WO2021095649A1 - Resin molded article, resin molded article for vehicle window, and method for producing resin molded article - Google Patents

Resin molded article, resin molded article for vehicle window, and method for producing resin molded article Download PDF

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Publication number
WO2021095649A1
WO2021095649A1 PCT/JP2020/041512 JP2020041512W WO2021095649A1 WO 2021095649 A1 WO2021095649 A1 WO 2021095649A1 JP 2020041512 W JP2020041512 W JP 2020041512W WO 2021095649 A1 WO2021095649 A1 WO 2021095649A1
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layer
resin molded
hard coat
molded article
resin
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PCT/JP2020/041512
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French (fr)
Japanese (ja)
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信行 堀川
康章 堤
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株式会社小糸製作所
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Priority to JP2021556067A priority Critical patent/JPWO2021095649A1/ja
Publication of WO2021095649A1 publication Critical patent/WO2021095649A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/18—Handling of layers or the laminate
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings

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 lower scratch resistance and weather resistance than the glass material, there is a problem that scratches and discoloration are likely to occur due to the friction of the wiper and the ultraviolet rays contained in the sunlight.
  • a technique has been developed in which a special hard coat is applied to the surface of the resin material to improve the scratch resistance and weather resistance of the surface of the resin material.
  • a method of applying an acrylic hard coat to a resin material a method of applying a silicone hard coat on a resin material after forming a primer layer for preventing peeling, and a method of applying a silicone hard coat to the surface of the hard coat for reinforcement.
  • Techniques such as a method of forming a hard layer with silicon dioxide (SiO2) are disclosed.
  • the method of forming a hard layer for reinforcement is particularly higher than the conventional glass material ( ⁇ Haze value after taber wear is about 2%) in the taber wear test for evaluating scratch resistance. It is known to impart scratch resistance.
  • the vacuum film forming process is a method of forming a hard layer by spraying a raw material gas containing a hard layer component on a base material in a vacuum chamber and depositing a film by a chemical reaction on the surface of the base material or the gas phase.
  • the photomodification method is a method of irradiating a base material with ultraviolet rays at atmospheric pressure while applying nitrogen flow to an already coated silicone-based hard coat to modify the surface to form a hard layer.
  • the bond chain (Si—C bond chain) of the polymer is cut, and oxygen atoms slightly present in the atmosphere, hard coat, and base material are formed. It adopts the principle that silicon atoms are recombined to form a hard layer containing silicon dioxide as a main component.
  • Patent Documents 1 to 3 a hard layer is formed by using a vacuum film forming process such as a CVD method.
  • a vacuum film forming process such as a CVD method.
  • a molecular resin laminate is introduced.
  • Patent Document 2 introduces a polymer resin laminate in which a silicon oxide layer is laminated on a crosslinked resin layer by a vacuum film forming process such as a CVD method.
  • the hard coat layer formed on at least one surface of the transparent resin substrate includes an organic polymer thin film formed by vacuum vapor deposition polymerization.
  • the optical reforming method is superior in terms of cost because it does not require a large-scale device such as a vacuum chamber.
  • the vacuum film forming process since the hard layer is laminated by spraying the raw material gas, an interface is formed between the hard layer and the hard coat layer, and the hard layer may be peeled off at the interface portion.
  • the light reforming method there is no interface between the hard layer and the hard coat layer, and peeling does not occur.
  • the photo-modifying method is also excellent in scratch resistance and weather resistance.
  • a hard layer is formed by using a light reforming method.
  • a hard coat containing a silicone-based organopolysiloxane is irradiated with ultraviolet rays having a wavelength of 200 nm or less to increase the hardness of a portion having a thickness of less than 0.6 ⁇ m from the surface to form a hard layer.
  • a hard coating agent composition containing an organopolysiloxane is applied to at least one surface of a resin substrate to form a coating film, and the coating film is subjected to heat treatment, light irradiation treatment, oxidation treatment and the like. The method of forming a hard layer is introduced.
  • Patent Document 6 a silicone-based polymer is applied to a resin module substrate to form a hard coat, and the surface of the hard coat is irradiated with ultraviolet rays having a wavelength of 360 nm or less to form a hard layer.
  • the module is introduced.
  • an object of the present invention is to provide a resin molded product having improved scratch resistance and improved weather resistance, a resin molded product for a vehicle window, and a method for manufacturing the resin molded product.
  • the present invention employs the following means.
  • a step of coating at least a part of the transparent resin base material with a hard coat layer and a step of irradiating the surface of the hard coat layer with ultraviolet light to form a modified layer having a predetermined hardness or more are provided.
  • the resin molded product the resin molded product for vehicle windows, and the method for producing the resin molded product of the present invention, by setting the thickness of the modified layer to 70 nm or more, the scratch resistance is enhanced and the weather resistance is also improved. It becomes possible.
  • FIG. 1 is a schematic view of a rear module showing an embodiment of a resin molded product for a vehicle window of the present invention, and a vehicle equipped with the rear module.
  • FIG. 2 is a schematic view showing the structure of the resin layer according to the rear module of FIG.
  • FIG. 3 is a graph showing the correlation between the integrated light intensity and the surface Young's modulus.
  • FIG. 4 is a graph showing the correlation between the surface Young's modulus and the Taber wear test result.
  • FIG. 5 is a graph showing the correlation between illuminance and Young's modulus under a constant integrated light intensity.
  • FIG. 6 is a graph showing the correlation between the illuminance and the thickness of the modified layer under a constant integrated light intensity.
  • FIG. 1 is a schematic view of a rear module showing an embodiment of a resin molded product for a vehicle window of the present invention, and a vehicle equipped with the rear module.
  • FIG. 2 is a schematic view showing the structure of the resin layer according to the rear module of
  • FIG. 7 is a list showing the results of an experiment in which the illuminance, the irradiation distance, and the irradiation time were changed under a constant integrated light intensity.
  • FIG. 8 is a table showing a conventional hard coat.
  • FIG. 9 is a table comparing conventional methods for forming a hard layer.
  • FIG. 10 is a table showing the scratch resistance and weather resistance of the hard layer formed by the conventional method for each integrated light intensity.
  • the rear module 1 includes a rear window 3 as a resin molded product for a vehicle window, a rear combination lamp (RCL) 4, a window cleaner 5, a high mount stop lamp (HMSL) 6, and a license plate. It is composed of a lamp (LPL) 7, a display 8, and the like, and is fitted into the vehicle body 2 so as to cover the rear portion of the vehicle. It is also possible to preferably adopt the spoiler 9 formed on the rear module 1.
  • the weight of the entire vehicle can be reduced, and a complicated three-dimensional shape can be freely formed to improve the design of the vehicle appearance. Further, by integrating the parts at the rear of the vehicle into a module, the man-hours for assembling the vehicle can be reduced and the cost can be reduced.
  • the surface of the base 10 made of a polycarbonate resin, the primer layer 11 made of an acrylic resin, the hard coat layer 12 made of a silicone polymer, and the hard coat layer 12 is exposed to ultraviolet light. It is composed of a resin laminate including a modified layer 13 which has been photomodified by the above and modified into a hard layer, and the modified layer 13 is formed on the outside of the vehicle interior.
  • the primer layer 11 mainly has a role of relaxing the stress between the substrate 10 and the hard coat layer 12 to improve the adhesion between the substrate 10 and the hard coat layer 12, but also has the effect of improving the weather resistance.
  • the hard coat layer 12 has a hardness for protecting the substrate 10 and has an effect of improving weather resistance.
  • the modified layer 13 has an effect of improving scratch resistance.
  • the primer layer 11 is formed by applying a primer solvent made of an acrylic resin to the surface of the substrate 10 by a dip coating method (wet method), drying at room temperature, and heating for a predetermined time to cure and dry.
  • the hard coat layer 12 is formed by applying a hard coat solvent of a silicone polymer on the primer layer 11 by a dip coat method, drying at room temperature, heating for a predetermined time, and curing and drying.
  • the modified layer 13 is formed by photomodifying with ultraviolet light.
  • a high-output, high-illuminance excimer lamp capable of irradiating ultraviolet light having a peak at a wavelength of 172 nm is adopted.
  • the vicinity of the surface of the hard coat layer 12 is photomodified and hardened, and the modified layer 13 as a hard layer is formed.
  • the ultraviolet light has high output and high illuminance.
  • the modified layer 13 can be formed thicker than when low-power, low-illuminance ultraviolet light is used.
  • the modified layer 13 preferably has a thickness of 70 nm or more. By having a thickness of 70 nm or more, it is possible to form the modified layer 13 having weather resistance while improving the scratch resistance on the surface of the modified layer 13.
  • the hardness of the modified layer which is a hard layer, is determined by the predetermined measurement conditions by the nano indenter (device: KLA G200 type nano indenter, high resolution DCM-II head (maximum load: 30 mN), Berkovich indenter, measurement mode: continuous rigidity.
  • CSM measurement method
  • indentation depth 1000 nm
  • vibration frequency 65 Hz
  • vibration amplitude 1 nm
  • the term "modified layer” as used herein refers to a portion having a Young's modulus of 5 GPa or more, which indicates an elastic modulus.
  • the scratch resistance is confirmed by a taber wear test (wear wheel CS-10F, 0.5 kg load). It can be said that the smaller the ⁇ Haze value (%) around 1000 rotations of the taber wear, the less likely it is to be scratched.
  • Super UV test (SUV test, device: Eye Super UV tester S-UV-161 (manufactured by Iwasaki Electric)), which is an accelerated weather resistance test, test method: irradiation ⁇ darkness ⁇ repeated dew condensation, illuminance at the time of irradiation : Confirm the life at 900 w / m2 (300 to 400 nm)).
  • the integrated light amount is obtained by the product of illuminance and time, but as shown in FIG. 5, when the integrated light amount is the same, there is almost no effect of illuminance on the surface Young's modulus of the modified layer. That is, the surface Young's modulus is the same regardless of whether the ultraviolet rays having a strong illuminance are irradiated for a short time or the ultraviolet rays having a weak illuminance are irradiated for a long time if the integrated light amount is finally the same.
  • the thickness of the modified layer in the depth direction becomes thicker as the illuminance becomes stronger when the integrated light amount is the same. It is considered that this is because the stronger the illuminance of the ultraviolet rays to be irradiated, the deeper the light penetrates into the hard coat layer and the reform proceeds.
  • the thickness of the modified layer was 60 nm even when the same integrated light amount was irradiated, whereas in Example 1 and Example 2, the thickness could be increased to 70 nm and 100 nm, respectively, as compared with the conventional example.
  • the surface Young's modulus of these samples was able to form a modified layer of 7.8 GPa or more, and even in the Taber wear test, the ⁇ Haze value was recorded as 1.3% even in the conventional example, which is sufficient scratch resistance. It can be seen that it has.
  • the weather resistance was improved in Examples 1 and 2 in which the modified layer was thickened. doing. It is considered that the thicker the modified layer, the gentler the slope of Young's modulus in the modified layer, and the stress applied to the film is relaxed, so that the weather resistance is improved.
  • the thickness of the modified layer As a result of the above comparative test, by setting the thickness of the modified layer to 70 nm or more, it is possible to form a modified layer having high weather resistance without impairing high scratch resistance.
  • the method for producing the car resin molded product, the car window resin molded product, and the resin molded product of the present invention is not limited to the above embodiment, and the combination and material of the resin and the constituent coating layer are appropriately changed. It is also possible to arbitrarily change the configuration of each part within a range that does not deviate from the gist of the present invention.
  • the range in which the modified layer is formed may be limited to a specific location such as a wiper sliding portion.
  • a transparent resin substrate such as an acrylic resin, a cycloolefin polymer (COP), or polyethylene terephthalate (PET) can be used for the substrate 10.
  • the antifogging layer may be formed by superimposing it on the hard coat layer 12. Further, an antifouling functional layer may be provided on the hard coat layer 12, the modified layer 13, and the antifogging layer.

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  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Abstract

Provided are: a resin molded article having higher abrasion resistance and improved weather resistance; a resin molded article for a vehicle window; and a method for producing a resin molded article.　A rear module 1, which is a resin molded article, is constituted from: a substrate 10 made from a polycarbonate resin; a primer layer 11 made from an acrylic resin and formed on the substrate by applying a solvent and letting the solvent dry; and a hard coat layer 12 made from a silicone-based polymer and formed on the primer layer by applying a solvent and letting the solvent dry. The rear module also includes a modified layer 13 in which a hard layer is formed by irradiating and modifying the hard coat layer 12 with UV rays. The modified layer 13 is modified with high-illuminance UV light such that the modified layer 13 has a thickness of at least 70 nm, whereby a highly weather-resistant hard layer can be achieved while retaining high abrasion resistance.

Description

樹脂成形品、車窓用樹脂成形品、及び、樹脂成形品の製造方法Manufacturing method of resin molded products, resin molded products for car windows, and resin molded products
　本発明は、樹脂成形品、車窓用樹脂成形品、及び、樹脂成形品の製造方法に関する。 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.
　今日、車両用灯具、サンルーフ、ウィンドウなどに用いられていたガラス材をポリカーボネートやアクリルなどの透明樹脂材に置き換える技術が開発されている。樹脂材の採用は、車体重量の軽量化が図れるとともに、射出成形といった樹脂成形技術によって複雑な三次元形状などであっても自在に所望の形状に成形できるため、車両外観のデザイン性向上にも適している。 Today, a technology is being developed to replace the glass material used for vehicle lamps, sunroofs, windows, etc. with a transparent resin material such as polycarbonate or acrylic. The use of resin material can reduce the weight of the car body and can freely shape even complicated three-dimensional shapes by resin molding technology such as injection molding, which also improves the design of the vehicle appearance. Are suitable.
　しかし、樹脂材は、ガラス材に比べて耐擦傷性や耐候性が低いため、ワイパーの摩擦や太陽光に含まれる紫外線などによって、擦り傷や変色が生じやすいという問題があった。 However, since the resin material has lower scratch resistance and weather resistance than the glass material, there is a problem that scratches and discoloration are likely to occur due to the friction of the wiper and the ultraviolet rays contained in the sunlight.
　このため、従来、樹脂材表面に特殊なハードコートを施し、樹脂材表面の耐擦傷性や耐候性を向上させる技術が開発されている。例えば、図８に示すように、樹脂材にアクリル系ハードコートを施す方法、樹脂材に剥離防止用のプライマー層を形成した上にシリコーン系ハードコートを施す方法、ハードコート表面に、補強用の二酸化ケイ素（ＳｉＯ２）による硬質層を形成する方法等の技術が開示されている。これら３つの方法のうち、補強用の硬質層を形成する方法は、耐擦傷性を評価するテーバー摩耗試験において、従来のガラス材（テーバー摩耗後のΔＨａｚｅ値が２％程度）に比べ、特に高い耐擦傷性を付与することが分かっている。 For this reason, conventionally, a technique has been developed in which a special hard coat is applied to the surface of the resin material to improve the scratch resistance and weather resistance of the surface of the resin material. For example, as shown in FIG. 8, a method of applying an acrylic hard coat to a resin material, a method of applying a silicone hard coat on a resin material after forming a primer layer for preventing peeling, and a method of applying a silicone hard coat to the surface of the hard coat for reinforcement. Techniques such as a method of forming a hard layer with silicon dioxide (SiO2) are disclosed. Of these three methods, the method of forming a hard layer for reinforcement is particularly higher than the conventional glass material (ΔHaze value after taber wear is about 2%) in the taber wear test for evaluating scratch resistance. It is known to impart scratch resistance.
　硬質層を形成する方法としては、図９に示すように、化学蒸着法（ＣＶＤ法）といった真空成膜プロセスによる方法や、光改質法が採用できる。ここで、真空成膜プロセスとは、真空チャンバ内で、基材に硬質層成分を含む原料ガスを吹き付け、基材表面あるいは気相に化学反応による膜を堆積して硬質層を形成する方法であり、光改質法は、既にコーティングされたシリコーン系のハードコートに窒素フローをしながら、大気圧で基材に紫外線を照射し、表面を改質して硬質層を形成する方法である。ここでは、シリコーン系ポリマーに波長３６０ｎｍ以下の紫外線が照射されると、高分子の結合鎖（Ｓｉ－Ｃ結合鎖）が切断され、雰囲気中やハードコート、基材中に若干存在する酸素原子とケイ素原子が再結合し、二酸化ケイ素を主成分とする硬質層が形成される原理を採用している。 As a method for forming the hard layer, as shown in FIG. 9, a method by a vacuum film formation process such as a chemical vapor deposition method (CVD method) or a photoreforming method can be adopted. Here, the vacuum film forming process is a method of forming a hard layer by spraying a raw material gas containing a hard layer component on a base material in a vacuum chamber and depositing a film by a chemical reaction on the surface of the base material or the gas phase. The photomodification method is a method of irradiating a base material with ultraviolet rays at atmospheric pressure while applying nitrogen flow to an already coated silicone-based hard coat to modify the surface to form a hard layer. Here, when the silicone-based polymer is irradiated with ultraviolet rays having a wavelength of 360 nm or less, the bond chain (Si—C bond chain) of the polymer is cut, and oxygen atoms slightly present in the atmosphere, hard coat, and base material are formed. It adopts the principle that silicon atoms are recombined to form a hard layer containing silicon dioxide as a main component.
　特許文献１～３では、ＣＶＤ法等の真空成膜プロセスを用いて硬質層を形成している。特許文献１では、樹脂基板の少なくとも一方の面に、アクリル樹脂の第１層、オルガノシロキサン硬化物の第２層、真空成膜プロセスにより形成される二酸化ケイ素の第３層をこの順に積層した高分子樹脂積層体が紹介されている。また、特許文献２には、架橋樹脂層に酸化ケイ素層をＣＶＤ法等の真空成膜プロセスにより積層した高分子樹脂積層体が紹介されている。さらに、特許文献３では、透明な樹脂基板の少なくとも一方の面に形成されたハードコート層に、真空蒸着重合によって形成された有機高分子薄膜を含んで構成している。 In Patent Documents 1 to 3, a hard layer is formed by using a vacuum film forming process such as a CVD method. In Patent Document 1, a height in which a first layer of acrylic resin, a second layer of an organosiloxane cured product, and a third layer of silicon dioxide formed by a vacuum film forming process are laminated in this order on at least one surface of a resin substrate. A molecular resin laminate is introduced. Further, Patent Document 2 introduces a polymer resin laminate in which a silicon oxide layer is laminated on a crosslinked resin layer by a vacuum film forming process such as a CVD method. Further, in Patent Document 3, the hard coat layer formed on at least one surface of the transparent resin substrate includes an organic polymer thin film formed by vacuum vapor deposition polymerization.
　一方、上述の真空成膜プロセスに対し、光改質法では、真空チャンバのような大がかりな装置が不要となるため、コスト面において優れている。また、真空成膜プロセスによると、原料ガスを吹き付けて硬質層を積層するため、硬質層とハードコート層との間に界面が生じ、界面部分で硬質層が剥離するおそれがある。この点においても、光改質法では、硬質層とハードコート層との間に界面が無く、剥離は生じない。このように、光改質法は、耐擦傷性、耐候性においても優れている。 On the other hand, in contrast to the vacuum film formation process described above, the optical reforming method is superior in terms of cost because it does not require a large-scale device such as a vacuum chamber. Further, according to the vacuum film forming process, since the hard layer is laminated by spraying the raw material gas, an interface is formed between the hard layer and the hard coat layer, and the hard layer may be peeled off at the interface portion. In this respect as well, in the light reforming method, there is no interface between the hard layer and the hard coat layer, and peeling does not occur. As described above, the photo-modifying method is also excellent in scratch resistance and weather resistance.
　特許文献４～６では、光改質法を用いて硬質層を形成している。特許文献４では、シリコーン系のオルガノポリシロキサンを含むハードコートに、波長２００ｎｍ以下の紫外線を照射し、表面から厚み０．６μｍ未満の部分を高硬度化して硬質層を形成している。また、特許文献５では、オルガノポリシロキサンを含むハードコート剤組成物を樹脂基板の少なくとも一方の面に塗布して塗膜を形成し、その塗膜に熱処理、光照射処理、酸化処理等を施して、硬質層を形成する方法が紹介されている。さらに、特許文献６では、樹脂製モジュール基体にシリコーン系ポリマーを塗布してハードコートを形成し、ハードコート表面に波長３６０ｎｍ以下の紫外線を照射して、硬質層を形成した車両用の樹脂製複合モジュールが紹介されている。 In Patent Documents 4 to 6, a hard layer is formed by using a light reforming method. In Patent Document 4, a hard coat containing a silicone-based organopolysiloxane is irradiated with ultraviolet rays having a wavelength of 200 nm or less to increase the hardness of a portion having a thickness of less than 0.6 μm from the surface to form a hard layer. Further, in Patent Document 5, a hard coating agent composition containing an organopolysiloxane is applied to at least one surface of a resin substrate to form a coating film, and the coating film is subjected to heat treatment, light irradiation treatment, oxidation treatment and the like. The method of forming a hard layer is introduced. Further, in Patent Document 6, a silicone-based polymer is applied to a resin module substrate to form a hard coat, and the surface of the hard coat is irradiated with ultraviolet rays having a wavelength of 360 nm or less to form a hard layer. The module is introduced.
特許第４００７９２５号公報Japanese Patent No. 4007925 特許第４１７６５３８号公報Japanese Patent No. 4176538 特許第５４６８３６９号公報Japanese Patent No. 5468369 特許第４５３６８２４号公報Japanese Patent No. 4536824 特許第５７０８４９９号公報Japanese Patent No. 5708499 特開２０１９－５５３６６号公報Japanese Unexamined Patent Publication No. 2019-55366
　ところが、図１０に示すように、光改質法を用いた場合、シリコーン系ハードコートに照射する紫外線の積算光量を増加させて耐擦傷性を強めると、一方で耐候性が弱まってしまうという問題があった。 However, as shown in FIG. 10, when the light modification method is used, if 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 on the other hand. was there.
　そこで、本発明は、耐擦傷性を強めつつ、耐候性も向上させた樹脂成形品、車窓用樹脂成形品、および、樹脂成形品の製造方法を提供することを目的とする。 Therefore, an object of the present invention is to provide a resin molded product having improved scratch resistance and improved weather resistance, a resin molded product for a vehicle window, and a method for manufacturing the resin molded product.
　上記目的を達成するために、本発明は以下のような手段を採用した。
（１）透明樹脂基材の少なくとも一部をハードコート層により被覆してなる樹脂成形品であって、ハードコート層が、ハードコート層を所定の硬度以上となるように紫外光により改質した改質層を含み、改質層の厚さが７０ｎｍ以上であることを特徴とする樹脂成形品。
（２）（１）に記載の樹脂成形品を備えた車窓用樹脂成形品であって、改質層が車室外側に形成されたことを特徴とする車窓用樹脂成形品。
（３）透明樹脂基材の少なくとも一部をハードコート層により被覆する工程と、ハードコート層の表面に紫外光を照射して、所定の硬度以上の改質層を形成する工程と、を備え、ハードコート層が、改質層を含み、改質層の厚さが、７０ｎｍ以上であることを特徴とする樹脂成形品の製造方法。 In order to achieve the above object, the present invention employs the following means.
(1) A resin molded product in which at least a part of a transparent resin base material is coated with a hard coat layer, and the hard coat layer is modified by ultraviolet light so that the hard coat layer has a predetermined hardness or more. A resin molded product containing a modified layer and having a modified layer having a thickness of 70 nm or more.
(2) A resin molded product for a vehicle window provided with the resin molded product according to (1), wherein the modified layer is formed on the outside of the vehicle interior.
(3) A step of coating at least a part of the transparent resin base material with a hard coat layer and a step of irradiating the surface of the hard coat layer with ultraviolet light to form a modified layer having a predetermined hardness or more are provided. A method for producing a resin molded product, wherein the hard coat layer includes a modified layer and the thickness of the modified layer is 70 nm or more.
　本発明の樹脂成形品、車窓用樹脂成形品、および、樹脂成形品の製造方法によれば、改質層の厚みを７０ｎｍ以上とすることで、耐擦傷性を強めつつ、耐候性も向上することが可能となる。 According to the resin molded product, the resin molded product for vehicle windows, and the method for producing the resin molded product of the present invention, by setting the thickness of the modified layer to 70 nm or more, the scratch resistance is enhanced and the weather resistance is also improved. It becomes possible.
図１は、本発明の車窓用樹脂成形品の実施形態を示すリアモジュール、および、リアモジュールを搭載した車両の概略図である。FIG. 1 is a schematic view of a rear module showing an embodiment of a resin molded product for a vehicle window of the present invention, and a vehicle equipped with the rear module. 図２は、図１のリアモジュールに係る樹脂層の構成を示す模式図である。FIG. 2 is a schematic view showing the structure of the resin layer according to the rear module of FIG. 図３は、積算光量と表面ヤング率の相関を示すグラフである。FIG. 3 is a graph showing the correlation between the integrated light intensity and the surface Young's modulus. 図４は、表面ヤング率とテーバー摩耗試験結果の相関を示すグラフである。FIG. 4 is a graph showing the correlation between the surface Young's modulus and the Taber wear test result. 図５は、一定積算光量下における、照度と表面ヤング率の相関を示すグラフである。FIG. 5 is a graph showing the correlation between illuminance and Young's modulus under a constant integrated light intensity. 図６は、一定積算光量下における、照度と改質層厚さの相関を示すグラフである。FIG. 6 is a graph showing the correlation between the illuminance and the thickness of the modified layer under a constant integrated light intensity. 図７は、一定積算光量下で、照度・照射距離・照射時間を変更して実験を行った結果を示す一覧表である。FIG. 7 is a list showing the results of an experiment in which the illuminance, the irradiation distance, and the irradiation time were changed under a constant integrated light intensity. 図８は、従来のハードコートを示す表である。FIG. 8 is a table showing a conventional hard coat. 図９は、従来の硬質層の形成方法を比較した表である。FIG. 9 is a table comparing conventional methods for forming a hard layer. 図１０は、従来の方法により形成した硬質層の耐擦傷性および耐候性を積算光量ごとに示す表である。FIG. 10 is a table showing the scratch resistance and weather resistance of the hard layer formed by the conventional method for each integrated light intensity.
　以下、本発明を樹脂製のリアモジュールに具体化した実施形態を、図面に基づいて説明する。図１に示すように、リアモジュール１は、車窓用樹脂成形品としてのリアウィンドウ３と、リアコンビネーションランプ（ＲＣＬ）４と、ウィンドウクリーナー５と、ハイマウントストップランプ（ＨＭＳＬ）６と、ライセンスプレートランプ（ＬＰＬ）７と、ディスプレイ８等から構成され、車両後部を覆うように車体２に嵌め込まれている。リアモジュール１に、スポイラー９を形成することも好適に採用できる。リアモジュール１に樹脂材を用いることで、車両全体を軽量化することができ、また、複雑な三次元形状を自在に形成して車両外観のデザイン性を向上させることができる。さらに、車両後部の部品を一体にまとめてモジュール化することで、車両の組み立て工数を削減し、低コスト化することができる。 Hereinafter, embodiments in which the present invention is embodied in a resin rear module will be described with reference to the drawings. As shown in FIG. 1, the rear module 1 includes a rear window 3 as a resin molded product for a vehicle window, a rear combination lamp (RCL) 4, a window cleaner 5, a high mount stop lamp (HMSL) 6, and a license plate. It is composed of a lamp (LPL) 7, a display 8, and the like, and is fitted into the vehicle body 2 so as to cover the rear portion of the vehicle. It is also possible to preferably adopt the spoiler 9 formed on the rear module 1. By using a resin material for the rear module 1, the weight of the entire vehicle can be reduced, and a complicated three-dimensional shape can be freely formed to improve the design of the vehicle appearance. Further, by integrating the parts at the rear of the vehicle into a module, the man-hours for assembling the vehicle can be reduced and the cost can be reduced.
  図２に示すように、リアモジュール１は、ポリカーボネート樹脂よりなる基体１０と、アクリル系樹脂よりなるプライマー層１１と、シリコーン系ポリマーよりなるハードコート層１２と、ハードコート層１２の表面を紫外光により光改質して硬質層に改質した改質層１３とを含む、樹脂積層体から構成され、改質層１３が車室外側に形成されている。ここで、プライマー層１１は、主に、基体１０とハードコート層１２の応力を緩和して、基体１０とハードコート層１２の密着性を向上させる役割があるが、耐候性を向上させる効果も有する。また、ハードコート層１２は、基体１０を保護するための硬度を有し、耐候性を向上させる効果を有する。そして、改質層１３には、耐擦傷性を向上させる効果がある。 As shown in FIG. 2, in the rear module 1, the surface of the base 10 made of a polycarbonate resin, the primer layer 11 made of an acrylic resin, the hard coat layer 12 made of a silicone polymer, and the hard coat layer 12 is exposed to ultraviolet light. It is composed of a resin laminate including a modified layer 13 which has been photomodified by the above and modified into a hard layer, and the modified layer 13 is formed on the outside of the vehicle interior. Here, the primer layer 11 mainly has a role of relaxing the stress between the substrate 10 and the hard coat layer 12 to improve the adhesion between the substrate 10 and the hard coat layer 12, but also has the effect of improving the weather resistance. Have. Further, the hard coat layer 12 has a hardness for protecting the substrate 10 and has an effect of improving weather resistance. The modified layer 13 has an effect of improving scratch resistance.
  プライマー層１１は、基体１０の表面にアクリル系樹脂よりなるプライマー溶剤をディップコート法（湿式法）によって塗布し、室温で乾燥させ、所定時間加熱して硬化乾燥させ形成する。また、ハードコート層１２は、プライマー層１１の上にシリコーン系ポリマーのハードコート溶剤をディップコート法により塗布し、室温で乾燥させ、所定時間加熱して硬化乾燥させ形成する。 The primer layer 11 is formed by applying a primer solvent made of an acrylic resin to the surface of the substrate 10 by a dip coating method (wet method), drying at room temperature, and heating for a predetermined time to cure and dry. Further, the hard coat layer 12 is formed by applying a hard coat solvent of a silicone polymer on the primer layer 11 by a dip coat method, drying at room temperature, heating for a predetermined time, and curing and drying.
　そして、改質層１３は、紫外光により光改質させ形成する。ここでは、波長１７２ｎｍにピークを持つ紫外光を照射できる高出力・高照度のエキシマランプを採用する。紫外線が照射されることでハードコート層１２の表面付近が光改質されて硬化し、硬質層としての改質層１３が形成される。 Then, the modified layer 13 is formed by photomodifying with ultraviolet light. Here, a high-output, high-illuminance excimer lamp capable of irradiating ultraviolet light having a peak at a wavelength of 172 nm is adopted. When irradiated with ultraviolet rays, the vicinity of the surface of the hard coat layer 12 is photomodified and hardened, and the modified layer 13 as a hard layer is formed.
　このとき、紫外光は高出力・高照度であることが好ましい。高出力・高照度の紫外光を用いることにより、低出力・低照度の紫外光を用いた場合に比べて改質層１３を厚く形成できる。特に、改質層１３は、７０ｎｍ以上の厚みとすることが好ましい。７０ｎｍ以上の厚みを有することにより改質層１３表面の耐擦傷性を向上させつつ、耐候性も具備した改質層１３を形成することができる。 At this time, it is preferable that the ultraviolet light has high output and high illuminance. By using high-power, high-illuminance ultraviolet light, the modified layer 13 can be formed thicker than when low-power, low-illuminance ultraviolet light is used. In particular, the modified layer 13 preferably has a thickness of 70 nm or more. By having a thickness of 70 nm or more, it is possible to form the modified layer 13 having weather resistance while improving the scratch resistance on the surface of the modified layer 13.
　続いて、図３～図７に基づいて、本発明の実施形態の効果を裏付けるために発明者が行った各種評価試験について説明する。 Subsequently, various evaluation tests conducted by the inventor in order to support the effects of the embodiments of the present invention will be described with reference to FIGS. 3 to 7.
　硬質層である改質層の硬度は、ナノインデンターによる所定の測定条件（装置：ＫＬＡ社製Ｇ２００型ナノインデンター　高分解能　ＤＣＭ－ＩＩヘッド（最大荷重：３０ｍＮ）バーコビッチ圧子、測定モード：連続剛性測定法（ＣＳＭ）、押し込み深さ：１０００ｎｍ、振動周波数：６５Ｈｚ、振動振幅：１ｎｍ）で深さ方向のヤング率や硬度を測定する事により、光改質でハードコートがどの深さまで、どの程度硬くなったかを確認する。なお、ここでいう「改質層」とは、弾性率を示すヤング率が５ＧＰａ以上の部位をいう。耐擦傷性については、テーバー摩耗試験（摩耗輪ＣＳ－１０Ｆ、０．５ｋｇ荷重）により確認する。テーバー摩耗１０００回転前後のΔＨａｚｅ値（％）が小さいほど傷が付きにくいといえる。耐候性については、促進耐候性試験であるスーパーＵＶ試験（ＳＵＶ試験、装置：アイスーパーＵＶテスター　Ｓ－ＵＶ－１６１（岩崎電機製）、試験方法：照射→暗黒→結露の繰り返し、照射時の照度：９００ｗ／ｍ２（３００～４００ｎｍ））での寿命を確認する。 The hardness of the modified layer, which is a hard layer, is determined by the predetermined measurement conditions by the nano indenter (device: KLA G200 type nano indenter, high resolution DCM-II head (maximum load: 30 mN), Berkovich indenter, measurement mode: continuous rigidity. By measuring Young's modulus and hardness in the depth direction by measurement method (CSM), indentation depth: 1000 nm, vibration frequency: 65 Hz, vibration amplitude: 1 nm), to what depth and how much hard coat can be obtained by photomodification. Check if it has hardened. The term "modified layer" as used herein refers to a portion having a Young's modulus of 5 GPa or more, which indicates an elastic modulus. The scratch resistance is confirmed by a taber wear test (wear wheel CS-10F, 0.5 kg load). It can be said that the smaller the ΔHaze value (%) around 1000 rotations of the taber wear, the less likely it is to be scratched. Regarding weather resistance, Super UV test (SUV test, device: Eye Super UV tester S-UV-161 (manufactured by Iwasaki Electric)), which is an accelerated weather resistance test, test method: irradiation → darkness → repeated dew condensation, illuminance at the time of irradiation : Confirm the life at 900 w / m2 (300 to 400 nm)).
　図３に示すように、光改質時に照射する積算光量が多いほど、改質層の表面ヤング率は向上することが分かる。さらに、図４に示すように、テーバー摩耗試験によるΔＨａｚｅ値の変化を見ても、照射する積算光量が多いほど、耐擦傷性が向上する事が分かる。 As shown in FIG. 3, it can be seen that the surface Young's modulus of the modified layer improves as the integrated amount of light emitted during photomodification increases. Further, as shown in FIG. 4, it can be seen from the change in the ΔHaze value by the Taber wear test that the scratch resistance is improved as the integrated light intensity to be irradiated increases.
　積算光量は照度と時間の積によって求められるが、図５に示すように、積算光量が同じ場合、改質層の表面ヤング率への照度による影響はほとんどない。つまり、強い照度の紫外線を短時間照射した場合も、弱い照度の紫外線を長時間照射した場合も最終的に積算光量が同じであれば表面ヤング率は同等となる。それに対し、図６に示すように、改質層の深さ方向への厚さは積算光量が同じ場合、照度が強いほど厚くなる。これは、照射する紫外線の照度を強くすればするほどハードコート層の深くまで光が侵入し改質が進むためと考えられる。 The integrated light amount is obtained by the product of illuminance and time, but as shown in FIG. 5, when the integrated light amount is the same, there is almost no effect of illuminance on the surface Young's modulus of the modified layer. That is, the surface Young's modulus is the same regardless of whether the ultraviolet rays having a strong illuminance are irradiated for a short time or the ultraviolet rays having a weak illuminance are irradiated for a long time if the integrated light amount is finally the same. On the other hand, as shown in FIG. 6, the thickness of the modified layer in the depth direction becomes thicker as the illuminance becomes stronger when the integrated light amount is the same. It is considered that this is because the stronger the illuminance of the ultraviolet rays to be irradiated, the deeper the light penetrates into the hard coat layer and the reform proceeds.
　そこで、上述の実施形態の樹脂成形品の３つのサンプルを比較する試験を行った。紫外線照射の積算光量を全て２０００ｍＪ／ｃｍ２とした上で、光照射の出力を１０ｍＷ／ｃｍ２の照度のもの（従来例）、４０ｍＷ／ｃｍ２の照度のもの（実施例１）、１４０ｍＷ／ｃｍ２の照度のもの（実施例２）として光改質をしたハードコートの表面ヤング率と改質層の深さを比較した。図７に試験結果を示す。従来例では、同じ積算光量を照射しても改質層の厚さが６０ｎｍなのに対して、実施例１及び実施例２では、それぞれ７０ｎｍ、１００ｎｍと従来例より厚みを増すことができた。 Therefore, a test was conducted in which three samples of the resin molded product of the above-described embodiment were compared. After setting the integrated light amount of ultraviolet irradiation to 2000 mJ / cm 2 , the output of light irradiation is 10 mW / cm 2 illuminance (conventional example), 40 mW / cm 2 illuminance (Example 1), 140 mW / The surface young rate of the light-modified hard coat and the depth of the modified layer were compared with those having an illuminance of cm 2 (Example 2). FIG. 7 shows the test results. In the conventional example, the thickness of the modified layer was 60 nm even when the same integrated light amount was irradiated, whereas in Example 1 and Example 2, the thickness could be increased to 70 nm and 100 nm, respectively, as compared with the conventional example.
　これらのサンプルの表面ヤング率はいずれも７．８ＧＰａ以上の改質層を形成できており、テーバー摩耗試験においても、ΔＨａｚｅ値が従来例でも１．３％の値が記録され十分な耐擦傷性を有していることが分かる。一方、ＳＵＶ試験の結果に示されるように、従来例の光改質では十分な耐候性が得られていないが、改質層が厚くなった実施例１及び実施例２においては耐候性が向上している。これは、改質層が厚い方が改質層内のヤング率の傾斜が緩やかになっており、膜にかかる応力が緩和されるため、耐候性が向上したものと考えられる。 The surface Young's modulus of these samples was able to form a modified layer of 7.8 GPa or more, and even in the Taber wear test, the ΔHaze value was recorded as 1.3% even in the conventional example, which is sufficient scratch resistance. It can be seen that it has. On the other hand, as shown in the results of the SUV test, sufficient weather resistance was not obtained by the conventional photo-modification, but the weather resistance was improved in Examples 1 and 2 in which the modified layer was thickened. doing. It is considered that the thicker the modified layer, the gentler the slope of Young's modulus in the modified layer, and the stress applied to the film is relaxed, so that the weather resistance is improved.
　以上のような比較試験の結果、改質層の厚さを７０ｎｍ以上とすることで、高い耐擦傷性を損なわずに、耐候性の高い改質層を形成することができる。 As a result of the above comparative test, by setting the thickness of the modified layer to 70 nm or more, it is possible to form a modified layer having high weather resistance without impairing high scratch resistance.
　なお、本発明の車樹脂成形品、車窓用樹脂成形品、及び、樹脂成形品の製造方法は前記実施形態に限定されるものではなく、樹脂や構成するコーティング層の組み合わせや材質を適宜に変更するなど、本発明の趣旨を逸脱しない範囲で各部の構成を任意に変更して実施することも可能である。例えば、改質層を形成する範囲を、ワイパー摺動部など、特定の箇所に限定して形成してもよい。また、
基体１０にポリカーボネート系の樹脂に代えて、アクリル系樹脂、シクロオレフィンポリマー（ＣＯＰ）、ポリエチレンテレフタレート（ＰＥＴ）等の透明樹脂基材を使用することができる。そして、ハードコート層１２に重ねて防曇層を形成してもよい。さらに、ハードコート層１２や改質層１３、防曇層に重ねて防汚機能層を設けることもできる。 The method for producing the car resin molded product, the car window resin molded product, and the resin molded product of the present invention is not limited to the above embodiment, and the combination and material of the resin and the constituent coating layer are appropriately changed. It is also possible to arbitrarily change the configuration of each part within a range that does not deviate from the gist of the present invention. For example, the range in which the modified layer is formed may be limited to a specific location such as a wiper sliding portion. Also,
Instead of the polycarbonate resin, a transparent resin substrate such as an acrylic resin, a cycloolefin polymer (COP), or polyethylene terephthalate (PET) can be used for the substrate 10. Then, the antifogging layer may be formed by superimposing it on the hard coat layer 12. Further, an antifouling functional layer may be provided on the hard coat layer 12, the modified layer 13, and the antifogging layer.
　１　　リアモジュール
　２　　車体
　３　　リアウィンドウ
　４　　リアコンビネーションランプ
　５　　ウィンドウクリーナー
　６　　ハイマウントストップランプ
　７　　ライセンスプレートランプ
　８　　ディスプレイ
　９　　スポイラー
１０　　基体
１１　　プライマー層
１２　　ハードコート層
１３　　改質層

  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 Base 11 Primer layer 12 Hard coat layer 13 Modified layer

Claims (3)

  1. 　透明樹脂基材の少なくとも一部をハードコート層により被覆してなる樹脂成形品であって、
    　前記ハードコート層が、前記ハードコート層を所定の硬度以上となるように紫外光により改質した改質層を含み、
    　前記改質層の厚さが７０ｎｍ以上であることを特徴とする樹脂成形品。     A resin molded product obtained by coating at least a part of a transparent resin base material with a hard coat layer.
    The hard coat layer contains a modified layer obtained by modifying the hard coat layer with ultraviolet light so as to have a hardness equal to or higher than a predetermined hardness.
    A resin molded product having a modified layer having a thickness of 70 nm or more.
  2. 　請求項１に記載の樹脂成形品を備えた車窓用樹脂成形品であって、
    　前記改質層が車室外側に形成されたことを特徴とする車窓用樹脂成形品。     A resin molded product for a vehicle window provided with the resin molded product according to claim 1.
    A resin molded product for a vehicle window, wherein the modified layer is formed on the outside of the vehicle interior.
  3. 　透明樹脂基材の少なくとも一部をハードコート層により被覆する工程と、前記ハードコート層の表面に紫外光を照射して、所定の硬度以上の改質層を形成する工程と、を備え、
    　前記ハードコート層が、前記改質層を含み、前記改質層の厚さが、７０ｎｍ以上であることを特徴とする樹脂成形品の製造方法。


          A step of coating at least a part of the transparent resin base material with a hard coat layer and a step of irradiating the surface of the hard coat layer with ultraviolet light to form a modified layer having a predetermined hardness or more are provided.
    A method for producing a resin molded product, wherein the hard coat layer includes the modified layer, and the thickness of the modified layer is 70 nm or more.
PCT/JP2020/041512 2019-11-12 2020-11-06 Resin molded article, resin molded article for vehicle window, and method for producing resin molded article WO2021095649A1 (en)

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JP2016030392A (en) * 2014-07-29 2016-03-07 旭硝子株式会社 Resin substrate with hard coat layer and method for producing the same
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