the optical system magnification was 100 times, the slit width was 1μ, Using a height of 10μ,
Film movement speed is 50μ/sec and chart speed is 1m7r
L/sec.

〔Example〕

Next, the present invention will be explained in detail by giving examples.

Example 1 (1) PP5-80 adjustment used in the present invention.

(a) Preparation of PPS polymer Sodium sulfide 32.6 kcJ (2
50 mol, containing 40% crystalline water), sulfur hydroxide to 00 g thulium, 36° sodium benzoate (25
0 mol), and N-methyl-2-pyrrolidone (hereinafter referred to as NM
It is abbreviated as P. >79.2kq was charged and the temperature was gradually raised to 205°C while stirring to produce a distillate containing 6.9% of water.
(l was removed. The remaining mixture contained 37.5 kq (255 mol) of 1,4-dichlorobenzene and 20.0 kq (255 mol) of NMP.
was added and heated at 265°C for 4 hours. The reaction product was washed 8 times with boiling water, μ, 2900 bois, N, 1.17, T
High polymerization degree PP521 with C+91℃ and Tm 285℃
．． 1 q of 1 kCJ (yield 78%) was obtained.

(b) Melt molding After drying the composition obtained in (a) above at 180'C for 2 hours under reduced pressure, 0.1% by weight of calcium stearate powder is added to the composition as a lubricant, The mixture was stirred and mixed with a mixer and then put into a 407rLmφ Ex1~Ruda hopper. The composition melted at 310° C. was extruded from a die having a linear lip with a length of 250 Tn, TrL, and a width of 1.5 IrLTrL, and was cast onto a metal drum whose surface temperature was maintained at 30° C. and solidified by cooling.

The obtained film has a width of 230 mm and a thickness of 450 μm.
, it was an unstretched film with a density of 1.315.

(C) Biaxial stretching, heat treatment The film subjected to 1q in (b) above is stretched in the longitudinal direction of the film at a temperature of 98°C using a longitudinal stretching device consisting of a group of rolls.
The film was stretched 3.9 times at ℃, and then the film was fed into a tenter and stretched 3.7 times in the width direction at a stretching temperature of 98℃, and then roughly heat-treated at 270℃ for 10 seconds in a subsequent heat treatment chamber in the same tenter. A biaxially oriented film was obtained. Furthermore, the film was forcibly shrunk at 250° C. for 2 minutes in a free state. Furthermore, one side of the film was subjected to a corona discharge treatment of 6000 pieces/T112, and this film was made into PP5-BO-1 (thickness 3
0μTrL).

(2) Preparation of biaxially oriented polyester film used in the present invention Polyethylene terephthalate 1 having an intrinsic viscosity of 0.62 and polymerized from dimethyl terephthalate and ethylene glycol
~ (hereinafter sometimes abbreviated as PET) Resin raw material chips are dried under reduced pressure and silica powder (pazyloid) is dried under reduced pressure.
150" (manufactured by Fuji Davison) and mixed with a mixer, the mixture was poured into the hopper of a 40TrLTn, φ extruder. The composition melted at 290°C was 2507rLTrL1 gap 1.0m
The film was extruded from a die having a straight lip of 100 m in diameter, cast onto a metal drum whose surface temperature was maintained at 50'C, and solidified by cooling to obtain an unstretched film. 3. The film is stretched in the longitudinal direction at a temperature of 90° C. by a longitudinal stretching device consisting of a group of rolls.
Stretched 3 times, then fed the film into a tenter, stretched 3.5 times in the width direction at a stretching temperature of 95°C, and further heat-treated at 240°C for 10 seconds in a subsequent heat treatment chamber in the same tenter to achieve two-way orientation. A PET film was obtained. Roughly spread the film 2
Free contraction was allowed for 2 minutes at 0°C. Roughly, both sides of the film were subjected to corona discharge treatment at 6000 J/T112 to obtain a biaxially oriented polyester film with a thickness of 50 μm. (
This film is referred to as PET-BO-1).

(3) Adjustment of adhesive The following commercially available heat-resistant polyurethane adhesive was used.

"Atocoat" 76P1 manufactured by Toyo Morton Co., Ltd. (this adhesive is referred to as adhesive-1).

The mixing ratio of the main resin and curing agent of the above adhesive is
100/8 and solid content concentration is 3 using ethyl acetate as a solvent.
The content was adjusted to 2% by weight.

(4) Laminated film preparation The corona-treated surface of PP5-BO-1 was coated with the adhesive prepared previously using a gravure roll method.

The drying conditions for the solvent were 80° C. for 3 minutes, and the thickness of the adhesive was adjusted to 7 μml after curing. Subsequently, it was laminated with PET-BO-1 using a subsequent roll laminator. The bonding conditions are temperature 80'C1 linear pressure 3 ki/c
It was set as m. Next, the corona-treated surface of another layer of PP5-BO-1 was coated under the above conditions, and the previously obtained PP
5-BO-1/PET-BO-1 two-layer body (7) PET
- It was attached to the BO-1 side under the above conditions. The 1q Vi layer film was cured at 60°C for 50 hours and further at 150°C for 10 hours. (Laminated film-1
) The hardness index of the adhesive of the obtained laminated film is
The layer laminated first was 547, and the layer laminated later was 519.

(5) Evaluation The impact resistance and heat resistance of the laminated film prepared above were measured. Also, for comparison, 125μ7rL PP5-BO
conducted a similar evaluation. The results are shown in Table 1. From these results, it is clear that the impact resistance of the laminated film is significantly improved without substantially reducing the excellent heat resistance of PP5-BO.

Table 1 Example 2 (1) Creation of laminated film PP5-BO with different thicknesses were created in the same manner as in Example-1. The thickness of the film is 8μm, 112μ skin, 15
There are six types: μm, 30μm, 38μm, and 50μm.

On the other hand, for PET-BO, 25 μm and 38 μm15
Six different thicknesses were made: 0μm, 175μm, 100μm, and 125μ7n.

A/B/A by changing the thickness structure using the above film
- Nine types of laminated films were created. The lamination conditions were the same as in Example 1, and the thickness of each adhesive layer was 4% of the total thickness of the laminated film.

(Laminated Films 2 to 10) The hardness index of each adhesive layer was measured and was in the range of 400 to 700.

(2) Evaluation Table 2 shows the evaluation results of the produced laminated film.

Table 2 Example 3 (1) Creation of laminated film The films used in Example 1 were used as PP5-BO and PET-BO. The adhesives used for lamination were Adhesive-1 used in Example 1 (Atocoat "76P1" manufactured by Toyo Morton Co., Ltd.) and "Riofall" 3 manufactured by Henkel Hakusuisha.
600/6200 (This adhesive is referred to as adhesive-2.

) were used.

Adhesive-1 consists of 9 adhesives with different mixing ratios of main agent and curing agent.
Created a type. Note that the other conditions were the same as in Example 1. On the other hand, three types of Adhesive-2 were prepared with different mixing ratios of the main agent and the curing agent.

In addition, the solvent was methyl-ethyl-ketone and the solid content concentration was 4.
The content was 5% by weight.

The lamination conditions were the same as in Example 1, and 12 types of laminated films were created. (Laminated Films 11 to 22) (2) Evaluation Table 3 shows the evaluation results of the 12 types of laminated films created.

This result shows that the hardness index of the adhesive that can be used in the laminated film of the present invention is in the range of 1 to 3000 mTrL/min. That is, the hardness index is 1am1m
Even if it is less than i n or more than 3000TrLTrL/min, there is no effect of improving impact resistance.

Table 3 Example 4 (1) Creation of laminated film PP5-BO and PET-BO created in Example 2 and new PP5-BO of 75t1m and 1ooμm were created,
Seven types of two-layer films (A/B) with different thickness composition ratios were created. (Laminated films 23 to 29) The lamination conditions were the same as in Example 1, and the thickness of the adhesive layer was the same as that of the entire laminated film. It was set to 7% of the thickness. The hardness index of the adhesive layer of each laminated film was between 400 and 700.

(2) Evaluation Table 4 shows the evaluation results of the produced laminated film.

Table 4 Example 5 PP5-BO with a thickness of 75.125.150 microns was prepared in the same manner as in Example 1, and these were combined.
Four types of laminated films shown in Table 5 (Laminated film 30
-33) were created. The lamination conditions were the same as in Example 1, and the thickness of the adhesive layer was 5% of the total thickness of the laminated film. In addition, the hardness index of the adhesive layer is 450 to 60.
It was between 0.

Table 5 shows the evaluation results of these laminated films. For comparison, 125 micron and 150 micron PP5-8
The characteristics of 0 were also evaluated.

From Table 5, it can be seen that the third embodiment of the present invention is also a film with excellent impact resistance and heat resistance. In terms of impact resistance, it is significantly superior not only to PP5-BO of approximately the same thickness, but also to the thinner p p s -BO>s1 layer that makes up the laminated film.

Table 5 [Effects of the Invention] The present invention provides a laminated film in which ppsLso is laminated with a 2@oriented polyester film or/and PP5-BO via an adhesive of a specific hardness, which provides both heat resistance and impact resistance. It was possible to make an excellent film.

Claims (1)

Scope of Claims: (1) A biaxially oriented poly-p-phenylene sulfide film, a biaxially oriented polyester film and/or a biaxially oriented poly-p-phenylene sulfide film are used as an adhesive having a hardness index of 1 to 3000. A laminated film characterized by being laminated through. (2) In the case where a biaxially oriented poly-p-phenylene sulfide film and a biaxially oriented polyester film are laminated, the thickness A of the biaxially oriented poly-p-phenylene sulfide film and the thickness of the biaxially oriented polyester film The laminated film according to claim 1, wherein B satisfies 0.1≦A/B≦1.8. (3) In the case where biaxially oriented poly-p-phenylene sulfide films are laminated on both sides of a biaxially oriented polyester film, the thickness A of one biaxially oriented poly-p-phenylene sulfide film is Oriented poly-P
-Claim (1) characterized in that the thickness A' of the phenylene sulfide film and the thickness B of the biaxially oriented polyester film satisfy 0.2≦(A+A')/B≦3.6. The laminated film described in .