TWI794550B - Production method of thermoplastic liquid crystal polymer structure - Google Patents

Abstract

Provided is a production method of a thermoplastic liquid crystal polymer structure. The production method is a method of producing a thermoplastic liquid crystal polymer structure in which a plurality of thermoplastic liquid crystal polymer substructures are integrated using autoclave, the method comprises: enveloping an overlaid stack comprising a plurality of thermoplastic liquid crystal polymer substructures with a bagging film and sealing the bagging film at the edge portion; evacuating inside of the bagging film, and elevating temperature to a first temperature that is a preparatory heating temperature; elevating temperature from the first temperature as the starting point to a second temperature that is a thermo-compression temperature while elevating internal pressure of autoclave to a predetermined pressure that 2.8 MPa or lower (gage pressure) so as to carry out thermo-compression bonding.

Description

Method for manufacturing thermoplastic liquid crystal polymer structure

The present invention relates to a method for producing a thermoplastic liquid crystal polymer structure, wherein the thermoplastic liquid crystal polymer structure system is made of a thermoplastic polymer capable of forming an optically anisotropic molten phase (hereinafter referred to as thermoplastic liquid crystal polymer) constitute.

Thermoplastic liquid crystal polymers with high strength, high modulus of elasticity, and heat resistance are attracting attention as parts used in the electrical and electronic fields, business equipment, and precision equipment fields.

For example, Patent Document 1 (Japanese Unexamined Patent Publication No. 2004-136671) has disclosed a multilayer structure comprising a first layer and a second layer, the first layer comprising a first LCP (liquid crystal polymer) dielectric material, and The aforementioned first layer and the aforementioned second layer are bonded in such a manner that the aforementioned first LCP dielectric material is directly bonded to the aforementioned second layer without using an extrinsic adhesive material for bonding the aforementioned first LCP dielectric material to the aforementioned second layer. 2 layers combined. This document has described that in an autoclave lamination press for lamination, a gas with a medium of high temperature and high pressure is supplied from a gas source to the chamber, and the lamination is carried out at a pressure of 1000psi (7MPa) to 3000psi (21MPa). thermocompression. [Prior Art Literature] [Patent Document]

Patent Document 1: Japanese Patent Laid-Open No. 2004-136671

However, in Patent Document 1, when manufacturing a multilayer structure, in an autoclave lamination press, heating and pressurizing gas may be supplied at one go from a gas source, so thermocompression bonding under high pressure may be required. Therefore, in the case of rapid heating, the outgassing of the generated volatile components becomes insufficient, and swelling occurs later when the thermoplastic liquid crystal polymer structure is processed. Also, when a circuit formed of a fine conductor pattern requires a clearance between circuits, the circuit is buried or moved due to the flow of the resin after rapid pressurization. Therefore, in Patent Document 1, although the overflow of the resin may be suppressed at the end portion, it cannot suppress the excessive flow of polymer molecules generated inside the structure.

Generally speaking, thermoplastic liquid crystal polymer molecules may be less entangled between the rigid rod-shaped molecules, so under high pressure thermocompression, the rod-shaped molecules slide and flow with each other, so if you want to improve the adhesion, it will lead to Excessive molecular flow, on the other hand, in order to suppress the excessive molecular flow, if the pressure is reduced, it will damage the predicament of adhesion.

Therefore, an object of the present invention is to provide a thermoplastic liquid crystal polymer structure having excellent adhesiveness while suppressing excessive molecular flow inside the structure.

Another object of the present invention is to provide a thermoplastic liquid crystal polymer structure, which generally has a thickness achieved by an injection molded product, and at the same time has an isotropy that cannot be obtained by an injection molded product.

Another object of the present invention is to provide a method for efficiently manufacturing such a thermoplastic liquid crystal polymer structure.

The inventors of the present invention, as a result of earnest research to achieve the above object, found that the thermoplastic liquid crystal polymer system extremely reduces the melt viscosity at an extremely low shear rate, so even if the autoclave lamination is carried out under sealing, if in order to improve Adhesive, when heating and pressurized gas is supplied from a gas source at one go, and thermocompression bonding is performed under high pressure, there may be no overflow of resin at the end, but the flow of molecules in the thermoplastic liquid crystal polymer becomes intense , especially the possibility that the flowing resin contaminates the breather used for exhausting becomes high.

Then, as a result of repeated studies, it was found that when a plurality of thermoplastic liquid crystal polymer substructures are integrated using an autoclave, (i) after degassing the inside of the packaging film (bagging film), the Temporarily raise the temperature in the autoclave to the preliminary heating temperature, (ii) from this state, through the packaging film, the pressure of the preliminary laminate in the sealed state is raised to the specified pressure, and at the same time, the temperature is raised by the heating gas in the autoclave To the thermocompression bonding temperature, the thermocompression bonding step is carried out, then (iii) the fluidity of molecules in the structure in which multiple thermoplastic liquid crystal polymer substructures are integrated can be extremely highly suppressed, thereby completing the present invention.

That is, the present invention can be configured in the following aspects. [Form 1] A method for manufacturing a thermoplastic liquid crystal polymer structure, which is a method of using an autoclave to manufacture a thermoplastic liquid crystal polymer structure in which multiple thermoplastic liquid crystal polymer substructures are integrated. The preliminary laminated body of the polymer substructure is covered with a packaging film, the sealing step of sealing the end of the packaging film, the exhaust of the inside of the packaging film, and the heating step of raising the temperature to the first temperature which is the preliminary heating temperature , and starting from the first temperature, the internal pressure of the autoclave is raised to below 2.8MPa (gauge pressure) (preferably below 2.5MPa (gauge pressure), more preferably below 2MPa (gauge pressure)) The required pressure, while raising the temperature to the thermocompression bonding step of the second temperature which is the thermocompression bonding temperature.

[Form 2]

In the method for producing a thermoplastic liquid crystal polymer structure as described in Aspect 1, when the melting point of the thermoplastic liquid crystal polymer element with the lowest melting point among the preliminary laminates is taken as ML, the first temperature is (ML-150)°C~(ML -50)°C (preferably (ML-130)°C~(ML-70)°C, or 150~250°C, preferably 180~230°C).

[Form 3]

In the manufacturing method of the thermoplastic liquid crystal polymer structure described in aspect 1 or 2, the holding time at the first temperature is about 1 to 120 minutes (preferably 3 to 60 minutes).

[Aspect 4]

In the manufacturing method of the thermoplastic liquid crystal polymer structure described in any one of aspects 1 to 3, the heating rate to the first temperature is 1-10°C/min (preferably 2-8°C/min).

[Aspect 5]

In the method for producing a thermoplastic liquid crystal polymer structure described in any one of aspects 1 to 4, when the melting point of the thermoplastic liquid crystal polymer element with the highest melting point among the preliminary laminates is set as MH, the second temperature is (MH- 30) °C~(MH+10)°C (preferably (MH-10)°C~(MH+5)°C).

[Form 6]

The manufacturing method of the thermoplastic liquid crystal polymer structure as described in any one of aspects 1 to 5, the holding time at the second temperature is 15 to 60 minutes (preferably 20 to 50 minutes, more preferably 20 to 40 minutes) )about.

[Aspect 7]

The method for producing a thermoplastic liquid crystal polymer structure as described in any one of aspects 1 to 6, the heating rate to the second temperature is 2~20°C/min (preferably 3~15°C/min, more preferably 4~10℃/min).

[Aspect 8]

In the method for producing a thermoplastic liquid crystal polymer structure described in any one of aspects 1 to 7, a degassing and drying step is performed before the temperature raising step.

[Aspect 9]

In the manufacturing method described in aspect 8, the moisture content of the thermoplastic liquid crystal polymer film after the degassing drying step is 380 ppm or less (300 ppm or less, or 200 ppm or less).

[Aspect 10]

In the manufacturing method of the thermoplastic liquid crystal polymer structure described in aspect 8 or 9, the holding time at the first temperature is about 1-20 minutes (preferably 2-15 minutes, more preferably 2-10 minutes).

[Form 11]

The production method according to any one of aspects 1 to 10, wherein the moisture content of the thermoplastic liquid crystal polymer element to be preheated after the temperature raising step is 380 ppm or less (300 ppm or less, or 200 ppm or less).

Here, the thermoplastic liquid crystal polymer element means the thermoplastic liquid crystal polymer part in the thermoplastic liquid crystal polymer structure. Also, when the thermoplastic liquid crystal polymer element contained in the thermoplastic liquid crystal polymer substructure of the thermoplastic liquid crystal polymer structure is layered, the thermoplastic liquid crystal polymer element may be referred to as a thermoplastic liquid crystal polymer layer. Furthermore, when the thermoplastic liquid crystal polymer substructure before thermocompression bonding includes a thermoplastic liquid crystal polymer film, after thermocompression bonding, the aforementioned thermoplastic liquid crystal polymer film forms a thermoplastic liquid crystal polymer in the thermoplastic liquid crystal polymer structure. layer.

Furthermore, any combination of at least two components disclosed in the scope of claims and/or the specification and/or drawings is included in the present invention. In particular, any combination of two or more of the claims described in the claims is also included in the present invention.

In the present invention, a thermoplastic liquid crystal polymer structure that suppresses excessive molecular flow inside the structure can be efficiently obtained by integrating it by thermocompression bonding without using an adhesive.

[Mode for Carrying Out the Invention]

In the present invention, an autoclave can be used to manufacture a thermoplastic liquid crystal polymer structure in which a plurality of thermoplastic liquid crystal polymer substructures are integrated. The thermoplastic liquid crystal polymer structure is a structure in which multiple thermoplastic liquid crystal polymer substructures are integrated. As long as the number of thermoplastic liquid crystal polymer substructures is 2 or more, a required number of thermoplastic liquid crystal polymer substructures can be appropriately used depending on the desired shape. The upper limit of the number of thermoplastic liquid crystal polymer substructures is not particularly set, and it may be about 1000. The thermoplastic liquid crystal polymer substructure includes at least a thermoplastic liquid crystal polymer.

(thermoplastic liquid crystal polymer) The thermoplastic liquid crystal polymer is composed of a melt-formable liquid crystal polymer (or a polymer capable of forming an optically anisotropic molten phase), and the thermoplastic liquid crystal polymer, as long as it is a melt-formable liquid crystal polymer, In particular, its chemical constitution is not particularly limited, and examples thereof include thermoplastic liquid crystal polyester, thermoplastic liquid crystal polyester amide having an amide bond introduced thereto, and the like.

In addition, the thermoplastic liquid crystal polymer may be derived from isocyanate, such as an imide bond, a carbonate bond, a carbodiimide bond, or an isocyanurate bond, etc., in an aromatic polyester or an aromatic polyester amide. Polymers such as bonds.

Specific examples of the thermoplastic liquid crystal polymer used in the present invention include known thermoplastic liquid crystal polyesters and thermoplastic liquid crystal polyesters derived from compounds classified as (1) to (4) and derivatives thereof as exemplified below. Amide. However, in order to form a polymer capable of forming an optically anisotropic melt phase, the combination of various raw material compounds naturally has an appropriate range.

(1) Aromatic or aliphatic dihydroxy compounds (refer to Table 1 for representative examples) [Table 1]

(2) Aromatic or aliphatic dicarboxylic acids (refer to Table 2 for representative examples) [Table 2]

(3) Aromatic hydroxycarboxylic acid (refer to Table 3 for representative examples) [Table 3]

(4) Aromatic diamine, aromatic hydroxylamine, or aromatic aminocarboxylic acid (refer to Table 4 for representative examples) [Table 4]

Typical examples of liquid crystal polymers obtained from these raw material compounds include copolymers having structural units shown in Tables 5 and 6.

[表6]

[table 5]

[Table 6]

Among these copolymers, preferably a polymer comprising at least p-hydroxybenzoic acid and/or 6-hydroxy-2-naphthoic acid as repeating units, especially preferably (i) comprising p-hydroxybenzoic acid and 6-hydroxybenzoic acid - A polymer of repeating units of 2-naphthoic acid, or (ii) comprising at least one aromatic hydroxycarboxylic acid selected from the group consisting of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, at least one aromatic A copolymer of repeating units of aromatic diol and at least one aromatic dicarboxylic acid.

For example, in the polymer of (i), when the thermoplastic liquid crystal polymer at least includes repeating units of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, the p-hydroxybenzoic acid of the repeating unit (A) and the repeating unit of the repeating unit (B) The molar ratio (A)/(B) of 6-hydroxyl-2-naphthoic acid is preferably about (A)/(B)=10/90～90/10 in the liquid crystal polymer, more preferably also can be ( A)/(B)=about 15/85 to 85/15, more preferably about (A)/(B)=20/80 to 80/20.

Also, in the case of the polymer of (ii), at least one aromatic hydroxycarboxylic acid (C) selected from the group consisting of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, selected from the group consisting of 4,4' - at least one aromatic diol (D) selected from the group consisting of dihydroxybiphenyl, hydroquinone, phenylhydroquinone, and 4,4'-dihydroxydiphenyl ether, and an aromatic diol (D) selected from the group consisting of terephthalic acid, m- The molar ratio of each repeating unit in the liquid crystal polymer of at least one aromatic dicarboxylic acid (E) of the group of phthalic acid and 2,6-naphthalene dicarboxylic acid can be the aromatic hydroxycarboxylic acid (C ): the aforementioned aromatic diol (D): the aforementioned aromatic dicarboxylic acid (E) = (30-80): (35-10): about (35-10), more preferably (C): ( D): (E)=(35～75): (32.5～12.5): around (32.5～12.5), and it can be even better (C): (D): (E)=(40～70): (30~15): About (30~15).

In addition, in the aromatic hydroxycarboxylic acid (C), the molar ratio of the repeating unit derived from 6-hydroxy-2-naphthoic acid may be, for example, 85 mole % or more, preferably 90 mole % or more, and more preferably Preferably it is more than 95 mole%. In the aromatic dicarboxylic acid (E), the molar ratio of the repeating unit derived from 2,6-naphthalene dicarboxylic acid may be, for example, 85 mole % or more, preferably 90 mole % or more, and more preferably It is more than 95 mole%.

In addition, the aromatic diol (D) may be derived from the group consisting of hydroquinone, 4,4'-dihydroxybiphenyl, phenylhydroquinone, and 4,4'-dihydroxydiphenyl ether Repeating units (D1) and (D2) of the two different aromatic diols, in this case, the molar ratio of the two aromatic diols can be (D1)/(D2)=23/77～ 77/23, more preferably 25/75-75/25, more preferably 30/70-70/30.

Moreover, the molar ratio of the repeating structural unit derived from an aromatic diol to the repeating structural unit derived from an aromatic dicarboxylic acid is preferably (D)/(E)=95/100 to 100/95. When it exceeds this range, there exists a tendency for mechanical strength to fall, without raising a degree of polymerization.

Furthermore, the formation of an optically anisotropic molten phase as mentioned in the present invention can be identified, for example, by placing a sample on a thermal stage, heating it under a nitrogen atmosphere, and observing the transmitted light of the sample.

The thermoplastic liquid crystal polymer may have a melting point (hereinafter referred to as Tm) in the range of 200 to 360°C, preferably in the range of 240 to 360°C, more preferably in the range of 260 to 360°C, still more preferably Those whose Tm is 270-350°C. In addition, Tm was obtained by measuring the temperature at which the main endothermic peak appears with a differential scanning calorimeter (Shimadzu Corporation DSC).

The aforementioned thermoplastic liquid crystal polymers may also be added with polyethylene terephthalate, modified polyethylene terephthalate, polyolefin, polycarbonate, polyaromatic Thermoplastic polymers such as ester, polyamide, polyphenylene sulfide, polyether ether ketone, fluororesin, various additives, fillers, etc.

The thermoplastic liquid crystal polymer film is obtained, for example, by extruding a molten kneaded product of the aforementioned thermoplastic liquid crystal polymer. Any method may be used as the extrusion molding method, but industrially known T-die methods, inflation methods, and the like are advantageous. In particular, the inflation method applies stress not only to the mechanical axis direction (hereinafter referred to as the MD direction) of the thermoplastic liquid crystal polymer film, but also to the direction perpendicular to it (hereinafter referred to as the TD direction), because it can be directed toward the MD direction and the TD direction. Uniformly stretched, so a thermoplastic liquid crystal polymer film with controlled molecular alignment, dielectric properties, etc. in the MD and TD directions is obtained.

For example, in the extrusion molding by the T-die method, the melt sheet extruded from the T-die can be stretched not only in the MD direction of the thermoplastic liquid crystal polymer film, but also in both the TD direction and the TD direction. Alternatively, a melt sheet extruded from a T-die may be stretched in the MD direction once, and then stretched in the TD direction to form a film.

In addition, extrusion molding by the inflation method can be performed at a predetermined draw ratio (equivalent to the draw ratio in the MD direction) and inflation ratio (equivalent to The stretch ratio in the TD direction) is stretched to form a film.

As mentioned above, the stretching ratio of extrusion molding is, for example, about 1.0-10, preferably about 1.2-7, and more preferably about 1.3-7 as the stretching ratio (or drawing ratio) in the MD direction. In addition, the draw ratio (or blow ratio) in the TD direction may be, for example, about 1.5 to 20, preferably about 2 to 15, and more preferably about 2.5 to 14.

If necessary, known or customary heat treatment may be performed to adjust the thermal expansion coefficient of the thermoplastic liquid crystal polymer film in the plane direction to a desired range. The coefficient of thermal expansion in the plane direction of the thermoplastic liquid crystal polymer film can be adjusted to a desired value by, for example, the method described in JP-A-2005-103989.

The coefficient of thermal expansion of the thermoplastic liquid crystal polymer film can also be adjusted to any value within the range of -10 ppm/°C to 50 ppm/°C, for example. Among multiple thermoplastic liquid crystal polymer substructures, the thermal expansion coefficient of the thermoplastic liquid crystal polymer film constituting each substructure, depending on the application, for example, the tolerance between the highest thermal expansion coefficient and the lowest thermal expansion coefficient can also be 50ppm/℃ Below, below 40ppm/°C, below 30ppm/°C, below 20ppm/°C, below 15ppm/°C, below 10ppm/°C, below 5ppm/°C, below 3ppm/°C, or below 1ppm/°C.

On the other hand, in order to impart bimetallic properties to the thermoplastic liquid crystal polymer structure, the thermal expansion coefficients of the thermoplastic liquid crystal polymer films constituting each substructure can be separated and the substructures can be combined. In this case, for example, adjacent thermoplastic The thermal expansion coefficients of the liquid crystal polymer films can be separated by at least 15 ppm/°C, preferably at least 18 ppm/°C, and more preferably at least 20 ppm/°C.

(Integration step of conductor layer and thermoplastic liquid crystal polymer film) For the thermoplastic liquid crystal polymer film, when forming a conductive layer (a conductive layer such as a signal layer, a power supply layer, and a ground layer, for example, a layer formed with a conductive pattern, a conductive foil, a conductive film, etc.), known or customary methods can be used. In the method, the step of integrating the conductor layer and the thermoplastic liquid crystal polymer film is carried out. Through this integration step, a thermoplastic liquid crystal polymer film having a conductive layer on one side can be produced, and a thermoplastic liquid crystal polymer film having a conductive layer on both sides can also be produced. For example, for a thermoplastic liquid crystal polymer film, a metal foil or the like is bonded by thermocompression to form a single-sided metal-clad laminate or a double-sided metal-clad laminate, and if necessary, further etching or the like is performed to form a required conductor layer. shape.

As the conductor forming the conductor layer, various metals having conductivity may be used, for example, gold, silver, copper, iron, nickel, aluminum, or alloy metals thereof. The thickness of the conductor layer can be appropriately set as needed, and may be, for example, about 5 to 50 μm, more preferably in the range of 8 to 35 μm.

As described above, for example, as a thermoplastic liquid crystal polymer substructure used in a thermoplastic liquid crystal polymer multilayer structure, (i) a thermoplastic liquid crystal polymer film, (ii) a thermoplastic liquid crystal polymer having a conductive layer on one side can be produced. and (iii) a thermoplastic liquid crystal polymer film having a conductive layer on both sides.

(degassing drying step) If necessary, the thermoplastic liquid crystal polymer substructure may be subjected to a degassing drying step for removing air or moisture present in the thermoplastic liquid crystal polymer film before the temperature raising step described later. The degassing drying step may be carried out for individual thermoplastic liquid crystal polymer substructures and combinations thereof, may be performed for the preliminary laminate, or may be performed prior to forming a preliminary laminate having superimposed thermoplastic liquid crystal polymer substructures both sides. By performing the degassing and drying step, the integrity of the thermoplastic liquid crystal polymer structure can be strengthened. In addition, the time spent in the temperature raising step or the thermocompression bonding step can be shortened.

When performing before forming a preliminary laminate, the degassing and drying step can be performed in the thermoplastic liquid crystal polymer film before the step of integrating the thermoplastic liquid crystal polymer film and the conductor layer, and can also be used as a thermoplastic liquid crystal polymer film and conductor layer. part of the integration step. Through the degassing drying step, the thermal adhesiveness of the thermoplastic liquid crystal polymer substructure can be improved, and the interlayer adhesion of the thermoplastic liquid crystal polymer substructure can be improved.

The shape of the thermoplastic liquid crystal polymer substructure to be subjected to the outgassing drying step is not particularly limited as long as the thermoplastic liquid crystal polymer film can be outgassed and dried. For example, in the degassing drying step, the thermoplastic liquid crystal polymer substructure can be the thermoplastic liquid crystal polymer film itself, or it can be used as a thermoplastic liquid crystal polymer substructure forming a conductive layer on one or both sides of the thermoplastic liquid crystal polymer film. supply of flakes. Furthermore, the thermoplastic liquid crystal polymer substructures can also be supplied as a roll if necessary.

Even if desired, the thermoplastic liquid crystal polymer substructure may also be in the form of a multilayer laminate of a plurality of thermoplastic liquid crystal polymer substructures (e.g., a multilayer laminate of multiple layers of thermoplastic liquid crystal polymer substructures, a temporarily assembled multilayer circuit, etc.) , supplied to the degassing drying step.

The outgassing drying step, by performing specific outgassing drying under vacuum (for example, vacuum drying) and/or outgassing drying under heating (for example, heat drying) for the thermoplastic liquid crystal polymer substructure, can be extremely highly Minimize the air or moisture present in the interior or surface of the thermoplastic liquid crystal polymer film. Then, through the TLP substructure through the outgassing drying step as described above, its thermal adhesion can be improved.

For example, a thermoplastic liquid crystal polymer film subjected to a degassing drying step can achieve high adhesiveness even without softening treatment that damages the skin layer. However, softening treatment is not negated. The thermoplastic liquid crystal polymer film can also be treated with surface treatment such as softening treatment if necessary.

In the degassing and drying step, the thermoplastic liquid crystal polymer substructure is degassed and dried under vacuum by (a) degassing and drying at a vacuum degree of less than 1500 Pa for more than 30 minutes, and/or (b) at 80° C. to 300° C. In the range of ℃, the thermoplastic liquid crystal polymer film can be degassed and dried by degassing and drying under heating. In the degassing drying step, as long as the degassing drying is carried out under any one of the above-mentioned (a) degassing drying step under vacuum or (b) degassing drying step under heating, it is preferable to use The conditions of both (a) and (b) above are degassed and dried.

When the degassing drying is carried out under the conditions satisfying both (a) and (b), it may be a degassing drying step under the conditions satisfying both (a) and (b) simultaneously (that is, under vacuum heating), It is also possible to carry out the degassing drying steps of (a) and (b) conditions separately for the thermoplastic liquid crystal polymer substructure, that is, in the order of (a) to (b), or (b) to (a ) in the order of degassing and drying steps carried out separately.

Furthermore, when carrying out the degassing drying step separately, it is also possible to perform the degassing and drying step between (a) and (b), or between (b) and ( a) with further drying steps in between.

In addition, in the gas drying step, from the viewpoint of improving the degassing drying property, degassing drying may be performed under no pressurization (under pressure release) that does not substantially pressurize. For example, the degassing and drying step can also be carried out in a low pressurized or pressure released state (for example, at a pressure of about 0-0.7 MPa (gauge pressure), preferably at a pressure of about 0-0.5 MPa (gauge pressure)).

(a) Degassing and drying under vacuum can be carried out at a vacuum degree below 1500Pa, preferably below 1300Pa, more preferably below 1100Pa. When degassing and drying under vacuum are carried out independently, it can be carried out at normal temperature (for example, in the range of 10 to 50° C., preferably 15 to 45° C.), but from the viewpoint of improving the degassing and drying efficiency, it can also be carried out at Proceed under heating. The heating temperature at this time may be, for example, 50 to 300°C (for example, 50 to 250°C), preferably 80 to 250°C, more preferably about 80 to 200°C.

(b) Degassing drying under heating can be carried out in the range of 80-300°C, preferably in the range of 80-250°C, more preferably in the range of 80-200°C. In addition, the outgassing drying under heating may be performed within a predetermined temperature range relative to the melting point Tm of the thermoplastic liquid crystal polymer or thermoplastic liquid crystal polymer film. In this case, heating can be carried out in the range of (Tm-235) °C to (Tm-10) °C (for example, the range of (Tm-200) °C to (Tm-50) °C), preferably at (Tm- 225)°C to (Tm-50)°C (for example, (Tm-190)°C to (Tm-60)°C), more preferably (Tm-215)°C to (Tm-70)°C (for example, in the range of (Tm-180)°C to (Tm-70)°C). Furthermore, the melting point (Tm) of the thermoplastic liquid crystal polymer film can be, for example, 270-380°C, preferably in the range of 280-370°C.

By heating in the above-mentioned specific temperature range, the rapid generation of moisture from the film can be suppressed, and the moisture in the film (for example, inside the film or on the surface of the film) can be degassed and dried as water vapor, or the presence of water can be increased. The kinetic energy of the air on the surface degasses and dries from the surface of the film.

Furthermore, when degassing and drying under heating are carried out alone, it can be carried out without vacuum degree below 1500 Pa, and can also be carried out, for example, under atmospheric pressure (or normal pressure) without adjusting the pressure, but it can also be carried out if necessary. Heating is performed under reduced pressure from atmospheric pressure (for example, more than 1,500 Pa and less than 100,000 Pa, preferably about 3,000 to 50,000 Pa).

The time required for the degassing and drying step can be appropriately set according to various conditions such as the state of the thermoplastic liquid crystal polymer film in the thermoplastic liquid crystal polymer substructure, the degree of vacuum and/or the heating temperature, but from the overall temperature of the thermoplastic liquid crystal polymer film From the viewpoint of removing moisture or air, for example, each degassing drying step (under vacuum, under heating, under vacuum heating) may be the same or different, and may be 30 minutes or more, 40 minutes or more, or 50 minutes or more , may be less than 6 hours, less than 4 hours, less than 3 hours, less than 2 hours, or less than 1.5 hours. Also, the time required for the degassing drying step can be appropriately set by estimating, for example, the time when the moisture content of the thermoplastic liquid crystal polymer film falls within a predetermined range (for example, 380 ppm or less, 300 ppm or less, or 200 ppm or less).

As mentioned above, in the degassing drying step, the combination of (a) degassing drying under vacuum and (b) degassing drying under heating can improve the thermal adhesiveness of the thermoplastic liquid crystal polymer substructure The order of (a) degassing drying under vacuum and (b) degassing drying under heating can be either first, but it is preferable to carry out degassing drying under heating as the second After the first degassing drying step, degassing drying under vacuum is carried out as the second degassing drying step. Specifically, for example, the degassing drying step may include: a first degassing drying step of performing degassing and drying by heating in the range of 80° C. to 300° C. for a predetermined time; The second degassing drying step of degassing drying for a specified time. When performing these degassing drying steps, it can carry out combining suitably the above-mentioned conditions.

(Method for producing thermoplastic liquid crystal polymer structure) In the present invention, it is possible to manufacture a thermoplastic liquid crystal polymer structure in which a plurality of thermoplastic liquid crystal polymer substructures are laminated in an autoclave and these are integrated by thermocompression bonding. The aforementioned manufacturing method at least includes: covering the pre-laminated body with a plurality of thermoplastic liquid crystal polymer substructures with a packaging film, and sealing the end of the packaging film; performing exhaust inside the packaging film, performing The step of raising the temperature to the first temperature which is the preheating temperature; and taking the first temperature as a starting point, raising the internal pressure of the autoclave to the required pressure below 2.8MPa (gauge pressure), and simultaneously raising the temperature to The thermocompression bonding step of the second temperature of the crimping temperature.

(Prepare the step of encapsulating the laminate into the packaging film) The enclosing step is to prepare a pre-laminate with a plurality of thermoplastic liquid crystal polymer substructures overlapped, cover the pre-laminate with a packaging film (preferably after wrapping), and seal the end of the packaging film. The layered structure of the aforementioned preliminary layered body is appropriately determined depending on the application and the like.

The packaging film is not particularly limited as long as it can cover the pre-laminate and withstand the heating conditions of the autoclave, and it may be a single layer or a multi-layer composed of a plurality of materials.

The packaging film can be, for example, a heat-resistant polymer film (eg, polyimide film, fluorine-based film), or a composite material of metal and heat-resistant polymer film.

The preliminary laminate can be directly covered with a packaging film, and from the viewpoint of improving air exhaust, a release material, metal plate, air-permeable sheet, etc. can also be properly interposed between the preliminary laminate and the packaging film. At this time, in addition to the pre-laminated body, other constituent members (for example, a release material, a metal plate, an air-permeable sheet, etc.) may be covered with a packaging film or covered.

As the release material, it is not particularly limited as long as it is a material having releasability with respect to thermoplastic liquid crystal polymers, for example, polyimide film or fluorine-based film (for example, polytetrafluoroethylene film), releasability Multilayer composite material (for example, a first metal foil, a pair of high-density polyethylene sheets perpendicular to each other in MD directions, a second metal foil, and a low-friction film), etc. Here, the first and second metal foils are preferably aluminum foils, or low-friction films that have a static friction coefficient defined in JIS K 7125 of 0.30 or less (preferably about 0.05 to 0.25). The film, specifically, may also be an ultra-high molecular weight polyethylene film, a polytetrafluoroethylene film, or the like.

The air-permeable sheet is not particularly limited as long as it is formed of a heat-resistant porous material, and for example, a glass cloth, a heat-resistant fiber cloth, or a metal mesh sheet can be used.

In addition, when using an air-permeable sheet, in order to prevent the texture from being transferred from the air-permeable sheet to the surface of the preliminary laminate, a metal plate may be appropriately interposed between the preliminary laminate and the air-permeable sheet. As the metal constituting the metal plate, for example, known or commonly used metal materials having high compression resistance can be used, and stainless steel is preferred.

The metal plate, for example, may have a thickness of about 0.1 mm to 1 cm, preferably about 0.2 mm to 0.8 mm, more preferably about 0.3 mm to 0.6 mm.

After covering the preliminary laminate with a packaging film, the ends of the packaging film are sealed in order to ventilate the inside of the packaging film. When sealing the ends, as long as the opposite ends of the packaging film can be sealed, there are no particular limitations. Sealing means such as tapes can be used for sealing, and jigs such as vise can also be used for sealing, or a combination of these can be used. seal.

(heating step) The temperature raising step is to exhaust the inside of the packaging film and raise the temperature to the first temperature which is the preheating temperature. The exhaust mechanism inside the packaging film is not particularly limited as long as it can exhaust gas. For example, after sealing the end of the packaging film, the inside of the packaging film is exhausted. The temperature rise may be performed before the degassing of the packaging film, may overlap with the degassing, or may be performed after the degassing, either.

In the temperature raising step, preliminary heating can be performed by maintaining the first temperature for a predetermined time. It is preferable not to actively pressurize the inside of the autoclave by supplying pressurized gas until the preliminary heating.

The first temperature is the preliminary heating temperature. Preferably, at the first temperature, the thermoplastic liquid crystal polymer molecules do not have severe fluidity.

The first temperature, for example, when the melting point of the thermoplastic liquid crystal polymer element to be heated in the formation of the preliminary laminate is ML, the first temperature can be, for example, (ML-150)°C to (ML-50)°C The range can also be preferably about (ML-130)°C to (ML-70)°C. From the viewpoint of preventing the rapid flow of the thermoplastic liquid crystal polymer molecules, the thermoplastic liquid crystal polymer element to be preheated may be the thermoplastic liquid crystal polymer element having the lowest melting point in the preliminary laminate. The first temperature can be appropriately set according to the flow initiation temperature of the thermoplastic liquid crystal polymer, and may be, for example, in the range of 150 to 250°C, preferably about 180 to 230°C.

The temperature raising rate in the temperature raising step can be, for example, 1-10°C/min, preferably 2-8°C/min.

The holding time at the first temperature (or the preliminary heating time) is not particularly limited as long as the thermal compression bonding between the layers of the preliminary laminate is carried out, and it varies appropriately depending on the presence or absence of degassing treatment and the preliminary heating temperature. The temperature holding time (or preheating time) may be, for example, about 1 to 120 minutes, preferably about 3 to 60 minutes. Also, when the predetermined holding time (or preheating time) at the first temperature has elapsed, for example, the moisture content of the thermoplastic liquid crystal polymer element to be preheated may be within a predetermined range (for example, 380ppm or less, 300ppm or less, or 200ppm or less).

When performing the degassing drying step, the holding time at the first temperature may be about 1 to 20 minutes, preferably about 2 to 15 minutes, more preferably about 2 to 10 minutes.

(Thermocompression step) The thermocompression bonding step is to start from the first temperature, increase the internal pressure of the autoclave to the required pressure below 2.8MPa (gauge pressure), and simultaneously raise the temperature to the second temperature, which is the thermocompression bonding temperature, for preparation Thermocompression bonding between layers of a laminate.

Simultaneously with increasing the pressure, a second temperature raising step is carried out to the desired second temperature. The heating rate may be 2-20°C/min, preferably 3-15°C/min, more preferably 4-10°C/min. The second temperature may be the highest heating temperature, and the thermoplastic liquid crystal polymer substructure in the pre-laminate is thermocompressed by the second temperature. Afterwards, the laminated body of the thermoplastic liquid crystal polymer substructure is cooled, and after the pressure is released, a thermoplastic liquid crystal polymer structure can be obtained.

In order to prevent the thermoplastic liquid crystal polymer from excessively flowing under pressure, the maximum pressure in the autoclave needs to be 2.8MPa or less (gauge pressure), preferably 2.5MPa or less (gauge pressure), more preferably 2MPa or less (gauge pressure). As long as the thermoplastic liquid crystal polymer substructure can be adhered, the lower limit of the maximum pressure is not particularly limited, and may be, for example, 1.5 MPa (gauge pressure).

The second temperature is the thermocompression bonding temperature. The thermocompression bonding temperature is not particularly limited as long as it is within a range in which any of the adjacent substructures can be fused between the thermoplastic liquid crystal polymer elements of the thermoplastic liquid crystal polymer substructure. For example, the thermocompression bonding temperature can be determined after grasping the thermal fusion bonding temperature of the thermoplastic liquid crystal polymer substructure in advance. For example, when the melting point of the thermoplastic liquid crystal polymer element to be fused is set to MH in forming the preliminary laminate, the second temperature may be, for example, in the range of (MH-30)°C to (MH+10)°C, preferably It may be about (MH-10)°C to (MH+5)°C. From the viewpoint of performing reliable fusion, the thermoplastic liquid crystal polymer element to be welded may be the thermoplastic liquid crystal polymer element having the highest melting point among the preliminary laminates.

The holding time at the second temperature (or thermocompression bonding time) is not particularly limited as long as the thermocompression bonding between the layers of the preliminary laminate is performed, and can be appropriately changed depending on the presence or absence of degassing drying treatment or the thermocompression bonding temperature For example, it can be performed for about 15 to 60 minutes, preferably for about 20 to 50 minutes, and more preferably for about 20 to 40 minutes.

By the above-mentioned manufacturing method, the rapid flow of TLC molecules can be suppressed, and at the same time, good adhesion can be achieved between adjacent TLC substructures.

Hereinafter, a method for manufacturing a thermoplastic liquid crystal polymer structure using an autoclave will be exemplified and further described.

FIG. 1 shows a schematic diagram for explaining an autoclave thermocompression bonding method using an embodiment of the present invention. The interior of the autoclave 9 is covered with a packaging film 1 , and a pre-laminated body 5 in which a plurality of thermoplastic liquid crystal polymer substructures are overlapped is mounted on a carrier plate 6 according to a desired configuration. Here, in the inside of the packaging film 1, the release materials 4a, 4b are arranged on the upper and lower sides of the preliminary laminate 5, and even on the upper release material 4a, the air-permeable sheet 2 is arranged through the top plate 3.

The packaging film 1 is sealed by a vacuum sealing tape 8, and a vacuum nozzle 7 for vacuuming is connected to an appropriate position of the packaging film 1. The air inside the packaging film 1 is exhausted through the vacuum nozzle 7 . Furthermore, on the inner side of the packaging film 1, the air-permeable sheet 2 may also be arranged if necessary. By the presence of the air-permeable sheet 2, the air permeability inside the packaging film 1 can be further improved.

Furthermore, in FIG. 1 , the air-permeable sheet 2 is disposed so as to pass through the side of the preliminary laminate 5 from above the preliminary laminate 5 and lead to the vacuum nozzle 7 . However, the setting position of the air-permeable sheet 2 is not limited as long as the air-gas performance can be improved in the periphery of the preliminary laminated body 5 . For example, the air-permeable sheet 2 may be arranged in at least one of the upper, lower, and side surfaces of the preliminary laminate 5 . Moreover, when installing the air permeable sheet 2 above and/or below the preliminary laminate 5 , it is preferable to provide a metal plate between the release materials 4 a , 4 b and the air permeable sheet 2 .

In addition, in FIG. 1 , the packaging film 1 is arranged on both the upper and lower sides of the preliminary laminated body 5 , and the ends are sealed with vacuum sealing tape 8 to cover the preliminary laminated body 5 in a packaged state.

Furthermore, as long as the inside of the packaging film 1 can be exhausted, the packaging film 1 below may not be arranged. The pre-laminated body 5 may be covered with the packaging film 1 from above, and the end of the packaging film 1 may be sealed with respect to the carrier plate 6 using a predetermined sealing means (for example, tapes such as vacuum sealing tape). Taking advantage of the low adhesion of the aforementioned sealing means, the sealing means and the imide film can be further fixed with jigs such as vise.

When thermocompression bonding is performed, pressurized gas is supplied to the inside of the autoclave 9 from a gas source (not shown in the figure). Since the supplied pressurized gas exists uniformly around the packaging film 1, the inside of the packaging film 1 can be uniformly pressurized.

On the other hand, since the inside of the packaging film 1 is exhausted, the pressure applied to the packaging film 1 is directly applied to the laminate 5 . As a result, not only the upper and lower surfaces of the pre-laminated body 5 but also the side surfaces thereof are subjected to equal pressure, and the respective thermoplastic liquid crystal polymer substructures inside the pre-laminated body 5 can be adhered to each other.

For various members used in the autoclave 9, well-known or conventional ones can be used. In addition, other members may be used instead of or in addition to the above-mentioned members.

For example, the packaging film 1 is not particularly limited as long as it is a flexible material having heat resistance and pressure resistance, and examples thereof include polyimide films and the like. As the release materials 4a and 4b, for example, a polyimide film, a fluorine-based film, a releasable multilayer composite material, etc. are used.

Also, the air-permeable sheet 2 is not particularly limited as long as it can be used to exhaust the air existing between the packaging film 1 and the preliminary laminate 5, and for example, glass cloth, heat-resistant fiber cloth, or metal mesh can be used. flakes etc.

In addition, the metal plate is arranged to prevent the shape derived from the air-permeable sheet 2 from being imprinted on the surface of the thermoplastic liquid crystal polymer structure. Therefore, when the air-permeable sheet 2 is not arranged, the metal plate need not be arranged.

The pressurized gas is not particularly limited as long as it is not a gas having high reactivity under heating, and it may be normal air or the like, but nitrogen or the like may be suitably used.

In the present invention, in the autoclave-type thermocompression bonding method, by performing specific heating conditions, the excessive flow of the thermoplastic liquid crystal polymer molecules can be suppressed, and at the same time, the adhesion between the thermoplastic liquid crystal polymer substructures can be achieved. Then, the flow of the thermoplastic liquid crystal polymer molecules can be slowed down, so that the alignment of the thermoplastic liquid crystal polymer structure can be made uniform, and at the same time, the integrity of the thermoplastic liquid crystal polymer structure can be improved. In addition, when there is a circuit formed by the conductor pattern, the flow of the thermoplastic liquid crystal polymer in the vicinity of the circuit is slowed down, and even if the circuit is present, the alignment of the thermoplastic liquid crystal polymer can be made uniform.

Starting from the first temperature, a heated and pressurized gas is supplied inside the autoclave to increase the internal pressure of the autoclave to the required maximum pressure. At this time, the pre-laminated body is pressurized under a required pressure of 2.8 MPa or less (gauge pressure), and thermocompression bonding is performed.

(thermoplastic liquid crystal polymer structure) The resulting thermoplastic liquid crystal polymer structure is excellent in the integrity of the thermoplastic liquid crystal polymer substructure, and can suppress the occurrence of resin flow caused by excessive flow of the thermoplastic liquid crystal polymer molecules constituting the structure during the manufacturing process.

In the thermoplastic liquid crystal polymer structure of the present invention, a plurality of thermoplastic liquid crystal polymer substructures can be integrated using an autoclave, thereby controlling the coefficient of thermal expansion of the thermoplastic liquid crystal polymer elements of each substructure after lamination to a predetermined value , the thermal expansion coefficient of the thermoplastic liquid crystal polymer film can also be adjusted in advance before forming the thermoplastic liquid crystal polymer structure. Furthermore, when the thermal expansion coefficient of the thermoplastic liquid crystal polymer element is not adjusted during thermocompression bonding at the time of lamination, the thermal expansion coefficient of the thermoplastic liquid crystal polymer element (or thermoplastic liquid crystal polymer layer) can also be judged to be related to the composition of the thermoplastic liquid crystal. The thermoplastic liquid crystal polymer films used for each thermoplastic liquid crystal polymer substructure of the polymer structure have the same thermal expansion coefficient.

The thermal expansion coefficient of the thermoplastic liquid crystal polymer element in the thermoplastic liquid crystal polymer structure in the plane direction may be, for example, in the range of -10ppm/°C to 50ppm/°C, preferably in the range of 10ppm/°C to 50ppm/°C, more preferably It is in the range of 15 ppm/°C to 45 ppm/°C. Furthermore, the thermal expansion coefficient of the thermoplastic liquid crystal polymer element in the thermoplastic liquid crystal polymer structure in the plane direction can also be respectively for the surface or the back surface of the thermoplastic liquid crystal polymer structure, by adopting a predetermined thickness (for example, 10~ In the range of 100 μm, the thickness of the outermost thermoplastic liquid crystal polymer layer was evaluated as the thickness) of the thermoplastic liquid crystal polymer element.

In addition, the tolerance of the thermal expansion coefficient of the thermoplastic liquid crystal polymer element in the thermoplastic liquid crystal polymer structure in the plane direction may be, for example, 50 ppm/°C or less, 40 ppm/°C or less, 30 ppm/°C or less, or 20 ppm/°C or less depending on the application. , may be 15 ppm/°C or less, 10 ppm/°C or less, 5 ppm/°C or less, 3 ppm/°C or less, or 1 ppm/°C or less. Furthermore, the tolerance of the thermal expansion coefficient of the thermoplastic liquid crystal polymer element in the thermoplastic liquid crystal polymer structure in the plane direction is that a plurality of thermoplastic liquid crystal polymer elements are randomly selected from the thermoplastic liquid crystal polymer structure as sample pieces, and can be obtained The difference between the maximum value and the minimum value of the thermal expansion coefficient in the surface direction of the sample sheet, but from the viewpoint of simplicity, it is also possible to adopt a predetermined thickness for the surface and the back surface of the thermoplastic liquid crystal polymer structure (for example, The range of 10 to 100 μm, the thickness of the thermoplastic liquid crystal polymer element when the layered state of the outermost thermoplastic liquid crystal polymer layer is clear), and the difference in the thermal expansion coefficient in the plane direction is taken as a tolerance.

In the thermoplastic liquid crystal polymer structure, the aforementioned thermoplastic liquid crystal polymer substructure can also preferably be selected from the group consisting of (i) a thermoplastic liquid crystal polymer layer, (ii) a thermoplastic liquid crystal polymer layer having a conductor layer on one side, and (iii) at least 2 layers of thermoplastic liquid crystal polymer substructure of the group of thermoplastic liquid crystal polymer layers having conductive layers on both sides.

As the thermoplastic liquid crystal polymer substructure, as long as it is formed of thermoplastic liquid crystal polymer and a plurality of substructures can be integrated, various shapes of substructures can be used. A thermoplastic liquid crystal polymer substructure is preferred, selected from the group consisting of (i) a single thermoplastic liquid crystal polymer layer (L), (ii) a thermoplastic liquid crystal polymer layer (CL) with a conductor layer on one side, and ( iii) A group of thermoplastic liquid crystal polymer layers (CLC) with conductor layers on both sides. Here, examples of the conductive layer include conductive layers such as signal layers, power supply layers, and ground layers, and specifically, layers formed of conductive patterns, conductive foils, and conductive films. , and these conductor layers can also be formed into appropriate desired shapes as needed.

Examples of preferred combinations of thermoplastic liquid crystal polymer substructures include the following combinations. (I) multiple L (II) Multiple CLs (III) Multiple CLCs (IV) One or more L and one or more CL (V) one or more L and one or more CLC (VI) one or more L, one or more CL, and one or more CLC, and (VII) One or more CLs and one or more CLCs. Here, L: a single thermoplastic liquid crystal polymer layer, CL: a thermoplastic liquid crystal polymer layer having a conductive layer on one side, and CLC: a thermoplastic liquid crystal polymer layer having a conductive layer on both sides. Among them, the order or direction of overlapping L, CL, and LCL can be appropriately set according to the application.

The thickness of the thermoplastic liquid crystal polymer film (the thermoplastic liquid crystal polymer layer after thermocompression bonding) constituting the thermoplastic liquid crystal polymer substructure can be appropriately set according to the application, but it is also preferably all below 140 μm, more preferably 120 μm It is not more than 110 μm, and more preferably not more than 110 μm. In addition, the lower limit of the thickness of the thermoplastic liquid crystal polymer film (or thermoplastic liquid crystal polymer layer) may be about 10 μm, but it may be 15 μm or more, 30 μm or more, 60 μm or more, or 85 μm or more depending on the intended thickness. The thicknesses of the thermoplastic liquid crystal polymer films (or thermoplastic liquid crystal polymer layers) constituting each substructure can be the same or different, but preferably at the same level (for example, the difference between each thickness is 10% or less, preferably 5% the following).

Depending on the application, the number of substructures of the thermoplastic liquid crystal polymer can be appropriately set. When the number of substructures of the thermoplastic liquid crystal polymer is used for light and thin applications, it is, for example, about 2-10, preferably about 3-8. In this case, the thickness of each thermoplastic liquid crystal polymer substructure is about 10-70 μm, preferably about 10-60 μm. For light and thin applications, for example, the thickness of the thermoplastic liquid crystal polymer structure may be 30 μm or more, 50 μm or more, or 100 μm or more. The upper limit of the thickness can be appropriately set, and may be, for example, 150 μm or less.

In addition, the number of thermoplastic liquid crystal polymer substructures, when used as a thick application, can be, for example, 2 or more, 3 or more, 4 or more depending on the thickness required for the thermoplastic liquid crystal polymer structure or the thickness of the thermoplastic liquid crystal polymer substructure. Above, above 9, or above 10. In addition, the upper limit is not particularly limited, and may be, for example, 200 or less, 150 or less, 100 or less, 50 or less, 20 or less, or 15 or less. In addition, the description about these upper limits and lower limits can be freely combined. In this case, the thickness of each thermoplastic liquid crystal polymer substructure is about 50-140 μm, preferably about 70-120 μm. In the case of heavy application, for example, a thermoplastic liquid crystal polymer structure may be more than 150 μm, and may be 250 μm or more, 350 μm or more, 450 μm or more, or 550 μm or more. The upper limit of the thickness can be appropriately set, and may be, for example, 5 mm or less.

In addition, the thermoplastic liquid crystal polymer elements of the respective thermoplastic liquid crystal polymer substructures constituting the thermoplastic liquid crystal polymer structure may have the same or different melting points. In different cases, the temperature difference between the thermoplastic liquid crystal polymer element with the lowest melting point and the thermoplastic liquid crystal polymer element with the highest melting point is more than 0°C and less than 100°C, preferably 10°C to 90°C, more preferably 20°C Above 80°C and below 80°C.

The aforementioned thermoplastic liquid crystal polymer structure may have three or more conductive layers (for example, a metal foil layer or a conductive pattern including a metal foil). Also, depending on the application, it may have 5 or more conductor layers, or 7 or more conductor layers. The upper limit of the conductor layer is not particularly limited, and may be about 20 layers.

When the thermoplastic liquid crystal polymer structure is a laminate of thermoplastic liquid crystal polymer substructures composed of the aforementioned thermoplastic liquid crystal polymer layers, the thermoplastic liquid crystal polymer structure of the present invention is excellent in integrity, so the adjacent thermoplastic liquid crystal polymer There is thermocompression bonding between the substructures. Here, having thermocompression bondability (or adhesiveness) means that the adhesive strength evaluated by the method described in the examples described later is, for example, 0.4 N/mm or more, preferably 0.5 N/mm or more, and further higher It is preferably at least 0.6 N/mm, more preferably at least 0.7 N/mm, further preferably at least 0.8 N/mm, particularly preferably at least 0.9 N/mm, and still more preferably at least 1.0 N/mm. The upper limit of the adhesive strength is not particularly limited, and may be about 2.0 N/mm. Especially when the present invention is used for thick and heavy applications, the structure can also be integrated by thermocompression bonding, and the adhesive strength between adjacent substructures can be improved, so it is preferable.

In addition, the present invention can also obtain a thermoplastic liquid crystal polymer structure with excellent isotropy. In this case, the molecular orientation SOR of the thermoplastic liquid crystal polymer structure can be, for example, about 0.95 to 1.25, preferably 0.98 to 1.18 about. In addition, the degree of molecular orientation SOR of the thermoplastic liquid crystal polymer structure is a numerical value measured by a method described in Examples described later.

Also, in the present invention, the difference in the thermal expansion coefficients of the respective thermoplastic liquid crystal polymer elements in the plane direction in adjacent thermoplastic liquid crystal polymer substructures may be, for example, 15 ppm/°C or more, preferably 18 ppm/°C or more, More preferably, it is 20 ppm/°C or higher. In this case, also, a thermoplastic liquid crystal polymer structure having a bimetallic property can be obtained in which the side of the thermoplastic liquid crystal polymer substructure having a low thermal expansion coefficient is bent at a predetermined temperature.

The thermoplastic liquid crystal polymer structure of the present invention can obtain a three-dimensional structure such as a plate, a two-dimensional structure such as a rod, etc. by combining various thermoplastic liquid crystal polymer substructures, and the structure , high integrity, and suppress excessive flow of molecules inside the structure. For example, the thermoplastic liquid crystal polymer structure of the present invention can be effectively used as parts used in the electric and electronic fields, or in the field of business equipment and precision equipment, for example, as a multilayer circuit board (especially for millimeter-wave radar) substrate), power modules, etc. are usefully used. [Example]

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, in the following examples and comparative examples, various physical properties were measured by the following methods.

[melting point] Using DSC Q2000 manufactured by TA Instruments, for 5 mg of the sample, the temperature was raised from room temperature at a rate of 20°C per minute to the temperature of the polymerized sample, kept at this temperature for 2 minutes, and cooled to 25°C at a rate of 20°C per minute , and kept at 25° C. for 2 minutes, and the endothermic peak temperature when the temperature was raised again at a rate of 20° C. per minute was defined as the melting point.

[Thermal expansion coefficient] The coefficient of thermal expansion of the thermoplastic liquid crystal polymer film is based on a thermomechanical analysis device (TMA-60 manufactured by Shimadzu Corporation), and a tensile load of 1 g is applied to both ends of a thermoplastic liquid crystal polymer film with a width of 5 mm and a length of 20 mm. After the temperature is raised to 200°C at a speed of 5°C/min, it is cooled to 30°C at a speed of 20°C/min, and the length between 30°C and 150°C is changed when the temperature is raised again at a speed of 5°C/min. figured out. The coefficient of thermal expansion in the plane direction of the thermoplastic liquid crystal polymer element in the thermoplastic liquid crystal polymer structure is taken as a representative value, and the outermost thermoplastic liquid crystal polymer layer is peeled off for the front surface and the back surface respectively, and the obtained two layers are respectively viewed. It is a thermoplastic liquid crystal polymer film. Then, as described above, the measurement of each layer was carried out by the same method as the measurement of the thermal expansion coefficient of the thermoplastic liquid crystal polymer film. Regarding the tolerance of the coefficient of thermal expansion in the plane direction of the thermoplastic liquid crystal polymer element in the thermoplastic liquid crystal polymer structure, one of the thermal expansion coefficients of the obtained two layers is taken as the maximum value, the other is taken as the minimum value, and The difference serves as a tolerance for the coefficient of thermal expansion of the thermoplastic liquid crystal polymer element.

[Adhesive Strength] According to JIS C5016-1994, at a speed of 50 mm per minute, between adjacent thermoplastic liquid crystal polymer films, one side is peeled in a direction of 90° with respect to the other side, and at the same time, it is tested by a tensile tester (IMADA Co., Ltd.) Digital dynamometer ZTS-500N), measure the peel strength, and use the obtained value as the adhesive strength. For the judgment of thermocompression bondability, after confirming that there is no peeling between the adjacent thermoplastic liquid crystal polymer substructures, the lower limit of the practically no problem adhesive strength is 0.4N/mm, and then the adjacent thermoplastic liquid crystal polymer substructures are separated. When the adhesive strength is 0.4 N/mm or more, it is considered that the adhesiveness is good, and it is judged to be within the acceptable range. Furthermore, for one direction (MD direction) of the thermoplastic liquid crystal polymer film, and the orthogonal direction (TD direction) relative thereto, by peeling from both sides respectively, for MD forward direction (or MD forward direction), MD Measure the adhesion strength in the four directions of reverse direction (or MD non-progressive direction), TD forward direction (or TD right direction), TD reverse direction (or TD left direction), and use the average value as the adhesion between thermoplastic liquid crystal polymer films A representative value of strength. In addition, the adhesion strength was evaluated by peeling off adjacent two layers randomly selected, and evaluating the strength.

[Molecular Orientation (SOR)] From the thermoplastic liquid crystal polymer structure, slices of an extent capable of being inserted into a microwave resonance waveguide were cut out and used as samples. Furthermore, when the thermoplastic liquid crystal polymer structure can be inserted directly, there is no need to cut out slices to serve as samples. In the microwave molecular orientation measuring machine, the sample surface is perpendicular to the direction of the microwave, the sample is inserted into the microwave resonant waveguide, and the electric field intensity (microwave transmission intensity) of the microwave transmitted through the sample is measured. And based on this measured value, m value (referred to as a refractive index) was computed by the following formula. m=(Zo/Δz)X[1-νmax/νo] Here, Zo is the device constant, Δz is the average thickness of the object, νmax is the frequency that gives the maximum microwave transmission intensity when the microwave frequency is changed, and νo is when the average thickness is zero (that is, when there is no object), The frequency at which the maximum microwave transmission intensity is given.

Next, when the rotation angle of the object in the vibration direction of the microwave is 0°, that is, the direction in which the vibration direction of the microwave and the molecules of the object are optimally aligned, the m value when it coincides with the direction that gives the minimum microwave transmission intensity is taken as m0, the value of m when the rotation angle is 90° is taken as m90, and the degree of molecular orientation SOR is calculated from m0/m90.

[resin flow] The presence or absence of resin flow, using the end face of the thermoplastic liquid crystal polymer structure after lamination, compared with the cut size before thermocompression, will confirm that the end face spans a width of 3 mm or more and has a width of 1.5 mm or more. Those that flowed out were regarded as "existing" in resin flow, and judged to be defective.

[Moisture content] Based on the Karl Fischer method (using the principle of Karl-Fischer titration, the method of measuring moisture by changing the potential difference that causes moisture to be absorbed by the solvent), using a trace moisture measuring device (Mitsubishi Chemical Analytech (Karl Fischer VA-100 manufactured by Co., Ltd.), 7.0 to 1.5 g of thermoplastic liquid crystal polymer films were cut into widths of 3 mm and lengths of 10 mm, and were put into the sample port, and the values obtained by measuring under the following conditions were used as thermoplastic liquid crystal Moisture content of the polymer film.・Heating temperature: 300℃ ・_N2 gauge pressure: 0.2MPa ・Measurement preparation (automatic) Purge (Purge) 1 minute preheating (Preheat) 2 minutes sample port cooling (Cooling) 4 minutes sample port cooling ・Measurement titration tank Internal storage time (time to send out water with N2): 15 minutes

[Example 1] As the thermoplastic liquid crystal polymer substructure, a thermoplastic liquid crystal polymer film (VECSTAR (registered trademark) manufactured by Kuraray Co., Ltd.) with a melting point of 310°C, a thermal expansion coefficient of 18ppm/°C, and a thickness of 18 μm was used, and three sheets were stacked as a preliminary laminate. And this preliminary laminate was thermocompression-bonded using an autoclave (AC-1200×2100, manufactured by Ashida Seisakusho Co., Ltd.).

The preliminary laminate was sandwiched between release sheets, and a metal plate and an air-permeable sheet (glass cloth) were further arranged on the upper and lower surfaces thereof, and mounted on a carrier plate. Next, the entire mounting object was covered with a packaging film (polyimide film), and the end of the packaging film was sealed with a sealing material (vacuum sealing tape GS-8003-G manufactured by AIRTECH Co., Ltd.) to seal the whole as a sample. Bag. Furthermore, the air inside the packaging film is exhausted through the vacuum nozzle, and in order to improve the exhaust of the vacuum nozzle, a breathable sheet is also arranged on the side of the mounting plate.

Next, thermocompression bonding in an autoclave was performed while measuring the actual temperature of the sample. First, the inside of the sample pack was exhausted, and then, the temperature was raised to 200° C. which is the first temperature. The heating rate is implemented at 5°C/min. After the moisture content of the film was kept at 200°C for 30 minutes for preliminary heating, the moisture content of the film was kept below 100ppm, and then the internal pressure of the autoclave was gradually increased from atmospheric pressure to 2MPa (gauge pressure). Simultaneously, the temperature was raised to 300°C, which is the second temperature, and kept for 30 minutes. The cooling system is implemented at 6°C/min. The coefficient of thermal expansion in the plane direction of the thermoplastic liquid crystal polymer element of the outermost layer, which is a representative value, is 18 ppm/°C for the front surface and the back surface, respectively. Furthermore, when the thermal expansion coefficient was also measured for the thermoplastic liquid crystal polymer element existing in the center, the thermal expansion coefficient was 18 ppm/°C. Also, the SOR of the thermoplastic liquid crystal polymer structure was 1.02.

[Example 2] A thermoplastic liquid crystal polymer structure was obtained in the same manner as in Example 1 except that the thermoplastic liquid crystal polymer film in Example 1 was used as the thermoplastic liquid crystal polymer substructure in which a conductive pattern was formed on one side. The coefficient of thermal expansion in the plane direction of the thermoplastic liquid crystal polymer element of the outermost layer, which is a representative value, is 18 ppm/°C for the front surface and the back surface, respectively. In addition, copper foil CF-H9A-DS-HD2-12 (manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.) was used as the conductor pattern, and vacuum batch pressure (manufactured by Kitagawa Seiki Co., Ltd., product name: VH2-1600) was used. ), after lamination at 290°C and 2MPa (gauge pressure), a copper foil pattern was formed by etching.

[Example 3] As the thermoplastic liquid crystal polymer substructure, six thermoplastic liquid crystal polymer films with a melting point of 310° C. and a thickness of 100 μm were used, and the heating temperature was set to 310° C., except that it was carried out in the same manner as in Example 1 to obtain a thermoplastic liquid crystal polymer structure. body. The coefficient of thermal expansion in the plane direction of the thermoplastic liquid crystal polymer element of the outermost layer, which is a representative value, is 20 ppm/°C for the front surface and the back surface, respectively.

[Example 4] A thermoplastic liquid crystal polymer structure was obtained in the same manner as in Example 3, except that the thermoplastic liquid crystal polymer film of Example 3 having a conductor pattern formed on one side thereof was used as the thermoplastic liquid crystal polymer substructure. The coefficient of thermal expansion in the plane direction of the thermoplastic liquid crystal polymer element of the outermost layer, which is a representative value, is 20 ppm/°C for the front surface and the back surface, respectively. In addition, copper foil CF-H9A-DS-HD2-12 (manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.) was used as the conductor pattern, and vacuum batch pressure (manufactured by Kitagawa Seiki Co., Ltd., product name: VH2-1600) was used. ), after lamination at 290°C and 2MPa (gauge pressure), a copper foil pattern was formed by etching.

[Example 5] A thermoplastic liquid crystal polymer structure was obtained in the same manner as in Example 1 except that 12 thermoplastic liquid crystal polymer films having a melting point of 310° C. and a thickness of 100 μm were used as the thermoplastic liquid crystal polymer substructure. The coefficient of thermal expansion in the plane direction of the thermoplastic liquid crystal polymer element of the outermost layer, which is a representative value, is 18 ppm/°C for the front surface and the back surface, respectively.

[Example 6] Except having set the pressure at the time of thermocompression bonding to 1 MPa (gauge pressure), it carried out similarly to Example 5, and obtained the thermoplastic liquid crystal polymer structure. The coefficient of thermal expansion in the plane direction of the thermoplastic liquid crystal polymer element of the outermost layer, which is a representative value, is 18 ppm/°C for the front surface and the back surface, respectively.

[Example 7] A thermoplastic liquid crystal polymer structure was obtained in the same manner as in Example 1 except that 100 thermoplastic liquid crystal polymer films having a melting point of 310° C. and a thickness of 100 μm were used as the thermoplastic liquid crystal polymer substructure. The coefficient of thermal expansion in the plane direction of the thermoplastic liquid crystal polymer element of the outermost layer, which is a representative value, is 18 ppm/°C for the front surface and the back surface, respectively.

[Example 8] A thermoplastic liquid crystal polymer structure was obtained in the same manner as in Example 1, except that two thermoplastic liquid crystal polymer films with different thermal expansion coefficients and a melting point of 310° C. and a thickness of 100 μm were used as the thermoplastic liquid crystal polymer substructure. The thermal expansion coefficients of the respective thermoplastic liquid crystal polymer films are 10 ppm/°C and 30 ppm/°C. The laminated structure has a characteristic of changing shape due to temperature change, that is, a bimetallic characteristic. That is, the obtained laminate has warpage after lamination, and even if the warpage is temporarily mechanically formed flat by heat and pressure, it is bent again on the side with a low thermal expansion rate due to temperature changes, thereby changing its shape. .

[Example 9] A thermoplastic liquid crystal polymer structure was obtained in the same manner as in Example 3 except that the heating temperature during thermocompression bonding was 260° C. and the pressure was 1 MPa (gauge pressure). The coefficient of thermal expansion in the plane direction of the thermoplastic liquid crystal polymer element of the outermost layer, which is a representative value, is 18 ppm/°C for the front surface and the back surface, respectively.

[Example 10] The thermoplastic liquid crystal polymer substructure is degassed and dried at 200°C for 60 minutes using a hot air oven, and after the moisture content is reduced to 100ppm or less, it is used as a preliminary laminate, and the temperature increase rate in the preliminary heating is changed to 20°C /min, except that the holding time was changed to 5 minutes, the same procedure as in Example 3 was carried out to obtain a thermoplastic liquid crystal polymer structure. The coefficient of thermal expansion in the plane direction of the thermoplastic liquid crystal polymer element of the outermost layer, which is a representative value, is 20 ppm/°C for the front surface and the back surface, respectively.

[Comparative example 1]

Three sheets of thermoplastic liquid crystal polymer films with a melting point of 310°C and a thickness of 100 μm were stacked, and pressure was applied in batches using a vacuum (manufactured by Kitagawa Seiki Co., Ltd., trade name: VH2-1600). Press for 30 minutes.

[Comparative example 2]

Except having set the temperature at the time of thermocompression bonding to 290 degreeC, it carried out similarly to the comparative example 1, and obtained the thermoplastic liquid crystal polymer structure.

[Comparative example 3]

A thermoplastic liquid crystal polymer structure was obtained in the same manner as in Comparative Example 1 except that the temperature at the time of thermocompression bonding was 310° C. and the pressure was 2 MPa (gauge pressure).

[Comparative example 4]

Overlap 6 sheets of thermoplastic liquid crystal polymer films with the conductor pattern used in Example 4 formed on one side, and use vacuum batch press (trade name: VH2-1600 manufactured by Kitagawa Seiki Co., Ltd.) at a vacuum of 4 torr, 300°C, Pressurize at 2 MPa (gauge pressure) for 30 minutes.

[Comparative Example 5]

Using three thermoplastic liquid crystal polymer films with a melting point of 310°C and a thickness of 100 μm, and setting the pressure at 3 MPa (gauge pressure) at the time of thermocompression bonding, the same procedure was carried out as in Example 3 to obtain a thermoplastic liquid crystal polymer structure. .

Table 7 shows the layered configuration of the thermoplastic liquid crystal polymer structures obtained in Examples and Comparative Examples, Table 8 shows the layered method, and Table 9 shows the physical properties.

[Table 7] Thickness of laminated film (µm) Total thickness (µm) Example 1 18/18/18 54 Example 2 18/18/18 ※ 54 Example 3 100/100/100/100/100/100 600 Example 4 100/100/100/100/100/100 ※ 600 Example 5 100/100/100/100/100/100/100/100/100/100/100/100 1200 Example 6 100/100/100/100/100/100/100/100/100/100/100/100 1200 Example 7 (100/100/100/100/100/100/100/100/100/100)×10 groups 10000 Example 8 100/100 200 Example 9 100/100/100/100/100/100 600 Example 10 100/100/100/100/100/100 600 Comparative example 1 100/100/100 300 Comparative example 2 100/100/100 300 Comparative example 3 100/100/100 300 Comparative example 4 100/100/100/100/100/100 ※ 600 Comparative Example 5 100/100/100 300 ※Conductor patterns are included in each layer

[Table 8] Layer method Degassing drying step preheating thermocompression 1st temperature (°C) time (minutes) temperature(℃) time (minutes) Pressure (MPa) Example 1 Autoclave none 200 30 300 30 2 Example 2 Autoclave none 200 30 300 30 2 Example 3 Autoclave none 200 30 310 30 2 Example 4 Autoclave none 200 30 310 30 2 Example 5 Autoclave none 200 30 300 30 2 Example 6 Autoclave none 200 30 300 30 1 Example 7 Autoclave none 200 30 300 30 2 Example 8 Autoclave none 200 30 300 30 2 Example 9 Autoclave none 200 30 260 30 1 Example 10 Autoclave have 200 5 310 30 2 Comparative example 1 vacuum batch pressurization none - - 260 30 4 Comparative example 2 vacuum batch pressurization none - - 290 30 4 Comparative example 3 vacuum batch pressurization none - - 310 30 2 Comparative example 4 vacuum batch pressurization none - - 300 30 2 Comparative Example 5 Autoclave none 200 30 310 30 3

[Table 9] Adhesion (N/mm) resin flow Example 1 0.7 none Example 2 0.7 none Example 3 1.2 none Example 4 1.1 none Example 5 0.9 none Example 6 0.8 none Example 7 0.9 none Example 8 0.9 none Example 9 0.4 none Example 10 1.1 none Comparative example 1 0.3 none Comparative example 2 0.3 none Comparative example 3 0.8 have Comparative example 4 0.6 have Comparative Example 5 1.2 have

As shown in Table 9, there is no resin flow in Examples 1 to 10, and the thermocompression bondability between the thermoplastic liquid crystal polymer substructures is good. That is, all of the obtained thermoplastic liquid crystal polymer structures suppressed the fluidity of molecules, and in the observation of the external shape by visual observation, no discoloration or deformation due to the flow of molecules was confirmed as described above.

Furthermore, in Examples 2 and 4, conductive patterns are formed, but even in the case of forming conductive patterns, the liquid crystal polymer around the conductors does not flow too much, so even between circuits that require circuits such as circuits formed by fine conductive patterns The safety distance can also meet this requirement.

In addition, Example 9 not only has a lower thermocompression bonding temperature than Comparative Example 2 using vacuum batch pressurization, but also has no practical problems in thermocompression even though the number of laminated sheets is twice that of Comparative Example 2. connection.

Furthermore, when the thermoplastic liquid crystal polymer substructure after the degassing drying step is integrated as a preliminary structure, although the preliminary heating time is only 1/6 of that of Example 3, the same degree of adhesion as that of Example 3 can be achieved.

Furthermore, the SOR of the thermoplastic liquid crystal polymer structure obtained in Example 1 was 1.02. In addition, the tolerance of the thermal expansion coefficient in the plane direction of the thermoplastic liquid crystal polymer element of the outermost layer in the thermoplastic liquid crystal polymer structures obtained in Examples 1 to 10 was 1 ppm/°C or less.

On the other hand, Comparative Examples 1 and 2, which use vacuum batch pressurization, do not have resin flow and excessive molecular flow, but the adhesive strength is not within the acceptable range. Although the thermocompression bonding temperature of Comparative Example 1 is the same as that of Example 6, and that of Comparative Example 2 is higher than that of Example 6, the vacuum batch pressure is applied, and the thermoplastic liquid crystal polymer film of each layer is 100 μm. , sufficient adhesive strength cannot be achieved.

In Comparative Examples 3 and 4, since the thermocompression bonding temperature is higher than that of Comparative Example 2, the adhesive strength falls within the acceptable range, but on the other hand, resin flow occurs.

In Comparative Example 5, since the pressure at the time of thermocompression bonding in autoclave lamination pressurization was 3 MPa (gauge pressure), the adhesive strength fell within the acceptable range, but on the other hand, resin flow occurred. Also, referring to the results of Comparative Example 5, it can be predicted that resin flow would occur due to excessive molecular flow when thermocompression bonding was performed at high pressure with heated and pressurized gas from an autoclave without preheating. [Possibility of industrial use]

The production method of the present invention is useful for obtaining a thermoplastic liquid crystal polymer structure that suppresses resin flow, and the obtained thermoplastic liquid crystal polymer structure can be used as a Parts used in fields etc. are used effectively.

As mentioned above, although the suitable embodiment of this invention was demonstrated, various additions, changes, and deletions are possible in the range which does not deviate from the summary of this invention, and such invention is also included in the scope of this invention.

1: Packaging film 2: breathable sheet 3: top plate 4a, 4b: release material 5: Preparing the laminate 6: carrier board 7: Vacuum nozzle 8: Vacuum sealing tape 9: Autoclave

The present invention can be understood more clearly from the description of the following suitable embodiments with reference to the attached drawings. However, the embodiments and drawings are for simple illustration and description, and are not used to define the scope of the present invention. The scope of the invention is defined by the appended claims. In the attached drawings, the same part number in multiple drawings indicates the same part. The drawings are not necessarily to scale and are exaggerated in illustrating the principles of the invention. FIG. 1 is a schematic diagram illustrating an autoclave thermocompression bonding method using an embodiment of the present invention.

1: Packaging film

2: breathable sheet

3: top plate

4a, 4b: release material

5: Preparing the laminate

6: carrier board

7: Vacuum nozzle

8: Vacuum sealing tape

9: Autoclave

Claims (11)

A method for manufacturing a thermoplastic liquid crystal polymer structure, which is a method of using an autoclave to manufacture a plurality of thermoplastic liquid crystal polymer substructures integrated with a thermoplastic liquid crystal polymer structure, which at least includes: an enclosing step, which will overlap The pre-laminated body of a plurality of thermoplastic liquid crystal polymer substructures is covered with a bagging film, and the end of the bagging film is sealed; the temperature raising step is performed to exhaust the inside of the bagging film, and the temperature is raised to a preparatory The first temperature of the heating temperature; and the step of thermocompression, which takes the first temperature as the starting point, raises the internal pressure of the autoclave to the required pressure below 2.8MPa (gauge pressure), and simultaneously raises the temperature to the pressure required for hot pressing The second temperature of the contact temperature. The method for producing a thermoplastic liquid crystal polymer structure according to claim 1, wherein when the melting point of the thermoplastic liquid crystal polymer element having the lowest melting point among the preliminary laminates is set as ML, the first temperature is (ML-150)°C~( ML-50) °C range. The method for manufacturing a thermoplastic liquid crystal polymer structure according to claim 1 or 2, wherein the holding time at the first temperature is 1 to 120 minutes. The method for producing a thermoplastic liquid crystal polymer structure according to Claim 1 or 2, wherein the temperature increase rate to the first temperature is 1-10°C/min. The method for producing a thermoplastic liquid crystal polymer structure according to claim 1 or 2, wherein when the melting point of the thermoplastic liquid crystal polymer element with the highest melting point among the preliminary laminates is set as MH, the second temperature is (MH-30)°C~ (MH+10)°C range. Manufacture of thermoplastic liquid crystal polymer structure as claimed in item 1 or 2 method, wherein the holding time at the second temperature is 15 to 60 minutes. The method for manufacturing a thermoplastic liquid crystal polymer structure according to claim 1 or 2, wherein the temperature increase rate to the second temperature is 2~20°C/min. The method for manufacturing a thermoplastic liquid crystal polymer structure according to claim 1 or 2, wherein a degassing drying step is performed before the temperature raising step. The production method according to claim 8, wherein the moisture content of the thermoplastic liquid crystal polymer film after the degassing drying step is 380 ppm or less. The method for manufacturing a thermoplastic liquid crystal polymer structure according to claim 8, wherein the holding time at the first temperature is 1 to 20 minutes. The production method according to claim 1 or 2, wherein the moisture content of the thermoplastic liquid crystal polymer element to be heated after the temperature raising step is 380 ppm or less.

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