KR20220005006A - Thermoplastic liquid crystal polymer film, laminate, and molded article, and manufacturing method thereof - Google Patents

Abstract

Provided are a thermoplastic liquid crystal polymer film, a laminate, and a molded article having a wide process window and achieving both high heat resistance and productivity when multilayering a wiring board. The thermoplastic liquid crystal polymer film is a film composed of a thermoplastic polymer capable of forming an optically anisotropic melt phase. , the storage elastic modulus E' of the rubbery flat region at 200 to 280°C is 80 MPa or more.

Description

Thermoplastic liquid crystal polymer film, laminate, and molded article, and manufacturing method thereof

This application claims the priority of Japanese Patent Application No. 2019-082064 for which it applied on April 23, 2019, The whole is taken in as making a part of this application by reference.

The present invention relates to a film, a laminate, and a molded article made of a polymer capable of forming an optically anisotropic melt phase (hereinafter referred to as a thermoplastic liquid crystal polymer) and having excellent heat resistance, and a method for producing the same.

In recent years, from the request|requirement of size reduction and weight reduction of an apparatus in the field of the electronic/electric/communications industry, the necessity of the density increase of a printed wiring board is increasing. Accompanying this, various studies such as multilayering of wiring boards, narrowing of wiring pitches, and miniaturization of via holes are being conducted. For example, a high-density circuit is manufactured by multiplying the metal-clad laminated board which consists of a non-metal layer and a metal layer through a non-metal layer. Conventionally, in printed wiring boards and circuits, thermosetting resins such as phenol resins and epoxy resins are mainly used as non-metal layers and are manufactured by laminating with metal layers such as copper foil. It is known that it takes time.

On the other hand, for the purpose of improving productivity, simultaneous lamination of a plurality of sheets and simultaneous multi-stage manufacturing by means of an apparatus are generally employed. Under such circumstances, a thermoplastic liquid crystal polymer material can be expected to improve productivity by utilizing that it is a thermoplastic resin, and also in terms of physical properties, it has a very low absorption and dielectric loss compared to other materials, making it a high-frequency transmission application as a representative. attracts attention.

The thermoplastic liquid crystal polymer material can be multilayered by thermocompression using thermoplasticity, but on the other hand, heat resistance at the time of multilayering is also required. In other words, even when the laminate is manufactured under the condition that the non-metal layer used for multi-layering is moderately softened and plasticized, and the laminate is firmly in close contact with the metal layer or non-metal layer of the laminate, if the non-metal layer of the laminate has high heat resistance, the process window ( (optimal range of manufacturing conditions) This wide and stable product can be manufactured.

As an example of a stable manufacturing method of a multilayer laminate without the use of an adhesive, Patent Document 1 (Japanese Patent Publication No. 4004139) and Patent Document 2 (Japanese Patent Publication No. 4138995) disclose a thermoplastic liquid crystal polymer film and a metal layer having different melting points. A method for manufacturing a multi-layer laminate of a metal laminate and a non-metal layer comprising

In the method for manufacturing a multilayer substrate proposed in Patent Document 3 (Japanese Patent Publication No. 3893930), a plurality of sheet materials made of a thermoplastic resin are laminated, and the laminated sheet materials are held in a flexible state one by one in a sheet material holder. By heating and pressurizing through a cast material, a multilayer substrate can be manufactured without using the conventional batch type vacuum chamber. Therefore, according to the manufacturing method, compared with the process using the conventional batch type vacuum chamber, production efficiency can be improved significantly.

Regarding the heat resistance of the material itself, Patent Document 4 (Japanese Patent Publication No. 3878741) describes a method of increasing the melting point of a thermoplastic liquid crystal polymer having a melting point of 300° C. or less to 300° C. or more as a heat resistance of the thermoplastic liquid crystal polymer material. has been

Japanese Patent Publication No. 4004139 Japanese Patent Publication No. 4138995 Japanese Patent Publication No. 3893930 Japanese Patent Publication No. 3878741

However, in the multilayer laminates proposed in Patent Documents 1 and 2, it is difficult to widen the process window because of the use of a low-melting-point thermoplastic liquid crystal polymer film. Further, when the melting point of the thermoplastic liquid crystal polymer film is increased, there is a problem in that productivity is insufficient because heat treatment of 4 hours or more in multiple steps is required.

Further, in the method proposed in Patent Document 3, when the laminated sheet material is rapidly heated through a flexible material, the thermoplastic resin causes a hydrolysis reaction, for example, in the case of a thermoplastic liquid crystal polymer or the like, the fluidity of the resin increases and the conductor pattern There is a problem in that the position of the is shifted or voids are generated in the resin film.

Further, also in the method described in Patent Document 4, although it is possible to increase the melting point of the thermoplastic liquid crystal polymer by heating for 4 hours or more in multiple steps, this method has a problem in that productivity is insufficient.

Therefore, in order to widen the process window in performing multilayering using a thermoplastic liquid crystal polymer film, there is a limit to the improvement of equipment and adhesives, and it has not been able to fully satisfy the request for further multilayering. In addition, simply by increasing the melting point, it was not possible to satisfy the market demand, including productivity at the time of manufacturing the thermoplastic liquid crystal polymer film.

Accordingly, it is an object of the present invention to provide a thermoplastic liquid crystal polymer film, a laminate, and a molded article having a wide process window during multilayering, and a method capable of easily manufacturing these films.

As a result of intensive studies to solve the above problems, the present inventors surprisingly found that a rubbery flat region exists in relation to the temperature dependence of the storage elastic modulus obtained by dynamic viscoelasticity measurement, and the storage elastic modulus in the rubbery flat region is surprisingly It was found that the thermoplastic liquid crystal polymer film in which E' is in a specific range has remarkably high heat resistance required for manufacturing a multilayer laminate, and in particular, it is possible to suppress the flow of resin, perhaps because of its specific dynamic viscoelastic properties. came to complete.

That is, the present invention can be configured in the following aspects.

[Aspect 1]

A film composed of a polymer (hereinafter referred to as a thermoplastic liquid crystal polymer) capable of forming an optically anisotropic melt phase, in the profile of the storage modulus obtained by dynamic viscoelasticity measurement, 180 ° C. or higher (preferably 190 ° C. or higher, More preferably, a rubbery flat region exists at a temperature of 200° C. or higher, and the storage modulus E′ of the rubbery flat region at 200 to 280° C. is 80 MPa or more (preferably 100 MPa or more, more preferably is 120 MPa or more), a thermoplastic liquid crystal polymer film.

[Aspect 2]

The thermoplastic liquid crystal polymer film according to aspect 1, wherein the storage elastic modulus at 280°C is 60 MPa or more (preferably 70 MPa or more, more preferably 80 MPa or more).

[Aspect 3]

Using a differential scanning calorimeter, the endothermic peak position that appears when the temperature is raised at a rate of 10 °C/min from room temperature to 400 °C is 310 °C or higher (preferably 315 °C or higher, more preferably 320 °C or higher) Phosphorus, the thermoplastic liquid crystal polymer film according to aspect 1 or 2.

[Aspect 4]

A laminate comprising at least one layer of the thermoplastic liquid crystal polymer film according to any one of aspects 1 to 3.

[Aspect 5]

The laminate according to aspect 4, further comprising at least one metal layer.

[Aspect 6]

Lamination according to aspect 5, wherein the metal layer is composed of at least one selected from copper, copper alloy, aluminum, aluminum alloy, nickel, nickel alloy, iron, iron alloy, silver, silver alloy, and composite metal species thereof. sifter.

[Aspect 7]

A molded article formed of the thermoplastic liquid crystal polymer film according to any one of aspects 1 to 3 or the laminate according to any one of aspects 4 to 6.

[Aspect 8]

The molded object according to aspect 7, which is a wiring board.

[Aspect 9]

The molded object according to aspect 7 or 8, which is a circuit board for high frequency, a sensor for vehicle mounting, a circuit board for mobile, or an antenna.

[Aspect 10]

A thermoplastic liquid crystal polymer composed of a thermoplastic liquid crystal polymer having a melting point rise rate Rtm of 0.20°C/min or more (preferably 0.22°C/min or more, more preferably 0.25°C/min or more, still more preferably 0.26°C/min or more) The method for producing a thermoplastic liquid crystal polymer film according to any one of Aspects 1 to 3, wherein the film (material film) is heat-treated to make it heat-resistant.

[Aspect 11]

When the heat treatment is a heat treatment in one step or a plurality of steps, and the melting point (Tm ₀ ) of the thermoplastic liquid crystal polymer is set to, Tm ₀ °C or less (preferably _{less than Tm 0} °C, more preferably (Tm _0-2 )°C) The method for producing a thermoplastic liquid crystal polymer film according to Aspect 10, wherein the first heat treatment is performed in the following) to make the film resistant to heat.

[Aspect 12]

A method for producing a thermoplastic liquid crystal polymer film according to Aspect 10 or 11, wherein at least one selected from a hot air oven, a steam oven, an electric heater, an infrared heater, a ceramic heater, a heat roll, a heat press, and an electromagnetic wave irradiator is used as the heat source.

[Aspect 13]

The method for producing a thermoplastic liquid crystal polymer film according to any one of aspects 10 to 12, wherein the heat treatment is one step.

[Aspect 14]

A laminate comprising a polymer layer composed of a thermoplastic liquid crystal polymer, wherein the polymer layer has a melting point increase rate Rtm of 0.20°C/min or more (preferably 0.22°C/min or more, more preferably 0.25°C/min or more, still more preferably The method for producing a laminate according to any one of Aspects 4 to 6, wherein the laminate composed of a thermoplastic liquid crystal polymer having a temperature of 0.26° C./min or more) is subjected to heat treatment to make it heat resistant.

[Aspect 15]

When the heat treatment is a heat treatment in one step or a plurality of steps, and the melting point (Tm ₀ ) of the thermoplastic liquid crystal polymer is set to, Tm ₀ °C or less (preferably _{less than Tm 0} °C, more preferably (Tm _0-2 )°C) The method for producing a laminate according to Aspect 14, wherein the first heat treatment is performed in the following) to improve heat resistance.

[Aspect 16]

A method for producing a laminate according to Aspect 14 or 15, wherein at least one selected from a hot air oven, a steam oven, an electric heater, an infrared heater, a ceramic heater, a heat roll, a heat press, and an electromagnetic wave irradiator is used as the heat source.

[Aspect 17]

A method for producing a molded article by subjecting the thermoplastic liquid crystal polymer film according to any one of aspects 1 to 3 and/or the laminate according to any one of aspects 4 to 6 to post-processing.

In the present specification, the melting point increase rate of the thermoplastic liquid crystal polymer refers to a temperature of the thermoplastic liquid crystal polymer film (raw material film) between room temperature (for example, 25° C.) and a predetermined temperature (for example, 400° C.) in differential scanning calorimetry. ) is heated, cooled, and reheated, the temperature at which the endothermic peak appears during reheating is the melting point Tm ₀ of the thermoplastic liquid crystal polymer, and the thermoplastic liquid crystal polymer film is _{heat treated at a temperature of Tm 0} - 10 ° C for 1 hour, and then differential scanning In calorimetry, when the temperature at which the endothermic peak appears when heating from room temperature (for example, 25 ° C.) to a predetermined temperature (for example, 400 ° C.) is Tm', Rtm = (Tm' - Tm ₀ ) This is a value calculated as /60. The temperature change rate (temperature increase rate, temperature fall rate) in the said differential scanning calorimetry measurement may be 10 degreeC/min.

In this specification, a laminate means a structure in which an adherend is laminated with respect to a thermoplastic liquid crystal polymer film, and a molded article means a structure in which a circuit or the like is formed with respect to a thermoplastic liquid crystal polymer film.

Further, any combination of at least two elements disclosed in the claims and/or the specification and/or the drawings is encompassed by the present invention. In particular, any combination of two or more of the claims recited in the claims is encompassed by the present invention.

The thermoplastic liquid crystal polymer film of the present invention has very high heat resistance required for manufacturing a multilayer laminate and has a wide process window during lamination and circuit processing, leading to, for example, simplification of the multilayer lamination process, which has been complicated so far, It is possible to manufacture the laminate at low cost. Moreover, it becomes possible to manufacture an ultra-multilayer laminated board without using special equipment or a jig.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing of the metal-clad laminated board in one aspect of this invention.
Fig. 2 is a cross-sectional view of an assembly in manufacturing a multilayer laminated substrate according to an embodiment of the present invention.
Fig. 3 is a graph showing the profile regarding the temperature dependence of the storage elastic modulus by dynamic viscoelasticity measurement of the film after heat treatment obtained in Example 1 of the present invention.
Fig. 4 is a graph showing the profile regarding the temperature dependence of the storage elastic modulus by dynamic viscoelasticity measurement of the film obtained in Comparative Example 2;
Fig. 5 is a graph showing the profile regarding the temperature dependence of the storage elastic modulus by dynamic viscoelasticity measurement of the film after heat treatment obtained in Comparative Example 4;

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described. In addition, in the following description, although specific examples are shown as a compound which expresses a specific function, this invention is not limited to this. In addition, unless otherwise indicated, the illustrated material may be used independently and may be used in combination.

[Thermoplastic liquid crystal polymer]

The thermoplastic liquid crystal polymer film of the present invention is composed of a thermoplastic liquid crystal polymer. The thermoplastic liquid crystal polymer is composed of a liquid crystal polymer that can be melt molded (or a polymer that can form an optically anisotropic melt phase), and if it is a liquid crystal polymer that can be melt molded, the chemical composition is not particularly limited. , for example, a liquid crystal thermoplastic polyester, or a liquid crystal polyester amide in which an amide bond is introduced thereto.

Further, the thermoplastic liquid crystal polymer may be a polymer in which an isocyanate-derived bond such as an imide bond, a carbonate bond, a carbodiimide bond or an isocyanurate bond is introduced into an aromatic polyester or an aromatic polyesteramide.

Specific examples of the thermoplastic liquid crystal polymer used in the present invention include known thermoplastic liquid crystal polyesters and thermoplastic liquid crystal polyesteramides derived from compounds classified into (1) to (4) and derivatives thereof, which are exemplified below. have. However, in order to form a polymer capable of forming an optically anisotropic melt phase, it goes without saying that there is an appropriate range for the combination of various raw material compounds.

(1) aromatic or aliphatic diol (refer to Table 1 for representative examples)

(2) aromatic or aliphatic dicarboxylic acids (refer to Table 2 for representative examples)

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

(4) aromatic diamine, aromatic hydroxyamine or aromatic aminocarboxylic acid (refer to Table 4 for representative examples)

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

Among these copolymers, copolymers containing at least p-hydroxybenzoic acid and/or 6-hydroxy-2-naphthoic acid as repeating units are preferable, and in particular, (i) p-hydroxybenzoic acid and 6-hydroxy A copolymer comprising a repeating unit of -2-naphthoic acid, or (ii) at least one aromatic hydroxycarboxylic acid selected from the group consisting of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid; The copolymer containing the repeating unit of at least 1 type of aromatic diol and at least 1 type of aromatic dicarboxylic acid is preferable.

When the thermoplastic liquid crystal polymer is a copolymer including repeating units of p-hydroxybenzoic acid (A) and 6-hydroxy-2-naphthoic acid (B), the molar ratio (A)/(B) is (A) /(B) = 10/90 to 90/10 are preferable, 50/50 to 90/10 are more preferable, 75/25 to 90/10 are still more preferable, and 75/25 to 85/15 are still more It is preferable, and 77/23 - 80/20 are especially preferable.

For example, in the case of the copolymer of (i), in addition to the repeating units of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, an aromatic diol or an aromatic dicarboxylic acid (e.g. For example, terephthalic acid) may contain a repeating unit.

Further, in the case of the copolymer of (ii), at least one aromatic hydroxycarboxylic acid selected from the group consisting of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, and 4,4'-dihydroxy acid; At least one aromatic diol selected from the group consisting of cibiphenyl, hydroquinone, phenylhydroquinone, and 4,4'-dihydroxydiphenyl ether, terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid The copolymer containing the repeating unit of at least 1 sort(s) of aromatic dicarboxylic acid selected from the group which consists of may be sufficient.

In addition, that the optically anisotropic molten phase according to this invention can be formed can be recognized by, for example, placing a sample on a hot stage, heating it at elevated temperature in nitrogen atmosphere, and observing the transmitted light of a sample.

The thermoplastic liquid crystal polymer film of the present invention is preferably composed of a thermoplastic liquid crystal polymer having a melting point increase rate Rtm of 0.20° C./min or more, among the above copolymers. More preferably, it is 0.22 degreeC/min or more, More preferably, it is 0.25 degreeC/min or more, More preferably, 0.26 degreeC/min or more may be sufficient. The upper limit of the melting point increase rate Rtm of the thermoplastic liquid crystal polymer is not particularly limited, but may be 1.0°C/min or less.

The melting point rising rate Rtm is calculated as follows. First, using a differential scanning calorimeter, a portion of the thermoplastic liquid crystal polymer film is placed in a sample container, and the temperature is raised from room temperature (eg, 25°C) to 400°C at a rate of 10°C/min, and then to room temperature at 10°C/min. The position of the endothermic peak that appears when cooling at a rate of 1 minute and then raising the temperature from room temperature to 400 °C at a rate of 10 °C/min is defined as the intrinsic melting point of the thermoplastic liquid crystal polymer constituting the thermoplastic liquid crystal polymer film (hereinafter referred to as Tm ₀ ). measured as

Further, after treating the thermoplastic liquid crystal polymer film used for the measurement of _{Tm 0 at Tm 0-10} °C for 60 minutes, a part of the treated thermoplastic liquid crystal polymer film is placed in a sample container, from room temperature to 400°C, 10°C/min. the position of the heat absorption peak appearing when the temperature was raised at a rate of sikyeoteul, Tm ₀ - measured as the melting point Tm 'of the thermotropic liquid crystal polymer film for 60 minutes under 10 ℃ atmosphere. Based on these measured values, the melting point increase rate Rtm (°C/min) of the thermoplastic liquid crystal polymer constituting the thermoplastic liquid crystal polymer film is calculated by the following formula.

Rtm = (Tm' - Tm ₀ )/60

Thermoplastic liquid crystal polymers with a rapid melting point increase rate can provide specific dynamic viscoelastic properties as well as improved heat resistance, perhaps because orthorhombic crystals with high crystal structure uniformity are easily formed by heat treatment.

The thermoplastic liquid crystal polymer preferably has a melting point (Tm ₀ ) of, for example, in the range of 300 to 380°C, more preferably in the range of 305 to 360°C, still more preferably in the range of 310 to 350°C. . In addition, the melting point can be obtained by observing the thermal behavior of the thermoplastic liquid crystal polymer sample as described above using a differential scanning calorimeter.

Further, the thermoplastic liquid crystal polymer may have a melt viscosity of 30 to 120 Pa·s at a shear rate of 1000/s at _{(Tm 0} + 20)°C, for example, from the viewpoint of melt moldability, and preferably melt You may have a viscosity of 50-100 Pa.s.

Polyethylene terephthalate, modified polyethylene terephthalate, polyolefin, polycarbonate, polyarylate, polyamide, polyphenylene sulfide, polyether ether ketone, fluorine You may add thermoplastic polymers, such as resin, and various additives. Moreover, you may add a filler as needed.

[Method for Producing Thermoplastic Liquid Crystal Polymer Film, Laminate or Molded Body]

The thermoplastic liquid crystal polymer film of the present invention can be produced by heat-treating a thermoplastic liquid crystal polymer film (pre-heat-resistant film, material film) composed of a thermoplastic liquid crystal polymer having a melting point rising rate Rtm of 0.20°C/min or more. .

The method for producing the thermoplastic liquid crystal polymer film (film before heat-resistance) is not particularly limited as long as it is composed of a thermoplastic liquid crystal polymer having a specific melting point increase rate Rtm. For example, the thermoplastic liquid crystal polymer is cast-molded to obtain a film Alternatively, a film may be obtained by extrusion molding the melt-kneaded product of the thermoplastic liquid crystal polymer. As the extrusion molding method, any method is used, but well-known T-die method, inflation method, etc. are industrially advantageous. In particular, in the inflation method, stress is applied not only in the machine axial direction (hereinafter, abbreviated to MD direction) of the thermoplastic liquid crystal polymer film but also in a direction orthogonal thereto (hereinafter, abbreviated as TD direction); A thermoplastic liquid crystal polymer film in which molecular orientation, dielectric properties, and the like in the MD and TD directions can be uniformly stretched can be obtained.

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

Further, in extrusion molding by the inflation method, a predetermined draw ratio (corresponding to the draw ratio in the MD direction) and a blow ratio (corresponding to the draw ratio in the TD direction) to the cylindrical sheet melt-extruded from the ring die It may be stretched and formed into a film.

The draw ratio of such extrusion molding, as a draw ratio (or draw ratio) in the MD direction, may be, for example, about 1.0 to 10, preferably about 1.2 to 7, more preferably about 1.3 to 7 . Moreover, as a draw ratio (or blow ratio) of TD direction, it may be, for example, about 1.5-20, Preferably it is about 2-15, More preferably, it may be about 2.5-14.

The thus-obtained thermoplastic liquid crystal polymer film (film before heat-resistance) is heat-treated to make it heat-resistant.

The method of heat treatment is not particularly limited as long as the heat-resistant TLCP film has specific dynamic viscoelastic properties. For example, the heat-resistant TLCP film (film before heat-resistance) may be directly heat-treated by a roll-to-roll or the like, A laminate obtained by laminating the TLCP film (film before heat-resistance) and an adherend may be heat-treated, or the laminate in which a metal layer is directly formed on the TLCP film (film before heat-resistance) by sputtering or plating, etc. is heat-treated You can do it. Although it is possible to manufacture such a laminated body using thermocompression-compression methods, such as a hot press, a hot roller, and a double belt press, it is not specifically limited to this.

As a heat source at the time of heat processing, it is possible to use a well-known or customary heat source. As a preferable heat source, a hot air oven, a steam oven, an electric heater, an infrared heater, a ceramic heater, a heat roll, a heat press, an electromagnetic wave irradiator (for example, microwave irradiation machine, etc.) etc. are mentioned, for example. You may use these heat sources individually or in combination of 2 or more types.

Although heat resistance can be carried out by heat treatment in one step or multiple steps, in the thermoplastic liquid crystal polymer film of the present invention, heat treatment is preferably performed in 1 or 2 steps, and more preferably heat treatment is performed in 1 step. It is preferable to practice

In the one-step or multiple-step heat treatment, for example, as the first heat treatment, when the melting point of the thermoplastic liquid crystal polymer is (Tm ₀ ), Tm ₀ ° C. or less, preferably _{less than Tm 0} ° C., more preferably ( Heat treatment may be performed at Tm ₀ -2)°C or lower. The heating temperature is, preferably, may be at least _{- - (40 Tm 0) ℃} (Tm 0 50) ℃ or more, more preferably. Here, the melting point (Tm ₀ ) of the thermoplastic liquid crystal polymer can be determined by the method for measuring the melting point described above. In the heat treatment of one step, heat resistance is made only by the first heat treatment, and in the heat treatment of a plurality of steps, after the first heat treatment, the heat treatment temperature of the next step may be performed at a higher heating temperature than the heat treatment temperature of the previous step. .

Although the melting point of the thermoplastic liquid crystal polymer film rises with heat treatment, in the present invention, rapid heat resistance is possible, so the heating temperature may be determined based on the _{melting point (Tm 0 ) of the thermoplastic liquid crystal polymer.}

Therefore, the heating temperature after the second heat treatment may _{be carried out above the melting point (Tm 0} ) of the thermoplastic liquid crystal polymer if necessary. For example, the maximum achieved temperature in the heat treatment in multiple steps is (Tm _{0 )} +30) °C or lower, preferably (Tm ₀ +20) °C or lower.

The heating time in each step in the heat treatment can be appropriately set according to the heating temperature, the step of the heat treatment, and the like. In the present invention, since rapid heat resistance is possible, the total heating time may be, for example, about 10 minutes to about 3 hours, and preferably about 10 minutes to about 2 hours (for example, about 30 minutes to about 2 hours). , More preferably, it may be about 10 minutes - about 1.3 hours (for example, about 45 minutes - about 1.3 hours).

It does not specifically limit as a to-be-adhered body as long as it can use as a support body for heat processing, A metal layer, a heat resistant resin layer, etc. are mentioned.

The metal constituting the metal layer is not particularly limited as long as it is a metal having conductivity, and for example, copper, copper alloy, aluminum, aluminum alloy, nickel, nickel alloy, iron, iron alloy, silver, silver alloy, and these Composite metal species, etc. are mentioned. Other metal species may be contained in these metals at 2000 mass ppm or less, and an unavoidable impurity may exist.

When a metal layer is used as the adherend, it is possible to use it as it is as a laminate in which the portion of the thermoplastic liquid crystal polymer film is heat-resistant after heat treatment. For example, if conductivity and heat dissipation are required, copper, copper alloy, silver, or a silver alloy may be used. If ferromagnetism is required, an iron alloy may be used. If inexpensive, aluminum or the like may be used.

Preferably, copper may be used as a metal species for circuit boards, and specifically, 99.8 mass % or more of copper is contained in a metal layer, and silver, tin, zinc, chromium, boron, titanium, magnesium, It may be comprised from copper containing 2000 mass ppm or less of at least 1 sort(s) of other metal species selected from the group which consists of phosphorus, silicon, iron, gold|metal|money, praseodymium, nickel, and cobalt, and remainder unavoidable impurity.

As a method of forming the metal layer on the thermoplastic liquid crystal polymer film, a known method can be used. For example, on the thermoplastic liquid crystal polymer film, a metal layer may be vapor-deposited, and a metal layer may be formed by electroless plating or electrolytic plating. Further, a metal foil (eg, copper foil) may be laminated on the surface of the thermoplastic liquid crystal polymer film by thermocompression bonding. Copper foil will not be specifically limited if it is copper foil which can be used in a circuit board, Any of a rolled copper foil and an electrolytic copper foil may be sufficient.

Examples of the resin constituting the heat-resistant resin layer include a resin or a thermosetting resin having a melting point higher than the maximum attained temperature subjected to heat treatment, preferably polyimide, polyphenylene ether, polyphenylene sulfide, or fluororesin. (For example, polytetrafluoroethylene) etc. are mentioned.

As a method of forming the heat-resistant resin layer on the thermoplastic liquid crystal polymer film, a known method can be used. For example, the heat-resistant resin film may be laminated on the surface of the thermoplastic liquid crystal polymer film by thermocompression bonding.

In the laminate of the thermoplastic liquid crystal polymer film and the metal layer, when the thickness of each single layer is Ta (μm) and Tb (μm), Ta and Tb can be selected in the range of 0.1 to 500 μm, respectively. From a viewpoint of recent thickness reduction and weight reduction, Ta becomes like this. Preferably it is 1-175 micrometers, More preferably, it may be about 5-130 micrometers. Moreover, Tb becomes like this. Preferably it is 1-20 micrometers, More preferably, it may be about 2-15 micrometers.

Further, the laminate has a multilayer structure of a thermoplastic liquid crystal polymer film and a metal layer, and includes at least one layer of the thermoplastic liquid crystal polymer film and at least one metal layer. For example, as a laminate of a multilayer structure,

(i) Metal layer/thermoplastic liquid crystal polymer film

(ii) metal layer/thermoplastic liquid crystal polymer film/metal layer

(iii) Thermoplastic liquid crystal polymer film/thermoplastic liquid crystal polymer film/metal layer

(iv) Thermoplastic liquid crystal polymer film/metal layer/thermoplastic liquid crystal polymer film

(v) metal layer/thermoplastic liquid crystal polymer film/thermoplastic liquid crystal polymer film/metal layer

(vi) metal layer/thermoplastic liquid crystal polymer film/metal layer/thermoplastic liquid crystal polymer film/metal layer

Although those having a laminated structure, such as these, are mentioned, It is not limited to these.

In addition, the thermoplastic liquid crystal polymer film may be used as a laminate as it is in a state in which it is laminated with an adherend, or may be used alone as a thermoplastic liquid crystal polymer film separately from the adherend. Further, the thermoplastic liquid crystal polymer film may be multilayered through an appropriate adhesive layer. As an adhesive layer, polyphenylene ether, an epoxy resin, a polyurethane, a thermoplastic polyimide, polyetherimide etc. are mentioned, for example.

Further, for example, the molded article may be produced by subjecting the thermoplastic liquid crystal polymer film and/or the laminate to post-processing.

For example, a molded article (or unit circuit board) such as a wiring board may be manufactured by forming a conductor pattern on the surface of the thermoplastic liquid crystal polymer film. Moreover, you may manufacture molded objects (or unit circuit boards), such as a wiring board, by forming a conductor pattern with respect to the metal layer of a laminated body.

Moreover, you may manufacture molded objects (or circuit boards), such as a wiring board, by superimposing and multilayering the unit circuit board in which the conductor pattern was formed with respect to other board|substrate material. As a substrate material, the above-mentioned thermoplastic liquid crystal polymer film, a metal layer (metal foil), a unit circuit board, etc. can be illustrated, You may use an adhesive bond layer as needed.

Alternatively, a green body having a polymer layer composed of a thermoplastic liquid crystal polymer, wherein the polymer layer is made of a thermoplastic liquid crystal polymer having a melting point increase rate Rtm of 0.20° C./min or more, is subjected to heat treatment to obtain a molded body do. In that case, the polymer portion of the molded article has a storage modulus E' of the rubbery flat region in a specific range described later.

[Thermoplastic liquid crystal polymer film, laminate and molded article]

In the thermoplastic liquid crystal polymer film, laminate, and molded article of the present invention, whether a specific crystal structure is formed in the thermoplastic liquid crystal polymer by heat treatment, the thermoplastic liquid crystal polymer portion has a profile of storage modulus obtained by dynamic viscoelasticity measurement. , a rubbery flat region exists at a temperature of 180°C or higher, and the storage elastic modulus E′ of the rubbery flat region at 200 to 280°C is 80 MPa or more.

Here, the rubber-like flat region is a region in which the molecular chains of the polymer move but not completely melt, and refers to a region in which the storage modulus does not depend on temperature and takes a substantially constant value. In the present invention, when the absolute value of the slope calculated from the change amount of the storage elastic modulus (MPa) in the temperature range of ± 5°C of the predetermined temperature is 5 MPa/°C or less, the storage elastic modulus at the predetermined temperature is flat considered to belong to the realm. In addition, the case where the rubber-like flat region exists at a temperature within a predetermined range (for example, 180° C. or higher) means that the entire rubber-like flat region falls within the temperature of the predetermined range. The rubber-like flat region may preferably exist at 190°C or higher, and more preferably at 200°C or higher. Moreover, the rubber-like flat region may exist at 350 degrees C or less, Preferably it is 340 degrees C or less, More preferably, it may exist at 330 degrees C or less. Further, a region in which the absolute value of the inclination exceeds 5 MPa/°C on the high temperature side and the storage elastic modulus rapidly decreases is defined as a flow region.

It has been found that the thermoplastic liquid crystal polymer film of the present invention can be imparted with specific dynamic viscoelastic properties by the above-described manufacturing method. Specifically, by heat-treating the thermoplastic liquid crystal polymer film (film before heat resistance), a rubbery flat region can exist in a high temperature region of the storage elastic modulus, and a specific melting point as the thermoplastic liquid crystal polymer constituting the thermoplastic liquid crystal polymer film By using the one having a rising rate, the storage elastic modulus E' of the rubbery flat region can be raised to a specific range. And it was found that such a thermoplastic liquid crystal polymer film can suppress the flow of resin during the production of a laminate.

From a viewpoint of suppressing the flow of resin at the time of laminated body manufacture, the storage elastic modulus E' of the rubbery flat region in 200-280 degreeC becomes like this. Preferably it is 100 MPa or more, More preferably, 120 MPa or more may be sufficient. . Although the upper limit of the storage elastic modulus E' of the rubber-like flat area|region in 200-280 degreeC is not specifically limited, For example, it may be about 1000 Mpa. The storage modulus E' of the rubbery flat region at 200 to 280°C is a value measured by the method described in Examples to be described later, and continues until the rubbery flat region is outside the range of 200 to 280°C. Even when it exists, it is a value measured between 200-280 degreeC.

Moreover, from a viewpoint of suppressing the flow of resin at the time of laminated body manufacture, the storage elastic modulus in 280 degreeC is, for example, 60 MPa or more, Preferably it is 70 MPa or more, More preferably, even if it is 80 MPa or more, do. Although the upper limit of the storage elastic modulus in 280 degreeC is not specifically limited, For example, about 800 Mpa may be sufficient.

In the thermoplastic liquid crystal polymer film of the present invention, from the viewpoint of excellent heat resistance, the end point temperature of the rubbery flat region may be 280°C or higher, preferably 285°C or higher, more preferably 300°C or higher. Although the upper limit of the endpoint temperature of a rubber-like flat region is not specifically limited, For example, it may be about 400 degreeC. In addition, the end point temperature of a rubbery flat region is a value measured by the method described in the Example mentioned later.

Further, in the thermoplastic liquid crystal polymer film of the present invention, the endothermic peak position that appears when the temperature is raised at a rate of 10°C/min in a temperature range of from room temperature (eg, 25°C) to 400°C using a differential scanning calorimeter is thermoplastic. Let it be melting|fusing point (Tm) of a liquid crystal polymer film. For example, the melting point (Tm) of the thermoplastic liquid crystal polymer film may be 310°C or higher, preferably 315°C or higher, and more preferably 320°C or higher. Although the upper limit of melting|fusing point (Tm) is not specifically limited, For example, about 400 degreeC may be sufficient.

Further, in the thermoplastic liquid crystal polymer film, laminate, and molded article of the present invention, a specific crystal structure is generated in the thermoplastic liquid crystal polymer by heat treatment. In , the integrated intensity on the baseline at 2θ = 14 to 26 degrees is A, the profile of the main peak is approximated to a linear function in 2θ = 22.3 to 24.3 degrees and the integrated intensity of the sub-peak profile after removal is B, When B/A x 100 = UC, the following formula (1) may be satisfied, More preferably, the following formula (2) may be satisfied.

0 ≤ UC ≤ 2.0 (One)

0.1 ≤ UC ≤ 1.5 (2)

UC in the present invention can be regarded as an index of the uniformity (crystallinity) of the structure of an orthorhombic crystal. The larger the numerical value, the sharper the diffraction signal of the (200) plane of the orthorhombic crystal. That is, orthorhombic crystals with high crystal structure uniformity are growing significantly. In addition, UC by wide-angle X-ray diffraction measurement is a value measured by the method described in the Example mentioned later.

Even when UC does not exist in a predetermined range, for example, a thermoplastic liquid crystal polymer film having a melting point of 280 to 340°C exists. However, in such a thermoplastic liquid crystal polymer film, since heat resistance is mainly performed not by formation of orthorhombic crystals but by a solid-state polymerization process, heat resistance tends to require extensive heat treatment for a long time.

For example, the thermoplastic liquid crystal polymer film, laminate, and molded article of the present invention are excellent in heat resistance and have a wide process window, so they can be preferably used in various applications.

For example, a laminate including at least one thermoplastic liquid crystal polymer film and at least one metal layer can form a circuit pattern in the metal layer, and is useful as a wiring board. Moreover, since it is possible to satisfy the request|requirement of high density increase and high functionalization when a molded object is equipped with a some circuit layer, a molded object is preferable as a multilayer circuit board.

The thermoplastic liquid crystal polymer film, laminate, and molded article of the present invention have remarkably high heat resistance, and therefore are preferable in applications such as high-frequency circuit boards, in-vehicle sensors, mobile circuit boards, and antennas, but are not limited thereto.

Example

Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited in any way by this Example. In addition, in the following examples and comparative examples, various physical properties were measured by the following method.

(film thickness)

Using a digital thickness meter (manufactured by Mitsutoyo Co., Ltd.), the obtained thermoplastic liquid crystal polymer film was measured at intervals of 1 cm in the TD direction, and the average value of 10 points arbitrarily selected at the center and the end was taken as the film thickness.

(Differential scanning calorimetry)

(Tm)

Using a differential scanning calorimeter (manufactured by Shimadzu Corporation), a predetermined size is sampled from the thermotropic liquid crystal polymer films obtained in Examples and Comparative Examples after heat treatment, and placed in a sample container, from room temperature to 400°C at a rate of 10°C/min. The position of the endothermic peak appearing when the temperature was raised was defined as the melting point Tm of the thermoplastic liquid crystal polymer film.

(Tm ₀ and Rtm)

Using a differential scanning calorimeter (manufactured by Shimadzu Corporation), a predetermined size is sampled from the thermoplastic liquid crystal polymer film (film before heat-resistance), placed in a sample container, and the temperature is raised from room temperature to 400°C at a rate of 10°C/min. , it cooled to 10 ℃ / min to room temperature, the melting point of the thermoplastic liquid crystal polymer to the position of the heat absorption peak appearing when re-sikyeoteul temperature was raised to 10 ℃ / min from room temperature to 400 ℃, constituting the thermoplastic liquid crystal polymer film Tm ₀ was done with

In addition, the thermoplastic liquid crystal polymer film (film before heat-resistance) was processed for 60 minutes in an atmosphere of _{Tm 0-10 degreeC in oven arrangement|positioning.} Using a differential scanning calorimeter, sample a predetermined size from the treated thermoplastic liquid crystal polymer film, put it in a sample container, and determine the position of the endothermic peak that appears when the temperature is raised from room temperature to 400 °C at a rate of 10 °C/min. The melting point Tm' of the thermoplastic liquid crystal polymer film was taken as the melting point rising rate Rtm (°C/min) of the thermoplastic liquid crystal polymer constituting the thermoplastic liquid crystal polymer film was calculated by the following equation.

Rtm = (Tm' - Tm ₀ )/60

(dynamic viscoelasticity measurement)

The thermoplastic liquid crystal polymer film was cut out to a length of 10 mm and a width of 5 mm to prepare a test piece. Using a viscoelasticity measuring device (“DMA242E Artemis” manufactured by NETZSCH), the test piece is mounted on a sample holder, the frequency is 1 Hz, the load is 0.2 N, the measurement mode is the tensile mode, and the temperature range is from room temperature to 350°C. The storage modulus was measured at a temperature increase rate of 5°C/min.

In the obtained storage elastic modulus profile (vertical axis: storage elastic modulus (MPa), horizontal axis: temperature (°C)), the slope was calculated from the amount of change in the storage elastic modulus with respect to the temperature change at every 10°C from 200°C to 280°C. . If the absolute value of the calculated slope is 5 MPa/° C. or less, find the smallest temperature change range, and determine the storage modulus at the central temperature in the temperature change range (for example, 205° C. if 200 to 210° C.) It was calculated as the storage modulus E' of the free flat region. Moreover, the storage elastic modulus in 280 degreeC was computed.

Further, the temperature at the intersection of the tangent of the rubbery flat region existing at a temperature of 180° C. or higher and the tangent of the flow region on the higher temperature side than the rubbery flat region was calculated as the end point temperature of the rubbery flat region.

(Wide-angle X-ray diffraction measurement)

For wide-angle X-ray diffraction measurement, a D8 Discover apparatus manufactured by Bruker AXS was used. The thermoplastic liquid crystal polymer film was cut out to a square of 10 mm and affixed to a standard sample holder. In order to increase the S/N ratio of the data, a plurality of thermoplastic liquid crystal polymer films were superimposed to match the MD directions, and the thickness was adjusted to be about 0.5 mm. The X-ray source was CuKα, the filament voltage was 45 kV, and the current was 110 mA. The collimator used was 0.3 mm.

A standard sample holder was mounted on the apparatus, and the position was adjusted so that X-rays were irradiated from the direction coincident with the normal line of the thermoplastic liquid crystal polymer film. That is, X-rays were irradiated perpendicularly to the surface of the thermoplastic liquid crystal polymer film. The distance between the thermoplastic liquid crystal polymer film and the detector (camera distance) was 100 mm. A two-dimensional PSPC detector was used for the detector, and two-dimensional diffraction images were acquired. The detector was installed behind the sample, and the normal line of the thermoplastic liquid crystal polymer film, the normal line of the detector, and the X-ray irradiation direction were all aligned. The exposure time was 600 seconds.

The obtained two-dimensional diffraction image was subjected to toric averaging and converted into a one-dimensional profile (data 1). The range of the annular average was 10 to 30 degrees in terms of the diffraction angle (2θ). The azimuth angle range was set to 0 to 180 degrees. The step of 2θ was 0.05 degrees. In addition, the azimuth angle of 0 degrees corresponded to the MD direction of the thermoplastic liquid crystal polymer film.

The converted one-dimensional profile (data 1) was subjected to processing such as parasitic scattering using background data (measured data when no sample was mounted) acquired under the same conditions. That is, after one-dimensional profiling of the background data, it was subtracted from the data of the thermoplastic liquid crystal polymer film. This was referred to as data 2.

For the background-processed data 2, a baseline was set and subtracted. The baseline was set as a linear function connecting the intensity values at 14 degrees and 26 degrees with 2θ in the data after background processing. In addition, the intensity values at 14 degrees and 26 degrees were made into the average value (interval of 0.05 degree|times) of the intensity|strength in the range of 13.8-14.2 degrees and 25.8-26.2 degrees, respectively. The linear function described above was subtracted from data 2. This was made into data 3. For data 3, the integral intensity was calculated|required in the range of 14-26 degree|times as diffraction angle 2(theta), and the calculated|required integral intensity was made into A.

In addition, in data 3, a linear function linking intensity values at diffraction angle 2θ at 22.3 degrees and 24.3 degrees was calculated, and the linear function was further subtracted from data 3 . This was referred to as data 4. For data 4, the integral intensity in the range of 2θ of 22.3 to 24.3 degrees was calculated (B). Also, B/A x 100 was calculated (= UC).

(Manufacture of metal clad laminate)

As shown in Fig. 1, the thermoplastic liquid crystal polymer film (1) and the metal foil (2) were overlapped to prepare granules. For the metal foil, CF-H9A-DS-HD2-12 (thickness: 12 µm) manufactured by Fukuda Metal Foil Powder Industry Co., Ltd. was used. In a vacuum press machine manufactured by Kitagawa Seiki Co., Ltd., the granulated body was heated from room temperature (25°C) to 250°C at 6°C/min under vacuum, held for 15 minutes, and then heated to 300°C at 6°C/min. After thermocompression under the conditions of 4 MPa of surface pressure, the temperature was lowered to 250 ° C. at 7 ° C./min after 10 minutes, and after reaching 250 ° C, it was confirmed that the temperature was 50 ° C by rapid cooling, the vacuum was opened, and the thermoplastic liquid crystal polymer film (1) And the metal-clad laminated board 3 provided with the metal foil 2 was manufactured.

(Heat resistance - laminated flow/process window)

The heat resistance by lamination flow was evaluated by observing the shape change of the thermoplastic liquid crystal polymer film at the four corners of the multilayer laminated substrate. As shown in FIG. 2, two metal-clad laminates 3 obtained in FIG. 1 were superimposed on each other so that the thermoplastic liquid crystal polymer films 1 were put together to prepare granules. The SUS plate 4 and the cushioning material 5 were respectively arranged and formed on the upper and lower surfaces of the granulated body, the granules were clamped, and thermocompressed under the conditions of 310° C. and 2 MPa of surface pressure in a vacuum press to prepare a multilayer laminated substrate. Changes in the shape of the thermoplastic liquid crystal polymer film at the four corners of the produced multilayer laminated substrate were visually observed, and evaluated according to the following criteria.

A: Under the lamination conditions, the thermoplastic liquid crystal polymer hardly flowed, and only burrs of 0.7 mm or less were observed from the metal layer.

B: Under the lamination conditions, the thermoplastic liquid crystal polymer hardly flowed, and only burrs larger than 0.7 mm and 1 mm or less were observed from the metal layer.

C: In the lamination condition, burrs larger than 1 mm were observed from the metal layer due to the flow of the thermoplastic liquid crystal polymer.

(Production of thermoplastic liquid crystal polymer)

The method of Example 1 as a representative example of polymerization of a thermoplastic liquid crystal polymer is as follows. p-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, and acetic anhydride are added, and after acetylation (160°C, reflux for about 2 hours), the temperature is raised at 1°C/min and maintained at 340°C, A reduced pressure treatment (1000 Pa) was performed for 60 minutes to perform melt polycondensation.

<Example 1>

(1) A thermotropic liquid crystalline polyester composed of 23 mole parts of 6-hydroxy-2-naphthoic acid units and 77 mole parts of p-hydroxybenzoic acid units is polymerized and extruded from an inflation die to have a thickness of 50 µm A thermoplastic liquid crystal polymer film (film before heat-resistance) was obtained. _{Tm 0} of the thermoplastic liquid crystal polymer constituting the obtained thermoplastic liquid crystal polymer film (film before heat resistance) was 310°C.

(2) The thermoplastic liquid crystal polymer film (film before heat-resistance) obtained above was heat-treated at 280°C for 3 hours. Tm of the obtained thermoplastic liquid crystal polymer film was 317 degreeC.

(3) A metal-clad laminate and a multilayer laminate were manufactured using the thermoplastic liquid crystal polymer film obtained in (2) above. Table 7 shows the results of evaluation of differential scanning calorimetry, dynamic viscoelasticity measurement, wide-angle X-ray diffraction measurement, and lamination flow on the obtained thermoplastic liquid crystal polymer film and multilayer laminated substrate. 3 is a graph showing the temperature dependence of the storage elastic modulus by dynamic viscoelasticity measurement of the thermoplastic liquid crystal polymer film after heat treatment obtained in Example 1, wherein the storage elastic modulus E' is a numerical value of the storage elastic modulus at 245°C. indicates

<Example 2>

(1) Polymerizing a thermotropic liquid crystalline polyester consisting of 20 mole parts of 6-hydroxy-2-naphthoic acid unit, 80 mole parts of p-hydroxybenzoic acid unit, and 1 mole part of terephthalic acid unit, and extrusion molding from an inflation die , a thermoplastic liquid crystal polymer film (film before heat-resistance) having a thickness of 50 µm was obtained. _{Tm 0} of the thermoplastic liquid crystal polymer constituting the obtained thermoplastic liquid crystal polymer film (film before heat resistance) was 320°C.

(2) The thermoplastic liquid crystal polymer film (film before heat-resistance) obtained above was heat-treated at 300°C for 1 hour. Tm of the obtained thermoplastic liquid crystal polymer film was 334 degreeC.

(3) A metal-clad laminate and a multilayer laminate were manufactured using the thermoplastic liquid crystal polymer film obtained in (2) above. Table 7 shows the results of evaluation of differential scanning calorimetry, dynamic viscoelasticity measurement, wide-angle X-ray diffraction measurement, and lamination flow on the obtained thermoplastic liquid crystal polymer film and multilayer laminated substrate. In addition, storage elastic modulus E' shows the numerical value of the storage elastic modulus in 265 degreeC.

<Example 3>

(1) Polymerizing a thermotropic liquid crystalline polyester consisting of 20 mole parts of 6-hydroxy-2-naphthoic acid unit, 80 mole parts of p-hydroxybenzoic acid unit, and 1 mole part of terephthalic acid unit, and extrusion molding from an inflation die , a thermoplastic liquid crystal polymer film (film before heat-resistance) having a thickness of 50 µm was obtained. _{Tm 0} of the thermoplastic liquid crystal polymer constituting the obtained thermoplastic liquid crystal polymer film (film before heat resistance) was 320°C.

(2) The thermoplastic liquid crystal polymer film (film before heat-resistance) obtained above was heat-treated at 310°C for 1 hour. Tm of the obtained thermoplastic liquid crystal polymer film was 347 degreeC.

(3) A metal-clad laminate and a multilayer laminate were manufactured using the thermoplastic liquid crystal polymer film obtained in (2) above. Table 7 shows the results of evaluation of differential scanning calorimetry, dynamic viscoelasticity measurement, wide-angle X-ray diffraction measurement, and lamination flow on the obtained thermoplastic liquid crystal polymer film and multilayer laminated substrate. In addition, storage elastic modulus E' shows the numerical value of the storage elastic modulus in 265 degreeC.

<Comparative Example 1>

(1) Thermotropic liquid crystalline polyester consisting of 27 mol parts of 6-hydroxy-2-naphthoic acid units and 73 mol parts of p-hydroxybenzoic acid units is polymerized, extruded from an inflation die, and a thermoplastic having a thickness of 50 µm A liquid crystal polymer film was obtained. _{Tm 0} of the thermoplastic liquid crystal polymer constituting the obtained thermoplastic liquid crystal polymer film was 280°C.

(2) A metal-clad laminate and a multilayer laminate were manufactured using the thermoplastic liquid crystal polymer film obtained in (1) above. Table 7 shows the results of evaluation of differential scanning calorimetry, dynamic viscoelasticity measurement, wide-angle X-ray diffraction measurement, and lamination flow on the obtained thermoplastic liquid crystal polymer film and multilayer laminated substrate. Further, in the dynamic viscoelasticity measurement, no rubbery flat region of storage modulus was detected at a temperature of 180°C or higher.

<Comparative Example 2>

(1) Thermotropic liquid crystalline polyester consisting of 23 mole parts of 6-hydroxy-2-naphthoic acid units and 77 mole parts of p-hydroxybenzoic acid units is polymerized, extruded from an inflation die, and a thermoplastic having a thickness of 50 µm A liquid crystal polymer film was obtained. _{Tm 0} of the thermoplastic liquid crystal polymer constituting the obtained thermoplastic liquid crystal polymer film was 310°C.

(2) A metal-clad laminate and a multilayer laminate were manufactured using the thermoplastic liquid crystal polymer film obtained in (1) above. Table 7 shows the results of evaluation of differential scanning calorimetry, dynamic viscoelasticity measurement, wide-angle X-ray diffraction measurement, and lamination flow on the obtained thermoplastic liquid crystal polymer film and multilayer laminated substrate. 4 is a graph showing the temperature dependence of the storage elastic modulus by dynamic viscoelasticity measurement of the thermoplastic liquid crystal polymer film obtained in Comparative Example 2. As shown in this figure, the storage elastic modulus at a temperature of 180 ° C. or higher is high. No gratuitous flat regions were detected.

<Comparative example 3>

(1) Thermotropic liquid crystalline polyester consisting of 20 mole parts of 6-hydroxy-2-naphthoic acid units, 80 mole parts of p-hydroxybenzoic acid units, and 1 mole part of terephthalic acid is polymerized and extruded from an inflation die to a thickness A 50-micrometer-thick thermoplastic liquid crystal polymer film was obtained. _{Tm 0} of the thermoplastic liquid crystal polymer constituting the obtained thermoplastic liquid crystal polymer film was 320°C.

(2) A metal-clad laminate and a multilayer laminate were manufactured using the thermoplastic liquid crystal polymer film obtained in (1) above. Table 7 shows the results of evaluation of differential scanning calorimetry, dynamic viscoelasticity measurement, wide-angle X-ray diffraction measurement, and lamination flow on the obtained thermoplastic liquid crystal polymer film and multilayer laminated substrate. Further, in the dynamic viscoelasticity measurement, no rubbery flat region of storage modulus was detected at a temperature of 180°C or higher.

<Comparative example 4>

(1) The material of Comparative Example 1 was heat-treated at 280°C for 3 hours. Tm of the obtained thermoplastic liquid crystal polymer film was 313 degreeC.

(2) A metal-clad laminate and a multilayer laminate were manufactured using the thermoplastic liquid crystal polymer film obtained in (1) above. Table 7 shows the results of evaluation of differential scanning calorimetry, dynamic viscoelasticity measurement, wide-angle X-ray diffraction measurement, and lamination flow on the obtained thermoplastic liquid crystal polymer film and multilayer laminated substrate. 5 is a graph showing the temperature dependence of the storage elastic modulus by dynamic viscoelasticity measurement of the thermoplastic liquid crystal polymer film after heat treatment obtained in Comparative Example 4, wherein the storage elastic modulus E' is a numerical value of the storage elastic modulus at 245°C. indicates

As is clear from Table 7, in the thermoplastic liquid crystal polymer films obtained in Comparative Examples 1 to 3, since the rubbery flat region did not exist, the lamination flow could not be satisfied. Further, in Comparative Example 4, a rubbery flat region was generated by heat treatment. However, when a thermoplastic liquid crystal polymer having a small Rtm is used as in Comparative Example 4, the storage elastic modulus E' of the rubbery flat region cannot be increased. Therefore, the lamination flow could not be satisfied.

On the other hand, in Examples 1 to 3, since the rubbery flat region exists and has a storage elastic modulus E' of the rubbery flat region within a specific range, the lamination flow is satisfied with respect to Comparative Examples 1 to 4. . When a metal-clad laminate having such a film is used, since it has a wide process window at the time of lamination and circuit processing, it is possible to manufacture a laminate at low cost without using special equipment or a jig.

Industrial Applicability

The thermoplastic liquid crystal polymer film and laminate of the present invention are suitable as a material for various molded articles (eg, wiring boards), particularly as a material for multilayer laminated circuits, etc. For example, printed wiring boards in the field of electronics, electricity, and communication industries. It is useful in uses, such as a circuit board for high frequency use, an on-vehicle sensor, a circuit board for mobile, and an antenna.

As described above, preferred embodiments of the present invention have been described, but various additions, changes, or deletions can be made without departing from the spirit of the present invention, and these are also included within the scope of the present invention.

1: Thermoplastic liquid crystal polymer film
2: metal layer (copper foil)
3: Metal clad laminate
4: SUS plate
5: cushion material

Claims (17)

A film composed of a polymer capable of forming an optically anisotropic melt phase (hereinafter referred to as a thermoplastic liquid crystal polymer). and the storage elastic modulus E' of the rubbery flat region at 200 to 280°C is 80 MPa or more. The method of claim 1,
A thermoplastic liquid crystal polymer film having a storage elastic modulus at 280°C of 60 MPa or more. 3. The method according to claim 1 or 2,
A thermoplastic liquid crystal polymer film, wherein an endothermic peak position that appears when the temperature is raised at a rate of 10°C/min from room temperature to 400°C using a differential scanning calorimeter is 310°C or higher. A laminate comprising at least one layer of the thermoplastic liquid crystal polymer film according to any one of claims 1 to 3. 5. The method of claim 4,
Furthermore, the laminated body provided with at least 1 layer of a metal layer. 6. The method of claim 5,
The said metal layer is comprised by at least 1 sort(s) selected from copper, a copper alloy, aluminum, an aluminum alloy, nickel, a nickel alloy, iron, an iron alloy, silver, a silver alloy, and these composite metal types, The laminated body of. A molded article formed from the thermoplastic liquid crystal polymer film according to any one of claims 1 to 3 or the laminate according to any one of claims 4 to 6. 8. The method of claim 7,
A molded body, which is a wiring board. 9. The method according to claim 7 or 8,
The molded object which is a circuit board for high frequency use, an on-vehicle sensor, a circuit board for mobile, or an antenna. The production of the thermoplastic liquid crystal polymer film according to any one of claims 1 to 3, wherein the thermoplastic liquid crystal polymer film made of the thermoplastic liquid crystal polymer having a melting point increase rate Rtm of 0.20° C./min or more is heat-treated to make it heat resistant. Way. 11. The method of claim 10,
The method for producing a thermoplastic liquid crystal polymer film, wherein when the heat treatment is a heat treatment in one step or a plurality of steps, and the melting point (Tm ₀ ) of the _{thermoplastic liquid crystal polymer is set, the first heat treatment is performed at Tm 0° C. or less to heat resistance.} 12. The method of claim 10 or 11,
A method for producing a thermoplastic liquid crystal polymer film, wherein at least one selected from a hot air oven, a steam oven, an electric heater, an infrared heater, a ceramic heater, a heat roll, a heat press, and an electromagnetic wave irradiator is used as the heat source. 13. The method according to any one of claims 10 to 12,
The method for producing a thermoplastic liquid crystal polymer film, wherein the heat treatment is one step. 5. A laminate comprising a polymer layer made of a thermoplastic liquid crystal polymer, wherein the polymer layer is made of a thermoplastic liquid crystal polymer having a melting point increase rate Rtm of 0.20 ° C./min or more, which is subjected to heat treatment to reduce heat resistance. The manufacturing method of the laminated body in any one of Claims -6. 15. The method of claim 14,
Wherein the heat treatment is a heat treatment in one step or a plurality of steps, and when the melting point (Tm ₀ ) of the _{thermoplastic liquid crystal polymer is set, the first heat treatment is performed at Tm 0} ° C. or less to make the laminate heat resistant. 16. The method according to claim 14 or 15,
A method for producing a laminate, wherein at least one selected from a hot air oven, a steam oven, an electric heater, an infrared heater, a ceramic heater, a heat roll, a heat press, and an electromagnetic wave irradiator is used as the heat source. A method for producing a molded article by subjecting the thermoplastic liquid crystal polymer film according to any one of claims 1 to 3 and/or the laminate according to any one of claims 4 to 6 to post-processing.

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