JP2018070762A - Liquid crystal polymer powder, paste, resin multilayer substrate, and method for producing resin multilayer substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal polymer powder, a paste, a resin multilayer substrate, and a method for producing a resin multilayer substrate such that the adhesion between resin layers is stably ensured.SOLUTION: A liquid crystal polymer powder includes a C=O peak 65 in a C1s peak 61 of C1s narrow scan spectra obtained by X-ray photoelectron spectroscopy.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a liquid crystal polymer powder, a paste, a resin multilayer substrate, and a method for producing a resin multilayer substrate.

  In International Publication WO2014 / 109139 (Patent Document 1), when a resin multilayer substrate is manufactured by laminating a plurality of resin layers and thermocompression bonding, a coating layer is formed in a partial region of the resin layer. It is described that a powdery liquid crystal polymer dispersed in a liquid is used as a material for the paint layer.

International Publication WO2014 / 109139

  Even when a liquid crystal polymer dispersed in a liquid is used as a paint, the adhesion between resin layers is not always stably obtained.

  Accordingly, an object of the present invention is to provide a liquid crystal polymer powder, a paste, a resin multilayer substrate, and a method for producing the resin multilayer substrate that can stably obtain adhesion between resin layers.

  In order to achieve the above object, the liquid crystal polymer powder according to the present invention includes a C═O peak in the C1s peak of the C1s narrow scan spectrum obtained by X-ray photoelectron spectroscopy.

  According to the present invention, the adhesion between the resin layers can be stably obtained.

It is a schematic diagram of the liquid crystal polymer powder in Embodiment 1 based on this invention. It is a figure which shows an example of the C1s narrow scan spectrum obtained from the liquid crystal polymer powder in Embodiment 1 based on this invention. It is a figure which shows the state which further decomposed | disassembled the C1s peak of the C1s narrow scan spectrum obtained from the liquid crystal polymer powder in Embodiment 1 based on this invention. It is a schematic diagram of the liquid crystal polymer powder obtained by freeze-pulverizing a liquid crystal polymer film and sieving. It is a schematic diagram of the dispersion liquid produced by disperse | distributing liquid crystal polymer powder. It is an exploded view of the ultraviolet irradiation device of a double tube structure. It is explanatory drawing of the use condition of the ultraviolet irradiation apparatus of a double tube structure. In an experiment example, it is explanatory drawing of a mode that a sample and a dispersion medium are mixed. In an experiment example, it is explanatory drawing of a mode that the paste was obtained by fully disperse | distributing a sample in a dispersion medium. In an experiment example, it is explanatory drawing of a mode that a coating film is produced on the surface of a liquid crystal polymer film. In an experiment example, it is explanatory drawing of a mode that the liquid crystal polymer film in which the coating film was formed, and another liquid crystal polymer film are piled up. In an experiment example, it is a perspective view of a layered product obtained by superposing two liquid crystal polymer films. In an experimental example, it is a perspective view of the state where a layered product was cut into strips. In an experiment example, it is explanatory drawing of a mode that a T peel strength is calculated | required using a strip-shaped laminated body. It is a schematic diagram of the paste in Embodiment 2 based on this invention. It is a flowchart of the manufacturing method of the resin multilayer substrate in Embodiment 3 based on this invention. It is sectional drawing of the state which formed the coating material layer in the resin sheet as part of the manufacturing method of the resin multilayer substrate in Embodiment 3 based on this invention. It is explanatory drawing of the process of accumulating the resin sheet which apply | coated the paste, and obtaining a laminated body as part of the manufacturing method of the resin multilayer substrate in Embodiment 3 based on this invention. It is sectional drawing of the resin multilayer substrate obtained with the manufacturing method of the resin multilayer substrate in Embodiment 3 based on this invention. It is sectional drawing of the other example of the resin multilayer substrate.

  The dimensional ratios shown in the drawings do not always faithfully represent the actual ones, and the dimensional ratios may be exaggerated for convenience of explanation. In the following description, when referring to a concept above or below, it does not necessarily mean absolute above or below, but may mean relative above or below in the illustrated posture. .

(Embodiment 1)
(Constitution)
With reference to FIGS. 1-3, the liquid crystal polymer powder in Embodiment 1 based on this invention is demonstrated.

  FIG. 1 shows an enlarged view of an example of the liquid crystal polymer powder in the present embodiment. This is the liquid crystal polymer powder 101. The liquid crystal polymer powder 101 in this embodiment includes a C═O peak in the C1s peak of the C1s narrow scan spectrum obtained by X-ray photoelectron spectroscopy. An example of a C1s narrow scan spectrum obtained by performing X-ray photoelectron spectroscopy on the liquid crystal polymer powder 101 is shown in FIG. In FIG. 2, a C1s peak 61 is shown. Since the C1s peak 61 is obtained by superimposing a plurality of peaks, if it is further broken down into individual types of peaks, it is as shown in FIG. In FIG. 3, a C—C, C—H peak 62, an O—C═O peak 63, an O—C peak 64, and a C═O peak 65 appear. The result of superimposing these peaks corresponds to the C1s peak 61. In FIG. 3, the C1s peak 61 is indicated by a broken line for reference.

(Action / Effect)
According to the liquid crystal polymer powder 101 in the present embodiment, the adhesion between the resin layers can be stably obtained. Experimental examples conducted by the inventors to confirm this effect will be described below.

(Experimental example)
Liquid crystal polymer powder 1 was prepared as shown in FIG. 4 by sieving the freeze-pulverized liquid crystal polymer film. The liquid crystal polymer is also called “LCP”. 980g of the liquid mixture which mixed ethanol and the pure water 1: 4 was prepared. As shown in FIG. 5, 20 g of liquid crystal polymer powder 1 was added to and dispersed in the mixed solution 4 to prepare a dispersion 5.

  An ultraviolet irradiation apparatus having a double tube structure using a 20 W low-pressure mercury lamp having a main wavelength of 254 nm was prepared. An ultraviolet irradiation device having a double tube structure is as shown in an exploded view in FIG. This apparatus includes an inner layer pipe 51 and an outer layer pipe 52. The inner layer tube 51 is a translucent tubular body. The inner tube 51 is made of quartz, for example. The inner layer pipe 51 is tubular in the middle part, and one end is closed. In the example shown in FIG. 6, the end on the closed side of the inner layer pipe 51 is hemispherical. Referring to the vertical relationship in FIG. 6, the inner layer pipe 51 has a lower end closed and an upper end being an opening 51 c. The outer layer pipe 52 has an opening 52c at the upper end. The outer layer pipe 52 has a supply port 52a facing sideways at the lower part of the outer peripheral surface. The outer layer pipe 52 has a discharge port 52b facing sideways at the top of the outer peripheral surface. As shown in FIG. 6, the inner layer pipe 51 is inserted into the outer layer pipe 52 through the opening 52c. The rod-shaped ultraviolet light source 10 is inserted into the inner tube 51 made of quartz from the opening 51c. The ultraviolet light source 10 is a 20 W low-pressure mercury lamp. The opening 52c of the outer tube 52 is closed by the lid member 53. However, the lid member 53 has a through hole in the center. FIG. 7 shows a state where the ultraviolet irradiation device is actually used after being assembled. Two ultraviolet light sources 10 are arranged inside the inner layer tube 51. The shapes, positions, and numbers of the ultraviolet light source 10, the supply port 52a, and the discharge port 52b shown in FIGS. 6 and 7 are merely examples, and are not necessarily the same.

  In this ultraviolet irradiation apparatus, as shown in FIG. 7, a double tube structure is realized by an inner layer tube 51 and an outer layer tube 52. Dispersion liquid 5 (see FIG. 5) is caused to flow through a gap between inner layer pipe 51 and outer layer pipe 52. As shown by an arrow 92 in FIG. 7, the dispersion 5 is supplied from the supply port 52a to the inside of the outer layer pipe 52 and discharged from the discharge port 52b. Since the ultraviolet light source 10 is disposed inside the inner layer tube 51 that is a light transmitting member, the ultraviolet light emitted from the ultraviolet light source 10 passes through the inner layer tube 51 and enters the dispersion liquid 5.

  Using this ultraviolet irradiation device, the dispersion 5 was circulated around the ultraviolet light source 10 with a liquid feed pump for 30 minutes. During this time, the surface treatment was applied to the liquid crystal polymer powder 1 in the dispersion 5 by being exposed to ultraviolet light. Dispersion 5 was dried to obtain liquid crystal polymer powder 101 that had been subjected to ultraviolet irradiation treatment. This is the liquid crystal polymer powder 101 as shown in FIG.

  Here, the time for which the dispersion liquid 5 is continuously circulated in the state of being irradiated with ultraviolet light by the ultraviolet irradiation device is set to 30 minutes, but the length of this time (hereinafter referred to as “treatment time”) is changed in several ways. A plurality of liquid crystal polymer powders 101 were obtained. Specifically, the processing time was set to 50 minutes, 100 minutes, and 300 minutes in addition to 30 minutes. The processing times of 30 minutes, 50 minutes, 100 minutes, and 300 minutes are hereinafter referred to as Examples 1, 2, 3, and 4, respectively. Furthermore, as a comparative example, a treatment time of 10 minutes (hereinafter referred to as “Comparative Example 1”) and a device that does not perform such ultraviolet light irradiation treatment (hereinafter referred to as “Comparative Example 2”) were prepared. . Therefore, a total of six samples of Examples 1 to 4 and Comparative Examples 1 and 2 were prepared as samples. Using these liquid crystal polymer powders prepared as samples, the following items were measured.

(Measurement item 1)
As shown in FIG. 8, the liquid crystal polymer powder as a sample and the dispersion medium 6 were mixed. The dispersion medium 6 is 1,3-butanediol 180 g. Here, for convenience of explanation, the sample and the dispersion medium 6 are placed in the container 11. The shape of the container 11 is not limited to that shown here. By sufficiently dispersing the liquid crystal polymer powder, a paste 7 was obtained as shown in FIG. The paste 7 does not contain a binder component. The paste 7 is accommodated in a container 11. In the paste 7, liquid crystal polymer powder is dispersed. This paste is used as a paint.

  As shown in FIG. 10, the paste 7 was apply | coated to the surface of the liquid crystal polymer film 41, and the coating film was produced by making it dry at 100 degreeC on a hotplate. As shown in FIG. 11, a liquid crystal polymer film 41 and another liquid crystal polymer film 42 were stacked and thermocompression bonded by hot pressing to obtain a laminate as shown in FIG. 12. In this laminated body, the coating film is sandwiched between two liquid crystal polymer films 41 and 42.

  As shown in FIG. 13, the laminate was cut into a strip shape having a width of 5 mm. At this time, the longitudinal direction 91 of the strip shape was made to coincide with the tensile processing direction when the liquid crystal polymer film as the base material was initially formed. Using the method of JIS K6854-3 (adhesive-peeling adhesion strength test method-Part 3: T-shaped peeling), as shown in FIG. 14, it is peeled off at an average speed of 50 mm / min by a tensile tester, and T peel strength Asked. A value obtained by dividing the magnitude of the obtained force by the width of the strip shape, that is, 5 mm is the T peel strength.

(Measurement item 2)
X-ray photoelectron spectroscopic analysis was performed on the liquid crystal polymer powder. In the obtained C1s narrow scan spectrum, the binding energy of C—C, C—H was normalized to 284.6 eV, and C—C (284.6 eV), C—O (286.4 eV), C═O (286) .8 eV) and O—C═O (288.9 eV), and the ratio of the state of the C—O peak and the C═O peak serving as a change index was calculated from the peak area of each peak.

(Measurement item 3)
The obtained liquid crystal polymer powder is compacted at 200 MPa or more using a mold, and the softening temperature is adjusted by a thermomechanical device using the method of JISK7196 (thermomechanical analysis of thermoplastic film and sheet by thermomechanical analysis). Asked.

  Table 1 shows the measurement results of Examples 1 to 4 and Comparative Examples 1 and 2 for the measurement items 1 to 3. Table 1 also shows the presence or absence of the C = O peak.

  As shown in Table 1, in Example 1, the T peel strength was sufficiently high and sufficient adhesion was obtained. In Example 1, since the surface treatment of the liquid crystal polymer powder by ultraviolet light irradiation sufficiently progressed, the softening point was greatly lowered. When the softening point is lowered, the coating layer is easily melted, and the adhesion during hot pressing is increased. These effects are the same not only in the first embodiment but also in the second, third, and fourth embodiments.

  As shown in Table 1, in Comparative Example 1, the decrease in softening point was 2 ° C., and the degree of decrease was small. In Comparative Example 1, sufficient adhesion was not obtained. In Comparative Example 1, it seems that the surface treatment of the liquid crystal polymer powder by ultraviolet light irradiation did not proceed sufficiently.

  In Comparative Example 2, the surface treatment of the liquid crystal polymer powder by ultraviolet light irradiation was not performed at all, so that sufficient adhesion was not obtained.

  In the liquid crystal polymer powder 101 in the present embodiment, it is preferable that the following conditions are satisfied. 284.6 eV, C, which is a peak of C—C or C—H when the binding energy of C—C or C—H is normalized to 284.6 eV in the peak that is apparent when the C1s peak is divided. The ratio of the area of the C = O peak to the total area of 286.8 eV being the O peak, 286.4 eV being the CO peak, and 288.9 eV being the O-C = O peak is 1% or more and less than 10% It is preferable that The area of each peak is a mountain-shaped area formed by the curve of each peak.

(Embodiment 2)
(Constitution)
With reference to FIG. 15, the paste in Embodiment 2 based on this invention is demonstrated. An example of this paste is shown in FIG. The paste 201 in the present embodiment includes the liquid crystal polymer powder 101 described in the first embodiment and the dispersion medium 6. The liquid crystal polymer powder 101 is dispersed in the dispersion medium 6.

(Action / Effect)
If the paste 201 in the present embodiment is used as a paint and applied to the surface of the resin film, the adhesiveness of the resin film can be enhanced as is apparent from the experimental results of the first embodiment.

(Embodiment 3)
(Production method)
With reference to FIG. 16, the manufacturing method of the resin multilayer substrate in Embodiment 3 based on this invention is demonstrated. A flowchart of this manufacturing method is shown in FIG.

  The manufacturing method of the resin multilayer substrate in the present embodiment includes a step S2 of preparing a paste 201 in which a liquid crystal polymer powder having a C = O peak in a C1s peak is dispersed in a dispersion medium, and a resin mainly composed of a thermoplastic resin. A process S3 for applying the paste 201 to the sheet 2, a process S4 for stacking the resin sheets 2 applied with the paste 201 to obtain a laminate, and a thermocompression bonding process S5 for applying heat and pressure to the laminate. In FIG. 17, the paint layer 8 is formed on the surface of the resin sheet 2 by applying the paste 201 as a paint. This manufacturing method may include a step S1 of preparing a liquid crystal polymer powder including a C═O peak in the C1s peak before the step S2.

  An example of step S4 is shown in FIG. A coating layer 8 is partially formed on the surface of the resin sheet 2. As shown in FIG. 18, the conductor pattern 17 may be formed so as to partially cover any surface of the resin sheet 2. In the example shown here, the conductor pattern 17 is formed on the surface opposite to the surface on which the paint layer 8 is formed. The resin sheet 2 may include a conductor via 16. The conductor via 16 is provided so as to penetrate the resin sheet 2.

  After finishing the thermocompression bonding step S5 on the laminate obtained by stacking a plurality of resin sheets 2 as shown in FIG. 18, a resin multilayer substrate 301 is obtained as shown in FIG. The coating layer 8 becomes a layer 18 by volatilization of the dispersion medium component through the thermocompression bonding step S5. The layer 18 is mainly made of liquid crystal polymer powder. That is, the resin multilayer substrate 301 includes the layer 18 whose main material is the liquid crystal polymer powder as described in the first embodiment.

  In FIG. 19, the resin multilayer substrate 301 including the conductor via 16, the conductor pattern 17, and the like is shown. However, the resin multilayer substrate 301 is not limited to this, and may be a resin multilayer substrate 302 shown in FIG. 20, for example. The resin multilayer substrate 302 is obtained by laminating a plurality of resin sheets 2 and thermocompression bonding, and the layer 18 is disposed at a part of the interface where the resin sheets 2 are in contact with each other. The layer 18 is mainly composed of liquid crystal polymer powder as described above. The layer 18 may be provided for any purpose.

  In the resin multilayer substrate 301, the layer 18 preferably has a softening point that is lower by 4 ° C. or more and less than 20 ° C. compared to the softening point of the liquid crystal polymer powder not subjected to ultraviolet treatment. When the decrease in softening point is less than 4 ° C., the adhesion is insufficient. When the decrease in the softening point is 20 ° C. or higher, the material of the layer 18 flows too much during the thermocompression bonding step S5, which is not preferable. Therefore, the layer 18 preferably has a softening point that is lower by 4 ° C. or more and less than 20 ° C. compared to the softening point of the liquid crystal polymer powder that has not been subjected to ultraviolet treatment.

  The liquid crystal polymer powder can be obtained by crushing a biaxially oriented liquid crystal polymer sheet. The liquid crystal polymer powder may be used as it is in a powder form. The liquid crystal polymer powder may be fibrillated. That is, the liquid crystal polymer powder may be fibrillated and then dispersed in a dispersion medium to obtain a paste. The paste thus obtained may be applied to the resin film as a paint. Thus, the resin multilayer substrate may be obtained by laminating the resin films coated with the paste.

In addition, you may employ | adopt combining suitably two or more among the said embodiment.
In addition, the said embodiment disclosed this time is an illustration in all the points, Comprising: It is not restrictive. The scope of the present invention is defined by the terms of the claims, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

  DESCRIPTION OF SYMBOLS 1 Liquid crystal polymer powder, 2 Resin sheet, 4 Liquid mixture, 5 Dispersion liquid, 6 Dispersion medium, 7 Paste, 8 Paint layer, 10 Ultraviolet light source, 11 Container, 16 Conductor via, 17 Conductor pattern, 18 (The paint layer is thermocompression bonding Layer, 41, 42 liquid crystal polymer film, 51 inner layer tube, 51c opening, 52 outer layer tube, 52a supply port, 52b discharge port, 52c opening, 53 lid member, 61 C1s peak, 62 C—C, C—H peak, 63 O—C═O peak, 64 O—C peak, 65 C═O peak, 91 longitudinal direction, 92 arrow, 101 liquid crystal polymer powder, 201 paste, 301 resin multilayer substrate.

Claims (6)

  Liquid crystal polymer powder containing a C═O peak in the C1s peak of the C1s narrow scan spectrum obtained by X-ray photoelectron spectroscopy.   284.6 eV which is a peak of C—C or C—H when the binding energy of C—C or C—H is normalized to 284.6 eV in the peak which becomes apparent when the C1s peak is divided. The ratio of the area of the C = O peak to the total area of 286.8 eV which is C = O peak, 286.4 eV which is C—O peak and 288.9 eV which is O—C═O peak is 1% or more and 10%. The liquid crystal polymer powder according to claim 1, which is less than 1.   A paste comprising the liquid crystal polymer powder according to claim 1 and a dispersion medium, wherein the liquid crystal polymer powder is dispersed in the dispersion medium.   A resin multilayer substrate comprising a layer mainly composed of the liquid crystal polymer powder according to claim 1.   The resin multilayer substrate according to claim 4, wherein the layer has a softening point that is lower by 4 ° C. or more and less than 20 ° C. as compared to a softening point of liquid crystal polymer powder not subjected to ultraviolet treatment. Preparing a paste according to claim 3;
Applying the paste to a resin sheet mainly composed of a thermoplastic resin;
Stacking the resin sheets coated with the paste to obtain a laminate; and
And a thermocompression bonding step of applying heat and pressure to the laminate.

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