JP2005220335A - Resin composition and molded product using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a resin composition which has little change in the outward appearance even when it is exposed to high temperatures for a long time, and besides, has good heat resistance and dimensional stability, and to provide a molded product obtained by using this resin composition. <P>SOLUTION: The resin composition comprises, on the basis of 100 pts.mass of the total amount of (A) a thermoplastic polyimide resin and (B) a polyarylketone resin, 5-50 pts.mass of (C) a filler which is surface-treated with an organic silicone compound expressed by the formula (1): R<SB>n</SB>SiX<SB>4-n</SB>(wherein, R is a 1-30C hydrocarbyl group which may contain an oxygen atom; X is one or more kinds of hydrolytic groups selected from a 1-6C alkoxy group, a halogen atom, acetoxy group and hydroxy group; and (n) is 1 or 2), having an absolute value of 10 or less in the yellowness difference according to JIS K 7105-1981 between before and after the treatment at 200°C for 350 hours, and the molded product is formed of this resin composition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention is a resin composition that has little hue change at high temperature, good heat resistance and dimensional stability, and can be suitably used as a member for electronics such as a printed wiring board, and a molded article such as a film obtained using the resin composition About.

Among thermoplastic resins, thermoplastic resins with high glass transition temperature and melting point represented by polyetherimide resin and polyaryl ketone resin are superior in heat resistance, flame retardancy, chemical resistance, etc. It is widely used mainly for parts and electrical / electronic parts. Among them, the polyaryl ketone resin is very expensive, and the glass transition temperature of the resin itself is relatively low at about 140 to 170 ° C., so various studies for improving heat resistance and the like have been made. . Among them, a blend with a polyetherimide resin has attracted attention as a system exhibiting good compatibility.
As such a blend, a mixed composition of a crystalline polyaryl ketone resin and an amorphous polyetherimide resin is disclosed (see, for example, Patent Documents 1 and 2). It is also disclosed that these compositions are useful for circuit board substrates (see, for example, Patent Document 3). Furthermore, the printed wiring board using the said mixed composition and its manufacturing method are disclosed (for example, refer patent document 4 and 5).

However, these resin mixed compositions alone have a larger coefficient of linear expansion than metals such as copper and aluminum, and when a molded body such as a film made of these compositions is bonded, warping occurs according to temperature changes. In order to improve dimensional stability, fillers are added. However, when the filler is added alone, the filler is poorly dispersed in the resin, which may cause problems in appearance and mechanical properties such as tensile elongation and impact strength. In order to solve this problem, the filler is subjected to a surface treatment and added to the resin. However, when a molded product obtained from a composition containing a surface-treated filler is exposed to a high temperature for a long time, the hue change may be noticeable depending on the surface treatment agent used.
When the molded body is used as an electronic circuit board, if the hue change, that is, the appearance change is significant, the user may be uneasy or the product value may be reduced even if the performance as an electronic circuit board is not substantially problematic. The problem may occur, and the improvement was necessary. In addition, when used in electronic circuit substrates, there are many opportunities to be exposed to high heat such as soldering and baking treatment, and appearance changes when exposed to high temperatures for a long time are regarded as problems related to performance changes. There was a concern, and an improvement to reduce the appearance change was awaited. The same applies to applications such as energy generators, automotive engine compartment parts, space, and aircraft. However, the above patent document has no technical disclosure or suggestion regarding the cause of the appearance change and the improvement method.

JP 59-187054 A JP-T 61-500023 Publication JP 59-115353 A JP 2000-38464 A JP 2002-144436 A

  The present invention has been made in view of the above circumstances, and has a resin composition suitable for an electronic member or the like, having little change in appearance, especially hue change, good heat resistance and dimensional stability even when exposed to high temperature for a long time. It aims at providing molded objects, such as a thing and a resin film obtained using this.

As a result of intensive studies, the present inventors can solve the above problem by combining a specific surface-treated filler with a resin mixture of a thermoplastic polyimide resin and a polyaryl ketone resin. The present inventors have found a resin composition and have completed the present invention.
That is, the present invention relates to (C) the following general formula (1) with respect to 100 parts by mass of the total amount of (A) thermoplastic polyimide resin and (B) polyarylketone resin.
R _n SiX _4-n (1)
(In the formula, R is a hydrocarbon group having 1 to 30 carbon atoms which may contain an oxygen atom, and X is selected from an alkoxy group having 1 to 6 carbon atoms, a halogen atom, an acetoxy group and a hydroxyl group. One or more hydrolyzable groups, n is 1 or 2)
The absolute value of the difference in yellowness as defined in JIS K 7105-1981 before and after treatment at 200 ° C. for 350 hours, including 5 to 50 parts by mass of a filler surface-treated with an organosilicon compound represented by The present invention provides a resin composition characterized by the above. Moreover, this invention provides the molded object formed by shape | molding this resin composition.

  According to the present invention, even when exposed to a high temperature for a long time, there are few appearance changes, particularly hue changes, heat resistance and dimensional stability are good, and a resin composition suitable as an electronic member and the like, and this resin composition A molded body such as a resin film using can be provided.

The resin composition of the present invention comprises (C) the following general formula (1) with respect to 100 parts by mass of the total amount of (A) thermoplastic polyimide resin and (B) polyarylketone resin.
R _n SiX _4-n (1)
(In the formula, R is a hydrocarbon group having 1 to 30 carbon atoms which may contain an oxygen atom, and X is selected from an alkoxy group having 1 to 6 carbon atoms, a halogen atom, an acetoxy group and a hydroxyl group. One or more hydrolyzable groups, n is 1 or 2)
The absolute value of the difference in yellowness as defined in JIS K 7105-1981 before and after treatment at 200 ° C. for 350 hours, including 5 to 50 parts by mass of a filler surface-treated with an organosilicon compound represented by It is the resin composition which is.

  The thermoplastic polyimide resin of component (A) in the resin composition of the present invention is a thermoplastic resin containing an aromatic nucleus bond, an ether bond and an imide bond in its structural unit, and is not particularly limited. Specifically, the following structural formula (2)

[Product name “Ultem1000” (glass transition temperature Tg: 216 ° C.) manufactured by General Electric Co., Ltd.] having the repeating unit represented by the following structural formula (3)

And a polyetherimide having a repeating unit represented by the formula [trade name “Ultem CRS 5001” (glass transition temperature Tg: 226 ° C.) manufactured by General Electric Co., Ltd.], and other specific examples are trade names of Mitsui Chemicals, Inc. “New Aurum” (glass transition temperature Tg: 258 ° C.) and the like. Of these, amorphous is preferable, and polyetherimide having a repeating unit represented by the structural formula (2) or (3) is more preferable.
The method for producing the polyetherimide resin is not particularly limited. Usually, the amorphous polyetherimide resin having the repeating unit represented by the structural formula (2) is 4,4 ′-[isopropylidene. As a polycondensate of bis (p-phenyleneoxy) diphthalic dianhydride and m-phenylenediamine, and an amorphous polyetherimide resin having a repeating unit represented by the structural formula (3), It is synthesized by a known method as a polycondensation product of 4 '-[isopropylidenebis (p-phenyleneoxy) diphthalic dianhydride and p-phenylenediamine.
Further, the polyetherimide resin used in the present invention may contain other copolymerizable monomer units such as an amide group, an ester group, and a sulfonyl group within the range not exceeding the gist of the present invention. In addition, polyetherimide resin can be used individually by 1 type or in combination of 2 or more types.

  The (A) component polyarylketone resin is a thermoplastic resin having an aromatic nucleus bond, an ether bond and a ketone bond in its structural unit, and representative examples thereof include polyetherketone, polyetheretherketone, polyetherketone. There may be a ketone or the like, and it may contain a biphenyl structure, a sulfonyl group or another copolymerizable monomer unit within the scope of the present invention. In the present invention, the following structural formula (4)

A polyether ether ketone having a repeating unit represented by the formula is preferably used. Polyether ether ketones having this repeating unit are commercially available as trade names “PEEK151G”, “PEEK381G”, “PEEK450G”, etc., manufactured by VICTREX. In addition, polyaryl ketone resin can be used individually by 1 type or in combination of 2 or more types. When the film using the resin composition of the present invention is applied as a base material for an electronic substrate such as a printed wiring board, the polyaryl ketone resin as the component (B) is preferably one having crystallinity, Those having a melting peak temperature of 260 ° C. or higher are preferred.

In the resin composition of the present invention, the mixing mass ratio of the thermoplastic polyimide resin (A) and the polyaryl ketone resin (B) (B) is usually (A) / (B) = 95 to 5/5. About 95. When the film using the resin composition of the present invention is applied as a substrate of an electronic substrate such as a printed wiring board, the mixing mass ratio of the component (A) to the component (B) is (A) / ( B) = 70-30 / 30-70 is preferred.
When the component (A) is 95 mass ratio or less and the component (B) is 5 mass ratio or more, the polyaryl ketone resin of the component (B) sufficiently exhibits the excellent heat resistance and low water absorption characteristics. be able to. Further, when the component (A) is 5 mass ratio or more and the component (B) is 95 mass ratio or less, in a molded article such as a film made of the resin composition of the present invention, Workability such as heat-sealing between films is good.
Further, when a crystalline polyaryl ketone resin is used as the component (B), when the component (A) is 95 mass ratios or less and the component (B) is 5 mass ratios or more, crystals as the entire resin composition It has high properties, high crystallization speed, and good solder heat resistance. In the same case, when the component (A) is 5 mass ratio or more and the component (B) is 95 mass ratio or less, volume shrinkage (dimensional change) accompanying crystallization of the crystalline polyaryl ketone resin is large. Therefore, reliability as a circuit board can be obtained. Therefore, when a resin composition containing a crystalline polyaryl ketone resin as the component (B) is used as the base material of the substrate for electronics, the mixing mass ratio of the component (A) and the component (B) Is preferably (A) / (B) = 65 to 35/35 to 65.

As the filler constituting the surface-treated filler (hereinafter abbreviated as filler (C)) of the component (C) in the resin composition of the present invention, known materials can be used, for example, Inorganic fillers such as clay, glass, alumina, silica, aluminum nitride, silicon nitride, fibers such as glass fibers, aramid fibers, carbon fibers, inorganic scale-like (plate-like) powders such as synthetic mica, natural mica, Examples include boehmite, talc, sericite, illite, kaolinite, montmorillonite, vermiculite, smectite, plate-like alumina, and flaky titanate (for example, flaky magnesium potassium titanate and flaky lithium potassium titanate). Among these, inorganic scale-like (plate-like) powders such as synthetic mica, natural mica, talc, sericite, illite, kaolinite, montmorillonite, vermiculite, and smectite are preferable, and synthetic mica and natural mica are more preferable. These fillers can be used alone or in combination of two or more.
The shape of the filler (C) is preferably a plate shape, and the average particle diameter is about 0.01 to 200 μm, preferably 0.1 to 20 μm, more preferably 1 to 10 μm, and the average aspect ratio (particle diameter / thickness). Is preferably about 20 to 30 or more, preferably 50 or more. Here, the shape of the filler before the surface treatment and the shape of the filler (C) after the treatment are treated as the same.

In the present invention, the surface treatment agent constituting the filler (C) is represented by the following general formula (1):
R _n SiX _4-n (1)
(In the formula, R is a hydrocarbon group having 1 to 30 carbon atoms which may contain an oxygen atom, and X is selected from an alkoxy group having 1 to 6 carbon atoms, a halogen atom, an acetoxy group and a hydroxyl group. One or more hydrolyzable groups, n is 1 or 2)
It is an organosilicon compound represented by In the general formula (1), when n is 2, two Rs may be the same or different from each other. A plurality of Xs may be the same as or different from each other.
As this organosilicon compound, those in which R is a linear or branched alkyl group having 1 to 20 carbon atoms and X is an alkoxy group and / or hydroxyl group having 1 to 6 carbon atoms are preferred, and more preferably, R Is a linear alkyl group having 3 to 10 carbon atoms, X is an alkoxy group having 1 to 3 carbon atoms, and n is 1.

  Specific examples of the organosilicon compound include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltri (2-propoxy) silane, methyltributoxysilane, methyltri (sec-butoxy) silane, methyltri (t-butoxy). ) Silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, butyltri (2-propoxy) silane, ethyltributoxysilane, ethyltri (sec-butoxy) silane, ethyltri (t-butoxy) silane, propyltrimethoxy Silane, propyltriethoxysilane, propyltripropoxysilane, propyltri (2-propoxy) silane, propyltributoxysilane, propyltri (sec-butoxy) silane, propyltri t-butoxy) silane, 2-propyltrimethoxysilane, 2-propyltriethoxysilane, 2-propyltripropoxysilane, 2-propyltri (2-propoxy) silane, 2-propyltributoxysilane, 2-propyltri ( sec-butoxy) silane, 2-propyltri (t-butoxy) silane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, butyltri (2-propoxy) silane, butyltributoxysilane, butyltri (sec-butoxy) ) Silane, butyltri (t-butoxy) silane, sec-butyltrimethoxysilane, sec-butyltriethoxysilane, sec-butyltripropoxysilane, sec-butyltri (2-propoxy) silane, sec-butyltributoxy Silane, sec-butyltri (t-butoxy) sisilane, pentyltrimethoxysilane, pentyltriethoxysilane, pentyltripropoxysilane, pentyltri (2-propoxy) silane, pentylriboxysilane, pentyltri (sec-butoxy) silane, pentyltri ( t-butoxy) silane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltripropoxysilane,

Hexyltri (2-propoxy) silane, hexyltributoxysilane, hexyltri (sec-butoxy) silane, hexyltri (t-butoxy) silane, heptyltrimethoxysilane, heptyltriethoxysilane, heptyltripropoxysilane, heptyltri (2-propoxy) Silane, heptyl riboxysilane, heptyltri (t-butoxy) silane, octyltrimethoxysilane, octyltriethoxysilane, octyltripropoxysilane, octyltri (2-propoxy) silane, octyltributoxysilane, octyltri (t-butoxy) silane 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, 2-ethylhexyltripropoxysilane, 2-ethylhexyltri (2-pro Xy) silane, 2-ethylhexyl tributoxysilane, 2-ethylhexyltri (t-butoxy) silane, nonyltrimethoxysilane, nonyltriethoxysilane, nonyltripropoxysilane, nonyltri (2-propoxy) silane, nonyltributoxysilane, Nonyltri (t-butoxy) silane, decyltrimethoxysilane, decyltriethoxysilane, decyltripropoxysilane, decyltri (2-propoxy) silane, decyltributoxysilane, decyltri (t-butoxy) silane, undecyltrimethoxysilane, Undecyltriethoxysilane,

Undecyltripropoxysilane, undecyltri (2-propoxy) silane, undecyltributoxysilane, undecyltri (t-butoxy) silane, dodecyltrimethoxysilane, dodecyltriethoxysilane, dodecyltripropoxysilane, dodecyltri (2-propoxy) silane , Dodecyltributoxysilane, dodecyltri (t-butoxy) silane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, hexadecyltripropoxysilane, hexadecyltri (2-propoxy) silane, hexadecyltributoxysilane, hexadecyl Tri (t-butoxy) silane, octadecyltrimethoxysilane, octadecyltriethoxysilane, octadecyltripropoxysilane, octadecyltri (2-propo Si) silane, octadecyltributoxysilane, octadecyltri (t-butoxy) silane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldi (2-propoxy) silane, dimethyldibutoxysilane, dimethyldi (t-butoxy) ) Silane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldi (2-propoxy) silane, diethyldibutoxysilane, diethyldi (t-butoxy) silane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyl Ethyldipropoxysilane, methylethyldi (2-propoxy) silane, methylethyldibutoxysilane, methylethyldi (t-butoxy) silane, dipropyldimethoxysilane, Propyl diethoxy silane, dibutyl dimethoxy silane, dibutyl silane, dipentyl dimethoxysilane,

Dipentyldiethoxysilane, methylhexyldimethoxysilane, methylhexyldiethoxysilane, butylhexyltrimethoxysilane, butylhexyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- Glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-methoxyethyltrimethoxysilane, 2-methoxyethyltriethoxysilane, 2-ethoxyethyltrimethoxysilane, 2-ethoxyethyltriethoxysilane 2-propoxyethyltrimethoxysilane, 2-propoxyethyltriethoxysilane, 2- (2-propoxy) ethyltrimethoxysilane, 2- (2-propoxy) ethyltriethoxysilane 2-butoxyethyltrimethoxysilane, 2-butoxyethyltriethoxysilane, 2-hexyloxyethyltrimethoxysilane, 2-hexyloxyethyltriethoxysilane, 2-octyloxyethyltrimethoxysilane, 2-octyloxyethyl Triethoxysilane, 2-methoxypropyltrimethoxysilane, 2-methoxypropyltriethoxysilane, 3-methoxypropyltrimethoxysilane, 3-methoxypropyltriethoxysilane, 2-ethoxypropyltrimethoxysilane, 2-ethoxypropyltriethoxy Silane, 3-ethoxypropyltrimethoxysilane, 3-ethoxypropyltriethoxysilane, 2-propoxypropyltrimethoxysilane, 2-propoxypropyltriethoxysilane, 3- Ropo trimethoxysilane, 3-propoxy-propyl triethoxysilane, 2-butoxy silane, 2-butoxy-propyl triethoxysilane, 3-butoxy propyl trimethoxy silane, 3-butoxy-propyl triethoxysilane,

2-hexyloxypropyltrimethoxysilane, 2-hexyloxypropyltriethoxysilane, 3-hexyloxypropyltrimethoxysilane, 3-hexyloxypropyltriethoxysilane, 2-methoxybutyltrimethoxysilane, 2-methoxybutyltriethoxysilane Silane, 4-methoxybutyltrimethoxysilane, 3-methoxybutyltriethoxysilane, 2-ethoxybutyltrimethoxysilane, 2-ethoxybutyltriethoxysilane, 3-ethoxybutyltrimethoxysilane, 4-ethoxybutyltriethoxysilane, 2-propoxybutyltrimethoxysilane, 2-propoxybutyltriethoxysilane, 4-propoxybutyltrimethoxysilane, 3-propoxybutyltriethoxysilane, 2-butoxybutyl Limethoxysilane, 2-butoxybutyltriethoxysilane, 3-butoxybutyltrimethoxysilane, 4-butoxybutyltriethoxysilane, 2-hexyloxybutyltrimethoxysilane, 2-hexyloxybutyltriethoxysilane, 3-hexyloxy Butyltrimethoxysilane, 3-hexyloxybutyltriethoxysilane, 4-hexyloxybutyltrimethoxysilane, 4-hexyloxybutyltriethoxysilane, 2-methoxyhexyltrimethoxysilane, 2-methoxyhexyltriethoxysilane, 6- Methoxyhexyltrimethoxysilane, 6-methoxyhexyltriethoxysilane, 2-ethoxyhexyltrimethoxysilane, 5-ethoxyhexyltriethoxysilane, 6-ethoxyhexyltrimeth Shishiran, 6-ethoxy-hexyl triethoxysilane, 2-propoxy-hexyl trimethoxy silane, 5-propoxy-hexyl triethoxysilane, 6-propoxy-hexyl trimethoxy silane, 6-propoxy-hexyl triethoxysilane, 2-butoxy-hexyl trimethoxy silane,

5-butoxyhexyltriethoxysilane, 6-butoxyhexyltrimethoxysilane, 6-butoxyhexyltriethoxysilane, 2-hexyloxyhexyltrimethoxysilane, 5-hexyloxyhexyltriethoxysilane, 6-hexyloxyhexyltrimethoxysilane 6-hexyloxyhexyltriethoxysilane, 2-methoxyoctyltrimethoxysilane, 7-methoxyoctyltriethoxysilane, 8-methoxyoctyltrimethoxysilane, 8-methoxyoctyltriethoxysilane, 2-ethoxyoctyltrimethoxysilane, 7-ethoxyoctyltriethoxysilane, 8-ethoxyoctyltrimethoxysilane, 8-ethoxyoctyltriethoxysilane, 2-propoxyoctyltrimethoxysilane, -Propoxyoctyltriethoxysilane, 8-propoxyoctyltrimethoxysilane, 8-propoxyoctyltriethoxysilane, 2-butoxyoctyltrimethoxysilane, 7-butoxyoctyltriethoxysilane, 8-butoxyoctyltrimethoxysilane, 8-butoxy Octyltriethoxysilane, 2-octyloxyoctyltrimethoxysilane, 7-octyloxyoctyltriethoxysilane, 8-octyloxyoctyltrimethoxysilane, 8-octyloxyoctyltriethoxysilane, methyl-2-methoxyethyldiethoxysilane Ethyl-3-methoxypropyldimethoxysilane, methyl-4-propoxybutyldimethoxysilane, methyl-6-ethoxyhexyltriethoxysilane and methyl-8 Such as butoxy octyl dimethoxy silane.
Among these, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane and Decyltriethoxysilane is preferred.

The reason why the affinity between the surface of the filler (C) and the thermoplastic resin (component (A) and component (B)) is improved when the surface treatment of the filler is performed with the organosilicon compound is as follows. The hydrolyzable group of the organosilicon compound generates a hydroxyl group by hydrolysis and causes a dehydration condensation reaction with the hydroxyl group on the surface of the filler by heating to bond the silyl group having an alkyl group to the surface of the filler. It is estimated to be.
The filler surface treatment agent (the organosilicon compound) used in the present invention does not need to act as a so-called “coupling agent” that reacts with and combines both the filler and the resin. Even if it adheres and reacts to increase the affinity of the surface state to the resin and is exposed to a heat treatment for a long time at a high temperature (for example, about 200 ° C.) as a resin composition or molded article The effect of not significantly changing the hue is high. In addition, so-called titanate coupling agents do not exhibit a sufficient effect on the combination of the thermoplastic resin and the filler according to the present invention by a long-time heat treatment at a high temperature.
The usage-amount of a surface treating agent is about 0.1-8 mass parts normally with respect to 100 mass parts of fillers, Preferably it is 0.5-5 mass parts, More preferably, it is the range of 1-3 mass parts. When the amount used is 0.1 parts by mass or more, a sufficient surface treatment effect can be obtained, so that the mechanical strength of the resin composition becomes sufficient. Moreover, even if the usage-amount of a surface treating agent exceeds 5 mass parts, since the effect of surface treatment is not improved, up to 5 mass parts is enough.

Various known methods can be applied as the surface treatment method. For example, in a solvent in which a surface treatment agent is dissolved, a wet method in which the solvent is removed after contacting the filler and the surface treatment agent, a solution in which the surface treatment agent is dissolved and the filler are sprayed, stirred, or the like. Integral blend that mixes and stirs the surface treatment agent dissolved in a semi-wet method, resin, filler and surface treatment agent, or a small amount of solvent after removing the solvent after contacting the surface treatment agent with the contact. Law. Of these surface treatment methods, the wet method and the semi-wet method are preferable from the viewpoint of efficiently attaching the surface treatment agent to the filler surface.
The density | concentration of the surface treating agent (the said organosilicon compound) in a solvent can be about 0.1-50 mass%. As the solvent, for example, isopropyl alcohol, ethanol, methanol, hexane and the like that are easy to remove are preferable. This solvent may contain a small amount of water or a small amount of an acid component that promotes hydrolysis.
After mixing the filler and the surface treatment agent diluted with the solvent by the above surface treatment method, leave it in the air for several hours to several days, bring it into contact with moisture in the air and cause hydrolysis. It is recommended to evaporate the solvent removed.
This evaporation removal treatment is performed under normal pressure or reduced pressure by hydrolyzing alkoxysilyl groups or by dehydrating condensation of generated hydroxylsilyl groups with hydroxyl groups on the surface of the filler, and removing generated alcohol and used solvents. The temperature is usually about 80 to 150 ° C., preferably 100 to 130 ° C. The treatment time is usually about 4 to 200 hours, preferably 24 to 100 hours.

  The amount of the filler (C) used in the resin composition of the present invention is 5 with respect to 100 parts by mass of the total amount of the thermoplastic polyimide resin as the component (A) and the polyaryl ketone resin as the component (B). It is the range of -50 mass parts. When the amount of the filler to be mixed is 50 parts by mass or less, the flexibility of the film and the end tear resistance value (according to the end tear resistance test of JIS C2151) are good. On the other hand, if it is 5 parts by mass or more, the effect of reducing the linear expansion coefficient is sufficient, and the effect of improving the dimensional stability is enhanced. Therefore, the preferred mixing amount of the filler is 10 to 40 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B), and further the dimensional stability and flexibility or end of the film. When importance is attached to the balance with the fissure resistance value, it is preferably controlled in the range of 20 to 35 parts by mass.

In the resin composition of the present invention, various additives other than the resin (A) and the component (B) and the filler (C), for example, a heat stabilizer, an ultraviolet absorber, etc. , Light stabilizers, nucleating agents, colorants, lubricants, flame retardants, and the like may be appropriately blended. Moreover, a well-known method can be used for the mixing method of various additives including a filler (C). As an example of a mixing combination,
(I) A method of mixing and dispersing the three components (A), (B) and (C) at the same time,
(II) A method in which the component (A) and the component (B) are mixed in advance, and the component (C) is mixed and dispersed in the mixture,
(III) The filler (C) component is mixed and dispersed in advance in the component (A) or the component (B), and the mixture of the component (A) and the component (C) or the mixture of the component (B) and the component (C). And then mixing the component (B) with the mixture of the components (A) and (C) or mixing the component (A) with the mixture of the components (B) and (C) (IV) A method in which (C) component is mixed and dispersed in each of (A) component and (B) component, and these mixtures are mixed [in this case, the ratio of (C) component to (A) component and (B The ratio of the component (C) to the component) may be the same or different. ],
(V) When using a plurality of types of (A) component and / or a plurality of types of (B) component, at least one of them is blended with a mixture in which component (C) is mixed and dispersed at a high concentration The other component (A) and / or the component (B) to be mixed are mixed, or the component (C) is mixed at a low concentration with the above mixture and the other component (A) and / or the component (B) to be blended. A method of mixing and dispersing the mixed and dispersed mixture;
Etc.

As a method of mixing / dispersing, for example, (A) component, (B) component, (C) component and various additives used as required are separately supplied to a uniaxial melt kneader or a biaxial melt kneader. Each component can be sequentially supplied to the melt-kneader using a melt-kneader having a plurality of supply units. In addition, using a mixer such as a Henschel mixer, a super mixer, a ribbon blender, or a tumbler in advance, after premixing them, the mixture is supplied to a melt kneader and the glass transition temperature of component (A) or component (B) or It can also be melt kneaded at a temperature of the melting point or higher, specifically at a temperature of 340 to 430 ° C. Further, depending on the purpose, it can be dispersed in an aqueous medium or an organic solvent and mixed by a wet method. Furthermore, a master batch in which filler (C) and various additives are mixed at a high concentration (typically about 10 to 60% by mass) with component (A) and / or component (B) as a base resin. May be prepared separately, the concentration of the resin used may be adjusted and mixed, and mechanically blended using a kneader or an extruder. Among the mixing methods, a method of preparing and mixing a master batch is preferable from the viewpoint of dispersibility and workability.
The mixed resin composition is extruded in the form of a strand or sheet and cut to obtain a form suitable for molding processing of pellets, granules, powders, and the like.

The resin composition of the present invention can be molded into a desired molded body by a molding method such as an injection molding method, an extrusion molding method, or a compression molding method. Especially, it is suitable for extruding into forms, such as a film and a sheet | seat. Further, a molding device of various forms such as an extrusion cast using a T die, a calender molding machine, a pipe or the like can be attached to the subsequent stage of the melt-kneading machine to directly form a molded body following the melt-kneading.
As a film forming method of the molded body, a known method, for example, an extrusion casting method using a T-die or a calendering method can be adopted, and the film forming property of the film is not particularly limited. From the standpoint of stability and productivity, an extrusion casting method 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, but is generally about the outflow start temperature, the glass transition temperature or the melting point or higher, specifically 430 ° C. or lower, Preferably it is 340 to 400 degreeC. The thickness of the film of the present invention is not particularly limited, but is usually about 10 to 800 μm.
The surface of the film of the present invention may be appropriately subjected to embossing, corona treatment or the like in order to improve handling properties. In addition, the metal laminate can be heat-fused by heating and pressurizing the metal body through an adhesive layer on at least one surface of the above-described film or without an adhesive layer, and further, an etching treatment, A circuit can be formed on the film surface by plating or the like, and further laminated.

When the molded product of the present invention is made of a resin composition containing a crystalline polyimide as the (A) component thermoplastic polyimide and / or the (B) component polyaryl ketone resin, the molded product is crystallized. By making it, heat resistance and dimensional stability can be improved. However, in a molding process involving normal melting and cooling processes, it may be difficult to crystallize sufficiently during the molding process, and the resin composition of the present invention is used for improving heat resistance and dimensional stability. Or it is necessary to crystallize a molded object at the temperature selected suitably in the range below glass transition temperature and below crystal melting temperature.
Here, the method and time of the crystallization treatment are not particularly limited. For example, the crystallization treatment may be performed by a heat treatment roll or a hot air oven in a film formation line (cast crystallization method) or a film forming line. Examples include a method for crystallization (in-line crystallization method) and a method for crystallization by a thermostatic bath, heat press, etc. (outline crystallization method) and the like outside the film production line. In the present invention, the outline crystallization method is preferably used from the viewpoint of production stability and uniformity of physical properties. Further, the heat treatment time is usually about 2 seconds to 100 hours, preferably about 5 minutes to 50 hours, although it depends on the heat treatment temperature.

When the resin composition of the present invention and a molded article using the resin composition are heat-treated in air at 200 ° C. for 350 hours, the difference in yellowness (abbreviated as YI) from that before the heat treatment is performed. The absolute value (abbreviated as ΔYI) is 10 or less. If ΔYI is 10 or less, the difference in appearance between the hue surface of the product in use and the product before use is reduced. From this viewpoint, ΔYI is preferably 6 or less.
The yellowness is measured using a commercially available apparatus according to the method shown in JIS K 7105-1981 “Testing methods for optical properties of plastics”. Examples of commercially available measuring instruments include a spectrocolorimeter manufactured by Suga Test Instruments Co., Ltd., model SC-T, and the like. From the measured tristimulus values X, Y, and Z, YI is calculated using the calculation formula [YI = 100 (1.28X−1.06Z) / Y] described in JIS K 7105-1981.
In addition, as described above, when the molded body is made of a resin composition containing a crystalline polyimide as the (A) component thermoplastic polyimide and / or the (B) component polyaryl ketone resin, In a molding process involving melting and cooling processes, it may be difficult to crystallize sufficiently during the molding process. When the resin composition or molded product of the present invention is heat-treated at 200 ° C., the influence of hue change due to crystallization is large at the initial stage of the treatment. The processing time is 350 hours from the start of the conversion process. That is, a difference between YI after 398 hours treatment and YI after 48 hours treatment (abbreviated as ΔYI−48) is obtained. However, for a sufficiently crystallized molded body, the state before the heat treatment at 200 ° C. is used as a starting point.

  Applications of molded articles such as the resin composition and film of the present invention include wiring boards, rigid flex boards, build-up multilayer boards, batch multilayer boards, substrates for electronics boards such as metal base boards, and protection of flexible printed boards. Examples include plates, heat shielding plates, trays formed by thermoforming and vacuum forming, housings for various electronic devices, automobile engine compartment components, and partition walls. In addition, copper, silver, gold, iron, zinc, aluminum, magnesium, nickel, etc., or alloys of these metals, such as foils, plates, wires, etc., or by etching or plating There is also an attached one.

  EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. In addition, various measurement and evaluation about the film displayed in this specification were performed as follows. Here, the flow direction from the extruder of the film is called the vertical direction, and the orthogonal direction is called the horizontal direction.

(1) Hue measurement Using a spectrocolorimeter manufactured by Suga Test Instruments Co., Ltd., model SC-T, tristimulus values (X, Y, Z) of the color of the film were measured according to JIS K 7105-1981. , YI was calculated.
(2) ΔYI
The film was heat treated at a temperature of 200 ° C. using an oven (model: HPS-212) manufactured by Tabai Espec. Up to 48 hours from the beginning, sandwiched between two 50 μm-thick polyimide films (trade name: Upilex 50S, manufactured by Ube Industries Co., Ltd.) to prevent undulation due to initial deformation of the film and fusion between the films. One set was made, and 5 sets were stacked horizontally and heat-treated. After 48 hours, it was hung in the oven without being sandwiched between the polyimide films.
It was taken out from the oven at the times shown in each table, and the hue was measured by the method shown in (1) above. After 48 hours, the difference between YI at each time and YI at 48 hours (ΔYI−48) was calculated. After each hour of hue measurement, the film sample was returned to the oven and subsequently heat treated. It should be noted that the time required for the operation after taking out the oven and measuring the hue and returning it to the oven was not included in the heat treatment time.
(3) Visual determination of appearance A part of the film heat treated at 200 ° C. for 48 hours was stored at room temperature, and used as a reference sample for visual determination. This was subsequently compared with a sample processed up to 398 hours, and a change in appearance was visually determined. As a criterion for appearance change, 1 is the one that does not feel the change of the color or is not so noticeable even if there is a change, 2 can clearly see the change of the color, 2 is not so severe, 3 is the change of the color is severe It was.

(Example 1)
(1) Production of surface-treated synthetic mica 2 kg of synthetic mica PDM-5B (average particle diameter 6 μm, aspect ratio 25) manufactured by Topy Industries, Ltd. was placed in a Henschel mixer. Further, 40 g (2 parts by mass with respect to 100 parts by mass of mica) of a surface treatment agent hexyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-3063, abbreviation S6 in Table 1) with a water content of about 5% by mass. 200 g of a 20% by mass solution obtained by dissolving in 160 g of isopropyl alcohol was sprinkled, and the top of the mixer was covered. While supplying nitrogen gas, the mixer was operated for 10 minutes to stir and mix.
This mixture was spread on a stainless steel vat and allowed to stand indoors for 4 days, then heat-treated in an oven at 120 ° C. for 48 hours, cooled to room temperature and surface-treated synthetic mica (abbreviated as F1). Obtained.

(2) Production of film Amorphous polyetherimide resin [manufactured by General Electric Co., Ltd., trade name: Ultem 1000, glass transition temperature Tg: 216 ° C.] (hereinafter sometimes simply referred to as PEI-1) 1.856 kg ( 29 parts by mass), amorphous polyetherimide resin [manufactured by General Electric Co., Ltd., trade name: Ultem-CRS5001, Tg: 226 ° C.] (hereinafter sometimes simply referred to as PEI-2) 1.856 kg (29 masses) Part), polyetheretherketone resin (manufactured by Victrex, PEEK450G, Tg: 143 ° C., melting point Tm: 334 ° C.) (hereinafter sometimes simply referred to as PEEK) 2.688 kg (42 parts by mass), and the above Filler (F1) 1.6 kg (resin component total 6.4 kg is 100 parts by mass, 25 quality Part) is melt-kneaded at a set temperature of 380 ° C. with a twin-screw kneader, extruded into a sheet form from a T die, and rapidly cooled with a cast roll at 155 ° C. to form a 100 μm thick amorphous state Film (hereinafter abbreviated as amorphous film). The hue of this amorphous film was measured.
In addition, this amorphous film is sandwiched between two 50 μm-thick polyimide films (trade name: Upilex 50S, manufactured by Ube Industries, Ltd.). A crystallized film was obtained by performing crystallization treatment at a temperature of 200 ° C. for 48 hours in a company oven (model: HPS-212). The hue of this crystallized film was measured.
The crystallized film was taken out from between the polyimide films and the hue was measured. Then, the crystallized film was hung in the oven and heat-treated at a temperature of 200 ° C.
The sample was taken out from the oven at the time shown in the Example Table, and the hue was measured by the method shown in (1) above.
After 48 hours, ΔYI-48 for each hour was calculated. After each hour of hue measurement, the film sample was returned to the oven and subsequently heat treated. The time required for the operation after taking out the oven and measuring the hue and returning it to the oven was not included in the heat treatment time.
Evaluation of YI of the obtained amorphous film or crystallized film, visual evaluation result of appearance of crystallized film, YI, ΔYI-48, ΔYI and color tristimulus values (X, Y, Z) at each processing time The results are shown in Tables 1-7.

(Example 2)
In Example 1, the amount of S6 used for the surface treatment of the filler is changed to 26 g (1.3 parts by mass with respect to 100 parts by mass of synthetic mica) and the amount of isopropyl alcohol containing about 5% by mass of water is changed to 104 g. The same operation as in Example 1 except that the amount of PEI-1, PEI-2, and PEEK mixed in 6.4 kg (100 parts by mass) of the resin component changed to 55 parts by mass, 0 parts by mass, and 45 parts by mass, respectively. To obtain an amorphous film. A crystallized film was obtained in the same manner as in Example 1. The results of the same evaluation as in Example 1 are shown in each table.

(Example 3)
In Example 1, 36 g of propyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd., reagent grade, abbreviation S3 in Table 1) was used instead of the surface treatment agent hexyltrimethoxysilane (S6) used for the surface treatment of the filler. An amorphous film was obtained in the same manner as in Example 1 except that the mass was changed to 1.8 parts by mass with respect to 100 parts by mass of synthetic mica. A crystallized film was obtained in the same manner as in Example 1. The results of the same evaluation as in Example 1 are shown in each table.

Example 4
In Example 1, S6 used for the surface treatment of the filler is hexyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-3103C, abbreviation S10 in Table 1), 36 g (1 for 100 parts by mass of synthetic mica). 8 parts by mass), the amount of isopropyl alcohol containing about 5% by mass of water is changed to 144 g, and PEI-1, PEI-2, and PEEK are mixed in 6.4 kg (100 parts by mass) of resin components to be used. An amorphous film was obtained in the same manner as in Example 1 except that the amounts were changed to 25 parts by mass, 35 parts by mass and 40 parts by mass, respectively. A crystallized film was obtained in the same manner as in Example 1. The results of the same evaluation as in Example 1 are shown in each table.

(Comparative Example 1)
In Example 1, isopropyltri (dodecylbenzenesulfonyl) titanate (manufactured by Ajinomoto Fine Techno Co., Ltd., trade name: Preneact 9SA, abbreviated as T1 in Table 1) was used instead of S6 as the surface treatment agent used for the surface treatment of the filler. The same operation as in Example 1 was carried out except that was used to obtain an amorphous film. A crystallized film was obtained in the same manner as in Example 1. The results of the same evaluation as in Example 1 are shown in each table.

(Comparative Example 2)
In Example 1, except that the surface treatment agent used for the surface treatment of the filler was changed to S6 and isopropyl tristearoyl titanate (Ajinomoto Fine Techno Co., Ltd., trade name: Preneact TTS, abbreviation T2 in Table 1) was used. The same operation as in Example 1 was performed to obtain an amorphous film. A crystallized film was obtained in the same manner as in Example 1. The results of the same evaluation as in Example 1 are shown in each table.

From Table 1, the crystallized films of Examples 1 to 4 formed using the resin composition of the present invention were subjected to heat treatment at 200 ° C. and 350 hours from the time of heat treatment at 200 ° C. for 48 hours (that is, a total of 398). ΔYI-48 (after time) is 4.7 to 4.9, which is 10 or less, and a change in appearance visually, that is, a change in color is clearly seen, but it is not a severe level. On the other hand, in the crystallized films of Comparative Example 1 and Comparative Example 2 in which ΔYI-48 exceeds 10, it is recognized that the change in appearance by visual observation is remarkable.
In addition, when the crystallized films of Examples 1 to 4 containing the filler surface-treated with the surface treating agent according to the present invention were heat-treated at 200 ° C., ΔYI in any treatment time after 24 hours. And the value of ΔYI-48 is lower than the values of the crystallized films of Comparative Examples 1 and 2 containing a filler surface-treated with a surface treatment agent other than the surface treatment agent according to the present invention. It is clear that the effect of reducing the hue change when the resin composition is heat-treated is obtained by the surface treatment agent.

  Since the resin composition and the molded body of the present invention have little hue change when exposed to high temperature for a long time and are excellent in heat resistance, dimensional stability, etc., their uses include printed wiring boards, rigid flex boards, Base materials for electronics boards such as build-up multilayer boards, batch multilayer boards, metal base boards, protective boards for flexible printed boards, heat shields, trays by thermoforming and vacuum forming, housings for various electronic devices, automobile engine rooms These include internal parts, bulkheads, protection plates for aerospace equipment, and energy generator parts exposed to high temperatures. Moreover, the use of an electromagnetic shielding plate or the like is also mentioned by laminating and bonding with a metal foil such as copper or aluminum.

Claims (10)

(C) with respect to 100 parts by mass of the total amount of the thermoplastic polyimide resin and (B) polyaryl ketone resin, (C) the following general formula (1)
R _n SiX _4-n (1)
(In the formula, R is a hydrocarbon group having 1 to 30 carbon atoms which may contain an oxygen atom, and X is selected from an alkoxy group having 1 to 6 carbon atoms, a halogen atom, an acetoxy group and a hydroxyl group. One or more hydrolyzable groups, n is 1 or 2)
The absolute value of the difference in yellowness as defined in JIS K 7105-1981 before and after treatment at 200 ° C. for 350 hours, including 5 to 50 parts by mass of a filler surface-treated with an organosilicon compound represented by A resin composition characterized by the above.   The resin composition according to claim 1, wherein the mixing mass ratio of the component (A) and the component (B) is (A) / (B) = 95-5 / 5-95. The thermoplastic polyimide resin of component (A) is mainly a polyetherimide resin having a repeating unit represented by the following structural formula (2) or a polyetherimide resin having a repeating unit represented by the following structural formula (3). The component (B), which is a polyaryl ketone resin as a component (B), is mainly composed of a crystalline polyether ether ketone resin having a repeating unit represented by the following structural formula (4). Or the resin composition of 2.

  The resin composition according to any one of claims 1 to 3, wherein in the surface-treated filler of component (C), the filler is inorganic.   The resin composition according to claim 4, wherein in the surface-treated filler of component (C), the filler is plate-shaped.   6. The resin composition according to claim 5, wherein in the surface-treated filler of component (C), the filler is mica.   The resin composition according to any one of claims 1 to 6, wherein the surface-treated filler of component (C) has an average particle size of 0.01 to 200 µm.   The surface-treated filler of component (C) is surface-treated with an organosilicon compound represented by the general formula (1) in an amount of 0.1 to 8 parts by mass with respect to 100 parts by mass of the filler. Item 8. The resin composition according to any one of Items 1 to 7.   The molded object formed by shape | molding the resin composition in any one of Claims 1-8.   The molded product according to claim 9, wherein the molded product is crystallized.