JP2002105221A - Heat-resistant film and print circuit board using it as substrate, and method of manufacturing them - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat resistant film suitable for an electronics member or the like and particularly having improved edge tearing strength and a print circuit board using it as a substrate, and a method of manufacturing them. SOLUTION: The heat resistant film comprises a mixture of 100 pts.wt. of a resin composition and an inorganic filler in a range of 5-50 pts.wt., which is treated for crystallization. The resin composition consisting of 70-30 wt.% of a polyarylketone resin (A) has a crystal melting temperature of 260 deg.C and 30-70 wt.% of a non-crystalline polyetherimide resin (B), wherein when the film is heated at a rate of 10 deg.C/min. in a differential scanning calorimetry at least two endothermic peaks are observed, and the two endothermic peaks of which appear at a lower temperature than the peak due to crystal melting of the polyarylketone resin (A) at 260 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant film which can be suitably used as an electronic member, a printed wiring board using the same as a base material, and a method for producing the same.

[0002]

2. Description of the Related Art Crystalline polyaryl ketone resins typified by polyether ether ketone resins are excellent in heat resistance, flame retardancy, hydrolysis resistance, chemical resistance, etc., and are therefore used in aircraft parts, electric and electronic equipment. It is widely used mainly for parts.
However, polyaryl ketone resins are very expensive in raw materials and have a glass transition temperature of about 140 to
Since the temperature is relatively low at about 170 ° C., various studies for improving heat resistance and the like have been made. Among them, a blend with an amorphous polyetherimide resin has attracted attention as a system showing good compatibility. For example, JP-A-59-187054
JP-A No. 61-500023 and JP-A-61-500023 disclose a mixed composition of a crystalline polyarylketone resin and an amorphous polyetherimide resin.
JP-A-115353 also discloses that these compositions are useful for circuit board substrates. Further, the present inventors have also disclosed JP-A-2000-38464 and JP-A-2000-38464.
-200950 and the like have proposed a printed wiring board using the above mixed composition and a method for producing the same.

[0003] However, flexible printed wiring is used by using a film made of a mixed composition of a crystalline polyarylketone resin and an amorphous polyetherimide resin (usually containing an inorganic filler or the like for improving dimensional stability). When a board is manufactured, the dimensional stability and heat resistance are good, but the mechanical strength, especially the edge crack strength, is not always at a sufficient level, and the folding and bending resistances are impaired. However, there is a problem that the range of use is limited, and improvement thereof has been desired. In addition, the above patent publication has no technical disclosure about this cause or improvement method, and has no suggestion.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a heat-resistant film which is suitable for use as a member for electronics and the like, and in particular, has an improved edge crack strength, a printed wiring board using the same as a base material, and a method for producing the same. To provide.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventor has found that a resin composition comprising a crystalline polyarylketone resin and an amorphous polyetherimide resin as a main component has a specific thermal property. By providing such a film, a heat-resistant film, a printed wiring board using the same as a base material, and a method for producing the same, which can solve the above-described problems, have been completed, and the present invention has been completed. That is, the gist of the present invention is that the polyarylketone resin (A) having a crystal melting peak temperature of 260 ° C. or more is 70 to 30% by weight and the amorphous polyetherimide resin (B) is 30 to 70% by weight. A crystallization-treated film obtained by mixing an inorganic filler in a range of 5 to 50 parts by weight with respect to 100 parts by weight of a resin composition comprising
At least two endothermic peaks appear when the temperature is raised at a rate of ° C./min, and of these endothermic peaks, the endothermic peak temperature that appears on the lower temperature side than the endothermic peak derived from the crystal melting of the polyarylketone resin is less than 260 ° C. A heat-resistant film characterized by that.

Another gist of the present invention is that a polyarylketone resin (A) having a crystal melting peak temperature of 260 ° C. or more is 70 to 30% by weight and an amorphous polyetherimide resin (B) is 30 to 70% by weight. % Of the resin composition 100
A conductive foil is heat-sealed and crystallized on at least one side of a film in which an inorganic filler is mixed in a range of 5 to 50 parts by weight with respect to parts by weight, without using an adhesive layer. In the printed wiring board thus formed, at least two endothermic peaks appear when the film is heated at a heating rate of 10 ° C./min by differential scanning calorimetry, and of these endothermic peaks, the crystal melting of the polyarylketone resin Wherein the temperature of the endothermic peak appearing on the lower temperature side than the endothermic peak derived from is less than 260 ° C.

Still another aspect of the present invention resides in the above-mentioned method for producing a heat-resistant film or printed wiring board, wherein the crystallization treatment is performed in a temperature range satisfying the following relational expression. Tc (A + B) -20 ≦ Tx ≦ Tg (B) +20 where Tc (A + B) is a crystalline polyarylketone resin (A) and an amorphous polyetherimide resin (B)
Shows the crystallization temperature (° C.) that appears when the temperature of the resin composition is increased by differential scanning calorimetry.
(B) shows the glass transition temperature (° C.) of the amorphous polyetherimide resin (B) alone, and Tx shows the crystallization temperature (° C.). The crystalline polyaryl ketone resin has a repeating unit represented by the following structural formula (1), and the amorphous polyether imide resin has a repeating unit represented by the following structural formula (2). Polyetherimide resin can be particularly preferably used as a main component.

[0008]

(Equation 1)

[0009]

(Equation 2)

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The film of the present invention comprises a resin composition 100 comprising 70 to 30% by weight of a crystalline polyarylketone resin (A) and 30 to 70% by weight of an amorphous polyetherimide resin (B).
It is a film in which an inorganic filler is mixed in a range of 5 to 40 parts by weight with respect to parts by weight. The film according to the present invention includes a relatively thick sheet of about 500 μm or more. Here, the crystalline polyarylketone resin constituting the present invention is a thermoplastic resin having an aromatic nucleus bond, an ether bond and a ketone bond in its structural unit, and typical examples thereof include polyetherketone and polyetherether. There are ketone, polyether ketone ketone and the like, and in the present invention, polyether ether ketone having a repeating unit represented by the following structural formula (1) is preferably used. A polyetheretherketone having this repeating unit is a product name “PEEK151G” manufactured by VICTREX.
It is commercially available as “PEEK381G”, “PEEK450G” and the like. In addition, the crystalline polyaryl ketone resin used can be used individually by 1 type and in combination of 2 or more types.

[0011]

(Equation 1)

Further, the amorphous polyetherimide resin is
It is an amorphous thermoplastic resin having an aromatic nucleus bond, an ether bond and an imide bond in its structural unit, and is not particularly limited. Specifically, polyetherimides having the repeating units represented by the following structural formulas (2) and (3) are each manufactured by General Electric Corporation under the trade name “Ultem”.
It is commercially available as “CRS5001” and “Ultem 1000”, and both can be applied. In the present invention, a polyetherimide having a repeating unit represented by the following structural formula (2) is particularly preferably used. Although the reason for this is not clear, probably, in a mixed composition of the polyetheretherketone having the above structural formula (1) and the polyetherimide resin having the following structural formula (2), electronic interaction between molecules may be suppressed. Unlike a mixed composition of a polyetheretherketone having the above structural formula (1) and a polyetherimide resin having the following structural formula (3),
Due to the difference in compatibility, a unique higher-order structure is formed, which also seems to contribute to the improvement of mechanical strength (end crack strength).

[0013]

(Equation 2)

[0014]

(Equation 3)

The method for producing the amorphous polyetherimide resin is not particularly limited, but usually, the amorphous polyetherimide resin having the structural formula (2) is 4,4.
As a polycondensate of 4 '-[isopropylidenebis (p-phenyleneoxy) diphthalic dianhydride and p-phenylenediamine, and an amorphous polyetherimide resin having the above structural formula (3), It is synthesized by a known method as a polycondensate of 4 '-[isopropylidenebis (p-phenyleneoxy) diphthalic dianhydride and m-phenylenediamine. Further, other monomer units that can be copolymerized may be introduced into the above-mentioned amorphous polyetherimide resin without departing from the scope of the present invention. In addition,
As the amorphous polyetherimide resin to be used, one kind can be used alone, and two or more kinds can be used in combination.

In the above resin composition, when the content of the crystalline polyarylketone resin exceeds 70% by weight or the content of the amorphous polyetherimide resin is less than 30% by weight, the crystallinity of the whole composition is high, and the crystallization treatment is performed. The crystal structure such as spherulite grows and develops to a high degree, so that mechanical strength (end crack strength) tends to decrease, and volume shrinkage (dimensional change) due to crystallization increases, resulting in reliability as a circuit board. It is not preferable because the property is lowered. If the content of the crystalline polyarylketone resin is less than 30% by weight or the content of the amorphous polyetherimide resin exceeds 70% by weight, the crystallinity itself of the composition as a whole is low, and the crystallization rate is too slow. However, even if the crystal melting peak temperature is 260 ° C. or more, the solder heat resistance decreases, which is not preferable. From this, in the present invention, 65 to 35% by weight of the polyaryl ketone resin is used.
And a resin composition comprising 35 to 65% by weight of an amorphous polyetherimide resin.

When the amount of the inorganic filler mixed with 100 parts by weight of the above resin composition exceeds 50 parts by weight, the mechanical strength such as the flexibility and tear strength of the film is undesirably reduced. On the other hand, if the amount is less than 5 parts by weight, the effect of lowering the linear expansion coefficient and improving the dimensional stability is small, which is not preferable. For this reason, the preferable mixing amount of the inorganic filler is 1 to 100 parts by weight of the above resin composition.
0 to 30 parts by weight. The inorganic filler used is not particularly limited, and any known inorganic filler can be used. For example, talc, mica, clay, glass, alumina, silica, aluminum nitride, silicon nitride and the like can be mentioned, and these can be used alone or in combination of two or more. In addition, the inorganic filler used,
Coupling agent treatment such as titanate, fatty acid, resin acid,
Surface treatment such as various surfactant treatments may be performed. In particular, an inorganic filler having an average particle diameter of about 1 to 20 μm and an average aspect ratio (particle diameter / thickness) of about 20 to 30 or more decreases mechanical strength at a low addition amount (about 10 to 25 parts by weight). The effect of improving the dimensional stability without causing the above is preferable.

Next, the film of the present invention is a film obtained by crystallizing a film comprising the above-mentioned mixed composition, and the film is heated at a heating rate of 10 by differential scanning calorimetry.
At least two endothermic peaks appear when the temperature is raised at a rate of ° C./min, and of these endothermic peaks, the endothermic peak temperature that appears on the lower temperature side than the endothermic peak derived from the crystal melting of the polyarylketone resin is less than 260 ° C. It is a heat-resistant film characterized by the above-mentioned. Here, in the present invention, the crystallization treatment means that a characteristic value obtained when performing differential scanning calorimetry using a film after the crystallization treatment satisfies the following relational expression. [(ΔHm−ΔHc) / ΔHm] ≧ 0.90 In the above equation, ΔHm is the heat of crystal fusion (J / g) measured when the temperature is increased by differential scanning calorimetry. The heat of crystallization (J / g) generated by crystallization during warming. The heat of crystal fusion Δ
Hm (J / g) and heat of crystallization ΔHc (J / g) are values obtained as follows. That is, using Perkin Elmer's DSC-7, 10 mg of a sample was subjected to JIS-K
According to 7122, a heating rate of 10 ° C./min.
It was determined from a thermogram when the temperature was raised to 0 ° C.

The above relational expression [(ΔHm−ΔHc) / ΔH]
The value of m] also depends on the type, molecular weight, composition ratio and the like of the raw material polymer, but greatly depends on the film forming and processing conditions, particularly the crystallization treatment conditions. That is, when a raw material polymer is melted at the time of forming a film and then cooled immediately, the numerical value becomes smaller. Further, if the processing time is increased at a certain processing temperature under the crystallization processing conditions, the numerical value can be increased. The maximum value of the numerical value is 1.
The value is 0, which means that the larger the value is, the more the crystallization is progressing. Here, when the numerical value is less than 0.90,
Crystallization is not sufficiently advanced, and dimensional stability is lowered, and solder heat resistance is likely to be insufficient, which is not preferable.

Further, the endothermic peak temperature derived from the crystal melting of the polyarylketone resin by differential scanning calorimetry is as follows:
Depending on the type of crystalline polyaryl ketone resin,
For example, in polyetheretherketone (PEEK),
330-340 ° C, polyetherketone (PEK)
Appears at about 370 to 380 ° C. In the present invention, the endothermic peak temperature which appears on a lower temperature side than the endothermic peak derived from crystal melting of the polyarylketone resin obtained when the temperature is increased at a heating rate of 10 ° C./min by differential scanning calorimetry is lower than 260 ° C. That is most important.

Here, if the endothermic peak temperature which is lower than the endothermic peak derived from the melting of the crystal of the polyarylketone resin is 260 ° C. or higher, it is not preferable because the end crack strength decreases. The reason for this is not clear, but as the peak temperature increases, a crystal structure such as a spherulite derived from the crystal component of the polyarylketone resin (A) grows and develops to a high degree, and these interfaces become defects and mechanical It seems that the strength (end crack strength) decreases. From this, the preferred range of the endothermic peak temperature that appears on the lower temperature side than the endothermic peak derived from the crystal melting of the polyarylketone resin is 200 ° C.
As described above, the temperature is lower than 260 ° C. If the endothermic peak temperature, which appears on the lower temperature side than the endothermic peak derived from crystal melting of the polyarylketone resin, is less than 200 ° C., crystallization is insufficient, which is not preferable. In the present invention, the endothermic peak temperature that appears on the lower temperature side than the endothermic peak derived from the crystal melting of the polyarylketone resin mainly depends on the crystallization treatment conditions. That is, the higher the crystallization temperature and the longer the processing time, the higher the peak temperature shifts to a higher temperature, and conversely, the lower the crystallization temperature and the shorter the processing time, the lower the peak temperature shifts to a lower temperature.

In the present invention, it is preferable that the above-mentioned crystallization treatment is performed in a temperature range satisfying the following relational expression. Tc (A + B) -20 ≦ Tx ≦ Tg (B) +20 where Tc (A + B) is a crystalline polyarylketone resin (A) and an amorphous polyetherimide resin (B)
Shows the crystallization temperature (° C.) that appears when the temperature of the resin composition is increased by differential scanning calorimetry.
(B) shows the glass transition temperature (° C.) of the amorphous polyetherimide resin (B) alone, and Tx shows the crystallization temperature (° C.). In the above relational expression, the crystallization temperature (Tx) is less than Tc (A + B) -20, that is, a resin composition comprising a crystalline polyarylketone resin (A) and an amorphous polyetherimide resin (B) At a crystallization temperature (Tx) of less than −20 ° C., which is a crystallization temperature (° C.) that appears when the temperature is raised by differential scanning calorimetry, the crystallization proceeds slowly, and crystallization tends to be insufficient. On the other hand, if the temperature exceeds Tg (B) + 20 ° C., that is, the amorphous polyetherimide resin (B)
If the temperature exceeds the glass transition temperature + 20 ° C. of the simple substance, crystallization proceeds sufficiently and solder heat resistance is also exhibited, but as described in the examples described later, the end crack strength tends to decrease, which is not preferable.

The reason for this is not clear, but probably when the crystallization temperature (Tx) exceeds the glass transition temperature of the amorphous polyetherimide resin (B) alone + 20 ° C., the amorphous polyetherimide resin (B )) The molecular mobility of the component becomes intense, which indicates that the polyarylketone resin (A)
It is considered that a crystal structure such as a spherulite derived from the crystal component of (1) grows and develops to a high degree, and these interfaces become defects to decrease the mechanical strength (end crack strength). From this, a preferable heat treatment temperature range is Tc (A + B) −15 ° C. or more,
g (B) + 15 ° C. or less.

In the resin composition constituting the film of the present invention, various additives other than other resins and inorganic fillers, such as a heat stabilizer, an ultraviolet absorber, a light stabilizer, A nucleating agent, a coloring agent, a lubricant, a flame retardant and the like may be appropriately blended. A known method can be used as a method for mixing various additives including the inorganic filler. For example,
(A) A masterbatch in which various additives are mixed with a suitable base resin such as a polyarylketone resin and / or an amorphous polyetherimide resin at a high concentration (typically about 10 to 60% by weight). Separately, a method of mixing and adjusting the concentration to the resin to be used, and mechanically blending using a kneader or an extruder, or (b) kneading various additives directly to the resin to be used. Examples include a method of mechanically blending using an extruder or the like. In the above mixing method, a master batch of (a) is prepared,
The method of mixing is preferable from the viewpoint of dispersibility and workability. Further, the surface of the film may be appropriately subjected to embossing, corona treatment, or the like, for the purpose of improving handling properties and the like.

As a method for forming the film of the present invention, a known method, for example, an extrusion casting method using a T-die, a calendar method, or the like can be employed. And stable productivity,
Extrusion casting using a T-die is preferred. The molding temperature in the extrusion casting method using a T die is appropriately adjusted depending on the flow characteristics and film forming properties of the composition.
430 ° C or lower. The thickness of the film is not particularly limited, but is usually about 10 to 500 μm.

Next, in the printed wiring board of the present invention, at least one surface of the above-mentioned film is subjected to heat fusion and crystallization treatment without interposing an adhesive layer to form a conductive circuit on the conductive foil. Substrate. As described above, the temperature condition is very important in the crystallization treatment, but the method is not particularly limited. For example, as a heat treatment method, a method of crystallizing at the time of extrusion casting (cast crystallization method) or a method of crystallizing with a heat treatment roll or a hot air furnace in a film forming line (in-line crystallization method)
And a method (outline crystallization method) in which crystallization is performed outside a film forming line by a hot-blast furnace, a hot press, or the like. In the present invention, the outline crystallization method is suitably used from the viewpoint of production stability and uniformity of physical properties. Further, the heat treatment time can be in the range of several seconds to several tens of hours, preferably several minutes to about 3 hours.

In the process of manufacturing a printed wiring board, as a method for heat-sealing the above-mentioned film and conductive foil without an interposition of an adhesive layer, a known method can be adopted as long as it can be heated and pressed. However, there is no particular limitation. For example, hot press method or hot laminating roll method,
Alternatively, a method in which these are combined can be suitably adopted. Also, as for the method of forming the conductive circuit on the conductive foil, any known method can be adopted,
There is no particular limitation. For example, known methods such as a subtractive method (etching), an additive method (plating), a die stamping method (die), and a conductor printing method (conductive paste) can be applied. Further, as a method of interlayer connection in the case of a multi-layer substrate, for example, a method of copper plating in a through hole or a method of filling a conductive paste or a solder ball into an inner via hole, containing fine conductive particles A method in which an anisotropic conductive material using an insulating layer is applied is exemplified.

Examples of the conductor foil used in the present invention include metal foils having a thickness of about 5 to 70 μm, such as copper, gold, silver, aluminum, nickel and tin. As the metal foil, a copper foil is usually used, and a foil whose surface has been subjected to a chemical conversion treatment such as a black oxidation treatment is preferably used. It is preferable to use a conductor foil whose contact surface (overlapping surface) with the film has been chemically or mechanically roughened in advance in order to enhance the adhesive effect. Specific examples of the conductor foil subjected to the surface roughening treatment include a roughened copper foil that has been electrochemically treated when producing an electrolytic copper foil.

[0029]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. In addition, various measured values and evaluations of the film displayed in this specification were performed as follows. Here, the direction of flow of the film from the extruder is referred to as the vertical direction, and the direction perpendicular thereto is referred to as the horizontal direction.

(1) Glass transition temperature (Tg), crystallization temperature (Tc), crystal melting peak temperature (Tm) Sample 1 was prepared using DSC-7 manufactured by Perkin Elmer Co., Ltd.
0 mg according to JIS K7121 at a heating rate of 10
It was determined from the thermogram when the temperature was raised at ° C / min. In addition,
The crystallization temperature of the resin composition in Table 1 was measured using a quenched film sample.

(2) (ΔHm−ΔHc) / ΔHm Sample 1 was obtained using DSC-7 manufactured by PerkinElmer Co., Ltd.
0 mg according to JIS K7122, heating rate is 10
The heat of crystal fusion ΔHm (J / g) and the heat of crystallization ΔHc (J / g) were calculated from the thermogram when the temperature was raised at a rate of ° C./min.

(3) Adhesive strength Measured in accordance with the normal peel strength of JIS C6481.

(4) Solder heat resistance According to the normal solder heat resistance of JIS C6481, 2
The test piece was floated in a solder bath at 60 ° C. for 10 seconds so that the copper foil side and the solder bath were in contact with each other, cooled to room temperature, and visually inspected for swelling or peeling to determine the quality.

(5) Edge crack strength A thickness of 7 mm was determined in accordance with the edge crack resistance test of JIS C2151.
A test piece having a width of 15 mm and a length of 300 mm was cut out from a 5 μm film, and a tensile rate of 500 mm
The vertical and horizontal directions were measured under the condition of mm / min.

(Example 1) As shown in Table 1, polyether ether ketone resin [PEEK, manufactured by Victrex Corporation]
381G, Tg: 143 ° C, Tm: 334 ° C] (hereinafter, referred to as
50 parts by weight of a polyetherimide resin [manufactured by General Electric Co., Ltd .;
Ultem-CRS5001, Tg: 226 ° C.] (hereinafter sometimes abbreviated as PEI-1) 50 parts by weight and 20 parts by weight of commercially available mica (average particle diameter: 10 μm, aspect ratio: 30) The product was prepared using an extruder equipped with a T-die at a set temperature of 380 ° C and a thickness of 75 ° C.
extruded into a film of thickness of 1 μm and simultaneously with copper foil (thickness: 18μ
m, surface roughening) to obtain a copper foil laminate. Furthermore, a roll of the obtained copper foil laminate (100 m
The wrapping was subjected to a crystallization treatment in a constant temperature bath at 220 ° C. for 180 minutes to obtain a desired crystallization-treated copper foil laminate.
Using the obtained crystallized copper foil laminate, evaluation results such as thermal properties and mechanical strength are shown in Table 1.

(Example 2) A target crystallized copper foil laminate was obtained in the same manner as in Example 1 except that the crystallization conditions were changed to 240 ° C for 120 minutes.
Using the obtained crystallized copper foil laminate, evaluation results such as thermal properties and mechanical strength are shown in Table 1.

(Example 3) P used in Example 1
EI-1 was converted to a polyetherimide resin [Ultem-1000, manufactured by General Electric Company, Tg: 216 ° C].
(Hereinafter, the target was simply abbreviated as PEI-2), and a target crystallized copper foil laminate was obtained in the same manner as in Example 1 except for changing to PEI-2. Using the obtained crystallized copper foil laminate, evaluation results such as thermal properties and mechanical strength are shown in Table 1.

(Comparative Example 1) A target crystallized copper foil laminate was obtained in the same manner as in Example 1 except that the crystallization conditions were changed to 260 ° C for 120 minutes.
Using the obtained crystallized copper foil laminate, evaluation results such as thermal properties and mechanical strength are shown in Table 1.

(Comparative Example 2) A target crystallized copper foil laminate was obtained in the same manner as in Example 1, except that the crystallization conditions were changed to 240 ° C for 120 minutes.
Using the obtained crystallized copper foil laminate, evaluation results such as thermal properties and mechanical strength are shown in Table 1.

[0040]

[Table 1]

From Table 1, it can be seen that the composition has the components specified in the present invention,
And an endothermic peak temperature appearing on a lower temperature side than an endothermic peak derived from crystal melting of the polyarylketone resin is 260 ° C.
The crystallized copper foil laminates of Examples 1 to 3 which are less than each have excellent properties of both solder heat resistance and mechanical strength (the end crack strength of the film is 50 N or more in both longitudinal and transverse directions). You can see that there is. On the other hand, a substrate having an endothermic peak temperature of 260 ° C. or higher, which appears on the lower temperature side than the endothermic peak derived from the crystal melting of the polyarylketone resin, has good soldering heat resistance but poor lateral edge crack strength. I understand.

[0042]

According to the present invention, it is possible to provide a heat-resistant film which is particularly suitable as a member for electronics and the like, and in particular, has improved edge crack strength, a printed wiring board using the same as a base material, and a method for producing these.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram showing an endothermic peak derived from crystal melting of a polyarylketone resin and an endothermic peak appearing on a lower temperature side when the temperature is raised by differential scanning calorimetry.

[Explanation of symbols]

1 Endothermic peak derived from crystal melting of polyarylketone resin 2 Endothermic peak appearing at lower temperature side than endothermic peak derived from crystal melting of polyarylketone resin

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08K 3/00 C08K 3/00 C08L 73/00 C08L 73/00 79/08 79/08 Z H05K 1/03 610 H05K 1 / 03 610H 3/00 3/00 RF term (reference) 4F071 AA51 AA60 AA83 AA84 AB30 AE17 AF11 AF45 AG28 AH13 BA01 BB06 BC01 BC02 4F100 AA00A AA00H AB01B AB01C AB17 AB33B AB33C AK49A AK54A03A03 BA03 BA06 EJ42 GB43 JA04A JA11A JG01B JG01C JJ03 JJ03A JJ10A JK01 JK03A JK06 YY00A 4J002 CH09W CM04X DE146 DF016 DJ016 DJ036 DJ046 DJ056 DL006 FD016 GQ00

Claims (5)

[Claims] 1. A resin composition 100 comprising 70 to 30% by weight of a polyarylketone resin (A) having a crystal melting peak temperature of 260 ° C. or higher and 30 to 70% by weight of an amorphous polyetherimide resin (B). A crystallization-treated film obtained by mixing an inorganic filler in a range of 5 to 50 parts by weight with respect to parts by weight, and an endothermic peak when the film is heated at a heating rate of 10 ° C./min by differential scanning calorimetry. Wherein at least two endothermic peaks appear, and among these endothermic peaks, the endothermic peak temperature that appears on the lower temperature side than the endothermic peak derived from the crystal melting of the polyarylketone resin is less than 260 ° C. 2. A resin composition 100 comprising 70 to 30% by weight of a polyarylketone resin (A) having a crystal melting peak temperature of 260 ° C. or higher and 30 to 70% by weight of an amorphous polyetherimide resin (B). A conductive foil is heat-sealed and crystallized on at least one side of a film in which an inorganic filler is mixed in a range of 5 to 50 parts by weight with respect to parts by weight, without using an adhesive layer. In the printed wiring board thus formed, at least two endothermic peaks appear when the film is heated at a heating rate of 10 ° C./min by differential scanning calorimetry, and of these endothermic peaks, the crystal melting of the polyarylketone resin Wherein the endothermic peak temperature which appears on the lower temperature side than the endothermic peak derived from the above is less than 260 ° C. 3. An endothermic peak temperature appearing on a lower temperature side than an endothermic peak derived from crystal melting of the polyarylketone resin is in a range of 200 ° C. or more and less than 260 ° C., and a crack strength (crack resistance according to JIS C2151). 3. The heat-resistant film or the printed wiring board according to claim 1, wherein the thickness is 50 N or more in both the vertical and horizontal directions. 4. The method for producing a heat-resistant film or printed wiring board according to claim 1, wherein the crystallization treatment is performed in a temperature range satisfying the following relational expression. Tc (A + B) -20 ≦ Tx ≦ Tg (B) +20 where Tc (A + B) is a crystalline polyarylketone resin (A) and an amorphous polyetherimide resin (B)
Shows the crystallization temperature (° C.) that appears when the temperature of the resin composition is increased by differential scanning calorimetry.
(B) shows the glass transition temperature (° C.) of the amorphous polyetherimide resin (B) alone, and Tx shows the crystallization temperature (° C.). 5. The crystalline polyarylketone resin (A) is mainly composed of a polyetheretherketone resin having a repeating unit represented by the following structural formula (1), and the amorphous polyetherimide resin (B) has the following structure. 3. The heat-resistant film or printed wiring board according to claim 1, wherein a polyetherimide resin having a repeating unit represented by the formula (2) is a main component. (Equation 1) (Equation 2)