TW202208152A - Thermoplastic liquid crystal polymer molded body - Google Patents

Abstract

Provided is a thermoplastic liquid crystal polymer molded body capable of maintaining adhesion even where stored for a long period of time. The thermoplastic liquid crystal polymer molded body includes an adhesive region on at least a part thereof, and the adhesive region satisfies a ratio Er(S)/Er(I) of 0 or higher and 1.50 or lower, wherein the Er(S) denotes an elastic modulus of a surface layer in an indentation depth of 20 nm and the Er(I) denotes an elastic modulus of an inner layer in an indentation depth of 200 nm, both measured in accordance with nanoindentation method.

Description

Thermoplastic liquid crystal polymer molded body

This application claims the priority of Japanese Patent Application No. 2020-100180 for which it applied on June 9, 2020, The whole is taken in as a part of this application by reference.

The present invention relates to a thermoplastic liquid crystal polymer molded body having excellent adhesiveness.

The thermoplastic liquid crystal polymer molding system is derived from the properties of the thermoplastic liquid crystal polymer, and has excellent dielectric properties (low dielectric constant and low dielectric tangent), and thus attracts attention in applications where dielectric properties are important.

For example, in recent years, along with the speed-up of the transmission signal of a printed wiring board, the high frequency of a signal is progressing. At the same time, substrates used for printed wiring boards are required to have excellent dielectric properties in a high-frequency region. In response to such a demand, as a substrate film for printed wiring boards, instead of conventional polyimide (PI) and polyethylene terephthalate films, thermoplastic liquid crystal polymer films with excellent dielectric properties have received Attention. However, thermoplastic liquid crystal polymer films have inherently low adhesive properties.

For example, in Patent Document 1 (Japanese Patent Application Laid-Open No. 1-216824) and Patent Document 2 (Japanese Patent Application Laid-Open No. 1-236246), as a liquid crystal polymer molded body, it is used for coating, printing, bonding, Surface modification methods such as vapor deposition and plating reveal a surface treatment method for irradiating ultraviolet rays with a wavelength of 184.9 nm. In Patent Documents 1 and 2, by irradiating the surface of the liquid crystal polyester molded body with ultraviolet rays having a wavelength of 184.9 nm, a hydroxyl group or an oxygen-containing group is generated, and the surface of the molded body is activated.

In addition, Patent Document 3 (Japanese Patent No. 4892274) discloses a liquid crystal polymer molded body in which C (Is) The sum of the peak intensities of [-CO-bond] and [-COO-bond] is 21% or more, and the ratio of the peak intensities [-CO-bond]/[-COO-bond] is 1.5 or less . Furthermore, as a method for producing the same, a method for producing a liquid crystal polymer molded body is described, which comprises irradiating a liquid crystal with plasma under the conditions of output: 0.6 W/cm ² or less and pressure: 0.1 Torr or more in an acidic gas atmosphere The step of subjecting at least the adhered portion of the polymer molded body to surface treatment. In this document, the ratio of the functional groups on the surface of the molded body is adjusted by such plasma treatment conditions, and the adhesion strength of the liquid crystal polymer molded body to the epoxy resin is improved. [Prior Art Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 1-216824 Patent Document 2: Japanese Patent Application Laid-Open No. 1-236246 Patent Document 3: Japanese Invention Patent No. 4892274

[The problem to be solved by the invention]

However, in Patent Documents 1 to 3, the surface of the thermoplastic liquid crystal polymer molded body is chemically modified, and in such a surface treatment method, although adhesion immediately after the treatment is imparted, thermal movement and surface contamination occur. The resulting inactivation of the functional group caused the problem that the adhesiveness after being stored for a long period of time in an unattached state could not be ensured. Moreover, in the surface treatment methods described in Patent Documents 1 to 3, since hydrophilic functional groups are imparted to the surface, there are problems such as poor adhesion to the adherend material having a low interaction with the chemical structure of the surface.

Therefore, the objective of this invention is to provide the thermoplastic liquid crystal polymer molded object which can maintain adhesiveness even if it is stored for a long period of time. [means to solve the problem]

The inventors of the present invention focused on the physical properties of the surface of the thermoplastic liquid crystal polymer molded body, rather than the chemical structure of the surface, which is easily affected during long-term storage, as a result of intensive research to achieve the above-mentioned object. Furthermore, it was found that the surface of the thermoplastic liquid crystal polymer molded body can be physically densely modified under the conditions of the plasma treatment. Furthermore, by repeating the detailed analysis of the surface of the thermoplastic liquid crystal polymer molded body by the nano-indentation method, which can analyze the physical properties of the surface in detail, it was found that the ratio of the elastic moduli of the surface layer and the inner layer satisfies a specific relationship. In the liquid crystal polymer molded body, the adhesiveness can be maintained even when stored for a long period of time.

That is, the present invention provides the following suitable forms. [1] A thermoplastic liquid crystal polymer molded body having at least a part of an adhesive region in which the elastic modulus Er (S ) to the elastic modulus Er(I) of the inner layer having an indentation depth of 200 nm (Er(S)/Er(I)) is 0 or more (preferably 0.5 or more, more preferably 0.9 or more, 1.0 or more is especially preferable, 1.1 or more is more preferable) 1.50 or less (1.45 or less is preferable, 1.40 or less is more preferable). [2] The thermoplastic liquid crystal polymer molded body according to [1], wherein the elastic modulus Er(S) of the surface layer is 6.6 GPa or less (preferably 6.0 GPa or less). [3] The thermoplastic liquid crystal polymer molded body according to [1] or [2], which is in the form of a film. [4] The thermoplastic liquid crystal polymer molded body according to any one of [1] to [3], which has a metal portion. [5] The thermoplastic liquid crystal polymer molded body according to any one of [1] to [4], which is provided with a circuit.

In this specification, a thermoplastic liquid crystal polymer molded body means a molded body containing at least a thermoplastic liquid crystal polymer. ) and the formed body (joint body or laminate) after being joined to the material to be joined.

Furthermore, any combination of at least two constituent elements disclosed in the scope of the patent application and/or the specification is also included in the present invention. In particular, any combination of two or more of the claims described in the scope of the patent application is also included in the present invention. [Effect of invention]

According to the thermoplastic liquid crystal polymer molded body of the present invention, by controlling the elastic modulus of the inner layer and the elastic modulus of the surface layer to have a specific relationship, even a long period of time (for example, about 1 to 6 months, preferably 3 ~ About 6 months) can maintain the adhesiveness even when stored. Therefore, the thermoplastic liquid crystal polymer forming system of the present invention is very useful, for example, as an insulator material for electronic circuit substrates when forming metal layers or circuits.

[Form for carrying out the invention]

[thermoplastic liquid crystal polymer] The thermoplastic liquid crystal polymer forming system of the present invention is composed of 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). Specifically limited, for example, thermoplastic liquid crystal polyester, thermoplastic liquid crystal polyester amide into which an amide bond is introduced, and the like can be mentioned.

In addition, the thermoplastic liquid crystal polymer may be a source in which an imide bond, a carbonate bond, a carbodiimide bond, an isocyanurate bond, or the like is further introduced into an aromatic polyester or an aromatic polyester amide. A polymer derived from isocyanate bonds, etc.

Specific examples of the thermoplastic liquid crystalline polymer used in the present invention include well-known thermoplastic liquid crystalline polyesters and thermoplastic liquid crystalline polyester amides derived from compounds classified into (1) to (4) and derivatives thereof exemplified below. amine. However, in order to form a polymer capable of forming an optically anisotropic melt phase, there is of course an appropriate range in the combination of various starting compounds.

(1) Aromatic or aliphatic diols (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]

As a representative example of the thermoplastic liquid crystal polymer obtained from these raw material compounds, the copolymers having the repeating structural units shown in Tables 5 and 6 are mentioned.

[table 5]

[Table 6]

Among these copolymers, polymers containing at least p-hydroxybenzoic acid and/or 6-hydroxy-2-naphthoic acid as repeating units are preferred, and (i) p-hydroxybenzoic acid and 6-hydroxyl are particularly preferred. - a copolymer of repeating units of 2-naphthoic acid, or (ii) comprising: at least one aromatic hydroxycarboxylic acid, at least one aromatic hydroxycarboxylic acid, selected from the group comprising p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid Copolymers of diols and/or aromatic hydroxylamines and repeating units of at least one aromatic dicarboxylic acid.

For example, in the copolymer of (i), when the thermoplastic liquid crystal polymer contains at least the 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 (B) ), the molar ratio (A)/(B) of 6-hydroxy-2-naphthoic acid in the thermoplastic liquid crystal polymer is preferably (A)/(B)=about 10/90～90/10, more It is preferably about (A)/(B)=15/85～85/15, and especially preferable is about (A)/(B)=20/80～80/20.

Also, in the case of the copolymer 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) of the group of dihydroxybiphenyl, hydroquinone, phenylhydroquinone and 4,4'-dihydroxydiphenyl ether, and selected from the group consisting of terephthalic acid, m-phenylene The molar ratio of each repeating unit in the thermoplastic liquid crystal polymer of at least one aromatic dicarboxylic acid (E) of the group of dicarboxylic acid and 2,6-naphthalenedicarboxylic acid may be the aforementioned aromatic hydroxycarboxylic acid (C ): the aforementioned aromatic diol (D): the aforementioned aromatic dicarboxylic acid (E) = (30-80): (35-10): (35-10) or so, more preferably (C): (D ):(E)=(35～75):(32.5～12.5):(32.5～12.5) or so, preferably (C):(D):(E)=(40～70):(30～ 15): (30 to 15) or so.

Moreover, in the aromatic hydroxycarboxylic acid (C), the molar ratio of repeating units derived from 6-hydroxy-2-naphthoic acid may be, for example, 85 mol % or more, preferably 90 mol % or more, More preferably, it can be 95 mol% or more. Among the aromatic dicarboxylic acids (E), the molar ratio of repeating units derived from 2,6-naphthalenedicarboxylic acid may be, for example, 85 mol % or more, preferably 90 mol % or more, more preferably It can be more than 95 mol%.

Also, the aromatic diol (D) may be derived from a mutual bond selected from the group consisting of hydroquinone, 4,4'-dihydroxybiphenyl, phenylhydroquinone, and 4,4'-dihydroxydiphenyl ether Repeating units (D1) and (D2) of different two aromatic diols, at that time, the molar ratio of the two aromatic diols can be (D1)/(D2)=23/77～77/23, preferably It may be 25/75 to 75/25, preferably 30/70 to 70/30.

Moreover, the molar ratio of the repeating unit derived from the aromatic diol (D) and the repeating unit derived from the aromatic dicarboxylic acid (E) is preferably (D)/(E)=95/100 to 100/95. When it deviates from this range, the degree of polymerization does not increase, and the mechanical strength tends to decrease.

In addition, the molten phase which can form an optical anisotropy as used in the present invention can be identified by, for example, placing a sample on a hot stage, heating it under a nitrogen atmosphere, and observing the transmitted light of the sample.

The thermoplastic liquid crystal polymer preferably has a melting point (hereinafter referred to as Tm ₀ ), for example, in the range of ₂₀₀ to 360°C, more preferably in the range of 240 to 350°C, and particularly preferably in the range of 260 to 330°C. Furthermore, the melting point of the thermoplastic liquid crystal polymer can be obtained by observing the thermal behavior of the thermoplastic liquid crystal polymer sample using a differential scanning calorimeter. That is, the thermoplastic liquid crystal polymer sample can be heated at a rate of 10°C/min from room temperature (for example, 25°C) to completely melt, and then the melt can be rapidly cooled to 50°C at a rate of 10°C/min. , and then increase the temperature at a rate of 10°C/min, and record the position of the endothermic peak as the melting point of the thermoplastic liquid crystal polymer sample.

In addition, the thermoplastic liquid crystal polymer may have, for example, a melt viscosity of 30 to 120 Pa·s at a shear rate of 1000/s in (Tm ₀ +20)° C. from the viewpoint of melt moldability, and preferably has a melt viscosity 50～100Pa·s.

In the aforementioned thermoplastic liquid crystal polymer, polyethylene terephthalate, modified polyethylene terephthalate, polyolefin, polycarbonate, polyarylene can be added within the scope of not impairing the effect of the present invention. Thermoplastic polymers such as ester, polyamide, polyphenylene sulfide, polyether ether ketone, fluororesin, and various additives. Moreover, a filler can be added as needed.

[Thermoplastic liquid crystal polymer molded body] The thermoplastic liquid crystal polymer forming system of the present invention has at least a part of a bonding region, in which the elastic modulus Er(S) and the indentation depth of the surface layer measured by the nanoindentation method are in the range of 20 nm. The ratio (Er(S)/Er(I)) of the elastic modulus Er(I) of the inner layer in the range of the depth of 200 nm is in the range of 0 or more and 1.50 or less.

The so-called elastic modulus Er(S) of the surface layer with an indentation depth in the range of 20 nm means that when the surface of the thermoplastic liquid crystal polymer molded body is measured by nanoindentation, the needle is placed under the measurement conditions described in the following examples. The elastic modulus calculated when the tip was inserted from the outermost surface layer of the molded body to a depth of 20 nm was defined as reflecting the state of the extreme surface layer. On the other hand, the elastic modulus Er(I) of the inner layer with an indentation depth in the range of 200 nm is the elastic modulus calculated when the needle tip is inserted from the outermost layer of the molded body to a depth of 200 nm, and is defined as reflecting A state that is more internal than Er(S). Here, the outermost layer means the peripheral surface of the contact point between the tip of the hand and the molded body.

The elastic moduli Er(S) and Er(I) measured by the nanoindentation method can be calculated from the stiffness S and the contact projected area Ac using the following formula (1).

The stiffness S is calculated from the slope of the unloading curve in the load-displacement curve. Furthermore, the aforementioned slope of the unloading curve refers to the slope of the unloading curve at high displacement, that is, the slope of the unloading curve immediately after the start of unloading after the probe is pressed. The contact projected area Ac is the difference between the contact depth (the difference between the surface displacement of the contact point on the peripheral surface obtained from the gradient of the specified indentation depth and the unloading curve under the maximum load) and the geometric shape of the probe. The correction term is obtained by the specified expression.

In general, since the thermoplastic liquid crystal polymer molded body has a highly molecularly aligned skin layer in the extreme surface layer, it is understood that the adhesiveness is poor. With Er(S)/Er(I) in a specific range in the thermoplastic liquid crystal polymer molding system of the present invention, the extreme surface layer easily penetrates into the unevenness of the surface of the adherend during thermocompression bonding, and the anchoring effect is improved. Therefore, it is considered that no matter whether Regardless of the chemical structure, the adhesiveness can be improved physically, and the adhesiveness can be maintained even when stored for a long period of time. When the value of Er(S)/Er(I) is greater than 1.50, the elastic modulus of the surface layer becomes too high compared to the inner layer in the bonding region of the thermoplastic liquid crystal polymer molded body, and the bonding force during thermocompression bonding becomes insufficient. . Er(S)/Er(I) is preferably 1.45 or less, more preferably 1.40 or less. On the other hand, when the elastic modulus of the surface layer of the adhering region of the thermoplastic liquid crystal polymer molded body is low, the molecular alignment on the surface of the molded body is disordered, and the dielectric loss tends to increase, so, for example, Er(S)/Er(I) It is preferably 0.5 or more, more preferably 0.9 or more, still more preferably 1.0 or more, and even more preferably 1.1 or more.

Er(S) is not particularly limited as long as Er(S)/Er(I) is 0 to 1.50, but is preferably 3.0 GPa or more, more preferably 4.0 GPa or more, and particularly preferably 5.0 GPa or more. Moreover, 8.0 GPa or less is preferable, 7.0 GPa or less is more preferable, 6.6 GPa or less is especially preferable, and 6.0 GPa or less is especially preferable.

Er(I) is not particularly limited as long as Er(S)/Er(I) is 0 to 1.50, but is preferably 2.0 GPa or more, more preferably 3.0 GPa or more, and particularly preferably 4.0 GPa or more. Moreover, 7.0 GPa or less is preferable, 6.0 GPa or less is more preferable, and 4.3 GPa or less is especially preferable.

The thermoplastic liquid crystal polymer molded body of the present invention may be composed of at least the thermoplastic liquid crystal polymer, and may be formed by the thermoplastic liquid crystal polymer alone, or may be composed of the thermoplastic liquid crystal polymer and other substances. For example, the thermoplastic liquid crystal polymer molded body of the present invention may further include a conductive portion. The conductive portion may be made of metal, for example, the thermoplastic liquid crystal polymer molded body of the present invention may have a metal portion on the surface (surface of the bonded region and/or surface of the non-bonded region). Here, the so-called non-adjacent region means a region in which Er(S)/Er(I) is not within a specific range. Specifically, the film-like thermoplastic liquid crystal polymer molded body of the present invention (hereinafter referred to as a thermoplastic liquid crystal polymer film) may be a metal-clad laminate (a single-sided metal-clad laminate or a double-sided metal-clad laminate) on which metal foils are laminated. ). In addition, the thermoplastic liquid crystal polymer molded body of the present invention may be a laminate formed by laminating a thermoplastic liquid crystal polymer film layer and a metal layer through an adhesive layer (such as an adhesive), or may be a thermoplastic liquid crystal polymer film layer and a metal layer directly A layered body made of layers.

The metal can be appropriately determined according to the purpose, but copper, nickel, cobalt, aluminum, gold, tin, chromium, etc. are preferably used. The thickness of the metal layer can be 0.01-200 μm, preferably 0.1-100 μm, more preferably 1-80 μm, and particularly preferably 2-50 μm.

When the metal foil is directly laminated as the metal layer, the thickness of the metal foil may be 1-80 μm, preferably 2-50 μm. Further, the surface roughness (Rz) of the metal foil on the side in contact with the thermoplastic liquid crystal polymer molded body may be, for example, 2.0 μm or less, or preferably 1.5 μm or less. The lower limit of the surface roughness (Rz) may be, for example, 0.8 μm. In addition, the surface roughness (Rz) means the maximum height roughness measured with reference to JIS B 0601:2001.

In addition, the thermoplastic liquid crystal polymer molding system of the present invention may be provided with a circuit on the surface (surface of the bonded region and/or surface of the non-bonded region).

In particular, when the thermoplastic liquid crystal polymer molded body of the present invention is in the form of a film, since the thermoplastic liquid crystal polymer itself has excellent dielectric properties and low hygroscopicity, and the adhesion to adhesives or other materials is improved, it is particularly useful as a circuit Substrate materials (for example, insulators for electronic circuit boards, reinforcing plates for flexible circuit boards, cover films for circuit surfaces, etc.). Furthermore, on the thermoplastic liquid crystal polymer film, a laminate with a metal layer (such as a metal-clad laminate) or a circuit substrate with a circuit formed thereon, due to the improved adhesion between the thermoplastic liquid crystal polymer film and the metal layer or circuit, and Reliable and affordable.

[Production method of thermoplastic liquid crystal polymer molded body] The method for producing a thermoplastic liquid crystal polymer molded body of the present invention includes a surface treatment step of performing plasma treatment on at least a part of the surface of the thermoplastic liquid crystal polymer molded body. By adjusting the plasma treatment conditions described later, the surface layer can be adjusted. The ratio of the elastic modulus Er(S) to the elastic modulus Er(I) of the inner layer (Er(S)/Er(I)). In order to adjust the ratio of the elastic modulus of the surface layer to the elastic modulus of the inner layer on the surface of the thermoplastic liquid crystal polymer molded body, it is particularly preferable to set plasma treatment conditions such as gas species, pressure, and output. The thermoplastic liquid crystal polymer molding system to be subjected to the plasma treatment is not particularly limited, but for example, at least a part of the surface of the thermoplastic liquid crystal polymer molded body may be subjected to physical polishing treatment, corona discharge treatment, ultraviolet irradiation treatment, and Thermoplastic liquid crystal polymer moldings, such as forming treatment of peeling off the roughened metal foil by heating and pressing, lamination and peeling, copper foil replication treatment of etching and removing copper foil after lamination of copper foil, surface treatment by corrosive solution, etc. , plasma treatment is performed, and plasma treatment can also be performed for the thermoplastic liquid crystal polymer molded body that has not undergone the aforementioned surface treatment.

The gas species in the plasma treatment is preferably selected from the group consisting of N ₂ , Ar, H ₂ O and CF ₄ from the viewpoint of adjusting the ratio of the elastic modulus of the surface layer to the elastic modulus of the inner layer at least one of. N ₂ , Ar and H ₂ O systems have strong etching properties due to the ion bombardment effect in the reaction during plasma treatment, and CF ₄ systems can generate highly reactive F radicals and perform etching. It is considered that when these gas species are used, when the surface of the thermoplastic liquid crystal polymer molded body is subjected to plasma treatment, electrons, ions, and free radicals directly collide with the surface to selectively cut the bonds possessed by the thermoplastic liquid crystal polymer molecules. Since the surface can be densely roughened, the elastic modulus of the surface layer can be lowered, and the relationship between the surface layer and the inner layer can be adjusted to a specific elastic modulus. On the other hand, it is considered that when O ₂ is used as the gas species, the entire surface is etched because the bonds of the thermoplastic liquid crystal polymer molecules are cut regardless of the bonds possessed by the molecules, so that it is difficult to adjust the specific elasticity in the surface layer and the inner layer. Modulus relationship. The gas species used in the plasma treatment is more preferably N ₂ in that the surface roughness of the thermoplastic liquid crystal polymer molded body is high. Moreover, in the range which does not impair the effect of this invention, you may mix and use gas species (for example, O ₂ etc.) other than the above-mentioned gas species.

The plasma treatment is preferably vacuum plasma treatment from the viewpoint of adjusting the ratio of the elastic modulus of the surface layer to the elastic modulus of the inner layer on the surface of the thermoplastic liquid crystal polymer molded body. When the degree of vacuum increases, the plasma generation efficiency becomes good, the plasma reacts with the gas, and the effect of the gas plasma etching the polymer surface becomes high. In the vacuum plasma treatment, the pressure in the treatment apparatus is preferably 0.1 to 50 Pa, from the viewpoint of making the density of generated electrons and ions within the range to sufficiently modify the surface of the thermoplastic liquid crystal polymer molded body. It is preferably 0.3 to 30 Pa, and more preferably 0.5 to 15 Pa.

The output in the plasma treatment is preferably 3.5 W/cm ² or more from the viewpoint of adjusting the ratio of the elastic modulus of the surface layer to the elastic modulus of the inner layer on the surface of the thermoplastic liquid crystal polymer molded body, More preferably, it is 5.0 W/cm ² or more, and even more preferably 6.0 W/cm ² or more. By increasing the output in plasma processing, more active species of gas species such as electrons, ions, and radicals can be generated, and their density or temperature can be increased, thereby maximizing the effect of a specific gas species. The upper limit of the output in the plasma treatment is not particularly limited, but it is preferable to perform a stronger treatment. For example, from the viewpoint of suppressing excessive damage on the surface of the thermoplastic liquid crystal polymer molded body, it may be 30 W/cm ² or less, preferably 25 W/cm ² or less, and more preferably 20 W/cm ² or less.

By increasing the output in the plasma treatment, the time required for the plasma treatment of the thermoplastic liquid crystal polymer molded body can be shortened. Specifically, the plasma treatment time may be 180 seconds or less, preferably 60 seconds or less, and more preferably 5 seconds or less. The lower limit of the plasma treatment time is not particularly limited, but for example, from the viewpoint of sufficiently modifying the surface of the thermoplastic liquid crystal polymer molded body, it can be 0.1 second or more, preferably 0.5 second or more, more preferably 1.0 seconds or more. Also, the time for plasma treatment refers to the time for performing plasma irradiation on the same part of the thermoplastic liquid crystal polymer molded body.

In the method for producing the thermoplastic liquid crystal polymer molded body of the present invention, in the plasma treatment, the frequency of discharge between the discharge electrodes is not particularly limited, but for example, it can be in the range of 40 kHz to 2.45 GHz, preferably 40kHz～915MHz, preferably 110kHz～13.56MHz.

As plasma treatment, among those using AC power, there are (i) capacitively coupled plasma (CCP method), and (ii) inductively coupled plasma (ICP method) that uses a coil to apply an induced electric field caused by a change in magnetic flux ). CCP is a generally used plasma generation method, and a substrate to be treated is provided between a pair of electrodes, and the substrate to be treated can be treated with plasma. On the other hand, since the ICP generates plasma by the fluctuating magnetic field of the induction coil, the potential difference between the electrode and the plasma does not increase, and the controllability of the plasma treatment is high. In addition, generally speaking, a high-frequency power supply is used, and the processing capability is high. In addition, in recent years, capacitively coupled plasma (CCP), inductively coupled plasma (ICP), electron cyclotron resonance plasma (ECP), helical excited plasma (HWP), and microwave excited surface wave plasma (SWP) have been developed. The treatment method for high frequency power supply is considered to be more effective. However, in the present invention, the processing method and the power supply frequency can be selected within the range in which the relationship between the surface layer and the inner layer can be adjusted to a specific elastic modulus, and is not particularly limited.

Furthermore, in the method for producing the thermoplastic liquid crystal polymer molded body of the present invention, (i) capacitively coupled plasma (CCP), which is a general plasma treatment method, can be used. In the examples to be described later, using CCP, in an environment in which gas species is introduced, power is supplied between the electrodes of a pair of discharge parallel plates to generate plasma discharge, and the surface of the thermoplastic liquid crystal polymer molded body is affected. At least a part is subjected to plasma irradiation.

Plasma treatment may be a discharge method in which a voltage of a continuous waveform (AC waveform) is applied, or a discharge method in which a voltage of a pulse waveform is applied. From the viewpoint of stabilizing the discharge, a discharge method in which a voltage of a pulse-shaped waveform is applied is preferable. In this case, the surface modification effect can be uniformly obtained even in a short-time treatment.

Other conditions in the plasma treatment may be appropriately adjusted. For example, the distance between the irradiation head of the plasma processing apparatus and the surface of the thermoplastic liquid crystal polymer formed body (eg, head-film distance) may be 3-50 mm, preferably 4-30 mm, more preferably 5-25 mm.

In the method for producing the thermoplastic liquid crystal polymer molded body of the present invention, the surface treatment can be carried out continuously or batchwise. In order to shorten the time of the plasma treatment, it is preferable to perform it continuously from the viewpoint of productivity.

In particular, when the thermoplastic liquid crystal polymer molded body is capable of being rolled, it can be continuously processed by roll-to-roll, and a plasma continuum in which unwinding and winding of the molded body are provided inside can be used. A processing device, or a plasma continuous processing device that installs the unwinding and winding of the formed body outside.

When the roll-to-roll plasma treatment of the rollable thermoplastic liquid crystal polymer molded body is performed, the conveying speed of the molded body may be about 0.1 to 10 m/min, preferably from the viewpoint of productivity and processing time. About 0.2 to 8.0 m/min, more preferably 0.3 to 5.0 m/min.

Moreover, the shape of the thermoplastic liquid crystal polymer molded body of the present invention is not particularly limited, for example, it may be a shape that can be formed by casting molding of a thermoplastic liquid crystal polymer, or a shape that can be formed by injection molding or extrusion molding. formed shape. The thermoplastic liquid crystal polymer molded body is preferably in a shape of a film, a sheet, a fiber, a cloth, or the like, and more preferably a film.

The thermoplastic liquid crystal polymer film can also be obtained by extruding the above thermoplastic liquid crystal polymer. In this case, any extrusion molding method can be used, but the well-known T-die film stretching method, laminate stretching method, and inflation method are industrially advantageous. For example, the thickness of the thermoplastic liquid crystal polymer film may be 10-500 μm, preferably 20-200 μm, and more preferably 25-125 μm. In particular, when a thermoplastic liquid crystal polymer film is used as an electronic circuit substrate material, the thickness is preferably in the range of 20 to 150 μm, more preferably in the range of 20 to 100 μm.

[the attached material] The thermoplastic liquid crystal polymer molding system of the present invention has high adhesiveness with the material to be adhered, and can maintain the adhesiveness even when stored for a long period of time. The material to be bonded is not particularly limited as long as it can be directly bonded to the bonded portion of the thermoplastic liquid crystal polymer molded body, and can be appropriately selected according to the purpose. For example, as an adherend material, an adhesive agent (preferably an adhesive agent sheet), a thermoplastic liquid crystal polymer adherend (preferably a thermoplastic liquid crystal polymer film), etc. are mentioned. Furthermore, for the adhered material (for example, a thermoplastic liquid crystal polymer adherend), it can also be processed in a manner that the elastic modulus in the above-mentioned inner layer and surface layer has a specific relationship as required.

As an adhesive agent, polar adhesive agents, such as an epoxy adhesive agent and an acrylic adhesive agent, may be sufficient, and the nonpolar adhesive agent which contains a nonpolar skeleton in a part may be sufficient as it.

Examples of polar adhesives include urea resin adhesives, melamine resin adhesives, phenol resin adhesives, vinyl acetate resin adhesives, isocyanate adhesives, epoxy adhesives, and unsaturated polyesters. Adhesives, cyanoacrylate-based adhesives, polyurethane-based adhesives, acrylic resin-based adhesives, and the like.

Examples of the nonpolar adhesive include known adhesives (for example, urea resin-based adhesives, melamine resin-based adhesives, phenol resin-based adhesives, vinyl acetate resin-based adhesives, isocyanate-based adhesives, cyclic adhesives, etc.) Oxygen-based adhesives, unsaturated polyester-based adhesives, cyanoacrylate-based adhesives, polyurethane-based adhesives, acrylic resin-based adhesives, etc.), mixed with non-polar skeleton-based polymerization The adhesive composition of the above-mentioned adhesive agent, and the adhesive composition of the non-polar skeleton introduced into the chemical structure of the main component polymer of the adhesive agent, etc.

When a thermoplastic liquid crystal polymer film is used as an electronic circuit substrate material, the dielectric properties of the adhesive are preferably 3.3 or less and 0.05 or less in dielectric tangent (tanδ) at a frequency of 10 GHz. In particular, when the entire substrate is required to have low dielectric properties, an adhesive having low dielectric properties (low-dielectric adhesive) is preferred. For the adhesive having low dielectric properties, for example, the specific permittivity (ε) at a frequency of 10 GHz is preferably 3.3 or less, and the dielectric tangent (tanδ) is preferably 0.04 or less, more preferably 0.03 or less.

Preferable low-dielectric adhesives include, for example, adhesive compositions containing olefin skeletons (for example, adhesive compositions containing at least crystalline acid-modified polyolefin and epoxy resin, modified olefin skeleton-containing adhesive compositions, etc.) Polyamide adhesive composition, adhesive composition using aromatic olefin oligomer type modifier and epoxy resin, etc.), adhesive composition containing polyphenylene ether skeleton, etc.

For example, as an adhesive composition containing at least a crystalline acid-modified polyolefin and an epoxy resin, the adhesive described in International Publication No. WO 2016/031342, etc. can be mentioned, as an olefin skeleton-containing modified polyamide adhesive As the adhesive composition, the adhesives described in JP-A No. 2007-284515 can be mentioned, and as the adhesive composition using the aromatic olefin oligomer type modifier and epoxy resin, Japanese Laid-Open Patent Application The adhesive agent etc. described in Gazette 2007-63306, as an adhesive agent composition containing a polyphenylene ether skeleton, the adhesive layer etc. which are described in International Publication No. WO 2014/046014 can be mentioned. Among these adhesives, for example, from the viewpoint of dielectric properties, an adhesive composition containing at least a crystalline acid-modified polyolefin and an epoxy resin is more preferably 5 mass % or more of the adhesive. The aforementioned crystalline acid-modified polyolefin.

The adhesive may be an adhesive sheet, or may be a thermoplastic liquid crystal polymer molded body coated with an adhesive composition and dried. The thickness of the subsequent layer can be 1-50 μm, preferably 5-40 μm, and more preferably 10-30 μm.

The thermoplastic liquid crystalline polymer to-be-adhered body may be composed of at least the above-mentioned thermoplastic liquid crystalline polymer, and may have the same components as the thermoplastic liquid crystalline polymer molded body, or may have different components.

In addition, the thermoplastic liquid crystal polymer to be adhered can be surface-treated in such a manner that the elastic modulus of the inner layer and the surface layer has a specific relationship, or not. At least a part of the adherend and the adhered region of the thermoplastic liquid crystal polymer molded body are surface-treated in such a manner that the elastic modulus in the above-mentioned inner layer and surface layer has a specific relationship. At that time, in the thermoplastic liquid crystal polymer adherend, the elastic modulus Er(S) of the surface layer and the elastic modulus Er(I(I) of the inner layer were measured by the nanoindentation method as in the thermoplastic liquid crystal polymer molded body. ) ratio (Er(S)/Er(I)) may range from 0 to 1.50.

When bonding thermoplastic liquid crystal polymer films of the same composition or different compositions, it is preferable that the respective thermoplastic liquid crystal polymer films have a surface treated so that the elastic modulus of the inner layer and the surface layer has a specific relationship. face each other for thermocompression bonding.

The bonding strength between the liquid crystal polymer surface and the bonded material in the bonding region of the thermoplastic liquid crystal polymer molded body may be 0.6 N/mm or more, preferably 0.7 N/mm or more, and more preferably 0.8 N/mm or more. In addition, the adhesive strength was evaluated by the adhesive strength measured by the method described in the Example mentioned later.

In addition, the thermoplastic liquid crystal polymer molding system of the present invention can maintain adhesive strength even after long-term storage. For example, the ratio of the adhesive strength immediately after the above-mentioned surface treatment (the adhesive strength immediately after the treatment) to the adhesive strength after storage for 6 months (the adhesive strength after storage) (the adhesive strength after storage) /adhesion strength immediately after treatment) may be 70% or more, preferably 80% or more, and more preferably 90% or more. [Example]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by these examples at all. Furthermore, each evaluation method of the surface-treated thermoplastic liquid crystal polymer film employed in the following Examples and Comparative Examples is shown below.

(1) Nanoindentation determination of SPM ＜Sample adjustment＞ The thermoplastic liquid crystal polymer film or single-sided metal-clad laminate (adhesive material) produced in the examples and comparative examples was cut into a size of 5mm × 5mm, and the plasma-treated film was passed through double-sided tape. The surface was used as the measurement surface, fixed on the measurement stand, and the elastic modulus calculated when the needle tip was inserted from the outermost surface layer of the molded body to a depth of 20 nm was regarded as Er(S) under the following apparatus and measurement conditions. The elastic modulus calculated when the outermost layer of the film was inserted to a depth of 200 nm was regarded as Er(I). From the load-displacement curve of the indentation depth, the elastic modulus was obtained by the analysis software attached to the following device. In addition, in order to exclude the inconsistency of the measurement location, 10 arbitrary points were sampled, and the average value was used as the analysis result. <SPM measurement conditions> Measuring device: Multifunctional SPM device (manufactured by Hitachi High-Tech Co., Ltd.) Analysis software: Analysis software attached to the device Measurement temperature: 23℃ Determination of relative humidity: 40% Nanoindentation device: Triboscope (manufactured by HYISTRON) Measuring needle shape: diamond indenter (Berkovich type) Measuring needle tip diameter: 150nm Set load: Er(S): 10μN, push in for 3 seconds, pull out for 3 seconds (indentation depth about 20nm) Er(I): 300μN, press in for 3 seconds, pull out for 3 seconds (pressing depth is about 200nm)

(2) Adhesion strength The laminated body of the thermoplastic liquid crystal polymer film or the single-sided metal-clad laminate (adhesive material) and the material to be adhered immediately after the treatment produced in the Examples and Comparative Examples was used as a sample for evaluation. In addition, as an evaluation of the adhesiveness after long-term storage, the treated adhesive was kept in a constant temperature chamber for 6 months under the conditions of temperature: 25°C, humidity: 40%, and then a laminate of the adhesive material was produced. The laminate was used as a sample for evaluation. A release test piece with a width of 1.0 cm was prepared from the laminated body of the sample for evaluation, and the adhesive material side was fixed to a flat plate with a double-sided adhesive tape. According to JIS C 6471:1995, it was measured by the 90° method at 50 mm/min. Velocity Strength (N/mm) when peeling occurs at the interface between the adhered material and the plasma-treated thermoplastic liquid crystal polymer film side of the adherent material.

[Reference Example 1] A thermoplastic liquid crystal polymer of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid with a melting point of 280°C, melt extruded at a discharge rate of 20kg/hour, with a horizontal stretch ratio of 4.77 times and a vertical stretch ratio of 2.09 times Under the same conditions, the film was blown into a film to obtain a thermoplastic liquid crystal polymer film with an average film thickness of 50 μm. An aluminum foil was laminated on one side of the obtained film, hung down in a hot air oven, heat-treated at 310° C. for 10 minutes, and after cooling, the aluminum foil was dissolved and removed with an aqueous solution of ferric chloride to obtain a thermoplastic liquid crystal polymer film.

[Examples 1 to 3] The long thermoplastic liquid crystal polymer film obtained in Reference Example 1 was placed in a continuous plasma device equipped with film unwinding and winding inside a vacuum chamber to pass between parallel plate electrodes (electrodes). The area is 5cm×60cm, and the distance between the head and the film is 20mm). After the vacuum chamber was evacuated to 2 Pa by a vacuum pump, N ₂ gas was introduced at the gas flow rate shown in Table 7, and the pressure was adjusted to the pressure shown in Table 7. Next, with the output of the power supply: 2 kW, and the frequency: 110 kHz, plasma was generated in the electrodes. The conveyance speed was set so that the treatment time was as shown in Table 7, and plasma treatment was continuously performed on one surface of the thermoplastic liquid crystal polymer film. The output per unit area (W/cm ² ) shown in Table 7 was calculated from the area of the electrode and the output of the power supply. Er(S) and Er(I) were measured by SPM on the surface of the plasma-treated single-sided metal-clad laminate. The results are shown in Table 7. Then, cut out two plasma-treated thermoplastic liquid crystal polymer films, and superimpose the plasma-treated surfaces of the two film sheets as the adhered surfaces, and put them together under the conditions of 300°C and 4MPa. The pressure was applied for 10 minutes to prepare a laminate of thermoplastic liquid crystal polymer films. The adhesive strength of this layered body was measured and regarded as the adhesive strength immediately after the treatment. In addition, after the plasma-treated single-sided metal-clad laminate was stored in a constant temperature room for 6 months (temperature 25°C, humidity 40%), two thin films were cut out, and the two thin film sheets were electrically energized. After the paste-treated surfaces were superimposed as to-be-adhered surfaces, they were pressurized under the conditions of 300° C. and 4 MPa for 10 minutes to produce a laminate of thermoplastic liquid crystal polymer films. The adhesive strength of this laminate was measured, and it was regarded as the adhesive strength after storage for 6 months.

[Example 4] The long thermoplastic liquid crystal polymer film obtained in Reference Example 1 and the long copper foil (manufactured by Futian Metal Foil Powder Co., Ltd., "CF-H9A-DS-HD2", thickness 12 μm, surface roughness Rz 1.2 μm), these were introduced continuously between heating rolls, and pressure-bonded and laminated at 270° C. and 3 MPa to produce a single-sided metal-clad laminate. This single-sided metal-clad laminate was placed in a continuous plasma device with film unwinding and winding inside the vacuum chamber, so as to pass between parallel plate electrodes (electrode area 5cm×60cm, head-film distance 20mm). mode setting. After the vacuum chamber was evacuated to 2 Pa by a vacuum pump, N ₂ gas was introduced at the gas flow rate shown in Table 7, and the pressure was adjusted to the pressure shown in Table 7. Next, with the output of the power supply: 2 kW, and the frequency: 110 kHz, plasma was generated in the electrodes. The conveying speed was set so that the treatment time was as shown in Table 7, and the plasma treatment was continuously performed on the surface on the thermoplastic liquid crystal polymer film side of the single-sided metal-clad laminate. The output per unit area (W/cm ² ) shown in Table 7 was calculated from the area of the electrode and the output of the power supply. For the surface of the thermoplastic liquid crystal polymer film side of the plasma-treated single-sided metal-clad laminate, Er(S) and Er(I) were measured by SPM. The results are shown in Table 7. Then, two sheets of the plasma-treated single-sided metal-clad laminate were cut out, and the plasma-treated thermoplastic liquid crystal polymer film side of the two cut sheets of the single-sided metal-clad laminate was cut out. After the surfaces were laminated as to-be-adhered surfaces, pressure was applied at 300°C and 4 MPa for 10 minutes to produce a laminate in which two single-sided metal-clad laminates were laminated on the film side of each other. The bonding strength of the interface portion between the thermoplastic liquid crystal polymer film surfaces of this laminate was measured and regarded as the bonding strength immediately after the treatment. In addition, after the plasma-treated single-sided metal-clad laminate was stored in a constant temperature room for 6 months (temperature 25°C, humidity 40%), two pieces were cut out, and two pieces of the single-sided metal-clad laminate were cut. In the filming process, the surfaces on the side of the thermoplastic liquid crystal polymer film that have been subjected to the plasma treatment are respectively laminated as the adhered surfaces, and then pressurized for 10 minutes under the conditions of 300°C and 4MPa to make two single-sided metal-coated sheets. The laminate is a laminate formed by stacking the film surfaces of each other. The adhesive strength of the interface portion between the thermoplastic liquid crystal polymer film surfaces of this laminate was measured and regarded as the adhesive strength after storage for 6 months.

[Example 5] The long thermoplastic liquid crystal polymer film obtained in Reference Example 1 and the long copper foil (manufactured by Futian Metal Foil Powder Co., Ltd., "CF-H9A-DS-HD2", thickness 12 μm, surface roughness Rz 1.2 μm ) and a long strip of PCM foil (manufactured by JX Metal Co., Ltd., "PCM", thickness 18μm, surface roughness Rz4.5μm, peelable copper foil) to become a copper foil/thermoplastic liquid crystal polymer film/PCM foil. After the layers were continuously pressed and laminated at 270°C and 3MPa between heating rollers, only the PCM foil was peeled off to obtain a single-sided laminate with the surface of the thermoplastic liquid crystal polymer film with the roughened surface of the PCM foil transferred. Metal laminate. The surface of the thermoplastic liquid crystal polymer film transferred on the roughened surface was subjected to plasma treatment under the same conditions as in Example 4 to obtain a single-sided metal-clad laminate as an adhesive material. Er(S) and Er(I) were measured by SPM on the surface of the thermoplastic liquid crystal polymer film side to which the roughened surface of the PCM foil of the single-sided metal-clad laminate was transferred and plasma-treated as an adhesive material. The results are shown in Table 7. Then, the plasma-treated roughened surface and the plasma-treated surface of the single-sided metal-clad laminate produced in Example 4 were superimposed, and then pressurized under the conditions of 300° C. and 4 MPa for 10 minutes to prepare a 2 A laminate in which single-sided metal-clad laminates of sheets are stacked on the film side of each other. The adhesive strength of the interface portion between the thermoplastic liquid crystal polymer film surfaces of this laminate was measured and regarded as the adhesive strength immediately after the treatment. In addition, these single-sided metal-clad laminates were stored in a constant temperature room for 6 months (temperature 25° C., humidity 40%), and then the plasma-treated roughened surfaces were compared with the single-sided surfaces prepared in Example 4. After the plasma-treated surfaces of the metal-clad laminates were superimposed, pressurized for 10 minutes at 300°C and 4 MPa to produce a laminate in which two single-sided metal-clad laminates were superimposed on the film side of each other. . The adhesive strength of the interface portion between the thermoplastic liquid crystal polymer film surfaces of this laminate was measured and regarded as the adhesive strength after storage for 6 months.

[Example 6] The long thermoplastic liquid crystal polymer film obtained in Reference Example 1 and the long copper foil (manufactured by Futian Metal Foil Powder Co., Ltd., "CF-H9A-DS-HD2", thickness 12 μm, surface roughness Rz 1.2 μm ) and a long protective sheet made of polyimide, overlapped so as to form a copper foil/thermoplastic liquid crystal polymer film/copper foil/protective sheet made of polyimide, and these were continuously introduced between heating rollers to 300°C and 3MPa were crimped and laminated to produce a double-sided metal-clad laminate with a protective sheet attached to one side. Then, while conveying the double-sided metal-clad laminate, one surface of the double-sided metal-clad laminate was etched with a 35% ferric chloride aqueous solution (manufactured by Sunhayato Co., Ltd.) heated to 40° C. using a shower-type etching apparatus. (non-protective surface) copper foil. Then, after drying at room temperature, the protective sheet was peeled off to prepare a single-sided metal-clad laminate having a transfer surface (roughened surface) of the thermoplastic liquid crystal polymer film. Plasma treatment was performed on this transfer surface under the same conditions as in Example 4 to obtain a single-sided metal-clad laminate as an adhesive material. Er(S) and Er(I) were measured by SPM on the replication side of the plasma-treated thermoplastic liquid crystal polymer film of the single-sided metal-clad laminate as the adhesive material. The results are shown in Table 7. Then, the plasma-treated replication surface and the plasma-treated surface of the single-sided metal-clad laminate produced in Example 4 were superimposed, and then pressurized under the conditions of 300° C. and 4 MPa for 10 minutes to produce two sheets of The single-sided metal-clad laminate is a laminate formed by superimposing the film sides of each other. The adhesive strength of the interface portion between the thermoplastic liquid crystal polymer film surfaces of this laminate was measured and regarded as the adhesive strength immediately after the treatment. In addition, these single-sided metal-clad laminates were stored in a constant temperature room for 6 months (temperature 25° C., humidity 40%), and then the plasma-treated replication surface was made with the single-sided coating produced in Example 4. After the plasma-treated surfaces of the metal laminates were superimposed, they were pressurized at 300°C and 4 MPa for 10 minutes to produce a laminate in which two single-sided metal-clad laminates were superimposed on the film side of each other. The adhesive strength of the interface portion between the thermoplastic liquid crystal polymer film surfaces of this laminate was measured and regarded as the adhesive strength after storage for 6 months.

[Example 7] A plasma-treated single-sided metal-clad laminate was produced as an adhesive material in the same manner as in Example 4, except that the gas flow rate and the pressure were changed as in Table 7 as the plasma treatment conditions. For the surface of the thermoplastic liquid crystal polymer film side of the plasma-treated single-sided metal-clad laminate, Er(S) and Er(I) were calculated by SPM. The results are shown in Table 7. Then, a single-sided metal-clad laminate without the plasma treatment of Example 4 was prepared as a material to be bonded, and the plasma-treated side of the single-sided metal-clad laminate and the single-sided metal-clad laminate without plasma treatment were After the thermoplastic liquid crystal polymer film side surfaces were superimposed, pressurized at 300°C and 4 MPa for 10 minutes to produce a laminate in which two single-sided metal-clad laminates were superimposed on the film surface sides of each other. The adhesive strength of the interface portion between the thermoplastic liquid crystal polymer film surfaces of this laminate was measured and regarded as the adhesive strength immediately after the treatment. In addition, after storing the plasma-treated single-sided metal-clad laminate in a constant temperature room for 6 months (temperature 25°C, humidity 40%), one piece was cut out to make the plasma-treated surface of the single-sided metal-clad laminate. After being superimposed on the surface of the thermoplastic liquid crystal polymer film side of the single-sided metal-clad laminate that has not undergone plasma treatment, pressurized for 10 minutes at 300°C and 4 MPa to produce two single-sided metal-clad laminates. A laminate formed by stacking the film surfaces of each other. The adhesive strength of the interface portion between the thermoplastic liquid crystal polymer film surfaces of this laminate was measured and regarded as the adhesive strength after storage for 6 months.

[Comparative Example 1] A laminate of thermoplastic liquid crystal polymer films was produced in the same manner as in Example 1, except that the conditions of the plasma treatment were not evacuated with a vacuum pump, but N ₂ gas was introduced and carried out at atmospheric pressure. Adhesion strength was measured.

[Comparative Example 2] A laminate of thermoplastic liquid crystal polymer films was produced in the same manner as in Example 1, except that the gas species and the pressure were changed as in Table 7 as the plasma treatment conditions, and the adhesive strength was measured.

[Comparative Example 3] The long thermoplastic liquid crystal polymer film obtained in Reference Example 1 and the long copper foil (manufactured by Futian Metal Foil Powder Co., Ltd., "CF-H9A-DS-HD2", thickness 12 μm, surface roughness Rz 1.2 μm ) and a long strip of PCM foil (manufactured by JX Metal Co., Ltd., "PCM", thickness 18μm, surface roughness Rz4.5μm, peelable copper foil) to become a copper foil/thermoplastic liquid crystal polymer film/PCM foil. After the layers were continuously pressed and laminated at 270°C and 3MPa between heating rollers, only the PCM foil was peeled off to obtain a single-sided laminate with the surface of the thermoplastic liquid crystal polymer film with the roughened surface of the PCM foil transferred. Metal laminate. Er(S) and Er(I) were determined by SPM on the surface of the transferred thermoplastic liquid crystal polymer film side of the roughened side of the PCM foil of the single-sided metal-clad laminate. The results are shown in Table 7. Then, the above-mentioned single-sided metal-clad laminate to which the roughened surface of the PCM foil was transferred and the unsurface-treated thermoplastic liquid crystal polymer film obtained in Reference Example 1 were prepared, so that the roughened surface of the single-sided metal-clad laminate and the thermoplastic liquid crystal polymer film were prepared. After the liquid crystal polymer films were laminated, pressure was applied at 300° C. and 4 MPa for 10 minutes to produce a laminate in which the film side of the single-sided metal-clad laminate was laminated with the thermoplastic liquid crystal polymer film. The adhesive strength of the interface portion between the thermoplastic liquid crystal polymer film surfaces of this laminate was measured and regarded as the adhesive strength immediately after the treatment. In addition, the above-mentioned single-sided metal-clad laminate to which the roughened surface of the PCM foil was transferred and the thermoplastic liquid crystal polymer film obtained in Reference Example 1 without surface treatment were stored in a constant temperature room (temperature 25°C, humidity) for 6 months. 40%), after superimposing the roughened surface of the single-sided metal-clad laminate with the thermoplastic liquid crystal polymer film, pressurized for 10 minutes under the conditions of 300 ° C and 4 MPa to prepare the film surface of the single-sided metal-clad laminate. A laminate formed by laminating a thermoplastic liquid crystal polymer film. The adhesive strength of the interface portion between the thermoplastic liquid crystal polymer films of this laminate was measured and regarded as the adhesive strength after storage for 6 months.

[Comparative Example 4] On the surface of the thermoplastic liquid crystal polymer film obtained in Reference Example 1 without surface treatment, Er(S) and Er(I) were measured by SPM. The results are shown in Table 7. Then, two sheets of the above-mentioned thermoplastic liquid crystal polymer films without surface treatment were cut out, and the two film sheets were laminated, and then pressurized under the conditions of 300° C. and 4 MPa for 10 minutes to prepare thermoplastic liquid crystal polymer films. Laminated body. The adhesive strength of this layered body was measured and regarded as the adhesive strength immediately after the treatment. In addition, after storing the above-mentioned thermoplastic liquid crystal polymer film without surface treatment in a constant temperature room for 6 months (temperature 25° C., humidity 40%), two films were cut out, and the two film sheets were laminated. It pressurized for 10 minutes under the conditions of 300 degreeC and 4 MPa, and produced the laminated body of thermoplastic liquid crystal polymer films. The adhesive strength of this laminate was measured, and it was regarded as the adhesive strength after storage for 6 months.

[Table 7] gas species Gas flow (sccm) Pressure (Pa) Frequency (kHz) Output (W/cm ² ) Processing time (seconds) Elastic Modulus (GPa) Er(S)/Er(I) Then make up Adhesion strength (N/mm) Next Strength Retention Rate (%) Er(S) Er(I) next material material to be attached just after processing After 6 months of storage Example 1 N ₂ 20 30 110 6.6 1 6.36 4.36 1.46 Thermoplastic Liquid Crystal Polymer Film Thermoplastic Liquid Crystal Polymer Film 0.63 0.61 97% Example 2 N ₂ 20 10 110 6.6 1 5.76 4.27 1.35 Thermoplastic Liquid Crystal Polymer Film Thermoplastic Liquid Crystal Polymer Film 0.81 0.80 99% Example 3 N ₂ 8 5 110 6.6 1 5.81 4.28 1.36 Thermoplastic Liquid Crystal Polymer Film Thermoplastic Liquid Crystal Polymer Film 1.00 0.97 97% Example 4 N ₂ 20 10 110 6.6 1 4.20 4.30 0.98 Single-sided metal-clad laminate Single-sided metal-clad laminate 1.00 0.97 97% Example 5 N ₂ 20 10 110 6.6 1 5.70 4.27 1.33 Single-sided metal-clad laminate (roughened surface of PCM foil) Single-sided metal-clad laminate 1.20 1.15 96% Example 6 N ₂ 20 10 110 6.6 1 4.10 4.11 1.00 Single-sided metal-clad laminate (copy side) Single-sided metal-clad laminate 1.20 1.20 100% Example 7 N ₂ 8 5 110 6.6 1 4.00 4.30 0.93 Single-sided metal-clad laminate Single-sided metal-clad laminate (untreated) 0.70 0.67 96% Comparative Example 1 N ₂ 20 atmospheric pressure 110 6.6 1 6.90 4.40 1.57 Thermoplastic Liquid Crystal Polymer Film Thermoplastic Liquid Crystal Polymer Film 0.60 0.40 67% Comparative Example 2 O ₂ 20 20 110 6.6 1 7.00 4.50 1.56 Thermoplastic Liquid Crystal Polymer Film Thermoplastic Liquid Crystal Polymer Film 1.00 0.20 20% Comparative Example 3 - - - - - - 8.69 5.70 1.52 Single-sided metal-clad laminate (roughened surface of PCM foil, untreated) Thermoplastic liquid crystal polymer film (untreated) 0.30 0.11 37% Comparative Example 4 - - - - - - 7.04 4.50 1.56 Thermoplastic liquid crystal polymer film (untreated) Thermoplastic liquid crystal polymer film (untreated) 0.30 0.20 67%

As shown in Table 7, the ratio of the elastic modulus Er(S) of the surface layer to the elastic modulus Er(I) of the inner layer (Er(S)/Er(I)) of the thermoplastic liquid crystal in the range of 0 to 1.50 was used. In Examples 1 to 7 of the polymer moldings, the adhesive strength was high even after storage for 6 months, and it was found that high adhesiveness was maintained even after long-term storage.

On the other hand, using a thermoplastic liquid crystal polymer in which the ratio of the elastic modulus Er(S) of the surface layer to the elastic modulus Er(I) of the inner layer (Er(S)/Er(I)) exceeds the range of 0 to 1.50 In Comparative Examples 1 to 4 of the molded body, the adhesive strength was low, and the adhesive strength after storage for 6 months decreased, and it was found that the adhesiveness could not be maintained when stored for a long period of time. [Possibility of Industrial Use]

According to the present invention, if it is a thermoplastic liquid crystal polymer molded body having a structure in which the elastic modulus of the inner layer and the elastic modulus of the surface layer have a specific relationship, the adhesiveness can be maintained even when stored for a long period of time. Therefore, it can be used in various applications according to its shape, and is particularly useful as a multilayer circuit board, an insulator for an electronic circuit board, a reinforcing plate for a flexible circuit board, a cover film for a circuit surface, a multilayer circuit using an adhesive, and the like.

As described above, the preferred embodiments of the present invention have been described, but those skilled in the art can easily conceive of various changes and corrections within the self-evident range by viewing this specification. Therefore, such changes and corrections are to be construed as being within the scope of the invention defined by the scope of the patent application.

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Claims (5)

A thermoplastic liquid crystal polymer molded body having at least a part of a bonded region, in which the elastic modulus Er(S) and the pressure of the surface layer with an indentation depth in the range of 20 nm measured by a nanoindentation method The ratio (Er(S)/Er(I)) of the elastic modulus Er(I) of the inner layer in the depth of 200 nm is 0 or more and 1.50 or less. The thermoplastic liquid crystal polymer molded body according to claim 1, wherein the elastic modulus Er(S) of the surface layer is 6.6 GPa or less. The thermoplastic liquid crystal polymer molded body according to claim 1 or 2, which is in the form of a film. The thermoplastic liquid crystal polymer molded body according to any one of claims 1 to 3, which has a metal portion. The thermoplastic liquid crystal polymer molded body according to any one of claims 1 to 4, which has a circuit.