Resin glass, method for producing resin glass, and device for producing resin glass

Abstract

Provided is a resin glass having excellent surface wear resistance. Also provided are a method and a device for producing the resin glass. The resin glass is provided with a substrate exhibiting visible light transmissivity and a hard coat layer formed on the upper layer of the substrate and containing a silicone polymer, the hard coat layer has, on the surface thereof, a modified region in which the ratio of an inorganic glass component is higher than the surface on the substrate side, and the ratio of the inorganic glass component in the modified region is 40%-50%.

Description

Technical Field

[0001] This invention relates to resin glass, a method for manufacturing resin glass, and an apparatus for manufacturing resin glass. Background Technology

[0002] For example, as a window material for openings in automobiles and construction machinery, the use of resin glass instead of silicate glass has been studied. Resin materials such as polycarbonate, which constitute resin glass, are expected to have the same light transmittance for visible light as silicate glass. Furthermore, resin materials such as polycarbonate have advantages such as ease of molding or excellent thermal insulation.

[0003] However, resin materials such as polycarbonate are prone to surface damage. To address this, techniques exist for forming a hard coating containing an organosilicon polymer on a substrate made of this resin material and then irradiating the hard coating with ultraviolet light. For example, as shown in Patent Document 1, by irradiating the hard coating with ultraviolet light, the surface of the hard coating is modified, thereby improving the wear resistance of the surface of the substrate made of this resin material.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent No. 6434350 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] The inventors investigated forming a hard coating containing an organosilicon polymer on a polycarbonate substrate and modifying the hard coating by ultraviolet light irradiation, thereby obtaining resin glass with improved surface abrasion resistance. However, they discovered the following problem: while modifying the hard coating improves the surface abrasion resistance of the resin glass, excessive modification of the hard coating reduces surface abrasion resistance, making it impossible to obtain resin glass with excellent abrasion resistance.

[0009] In view of the above, the object of the present invention is to provide a resin glass with excellent surface abrasion resistance. Furthermore, the object of the present invention is to provide a method and apparatus for manufacturing the aforementioned resin glass.

[0010] Methods for solving problems

[0011] The resin glass of the present invention is characterized in that it has a substrate that exhibits visible light transmittance and a hard coating layer containing an organosilicon polymer formed on the upper layer of the substrate, wherein the hard coating layer has a modified region on the surface having a higher ratio of inorganic glass components than the side of the substrate, and the ratio of inorganic glass components in the modified region is 40% to 50%.

[0012] "Displaying visible light transmittance" means that the transmittance of visible light is 70% or more, preferably 80% or more, and more preferably 90% or more.

[0013] In addition, in this specification, "organosilicon polymer" refers to a polymer having siloxane bonds and having organic groups such as methyl, phenyl, vinyl or alkoxy groups on its side chains.

[0014] The hard coating has modified regions on its surface formed by irradiation with ultraviolet light. Through in-depth research, the inventors discovered that the ratio of inorganic glass components in the modified regions is related to the abrasion resistance of the resin glass. Details are provided in the "Specific Embodiments" section. The inventors found that by setting the ratio of this inorganic glass component to 40% to 50%, a resin glass with excellent surface abrasion resistance can be obtained, thus proposing the above-described configuration.

[0015] Details will be provided later. The "ratio of inorganic glass components" is obtained by calculating the ratio of inorganic glass components to the sum of organosilicon components and inorganic glass components obtained by analyzing the surface of the hard coating using ATR-FTIR infrared spectroscopy.

[0016] The aforementioned resin glass can be used for automobile windshields.

[0017] Currently, for automotive windshields, the required abrasion resistance index, Δhaze value, is below 2% as obtained through the abrasion test specified in JIS R 3212 (Test Methods for Safety Glass for Automotive Use). The Δhaze value is an index representing the difference between the haze value before and after the abrasion test; the higher the abrasion resistance, the smaller the Δhaze value.

[0018] The haze value is a numerical value obtained by quantifying the degree of diffusion of light transmitted from the sample.

[0019] In addition, Europe and the United States have also established abrasion resistance standards for automotive windshields. Currently, standards such as ECE R43 have been established in Europe, and standards such as ANSI Z26.1 have been established in the United States.

[0020] Details will be described later. Based on the above composition, a resin glass with a Δ haze value of 2% or less can be obtained. That is, the above-mentioned resin glass is suitable for use in automotive windshields.

[0021] In the aforementioned resin glass, the thickness of the modified region in the direction orthogonal to the main surface of the substrate can be in the submicron range.

[0022] In this specification, "main surface" refers to the surface of a plate-shaped object whose area is much larger than other surfaces.

[0023] The method for manufacturing resin glass according to the present invention is characterized by comprising the following steps: irradiating a hard coating containing an organosilicon polymer formed on the upper layer of a substrate that exhibits visible light transmittance with ultraviolet light in a wavelength region with a main wavelength below 243 nm, modifying the surface of the hard coating to form a modified region, wherein the step of forming the modified region is to irradiate the hard coating with ultraviolet light in such a way that the ratio of inorganic glass component in the modified region reaches 40% to 50%.

[0024] Here, "dominant wavelength" refers to the wavelength λi in the emission spectrum that exhibits more than 40% of the integrated intensity relative to the total integrated intensity within a wavelength region Z(λ) defined relative to a certain wavelength λ ± 10 nm. For example, in light sources such as excimer lamps containing luminescent gases like Xe, which have extremely narrow half-widths and exhibit light intensity only at specific wavelengths, the wavelength with the highest relative intensity (main peak wavelength) can usually be used as the dominant wavelength.

[0025] Furthermore, in the resin glass manufacturing apparatus of the present invention, a substrate exhibiting visible light transmittance is irradiated with ultraviolet light to modify the surface of the hard coating having a hard coating containing an organosilicon polymer, thereby forming a modified region. The resin glass manufacturing apparatus is characterized by having a support portion for supporting the substrate and a light source for emitting ultraviolet light with a main wavelength in the wavelength region below 243 nm toward the substrate. The light source irradiates the hard coating with the ultraviolet light at a cumulative light intensity of 40% to 50% of the inorganic glass component ratio of the modified region.

[0026] The aforementioned resin glass manufacturing apparatus may include a storage unit that stores a cumulative light quantity in which the ratio of inorganic glass components in the modified region reaches 40% to 50%, and a control unit that controls the lighting operation of the light source based on the cumulative light quantity stored in the storage unit.

[0027] Specific examples of the manufacturing method and apparatus for the aforementioned resin glass will be described later.

[0028] Invention Effects

[0029] According to the present invention, a resin glass with excellent surface abrasion resistance is provided. Furthermore, according to the present invention, a method and apparatus for manufacturing the above-described resin glass are provided. Attached Figure Description

[0030] Figure 1 This is a cross-sectional view showing the structure of an embodiment of resin glass.

[0031] Figure 2 This diagram shows the substrate, the base coating, and the hard coating separately.

[0032] Figure 3 This diagram illustrates the process of irradiating a hard coating with ultraviolet light.

[0033] Figure 4 This is a schematic diagram illustrating the structure of the silicone polymer that constitutes the hard coating.

[0034] Figure 5 This is a schematic diagram showing the structure of a silicone polymer after being irradiated with ultraviolet light.

[0035] Figure 6 An example of the transmission spectrum of an organosilicon polymer obtained by infrared spectroscopy (ATR-FTIR).

[0036] Figure 7 This is a graph showing the results of verification 1.

[0037] Figure 8 This is a graph showing the results of verification 2.

[0038] Figure 9 This is a diagram showing an example of the configuration of a resin glass manufacturing apparatus. Detailed Implementation

[0039] The resin glass of the present invention will now be described with appropriate reference to the accompanying drawings. It should be noted that the following drawings are schematic illustrations, and the size ratios and numbers shown in the drawings may not necessarily correspond to the actual size ratios and numbers.

[0040] Figure 1 This is a cross-sectional view showing the structure of an embodiment of resin glass 1. (As shown) Figure 1 As shown, the resin glass 1 is a laminate comprising a substrate 3, a base coating 5 formed on the upper layer of the substrate 3, and a hard coating 7 formed on the upper layer of the substrate 3 through the base coating 5. Furthermore, the hard coating 7 has modified regions 9 on its surface formed by irradiation with ultraviolet light L1.

[0041] In the following figures, the XYZ coordinate system is appropriately referenced, in which the direction orthogonal to the main surface 3a of the substrate 3 is defined as the Z direction, and the plane orthogonal to the Z direction is defined as the XY plane.

[0042] Furthermore, in this specification, the phrase "layer B is formed on top of layer A" naturally includes the case where layer B is formed directly on the surface of layer A, and also intends to include the case where layer B is formed on the surface of layer A with a layer different from layer B in between. Additionally, "top layer" here refers to a direction moving away from a substrate such as a polycarbonate substrate in the Z direction.

[0043] The details of the resin glass 1 and its manufacturing method will be described below.

[0044] [Preparation of substrate 3]

[0045] Figure 2 This diagram illustrates the substrate 3, the base coating 5, and the hard coating 7 separately, from an easily understandable perspective. First, a substrate 3, exhibiting visible light transmittance, is prepared. The material constituting the substrate 3 is arbitrary as long as it exhibits visible light transmittance; for example, the substrate 3 is made of a synthetic resin such as polycarbonate or acrylic. Furthermore, the shape and size of the substrate 3 can be considered in various ways. For example, the substrate 3 may be a rectangular plate with a long side of 1500 mm.

[0046] [Formation of base coating 5]

[0047] Next, as Figure 2 As shown, a base coating 5 is formed on the upper layer of the substrate 3. Specifically, after cleaning the substrate 3 to remove dust and other contaminants adhering to the main surface 3a, the substrate 3 is immersed in a primer liquid, or the primer liquid is sprayed onto the substrate 3 using a spray gun or similar means, thereby applying the primer liquid onto the substrate 3. Then, by drying at a specified temperature for a certain period of time, the base coating 5 is formed on the upper layer of the substrate 3.

[0048] The base coating 5 is made of a material primarily composed of acrylic resin. For example, the base coating 5 is made of Momentive SHP470 FT-2050. The base coating 5 is provided to improve the adhesion between the substrate 3 and the hard coating 7, and the weather resistance of the resin glass 1. In this invention, whether or not the base coating 5 is formed is optional.

[0049] [Formation of hard coating 7]

[0050] Next, as Figure 2 As shown, a hard coating 7 is formed on top of the substrate 3, separated by a base coating 5. The hard coating 7 is composed of a material whose main component is an organosilicon polymer with organic groups such as methyl groups bonded to the main chain formed by siloxane bonds as side chains. For example, the hard coating 7 is composed of Momentive AS4700F. Here, "main component" can refer to, for example, the material with the highest composition among the materials constituting the hard coating 7.

[0051] A coating film of the solution is formed on the substrate 3 by immersing the substrate 3 in a solution containing the aforementioned silicone polymer, or by spraying the solution onto the substrate 3 using a spray gun. The coating film is then dried at a specified temperature for a certain period of time, thereby forming a hard coating layer 7 on the upper layer of the substrate 3.

[0052] In addition to the above-described coating methods, the coating liquid forming the base layer 5 and the solution forming the hard layer 7 can also be applied by flow coating or other coating methods.

[0053] [Modification of Hard Coating 7]

[0054] Figure 3 This is a diagram showing the process of irradiating the hard coating 7 with ultraviolet light L1.

[0055] like Figure 3 As shown, the hard coating 7 is irradiated with ultraviolet light L1. Thus, as... Figure 1 As shown, the surface of the hard coating 7 is modified to form the modified region 9.

[0056] Irradiation with ultraviolet light L1, for example, using an excimer lamp containing a luminescent gas containing Xe as the light source (in... Figure 3 (Not illustrated in the image) This process is performed. In this case, the dominant wavelength of ultraviolet light L1 is 172 nm. Furthermore, by changing the composition of the luminescent gas in the excimer lamp, the dominant wavelength of ultraviolet light L1 can be varied. For example, combinations of luminescent gases and dominant wavelengths include Kr (146 nm), ArBr (165 nm), ArF (193 nm), KrBr (207 nm), and KrCl (222 nm). The dominant wavelength value mentioned here includes a variation of approximately ±2 nm due to individual differences such as the partial pressure of the luminescent gas.

[0057] The modification mechanism of the hard coating 7 based on ultraviolet light L1 is explained. Figure 4 This is a schematic diagram illustrating the structure of the silicone polymer constituting the hard coating 7. Additionally, Figure 5 This is a schematic diagram showing the structure of an organosilicon polymer after irradiation with ultraviolet light L1. Figure 4 and Figure 5 In this context, R represents an organic group such as methyl, phenyl, vinyl, or alkoxy. Additionally, "O" represents an organic group. 1 / 2 "This indicates that the Si atom bonded to the oxygen atom is bonded together with the adjacent Si atom.

[0058] like Figure 4 As shown, in the siloxane bonds constituting the hard coating 7, Si atoms a1 with 4 oxygen atoms and Si atoms a2 with bonds to organic groups coexist. Then, by irradiating the hard coating 7 with ultraviolet light L1 and supplying light energy (hν) corresponding to the wavelength, the Si-R bonds in the side chains of the siloxane bonds undergo photolysis.

[0059] Furthermore, ultraviolet light L1 photodecomposes oxygen molecules present in the atmosphere, generating excited oxygen (hereinafter referred to as "oxygen free radicals"). These oxygen free radicals then diffuse within the hard coating 7 and undergo photolytic partial bonding with the Si-R bonds. Thus, as... Figure 5 As shown, in the hard coating 7, the number of Si atoms a2 bonded to organic groups decreases, while the number of Si atoms a1 bonded to 4 oxygen atoms increases.

[0060] The state in which Si atoms are bonded to four oxygen atoms represents the vitrification (SiO2ization) state of the organosilicon polymer, which can be referred to as the "inorganic glass composition." Alternatively, for convenience, the state in which Si atoms have bonds with organic groups is referred to as the "organosilicon composition." By irradiating the hard coating 7 with ultraviolet light L1, a modified region 9 is formed on the surface of the hard coating 7, characterized by a reduced organosilicon composition and an increased inorganic glass composition. That is, the modified region 9 is a "region rich in inorganic glass," and in the modified region 9, for example, compared to the surface 7a on the substrate 3 side of the hard coating 7, there is a greater amount of inorganic glass composition.

[0061] The penetration depth of ultraviolet light L1 on the hard coating 7 is limited to a certain extent. This is believed to be due to the low transmittance of ultraviolet light L1 on the hard coating 7, resulting in a penetration depth of less than 1 μm. Therefore, the thickness D1 in the Z direction of the modified region 9 formed by ultraviolet light L1 irradiation is less than 1 μm, becoming submicron level (also refer to...). Figure 1 ).

[0062] "Submicron" can refer to the range of 0.1μm to 0.9μm.

[0063] Regarding the thickness D1 of the modified region 9, it can be measured, for example, by etching the modified region 9 with an aqueous solution of hydrofluoric acid at a concentration of approximately 2% while partially masking it. Then, the mask is removed, and the boundary between the etched region and the masked region is scanned using an elevation difference meter, thereby determining the thickness. An elevation difference meter such as the Dektak3 manufactured by Veeco can be used as such.

[0064] From the viewpoint of photo-breaking Si-R bonds and oxygen molecule bonds, ultraviolet light L1 preferably contains wavelength components that exhibit light energy higher than the bond energies of Si-R bonds and oxygen molecules. The bond energy of a Si-R bond is approximately 3.2 eV, which is approximately 388 nm in wavelength terms. Furthermore, the bond energy of an oxygen molecule is approximately 5.1 eV, which is approximately 243 nm in wavelength terms. The bond energy of the Si-O bonds forming the main chain is approximately 4.7 eV, which is approximately 264 nm in wavelength terms. That is, from the viewpoint of breaking these bonds, ultraviolet light L1 is preferably ultraviolet light in the wavelength region where the dominant wavelength is below 243 nm.

[0065] As an indicator of the extent of modification of the hard coating 7 based on ultraviolet light L1, the absorbance in each vibrational mode shown by the O-Si-O bond can be used. Figure 6 This is an example of the transmission spectrum of the hard coating 7 obtained through ATR-FTIR infrared spectroscopy. For example... Figure 6 As shown, the silicone polymer constituting the hard coating 7 is at a wavenumber of approximately 900 cm⁻¹. -1 ~1200cm -1The location shows light absorption originating from the symmetric variable-angle vibration and the antisymmetric stretching vibration of O-Si-O. Additionally, at... Figure 6 The diagram shows the result of separating the waveform of the light absorption into two waveforms (T1, T2) with peaks (P1, P2) respectively, with a baseline B0 as the transmittance of 0%.

[0066] like Figure 6 As shown, the organosilicon polymer at a wavenumber of approximately 1020 cm⁻¹ -1 The position shows the peak P1 corresponding to the symmetrical variable-angle vibration of O-Si-O, and the wavenumber is about 1100 cm⁻¹. -1 The position shows peak P2, corresponding to the antisymmetric stretching vibration of O-Si-O. Both waveforms T1 containing peak P1 and T2 containing peak P2 are convex towards the direction of low transmittance.

[0067] Peak P1 originates from the symmetrical vibrational mode of oxygen atoms relative to Si atoms. Therefore, even when comparing Si atoms a1 bonded to four oxygen atoms and Si atoms a2 bonded to organic groups, the difference in absorbance is small, resulting in a small difference in the intensity of peak P1 in the transmission spectrum. On the other hand, peak P2 originates from the antisymmetric vibrational mode of oxygen atoms relative to Si atoms. In Si atoms a1 bonded to four oxygen atoms, adjacent Si atoms are bonded via oxygen atoms, making it difficult for oxygen atoms to vibrate antisymmetrically relative to Si atoms. Therefore, peak P2 is reduced by modification based on ultraviolet light L1.

[0068] In view of this, Figure 6 In this context, the ratio of peak area A1 to the sum of the area enclosed by waveform T1 and baseline B0 (peak area A1) and the area enclosed by waveform T2 and baseline B0 (peak area A2) can be said to reflect the ratio of Si atoms a1 bonded to four oxygen atoms in the hard coating 7. Furthermore, the ratio of peak area A2 to the sum of peak area A1 and peak area A2 can be said to reflect the ratio of Si atoms a2 with bonds to organic groups in the hard coating 7.

[0069] The inventors, considering that peak P2 decreases and peak P1 relatively increases when modified region 9, which has Si atoms a1 bonded to four oxygen atoms (i.e., an increased inorganic glass content), is formed by irradiation with ultraviolet light L1, define the ratio of peak area A1 to the sum of peak area A1 and peak area A2 as the ratio of the inorganic glass content of modified region 9. Similarly, the ratio of Si atoms a2 bonded to organic groups (i.e., organosilicon content) in modified region 9 is defined as the ratio of peak area A2 to the sum of peak area A1 and peak area A2.

[0070] That is, the "ratio of inorganic glass components" is obtained by calculating the ratio of the peak area A1 in the ATR-FTIR spectrum to the sum of the peak areas A1 of peak P1 and A2 of peak P2.

[0071] ATR-FTIR is an analytical method for obtaining the transmission spectrum of the sample surface, which will be described in detail later. That is, by obtaining the ATR-FTIR spectrum of the hard coating 7, the ratio of inorganic glass components in the modified region 9 can be obtained, and the state of the modified region 9 formed by ultraviolet light L1 can be evaluated.

[0072] In this embodiment, the ratio of inorganic glass component in modified region 9 is 40% to 50%. Details will be explained in the "Verification" section below. By setting the ratio of inorganic glass component to 40% to 50%, resin glass 1 with excellent wear resistance can be obtained.

[0073] In the above description, the case where the resin glass 1 is a rectangular plate-like body has been described, but the present invention is not limited to the shape of the resin glass 1. For example, the resin glass 1 can be appropriately processed such as bending according to its intended use.

[0074] For example, resin glass 1 can be used as window material for automobile windshields.

[0075] [Verification 1]

[0076] The relationship between the ratio of inorganic glass components in the modified region 9 formed on the surface of the hard coating 7 and the Δ haze value, which represents the wear resistance of the resin glass 1, was verified and will be explained below.

[0077] (Sample 1)

[0078] Based on the above-described method for manufacturing resin glass 1, the manufacturing reference is... Figure 2 The resin glass with a laminated structure is described. The substrate 3 is made of polycarbonate. In addition, the base coating 5 is formed using Momentive SHP470 FT-2050, and the hard coating 7 is formed using Momentive AS4700F.

[0079] Next, the hard coating 7 formed on the substrate 3 is irradiated with ultraviolet light L1 to form a modified region 9 on the surface of the hard coating 7. The irradiation with ultraviolet light L1 is performed using an Xe excimer lamp containing a luminescent gas containing Xe as the light source. That is, the hard coating 7 is irradiated with ultraviolet light L1 with a main wavelength of 172 nm.

[0080] The cumulative light intensity of L1 ultraviolet light is 1 J / cm. 2 The cumulative light intensity was measured using a UIT-250 manufactured by Ushio Electric Corporation, equipped with a VUV-S172 as the light receiver.

[0081] Transmission spectra of the hard coating 7, and more specifically, the modified region 9, were obtained using ATR-FTIR. In ATR-FTIR, a crystal with a higher refractive index than the sample is brought into close contact with the sample surface. Infrared light is irradiated onto the sample from the side of this crystal, and the total internal reflection light that penetrates near the surface is measured, thereby obtaining the transmission spectrum of the sample surface. The measuring apparatus used was an FT / IR-4600 manufactured by Nippon Spectrophotometer Co., Ltd. Ge crystal was used as the high refractive index crystal. Furthermore, the incident angle of the infrared light was set to 45 degrees.

[0082] Then, as referenced Figure 6 As explained, the peak area A1 of peak P1, which originates from the symmetric variable-angle vibration of O-Si-O, and the peak area A2 of peak P2, which originates from the antisymmetric stretching vibration of Si-O-Si, are calculated. Furthermore, the ratio of each peak area (A1, A2) to the sum of the peak areas of the two is calculated, thereby determining the ratio of inorganic glass components and organosilicon components in modified region 9.

[0083] The analysis of peaks in the transmission spectrum is performed using the "Spectrum Manager," which is standard software included in the aforementioned measurement device.

[0084] Next, the method for determining the Δhaze value (%) of the resin glass will be explained. The Δhaze value was determined using a Taber 5130 abrasion testing machine (manufactured by TABER) and an abrasion wheel CS-10F (manufactured by TABER), according to the method specified in JIS R 3212 (Test Methods for Safety Glass for Automobiles). Specifically, the haze value (%) of the resin glass before and after abrasion was measured using a haze meter HZ-0 (manufactured by Suga Testing Machines Co., Ltd.), and the change in haze value (%) before and after abrasion was calculated, thereby determining the Δhaze value (%). It should be noted that the lower the Δhaze value, the less susceptible it is to the effects of abrasion, and thus, the better its abrasion resistance.

[0085] (Sample 2)

[0086] In addition to the cumulative light intensity of L1 ultraviolet light being 3 J / cm², 2 Except for this, it was performed under the same conditions as sample 1.

[0087] (Sample 3)

[0088] In addition to the cumulative light intensity of L1 ultraviolet light being 5 J / cm², 2 Except for this, it was performed under the same conditions as sample 1.

[0089] (Sample 4)

[0090] In addition to the cumulative light intensity of L1 ultraviolet light being 7 J / cm², 2 Except for this, it was performed under the same conditions as sample 1.

[0091] (Sample 5)

[0092] In addition to the cumulative light intensity of L1 ultraviolet light being 9 J / cm², 2 Except for this, it was performed under the same conditions as sample 1.

[0093] [Results and Examination of Verification 1]

[0094] Table 1 below shows the ratio of inorganic glass components and organosilicon components in the modified region 9 of each sample, as well as the Δhaze value of each sample.

[0095] [Table 1]

[0096] According to Table 1, the higher the cumulative amount of ultraviolet light L1, the higher the proportion of inorganic glass components. Therefore, it can be concluded that the hard coating 7 is modified by ultraviolet light L1 irradiation.

[0097] Figure 7 This graph is obtained by plotting the Δ haze value on the vertical axis and the ratio of inorganic glass components on the horizontal axis. Figure 7 The figure shows approximate curves for each point. The inventors discovered that, as... Figure 7 As shown, there is a correlation between the Δhaze value and the ratio of inorganic glass components. Specifically, the Δhaze value decreases as the ratio of inorganic glass components increases, reaching a minimum at approximately 46%. Furthermore, it can be observed that the Δhaze value increases as the ratio of inorganic glass components increases. That is, when the modification of modification region 9 is excessive, the abrasion resistance of the resin glass decreases.

[0098] The inorganic glass composition of the hard coating 7 used in this verification before irradiation with ultraviolet light L1 was approximately 38%. That is, when the inorganic glass composition ratio significantly exceeds 50% due to modification based on ultraviolet light L1, the abrasion resistance of the resin glass is reduced compared to before irradiation with ultraviolet light L1.

[0099] Previously, in order to improve the wear resistance of the hard coating 7, studies were conducted on modifying the hard coating 7 by increasing its inorganic glass content. However, through in-depth research by the inventors, a new discovery has been made: Figure 7 As shown, if the modification of the hard coating 7 is excessive, the wear resistance of the resin glass will actually decrease.

[0100] A lower Δhaze value generally indicates better wear resistance. According to... Figure 7 It is understandable that by using the ratio of inorganic glass components as an indicator, resin glass with a low Δ haze value can be manufactured according to the intended use of the resin glass.

[0101] In addition, according to Figure 7 It is known that within the range of 40% to 50% inorganic glass content, the Δhaze value is below 2%. That is, by setting the inorganic glass content in modification region 9 to the above range, a resin glass with excellent wear resistance and a Δhaze value below 2% can be obtained. This resin glass can be suitable for, for example, automotive windshields.

[0102] Based on verification 1, it can be understood that, according to the above embodiments, resin glass with a Δ haze value of less than 2% and excellent wear resistance can be obtained.

[0103] Furthermore, by adjusting the cumulative light intensity of ultraviolet light L1, the hard coating 7 can be irradiated with ultraviolet light L1 in such a way that the ratio of inorganic glass components on the outermost surface of the modified region 9 reaches 40-50%. The cumulative light intensity can be appropriately adjusted, for example, by the illuminance of the light source emitting ultraviolet light L1 and the irradiation time.

[0104] [Verification 2]

[0105] From the perspective of verifying the state of the modified region 9 in more detail, the hard coating 7 with the modified region 9 formed was analyzed by X-ray photoelectron spectroscopy (also known as "XPS"), as described below. XPS allows us to obtain information related to the elemental composition of the hard coating 7.

[0106] XPS is performed using a photoelectron spectroscopy device (PHI Quantera II) manufactured by ULVAC-PHI.

[0107] As described above, the modified region 9 is formed by modifying the hard coating 7. This modification process is caused by the photolysis of the Si-R bonds in the hard coating 7 due to irradiation by ultraviolet light L1, and the bonding reaction of oxygen atoms with the photolyzed Si atoms. That is, it is believed that the O / Si ratio (the ratio of the amount of oxygen atoms to the amount of Si atoms) in the hard coating 7 decreases as it moves from the modified region 9 toward the substrate 3.

[0108] In other words, it is believed that the ratio of inorganic glass components in the modified region 9 is higher than that on the surface 7a of the substrate 3 side of the hard coating 7.

[0109] Figure 8 This is a graph showing the XPS analysis results of resin glass 1. Figure 8 In the figure, the vertical axis represents the O / Si ratio, and the horizontal axis represents the sputtering depth (nm) relative to the surface of resin glass 1. The presence of oxygen atoms is based on the energy level of the 1s orbital of oxygen atoms, and the presence of Si atoms is based on the energy level of the 2p orbital of Si atoms.

[0110] The specific measurement conditions for XPS are as follows.

[0111] Ion species: Ar

[0112] Accelerating voltage of the ion gun: 2kV

[0113] Sputtering rate: 8.3 nm / min

[0114] Sputtering range: 0.25mm 2

[0115] The sputtering rate was determined using a Si substrate with a 100 nm thick SiO2 layer as the standard sample. Therefore, Figure 8 The sputtering depth shown is not, for example, equivalent to the actual thickness of the modified region 9.

[0116] like Figure 8 As shown, the O / Si ratio decreases as the sputtering depth increases, i.e., as the resin glass 1 moves towards the substrate 3 from the modified region 9. Furthermore, it can be seen that when the sputtering depth is greater than approximately 300 nm, the O / Si ratio remains constant at around 1.7.

[0117] In other words, it can be understood that no modification reaction caused by ultraviolet light L1 occurred in the sputtering depth range of approximately 300 nm or more. Additionally, it can be understood that the O / Si ratio increased due to the modification reaction caused by ultraviolet light L1 in the sputtering depth range of 0 nm to approximately 300 nm, which corresponds to modification region 9.

[0118] In view of the above, it can be seen that the modified region 9 has a higher ratio of inorganic glass components compared to the region that is closer to the substrate 3 than the modified region 9, such as the surface 7a of the substrate 3 side of the hard coating 7.

[0119] Through verification 2, although Figure 8 The sputtering depth shown is not a value equivalent to the actual thickness of the modified region 9, but XPS can confirm that the modified region 9 is formed on the surface of the hard coating 7.

[0120] [Resin glass manufacturing apparatus]

[0121] Next, an embodiment of the apparatus for manufacturing resin glass 1 will be described. It should be noted that, in the following description, the matters already mentioned will be appropriately omitted.

[0122] Figure 9 This diagram shows an example of the configuration of the manufacturing apparatus 10 for resin glass 1, with some components represented by block diagrams. For example... Figure 9 As shown, the manufacturing apparatus 10 includes a processing chamber 11 for accommodating a workpiece W1, a support 12 for supporting the workpiece W1, a light source 14, a power supply 16, a control unit 18, and a storage unit 20.

[0123] Workpiece W1 is as referenced Figure 2 and Figure 3 As described, a substrate 3 with a hard coating 7 is formed on the upper layer. The manufacturing apparatus 10 manufactures resin glass 1 by irradiating the hard coating 7 on the substrate 3 with ultraviolet light L1, thereby forming a modified region 9 on the surface of the hard coating 7.

[0124] The processing chamber 11 houses the workpiece W1 and the light source 14, forming a processing space for modifying the workpiece W1.

[0125] In addition, such as Figure 9 As shown, the processing chamber 11 may also include a gas inlet 22 for introducing an inactive gas N1, such as nitrogen, from the storage section 21. Similarly, the processing chamber 11 may also include a gas inlet 24 for introducing an oxygen-containing gas G1 from the storage section 23. The oxygen-containing gas G1 may also be air, such as CDA (clean dry air). By introducing each gas from the gas inlets (22, 24), the oxygen concentration in the processing chamber 11 can be adjusted.

[0126] The support portion 12 supports the workpiece W1 in a manner that allows it to be irradiated with ultraviolet light L1 emitted by the light source 14. Figure 9 The example shown is an example of a rectangular platform supporting the workpiece W1, but the workpiece W1 can also be supported by a conveyor belt or the like. When processing the workpiece W1 while conveying it, for example, along the X direction, a take-out section through which the workpiece W1 can pass is appropriately provided on the wall of the processing chamber 11 in the X direction.

[0127] The light source 14 is, for example, an excimer lamp containing Xe as the luminescent gas. The power supply unit 16 includes a power circuit for converting the voltage supplied by a power source (not shown) into the voltage required to illuminate the light source 14 and supplying it.

[0128] The control unit 18 is a control unit that sends control signals to the power supply unit 16, and is configured, for example, to include a processor such as a CPU.

[0129] The storage unit 20 is configured to include a memory. As an example, the storage unit 20 stores the cumulative amount of ultraviolet light L1 required to obtain the modified region 9 which displays the ratio of the inorganic glass composition as a target.

[0130] Typically, the ratio of the target inorganic glass component is selected from the lowest Δ haze value of the resin glass 1 within the range of 40% to 50%. In addition, the cumulative light intensity of the modified region 9, which displays the ratio of the inorganic glass component, is set, for example, under conditions determined by the oxygen concentration in the processing chamber 11, the distance between the light source 14 and the workpiece W1, and other ultraviolet light L1 irradiation conditions.

[0131] The control unit 18 reads the cumulative light quantity stored in the storage unit 20 and controls the power supply unit 16.

[0132] Therefore, by adjusting the illuminance and illumination time of the light source 14, the hard coating 7 is modified with a specified cumulative light intensity, thereby obtaining the modified region 9 that displays the ratio of the inorganic glass components as the target.

[0133] That is, the cumulative light intensity required to obtain the ratio of the inorganic glass components to be displayed in the modified region 9 can be calculated in advance, and the light source 14 can be lit based on the cumulative light intensity, thereby manufacturing a resin glass 1 with excellent wear resistance, for example, a Δ haze value of less than 2%.

[0134] It should be noted that the method for setting the cumulative light amount is not limited to the above. For example, the storage unit 20 may also store the table shown in Table 2 below.

[0135] [Table 2]

[0136] For example, the storage unit 20 may also store the cumulative light intensity (S1, S2, ...) of the ratio R1 of the target inorganic glass components according to the oxygen concentration (C1, C2, ...) in the processing chamber 11, as shown in Table 2. In this case, after the control unit 18 adjusts the oxygen concentration in the processing chamber 11 by driving the gas inlet unit (22, 24) based on the predetermined oxygen concentration (C1, C2, ...), it controls the power supply unit 16 based on the predetermined cumulative light intensity (S1, S2, ...).

[0137] Furthermore, the storage unit 20 can store multiple tables depending on the material constituting the hard coating 7. In addition, when the workpiece W1 is irradiated with ultraviolet light L1 while being transported in the X direction, the tables stored in the storage unit 20 can also include the transport speed conditions of the workpiece W1.

[0138] Furthermore, the control unit 18 can also be configured to receive data related to a specified cumulative light quantity from any server. That is, whether the manufacturing apparatus 10 includes a storage unit 20 is arbitrary.

[0139] The present invention is not limited to the configuration of the above embodiments, and the above embodiments can be implemented by appropriate combination.

[0140] Symbol Explanation

[0141] 1: Resin glass

[0142] 3: Substrate

[0143] 5: Primer coating

[0144] 7: Hard coating

[0145] 9: Modified area

[0146] 10: Manufacturing equipment

[0147] 11: Processing Room

[0148] 12: Support section

[0149] 14: Light source

[0150] 16: Power Supply Section

[0151] 18: Control Department

[0152] 20: Storage Department

[0153] 21, 23: Storage Department

[0154] 22, 24: Gas inlet section

[0155] L1: Ultraviolet light

Claims

1. A resin glass, characterized in that, The substrate has visible light transmittance and a hard coating containing an organosilicon polymer formed on the upper layer of the substrate. The hard coating has a higher proportion of inorganic glass components on its surface compared to the modified region on the substrate side. The ratio of the inorganic glass component in the modified region is 40% to 50%.

2. The resin glass according to claim 1, characterized in that, Windshields for automobiles.

3. The resin glass according to claim 1 or 2, characterized in that, The thickness of the modified region in the direction orthogonal to the main surface of the substrate is in the submicron range.

4. A method for manufacturing resin glass, characterized in that, The process includes: irradiating a hard coating containing an organosilicon polymer, formed on the upper layer of a substrate that exhibits visible light transmittance, with ultraviolet light having a dominant wavelength below 243 nm, thereby modifying the surface of the hard coating to form a modified region. The process of forming the modified region is to irradiate the hard coating with ultraviolet light in such a way that the ratio of inorganic glass components in the modified region reaches 40% to 50%.

5. An apparatus for manufacturing resin glass, wherein an ultraviolet light is irradiated onto a substrate having a hard coating comprising an organosilicon polymer that exhibits visible light transmittance, thereby modifying the surface of the hard coating to form a modified region, the apparatus being characterized in that... It includes a support portion that supports the substrate and a light source that emits ultraviolet light with a main wavelength in the wavelength region below 243nm toward the substrate. The light source irradiates the hard coating with ultraviolet light at a cumulative light intensity of 40% to 50% of the inorganic glass composition of the modified region.

6. The resin glass manufacturing apparatus according to claim 5, characterized in that, have: A storage unit storing a cumulative light quantity in which the ratio of inorganic glass components of the modified region reaches 40% to 50%; and The control unit controls the lighting operation of the light source based on the cumulative light quantity stored in the storage unit.

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