WO2020209181A1

WO2020209181A1 - Vehicular resin member

Info

Publication number: WO2020209181A1
Application number: PCT/JP2020/015222
Authority: WO
Inventors: 信行堀川; 康章堤
Original assignee: 株式会社小糸製作所
Priority date: 2019-04-10
Filing date: 2020-04-02
Publication date: 2020-10-15
Also published as: CN113518714B; CN113518714A; JPWO2020209181A1

Abstract

This vehicular resin member (1) is provided with a resin-made substrate (10) and a hard coat layer (12) of silicone polymer formed on the resin-made substrate (10), wherein in the infrared absorption spectrum of at least a portion of the surface of the hard coat layer (12), the peak area ratio A1270/A1000 of the peak area A1270 of peaks in the vicinity of 1,270 cm^-1 and the peak area A1000 of peaks in the vicinity of 1,000 cm^-1 is 0.012 to 0.021 inclusive.

Description

Resin parts for vehicles

The present invention relates to a resin member for a vehicle.

Patent Document 1 discloses a method for producing a resin glass, which comprises a step of irradiating the surface of a silicone polymer layer with vacuum ultraviolet rays having a wavelength of 200 nm or less to modify it into a hard thin film containing silicon dioxide as a main component. ..

Japanese Patent No. 4536824

It is possible to manufacture parts with complicated shapes using resin materials such as polycarbonate and acrylic, and it is possible to realize shapes that were not possible with conventional glass. However, the surface of a part made of a resin material is more easily scratched than that of a part made of glass, and there are problems such as discoloration due to continuous exposure to ultraviolet rays. Therefore, a hard coat of silicone polymer is applied to the surface of the part to supplement it.

By modifying the surface of the hard coat with ultraviolet rays to form a hard film containing silicon dioxide (SiO ₂ ) as a main component, high scratch resistance can be imparted. On the other hand, the hard film is less likely to expand and contract due to heat as compared with the hard coat and other resin materials, and cracks may occur in the hard film as the temperature of the component made of the resin material is repeatedly changed. When used as a resin member for vehicles, not only high scratch resistance but also high heat resistance that can withstand long-term use is required.

An object of the present invention is to provide a resin member having excellent scratch resistance and heat resistance.

In order to achieve the above object, the resin member for a vehicle of the present invention is used.
(1) With a resin substrate
A hard coat layer of a silicone-based polymer formed on the resin substrate and
It is a resin member for vehicles equipped with
Wherein at least part of the infrared absorption spectrum of the surface of the hard coat layer, 1270 cm ^-1 peak area ratio of the peak area A1270 and 1000 cm ^-1 peak area in the vicinity of the peak A1000 peak around A1270 / A1000 0.012 It is 0.021 or less.

(2) Further, the resin member for the vehicle described in (1) is
At least part of the infrared absorption spectrum of the surface of the hard coat layer, the apex of the peaks present in the range of 870 cm ^-1 or more 960 cm ^-1 or less is located in a range of 870 cm ^-1 or more 910 cm ^-1 or less, and preferably ..

(3) Further, the resin member for a vehicle according to (1) or (2) is
The hard coat layer, silicone showing the infrared absorption spectrum peak area ratio A1336 / A1409 of the peak area A1409 peak around the peak area A1336 and 1409cm ^-1 peak around 1336cm ^-1 is 0.5 or more It is preferably formed by curing the polymer.

According to the present invention, it is possible to provide a resin member having excellent scratch resistance and heat resistance.

It is sectional drawing of the resin member. It is a schematic diagram which shows the state of manufacturing of a resin member. It is a figure which shows the infrared absorption spectrum of the surface of the resin member of Example 2 and Comparative Example 1. It is a figure which shows the peak area ratio A1270 / A1000 with respect to the number of times of irradiation of ultraviolet rays. It is a figure which shows the infrared absorption spectrum of the resin member made under the condition which the oxygen concentration is different. It is an enlarged view of the infrared absorption spectrum shown in FIG. It is a figure which shows the peak position which exists in the range of 890 cm ^-1 or more and 930 cm ^-1 or less with respect to oxygen concentration.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. The dimensions of each member shown in this drawing may differ from the actual dimensions of each member for convenience of explanation.

First, the resin member 1 for the vehicle of the present embodiment will be described. FIG. 1 is a cross-sectional view of the resin member 1. The resin member 1 is a member that constitutes a window for a vehicle. The term "window" as used herein refers to a window provided on the front, side, rear, etc. of a vehicle so that the inside of the vehicle can be visually recognized from the inside of the vehicle or the outside of the vehicle. As shown in FIG. 1, the resin member 1 includes a resin substrate 10 and a hard coat layer 12 formed on the resin substrate 10. The surface of the hard coat layer 12 is surface-modified to form the protective layer 14.

The resin substrate 10 is made of a polycarbonate resin. As the polycarbonate resin, one having a weight average molecular weight (Mw) of 20,000 or more and 25,000 or less may be adopted in consideration of the hard coat layer 12 described later. If Mw is less than 20,000, cracks may occur due to solvent attack of the hard coat paint, and if Mw exceeds 25,000, molding defects due to insufficient fluidity may occur. The Mw is preferably 20,000 or more and 23,000 or less. The resin substrate 10 has a curved plate shape (FIG. 1, FIG. 2 described later). Further, the resin substrate 10 is transparent. Here, in the present specification, "transparent" is a term including colorless transparent and colored transparent. Further, "transparent" is a term that does not mean only those that completely transmit light, but also includes those that are translucent to the extent that the object on the opposite side of the object can be visually recognized.

The hard coat layer 12 is a layer having better scratch resistance than the resin substrate 10, and is made of a silicone-based polymer. Here, the silicone-based polymer is a material based on an organopolysiloxane having an organic group attached to a siloxane bond. Hard coat layer 12 is silicone showing the infrared absorption spectrum peak area ratio A1336 / A1409 of the peak area A1409 peak around the peak area A1336 and 1409cm ^-1 peak around 1336cm ^-1 is 0.5 or more It is preferably formed by curing the polymer.

The protective layer 14 is a hard layer formed by irradiating a silicone-based polymer with ultraviolet rays having a wavelength of 360 nm or less. Specifically, the polymer bond chain (Si—C bond chain) is cleaved by irradiation with ultraviolet rays, and oxygen atoms and silicon atoms are recombined to form a hard layer containing silicon dioxide as a main component. The protective layer 14 is a layer having better scratch resistance than the hard coat layer 12. In the infrared absorption spectrum of the protective layer 14 of the present embodiment obtained by infrared spectroscopy, the absorption peak exists in a range of 600 cm ^-1 or more 4,000 cm ^-1 or less.

The resin member 1 of this embodiment, the protective layer 14 in an infrared absorption spectrum obtained by infrared spectroscopy (FT-IR) measurement, 1270 cm ^-1 vicinity of the peak around the peak area A1270 and 1000 cm ^-1 peak The peak area ratio A1270 / A1000 with the peak area A1000 is 0.012 or more and 0.021 or less. By providing this configuration, the resin member 1 does not crack on the surface even when exposed to a high temperature for a long time, and has excellent scratch resistance. The infrared spectroscopic measurement in this embodiment is performed using an infrared spectroscope. Further, the resin member 1, in the infrared absorption spectrum of the protective layer 14, the apex of the peaks present in the range of 870 cm ^-1 or more 960 cm ^-1 or less is located in a range of 870 cm ^-1 or more 910 cm ^-1 or less, and preferable.

In FIG. 1, the portion modified by irradiation with ultraviolet rays is shown as one region and described as the protective layer 14, but in reality, the ultraviolet rays are attenuated as the distance from the surface of the hard coat layer 12 increases. It is not modified much. That is, the boundary between the protective layer 14 and the hard coat layer 12 is not clearly formed, and the boundary line in FIG. 1 is shown for convenience.

Next, a method for manufacturing the resin member 1 will be described. The manufacturing method includes a step of applying a silicone-based polymer on the resin substrate 10 to form the hard coat layer 12, and a step of irradiating at least a part of the surface of the hard coat layer 12 with ultraviolet rays.

In the step of forming the hard coat layer 12 on the resin substrate 10, a silicone-based polymer material is applied onto the resin substrate 10 by a wet method, for example, a dip coating method. Then, after drying at room temperature for a predetermined time, the hard coat layer 12 is formed by curing and drying by heating for a predetermined time. Examples of the silicone-based polymer material, in the infrared absorption spectrum obtained by performing infrared spectroscopy of the hard coat layer 12, the peak area of the peak in the vicinity of the peak area A1336 and 1409cm ^-1 peak around 1336cm ^-1 It is preferable to use a material having a peak area ratio of A1336 / A1409 to A1409 of 0.5 or more. Further, the peak area ratio A1336 / A1409 is more preferably 0.9 or less, and particularly preferably 0.7 or less.

Subsequently, ultraviolet rays are irradiated to the entire surface of the hard coat layer 12 or a part where particularly high scratch resistance is required, such as a portion where the wiper hits. FIG. 2 is a schematic view showing a state of a process of irradiating ultraviolet rays. In FIG. 2, a resin member 1A whose surface modification of the hard coat layer 12 has not been completed is housed in the space 30 covered by the enclosure 20. The enclosure 20 is provided with a light source 22 that irradiates ultraviolet rays, a support 24 having a movable arm 25, an inert gas supply path 26, and a gas discharge unit 28. The resin member 1A is supported by the movable arm 25 and is movable with respect to the light source 22 and the position for supplying the inert gas. The light source 22 is not particularly limited as long as it is a light source that irradiates ultraviolet rays of 360 nm or less, but a light source that irradiates ultraviolet rays of 200 nm or less is preferable because it has a large force for cutting the bond chain of the silicone polymer. .. In this embodiment, a Xe ₂ excimer lamp having a wavelength of 172 nm is used. The inert gas is not particularly limited as long as it does not absorb ultraviolet rays, but nitrogen gas is used in the present embodiment.

In the step of irradiating ultraviolet rays, the oxygen concentration inside the enclosure 20 is set to 0% by volume or more and 0.5% by volume or less. Here, the oxygen concentration (volume%) is the amount of oxygen present per unit volume in an atmosphere irradiated with ultraviolet rays, expressed as a percentage with respect to the unit volume. The under atmosphere, the ultraviolet greater 4500mJ / cm ² less than the accumulated light quantity than 1000 mJ / cm ² from the light source 22 is irradiated to the hard coat layer 12, thereby surface-modified. As a result, the protective layer 14 is formed and the resin member 1 is manufactured.

In the above manufacturing method, by adopting a low oxygen concentration and a specific integrated amount of ultraviolet rays, the resin member 1 which does not crack on the surface even when exposed to a high temperature for a long time and has excellent scratch resistance can be obtained. Can be provided.

Further, in the resin member 1 manufactured by the above manufacturing method, in the infrared absorption spectrum of the surface (protective layer 14) of the hard coat layer 12 obtained by infrared spectroscopy, 600 cm ^-1 or more and 4,000 cm ^-1. Absorption peaks exist in the following range. Although preferably the absorption peak in the range of 870 cm ^-1 or more 910 cm ^-1 or less is present, the absorption peak, as shown in Examples described later, the oxygen concentration surface under greater atmosphere 0.5 vol% Not confirmed with modified hard coat. From this, it is presumed that a hard coat layer having a specific surface structure is formed depending on the specific conditions of the manufacturing method of the embodiment.

In the above-described embodiment, the Xe ₂ excimer lamp has been described as a light source or a light source unit that irradiates ultraviolet rays, but in addition, an Ar ₂ excimer lamp, a Kr ₂ excimer lamp, an Ar ₂ excimer laser, and an F ₂ excimer laser. ArF excimer lasers, low pressure mercury lamps, LEDs, semiconductor lasers and the like can be used.

Further, as understood from the above-described embodiment, the term "silicone-based polymer" is not a term that refers only to the silicone-based polymer constituting the formed hard coat layer 12, but the hard coat layer 12 is formed. The term also refers to a silicone-based polymer that is applied onto the resin substrate 10, that is, as a precursor of the hard coat layer 12. Further, the term "silicone-based polymer" does not mean only a pure polymer, and when used as a precursor of the hard coat layer 12, includes a solution in which the polymer is dispersed and an additive such as a cross-linking agent. It is a term including the aspect. When forming the hard coat layer 12, a commercially available silicone-based polymer may be used as it is, or a pre-condensed silicone-based polymer may be used. The silicone-based polymer can be appropriately modified as long as the hard coat layer 12 can be formed on the resin substrate 10.

In the above-described embodiment, an example in which nitrogen gas is used as an inert gas that does not absorb ultraviolet rays has been described, but a gas containing at least one of argon, helium, and carbon dioxide may also be used. Further, in order to make the entire work area an atmosphere in which ultraviolet rays are not easily absorbed, a method of reducing the pressure of a gas such as oxygen to reduce the pressure or vacuum, or the resin member 1A is made of quartz or the like through which ultraviolet rays are transmitted. A method of putting it in a container and irradiating it with ultraviolet rays can also be applied. Further, in order to promote the production of silicon dioxide, which is the main component of the protective layer 14, a substance containing silicon such as tetraethoxysilane, tetramethoxysilane, monosilane, and silazane is injected into the atmosphere, or the surface of the resin member 1A. May be applied to.

In the above-described embodiment, the example in which the hard coat layer 12 is formed on one side of the resin substrate 10 has been described, but the hard coat layer 12 may be formed on both sides of the resin substrate 10. Further, another layer (for example, a primer layer made of acrylic resin) may be provided between the resin substrate 10 and the hard coat layer 12.

In the above-described embodiment, the resin member 1 has been described as constituting the window, but the resin member 1 is partially mounted for a vehicle while being mounted in combination with other members such as a lamp and a sensor. It can also be a composite module that makes up a window. In this case, the protective layer 14 may be formed at least in the portion of the composite module that constitutes the window. Further, the shape of the resin member 1 is not limited to that of the above-described embodiment, but also includes a flat plate shape and a shape having a three-dimensional shape. It is desirable that the windows can ensure visibility, but if it is possible to ensure the safety of the vehicle if the electromagnetic waves of the sensors are transmitted even if the person cannot directly check the surrounding conditions, the visible light region Light does not have to be transmitted.

In the above-described embodiment, polycarbonate resin is mentioned as the material of the resin substrate 10, but acrylic resin, cycloolefin resin, polystyrene resin and the like can also be used.

Subsequently, the present invention will be specifically described with reference to Examples. It should be noted that the present embodiment is merely an example and does not limit the present invention. First, the test method performed in the examples will be described.

[Infrared spectroscopy (FT-IR) measurement]
Using an infrared spectroscope (PerkinElmer FrontierT), the infrared spectroscopic spectrum of the hard coat layer or the protective layer of the resin member described later was measured by the total reflection method using a Ge prism (45 ° incident).
[Taber wear test]
The Taber wear test (JIS K7204) was carried out by bringing the hard coat layer or the protective layer of the resin member, which will be described later, into contact with the wear wheel and rotating the wear wheel for 1000 rotations. Then, the amount of change in the haze value (%) (JIS K7136) before and after wear was measured. It should be noted that the value of the amount of change in the haze value is required to be 2.4% or less as the wear resistance of the member that can be used in the visible range of the automobile.
[Heat resistance test]
A resin member described later on which a hard coat layer or a protective layer was formed was placed in an environment of 100 ° C. for 1000 hours, and then the presence or absence of cracks was confirmed. In the table shown later, A indicates that no crack has occurred, B indicates that a minute crack that is difficult to recognize with the naked eye has occurred, and C indicates that a crack has occurred.

(Selection of silicone polymer)
The silicone-based polymer used in this example was selected. A silicone-based polymer was coated on a polycarbonate resin substrate (150x150x3 mm) to a thickness of 5 μm by spin coating, dried at 120 ° C. for 1 hour, and cured to form a hard coat layer. Then, the hard coat layer formed was, under a nitrogen atmosphere having an oxygen concentration of 0.5% or less, Hamamatsu Photonics Co. Xe ₂ wavelengths 172nm using an excimer lamp ultraviolet integrated light quantity of 170 mJ / cm ² per Irradiation was performed 12 times under the conditions, and the surface of the hard coat layer was modified to form a cured protective layer. According to this procedure, a resin member was prepared using four kinds of silicone-based polymers. Specifically, one type of silicone polymer was used in each of Example 1, Example 2, Comparative Example 1 and Comparative Example 2 shown in Table 1.

Some silicone-based polymers peel off when the protective layer is formed by irradiating with ultraviolet rays. As shown in Table 1, the protective layer was not peeled off in Example 1 and Example 2, but the protective layer was peeled off in Comparative Example 1 and Comparative Example 2. In order to examine the peelability, FT-IR measurement of the surface of the resin member of the hard coat layer before ultraviolet irradiation in Example 1, Example 2, Comparative Example 1 and Comparative Example 2 was performed. Table 1 shows the peak area ratio A1336 / A1409 of the peak area A1336 of the peak near 1336 cm ^-1 and the peak area A1409 of the peak near 1409 cm ^-1 in the obtained infrared absorption spectrum. Infrared absorption spectra of Example 2 and Comparative Example 1 are shown in FIG. As shown in FIG. 3, in the infrared absorption spectrum of the silicone-based polymer that does not peel off after UV irradiation, peaks exist near 1409 cm ^-1 and 1336 cm ^-1 , whereas the silicone-based polymer that peels off after UV irradiation has peaks. In the infrared absorption spectrum, the peak near 1336 cm ^-1 is smaller than the peak near 1409 cm ^-1 . In addition, a taber wear test and a heat resistance test of the resin members of Examples 1 and 2 were performed. The results are shown in Table 1. Capable of preventing the peeling, the peak area in the vicinity of 1336cm ^-1 as shown in Example 1 and Example 2 of Table 1 uses the silicone polymer is 0.5 or more with respect to the peak area in the vicinity of 1409cm ^-1 I decided.

(Examination of UV irradiation conditions)
Scratch resistance and heat resistance depend on how much ultraviolet rays having a wavelength of 172 nm are applied to the hard coat layer formed by using the silicone polymer selected by the above method (silicon polymer of Example 2, AS4700 manufactured by Momentive). Was examined to see if it would affect. Under a nitrogen atmosphere with an oxygen concentration of 0.5% or less, ultraviolet rays having a wavelength of 172 nm were irradiated using an Xe ₂ excimer lamp manufactured by Hamamatsu Photonics Co., Ltd. under the condition of an integrated light amount of 170 mJ / cm ^{2 each} time. The surface of the hard coat layer was modified to form a hardened protective layer. Then, FT-IR measurement was performed on the surface of the resin member on which the protective layer was formed. Between the obtained peak area ratio A1270 / A1000 of the peak area A1000 infrared absorption peak area A1270 of 1270 cm ^-1 in the spectrum and 1000 cm ^-1, shown in FIG. 4 the correlation between number of times of irradiation with ultraviolet rays. As shown in FIG. 4, the peak area ratio A1270 / A1000 decreases as the number of irradiations increases.

The taber wear test and heat resistance test were performed on the resin members of Examples 3 to 5, Comparative Example 3 and Comparative Example 4 shown in Table 2. The results are shown in Table 2. From the results in Table 2, it can be seen that good scratch resistance and heat resistance can be achieved at the same time in the resin member having a peak area ratio A1270 / A1000 of 0.012 or more and 0.021 or less.

(Examination of oxygen concentration)
The scratch resistance and scratch resistance are determined by the oxygen concentration at which the hard coat layer formed by using the silicone polymer selected by the above method (silicon polymer of Example 2, AS4700 manufactured by Momentive) is irradiated with ultraviolet rays having a wavelength of 172 nm. It was examined whether the heat resistance would be affected. Under a nitrogen atmosphere with a specific oxygen concentration, the surface of the hard coat layer was exposed to ultraviolet rays with a wavelength of 172 nm 12 times under the condition of an integrated light amount of 170 mJ / cm ² using a Xe ₂ excimer lamp manufactured by Hamamatsu Photonics. A modified and cured protective layer was formed. Then, FT-IR measurement was performed on the surface of the resin member on which the protective layer was formed.

5 and 6 show the infrared absorption spectrum (high oxygen concentration in FIGS. 5 and 6) and the oxygen concentration of the surface of the resin member prepared by irradiating with ultraviolet rays in a nitrogen atmosphere having an oxygen concentration of 2.0%. The infrared absorption spectrum (low oxygen concentration in FIGS. 5 and 6) of the surface of the resin member prepared by irradiating with ultraviolet rays in a 0.15% nitrogen atmosphere is shown. Further, Table 3 shows the positions of peaks existing in the range of 870 cm ^-1 or more and 960 cm ^-1 or less in the infrared absorption spectrum of the resin member (Example 4, Example 7 and Comparative Example 5 to 7) for each oxygen concentration. Is shown. Further, FIG. 7 shows the relationship between the peak position shown in Table 3 and the oxygen concentration.

If the oxygen concentration at the time of irradiation of ultraviolet rays is high, 925 cm whereas peak appears in the vicinity of ^-1, when the oxygen concentration is sufficiently low small peak appeared in the vicinity of 925 cm ^-1, 910 cm instead ^-1 A peak appears below (near 895 cm ^-1 ) (FIGS. 6 and 7). From this, it is inferred that a hard coat layer having a specific surface (protective layer) structure was formed when ultraviolet rays were irradiated in a state where the oxygen concentration was sufficiently low.

A taber wear test and a heat resistance test were performed on the resin members of Example 6, Example 7, and Comparative Examples 5 to 7. The results are shown in Table 3. The results in Table 3, the value of the peak area ratio A1270 / A1000 is 0.012 or more 0.021 or less, the apex of the peaks present in the range of 870 cm ^-1 or more 960 cm ^-1 or less is 870 cm ^-1 or more 910 cm ^-1 It can be seen that the resin members located in the following ranges have both good scratch resistance and heat resistance.

The present invention is not limited to the above-described embodiments and examples, and can be freely modified, improved, and the like as appropriate. In addition, the material, shape, size, numerical value, form, number, arrangement location, etc. of each component in the above-described embodiment are arbitrary and are not limited as long as the present invention can be achieved.

This application is based on a Japanese patent application (Japanese Patent Application No. 2019-0749113) filed on April 10, 2019, and the entire application is incorporated by citation. Also, all references cited here are taken in as a whole.

1: Resin member, 10: Resin substrate, 12: Hard coat layer

Claims

With a resin substrate
A hard coat layer of a silicone-based polymer formed on the resin substrate and
It is a resin member for vehicles equipped with
Wherein at least part of the infrared absorption spectrum of the surface of the hard coat layer, 1270 cm -1 peak area ratio of the peak area A1270 and 1000 cm -1 peak area in the vicinity of the peak A1000 peak around A1270 / A1000 0.012 A resin member for a vehicle, which is 0.021 or less.
Wherein at least part of the infrared absorption spectrum of the surface of the hard coat layer, the apex of the peaks present in the range of 870 cm -1 or more 960 cm -1 or less is located in a range of 870 cm -1 or more 910 cm -1 or less, claims The resin member for a vehicle according to 1.
The hard coat layer, silicone showing the infrared absorption spectrum peak area ratio A1336 / A1409 of the peak area A1409 peak around the peak area A1336 and 1409cm -1 peak around 1336cm -1 is 0.5 or more The resin member for a vehicle according to claim 1 or 2, which is formed by curing a polymer.