JPS6192828A - Biaxially orientated poly-p-phenylenesulfide film - Google Patents

Abstract

PURPOSE:To obtain a printed circuit board, excellent in thermal dimensional stability, by a method wherein a metallic thin film is laminated on the material of biaxially orientated poly-P-phenylenesulfide film containing the specified amount of biaxially orientated poly-P-phenylenesulfone chain. CONSTITUTION:Biaxially orientated poly-P-phenylenesulfide film is oxided by percarboxylic acid to obtain the biaxially orientated film of three-layer structure, which contains 1 mol%-70 mol% of biaxially orientated poly-P-phenylene sulfone chain. Next, the metallic thin film is laminated on said biaxially orientated film to constitute the printed circuit board. According to this method, the printed circuit board, excellent in thermal dimensional stability in high temperature and a resistance to soldering, may be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a biaxially oriented polyP-phenylene sulfide film and a printed wiring board using the film.

[Prior art]

Conventional biaxially oriented films made of p-phenylene sulfide are well known and have excellent performance in terms of electrical insulation, heat resistance, chemical resistance, etc. It is attracting attention as a material for printed wiring boards such as flexible circuit boards and chip carrier tapes for integrated circuits, thermal transfer film substrates, and various vapor-deposited film substrates such as capacitors and transfer foils.

However, the conventional biaxially oriented polyP-7 22lene sulfide film has the disadvantage of lacking dimensional stability at high temperatures of 200°C or higher, especially at temperatures near the melting point of IJ P-phenylene sulfide, about 285°C. Was. This has limited its application to applications where dimensional stability at high temperatures is strictly required.

In particular, materials for printed wiring boards that are exposed to high-temperature atmospheres such as when soldering components may wrinkle due to dimensional changes due to heat shrinkage.

Alternatively, it is known that the metal foil and film peel off, and poly-1,4 cyclosene sulfone is aromatically cyclized, poly-P-phenylene sulfite sulfone →→7
It is known that compounds obtained by acidifying X, O, and Q with hydrogen peroxide are known. The resulting granular or powdered poly-P-fluorinated sulfone is crystalline and has a melting point of 500° C. or higher, which is rare and has excellent heat resistance. However, because of this, melt molding is impossible due to its nature, and molding in a solution state is also impossible because there is no solvent that can sufficiently dissolve it. It has not been done.

Japanese Patent Publication No. 47-14470 discloses that the product is partially oxidized and then molded into a film or other product in the form of a solution, but the resulting product is extremely brittle and cannot be put to practical use.

Furthermore, in U.S.P. 3,948,865, it is proposed to oxidize polyP-phenylene sulfide molded products with hydrogen peroxide or sodium hypochlorite to make them infusible. It has the disadvantage of being small in size and easily forming cracks.

[Problems to be Solved by the Invention] An object of the present invention is to improve the dimensional stability at high temperatures, which is a drawback of polyP-fluoride sulfide film, by producing a film that inherently has excellent heat resistance. In order to introduce J P -phenylenesulfone chains and eliminate the flaw of brittleness observed in existing polyP-phenylenesulfone molded products, we created a film in which a biaxially oriented structure was introduced into the polyP-phenylenesulfone chains. and to provide a printed wiring board with excellent solder resistance.

[Means for solving problems]

The present invention has the following configuration to achieve the above object. Namely.

(1) Biaxially oriented polymer IJ p containing 1 molar or more and less than 70 molar polyP-phenylene sulfone chains with 21m orientation.
- Phenylene sulfide film.

(2) A printed wiring board formed by laminating a thin metal film on the film of item (1) above.

The poly p-phenylene sulfone chain referred to in the present invention has the general formula H! It is represented by ΣSO,- (R is carbon e and a hydrocarbon group of 20 or less) (E>co-.

(IXt)-, etc.), even if it contains less than 20%.

If 20% or more of the copolymer component is present, the orientation of polyP-phenyl sulfone will be impaired.

Mechanical properties tend to decrease and heat resistance also tends to decrease, so 1. <No.

The film of the present invention is a biaxially oriented polyP-phenylene sulfide film containing this polyP-phenylene sulfone chain in a molar proportion of 1 or more and less than 70, preferably 5 and less than 40. This is a film that simultaneously maintains the excellent thermal dimensional stability due to the heat resistance of IJ p-phenylene sulfone and the excellent mechanical stability of IJ p-phenylene sulfide.

If the poly p-phenylene sulfone chain is less than 1 mole φ, the thermal dimensional stability will be poor, which is not preferable.

When i14λ is 70 molar, retention of mechanical properties by polyP-7 enylene sulfide is reduced.

The film of the present invention has a six-layer structure with an outer layer consisting mainly of biaxially oriented polyP-phenylene sulfone chains and a center layer consisting of a biaxially oriented polyP-phenylene sulfide layer. and its outer layer is made of 65
It can be separated from the melted inner layer by heating at 0°C for 10 minutes, and its thickness is preferably 0.1 μm or more, and O, Sμ
m or more is more preferable. This outer layer provides thermal dimensional stability of the film, while the inner poly-P-fluoride sulfide layer retains the mechanical properties of the film.

In addition, if the thickness of the outer layer on one side is different from the thickness of both outer layers, 9
The ratio A/B between A and the thickness B of the inner layer (which is half the sum of the thicknesses of both outer layers) is preferably 0.01 to 1.5, and preferably 0.05 to 1.5.
035 is more preferable.

In addition, polyP-phenylene sulfide as used herein excludes polyP-phenylene sulfone chains. If the molar ratio is more than 20, the crystallinity of the polyP-phenylene sulfide may be impaired, resulting in a decrease in mechanical properties, which is undesirable.

In the present invention, polyP-phenylene axial orientation refers to the orientation of molecular chains within the film plane in the longitudinal direction of the film and in a direction perpendicular thereto and also perpendicular to the thickness direction, and the film satisfies the following conditions. is preferred.

Phil A's Edge, EndQ- and Throug
A photograph of the Xi plate was taken from the h direction using the method described below.

Based on the crystal phase of polyP-phenylene sulfone 2θ=1
The ratio of the degree of blackening (■φ=0°) when scanning the diffraction bed of No. 6 in the radial direction with a densitometer on the equator line and the degree of blackening in the 60° direction (1φ=60), that is, Iφ-60/Iφ =0°
When calculated by defining the degree of orientation (OF), the degree of orientation in the End+ and Edge directions is 01 to 07, and
The degree of orientation in the through direction is preferably 07 to 10 from the viewpoint of the mechanical properties of the film. Here E
The nd+ direction is the direction of X from the direction parallel to the longitudinal direction of the film.
The X-ray incidence is perpendicular to the edge direction and also perpendicular to the thickness direction, and Thr6
The ugh direction is the incidence of X-rays perpendicular to the film plane.

Similarly, for poIJ p-phenylene sulfide, Edge, End4P, and Throug of the film
In the XH plate photograph taken from the h direction, the degrees of orientation are determined for 2θ-21° representing the (200) plane of polyP-phenylene sulfide. Edge and Enc
The degree of orientation in the i=h direction is 01 to 07, respectively, and Thr
It is preferable that the degree of orientation in the outward direction is 0.7 to 1.0, and the relative crystallinity of the film is determined by the intensity of 2θ%16 (I
, 6), 2θ=21° intensity (I2.) and 2θ
-30' intensity (I,.) is measured and defined as relative crystallinity using the following formula. This value is preferably in the range of 3 to 50 from the viewpoint of mechanical properties.

(here x is not P-) mole% of unisulfone chain
) The tensile strength and elongation of the film are 10 kg/mm' or more in both longitudinal and width directions.

and preferably 20% or more.

Delicious.

Note that the thickness of the film of the present invention is not particularly limited, but is preferably 1 to 100μ, and more preferably f 200μ.

For the purpose of the film of the present invention as described above, known inorganic particles may be included as long as they do not impede the purpose of the present invention, and also to improve weather resistance.

There is no problem even if known organic additives are included for the purpose of improving heat resistance, etc., within a range that does not impair the practical properties of the article.

Furthermore, if necessary, the film may be subjected to electrical surface treatment such as corona discharge surface treatment, plasma surface treatment, or chemical surface treatment such as acid treatment or alkali treatment, either alone or in combination. I can't support it. Furthermore, there is no problem in using it in combination with other films or metal foils.

There are no particular limitations on the material and thickness of the metal thin film.

A metal foil or metal layer, typically made of copper or the like, having a thickness of 11[l[[1] or less is preferable. In this case, the presence of any adhesive layer between the film and the metal film is equally unsupportive.

Next, a specific method for manufacturing the biaxially oriented film of the present invention will be described.

The biaxially oriented film of the present invention is obtained by oxidizing a biaxially oriented p-phenylene sulfide film with percarboxylic acid, and the printed wiring board of the present invention is obtained by laminating a metal foil film on the film. It will be done.

Here we say biaxially oriented polyP-7E; 8 Rensulf units
Poly P-7 enylene sulfide containing 0 molt or more and having a melt viscosity at 600°C of 100 to 600,000 poise at a shear rate of 200 (seconds) and having a surface temperature of 120°C or less After extrusion onto a cooling medium, the extruded film is simultaneously or sequentially biaxially stretched by a factor of 6 to 4.7 at 85°C to 110°C. 20 more
Obtained by heat fixing at 0 to 275°C.

20 of this biaxially oriented polyP-phenylene sulfide etc.
It is acceptable even if it is contained in an amount less than mol%. If the molar ratio is more than 20, the crystallinity of the polyP-phenylene sulfide is impaired and the mechanical properties of the biaxially oriented film of the present invention are deteriorated, which is undesirable. .

This poly P-7 unilene sulfide film preferably satisfies the following three structural parameters. First of all, the relative crystallinity can be determined from the diffraction profile of the film by wide-angle X-rays, where the (200) peak is the intensity at 2θ-21° [Eng. 21] and the intensity CI at 20 = 60°. ] and the ratio of both I2. /I,. This value is defined as relative crystallinity, and it is preferable that this value is in the range of 5 to 65.

Second, it is preferable that the size of the microcrystals is within a certain range, which is 5 chel from the half width of the (200) diffraction peak.
It refers to the apparent crystal grain size obtained using the ler formula, and is preferably from 40 to 130'A.

Thirdly, regarding the degree of orientation, the degree of orientation in the Edge and Pjndm directions mentioned above at 2θ=21° is 021~
0.7, and the degree of orientation in the Through direction is 0.7.
It is preferable that it is 1.0.

The biaxially oriented poly p-phenylene sulfide film as described above may contain known inorganic particles for the purpose of imparting slipperiness, etc., to the extent that it does not impede the purpose of the present invention. Improving sex.

There is no problem even if known organic additives are included for the purpose of improving heat resistance, etc., within a range that does not impair the usable properties of the article.

This biaxially oriented polyP-phenylene sulfide film is also subjected to corona discharge surface treatment as required.

There is no problem in applying electrical surface treatment such as plasma surface treatment alone or in combination.

The general formula R+C00H) (R is the number of carbon atoms or 20
The following hydrocarbon groups (n is an integer from 1 to 4) are oxidized at the percarboxylic chain, but when oxidation is performed by a carboxyl group other than the percarboxylic branch, the main chain is cleaved or the oxidative crosslinking associated with it is oxidized. There are so many that it cannot be a useful biaxially oriented film.

Percarboxylic acids include performic acid, peracetic acid, perpropionic acid,
Examples include perbutyric acid, perbenzoic acid 9mchloroperbenzoic acid, pertrichloroacetic acid, pertrifluoroacetic acid, perphthalic acid, and the like. Peracetic acid is most preferred in view of the balance between ease of handling and reaction rate.

Percarboxylic acids can be produced by autoxidation of aldehydes, synthesis of hydrogen peroxide and carboxylic acids from anhydrides or chlorides, synthesis of hydrogen peroxide with carboxylic acids and sulfuric acid as catalysts, reaction of sialoyl peroxide with sodium methoxide 9 It can be generated by etc.

2 mentioned in KI to such percarboxylic acid or its water bath solution or solution in organic solvent or mixed solution Z.
An axially oriented polyP-phenylene sulfide film is immersed and reacted.

Here, when organic solvents are carboxylic acids and esters.

Examples include ketones, ethers, etc., and any solvent may be used as long as it has a percarboxylic acid phase and is not significantly altered by percarboxylic acid.

The reaction is carried out at room temperature to 150°C, preferably at room temperature to 100°C in view of the stability of the percarboxylic acid.

At this time, the reaction progresses gradually from the surface layer of the film toward the center layer. The reaction increases as the concentration of percarboxylic acid in the treatment agent increases.
The higher the reaction temperature.

Alternatively, the longer the reaction time, the faster the reaction progresses. By selecting appropriate conditions here, it is possible to obtain a polyP-phenylenesulfone film with any amount of polyp-phenylenesulfone chains, but it is important to determine the sulfonation reaction rate under several conditions in advance. Accordingly, the polyP-fuynylene sulfone chain is 1 molar or more and less than 70 molar,
It is possible to obtain a biaxially oriented film that preferably contains more than 5 moles and less than 40 moles.

If the polyP-phenylene sulfone chain is processed to have less than i molar number, the resulting film will have poor thermal dimensional stability, which is undesirable. If the processing is such that the number of polyP-phenylene sulfone chains is less than 70 mole, the resulting film will have poor mechanical properties. retention is reduced.

The outer layer, which is a layer mainly composed of biaxially oriented polyP-phenylene sulfone chains, is heated under conditions that yield a biaxially oriented film having a three-layer structure with a thickness of preferably 0.1 μm or more, more preferably 0.5 μm or more. It is desirable to treat the biaxially oriented polyP-phenylene sulfide film with a carboxylic acid.

The biaxially oriented film made of polyP-phenylene sulfone chains as the outer layer is the outer layer consisting mainly of polyP-phenylene sulfone chains, the center layer being a polyP-phenylene sulfide layer, and six Al-like layers. It is a film with a structure, that is, when the film is heated at 650°C for 10 minutes, the center layer melts and the film separates into three layers. At this time, the thickness of the outer layer is 0.1
It is preferable that the thickness is μm or more. More preferably 05μ
m or more.

The two reactions are continuous processing in which biaxially oriented polyP-7 22lene sulfide film is continuously passed through a percarboxylic acid bath, and batch processing in which the film is rolled up with spacers and processed in roll form. It is possible. After the reaction, the film is desirably washed with water or an organic solvent, and then dried by any method to obtain a film having even better thermal dimensional stability.

In addition, the film may be subjected to electrical surface treatment such as corona discharge surface treatment, plasma surface treatment, or chemical surface treatment such as acid treatment or alkali treatment, either alone or in combination, as necessary to improve adhesion. I can't help it.

Further, even if the film is laminated with other films or metal foils, there is no support at all.

Next, in order to obtain the printed wiring board of the present invention, generally, a metal foil such as a hook is attached to the film obtained by the above-mentioned method using an appropriate adhesive, or by plating, vacuum deposition, etc. A method of forming a metal layer on the surface of the film is used.

[Action and effect of the invention]

The thus obtained biaxially oriented polyP-phenylene sulfite film containing biaxially oriented polyP-phenylene sulfone chains of 2 molar or more and less than 70 molar ratio has excellent thermal dimensional stability and excellent mechanical properties. Because it maintains its characteristics, it can be used for flexible circuit boards, thermal transfer films, capacitors, transfer foils, and other vapor-deposited films.
The p-phenylene sulfide film can be applied to most fields of use.

Furthermore, the printed wiring board thus obtained has excellent solder resistance, and there are almost no problems such as wrinkles on the board due to heat shrinkage or peeling of the metal foil and film.

[Method of measuring characteristics] Measurement items were measured using the following method.

(1) The molar ratio of the hol, IF-phenylene sulfone chain.
After pulverizing a certain amount of polyP-phenylenesulfone film of each molar ratio, the IR was measured using the KBr method, and the molar ratio of the polyP-phenylenesulfone chain was determined by the absorbance ratio of the S-O antisymmetric stretching vibration at 1160 cm. We calculated the number of people in charge.

(Manufacturing method of standard material) A polyP-phenylene sulfite amorphous film (unstretched) with a thickness of 6 μm was immersed in a 40% peracetic acid bath solution (Mitsubishi Gas Chemical, commercially available product) for 24 hours at room temperature, and dried after being soaked in water. do. An examination of the atomic composition ratio reveals that it corresponds to approximately 100 molar polyP-phenylene sulfone, and CP/MAS CNMR
It was confirmed when measured.

(2) Wide-angle X-ray diffraction method OF=1 thickness with the stretching direction of each sample aligned.

Molded into a strip shape with a width of 1-2 and a length of 10-2 (each incidence during molding (
Edge, End=e and Through direction)
I then took a photo of the plate. The Xi generator used was a Rigaku D-3F type device, and the X-ray source was Cu - Ka rays passed through a Ni filter at 40 KV and 20 mA. Multiple exposures (15 minutes and 60 minutes) using Kodak non-screen type film with a distance between sample films of 41 mm.
adopted the law.

In addition, the densitometer device used is the Kura Microdensitometer Model PDM-5 Type A manufactured by Roku Konishi Photo Industry, and the measurement concentration range is 0.0 to 4.0D (minimum measurement area 4
Using a slit width of 1 μ and height of 10 μ with an optical system magnification of 100 times, a film movement speed of 50 μ/sec, and a chart speed of 1 ml/1 [17 seconds].

Microcrystal size and relative crystallinity index: A method of rotating the sample in the plane was adopted to eliminate the sample orientation effect9.
Diffraction patterns were measured using a reflection method.

The X-ray generator used was a Rigaku D-8C model.

Cu-
Ka was used as the Xat source. The goniometer is made by Rigaku PM.
Using the G-A2 model, the sample was mounted on a rotating sample stage that rotated at a rotation speed of 80 rpm, and the slit system had Di-1°/
minute, and the chart speed is 1/min. Each sample has 20
A measurement sample was cut out into a square of - and overlapped with a thickness of 05-.

(3) Strength, elongation 0 width 10mm by Tensilon type tensile testing machine.

Determine the breaking elongation and breaking strength of a 50mm sample.
Calculated as the average value of =5.

(4) Heat shrinkage test A film with a width of 200 mm and a width of 10 mto was heated for 10 minutes under no load in a hot air open oven at a constant temperature.

The shrinkage rate was calculated from the length of the sample before and after the heat.

〔Example〕

Next, the present invention will be explained with reference to examples.

Example 1 Polymerization of polyP-phenylene sulfide was carried out as follows.

2" as a polymerization solvent in an autoclave with an internal volume of 501"
07 N-methyl 2-pyrrolidone, 75 mol Na, S9H
, Q, and 25 mol of sodium acetate as a polymerization aid were charged, and the internal temperature of the autoclave was 200°C. 170
75 moles of P-dichlorobenzene and 0.15 moles of 1°2,4-trichlorobenzene were added. The autoclave was pressurized to 2.0 kg/cm with nitrogen. After raising the internal temperature to 260°C, polymerization was carried out by stirring for 2 hours. After cooling the system, the contents were taken out and poured into water, and washed with water. A white ZO heel polymer was obtained by vacuum drying at .degree. (For details, please refer to the Special Publication Act of 1973-
122.40). This polymer was measured using a Koka type flow tester under the conditions of 300° C. and a shear rate of 200 (seconds) and found to be 5200 Poise.

A part of this polymer was melted in a 30 mm diameter biaxial extrusion,
Extruded from a T-die with straight lips 200 mm long and 1.0 mm gap. Electrostatic printing force is cast onto a metal drum whose surface temperature is maintained at 20°C, then cooled and solidified to form a sheet with a width of 1.
A sheet having a size of 70 mm and a thickness of 610 μm was obtained.

Furthermore, the sheet was transferred to a film stretcher (US T,
Vertical/width 3.5 at 95℃ using M Long Co., Ltd.)
27-fold biaxial stretching, followed by hot air opening.
A fixed length heat treatment was performed at 0° C. for 1 minute to obtain a biaxially oriented poly p-phenylene sulfite film with a thickness of 25 μm.

When this film was subjected to wide-angle X-ray diffraction analysis, E
nd+ orientation degree 0.20 Edge orientation degree 02
The degree of orientation of 5Through was 0.90, and the relative crystallinity was 19 and the size of microcrystals was 70A.

stomach? A portion of the film was immersed in a commercially available 40% peracetic acid solution (manufactured by Mitsubishi Gas Chemical Co., Ltd.) for 6 hours at room temperature to react, washed with water, and then vacuum-dried at 100°C.

The poly P-phenylene sulfone chain was 22 moles.

When the degree of orientation of this film was measured, it was determined that the orientation was 2θ-16″ based on the crystalline phase of polyP-phenylene sulfone.
O, 35End◆0. ! +2 Througb O,
85, and polyP-phenylene sulfide (200
) surface at 2θ=21° Edge O, 28Enda
-0.25Through O.95, and it became clear that the egg was laid on two axes. The relative crystallinity was measured and found to be 18.

When examining the mechanical properties, the strength of 9 was 14.51 cg/mm.
'It has an elongation of 56% and exhibits excellent mechanical properties, and when this film was placed in an open oven at 350°C, it retained its film-like form.

The center part was melted, and it became clear that the center layer was a polyP-phenylene sulfide layer, and the outer layer was a polyP-phenylene sulfide layer, making it a three-layer structure. It is shown in Table 1.

Examples 2 and 3 A film containing 22 moles of polyP-phenylene sulfone chains prepared in Example 1 was heated at 200°C at 10°C in hot air.
and 240° C. for 10 minutes, respectively. The resulting film showed even better thermal dimensional stability. The results are shown in Table 1.

The sulfide film was immersed in a 10% acetone solution of m-chloroperbenzoic acid (Tokyo Kasei Reagent) and reacted at room temperature for 20 days. After washing with acetone, it was vacuum dried at 100°C. A film containing 25 moles of polyP-phenylene sulfone chains was obtained. The evaluation results are shown in Table 1.

The heat shrinkage rate of the sulfide film was measured. It became clear that the thermal dimensional stability was extremely inferior compared to the examples. The evaluation results are shown in Table 1.

Also, when I put the film in while it was open at 650℃,
It melted quickly and did not maintain its film shape.

The sulfide film was heat treated in a hot air oven at 200°C for 10 minutes and at 240°C for 10 minutes, respectively. When the heat shrinkage rate of the film was measured, it was found to be inferior to 250. Table 1 shows the evaluation results.

Comparative Example 4 An unstretched polyP-fuynylene sulfide film with a thickness of 25 μm was prepared, and it was added to a 40% peracetic acid solution at room temperature for 2 hours.
．． Soaked for 5 hours. PoIJ p-phenylenes, sulfone linkage was 22%. When the degree of orientation was measured, it was found to be 2
Edge 1. at θ-16°. OEndk O,9BTh
rough O, Edge 1.0 at 982θ-21°
2 End? 0.99Through 0.99, and was an unoriented film.

The relative crystallinity was 5.

Also, many cracks are formed on the film surface I1. That part peeled off, making it impossible to use it as a normal film. The evaluation results are shown in Table 1.

Comparative Example 5 The biaxially oriented polyP phenylene sulfide film produced in Example 1 was immersed in a 40% peracetic acid solution at room temperature for 12 hours, washed with water, and then vacuum dried at 100°C. Po IJ p-phenylene sulfone chain is 75 molar The mechanical properties were measured and the strength was 13.0 ka7mm''.

It became clear that the elongation was 18%, which was very inferior to the example.

Further, when heat treated at 650°C for 10 minutes, it was found to be infusible.

After corona discharge treatment by applying electrical energy of
It was coated to a thickness of 0 μm (after drying).Next, electrolytic copper foil for printed circuit boards (65 μm thick) was layered on top of this.
The materials were bonded by passing through a press roll maintained at 100° C. and having a linear pressure of 6 kg per 100°C. The obtained laminate was left in a hot air oven at 80° C. for 4 days to cure the adhesive, thereby obtaining a printed wiring board.

This printed wiring board was immersed in a 250° C. solder bath for 1 minute, and the shape was observed after taking it out.

Comparative Example 6 The biaxially oriented polyP-phenylene sulfide film produced in Example 1 was laminated with copper foil in the same manner as in Example 5 to produce a printed wiring board. .

Similarly, when immersed in a 250°C solder bath for 1 minute,
It curls greatly in the direction of the film side.

The copper foil and film were partially peeled off due to heat shrinkage.

Small wrinkles were also observed.

Claims (2)

[Claims] (1) A biaxially oriented polyP-phenylene sulfide film containing 1 mol% or more and less than 70 mol% of biaxially oriented polyP-phenylene sulfone chains. (2) A printed wiring board formed by laminating a metal thin film on a biaxially oriented polyP-phenylene sulfide film containing 1 mol% or more and less than 70 mol% of biaxially oriented polyP-phenylene sulfone chains.