JP2006341596A - Heat resistant resin plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat resistant resin plate which is a resin plate having an excellent heat resistance and cutting processability, and at the same time, has a low water-absorbing property and a low expansibility, and which can be used preferably for devices and parts of electronic and electric equipments, and members for machinery and applicances, parts for automobiles, etc. <P>SOLUTION: The heat resistant resin plate comprises a melt lamination of at least two original fabric sheets (X) consisting of a resin composition of containing a polyaryl ketone resin (A) and a thermoplastic resin (B) where Tg is 180-350°C, at a mass ratio of (A)/(B)=95/5-5/95, the thickness being 0.5-15 mm. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a heat-resistant resin plate, and more particularly to a heat-resistant resin plate that is excellent in heat resistance and cutting workability, and also excellent in low water absorption and low expansion.

Heat-resistant resin plates made of polyetheretherketone (PEEK), polyamideimide (PAI), polyphenylene sulfide (PPS), polyetherimide (PEI), etc. have excellent heat resistance, flame resistance, chemical resistance and electrical properties. Since it is excellent, it is widely used as a material for various machine tool parts.
These machine tool parts are used, for example, in various production / processing line related parts, chemical plant related parts, liquid crystal manufacturing equipment parts, inspection equipment parts, precision machine parts, electronic parts, semiconductors, etc. Printed circuit board or circuit board that constitutes a test stand for a test device that performs continuity and function tests of objects to be measured such as IC chips, semiconductor packages, and printed circuit board units, as well as fixtures (fixtures) for test fixtures, etc. There is.

In a board or fixture constituting such a test stand, in order to accommodate and arrange an IC chip, a semiconductor package or a printed board, it is usually necessary to cut a resin plate having a thickness of about 5 mm as a base material. Don't be. Since this cutting process is performed by cutting, drilling, or counterboring the resin plate, the resin plate used as the base material is particularly required to have low water absorption, low expansion, and heat resistance.
When a resin plate made of PEEK is used as a substrate or fixture base material constituting these test stands, there is a problem that cutting waste remains due to inferior cutting workability. In addition, PAI resin plates have problems that the linear expansion coefficient is excessive, the dimensional stability is poor, and the water absorption is high. Furthermore, the PPS and PEI resin plates also have an excessive linear expansion coefficient, which impedes practical use.

By the way, in general, resin plates are manufactured by an extrusion molding method. This extrusion molding method includes a melt extrusion molding method in which a molten resin is extruded from a die, and a molten resin in a die, mainly at the tip of the die. There is a solidification extrusion molding method in which at least a surface layer is solidified and a resin is extruded while applying back pressure.
When the melt extrusion molding method is employed as a method for obtaining the resin plate having a thickness of about 5 mm, there is a problem that voids (nests) are easily formed inside the resin plate. Further, in the solidification extrusion molding method, since the back pressure becomes too high and the production is not stable, a thick resin plate having a thickness of about 10 mm is manufactured and cut into a thickness of about 5 mm. . Thus, there has been a problem that the cutting of the resin plate is complicated and the productivity is extremely poor.

  Moreover, the heat resistant composite film comprised from the PEEK layer and the PEI layer is proposed as a laminated body using the said resin (refer patent document 1). However, when this heat-resistant composite film is laminated to form a resin plate and used as a material for the above-mentioned various machine tool parts, problems may arise in the adhesion between layers and the dimensional accuracy after lamination. It was a serious problem.

JP-A-62-148260

  It is an object of the present invention to provide a heat-resistant resin plate that solves the above-described problems, is excellent in heat resistance and cutting workability, and has low water absorption and low expansion.

As a result of diligent investigation focusing on the raw sheet constituting the heat-resistant resin plate, the present inventor has obtained a raw sheet made of a resin composition containing a polyaryl ketone-based resin and a specific adhesive resin in a specific ratio. It was found that the above-mentioned problems can be solved by melt laminating and the present invention was completed.
That is, the present invention provides a polyaryl ketone resin (A) and a thermoplastic resin (B) having a glass transition temperature of 180 to 350 ° C., wherein (A) / (B) = 95/5 to 5/95. Provided is a heat-resistant resin plate characterized by melting and laminating at least two original fabric sheets (X) made of a resin composition containing at a mass ratio, and having a thickness of 0.5 to 15 mm. .

ADVANTAGE OF THE INVENTION According to this invention, while being excellent in heat resistance and cutting workability, the heat resistant resin board which is low water absorption and low expansibility is provided.
The heat-resistant resin plate of the present invention having such characteristics can be suitably used in a wide range of fields such as members for electric and electronic devices, members for devices and machines, and members for automobiles and aircraft devices.

  The heat-resistant resin plate of the present invention comprises a polyaryl ketone resin (A) and a thermoplastic resin (B) having a glass transition temperature of 180 to 350 ° C. (A) / (B) = 95 / 5-5 It is characterized in that it is obtained by melting and laminating at least two original fabric sheets (X) made of a resin composition containing at a mass ratio of / 95, and having a thickness of 0.5 to 15 mm.

The polyaryl ketone resin (A) used in the present invention is a thermoplastic resin containing an aromatic nucleus bond, an ether bond and a ketone bond in its structural unit.
Specific examples thereof include polyether ketone (glass transition temperature [hereinafter referred to as “Tg”]: 157 ° C., crystal melting peak temperature (hereinafter referred to as “Tm”]: 373 ° C.), polyether ether ketone (Tg: 143 C, Tm: 334 ° C.), polyether ether ketone ketone (Tg: 153 ° C., Tm: 370 ° C.), and the like. Among these, from the viewpoint of improving the heat resistance, it exhibits crystallinity and preferably has a Tm of 260 ° C. or higher, particularly 300 to 380 ° C.
Moreover, as long as the effect of this invention is not inhibited, you may contain a biphenyl structure, a sulfonyl group, etc., or another repeating unit.

  Among the polyaryl ketone resins (A), a polyaryl ketone resin (A) mainly composed of a polyether ether ketone having a repeating unit represented by the following structural formula (1) is particularly preferably used. Here, the main component means that the content exceeds 50% by mass.

The number average molecular weight (Mn) of the polyaryl ketone resin (A) is preferably 7,000 to 30,000, more preferably 10,000, from the viewpoint of mechanical strength and ease of melt kneading / molding. 20,000, more preferably 12,000-18,000.
Commercially available polyether ether ketones are trade names “PEEK151G” (Tg: 143 ° C., Tm: 334 ° C.), “PEEK381G” (Tg: 143 ° C., Tm: 334 ° C.), “PEEK450G” manufactured by VICTREX. (Tg: 143 ° C., Tm: 334 ° C.) and the like.
In addition, polyaryl ketone-type resin (A) can be used individually or in combination of 2 or more types.

The thermoplastic resin (B) used in the present invention is a resin that can impart adhesiveness in the composition with the polyaryl ketone-based resin (A), and has a glass transition temperature (Tg) of 180 to 350 ° C. It is a certain resin.
The Tg of the thermoplastic resin (B) is preferably 200 to 300 ° C, more preferably 220 to 270 ° C. This is because if Tg is 180 ° C. or higher, the heat resistance of the resulting heat-resistant resin plate will not be remarkably lowered, and if it is 350 ° C. or lower, molding will be relatively easy. Tg is measured by the method defined in JIS K7122-1987.
The number average molecular weight (Mn) of the thermoplastic resin (B) is preferably 4,000 to 40,000, more preferably 6,000 to 25, from the viewpoints of mechanical strength and ease of melt kneading / molding. 8,000, more preferably 8,000 to 20,000.

Specific examples of the thermoplastic resin (B) include thermoplastic polyimide resins, aromatic polyether sulfone resins, and aromatic polysulfone resins.
A thermoplastic polyimide resin is a thermoplastic resin having an aromatic nucleus bond and an imide bond in its structural unit, and is a resin having excellent heat resistance.
Aromatic polyethersulfone (PES) (Tg: 230 ° C) is a thermoplastic resin whose structural unit contains an aromatic nucleus bond, an ether bond and a sulfonyl bond, and is a polycondensation using dichlorodiphenylsulfone as the main raw material. It is a resin obtained by reaction and having excellent heat resistance.
Aromatic polysulfone (PSF) (Tg: 190 ° C.) is a thermoplastic resin containing an aromatic nucleus bond and a sulfonyl bond in its structural unit.
Among these resins, a thermoplastic polyimide resin is preferable from the viewpoint of adhesion between the raw fabric sheets.

  Examples of the thermoplastic polyimide resin include polyetherimide resin, but are not particularly limited thereto. Specific examples include amorphous polyetherimide resins having a repeating unit represented by the following structural formula (2) or (3).

The amorphous polyetherimide resin having a repeating unit represented by the structural formula (2) or (3) is composed of 4,4 ′-[isopropylidenebis (p-phenyleneoxy)] diphthalic dianhydride and p- As a polycondensate with phenylenediamine or m-phenylenediamine, it can be produced by a known method.
Commercially available products of these amorphous polyetherimide resins include “Ultem 1000” (Tg: 216 ° C.), “Ultem 1010” (Tg: 216 ° C.) or “Ultem CRS 5001” (Tg 226) manufactured by General Electric. ° C) and the like.

Further, the polyetherimide resin may contain other copolymerizable monomer units such as an amide group, an ester group, and a sulfonyl group as long as the effects of the present invention are not impaired. Specific examples thereof include a trade name “Ultem XH6050” (Tg: 247 ° C.) manufactured by General Electric, which is a polyetherimide sulfone copolymer.
These polyetherimide resins or copolymers with other monomer units can be used alone or in combination of two or more.
Of the above polyetherimide resins and copolymers with other monomer units, an amorphous resin is preferable, and an amorphous polyetherimide resin having a repeating unit represented by the structural formula (3). Is particularly preferred.

The raw fabric sheet (X) used in the present invention is composed of a polyaryl ketone resin (A) [hereinafter sometimes simply referred to as a resin (A)] and a thermoplastic resin (B) having a glass transition temperature of 180 to 350 ° C. [Hereinafter sometimes referred to simply as “resin (B)”] is formed from a resin composition containing a specific ratio.
The blending ratio of the resin (A) and the resin (B) needs to be a mass ratio of (A) / (B) = 95/5 to 5/95, preferably 60/40 to 20/80, more preferably Is 50 / 50-30 / 70.
When the mass ratio of the resin (A) is 95 or less, when the raw sheet is multi-layered with each other, it can be integrated while avoiding a significant decrease in heat-fusibility. This is because the effect of improving the heat resistance of the resin (A) is exhibited. Moreover, when the mass ratio of the resin (B) is 5 or more, the heat-fusibility between the raw sheets is improved, and when it is 95 or less, the heat resistance is good.

The raw fabric sheet (X) used in the present invention may be formed from a resin composition containing an inorganic filler, if necessary. By containing an inorganic filler, the linear expansion coefficient of the obtained heat resistant resin plate can be reduced, and the warp and deformation of the heat resistant resin plate can be suppressed. Further, for example, it is possible to improve the machinability such as reducing thread-like waste generated during drilling with a drill or reducing burrs at the end during cutting such as cutting with a lathe.
A well-known thing can be used as an inorganic filler. For example, powdered filler such as clay, glass, alumina, spherical alumina, silicon dioxide powder (silica, spherical silica, natural or synthetic quartz powder, etc.), aluminum nitride, silicon nitride, graphite, etc .; glass fiber, carbon fiber, etc. Fibrous filler: synthetic mica, natural mica (mascobite, phlogopite, sericite, suzolite, etc.), calcined natural or synthetic mica, boehmite, talc, illite, kaolinite, montmorillonite, vermiculite, smectite, plate-like alumina Inorganic scaly (plate-like) fillers such as In these, it is preferable that it is a plate-shaped filler from a viewpoint of making the linear expansion coefficient of the surface direction of the obtained heat resistant resin board small, and suppressing curvature and a deformation | transformation.

Although there is no restriction | limiting in the average particle diameter of an inorganic filler, Usually, 0.01-200 micrometers, Preferably it is 0.1-50 micrometers, More preferably, it is 1-20 micrometers. When the average particle size is 0.01 μm or more, the handling of the resin (A) and the resin (B) with mixing and melt-kneading is not so difficult. This is because the overall toughness of the steel is not impaired.
Moreover, although the linear expansion coefficient of a heat resistant resin board can be reduced, so that the aspect ratio (particle size / thickness) of an inorganic filler is high, the average aspect-ratio is 1-100 normally, Preferably it is 10-50. is there.

The inorganic filler is preferably surface-treated with a surface treatment agent. As the surface treatment agent, aminosilane, epoxy silane, vinyl silane, silane coupling agent such as silane compound having acryloxy group or methacryloxy group, and linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms in silicon atom. Examples include one or two bonded alkoxysilanes, titanate coupling agents, aluminate coupling agents, zirconate coupling agents, and the like. The amount of the surface treatment agent used is usually 0.1 to 8 parts by mass, preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the inorganic filler.
As the surface treatment method, a known method such as a wet method, a semi-wet method, an integral blend method or the like can be employed. Among these, the wet method and the semi-wet method are preferable from the viewpoint of efficiently attaching the surface treatment agent to the surface of the inorganic filler.
An inorganic filler can be used individually or in combination of 2 or more types.

The blending amount of the inorganic filler is preferably 15 to 80 parts by mass, more preferably 15 to 70 parts by mass with respect to 100 parts by mass of the resin composition containing the resin (A) and the resin (B). More preferably, it is 25-55 mass parts, Most preferably, it is 30-50 mass parts. This is because if the content is 15 parts by mass or more, the coefficient of linear expansion of the resulting heat-resistant resin plate can be reduced, and the shape stability is improved. Moreover, it can avoid that the obtained heat resistant resin board becomes weak by setting it as 80 mass parts or less.
In the resin composition containing the resin (A) and the resin (B), various additives such as a heat stabilizer, an ultraviolet absorber, a light stabilizer, a nucleating agent, a colorant, a lubricant, A flame retardant etc. can also be mix | blended suitably.

There is no restriction | limiting in particular as a preparation method of the said resin composition. For example, the following methods (1) to (5) can be employed. In these, the method (5) by a masterbatch is preferable from a viewpoint of dispersibility and workability | operativity.
(1) A method in which the resin (A), the resin (B), the inorganic filler used as desired, and various additives are separately supplied to a single or biaxial melt kneader and kneaded.
(2) A method of sequentially melting and kneading each component using a melt kneader having a plurality of supply parts such as side feeds.
(3) Each component is premixed in advance using a mixer such as a Henschel mixer (trade name), a super mixer, a ribbon blender, a tumbler mixer, etc., and then supplied to a melt kneader, for example, at 300 to 430 ° C. Melting and kneading method.
(4) A method of dispersing in an aqueous medium or an organic solvent and mixing by a wet method.
(5) A master batch in which inorganic fillers and various additives are mixed at a high concentration (5 to 60% by mass as a typical content) using the resin (A) and / or the resin (B) as a base resin. A method of preparing separately, adjusting the concentration of the resin in which it is used, mixing it, and mechanically blending it using a kneader or an extruder.

  There is no restriction | limiting in particular as a manufacturing method of original fabric sheet (X), A well-known shaping | molding method is applicable. For example, a melt extrusion method for extruding the molten resin composition from a die, a solid extrusion method for extruding the molten resin composition from a die having a temperature not higher than Tg or a crystallization start temperature, an injection molding method, inflation A molding method or the like can be employed. Among these, it is relatively easy to suppress variations in the thickness of the raw sheet (X), and a melt extrusion molding method that allows easy molding of various thicknesses is preferable. The temperature of melt extrusion is usually 340 to 410 ° C, preferably 370 to 395 ° C. The temperature of the die is usually 350 to 410 ° C, preferably 360 to 390 ° C.

In the manufacture of the raw sheet (X), in order to facilitate melt lamination, one side of the extruded sheet-like molten resin is brought into contact with the first cooling body, and at the same time or subsequently, the other side is second. It is preferable to quench by contacting with a cooling body.
After the original sheet (X) is extruded from the die tip of the extruder, the time until the two surfaces of the original sheet come into contact with the first and second cooling bodies (pre-cooling time) is better. Usually 0 to 10 seconds, preferably 0.05 to 5 seconds, more preferably 0.1 to 2 seconds. This is because, if the pre-cooling time is 0 to 10 seconds, the first and second cooling bodies can be contacted before solidification of the surface of the original sheet (X) becomes significant. The pre-cooling time can be obtained by dividing the distance until the original sheet (X) leaving the die contacts the first cooling body by the molding speed.

The surface temperature of the first and second cooling bodies is usually 30 to 175 ° C, preferably 70 to 165 ° C. If the surface temperature is 30 ° C. or higher, it is possible to avoid moisture in the air from adhering to the surface of the cooling body, and it is possible to suppress irregularities and undulations on the surface of the original fabric sheet (X). If it is below, melt lamination property will become favorable.
The contact time (cooling time) with the first or second cooling body is preferably long, but is appropriately set depending on the temperature and production efficiency of the cooling body, and is usually 0.1 to 50 seconds, preferably 1 to 10 seconds. It is. When the cooling time is 0.1 seconds or more, the heat-resistant adhesiveness is sufficient, and within 50 seconds, the production efficiency is high.
In order to promote the cooling of the original fabric sheet (X), after the original fabric sheet (X) contacts the first and second cooling bodies, the cooling time is 0.1 to 10 seconds, preferably 0.1 to 5 seconds. The surface temperature of the original fabric sheet (X) is usually cooled to 30 to 175 ° C, preferably 70 to 165 ° C.
The cooling time is a time during which the raw sheet (X) is kept in contact with at least one of the first or second cooling body or cooled by another cooling body. The obtained distance (cooling distance) can be obtained by dividing by the molding speed. Moreover, the surface temperature of a cooling body and original fabric sheet | seat (X) can be measured with a well-known contact-type or non-contact-type measuring method.
After the raw sheet (X) is in contact with the first and second cooling bodies, the other cooling body (cooling body or air of the same material as the first or second cooling body or air, nitrogen gas, water) It is also possible to cool with an equal liquid heat medium.

The first and second cooling bodies are preferably rolls because the structure of the cooling device is simple and easy to handle.
In addition, as the outer layer material of the first and second cooling bodies, aluminum, copper, titanium and alloys thereof, such as iron, stainless steel, chromium alloy stainless steel, chromium steel, chromium plated or hard chrome plated iron, stainless steel, ceramic A hard material such as a metal that has been sprayed or a soft material having a rubber layer provided on a metal layer can be used.
Here, specific examples of the material of the rubber layer include silicon rubber, fluororubber, specifically, perfluoroalkoxyalkane, perfluoroethylene propene copolymer, ethylene tetrafluoro copolymer, and the like. The hardness of the rubber layer is usually A25 to A90, preferably A40 to A90, as measured using a spring type A durometer as defined in JIS K6253-1997.

The first cooling body is preferably the above-mentioned hard material, more preferably stainless steel, chrome alloy stainless steel and those whose surfaces are chrome plated or hard chrome plated, and the second cooling body is the above soft material. A system material is preferred.
Examples of the temperature control method for the first and second cooling bodies include a known heat medium method, a heat medium circulation method, an electric resistance heat method, and a dielectric heating jacket roll method. Further, when the first or second cooling body is a rubber roll, the surface can be further cooled by bringing a metal roll, a metal belt or a rubber roll into contact with each other, and the cooling inside the roll and the cooling of the surface can be combined. preferable.

  When the second cooling body uses a soft material such as rubber on the metal layer, the third cooling body is connected to the second cooling body for the purpose of cooling the second cooling body or preventing deterioration due to heat. Can be used in contact with each other. The third cooling body is preferably a roll because the structure of the cooling device is simple and easy to handle. As the outer layer material of the third cooling body, the same material as the outer layer material of the first and second cooling bodies can be exemplified, but a hard material is preferable, and further, stainless steel, chromium alloy stainless steel, and the surface thereof. More preferable is chrome plating or hard chrome plating.

  When using a 3rd cooling body, it is preferable that the surface temperature is lower than the surface temperature of a 2nd cooling body, It is preferable that it is especially 5 degreeC or more low, Usually, 5-160 degreeC, Preferably it is 25-120 degreeC. . Although the cooling method and the refrigerant temperature of the third cooling body can be determined as appropriate, for example, when using a refrigerant such as water, steam, heat medium oil, cooling air, the temperature of the refrigerant is 5 to 120 ° C, Preferably it is 20-60 degreeC. If the temperature of the refrigerant is 5 ° C. or higher, problems of the apparatus due to freezing can be avoided, and if it is 120 ° C. or lower, the cooling efficiency by heat transfer from the second cooling body can be improved.

  The thickness of the raw sheet (X) thus obtained is usually 5 to 1000 μm, and is appropriately selected according to the thickness required for the heat resistant resin plate. From the viewpoint of ease of molding, 10 to 200 μm is preferable, and from the viewpoint of saving labor by reducing the number of layers, 50 to 200 μm is preferable. If the thickness is 5 μm or more, the sheet can be taken out, and if it is 1000 μm or less, a cooling trouble during molding and an internal void (nest) hardly occur.

The heat-resistant resin plate of the present invention is a heat-resistant resin plate characterized by being obtained by laminating and laminating at least two original fabric sheets (X) and having a thickness of 0.5 to 15 mm.
Specifically, the heat-resistant resin plate is formed by stacking 2 to 200, preferably 4 to 60, sheets of the original sheet (X), and has a thickness of 0.5 to 15 mm, preferably 1 by melt lamination. It can be set to ˜8 mm. In this case, the mass ratio of the resin (A) and the resin (B) in each laminated raw sheet (X) may be the same or different, and the thickness of each original sheet (X) is the same or different. It may be. These can be appropriately determined depending on the purpose and application of the heat-resistant resin plate of the present invention.
In addition, when stacking the raw sheets and melt-laminating them, if the forming directions of the stacked original sheets (hereinafter referred to as “MD”) are laminated together, the MD of the physical properties of the original sheets and the orthogonal direction (hereinafter referred to as “MD”). , "TD") can be reflected in the laminate of the present invention. On the other hand, when MD and TD are alternately stacked so as to be orthogonal to each other, the anisotropy of physical properties in the vertical and horizontal directions of the obtained laminate can be reduced. Further, it is effective to reduce the anisotropy by shifting the phases by 90 degrees in order. It is more effective for reducing the anisotropy to stack the original sheets as polygons or circles other than a rectangle one by one in order or at random phases.

The melt lamination method is not particularly limited, and a known hot press method (compression molding method) or a thermocompression bonding method sandwiched between a plurality of hot rolls, a seamless belt, or a hot plate can be employed. Among these, the hot press method is preferable.
The stacking temperature is appropriately selected depending on the number of stacked layers and the apparatus used for stacking, and is usually 200 to 400 ° C., preferably 230 to 330 ° C. The pressure is usually 0.5 to 100 MPa, preferably 2 to 20 MPa, and the time is usually 0.1 to 12000 seconds, preferably 5 to 8000 seconds.
When laminating by a hot press method, the temperature is usually 210 to 310 ° C, preferably 250 to 300 ° C, the pressure is usually 1 to 20 MPa, preferably 3 to 10 MPa, and the time is usually 300 to 8000. Second, preferably 600 to 3600 seconds. Further, when the temperature during lamination is in the range of room temperature to 170 ° C., the pressure in the above range is applied, the temperature is raised to a predetermined temperature as it is, the temperature and pressure are applied for the time in the above range, and then 100 ° C. It is preferable to cool to around room temperature.

  The heat resistant resin plate of the present invention preferably has a tensile elongation at break of usually 15% or less, preferably 0.1 to 10%, more preferably 1 to 8%. The tensile elongation at break is the elongation at break measured using a Type-VI test piece according to the method of ASTM D638-1996 and under a tensile speed of 50 mm / min. If the tensile elongation at break is 15% or less, the machinability is good, and lint-like shavings are less likely to be clogged into the hole when drilling, and burrs and the like are generated during cutting. It becomes a heat-resistant resin plate with little.

In the heat-resistant resin plate of the present invention, the relationship between the heat of crystal fusion (ΔHm) in differential scanning calorimetry and the amount of heat of crystallization (ΔHc) generated by crystallization during temperature elevation is expressed by the following formula (I). It is preferable to satisfy.
[(ΔHm−ΔHc) / ΔHm] ≧ 0.6 (I)
The values of ΔHm (J / g) and ΔHc (J / g) are measured values of two transition heats appearing in the DSC curve when the temperature is raised in differential scanning calorimetry according to JIS K7121 and JIS K7122.
In formula (I), the value of [(ΔHm−ΔHc) / ΔHm] is more preferably 0.8 to 1, and still more preferably 0.9 to 1. If this value is 0.6 or more, even if the tool blade becomes hot due to frictional heat at the time of cutting, the generation of lint-like shavings and its clogging are less likely to occur when drilling. Occasionally, burrs and the like are less generated.

The value of the formula (I) depends on the type of the polyaryl ketone-based resin (A) and the thermoplastic resin (B), the molecular weight, and the blending ratio of the resin composition. It is greatly affected and can be controlled by adjusting the thermal history applied in each process. Here, the heat history refers to the temperature of the heat-resistant resin plate and the time during which the heat-resistant resin plate is maintained, and this value tends to increase as the temperature increases.
Furthermore, if necessary, heat treatment is performed in the vicinity of Tg after molding, whereby the above value can be increased and residual strain can be reduced. The heat treatment temperature is usually 160 to 200 ° C., preferably 170 to 190 ° C., and the time is usually 1 to 15000 minutes, preferably 30 to 3000 minutes.

As one embodiment of the heat-resistant resin plate of the present invention, in the heat-resistant resin plate obtained by melting and laminating at least two original fabric sheets (X), the outermost layer is a raw material made of a polyaryl ketone-based resin (A). The heat resistant resin board currently formed with the anti-sheet (Y) can be mentioned.
The heat-resistant resin plate of this embodiment is obtained by, for example, melting and laminating 2 to 200, preferably 4 to 60, raw sheet sheets (X) made of a resin composition containing the resin (A) and the resin (B). A raw sheet (Y) made of a polyaryl ketone-based resin (A) is laminated on one or both surfaces of the outermost layer of the sheet, and the thickness is 0.5 to 15 mm by the hot pressing method or the thermocompression bonding method. , Preferably 1 to 8 mm.
When the raw sheet (Y) is laminated on both surfaces of the outermost layer, the polyaryl ketone-based resin (A) of the original sheet (Y) may be the same or different, and the thickness is the same or different. It may be. These can be appropriately determined depending on the purpose and application of the heat-resistant resin plate of the present invention.
This heat-resistant resin plate has an advantage that the surface thereof is excellent in heat resistance, chemical resistance, wear resistance, etc., and becomes a resin plate having appropriate rigidity.
The outermost layer of the heat-resistant resin plate is not limited to the polyaryl ketone-based resin (A), but may be 50% by mass or less, preferably 15 to 40% by mass of the inorganic filler or solid lubricant as long as the properties are not impaired. Etc. may be included.

  The heat-resistant resin plate of the present invention is excellent in heat resistance and cutting workability, and is excellent in low water absorption and low expansibility. Therefore, it has convenience as a material for cutting work, parts for electronic and electrical equipment, It can be suitably used for apparatus / machine tool members, automotive parts and the like.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited at all by these Examples.

The evaluation method in this example is as follows.
[Evaluation method]
1. Specific gravity Measured by an underwater substitution method according to the method defined in JIS K7112: 1999.
2. Tensile test Tensile breaking strength and tensile elongation at break were measured at a tensile speed of 50 mm / min according to the method defined in ASTM D638-1980.
3. Water absorption rate The water absorption rate was measured under the conditions of 23 ° C., 50% relative humidity and 24 hours in accordance with the method defined in JIS K7209: 2000.
4). Linear expansion coefficient Using a thermal stress strain measuring device TMA / SS6100 manufactured by Seiko Instruments Inc., a strip-shaped test piece (length 10 mm, cross-sectional area 1 mm ² ) cut out from a heat-resistant resin plate was used for a tensile load of 9.807 × 10 ^−4. The sample was fixed with N, heated at a rate of 20 ° C. to 5 ° C./min, and the temperature dependence of the thermal expansion amount was determined in the range of 20 ° C. to 50 ° C.
5. Tm, Tg, [(ΔHm−ΔHc) / ΔHm]
Differential scanning calorimetry is performed according to JIS K 7121 and JIS K 7122, and Tg and two measured values of transition heat appearing in the DSC curve when the temperature is raised, values of ΔHm (J / g) and ΔHc (J / g) [(ΔHm−ΔHc) / ΔHm] was calculated.

6). Flame retardancy Measured according to the method specified in UL94.
7). Drilling workability Resin plates of each example and comparative example were cut into 240 mm length and 190 mm width, set in a drill drill for printed circuit boards, and a drill with a diameter of 0.2 mm (trade name, manufactured by Union Tool Co., Ltd.) MV-E720) was used, and a total of 2500 holes were formed in the center at 50 rpm at 2.5 mm intervals in the center at a rotational speed of 120,000 rpm and a feed rate of 1524 mm / min. When set in a drilling machine, a 1 mm thick paper-phenolic resin plate was laid under the resin plate, and an aluminum plate of 1 mm thickness was placed on the resin plate.
After the drilling operation, compressed air was blown onto the front and back of the resin plate to scrape off scraps. The state in which lint-like chips remained in the hole and in the vicinity of the entrance / exit was visually confirmed and divided into the following four ranks for evaluation.
Rank 1: No lint-like shavings (very good).
Rank 2: Lint-like shavings are generated and the holes are at least partially blocked, and the number of holes at least partially blocked is 10% or less (good).
Rank 3: A lint-like shaving residue is generated to at least partially block the hole, and the number of holes at least partially blocked is more than 10% and not more than 20% (defect).
Rank 4: Lint-like shavings are generated and the holes are at least partially blocked, and the number of holes at least partially blocked is more than 20% of the whole (bad)

8). Hygroscopic dimensional stability Using the resin plate evaluated in 7 above, for each side, a perpendicular line is drawn from a position 3 cm from the four corners, and a through-hole having a diameter of 1.05 mm is formed around the intersection (4 locations) of the perpendicular line. I opened it.
This resin plate was conditioned for 2 days in an environment of a temperature of 23 ° C. and a relative humidity of 50%, and then a 1.0 mm mm hole and a 1 mm diameter pin were inserted into each of the four locations, and a 2 mm thick aluminum plate. It was placed on top, a mark was attached to the position of the pin, a hole was made in the mark portion, and the pin with a diameter of 1 mm was placed upright. Next, the resin plate was conditioned for 2 days in an environment of a temperature of 40 ° C. and a relative humidity of 80%, and then allowed to cool for 30 minutes in an environment of a temperature of 23 ° C. and a relative humidity of 50%. Under the same environment, this resin plate is placed on the four pins provided on the aluminum plate and slowly pushed from above with the fingertips, and the pin pierces into the four holes and the finger feels as follows. The evaluation was divided into 4 ranks.
Rank 1: Sticks easily.
Rank 2: Although there is a sense of resistance, it is easily stabbed.
Rank 3: Great resistance, but barely sting.
Rank 4: Do not sting.

Example 1
Polyetheretherketone resin [manufactured by Victrex, PEEK450G, Tg: 143 ° C., Tm: 334 ° C., number average molecular weight of about 16800] (hereinafter referred to as “PEEK-1”) 3.5 kg (35 parts by mass), amorphous 6.5 kg (65 parts by mass) of a functional polyetherimide resin (manufactured by General Electric Co., Ltd., trade name: Ultem CRS 5001, Tg: 226 ° C., number average molecular weight of about 12000) (hereinafter referred to as “PEI-1”) 4.5 kg (45 parts by mass) of sericite (average particle size of about 10 μm, average aspect ratio of 30) is dried with hot air at 180 ° C. for 8 hours, and kneaded at a set temperature of 380 ° C. using a side-feed twin screw extruder, It was extruded into a strand shape and cut into pellets (P1).
The pellets were dried with hot air at 180 ° C. for 8 hours, and then extruded as a 100 μm-thick original sheet from a die (set temperature: 380 ° C.) connected to a single screw extruder having a diameter of 45 mmφ set at 380 ° C. The extruded raw sheet is taken up at a speed of 5 m / min, temperature-adjusted by circulating oil set at 152 ° C, and comes into contact with a 200 mm diameter metal cast roll whose surface is hard chrome plated. In this respect, the surface is pressed by a silicon rubber roll having a diameter of 80 mm from the opposite side of the metal cast roll and having a surface temperature of 100 ° C. Each of the three metal guide rolls was brought into contact with each other at a winding angle of 90 degrees, and then wound up by a take-up machine to produce an original sheet (X) (hereinafter referred to as “S1”).
The silicon rubber roll was cooled in contact with a hard chromium plated roll with a diameter of 80 mm cooled by water at 28 ° C. The distance from the die to the position where the extruded original sheet (X) contacts the metal cast roll was 40 mm, and the passage time of the original sheet (X) was calculated to be 0.48 seconds.
The extruded raw sheet (X) was cooled as it was in contact with the metal cast roll at a winding angle of 150 degrees, and the temperature was 152 ° C. at a position leaving the metal cast roll. The cooling time on the metal cast roll was calculated to be 3.1 seconds.
26 sheets of the original fabric sheet (S1) cut into a square with a side of 24 cm are stacked one by one so that MD and TD are alternately orthogonal to each other, and the following (1) to (7) The materials are stacked in order from the bottom and set in a high-performance high-temperature vacuum press molding machine (made by Kitagawa Seiki Co., Ltd., molding press, model: VH1-1747). , A maximum temperature holding time of 60 minutes, press molding at a set pressure of the press molding machine of 10.1 MPa (pressure of the bonded part is about 4.9 MPa), and a heat-resistant resin plate (G1) having a thickness of 2.5 mm is obtained. It was. The results of evaluating this heat-resistant resin plate by the above method are shown in Table 1.
(1) A cushion paper having a square of 30 cm on a side and a thickness of 1.6 mm.
(2) A stainless decorative plate having a square of 30 cm on a side and a thickness of 1.5 mm.
(3) A polyimide film having a length of 30 cm, a width of 25.5 cm, and a thickness of 50 μm (manufactured by Ube Industries, Ltd., trade name Upilex 50S).
(4) The above-mentioned original fabric sheet piled up.
(5) The same polyimide film as the above (3).
(6) A stainless steel decorative board similar to (2) above.
(7) Cushion paper similar to (1) above.

Example 2
PEEK-1 was 4.4 kg (44 parts by mass), PEI-1 was 5.1 kg (51 parts by mass), and an amorphous polyetherimide resin [manufactured by General Electric Co., Ltd., trade name: Ultem 1000, Tg: 216 ° C. , Number average molecular weight of about 12000] (hereinafter referred to as “PEI-2”) was added in an amount of 0.5 kg (5 parts by mass), and the calcined sericite was added to 5 kg of commercially available talc (average particle size: 5.1 μm) (PEEK-1). And PEI-1 and PEI-2 to 50 parts by mass with respect to the total mass of 100 parts by mass), and the rotational speed of the extruder is adjusted to a 120 μm-thick original sheet (X) (hereinafter “S2”) I got). Using this original fabric sheet (S2), the number of original fabrics used for the lamination was 13, and the maximum temperature at the time of press lamination was changed to 280 ° C. A 1.5 mm heat-resistant resin plate (G2) was obtained.
This heat-resistant resin plate was evaluated according to the method described above. The evaluation results are shown in Table 1.

Example 3
In press lamination, the same operation as in Example 1 was performed except that the number of the original fabric sheets (S1) was 63, and a heat-resistant resin plate (G3) having a thickness of 6 mm was obtained.
This heat-resistant resin plate was evaluated according to the method described above. The evaluation results are shown in Table 1.

Example 4
4 kg (40 parts by mass) of PEEK-1 was used, and an amorphous polyetherimide resin [manufactured by General Electric Co., Ltd., trade name: Ultem XH6050, Tg: 247 ° C.] instead of PEI-1 (hereinafter referred to as “PEI-3”) Except that the calcined sericite was changed to 4.3 kg (43 parts by mass with respect to 100 parts by mass of the total mass of PEEK-1 and PEI-3). The same operation as 1 was performed to obtain pellets (P4).
This pellet (P4) was used except that the set temperature of the extruder and the die was set to 390 ° C, the set temperature of the circulating oil for adjusting the temperature of the metal cast roll was set to 162 ° C, and the screw rotation speed of the extruder was adjusted. Perform the same operation as in Example 1. A 107 μm-thick original fabric sheet (X) (hereinafter referred to as “S4”) was obtained. Using this original fabric sheet (S4), the number of original fabrics used for lamination was set to 36, and the set maximum temperature during press lamination was changed to 310 ° C. A 3.6 mm heat-resistant resin plate (G4) was obtained.
This heat-resistant resin plate was evaluated according to the method described above. The evaluation results are shown in Table 1.

Example 5
PEEK-1 is 3.5 kg (35 parts by mass), PEI-3 is 6.5 kg (65 parts by mass), and baked sericite is 3.9 kg (total mass of PEEK-1 and PEI-3 is 100). Except having changed to 39 mass parts with respect to the mass part), operation similar to Example 1 was performed and the pellet (P5) was obtained.
This pellet (P5) was used except that the set temperature of the extruder and the die was set to 390 ° C, the set temperature of the circulating oil for adjusting the temperature of the metal cast roll was set to 162 ° C, and the screw rotation speed of the extruder was adjusted. Perform the same operation as in Example 1. An original sheet (X) having a thickness of 110 μm (hereinafter referred to as “S5”) was obtained. Using this original fabric sheet (S5), the number of original fabrics used for lamination was changed to 30 and the maximum temperature set during press lamination was changed to 310 ° C. A 3 mm heat-resistant resin plate (G5) was obtained.
This heat-resistant resin plate was evaluated according to the method described above. The evaluation results are shown in Table 1.

Comparative Example 1
A commercially available polyamideimide resin plate (manufactured by Nippon Polypenco, trade name: TORLON material TR-4203, thickness 2.5 mm, PAI) was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
Comparative Example 2
A commercially available polyetherimide resin plate (manufactured by Nippon Polypenco, Polypenco ULTEM UL-1000, thickness 2.5 mm, PEI) was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
Comparative Example 3
A commercially available polyether ether ketone resin plate (manufactured by Nippon Polypenco, polypenco PEEK PK-450, thickness 2.5 mm, PEEK) was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

  From the results shown in Table 1, the heat-resistant resin plate of the present invention has low elongation at break, water absorption, and linear expansion coefficient, and excellent dimensional stability, cutting workability during drilling, and moisture absorption dimensional stability. In addition, it can be seen that the heat resistance is good.

The heat-resistant resin plate of the present invention is excellent in cutting workability, hygroscopic dimensional stability and the like, and has excellent heat resistance. For this reason, various manufacturing / processing line related parts, chemical plant related parts, liquid crystal manufacturing equipment parts, inspection equipment parts, precision machine parts, electronic parts, printed circuit boards used in semiconductors, IC chips and semiconductors Fixtures (fixtures) for test fixtures, fixtures for test equipment that performs continuity and function tests of measured objects such as packages and printed circuit board units, IC chips in the electrical and electronic industries Socket for IC tester, IC chip alignment fixture used for IC chip tester, various machine parts, circuit boards for automobiles and aeronautical equipment, fuel cell parts, energy generating equipment parts, heat shield plates, various equipment It is suitable as a housing or the like.

Claims (9)

  Resin containing polyaryl ketone resin (A) and thermoplastic resin (B) having a glass transition temperature of 180 to 350 ° C. in a mass ratio of (A) / (B) = 95/5 to 5/95 A heat-resistant resin plate, which is obtained by melting and laminating at least two original fabric sheets (X) made of the composition and having a thickness of 0.5 to 15 mm.   The heat-resistant resin plate according to claim 1, wherein the thermoplastic resin (B) is at least one selected from a thermoplastic polyimide resin, a polyethersulfone resin, and a polysulfone resin.   The polyaryl ketone-based resin (A) is a resin having a crystalline polyether ether ketone resin as a main component, and the thermoplastic resin (B) is a resin having a polyether imide resin as a main component. 2. The heat resistant resin plate according to 2.   The heat-resistant resin board in any one of Claims 1-3 which contains 15-80 mass parts of inorganic fillers with respect to 100 mass parts of resin compositions.   The heat-resistant resin plate according to any one of claims 1 to 4, wherein the inorganic filler is at least one selected from talc, mica, clay, glass, silica, and alumina.   The heat-resistant resin plate according to any one of claims 1 to 5, which has an elongation at break of 15% or less. The heat-resistant resin plate according to any one of claims 1 to 6, wherein the heat of crystal fusion (ΔHm) and the heat of crystallization (ΔHc) in differential scanning calorimetry satisfy a relationship represented by the following formula (I): .
[(ΔHm−ΔHc) / ΔHm] ≧ 0.6 (I)   The heat-resistant resin plate according to any one of claims 1 to 7, wherein the heat-resistant resin plate (X) is obtained by alternately and alternately stacking the raw sheet (X).   The heat-resistant resin plate according to any one of claims 1 to 8, which is a material for machining.