JP2003082124A - Polyetherketoneketone film and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare an oriented polyetherketoneketone film which has a high Young's modulus, a small water absorption factor and a small humidity expansion coefficient, and is excellent in flame retardance, thermal resistance and insulation characteristics, and to provide a method for manufacturing the same. SOLUTION: There are provided the oriented polyetherketoneketone film prepared by stretching at least uniaxially a polyetherketoneketone which has a peak melting temperature of 300 deg.C or above, a glass transition temperature of 150 deg.C or above, measured at the time of increasing temperature by a differential scanning calorimeter, and a water absorption factor of 0.5% or less, and the method for manufacturing the polyetherketoneketone film comprising stretching at least uniaxially the polyetherketoneketone in a uniaxial draw ratio of 2.5-5 and at a drawing temperature Tg-Tcc and fixing thermally the resulting film at a temperature lower than the melting point of the film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oriented polyetherketoneketone film which can be suitably used for a flexible printed wiring board used for industrial materials, particularly electric and electronic applications, and a method for producing the same.

[0002]

2. Description of the Related Art A flexible printed circuit board (hereinafter abbreviated as FPC) is electrically conductive on the surface of a heat-resistant substrate film through an adhesive such as polyester base, acrylic base, epoxy base or polyimide base. On the surface of the heat resistant base film, which has a three-layer structure in which the metal foil of
A two-layer structure in which a conductive metal layer is directly laminated without using an adhesive is used.

In addition, the heat-resistant base film of FPC is
It is common to use a polyester film or a polyimide film. A polyimide film has been used in applications where heat resistance and flame retardancy are required, and particularly in applications where it is necessary to withstand high temperatures such as solder welding applied to a base film at the time of joining with metal wiring. Polyester films have been used in applications that require low prices, such as general-purpose IC cards.

That is, there is a problem that the polyester film has poor solder heat resistance. Further, the polyimide film has the problems that it is expensive, that it is difficult to recycle because it is thermosetting, and that it has a high water absorption rate.

In order to solve these problems at once,
High melting thermoplastic polymers have been investigated. Typical examples are liquid crystal polymers, polyarylketones, and polyethylene naphthalates. The liquid crystal polymer was difficult to handle because of large anisotropy due to orientation. Since polyethylene naphthalate has a melting point of 270 ° C., solder heat resistance (260 ° C.) was insufficient. Polyarylketones typified by polyetheretherketones were quick to crystallize, difficult to stretch and orient, and poor in stretchability. Therefore, it was sometimes blended with a polymer having a high glass transition temperature in order to reduce the crystallinity. However, the stretchability is insufficient, and a film having a high Young's modulus and uniformly oriented has not been obtained.

For example, JP-A-2000-200950 and JP-A-2000-200976 show specific examples of resin compositions of polyether ether ketone and polyether imide. However, when it is used as a single film such as TAB or when it is used for reinforcement such as cover film and lining, a Young's modulus of about 3 [GPa] or more is required, and conventional products are rigid in these applications. There was a shortage.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides an oriented polyetherketoneketone film having a high Young's modulus, a small water absorption coefficient and a low humidity expansion coefficient, and excellent flame retardancy, heat resistance, and insulating properties, and a method for producing the same. To do.

[0008]

The gist of the polyetherketoneketone film and the process for producing the same according to the present invention is that the polyetherketoneketone having a melting peak temperature of 300 ° C. or higher is heated by a differential scanning calorimeter. It is a polyetherketoneketone film obtained by stretching at least uniaxially a polyetherketoneketone having a glass transition temperature of 150 ° C. or higher and a water absorption rate of 0.5% or lower, which is sometimes measured. In addition, the Young's modulus obtained by biaxially stretching the polyetherketoneketone represented by the following formula (I) is 3 [GP
a) The above polyetherketoneketone film.

Tcc-Tg ≧ 40 ° C. (I) Tcc ... Crystallization peak Tg at the time of temperature rise ... Glass transition temperature Further, the uniaxial stretching ratio is 2.5 to 5 times, It is a method for producing a polyetherketoneketone film stretched at least uniaxially at a temperature of Tg or higher and Tcc or lower.

[0010]

[Function] By orienting polyetherketone ketone under a specific condition, molecules are oriented, and a high Young's modulus is obtained.
An oriented polyetherketoneketone film having excellent flatness and dimensional stability is obtained.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The film according to the present invention comprises polyetherketoneketone. The polyetherketoneketone is one having one ether group and two ketone groups in the repeating unit structure in the molecule as shown by the following chemical formula.

Specific examples are described in JP-A-61-195122 and JP-A-62-129313, and the compounds represented by the following formulas are preferable.

[0013]

[Chemical 1]

The compound represented by the following formula is more preferable.

[0015]

[Chemical 2]

Here, the unit ratio of p and m, p / m is 2
0/80 to 80/20 is preferable. The number average molecular weight is 5,
000 to 30,000.

The polyether ketone ketone of the present invention must have a melting peak temperature of 300 ° C. or higher. However, other thermoplastic resins, antioxidants, heat stabilizers, lubricants, UV absorbers, organic and inorganic fillers and the like may be added within the range not impairing the object of the present invention. When these are added, less than 5% by weight is preferable. The preferred melting point of polyetherketoneketone is 350 ° C. or higher. 300
When the temperature is lower than ℃, when used as a printed circuit board, the solder heat resistance is poor. Further, the glass transition temperature measured when the temperature is raised by a differential scanning calorimeter is preferably 150 ° C. or higher. If the temperature is lower than 150 ° C., dimensional changes occur when the copper foils are bonded together, and dimensional changes tend to occur during the soldering process.

The water absorption is 0.5% by weight or less. 0.5
If it is at least%, dimensional change due to moisture absorption occurs in the copper etching step.

Further, the film of the present invention preferably satisfies the formula (I).

Tcc-Tg ≧ 40 ° C. (I) Tcc ... Crystallization peak Tg at the time of temperature rise ... When the glass transition temperature (Tcc-Tg) is less than 40 ° C., crystallization tends to occur. However, the film is broken during drawing or the tension during drawing becomes high, which makes uniform drawing difficult.

Further, Tcc is preferably 200 ° C. or higher.
If Tcc is less than 200 ° C., the tension during stretching tends to be high, which may cause breakage.

In the method for producing a film of the present invention, first, polyetherketoneketone is melt-molded to form an unstretched film. Amorphous films cast by the method of rapid cooling by applying static electricity are preferable. When producing an unstretched film, a powdery or pelletized polyetherketoneketone raw material is supplied to an extruder and formed into a film with a slit-shaped die. At this time, it is effective to remove foreign matters by filtering in a molten state using a 20 μm cut metal fiber sintered filter. More preferably, it is a 10 μm cut metal fiber sintered filter, and most preferably 1
It is a metal fiber sintered filter of μm cut.

Next, the unstretched film is stretched in at least one axial direction. It is preferable to stretch in two axes orthogonal to each other. The biaxial stretching method includes simultaneous biaxial stretching and sequential biaxial stretching, but the sequential biaxial stretching method is preferable. It is preferable that the stretching ratio in at least the uniaxial direction is 2.5 to 5 times, and the surface stretching ratio in the case of biaxial stretching is 6 to 25 times. If the draw ratio is less than 2.5 times, the thickness unevenness of the film is large and the orientation may not be sufficient. If the magnification exceeds 5 times, the number of fractures increases.

The stretching temperature range at this time is not less than Tg of the polyetherketone ketone and less than Tm, preferably Tc.
c or less. Stretching less than Tg tends to cause stretch unevenness, and stretching at a temperature exceeding Tcc tends to cause stretch unevenness or thickness unevenness.

The film is then heat set at a temperature below its melting point. The heat setting temperature is preferably Tcc or higher. Above the melting point, it is difficult to maintain the film shape.

The heat setting treatment is preferably a method of fixing the film width. A method in which the film width is not fixed can also be adopted, but the relaxation rate is 10% or less. If it is heat-fixed under the condition of more than 10%, the flatness becomes poor. Preferably 4-10
Under running tension as low as kg / cm ² , (Tg + 30) ~ (Tg + 8)
It is preferable to carry out at a temperature of 0) ° C. for 0.1 to 120 seconds. The heat setting method is preferably performed using a heating levitation treatment device. A heated inert gas, particularly heated air, is preferably used as a medium for heating and floating the film. According to this heating and levitation treatment, heat fixation can be efficiently performed while maintaining stable film running.

The Young's modulus of the oriented film is preferably 3 [GPa] or more. More preferably, it is 4 [GPa] or more. The upper limit will be 10 [GPa] or less. If the Young's modulus is less than 3 [GPa], the rigidity is insufficient, and when a tape having a slit shape is used, running properties and handleability are deteriorated.

The thickness of the stretched film of the present invention is not particularly limited, but it is preferably about 1 μm to less than 1 mm.

After the above-mentioned treatment, the stretched film may be subjected to electric treatment or application of an adhesion-imparting agent.

The polyetherketoneketone film according to the present invention is suitable as a base film of FPC or a cover film (lining) thereof.

[0031]

EXAMPLES The polyetherketoneketone film and the method for producing the same according to the present invention will be described below with reference to examples. In the examples, all parts and percentages are by weight unless otherwise stated.

[0032]

[Measurement and Evaluation] (1) Strength, elastic modulus and elongation at break Elastic modulus is ORIE at room temperature according to JIS K7113.
It was determined from the slope of the initial rising portion of the tension-strain curve obtained at a tension rate of 300 mm / min using a Tensilon type tensile tester manufactured by NREC. The breaking elongation is the elongation at which the sample breaks. (2) Water absorption rate After being placed in a constant temperature and humidity machine (STPH-101, manufactured by Tabay Espec Co., Ltd.) for 48 hours at a temperature of 25 ° C. and a humidity of 95% RH, a water absorption rate was measured. The weight difference was calculated as a percentage. (3) Film Forming Property and Uniformity of Stretching The prepared film was set to 1 by a biaxially stretching polymer film for research (BIX-703, manufactured by Iwamoto Manufacturing Co., Ltd.).
At 60 ° C., the film was broken by a simultaneous biaxial or sequential biaxial drawing method to determine the film breakage area. Preheating time 60 seconds, one side drawing speed 10 cm / min. 5m in the plane of unstretched film
After drawing grid lines at intervals of m vertically and horizontally, a biaxially stretching polymer film for research (BIX-703, manufactured by Iwamoto Seisakusho Co., Ltd.) is used to stretch to a predetermined magnification. After stretching, the distance between the lattices was measured for each of 10 pieces in the longitudinal and lateral directions of the central portion to obtain the average stretching ratio, and the variation rate (standard deviation ÷ average value × 100%) was obtained from the average value and the standard deviation.

Variability is within 3% ◎ Variability is within 5% ○ Variability exceeds 5% × (4) Thermal characteristics; melting point (Tm), glass transition temperature (T
g), crystallization temperature (Tcc) About 10 mg of a sample was used according to JIS K7121. The device is SSC / 5200H (DS manufactured by Seiko Instruments Inc.
C220C) was used. The sample was preliminarily heat-treated at 400 ° C. for 5 minutes and then immediately cooled with liquid nitrogen, and the temperature rising process of the sample was measured. The temperature rising rate is 10 ° C / min, and the temperature and calorific value are calibrated with indium (melting point 156.61 ° C, heat of crystal fusion 6.8).
6 cal / g). A measurement example is shown in FIG. The vertical axis represents the amount of heat and the horizontal axis represents the temperature. This measurement example is PEKK (manufactured by Cytec Fiberite, product name CypekR grade name HT, MI = 25, melting point 351 ° C., glass transition temperature 158 ° C., Tcc 200 ° C.) used in Example 2. Tg was read in the middle of the transition temperature. The peak temperature was read for Tcc and Tm. (5) Evaluation of warpage of metal laminated plate (curl) Film and copper foil (electrolytic copper foil “3EC” 35 μm manufactured by Mitsui Mining & Smelting Co., Ltd.) using an acrylic adhesive (“Pyralax” manufactured by DuPont) (Thickness) and laminated, 150 ℃ × 1
The curing reaction of the adhesive was carried out over time to prepare a film / adhesive / copper foil laminate (hereinafter referred to as FC laminate). Got
The FC laminated plate was cut into a sample with a width of 10 mm and a length of 30 cm, and the obtained metallic laminated plate was cut into a sample size of 35 mm x 120 mm, and allowed to stand in an atmosphere of 25 ° C and 60 RH% for 24 hours. Was measured.
As for the warp, the sample was placed on a glass plate and the heights of the four corners were measured and averaged. The evaluation criteria were determined as follows according to the amount of warpage. When used as a metal wiring circuit board, the X level is a level at which handling becomes difficult during transportation in a subsequent process.

○ Warp amount less than 1 mm △ Warp amount 1 mm or more and less than 3 mm × Warp amount 3 mm or more (6) Coefficient of thermal expansion (CTE) The coefficient of thermal expansion was measured using a TMA-50 type thermomechanical analyzer manufactured by Shimadzu Corporation at a temperature rising rate of 10 ° C / min and a temperature decreasing rate of 5 ° C / min for the second time. 50 ℃ to 150 ℃ when the temperature rises / falls
It was calculated from the dimensional change during the period.

The average in-plane thermal expansion coefficient (CTEave) was calculated by the following equation from the thermal expansion coefficients in the maximum orientation angle direction and the minimum orientation angle direction, which were obtained when the in-plane anisotropy index was measured.

CTEave = (CTE + in the maximum orientation angle direction)
CTE in the direction of the minimum orientation angle / 2 [Example 1, Comparative Example 1] Polyether ketone ketone (hereinafter abbreviated as PEKK, manufactured by Cytec Fiberite Co., product name Cyp
ekR grade name DS, MI = 40) 1 under nitrogen atmosphere
It was dried at 20 ° C. for 10 hours. This dry raw material was supplied to a 50 mm vent type extruder (manufactured by Ikegai Seisakusho), melted at 390 ° C., extruded from a slit die having a width of 500 mm (gap 0.8 mm), and cast on a roll of 10 ° C. At the time of casting, it was brought into close contact with the roll by an electrostatic application method and cooled. An unstretched film having a thickness of about 500 μm was obtained.

This unstretched film was evaluated and designated as Comparative Example 1. The results are shown in Table 1.

The unstretched film was sampled into a square of 90 mm on a side, preheated at 160 ° C. for 3 minutes with a biaxially stretching polymer film for research (manufactured by Iwamoto Seisakusho), and then 3 in the longitudinal direction (MD) of the film. Uniaxially stretched 3 times, and then sequentially biaxially stretched 3.3 times in the direction (TD) at right angles, 30
It was heat set at 0 ° C. The film thickness was 45 μm.
The evaluation results are shown in Table 1.

[Examples 2 and 3 and Comparative Example 2] PEKK
(Manufactured by Cytec Fiberite, product name CypekR grade name H
T, MI = 25) was prepared in the same manner as in Example 1 to prepare an unstretched film.

This unstretched film was evaluated and designated as Comparative Example 2. The results are shown in Table 1.

The unstretched film was sampled into a square of 90 mm on a side and preheated at 160 ° C. for 3 minutes with a biaxially stretching polymer film for research (manufactured by Iwamoto Seisakusho Co., Ltd.). Right angle direction (TD)
Biaxially stretched 2.6 times and 3.3 times simultaneously to 300
Heat set at ℃. The thickness of each film is 74 μm
(Example 2) and 45 μm (Example 3). The evaluation results are shown in Table 1.

[Comparative Examples 3 and 4] PEKK (manufactured by DuPont, product name PEKK grade name PC, MI = 25) was used in the same manner as in Examples 2 and 3. At 3.3 times, the film broke during the stretching. The 2.5 times product had large thickness unevenness and the uniformity of stretching was poor.

[0043]

[Table 1]

[0044]

EFFECTS OF THE INVENTION Polyetherketone ketone is excellent in flame retardancy and insulating properties, but by stretching a polyetherketone ketone having specific thermal properties, it is possible to obtain uniform extensibility while maintaining these properties. A polyetherketoneketone film having high rigidity is obtained. Further, the present invention provides a production method characterized by uniform stretchability with less tearing under film forming conditions corresponding to specific thermal characteristics.

[Brief description of drawings]

FIG. 1 is a chart in which the thermal characteristics of PEKK in Example 2 are measured.

Claims (3)

[Claims] 1. A glass transition temperature measured when the melting peak temperature is 300 ° C. or higher and the temperature is raised with a differential scanning calorimeter.
An oriented polyetherketoneketone film obtained by stretching at least uniaxially a polyetherketoneketone having a water absorption rate of 0.5% or less at 50 ° C. or higher. 2. The oriented polyetherketoneketone film according to claim 1, which satisfies the formula (I), is biaxially stretched, and has a Young's modulus of 3 [GPa] or more. Tcc-Tg ≧ 40 ° C. (I) Tcc ... Crystallization peak Tg at the time of temperature rise ... Glass transition temperature 3. The glass transition temperature measured when the melting peak temperature is 300 ° C. or higher and the temperature is raised by a differential scanning calorimeter is 1.
A polyetherketoneketone having a water absorption rate of 0.5% or less at 50 ° C. or higher is stretched in a uniaxial direction of 2.5 times to 5 times.
A method for producing a polyetherketoneketone film, comprising stretching at least uniaxially at a stretching temperature of Tg to Tcc and then heat-setting at a temperature lower than the melting point of the film.