JP2010052366A - Resin laminate with reduced warp and process for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin laminate which exhibits excellently low moisture absorption and low linear expansion as well as superior heat resistance and cutting workability and is least prone to warp, and a process for producing the laminate. <P>SOLUTION: The producing of the resin laminate is carried out through: a melt lamination step to melt-laminate at lest two or more raw stock sheets (X) including (C) a resin composition containing (A) a polyarylketone-based resin and (B) a thermoplastic resin with a glass transition temperature of ≥180 and ≤350°C at a mass ratio of (A)/(B)=95/5-5/95; a holding step to hold the temperature of the melt-laminated raw stock (X) within the range of ≥Tg<SB>c</SB>being the transition temperature of the resin composition (C) and ≤Tg<SB>c</SB>+30°C for ≥10 minutes after the melt lamination step; and a cooling step to cool the melt-laminated raw stock (X) to 100°C or below after the holding step. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a resin laminate, and more particularly to a resin laminate having excellent heat resistance and cutting workability, low water absorption and low linear expansion, and small warpage, and a method for producing the same.

  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 bench, 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. . Therefore, the resin plate used as the substrate is required to have cutting workability, hole workability, and heat resistance against heat generated by the processing. Further, since positional accuracy is required even after processing, it is necessary to prevent expansion due to moisture absorption and expansion due to heat during use, and low water absorption and low expansion are required.

  However, for example, PEEK resin plates are inferior in machinability, PAI resin plates have high water absorption and inferior dimensional stability, and PPS and PEI resin plates also have excessive thermal expansion coefficients. There is a problem.

  Further, as a method of obtaining a resin plate of about 5 mm, there is a problem that voids (nests) are easily formed in the melt extrusion molding method, and in order to stably produce the solid extrusion molding method, a thickness of about 10 mm is required. There is a problem in that the productivity is extremely poor because it is necessary to manufacture the resin plate and cut it to a thickness of about 5 mm.

  In order to solve these problems, a method of manufacturing a heat-resistant resin plate by melting and laminating a raw sheet containing a polyaryl ketone-based resin and a thermoplastic resin having a glass transition temperature of 180 to 350 ° C. has been proposed (patent) Reference 1). According to this method, it is possible to produce a resin plate having a thickness as required by changing the number of raw sheets to be laminated, and by using a plate-like filler, cutting workability, low expansion property, and dimensional stability. A heat-resistant resin plate having low water absorption can be produced.

JP 2006-341596 A

  However, when a heat-resistant resin plate is produced by the method according to Patent Document 1, there is no particular problem if it is a 24 cm square resin plate described in Examples in Patent Document 1, When the resin plate has a large size such as a certain 50 cm square, there is a problem that warpage of the finished laminated plate becomes large due to the influence of internal strain at the time of the lamination press. In the case of mass production of resin laminates, it is common to use a multi-stage press machine, and since a plurality of heat-resistant resin plates are set and laminated between a set of hot plates, As the thickness of the plate increased, and as the number of sets increased, the temperature difference due to the difference in the distance from the hot plate increased, thereby increasing the internal strain and increasing the warpage.

  Further, Patent Document 1 discloses a heat treatment in the vicinity of Tg as a method for reducing the residual strain after molding. However, in the case of performing the heat treatment after molding, a time equivalent to that at the time of the first laminating press is disclosed. For this reason, there has been a problem in that productivity is significantly reduced.

  Then, this invention makes it a subject to provide the resin laminated board which is excellent in heat resistance and cutting workability, and is excellent also in low water absorption and low linear expansion property, and also with little curvature, and its manufacturing method.

  The present inventors can solve the above-mentioned problems by controlling the cooling temperature profile in a method for producing a resin laminate by melting and laminating an original sheet, and more specifically, melting an original sheet. When producing a resin laminate by laminating, in the cooling process, a cooling step of cooling to room temperature is performed after a holding step in which the resin composition is held for a certain period of time in a temperature range of the glass transition temperature Tg to Tg + 30 ° C. Therefore, when the length of one side of the resin laminate is L, and the maximum floating amount at the four corners when the resin laminate is placed on the surface plate (gap from the surface plate to the lower surface of the laminate) is warped D The present inventors have found that a resin laminate having a warpage rate D / L of 0.5% or less can be provided, and the present invention has been completed.

  That is, the first present invention comprises a polyaryl ketone resin (A) and a thermoplastic resin (B) having a glass transition temperature (Tg) of 180 ° C. or higher and 350 ° C. or lower, wherein (A) / (B) = The raw sheet (X) made of the resin composition (C) contained at a mass ratio of 95/5 to 5/95 is melt-laminated at least two sheets, and the thickness is 0.5 mm or more and 15 mm or less. When the length of one side of a resin laminate is L and the maximum floating amount at the four corners when the resin laminate is placed on a surface plate is D, the warping rate D / L is The said subject is solved by providing the resin laminated board which is 0.5% or less.

  In the first aspect of the present invention and the present invention described below, “the maximum floating amount of the four corners when the resin laminated plate is placed on the surface plate” means that the surface of the surface plate and the front or back surface of the resin laminated plate are in contact with each other. In addition, it is the largest of the sizes of the gaps between the surface plate and the resin laminated plate, which are generated when a resin laminated plate is installed on the surface plate and the four corners of the resin laminated plate are lifted by warping.

The resin laminate of the first aspect of the present invention, after the glass transition temperature of the resin composition (C) is Tg _C , at the time of melt lamination, is held at a temperature of Tg _C or more and Tg _C + 30 ° C. or less for 10 minutes or more, It is preferable to be obtained through a process of cooling to 100 ° C. or lower. By passing through such a process, it can be set as the resin laminated board which can reduce curvature.

  In the first aspect of the present invention, the thermoplastic resin (B) is preferably at least one selected from the group consisting of a thermoplastic polyimide resin, a polyethersulfone resin, and a polysulfone resin. By using such a thermoplastic resin (B), a resin laminate having excellent heat resistance, cutting workability, low expansion, dimensional stability, and low water absorption can be obtained.

  In the first aspect of the present invention, the polyaryl ketone-based resin (A) is a resin mainly composed of a crystalline polyether ether ketone resin, and the thermoplastic resin (B) is composed mainly of a polyether imide resin. It is preferable to be a resin. If the polyaryl ketone-based resin (A) and the thermoplastic resin (B) are limited to such materials, the heat resistance, cutting workability, low expansibility, dimensional stability, and low water absorption are excellent. It can be set as the resin laminated plate which can implement | achieve more suitably.

  In said 1st this invention, it is preferable to contain 15 to 80 mass parts inorganic filler with respect to 100 mass parts of resin compositions (C). By containing such an amount of the inorganic filler, the linear expansion coefficient of the resin laminate can be reduced, and deformation of the resin laminate can be suppressed.

  In the first aspect of the present invention, the inorganic filler is preferably at least one selected from the group consisting of talc, mica, clay, glass, silica, and alumina. By using such an inorganic filler, the linear expansion coefficient of the resin laminate can be reduced, deformation of the resin laminate can be suppressed, and a resin laminate excellent in economy can be obtained.

  It is preferable that the resin laminated board of said 1st this invention is a laminated board obtained by laminating | stacking so that original fabric sheet | seat (X) may mutually orthogonally cross. Here, “the raw sheets (X) are stacked so as to be alternately perpendicular” means, for example, that the sheet according to the first aspect of the present invention obtained by the melt extrusion molding method is directed in the melt extrusion direction. By superimposing sheets oriented in a direction perpendicular to the melt extrusion direction on the sheet, it means that the directions of the sheets are superimposed perpendicular to each other. By stacking in this way, it is possible to obtain a resin laminate superior in heat resistance, cutting workability, mechanical strength, low water absorption and low expansibility.

  In the first aspect of the present invention, a resin laminate can be suitably used as a material to be machined.

The second aspect of the present invention is a polyaryl ketone resin (A) and a thermoplastic resin (B) having a glass transition temperature of 180 ° C. or higher and 350 ° C. or lower. (A) / (B) = 95 / 5-5 A melt lamination step in which at least two original fabric sheets (X) comprising the resin composition (C) contained at a mass ratio of / 95 are melt-laminated, and a melt-laminated raw sheet after the melt lamination step (X) is held in a temperature range of Tg _{C to} Tg _C + 30 ° C. for 10 minutes or more, where the glass transition temperature of the resin composition (C) is Tg _C , and is melt-laminated after the holding step. The above-mentioned problem is solved by providing a method for producing a resin laminate having a cooling step of cooling the raw sheet (X) to 100 ° C. or less.

  In the second aspect of the present invention, the length of one side of the resin laminate is L, the maximum floating amount at the four corners when the resin laminate is placed on the surface plate is D, and the standard limit value of the warp rate is D / L. When ≦ 1%, the process capability index (Cpk) is preferably 1.3 or more. Here, the “process capability index (Cpk)” refers to an index for evaluating the ability to produce a product within a predetermined standard limit, and can be said to be the occurrence frequency of defective products in product production. In the present invention, when the standard deviation is σ, Cpk = (standard limit value of warpage rate−average value of warpage rate) / 3σ. When the standard limit value of warpage is set to the above value, if the process capability index is 1.3 or more, it can be a method for producing a resin laminate that is more productive than the conventional production method.

  In the second aspect of the present invention, when the length of one side of the laminate is L and the maximum floating amount of the four corners when the laminate is placed on the surface plate is D, the warp rate D / L is preferably 0.5% or less. When the warpage rate D / L is 0.5% or less, a preferable resin laminate with reduced warpage can be obtained.

  According to the first aspect of the present invention, there is provided a resin laminate having excellent heat resistance, cutting workability, mechanical strength, low water absorption and low expansibility, as well as small warpage and excellent workability. A resin laminated board having such characteristics is a substrate that constitutes a test stand of a test apparatus that performs continuity and function tests of an object to be measured such as an IC chip, a semiconductor package, and a printed circuit board unit, and also a fixture of a fixture apparatus for testing. It can use suitably as base materials, such as. Moreover, according to the manufacturing method of 2nd this invention, the resin laminated board of 1st this invention is suitably realizable.

  Hereinafter, embodiments of the resin laminate and the method for producing the resin laminate of the present invention will be described.

<Resin laminate>
The resin laminate according to the present invention comprises a polyaryl ketone resin (A) and a thermoplastic resin (B) having a glass transition temperature of 180 ° C. or higher and 350 ° C. or lower, wherein (A) / (B) = 95/5. A laminate having a thickness of 0.5 mm or more and 15 mm or less, which is obtained by melting and laminating at least two original fabric sheets (X) made of the resin composition (C) contained in a mass ratio of ˜5 / 95. When the length of one side of the laminated plate is L and the maximum floating amount at the four corners (gap from the surface plate to the lower surface of the laminated plate) is D when the laminated plate is placed on the surface plate, D / L is 0.5% or less.

  The warpage rate (D / L) of the resin laminate is required to be 0.5% or less, but is preferably 0.3% or less, and more preferably 0.25% or less.

(Polyaryl ketone resin (A))
The polyaryl ketone-based resin (A) used for the resin laminate according to the present invention is a thermoplastic resin that includes 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 heat resistance, it is preferable that it exhibits crystallinity and has a Tm of 260 ° C. or higher, particularly 300 ° C. or higher and 380 ° C. or lower. 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 or more and 30,000 or less, more preferably 10,000, from the viewpoint of mechanical strength and ease of melt kneading / molding. It is more than 20,000 and more preferably more than 12,000 and less than 18,000.

  Commercially available polyether ether ketones are trade names “PEEK151G” (Tg: 143 ° C., Tm: 334 ° C.) and “PEEK381G” (Tg: 143 ° C., Tm: 334 ° C.) manufactured by VICTREX. And “PEEK450G” (Tg: 143 ° C., Tm: 334 ° C.). In addition, polyaryl ketone-type resin (A) can be used individually or in combination of 2 or more types.

(Thermoplastic resin (B))
The thermoplastic resin (B) used in the resin laminate according to the present invention is a resin that can impart adhesiveness in a composition with the polyaryl ketone resin (A), and has a glass transition temperature (Tg). It is a resin that is 180 ° C. or higher and 350 ° C. or lower. The Tg of the thermoplastic resin (B) is preferably 200 ° C. or higher and 300 ° C. or lower, more preferably 205 ° C. or higher and 270 ° C. or lower. This is because if Tg is 180 ° C. or higher, the heat resistance of the resulting resin-metal laminate is not significantly lowered, and if it is 350 ° C. or lower, molding is relatively easy. Tg is measured by the method defined in JIS K7122-1987.

  Specific examples of the thermoplastic resin (B) include thermoplastic polyimide resins, aromatic polyethersulfone resins (PES), aromatic polysulfone resins (PSF), and the like. 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 those having a polyetherimide resin as a main component, but are not particularly limited thereto. Here, the main component means that the content exceeds 50% by mass. Specific examples include polyetherimide having a repeating unit represented by the following structural formula (2) or (3).

  The number average molecular weight (Mn) of the thermoplastic resin (B) is preferably 4,000 or more and 40,000 or less, more preferably 6,000 or more, from the viewpoint of mechanical strength and ease of melt kneading / molding. 25,000 or less, more preferably 8,000 or more and 20,000 or less. An amorphous polyetherimide resin having a repeating unit represented by the structural formula (2) or (3) includes 4,4′-isopropylidenebis (p-phenyleneoxy) diphthalic dianhydride and p-phenylenediamine. Or it can manufacture by a well-known method as a polycondensate with m-phenylenediamine.

  As commercial products of these resins, trade names “Ultem 1000” (Tg: 216 ° C.), “Ultem 1010” (Tg: 216 ° C.), “Ultem CRS 5001” (Tg 226 ° C.), etc. manufactured by SABIC are available. Can be mentioned.

  Other specific examples of the thermoplastic polyimide resin include a trade name “Ultem XH6050” (Tg: 247 ° C.) manufactured by SABIC, a trade name “Aurum PL500AM” (Tg: 258 ° C.) manufactured by Mitsui Chemicals, Inc. Etc.

  Among these, an amorphous resin is preferable, a polyetherimide resin having a repeating unit represented by the structural formula (2) or (3) is more preferable, and a repeating unit represented by the structural formula (3). Particularly preferred are polyetherimide resins having Moreover, the said polyetherimide resin may contain the other monomer units which can be copolymerized, such as an amide group, ester group, and a sulfonyl group, unless the effect of this invention is inhibited. These polyetherimide resins can be used alone or in combination of two or more.

(Resin composition (C))
The resin layer in the raw sheet (X) used in the present invention is composed of a polyarylketone resin (A) [hereinafter sometimes simply referred to as resin (A)] and a thermoplastic having a glass transition temperature of 180 to 350 ° C. It is formed from a resin composition (C) containing a resin (B) [hereinafter sometimes simply referred to as resin (B)] in a specific ratio.

The blending ratio of the resin (A) and the resin (B) contained in the resin composition (C) needs to be a mass ratio of (A) / (B) = 95/5 to 5/95, preferably It is 70 / 30-30 / 70, More preferably, it is 60 / 40-35 / 65. Further, the glass transition temperature Tg _C of the resin composition (C) containing the resin (A) and the resin (B) in the above ratio is usually 145 ° C. or higher and 253 ° C. or lower, preferably 165 ° C. or higher and 228 ° C. or lower. It is.

  When the mass ratio of the resin (A) is 95 or less, when the raw fabric sheet (X) is multilayered at 210 ° C. or more and 350 ° C. or less, they are integrated while avoiding a significant decrease in heat-fusability. be able to. On the other hand, when the mass ratio of the resin (A) is 5 or more, the effect of improving the heat resistance of the resin (A) can be achieved. Moreover, when the mass ratio of the resin (B) is 5 or more, a heat-bonding property between the original fabric sheets (X), or a resin laminate is produced from the original fabric sheet (X), for example. When the laminate is bonded to a metal foil to form a resin metal laminate, the heat-fusibility between the resin laminate and the metal layer is improved. On the other hand, if the mass ratio of the resin (B) is 95 or less, the heat resistance is good.

(Inorganic filler)
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 resin laminate can be reduced, and deformation of the resin laminate can be suppressed. Further, for example, it is possible to improve the machinability such as drilling with a drill, cutting with a lathe, and cutting.

  Known inorganic fillers can be used. 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 fillers: 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 Among these, a plate-like filler is preferable from the viewpoint of suppressing the deformation by reducing the linear expansion coefficient in the surface direction of the obtained resin laminate.

  Although there is no restriction | limiting in the average particle diameter of an inorganic filler, Usually, 0.01 micrometer or more and 200 micrometers or less, Preferably they are 0.1 micrometer or more and 50 micrometers or less, More preferably, they are 1 micrometer or more and 20 micrometers or less. When the average particle diameter is 0.01 μm or more, the handling of mixing (melting and kneading) of the resin (A) and the resin (B) is not so difficult. This is because there is little loss of the overall toughness. In the present specification, the “average particle diameter” means an average particle diameter measured by a laser diffraction / scattering method.

  Moreover, although the linear expansion coefficient of a resin layer can be reduced, so that the aspect ratio (particle size / thickness) of an inorganic filler is high, the average aspect ratio is 5-100 normally, Preferably it is 10-50. .

  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 inorganic filler. An inorganic filler can be used individually or in combination of 2 or more types.

(Other additives)
In the resin composition (C) 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, Lubricants, flame retardants, conductive fillers, and the like can be appropriately blended.

<Method for producing resin laminate>
(Preparation method of resin composition (C))
There is no restriction | limiting in particular as a preparation method of the said resin composition (C). 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 (for example, Mitsui Henschel mixer manufactured by Mitsui Mining Co., Ltd.), a super mixer, a ribbon blender, a tumbler mixer, etc., and then supplied to a melt kneader. For example, a method of melt kneading at 300 ° C. or higher and 430 ° C. or lower.
(4) A method of dispersing in an aqueous medium or an organic solvent and mixing by a wet method.
(5) Inorganic fillers and various additives were mixed at a high concentration (typically 3 mass% or more and 60 mass% or less) using the resin (A) and / or the resin (B) as a base resin. A method of preparing a master batch separately, adjusting the concentration of the master batch and mixing it, and mechanically blending it using a kneader or an extruder.

(Manufacturing method of raw fabric sheet (X) and resin laminate)
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 equal to or lower than Tg or a crystallization start temperature, an injection molding method, an inflation molding Laws can be adopted. 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 ° C. or higher and 410 ° C. or lower, preferably 360 ° C. or higher and 395 ° C. or lower. The temperature of the die is usually 350 ° C. or higher and 410 ° C. or lower, preferably 360 ° C. or higher and 390 ° C. or lower.

  There are no particular restrictions on the method of melting and laminating the original sheet (X) to form a resin laminate, and there is no particular limitation. A known hot press method (compression molding method) or thermocompression bonding between a plurality of hot rolls, seamless belts or hot plates. The law can be adopted. Of these, the hot press method is preferred in order to best exhibit the effects of the present invention. Furthermore, a hot press under a reduced pressure environment is preferable.

  At the same time, a resin metal laminate in which a metal foil is laminated on at least one side can be obtained. In addition, a raw material in which a metal foil such as a copper foil is laminated on a resin layer in advance is prepared, and a desired resin-metal laminate can be obtained by laminating in combination with a raw material having no other metal foil. it can.

  The laminating temperature is appropriately selected depending on the number of layers of the raw sheet (X) and the apparatus used for laminating, but is usually 190 ° C. or higher and 400 ° C. or lower, preferably 230 ° C. or higher and 330 ° C. or lower. The pressure is usually 0.5 MPa or more and 100 MPa or less, preferably 2 MPa or more and 20 MPa or less, and the time is usually 0.1 seconds or more and 12000 seconds or less, preferably 5 seconds or more and 8000 seconds or less.

When laminating by a hot press method, the temperature is usually 210 ° C. or higher and 310 ° C. or lower, preferably 240 ° C. or higher and 300 ° C. or lower, the pressure is usually 1 MPa or higher and 20 MPa or lower, preferably 3 MPa or higher and 10 MPa or lower, and time Is usually from 300 seconds to 8000 seconds, preferably from 600 seconds to 3600 seconds. Further, when the temperature at the time of lamination is in the range of room temperature to 170 ° C., the pressure in the above range is applied, the temperature is raised as it is to the predetermined temperature, the temperature and pressure are applied in the time in the above range, and then the cooling process starts. At this time, instead of cooling to the take-out temperature at once, the glass transition temperature Tg _{C to} Tg _C + 30 ° C. or less of the resin composition (C) constituting the raw sheet (X) is 5 to 10 ° C. per minute. cooled at a rate, the Tg _C above Tg C ₊ 30 ° C. or less in the range of 10 minutes or more, preferably holds less than 30 minutes 15 minutes, after being subjected to a holding step, 100 ° C. or less preferably cooled to about room temperature.

According to such a method passing through the holding step and the cooling step, the resin laminate can be manufactured while reducing the internal strain of the resin laminate, so that the internal strain of the resin laminate is released. There is no need. Therefore, compared with the case where it reheats and heat-processes after shaping | molding, productivity by the part which does not require the time of reheating is good. In the case of a crystalline resin such as the polyaryl ketone resin (A), crystallization proceeds even in the temperature range of Tg _{C to} Tg _C + 30 ° C. in the holding step, and the difference in the degree of crystallization progresses. It is also effective in suppressing distortion.

  The resin laminate according to the present invention is excellent in heat resistance and cutting workability, is excellent in low water absorption and low expansibility, and has low warpage, so that the workability during processing is good. It can be suitably used for parts for automobiles, parts for devices and machines, parts for automobiles, and the like.

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

Example 1
40 parts by mass of polyetheretherketone resin [PEEK450G manufactured by Victrex Co., Ltd.] (hereinafter referred to as “PEEK-1”), 40 parts by mass of polyetherimide resin [ULTEM UF5011S manufactured by Subic Co., Ltd.] (hereinafter referred to as “PEI-1”), commercially available 20 parts by mass of mica [average particle diameter: 10 μm, aspect ratio: 50] (hereinafter referred to as “mica-1”) was kneaded to produce pellets. The glass transition temperature of the resin composition containing PEEK-1 and PEI-1 in the above ratio was 185 ° C. Using this pellet, a raw sheet is manufactured by extrusion molding using the T-die method, and the raw sheet is cut into 540 mm □ and laminated so that the original sheets are alternately orthogonally crossed. Performance Using a high-temperature vacuum press molding machine (Kitakawa Seiki Co., Ltd.), press the material at a maximum pressure of 280 ° C, hold the maximum temperature for 30 minutes, and press the material at a pressure of 6 MPa. After being held, the laminate was cooled to room temperature to obtain a resin laminate having a thickness of 2 mm. At this time, a laminated raw material corresponding to three 2 mm plates was set in each stage of a five-stage high-performance high-temperature vacuum press molding machine. The results of evaluating the warpage of this laminated resin plate are shown in Example 1 of Table 1. In addition, the maximum floating amount in Example 1 of Table 1 represents an average value of 12 samples.

(Example 2)
A press original fabric is manufactured by the method described in Example 1, and the original fabric is cut into 540 mm □ and laminated so that the original fabrics are alternately perpendicular to each other. Kitagawa Seiki Co., Ltd.), press the material at a maximum pressure of 280 ° C, hold the maximum temperature for 30 minutes, press the material at a pressure of 6MPa, hold at the set temperature of 200 ° C for 20 minutes, and then cool to room temperature Thus, a 3.5 mm thick heat-resistant resin plate was obtained. At this time, a laminated raw material equivalent to two 3.5 mm plates was set in each stage of a five-stage high-performance high-temperature vacuum press molding machine. The results of evaluating the warpage of the laminated resin plate are shown in Example 2 of Table 1. In addition, the maximum floating amount in Example 2 in Table 1 represents an average value of 22 samples.

(Example 3)
A press original fabric is manufactured by the method described in Example 1, and the original fabric is cut into 540 mm □ and laminated so that the original fabrics are alternately perpendicular to each other. Kitagawa Seiki Co., Ltd.), press the material at a maximum pressure of 280 ° C, hold the maximum temperature for 30 minutes, press the material at a pressure of 6MPa, hold at the set temperature of 200 ° C for 20 minutes, and then cool to room temperature Thus, a heat-resistant resin plate having a thickness of 6 mm was obtained. At this time, a laminated raw material equivalent to two 6 mm plates was set in each stage of a five-stage high-performance high-temperature vacuum press molding machine. The results of evaluating the warpage of this laminated resin plate are shown in Example 3 of Table 1. In addition, the maximum floating amount in Example 3 in Table 1 represents an average value of six samples.

(Reference Example 1)
A press original fabric is manufactured by the method described in Example 1, and the original fabric is cut into 540 mm □ and laminated so that the original fabrics are alternately perpendicular to each other. Kitagawa Seiki Co., Ltd.), set the maximum temperature of 280 ° C, the maximum temperature holding time of 30 minutes, the material pressure is vacuum-pressed at a setting of 6 MPa, and then cooled to room temperature without being held in the intermediate temperature range in the cooling process Thus, a heat-resistant resin plate having a thickness of 2 mm was obtained. At this time, a laminated raw material corresponding to three 2 mm plates was set in each stage of a five-stage high-performance high-temperature vacuum press molding machine. The results of evaluating the warpage of the heat-resistant resin plate are shown in Reference Example 1 in Table 1. The maximum floating amount in Reference Example 1 in Table 1 represents an average value of 21 samples.

(Comparative Example 1)
A press original fabric is manufactured by the method described in Example 1, and the original fabric is cut into 540 mm □ and laminated so that the original fabrics are alternately perpendicular to each other. Kitagawa Seiki Co., Ltd.), set the maximum temperature of 280 ° C, the maximum temperature holding time of 30 minutes, the material pressure is vacuum-pressed at a setting of 6 MPa, and then cooled to room temperature without being held in the intermediate temperature range in the cooling process Thus, a heat-resistant resin plate having a thickness of 3.5 mm was obtained. At this time, a laminated raw material equivalent to two 3.5 mm plates was set in each stage of a five-stage high-performance high-temperature vacuum press molding machine. The results of evaluating the warpage of the heat-resistant resin plate are shown in Comparative Example 1 in Table 1. The maximum floating amount in Comparative Example 1 in Table 1 represents an average value of 24 samples.

(Comparative Example 2)
A press original fabric is manufactured by the method described in Example 1, and the original fabric is cut into 540 mm □ and laminated so that the original fabrics are alternately perpendicular to each other. Kitagawa Seiki Co., Ltd.), set the maximum temperature of 280 ° C, the maximum temperature holding time of 30 minutes, the material pressure is vacuum-pressed at a setting of 6 MPa, and then cooled to room temperature without being held in the intermediate temperature range in the cooling process Thus, a heat-resistant resin plate having a thickness of 6 mm was obtained. At this time, a laminated raw material equivalent to two 6 mm plates was set in each stage of a five-stage high-performance high-temperature vacuum press molding machine. The results of evaluating the warpage of the heat-resistant resin plate are shown in Comparative Example 2 in Table 1. In addition, the maximum floating amount in Comparative Example 2 in Table 1 represents an average value of four samples.

なお、最大浮き量Ｄは、積層板を定盤上においた場合の四隅の定盤から積層板下面までの隙間（高さ）を表し、反り率は最大浮き量Ｄと積層板１辺の長さＬとの比（Ｄ／Ｌ）を表し、Ｃｐｋは、反り規格限度値をＤ／Ｌ≦１％とした場合における工程能力指数を表す（ただし、Ｌは積層板の１辺の長さを表し、上記実施例、参考例、及び比較例においては５００ｍｍである。）。

The maximum floating amount D represents the gap (height) from the four corner surface plates to the lower surface of the laminated plate when the laminated plate is placed on the surface plate, and the warpage rate is the maximum floating amount D and the length of one side of the laminated plate. Represents the ratio (D / L) to the thickness L, and Cpk represents the process capability index when the warp standard limit value is D / L ≦ 1% (where L is the length of one side of the laminate) In the above Examples, Reference Examples, and Comparative Examples, it is 500 mm.)

  From Table 1, the warp is large in Reference Example 1, Comparative Example 1 and Comparative Example 2 which were held at the set maximum temperature and then cooled to room temperature without being held in an intermediate temperature range regardless of the thickness of the resin laminate. became. Further, since the variation is large, the process capability index Cpk is small, and it has been found that the probability of occurrence of a defect becomes very large when the warp standard value is D / L ≦ 1%. On the other hand, in Examples 1 to 3, in the cooling process, after holding at the set maximum temperature, and holding and manufacturing in the intermediate temperature range, the warp and the variation of the resin laminate were suppressed small. For this reason, the process capability index is also Cpk ≧ 1.5, and it has been found that the occurrence rate of defects can be suppressed to an extremely low level. From the above results, it was found that the resin laminate produced by the production method according to the present invention has a small warp and satisfies the process capability index.

  The heat resistant resin plate of the present invention is excellent in heat resistance, cutting workability, mechanical strength, low water absorption and low expansibility, and has low warpage and good workability. For this reason, various manufacturing and 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, etc., especially IC chips It is suitable for a substrate constituting a test stand of a test apparatus for conducting a continuity / function test of an object to be measured such as a semiconductor package or a printed circuit board unit, and a fixture of a test fixture apparatus.

  Although the present invention has been described with reference to the most practical and preferred embodiments at the present time, the invention is limited to the embodiments disclosed herein. However, the invention can be changed as appropriate without departing from the spirit or concept of the invention that can be read from the claims and the entire specification, and the resin laminate and the method of manufacturing the resin laminate with such a change are also disclosed in the present invention. Should be understood as being included in the scope.

Claims (11)

Contains a polyaryl ketone resin (A) and a thermoplastic resin (B) having a glass transition temperature of 180 ° C. or higher and 350 ° C. or lower in a mass ratio of (A) / (B) = 95/5 to 5/95. A resin laminated board having a thickness of 0.5 mm or more and 15 mm or less, wherein at least two sheets of the raw sheet (X) made of the resin composition (C) are melt laminated.
When the length of one side of the resin laminate is L and the maximum floating amount of the four corners when the resin laminate is placed on a surface plate is D, the warpage rate D / L is 0.5% or less. , Resin laminate. The glass transition temperature of the resin composition (C) is Tg _C , and is obtained through a step of cooling to 100 ° C. or lower after holding for 10 minutes or more at a temperature of Tg _C or higher and Tg _C + 30 ° C. or lower during the melt lamination. The resin laminate according to claim 1, wherein the resin laminate is obtained.   The resin laminate according to claim 1 or 2, wherein the thermoplastic resin (B) is at least one selected from the group consisting of 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. Item 4. The resin laminate according to any one of Items 1 to 3.   The resin laminated board in any one of Claims 1-4 which contains an inorganic filler 15 to 80 mass parts with respect to 100 mass parts of said resin compositions (C).   The resin laminate according to claim 5, wherein the inorganic filler is at least one selected from the group consisting of talc, mica, clay, glass, silica, and alumina.   The resin laminate according to any one of claims 1 to 6, wherein the resin sheet (X) is obtained by being alternately stacked so as to be orthogonal to each other.   The resin laminated board in any one of Claims 1-7 used as a material for to-be-cut processing. Contains a polyaryl ketone resin (A) and a thermoplastic resin (B) having a glass transition temperature of 180 ° C. or higher and 350 ° C. or lower in a mass ratio of (A) / (B) = 95/5 to 5/95. A melt lamination step of melt laminating at least two or more original fabric sheets (X) made of the resin composition (C)
After the molten laminating step, the raw sheet which has been melted laminated (X), the resin composition of the glass transition temperature of (C) as Tg _C, 10 minutes at Tg _C above _Tg C + 30 ° C. below the temperature range The above-described holding step, and after the holding step, the melt-laminated original sheet (X) is cooled to 100 ° C. or lower, a cooling step,
A method for producing a resin laminate, comprising:   When the length of one side of the resin laminate is L, the maximum floating height of the four corners when the resin laminate is placed on a surface plate is D, and the standard limit value of the warp rate is D / L ≦ 1% The method for producing a resin laminate according to claim 9, wherein the process capability index (Cpk) is 1.3 or more.   When the length of one side of the laminated plate is L and the maximum floating amount at the four corners when the laminated plate is placed on the surface plate is D, the warp rate D / L is 0.5. The manufacturing method of the resin laminated board of Claim 10 which is% or less.