WO2021112116A1 - Article moulé en résine, article moulé en résine pour vitres de véhicule, et procédé de production d'un article moulé en résine - Google Patents

Article moulé en résine, article moulé en résine pour vitres de véhicule, et procédé de production d'un article moulé en résine Download PDF

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WO2021112116A1
WO2021112116A1 PCT/JP2020/044824 JP2020044824W WO2021112116A1 WO 2021112116 A1 WO2021112116 A1 WO 2021112116A1 JP 2020044824 W JP2020044824 W JP 2020044824W WO 2021112116 A1 WO2021112116 A1 WO 2021112116A1
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Prior art keywords
hard coat
coat layer
layer
resin molded
molded product
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PCT/JP2020/044824
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English (en)
Japanese (ja)
Inventor
美由貴 米丸
康章 堤
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株式会社小糸製作所
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Application filed by 株式会社小糸製作所 filed Critical 株式会社小糸製作所
Priority to JP2021562681A priority Critical patent/JPWO2021112116A1/ja
Priority to CN202080084195.6A priority patent/CN114761229A/zh
Publication of WO2021112116A1 publication Critical patent/WO2021112116A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J1/00—Windows; Windscreens; Accessories therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J5/00—Doors
    • B60J5/04—Doors arranged at the vehicle sides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
    • B60R13/02—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners

Definitions

  • the present invention relates to a resin molded product, a resin molded product for a vehicle window, and a method for manufacturing the resin molded product.
  • the resin material has a drawback that it has lower scratch resistance and weather resistance than the glass material. Therefore, when the resin material is used for a vehicle window or the like, scratches due to friction of the wiper or discoloration due to sunlight occur. There was a problem that it became easier.
  • Patent Documents 1 and 2 a transparent resin plate (resin substrate) is coated with a primer layer and a hard coat layer, and the surface of the hard coat layer is irradiated with ultraviolet light to form a modified layer (cured film).
  • a transparent resin plate resin substrate
  • a hard coat layer is coated with a primer layer and a hard coat layer
  • the surface of the hard coat layer is irradiated with ultraviolet light to form a modified layer (cured film).
  • technologies with improved scratch resistance and weather resistance are disclosed.
  • Patent Document 3 a primer layer is formed on the surface of a substrate, a hard coat layer of a silicone polymer is formed on the surface of the primer layer, and the surface of the hard coat layer is irradiated with ultraviolet light having a wavelength of 200 nm or less.
  • Patent Document 4 describes a transparent cured product layer (hard coat) composed of two layers, an inner layer made of a cured product formed from an ultraviolet curable coating composition and an outermost layer made of silica derived from polysilazane in contact with the inner layer.
  • a technique for a transparent resin plate on which a layer) is formed is disclosed.
  • vehicle parts such as vehicle lamps, sunroofs, and windows are partially blackened or smoked in order to conceal rags and improve their appearance, and each part has a different endothermic capacity for sunlight.
  • the surface of these vehicle parts includes planes and curved surfaces with different curvatures depending on the design, and when attached to the vehicle body, each part inclines at a different angle, so each part receives sunlight. The irradiation angle is also different. As described above, since these vehicle parts have different endothermic capacities and different irradiation angles in each part, a different heat load is applied to each part.
  • the resin material has a problem that as the thickness of the primer layer, the hard coat layer, and the modified layer is increased, the scratch resistance and the weather resistance are increased, but the heat resistance is decreased (see FIG. 9). ..
  • an object of the present invention is to provide a resin molded product, a resin molded product for a vehicle window, and a method for manufacturing the resin molded product, which can achieve both scratch resistance and durability (heat resistance and weather resistance). ..
  • the resin molded product and the resin molded product for a vehicle window of the present invention are provided between the resin base material, the hard coat layer covering at least a part of the resin base material, and the resin base material and the hard coat layer.
  • the hard coat layer and / or the primer layer is based on the inclination angle and the total light transmittance of the resin base material when the resin molded product is assembled to a predetermined product. It is characterized in that the thickness is adjusted.
  • the hard coat layer includes a modified layer obtained by light-modifying the hard coat layer with ultraviolet light, and the modified layer is adjusted in degree of modification based on the inclination angle and the total light transmittance. ..
  • the method for producing a resin molded product of the present invention comprises a step of providing a primer layer on at least a part of a resin base material and a step of coating the primer layer with a hard coat layer.
  • the step of providing the primer layer and / or the step of coating with the hard coat layer is the thickness based on the inclination angle and the total light transmittance of the resin base material in the state where the resin molded product for the vehicle window is assembled to the vehicle body. It is characterized by being adjusted.
  • the hard coat layer includes a modified layer obtained by light-modifying the hard coat layer with ultraviolet light, and the modified layer is adjusted in degree of modification based on the inclination angle and the total light transmittance. ..
  • the resin molded product of the present invention comprises a resin base material, a hard coat layer covering at least a part of the resin base material, and a primer layer formed between the resin base material and the hard coat layer.
  • the layer thickness of the second hard coat layer is preferably 0.5 ⁇ m or less.
  • the hard coat layer may include a first modified layer formed by modifying the hard coat layer into silica by ultraviolet light.
  • the second hard coat layer is a second modification obtained by modifying the second hard coat layer to silica by ultraviolet light in an oxygen atmosphere or to silicon nitride by ultraviolet light in a nitrogen atmosphere. It may include a stratum layer.
  • the resin molded product for a vehicle window of the present invention includes the resin molded product according to any one of (3) to (6) above, and the second hard coat layer is formed on the outside of the vehicle interior. It is a feature.
  • the method for producing a resin molded product of the present invention includes a step of forming a primer layer on a resin base material and a step of coating the primer layer with a hard coat layer, and the step of coating with the hard coat layer includes a step of coating the primer layer with a hard coat layer.
  • the primer layer is coated with a first hard coat layer made of a silicone-based compound, and the first hard coat layer is coated with a second hard coat layer made of a polysilazane compound.
  • the second hard coat layer is characterized in that the layer thickness is 1 ⁇ m.
  • the layer thickness of the second hard coat layer is preferably 0.5 ⁇ m or less.
  • the step of coating with the hard coat layer includes a step of irradiating the hard coat layer with ultraviolet light and photomodifying at least a part of the hard coat layer to silica to form a first modified layer. May be.
  • the step of coating with the second hard coat layer comprises irradiating the second hard coat layer with ultraviolet light in a nitrogen atmosphere and photomodifying at least a part of the second hard coat layer to silicon nitride. (Ii) It may include a step of forming a modified layer.
  • the hard coat layer is subjected to the heat absorption capacity of sunlight and the inclination angle (inclination angle when assembled to the vehicle). Since it was decided to adjust the layer thickness of the primer layer and the degree of modification of the modified layer, the heat resistance is maintained for the parts with high heat load, and the scratch resistance and weather resistance for the parts with low heat load. It has the effect of strengthening sexuality.
  • the resin molded product for vehicle windows, and the method for producing the resin molded product is composed of a polysilazane compound capable of forming a dense film even at a low temperature, so that it is scratch resistant. It has the effect of achieving both property and durability. Further, when light-modified with ultraviolet light, a denser silicon dioxide film can be formed, and when reacted with ultraviolet light in a nitrogen atmosphere, a harder silicon nitride film can be formed. In this case, it also has an effect that scratch resistance and durability can be further improved.
  • FIG. (A) is a schematic view showing each part having a different total light transmittance
  • (b) is a schematic view showing each part having a different inclination angle ( ⁇ ) in a state of being assembled to a vehicle.
  • It is a comparison table which shows the example of the pattern of the resin layer structure. It is a comparison table which shows the example of the surface modification method of a hard coat layer.
  • the rear module 1 includes a rear window 3, a rear combination lamp (RCL) 4, a window cleaner 5, a high mount stop lamp (HMSL) 6, a license plate lamp (LPL) 7, and the like. It is composed of a display 8 and a spoiler 9, and is attached to the vehicle body 2 so as to cover the rear portion of the vehicle.
  • RCL rear combination lamp
  • HMSL high mount stop lamp
  • LPL license plate lamp
  • the rear module 1 includes a resin base material 10 made of polycarbonate (PC), a hard coat layer 12 in which at least a part of the resin base material 10 is coated with a silicone-based resin, and a resin base material 10. It is composed of a primer layer 11 made of an acrylic resin provided between the hard coat layers 12. Further, the hard coat layer 12 includes a modified layer 13 made of silicon dioxide (SiO 2). At this time, the configuration may not include the primer layer 11. When attached to the vehicle body 2, the side on which the modified layer 13 is formed is arranged so as to face the outside of the vehicle.
  • a resin base material 10 made of polycarbonate (PC)
  • a hard coat layer 12 in which at least a part of the resin base material 10 is coated with a silicone-based resin
  • a resin base material 10 It is composed of a primer layer 11 made of an acrylic resin provided between the hard coat layers 12.
  • the hard coat layer 12 includes a modified layer 13 made of silicon dioxide (SiO 2). At this time, the configuration may not include the primer layer 11.
  • a primer solvent is applied to the surface of the resin base material 10 by a dip coating method (wet method), dried at room temperature, heated for a predetermined time, and cured and dried to form the primer layer 11. To do.
  • the primer layer 11 relaxes the stress between the resin base material 10 and the hard coat layer 12, improves the adhesion of the hard coat layer 12, and prevents the hard coat layer 12 from peeling off. Further, by providing the primer layer 11, the weather resistance is also enhanced.
  • a hard coat solvent is applied to the surface of the primer layer 11 by a dip coating method, dried at room temperature, heated for a predetermined time, and cured and dried to be a hard coat layer. 12 is formed.
  • the hard coat layer 12 firmly protects the surface of the resin base material 10 and improves weather resistance.
  • the surface of the hard coat layer 12 is irradiated with ultraviolet light, and the silicone resin of the hard coat layer 12 is modified to silicon dioxide (SiO 2).
  • the layer 13 is formed.
  • a high-output, high-illuminance excimer lamp capable of irradiating ultraviolet light having a peak at a wavelength of 172 nm is adopted. This is because the modified layer 13 can be formed thicker by using high-power and high-illuminance ultraviolet light than when low-power and low-illuminance ultraviolet light is used.
  • the rear module 1 is composed of a plurality of parts having different total light transmittances, such as a black part 21, a visible part 22, and a clear part 23.
  • the visible portion 22 is smoked or the like, and is formed so that the total light transmittance is lower than that of the clear portion 23.
  • the visible portion 22 and the clear portion 23 indicate a portion having a total light transmittance of more than 70%
  • the black portion 21 indicates a portion having a total light transmittance of 70% or less.
  • the primer layer 11 is composed of 2 ⁇ m and the hard coat layer 12 is composed of 6 ⁇ m regardless of the total light transmittance.
  • the total light transmittance of the black portion 21 or the like is 70% or less.
  • the portion to be used is configured by the following patterns (1) to (3).
  • Primer layer 11 is 1 ⁇ m, hard coat layer 12 is 6 ⁇ m.
  • Primer layer 11 is 2 ⁇ m and hard coat layer 12 is 4 ⁇ m.
  • Primer layer 11 is 1 ⁇ m and hard coat layer 12 is 4 ⁇ m.
  • both the layer thicknesses of the primer layer 11 and the hard coat layer 12 are used. It is provided thinner than the conventional layer thickness.
  • the rear module 1 includes a plane or a curved surface having a different curvature in each part, and when assembled to the vehicle body 2, the inclination angle ( ⁇ ) from the horizontal H is different in each part. , The angle of incidence of sunlight is also different, and as a result, the endothermic capacity of each part is different.
  • the modified layer 13 having a uniform degree of modification surface hardness
  • the portion having a small inclination angle when assembled to the vehicle is modified. The degree was suppressed.
  • the portion where the total light transmittance is 70% or less and the portion where the inclination angle is 30 ° or less may exist separately or may be overlapped with each other. It is preferable to adjust both the layer thickness of the layer 11 and the hard coat layer 12 and the degree of modification of the modified layer 13.
  • (Plastic layer structure pattern) As shown in FIG. 4, there are a plurality of patterns in the layer structure of the primer layer 11, the hard coat layer 12, and the modified layer 13. For example, a pattern in which an acrylic or silicone-based hard coat layer is directly formed on the surface of the resin base material 10, a pattern in which a primer layer 11 is formed on the surface of the resin base material 10 and a silicone-based hard coat is applied thereto, and further. , There is a pattern in which the surface of the hard coat layer 12 is modified to form the modified layer 13 for reinforcement.
  • the conventional glass material ⁇ Haze value after tabor wear is about 2%. In particular, high scratch resistance is imparted.
  • a hard layer is formed by a vacuum film forming process such as a chemical vapor deposition method (CVD method) in addition to the photo-modification method used in Example 1.
  • CVD method chemical vapor deposition method
  • the resin base material 10 is irradiated with ultraviolet light at atmospheric pressure while nitrogen flow is applied to the already coated silicone-based hardcoat layer 12, and the surface is modified to form the modified layer 13. How to do it.
  • the hard coat layer 12 made of a silicone-based polymer is irradiated with ultraviolet light having a wavelength of 360 nm or less, the bond chain (Si—C bond chain) of the polymer is cut, and the atmosphere, the hard coat layer 12, and the resin group are broken. Oxygen atoms and silicon atoms slightly present in the material 10 are recombined to form a modified layer 13 containing silicon dioxide as a main component.
  • a raw material gas containing a hard layer component is sprayed onto a resin base material in a vacuum chamber, and a film formed by a chemical reaction is deposited on the surface or gas phase of the resin base material to form a hard layer.
  • the optical reforming method has the advantage that it can be carried out at low cost because it does not require a large-scale device such as a vacuum chamber.
  • a large-scale device such as a vacuum chamber.
  • the hard layer since the hard layer is laminated by spraying the raw material gas, an interface may be formed between the hard layer and the hard coat layer, and the hard layer may be peeled off at the interface portion.
  • the photo-modification method since an interface does not occur between the hard layer and the hard coat layer, there is no risk of peeling, and the scratch resistance and weather resistance are excellent.
  • the modified layer 13 refers to a thickness (layer) portion of the hard coat layer 12 modified to a hardness of 5 GPa or more.
  • the degree of modification is evaluated by measuring the Young's modulus in the layer thickness direction using a nanoindenter under the conditions (1) to (5) below, and confirming the correlation between the layer thickness and the Young's modulus.
  • Equipment KLA G200 type nano indenter High resolution DCM-II head (maximum load: 30 mN) Berkovich indenter
  • Measurement mode Continuous rigidity measurement method (CSM)
  • Vibration amplitude 1 nm
  • FIG. 8A shows the experimental results of the thickness, scratch resistance, and weather resistance of the modified layer 13 when the integrated light intensity was fixed and the irradiation distance and illuminance were changed. From this experimental result, it can be seen that the layer thickness of the modified layer 13 increases in proportion to the illuminance, and the scratch resistance and the weather resistance are improved as the layer thickness of the modified layer 13 increases. In particular, regarding the improvement of weather resistance, the thicker the modified layer 13, the gentler the slope of Young's modulus from the modified layer 13 to the hard coat layer 12, and the stress applied to the hard coat layer 12 is relaxed. It is possible that the reason was that it was done. On the other hand, as shown in FIG. 8B, there is a test result that when the integrated light amount of ultraviolet rays irradiating the silicone-based hard coat is increased to enhance the scratch resistance, the weather resistance is weakened.
  • FIG. 9A shows the experimental results of weather resistance and heat resistance when the layer thicknesses of the primer layer 11 and the hard coat layer 12 are changed.
  • the weather resistance improves in proportion to the layer thickness, but on the other hand, the heat resistance decreases.
  • the balance between scratch resistance, weather resistance, and heat resistance is preferable.
  • the thickness of the visible portion 22 and the clear portion 23 is larger than 2 ⁇ m and 20 ⁇ m or less, and the thickness of the black portion 21 is 0.01 ⁇ m or more and 2 ⁇ m or less.
  • the thickness of the visible portion 22 and the clear portion 23 is larger than 6 ⁇ m and 20 ⁇ m or less, and the thickness of the black portion 21 is 0.01 ⁇ m or more and 6 ⁇ m or less.
  • the thickness of the portion having an inclination angle of 30 ° or less is 0.01 ⁇ m or more and 2 ⁇ m or less, and the thickness of the portion having an inclination angle of more than 30 ° is greater than 2 ⁇ m and 20 ⁇ m or less.
  • the thickness of the portion having an inclination angle of 30 ° or less is 0.01 ⁇ m or more and 6 ⁇ m or less, and the thickness of the portion having an inclination angle of more than 30 ° is larger than 6 ⁇ m and 20 ⁇ m or less.
  • FIG. 9B shows the experimental results of scratch resistance and heat resistance when the integrated light intensity and the surface hardness (modification degree) of the modified layer 13 are changed.
  • the scratch resistance improves in proportion to the degree of modification, but on the other hand, the heat resistance decreases.
  • the balance between scratch resistance, weather resistance, and heat resistance is preferable.
  • (B1) The degree of modification of the visible portion 22 and the clear portion 23 is set to a surface hardness of 0.02 or less, and the degree of modification of the black portion 21 is not modified or the degree of modification is greater than the surface hardness of 0.02.
  • B2 The portion having an inclination angle of 30 ° or less is not modified, and the portion having an inclination angle exceeding 30 ° is modified to have a surface hardness of 0.02 or more.
  • the layer thicknesses of the primer layer 11 and the hard coat layer 12 are adjusted according to the endothermic capacity of sunlight and the inclination angle when assembled to the vehicle, and the modified layer 13 is modified. Since the quality is adjusted, the heat resistance is maintained for the parts with a high heat load, and the scratch resistance and weather resistance are enhanced for the parts with a low heat load.
  • the rear module 1 of Example 2-1 includes a resin base material 10 made of polycarbonate (PC) and a hard coat layer that covers at least a part of the resin base material 10.
  • the hard coat layer includes a first hard coat layer 12a made of a silicone-based compound and a second hard coat layer 12b made of a polysilazane compound, perhydroxypolysilazane (see FIG. 13B).
  • the rear module 1 also includes a primer layer 11 made of an acrylic resin provided between the resin base material 10 and the first hard coat layer 12a. Further, when the rear module 1 is attached to the vehicle body 2, the side on which the second hard coat layer 12b is formed is arranged so as to face the outside of the vehicle.
  • a primer solvent is applied to the surface of the resin base material 10 by a dip coating method (wet method), dried at room temperature, heated for a predetermined time, and cured and dried to form the primer layer 11. To do.
  • the primer layer 11 relaxes the stress between the resin base material 10 and the first hard coat layer 12a, improves the adhesion of the first hard coat layer 12a, and prevents the first hard coat layer 12a from peeling off. Further, by providing the primer layer 11, the weather resistance is also enhanced.
  • a hard coat solvent is applied to the surface of the primer layer 11 by a dip coating method, dried at room temperature, heated for a predetermined time, and cured and dried.
  • a hard coat layer 12a is formed. The surface of the resin base material 10 is hardly protected by the first hard coat layer 12a, and the weather resistance is also improved.
  • the surface of the hard coat layer 11 is coated with perhydroxypolysilazane, which is a polysilazane compound, and cured and dried at room temperature to cure and dry the second hard coat layer 12b. To form.
  • Example 2-2 The rear module 1 of Example 2-2 has the same resin layer structure as the rear module 1 of Example 2-1 but the thickness of the second hard coat layer 12b is provided to be thinner than that of Example 2-1. ing.
  • Example 2-3 As shown in FIG. 11, in the rear module 1 of Example 2-3, in addition to the resin layer structure of the rear module 1 of Example 2-2, the hard coat layers 12 and 13 are modified into silica by ultraviolet light. The first modified layer 13a is provided. The thickness of the second hard coat layer 12b of Example 2-3 is the same as the thickness of the second hard coat layer 12b of Example 2-2.
  • the surfaces of the hard coat layers 12 and 13 are irradiated with ultraviolet light to remove the silicone resin and perhydroxypolysilazane of the hard coat layers 12 and 13.
  • the first modified layer 13a is formed by modifying to silica, that is, silicon dioxide (SiO 2).
  • silica that is, silicon dioxide (SiO 2).
  • a high-output, high-illuminance excimer lamp capable of irradiating ultraviolet light having a peak at a wavelength of 172 nm is adopted. This is because the first modified layer 13a can be formed thicker by using high-power and high-illuminance ultraviolet light than when low-power and low-illuminance ultraviolet light is used.
  • the second hard coat layer 12b is made into silicon nitride by ultraviolet light in a nitrided atmosphere.
  • a second modified layer 13b formed by modification is provided.
  • the thickness of the second hard coat layer 12b is the same as the thickness of the second hard coat layer 12b of Example 2-2.
  • the surface of the second hard coat layer 12b is irradiated with ultraviolet light, and the perhydroxypolysilazane of the second hard coat layer 12b is silicon nitride (Si).
  • the second modified layer 13b is formed by modifying to 3 N 4). Similar to Examples 2-3, Example 2-4 employs a high-power, high-illuminance excimer lamp capable of irradiating ultraviolet light having a peak at a wavelength of 172 nm. This is because the second modified layer 13b can be formed thicker by using the ultraviolet light of high output and high illuminance than in the case of using the ultraviolet light of low output and low illuminance.
  • FIGS. 14 to 16 the experimental results of scratch resistance, heat resistance, and weather resistance showing the effects of the present invention will be described with reference to FIGS. 14 to 16.
  • the goodness is shown in the order of " ⁇ > ⁇ > ⁇ > ⁇ ", and ⁇ or more is regarded as acceptable.
  • the set temperature of the exposure device is 63 ⁇ 3 ° C, and measurement is performed using a black standard thermometer. Relative humidity in the exposure device is controlled to 50 ⁇ 5% during the dry phase of the test cycle. Deionized water was used in the water spray cycle.
  • the exposure device shall provide continuous light irradiation and intermittent water spraying in a 2-hour cycle. The work is exposed to ultraviolet rays for 102 minutes without water spraying, and is exposed to ultraviolet rays for 18 minutes while spraying water.
  • Comparative Examples 1 to 8 The experimental results of Comparative Examples 1 to 8 are shown in (1) to (8) below.
  • an acrylic hard coat currently used for headlamps was directly applied to a polycarbonate resin base material. However, it fails because it does not meet the scratch resistance specified in the safety window standard for automobiles.
  • a silicone-based hard coat which is expected to have higher hardness than the acrylic hard coat and excellent scratch resistance, was directly applied to the polycarbonate resin base material. However, the adhesion with the polycarbonate resin was poor and the material peeled off.
  • Comparative Example 3 a perhydroxypolysilazane-based hard coat was directly applied to the polycarbonate resin base material.
  • Example 2-1 an acrylic primer was applied, and a silicone-based hard coat and perhydroxysilazane were applied thereto in order to improve the adhesion to the polycarbonate resin substrate. Considering that perhydroxypolysilazane has high hardness and is prone to peeling and cracking, a thin film of 1 ⁇ m was formed in order to ensure followability with the substrate. As a result, the scratch resistance, heat resistance, and weather resistance were all passed.
  • Example 2-2 perhydroxypolysilazane was applied even thinner. As a result, we succeeded in further extending the life of heat resistance.
  • Example 2-3 the applied perhydroxypolysilazane was converted to silica by ultraviolet rays. As a result, even higher scratch resistance has been achieved.
  • Example 2-4 perhydroxypolysilazane was converted to silicon nitride by irradiating it with ultraviolet light in a nitrogen atmosphere. Silicon nitride has a higher hardness than silica and has improved scratch resistance. In addition, since silicon nitride also has the effect of absorbing ultraviolet light, the silicone-based hard coat is protected and the weather resistance life is improved.
  • the resin base material 10, the primer layer 11, the first hard coat layer 12a, and the second hard coat layer 12b are provided, and the second hard coat layer 12b is provided. Since the thickness of the hard coat layer 12b is 1.000 ⁇ m or less, it has an effect that all of scratch resistance, weather resistance, and heat resistance can be improved. Further, by providing the second hard coat layer 12b thinly as in Examples 2-2 to 2-4, the heat resistance can be further improved, or the hard coat layers 12 and 13 as in Examples 2-3. Is modified to form the first modified layer 13a to further improve scratch resistance, or the second hard coat layer 12b is modified in a nitriding atmosphere as in Example 2-4. By forming the dimodified layer 13b, silicon nitride also has the effect of absorbing ultraviolet light to protect the first hard coat layer 12a and further improving the weather resistance.
  • the present invention is not limited to the above embodiment, and the structure of each part is configured within a range that does not deviate from the gist of the present invention, such as appropriately changing the material, combination, and coating range of the resin base material 10 and the coating layer. Can be changed arbitrarily.
  • the range in which the modified layer 13 is formed is limited to a specific portion such as a wiper sliding portion, or the resin base material 10 is an acrylic resin, a cycloolefin polymer (COP), or polyethylene instead of polycarbonate. It is also possible to use a transparent resin base material such as terephthalate (PET). Further, an antifogging layer, an antifouling functional layer, or the like may be formed on the modified layer 13.
  • Rear module 1 Rear module 2 Body 3 Rear window 4 Rear combination lamp 5 Window cleaner 6 High mount stop lamp 7 License plate lamp 8 Display 9 Spoiler 10 Resin base material 11 Primer layer 12 Hard coat layer (a: First hard coat layer, b: Second hard coat layer) 13 Modified layer (a: first modified layer, b: second modified layer) 21 Black part 22 Visual part 23 Clear part L Sunlight

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Abstract

La présente invention concerne: un article moulé en résine qui présente une résistance améliorée à l'abrasion et une résistance améliorée aux intempéries, tout en maintenant la résistance à la chaleur; un article moulé en résine destiné à des vitres de véhicule; et un procédé de production d'un article moulé en résine. Un article moulé en résine et un article moulé en résine pour vitres de véhicule selon la présente invention sont tous deux munis d'un matériau (10) de base en résine, d'une couche (11) d'apprêt et d'une couche (12) de revêtement dur. L'épaisseur de la couche (11) d'apprêt et l'épaisseur de la couche (12) de revêtement dur sont ajustées en fonction de la transmittance totale de la lumière du matériau (10) de base en résine et des angles d'inclinaison respectifs des couches dans un état où l'article moulé en résine est monté sur une carrosserie (2) de véhicule. De plus, la couche (12) de revêtement dur comprend une couche modifiée (13) qui est modifiée par un procédé de modification de lumière, et le degré de modification de la couche modifiée (13) est également ajusté en fonction de l'angle d'inclinaison et de la transmittance totale de la lumière.
PCT/JP2020/044824 2019-12-05 2020-12-02 Article moulé en résine, article moulé en résine pour vitres de véhicule, et procédé de production d'un article moulé en résine WO2021112116A1 (fr)

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