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

Abstract

To provide a resin glass having a surface with excellent abrasion resistance, and also to provide a method and apparatus for producing the resin glass.SOLUTION: A resin glass comprises: a substrate that exhibits visible light transmittance; and a hard coat layer which is formed on an upper layer of the substrate and contains a silicone polymer. The hard coat layer has, on a surface thereof, a modified region having a higher proportion of inorganic glass components than a surface on the substrate side. The proportion of inorganic glass components in the modified region is 40-50%.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to resin glass, a method for manufacturing resin glass, and an apparatus for manufacturing resin glass.

Background Art

[0002] For example, it has been considered to adopt resin glass instead of silicate glass as a window material provided in an opening of an automobile or a construction machine. A resin material such as polycarbonate constituting the resin glass can be expected to have the same light transmittance as silicate glass with respect to visible light. In addition, a resin material such as polycarbonate has advantages such as easy molding or excellent heat insulation properties.

[0003] However, a resin material such as polycarbonate has a property that its surface is easily damaged. On the other hand, a technique is known in which a hard coat layer containing a silicone polymer is formed on a substrate made of the resin material and ultraviolet light is irradiated onto the hard coat layer. For example, as shown in Patent Document 1, by irradiating ultraviolet light onto the hard coat layer, the surface of the hard coat layer is modified, and the abrasion resistance of the surface of the substrate made of the resin material is improved.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The inventor considered forming a hard coat layer containing a silicone polymer on a substrate made of polycarbonate and modifying the hard coat layer by irradiation with ultraviolet light to obtain a resin glass with improved surface abrasion resistance. As a result, although the abrasion resistance of the surface of the resin glass was improved by modifying the hard coat layer, it was found that if the modification of the hard coat layer progressed too far, the surface abrasion resistance decreased and a resin glass with excellent abrasion resistance could not be obtained.

[0006] In view of the above, an object of the present invention is to provide a resin glass having excellent surface abrasion resistance. Another object of the present invention is to provide a method and an apparatus for manufacturing the above resin glass.

Means for Solving the Problems

[0007] The resin glass according to the present invention includes a substrate exhibiting visible light transmissibility, and a hard coat layer containing a silicone polymer formed on the upper layer of the substrate. The hard coat layer has a modified region on the surface where the ratio of the inorganic glass component is higher than that of the surface on the substrate side. The ratio of the inorganic glass component in the modified region is 40% to 50%, which is a feature.

[0008] "Exhibiting visible light transmissibility" means that the transmittance for visible light is 70% or more, preferably 80% or more, more preferably 90% or more.

[0009] In addition, in this specification, "silicone polymer" refers to a polymer having a siloxane bond and having an organic group such as a methyl group, a phenyl group, a vinyl group, or an alkoxy group in the side chain.

[0010] The hard coat layer has a modified region formed by irradiation with ultraviolet light on its surface. As a result of intensive studies, the present inventors have found that the ratio of the inorganic glass component in the modified region correlates with the abrasion resistance of the resin glass. Details will be described in the section "Mode for Carrying Out the Invention", but the present inventors have found that by setting the ratio of the inorganic glass component to 40% to 50%, a resin glass having excellent surface abrasion resistance can be obtained, and the above configuration has been devised.

[0011] Details will be described later, but the "ratio of the inorganic glass component" is obtained by analyzing the surface of the hard coat layer by infrared spectroscopy (ATR-FTIR) and determining the ratio of the inorganic glass component to the sum of the organic silicone component and the inorganic glass component.

[0012] The above resin glass may be used for the front glass of an automobile.

[0013] At present, for the front glass of an automobile, it is required that the Δ haze value, which is an index of abrasion resistance obtained in the abrasion test defined in JIS R 3212 (Test Methods for Safety Glass for Automobiles), be 2% or less. The Δ haze value is an index represented by the difference between the haze value before the abrasion test and the haze value after the abrasion test, and the higher the abrasion resistance, the smaller the Δ haze value. The haze value is a numerical value representing the degree of light diffusion transmitted through the sample.

[0014] Also, regarding the front glass of an automobile, similar standards are defined in Europe and the United States for determining the index of abrasion resistance. At present, for example, in Europe, standards such as ECE R43 and in the United States, standards such as ANSI Z26.1 are defined.

[0015] Details will be described later, but according to the above configuration, a resin glass having a Δ haze value of 2% or less can be obtained. That is, the above resin glass is suitable for use as the front glass of an automobile.

[0016] In the above resin glass, The thickness of the modified region in the direction perpendicular to the main surface of the substrate may be on the order of submicrons.

[0017] In this specification, the "main surface" refers to the surface that constitutes a plate-shaped object and has a much larger area than other surfaces.

[0018] The method for manufacturing a resin glass according to the present invention is A step of forming a modified region by irradiating ultraviolet light having a main wavelength in a wavelength range of 243 nm or less on a hard coat layer containing a silicone polymer formed on an upper layer of a substrate exhibiting visible light transmissivity to modify the surface of the hard coat layer, The step of forming the modified region is characterized in that the ultraviolet light is irradiated on the hard coat layer so that the ratio of the inorganic glass component in the modified region is 40% to 50%.

[0019] Here, the "main wavelength" refers to the wavelength λi in the wavelength range Z(λi) that exhibits an integrated intensity of 40% or more with respect to the total integrated intensity in the emission spectrum when a wavelength range Z(λ) of ±10 nm with respect to a certain wavelength λ is defined on the emission spectrum. For example, in a light source such as an excimer lamp in which an emission gas such as Xe is enclosed, having an extremely narrow half-value width and exhibiting light intensity only at a specific wavelength, usually, the wavelength (main peak wavelength) having the highest relative intensity may be regarded as the main wavelength.

[0020] Further, the manufacturing apparatus for resin glass according to the present invention is A manufacturing apparatus for resin glass that irradiates ultraviolet light on a substrate exhibiting visible light transmissivity on which a hard coat layer containing a silicone polymer is formed to modify the surface of the hard coat layer, thereby forming a modified region, A support portion for supporting the substrate, And a light source that emits ultraviolet light having a main wavelength in a wavelength range of 243 nm or less toward the substrate. The light source irradiates the hard coat layer with ultraviolet light at an integrated light quantity such that the ratio of the inorganic glass component in the modification region is 40% to 50%.

[0021] The manufacturing apparatus for the resin glass is as follows a storage unit that stores an integrated light quantity such that the ratio of the inorganic glass component in the modification region is 40% to 50%; It may be provided with a control unit that controls the lighting operation of the light source based on the integrated light quantity stored in the storage unit.

[0022] Specific examples of the manufacturing method and manufacturing apparatus for the resin glass will be described later.

Advantages of the Invention

[0023] According to the present invention, a resin glass having excellent surface abrasion resistance is provided. Further, according to the present invention, a manufacturing method and a manufacturing apparatus for the resin glass are provided.

Brief Description of the Drawings

[0024]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Embodiments for Carrying Out the Invention

[0025] Hereinafter, the resin glass according to the present invention will be described with appropriate reference to the drawings. Note that each of the following drawings is schematically illustrated, and the dimensional ratios and numbers on the drawings do not necessarily match the actual dimensional ratios and numbers.

[0026] FIG. 1 is a cross-sectional view showing the structure of an embodiment of the resin glass 1. As shown in FIG. 1, the resin glass 1 is a laminate including a substrate 3, a primer layer 5 formed on the upper layer of the substrate 3, and a hard coat layer 7 formed on the upper layer of the substrate 3 via the primer layer 5. Further, the hard coat layer 7 has a modified region 9 formed on the surface by irradiation with ultraviolet light L1.

[0027] In the following drawings, an X - Y - Z coordinate system is appropriately referred to, where the direction orthogonal to the main surface 3a of the substrate 3 is the Z direction, and the plane orthogonal to the Z direction is the XY plane.

[0028] Also, in this specification, the expression "layer B is formed on the upper layer of layer A" is intended to include not only the case where layer B is directly formed on the surface of layer A, but also the case where layer B is formed on the surface of layer A via a layer different from layer B. Here, the upper layer means the direction away from the substrate such as a polycarbonate substrate in the Z direction.

[0029] Hereinafter, the details of the resin glass 1 will be described together with the manufacturing method of the resin glass 1.

[0030] [Preparation of Substrate 3] Figure 2 is a drawing showing the substrate 3, the primer layer 5, and the hard coat layer 7 separately for ease of understanding. First, a substrate 3 showing visible light transmittance is prepared. The material constituting the substrate 3 is arbitrary as long as the substrate 3 shows visible light transmittance. As an example, the substrate 3 is made of a synthetic resin such as polycarbonate or acrylic. Also, various aspects can be considered for the shape and dimensions of the substrate 3. The substrate 3 is, for example, a rectangular plate-like body with a long side of 1500 mm.

[0031] [Formation of Primer Layer 5] Next, as shown in Figure 2, a primer layer 5 is formed on the upper layer of the substrate 3. As a specific example, after the substrate 3 is cleaned to remove dust and the like adhering to the main surface 3a, the substrate 3 is immersed in a primer solution, or the primer solution is sprayed onto the substrate 3 by a spray gun or the like, so that the primer solution is applied onto the substrate 3. Then, by drying at a predetermined temperature for a certain period of time, a primer layer 5 is formed on the upper layer of the substrate 3.

[0032] The primer layer 5 is made of a material mainly composed of, for example, an acrylic resin. As an example, the primer layer 5 is composed of Momentive's SHP470 FT-2050. The primer layer 5 is provided from the viewpoint of improving the adhesion between the substrate 3 and the hard coat layer 7 and the weather resistance of the resin glass 1. However, in the present invention, whether or not the primer layer 5 is formed is arbitrary.

[0033] [Formation of Hard Coat Layer 7] Next, as shown in Figure 2, a hard coat layer 7 is formed on the upper layer of the substrate 3 through the primer layer 5. The hard coat layer 7 is made of a material mainly composed of a silicone polymer in which an organic group such as a methyl group is bonded as a side chain to a main chain composed of a siloxane bond. As an example, the hard coat layer 7 is composed of Momentive's AS4700F. Here, the "main component" may refer to, for example, the material with the highest composition ratio among the materials constituting the hard coat layer 7.

[0034] The coating film of the solution is formed on the substrate 3 by a coating method such as immersing the substrate 3 in the solution containing the silicone polymer or spraying the solution onto the substrate 3 with a spray gun. Thereafter, the coating film is dried at a predetermined temperature for a certain period of time, whereby the hard coat layer 7 is formed on the upper layer of the substrate 3.

[0035] The application of the primer liquid for forming the primer layer 5 and the solution for forming the hard coat layer 7 may be carried out by a coating method such as flow coating (also referred to as "flow coat") in addition to the above-described coating method.

[0036] [Modification of Hard Coat Layer 7] FIG. 3 is a drawing showing a step of irradiating the hard coat layer 7 with ultraviolet light L1. As shown in FIG. 3, the hard coat layer 7 is irradiated with ultraviolet light L1. Thereby, as shown in FIG. 1, the surface of the hard coat layer 7 is modified, and a modified region 9 is formed.

[0037] The irradiation of the ultraviolet light L1 is performed, for example, using an excimer lamp filled with a luminescent gas containing Xe as a light source (not shown in FIG. 3). In this case, the main wavelength of the ultraviolet light L1 is located at 172 nm. Also, by changing the component of the luminescent gas of the excimer lamp, the main wavelength of the ultraviolet light L1 can be varied. For example, the combinations of each luminescent gas and the main wavelength are Kr (146 nm), ArBr (165 nm), ArF (193 nm), KrBr (207 nm), KrCl (222 nm). The value of the main wavelength here includes fluctuations of about ±2 nm caused by individual differences such as the partial pressure of the luminescent gas.

[0038] The modification mechanism of the hard coat layer 7 by the ultraviolet light L1 will be described. FIG. 4 is a drawing schematically showing the structure of the silicone polymer constituting the hard coat layer 7. Also, FIG. 5 is a drawing schematically showing the structure of the silicone polymer after irradiation with the ultraviolet light L1. In FIGS. 4 and 5, R is an organic group such as a methyl group, a phenyl group, a vinyl group, or an alkoxy group. Also, "O 1 / 2" indicates that, together with the Si to which the oxygen atom is bonded, it is also bonded to the adjacent Si.

[0039] As shown in FIG. 4, in the siloxane bond constituting the hard coat layer 7, Si atoms a1 having four oxygen atoms bonded thereto and Si atoms a2 having a bond with an organic group are mixed. Then, when the hard coat layer 7 is irradiated with ultraviolet light L1, light energy (hν) corresponding to the wavelength is supplied, and the Si-R bond in the side chain of the siloxane bond undergoes photo-cleavage. Further, the ultraviolet light L1 photolyzes oxygen molecules present in the atmosphere to generate excited oxygen (hereinafter referred to as "oxygen radicals"). Then, the generated oxygen radicals diffuse into the interior of the hard coat layer 7 and bond to the portion where the Si-R bond has undergone photo-cleavage. As a result, as shown in FIG. 5, in the hard coat layer 7, the Si atoms a2 having a bond with an organic group decrease, and the Si atoms a1 bonded to four oxygen atoms increase.

[0040] The state in which the Si atom is bonded to four oxygen atoms is a state in which the silicone polymer has been vitrified (SiO 2 -ified), and can be referred to as an "inorganic glass component". Also, for convenience, the state in which the Si atom has a bond with an organic group is referred to as an "organic silicone component". By irradiating the hard coat layer 7 with ultraviolet light L1, a modified region 9 is formed on the surface of the hard coat layer 7 where the organic silicone component decreases and the inorganic glass component increases. That is, the modified region 9 is an "inorganic glass-rich region", and in the modified region 9, for example, more inorganic glass components are present than on the surface 7a of the hard coat layer 7 on the substrate 3 side.

[0041] There is a certain limit to the penetration depth of the ultraviolet light L1 into the hard coat layer 7. This is due to the low transmittance of the ultraviolet light L1 in the hard coat layer 7, and it is considered that the penetration depth of the ultraviolet light L1 irradiated on the hard coat layer 7 is less than 1 μm. Therefore, the thickness D1 in the Z direction of the modified region 9 formed by the irradiation of the ultraviolet light L1 is less than 1 μm and is on the sub-micron order (see also FIG. 1).

[0042] The term "sub-micron order" may refer to the range of 0.1 μm to 0.9 μm.

[0043] The thickness D1 of the modified region 9 can be measured, for example, by etching the modified region 9 with a hydrofluoric acid aqueous solution having a concentration of about 2% while partially masking, removing the mask, and scanning a step gauge with respect to the boundary between the etched region and the masked region. As the step gauge, Dektak3 manufactured by Veeco can be used.

[0044] From the viewpoint of photo-cleaving the Si-R bond and the bond of oxygen molecules, the ultraviolet light L1 preferably contains a wavelength component showing a light energy higher than the bond energy of the Si-R bond and the bond of oxygen molecules. The bond energy of the Si-R bond is about 3.2 eV, which is about 388 nm in terms of wavelength. Further, the bond energy of oxygen molecules is about 5.1 eV, which is about 243 nm in terms of wavelength. The bond energy of the Si-O bond forming the main chain is about 4.7 eV, which is about 264 nm in terms of wavelength. That is, from the viewpoint of cleaving these bonds, the ultraviolet light L1 preferably has a main wavelength in the wavelength range of 243 nm or less.

[0045] As an index indicating the progress degree of the modification of the hard coat layer 7 by the ultraviolet light L1, the absorbance in each vibration mode shown by the O-Si-O bond can be used. FIG. 6 is an example of a transmission spectrum of the hard coat layer 7 obtained by infrared spectroscopic analysis (ATR-FTIR). As shown in FIG. 6, the silicone polymer constituting the hard coat layer 7 has an optical absorption derived from the symmetric angular vibration of O-Si-O and the antisymmetric stretching vibration of O-Si-O at positions where the wave number is about 900 cm -1 ~1200 cm -1 . Further, in FIG. 6, the result of separating the waveform related to the optical absorption into two waveforms (T1, T2) each having a peak (P1, P2) with the baseline B0 as a transmittance of 0% is shown.

[0046] As shown in FIG. 6, the silicone polymer has a wave number of about 1020 cm -1At the position of, there is a peak P1 corresponding to the symmetric angular vibration of O-Si-O, and the wavenumber is about 1100 cm -1 At the position of, there is a peak P2 corresponding to the antisymmetric stretching vibration of O-Si-O. Both the waveform T1 including the peak P1 and the waveform T2 including the peak P2 show a convex shape toward the side with lower transmittance.

[0047] Since the peak P1 is derived from the mode in which the oxygen atoms vibrate symmetrically with respect to the Si atom, even when comparing the Si atom a1 bonded to 4 oxygen atoms with the Si atom a2 having a bond with an organic group, the difference in absorbance between the two is small, and the difference in the intensity of the peak P1 in the transmittance spectrum is small. On the other hand, the peak P2 is derived from the mode in which the oxygen atoms vibrate antisymmetrically with respect to the Si atom. In the Si atom a1 bonded to 4 oxygen atoms, the adjacent Si atoms are bonded through oxygen atoms, making it difficult for the oxygen atoms to vibrate antisymmetrically with respect to the Si atom. Therefore, the peak P2 decreases as the modification by the ultraviolet light L1 progresses.

[0048] In view of this, in FIG. 6, the ratio of the peak area A1, which is the area of the figure surrounded by the waveform T1 and the baseline B0, to the sum of the peak area A1 and the peak area A2, which is the area surrounded by the waveform T2 and the baseline B0, can be said to reflect the ratio of the Si atom a1 bonded to 4 oxygen atoms in the hard coat layer 7. Also, the ratio of the peak area A2 to the sum of the peak area A1 and the peak area A2 can be said to reflect the ratio of the Si atom a2 having a bond with an organic group in the hard coat layer 7.

[0049] In view of the fact that when the Si atom a1 bonded to four oxygen atoms, i.e., the modified region 9 with an increased inorganic glass component, is formed by irradiation with ultraviolet light L1, the peak P2 decreases and the peak P1 relatively increases, the ratio of the peak area A1 to the sum of the peak areas A1 and A2 is defined as the ratio of the inorganic glass component in the modified region 9. Similarly, the ratio of the Si atom a2 having a bond with an organic group, i.e., the ratio of the organosilicon component, in the modified region 9 is defined as the ratio of the peak area A2 to the sum of the peak areas A1 and A2.

[0050] That is, the "ratio of the inorganic glass component" can be obtained by determining the ratio of the peak area A1 of the peak P1 to the sum of the peak areas A1 and A2 of the peak P2 in the ATR-FTIR spectrum.

[0051] Details will be described later, but ATR-FTIR is an analytical method for obtaining the transmission spectrum of the sample surface. That is, by acquiring the ATR-FTIR spectrum of the hard coat layer 7, the ratio of the inorganic glass component in the modified region 9 can be obtained, and the state of the modified region 9 formed by the ultraviolet light L1 can be evaluated.

[0052] In this embodiment, the ratio of the inorganic glass component in the modified region 9 is set to 40% to 50%. Details will be described in the "Verification" section in the following paragraphs. By setting the ratio of the inorganic glass component to 40% to 50%, the resin glass 1 with excellent abrasion resistance can be obtained.

[0053] In the above description, the resin glass 1 has been described as a rectangular plate-like body, 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 the application.

[0054] For example, the resin glass 1 can be used as a window material for the front glass of an automobile.

[0055] [Verification 1] Since the relationship between the ratio of the inorganic glass component in the modified region 9 formed on the surface of the hard coat layer 7 and the Δ haze value indicating the abrasion resistance of the resin glass 1 was verified, it will be described below.

[0056] (Sample 1) Based on the manufacturing method of the resin glass 1 described above, a resin glass having the laminated structure described with reference to FIG. 2 was manufactured. The substrate 3 was made of polycarbonate. Also, the primer layer 5 was formed using Momentive's SHP470 FT - 2050, and the hard coat layer 7 was formed using Momentive's AS4700F.

[0057] Next, ultraviolet light L1 was irradiated onto the hard coat layer 7 formed on the upper layer of the substrate 3 to form a modified region 9 on the surface of the hard coat layer 7. The irradiation of the ultraviolet light L1 was performed using a Xe excimer lamp filled with a light - emitting gas containing Xe as a light source. That is, the hard coat layer 7 was irradiated with ultraviolet light L1 having a main wavelength of 172 nm.

[0058] The integrated light amount of the ultraviolet light L1 was 1 J / cm 2 and was measured using UIT - 250 manufactured by Ushio Electric Co., Ltd. equipped with VUV - S172 as a light receiver.

[0059] The transmission spectrum of the hard coat layer 7, more specifically, the modified region 9 was obtained by 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 crystal side, and the total reflection light that penetrates near the surface and is reflected is measured to obtain the transmission spectrum of the sample surface. The measuring device used was FT / IR - 4600 manufactured by JASCO Corporation. A Ge crystal was used as the high - refractive - index crystal. Also, the incident angle of the infrared light was set to 45 degrees.

[0060] Then, as described with reference to FIG. 6, the peak area A1 of peak P1 derived from the symmetric angular vibration of O—Si—O and the peak area A2 of peak P2 derived from the antisymmetric stretching vibration of Si—O—Si were calculated. Further, by calculating the ratio of each peak area (A1, A2) to the sum of the peak areas of both, the ratio of the inorganic glass component and the ratio of the organosilicon component in the modified region 9 were calculated, respectively.

[0061] The analysis of the peaks on the transmission spectrum was performed using the "Spectrum Manager" installed as standard software in the above measuring apparatus.

[0062] Next, the method for measuring the Δ haze value (%) of the resin glass will be described. The Δ haze value was measured in accordance with the method specified in JIS R 3212 (Test Method for Automobile Safety Glass) using a Taber 5130 abrasion tester (manufactured by TABER) and an abrasion wheel CS-10F (manufactured by TABER). Specifically, the haze values (%) before and after abrasion of the resin glass were measured with a haze meter HZ-0 (manufactured by Suga Test Instruments Co., Ltd.), and the Δ haze value (%) was obtained by calculating the change in the haze values (%) before and after abrasion. It should be noted that the lower the Δ haze value, the less affected it is by abrasion and the better the abrasion resistance.

[0063] (Sample 2) The integrated light quantity of the ultraviolet light L1 was 3 J / cm 2 Except for the point where it was set, it was carried out under the same conditions as Sample 1.

[0064] (Sample 3) The integrated light quantity of the ultraviolet light L1 was 5 J / cm 2 Except for the point where it was set, it was carried out under the same conditions as Sample 1.

[0065] (Sample 4) The integrated light quantity of the ultraviolet light L1 was 7 J / cm 2 Except for the point where it was set, it was carried out under the same conditions as Sample 1.

[0066] (Sample 5) The integrated light quantity of the ultraviolet light L1 was 9 J / cm2 It was carried out under the same conditions as Sample 1, except for the specified points.

[0067] [Results and Considerations of Verification 1] Table 1 below shows the ratio of the inorganic glass component and the ratio of the organic silicone component in the modified region 9 of each sample, as well as the Δ haze value of each sample.

Table 1

[0068] According to Table 1, as the integrated light quantity of the ultraviolet light L1 increases, the ratio of the inorganic glass component increases. From this, it can be seen that the hard coat layer 7 was modified by the irradiation of the ultraviolet light L1.

[0069] Figure 7 is a graph in which the Δ haze value is plotted on the vertical axis and the ratio of the inorganic glass component is plotted on the horizontal axis. In Figure 7, an approximate curve for each plot is shown. The inventor has found that there is a correlation between the Δ haze value and the ratio of the inorganic glass component as shown in Figure 7. Specifically, the Δ haze value decreases as the ratio of the inorganic glass component increases, and the ratio of the inorganic glass component shows a minimum value at about 46%. Thereafter, it can be seen that the Δ haze value increases as the ratio of the inorganic glass component increases. That is, if the modification of the modified region 9 progresses too much, the abrasion resistance of the resin glass decreases.

[0070] The ratio of the inorganic glass component in the state before irradiating the hard coat layer 7 used in this verification with the ultraviolet light L1 is about 38%. That is, if the modification by the ultraviolet light L1 progresses and, for example, the ratio of the inorganic glass component greatly exceeds 50%, the abrasion resistance of the resin glass will be lower than before irradiating the ultraviolet light L1.

[0071] Conventionally, in order to improve the wear resistance of the hard coat layer 7, it has been considered to modify the hard coat layer 7 to increase the inorganic glass component of the hard coat layer 7. However, as a result of the intensive research by the present inventor, as shown in FIG. 7, it has been newly found that if the modification of the hard coat layer 7 progresses too much, the wear resistance of the resin glass decreases instead.

[0072] The lower the Δ haze value, the better the wear resistance. According to FIG. 7, it can be understood that by using the ratio of the inorganic glass component as an index, a resin glass with a low Δ haze value can be produced according to the use of the resin glass.

[0073] Further, according to FIG. 7, it can be seen that when the ratio of the inorganic glass component is in the range of 40% to 50%, the Δ haze value becomes 2% or less. That is, by setting the ratio of the inorganic glass component in the modified region 9 within the above range, a resin glass having excellent wear resistance with a Δ haze value of 2% or less can be obtained. The resin glass can be suitably used, for example, for the front glass of an automobile.

[0074] In view of Verification 1, according to the above embodiment, it can be understood that a resin glass having a Δ haze value of 2% or less and excellent wear resistance can be obtained.

[0075] Further, by adjusting the integrated light quantity of the ultraviolet light L1, the hard coat layer 7 can be irradiated with the ultraviolet light L1 so that the ratio of the inorganic glass component on the outermost surface of the modified region 9 becomes 40 to 50%. The integrated light quantity can be appropriately adjusted, for example, by the illuminance of the light source that emits the ultraviolet light L1 and the irradiation time.

[0076] [Verification 2] From the viewpoint of verifying the state of the modified region 9 in more detail, the hard coat layer 7 in which the modified region 9 is formed was analyzed by X-ray photoelectron spectroscopy (also referred to as "XPS"). This will be described below. By XPS, information on the elemental composition in the hard coat layer 7 can be obtained.

[0077] XPS was performed using a photoelectron spectrometer (PHI QuanteraII) manufactured by ULVAC-PHI.

[0078] As described above, the modified region 9 is formed by modifying the hard coat layer 7. This modification process is due to the photo-cleavage of the Si-R bond in the hard coat layer 7 by the irradiation of ultraviolet light L1 and the bonding reaction of oxygen atoms to the photo-cleaved Si atoms. That is, it is considered that the O / Si ratio (the ratio of the abundance of oxygen atoms to the abundance of Si atoms) in the hard coat layer 7 decreases from the modified region 9 toward the substrate 3 side.

[0079] In other words, it is considered that the modified region 9 has a higher ratio of inorganic glass components than the surface 7a of the hard coat layer 7 on the substrate 3 side.

[0080] Figure 8 is a graph showing the XPS analysis results of the resin glass 1. In Figure 8, the O / Si ratio is plotted on the vertical axis, and the sputter depth (nm) based on the surface of the resin glass 1 is plotted on the horizontal axis. The abundance of oxygen atoms is the abundance obtained based on the energy level of the 1s orbital of oxygen atoms, and the abundance of Si atoms is the abundance obtained based on the energy level of the 2p orbital of Si atoms.

[0081] The specific measurement conditions of XPS are as follows. Ion species: Ar Acceleration voltage of ion gun: 2 kV Sputter rate: 8.3 nm / min Sputter range: 0.25 mm 2

[0082] The sputter rate was determined using a Si substrate with a 100-nm-thick SiO 2 layer formed as a standard sample. Therefore, the numerical values of the sputter depth shown in Figure 8 do not correspond to the actual thickness of, for example, the modified region 9.

[0083] As shown in FIG. 8, in the direction in which the sputter depth increases, that is, in the resin glass 1, as it progresses in the depth direction from the modified region 9 toward the substrate 3, the O / Si ratio decreases. And when the sputter depth becomes larger than about 300 nm, it can be seen that the O / Si ratio becomes constant at around 1.7.

[0084] That is, it can be understood that in the range where the sputter depth is about 300 nm or more, the modification reaction by the ultraviolet light L1 does not occur. Also, in the range where the sputter depth is from 0 nm to about 300 nm, the O / Si ratio increases due to the modification reaction by the ultraviolet light L1, and it can be understood that this corresponds to the modified region 9.

[0085] In view of the above, it is clear that the modified region 9 has a higher ratio of inorganic glass components than the region on the substrate 3 side of the modified region 9, for example, the surface 7a on the substrate 3 side of the hard coat layer 7.

[0086] By Verification 2, although the sputter depth shown in FIG. 8 is not a value corresponding to the actual thickness of the modified region 9, it was confirmed by XPS that the modified region 9 is formed on the surface of the hard coat layer 7.

[0087] [Manufacturing Apparatus for Resin Glass] Next, an embodiment of the manufacturing apparatus for the resin glass 1 will be described. In the following description, descriptions of matters already mentioned will be omitted as appropriate.

[0088] FIG. 9 is a drawing showing a configuration example of the manufacturing apparatus 10 for the resin glass 1, and some of the components are shown in block diagrams. As shown in FIG. 9, the manufacturing apparatus 10 includes a processing chamber 11 in which a workpiece W1 to be processed is accommodated, a support portion 12 that supports the workpiece W1, a light source 14, a power supply portion 16, a control portion 18, and a storage portion 20.

[0089] As described with reference to FIGS. 2 and 3, the work W1 is a substrate 3 having a hard coat layer 7 formed on the upper layer. The manufacturing apparatus 10 manufactures the resin glass 1 by irradiating the hard coat layer 7 on the substrate 3 with ultraviolet light L1 to form a modified region 9 on the surface of the hard coat layer 7.

[0090] The processing chamber 11 houses the work W1 and the light source 14, and forms a processing space where the work W1 is modified.

[0091] Also, as shown in FIG. 9, the processing chamber 11 may be provided with a gas introduction part 22 capable of introducing an inert gas N1 such as nitrogen gas from a storage part 21. Similarly, the processing chamber 11 may be provided with a gas introduction part 24 capable of introducing an oxygen-containing gas G1 from a storage part 23. The oxygen-containing gas G1 may be air such as CDA (clean dry air). By introducing each gas from the gas introduction parts (22, 24), the oxygen concentration in the processing chamber 11 can be adjusted.

[0092] The support part 12 supports the work W1 so that the ultraviolet light L1 emitted from the light source 14 can be irradiated. In FIG. 9, for example, an example in which the work W1 is supported by a rectangular stage is shown, but the work W1 may be supported by a conveyor or the like capable of transporting the work W1. When processing the work W1 while transporting the work W1 in the X direction, for example, a take-out part through which the work W1 can pass is appropriately provided on the wall surface of the processing chamber 11 related to the X direction.

[0093] The light source 14 is, for example, an excimer lamp containing Xe as a light-emitting gas. The power supply part 16 includes a power supply circuit for converting the voltage supplied from a power source (not shown) into the voltage required for lighting the light source 14 and supplying it.

[0094] The control part 18 is a control means for transmitting a control signal to the power supply part 16, and is configured to include a processor such as a CPU.

[0095] The storage unit 20 is configured to include a memory. As an example, the storage unit 20 stores the integrated light amount of the ultraviolet light L1 necessary to obtain the modification region 9 indicating the ratio of the target inorganic glass component.

[0096] Typically, the ratio of the target inorganic glass component is in the range of 40% to 50%, and the value at which the Δ haze value of the resin glass 1 is the lowest is selected. Also, the integrated light amount for obtaining the modification region 9 indicating the ratio of the inorganic glass component is set under conditions where irradiation conditions of the ultraviolet light L1 such as the oxygen concentration in the processing chamber 11 and the separation distance between the light source 14 and the workpiece W1 are determined.

[0097] The control unit 18 reads out the integrated light amount stored in the storage unit 20 and controls the power supply unit 16. Thereby, the illuminance and the lighting time of the light source 14 are adjusted, and the modification region 9 indicating the ratio of the target inorganic glass component is obtained by modifying the hard coat layer 7 with a predetermined integrated light amount.

[0098] That is, in advance, the integrated light amount necessary to obtain the modification region 9 indicating the ratio of the target inorganic glass component is obtained, and by lighting the light source 14 based on the integrated light amount, for example, a resin glass 1 having excellent abrasion resistance with a Δ haze value of 2% or less can be manufactured.

[0099] Note that the method for setting the integrated light amount is not limited to the above. For example, the storage unit 20 may store a table shown in Table 2 below.

Table 2

[0100] For example, as shown in Table 2, the storage unit 20 may store the integrated light amounts (S1, S2,...) at which the ratio R1 of the target inorganic glass component can be obtained according to the oxygen concentrations (C1, C2,...) in the processing chamber 11. In this case, after the control unit 18 drives the gas introduction units (22, 24) based on a predetermined oxygen concentration (C1, C2,...) to adjust the oxygen concentration in the processing chamber 11, the control unit 18 controls the power supply unit 16 based on a predetermined integrated light amount (S1, S2,...).

[0101] Further, the storage unit 20 may be configured to store a plurality of tables according to the material constituting the hard coat layer 7. Furthermore, when the ultraviolet light L1 is irradiated while the workpiece W1 is being conveyed in the X direction, the table stored in the storage unit 20 may include the conveyance speed condition of the workpiece W1.

[0102] Also, the control unit 18 may be configured to be able to receive data related to a predetermined integrated light amount from an arbitrary server. That is, it is arbitrary whether the manufacturing apparatus 10 includes the storage unit 20 or not.

[0103] The present invention is not limited to the configuration of the above-described embodiment, and the above-described embodiments can be realized by being appropriately combined.

Explanation of Reference Numerals

[0104] 1: Resin glass 3: Substrate 5: Primer layer 7: Hard coat layer 9: Modified region 10: Manufacturing apparatus 11: Processing chamber 12: Support part 14: Light source 16: Power supply unit 18: Control unit 20: Storage unit 21, 23: Storage part 22, 24: Gas introduction part L1: Ultraviolet light

Claims

1. A substrate exhibiting visible light transparency; a hard coat layer containing a silicone polymer formed on the upper layer of the substrate; the hard coat layer has a modified region on a surface thereof, the modified region having a higher ratio of inorganic glass components than the surface thereof facing the substrate; A resin glass, characterized in that the ratio of the inorganic glass component in the modified region is 40% to 50%.

2. 2. The resin glass according to claim 1, which is used for a windshield of an automobile.

3. The resin glass according to claim 1 or 2, wherein a thickness of the modified region in a direction perpendicular to a main surface of the substrate is on the order of submicrons.

4. The method includes a step of irradiating a hard coat layer containing a silicone polymer formed on a substrate exhibiting visible light transmittance with ultraviolet light having a main wavelength in a wavelength range of 243 nm or less to modify the surface of the hard coat layer to form a modified region, A method for producing a resin glass, characterized in that the step of forming the modified region is a step of irradiating the hard coat layer with the ultraviolet light so that a ratio of inorganic glass components in the modified region is 40% to 50%.

5. An apparatus for producing a resin glass, comprising: an apparatus for irradiating a substrate having visible light transmittance and a hard coat layer containing a silicone polymer thereon with ultraviolet light to modify a surface of the hard coat layer, thereby forming a modified region, the apparatus comprising: A support portion that supports the substrate; A light source that emits ultraviolet light toward the substrate, the main wavelength of which is in a wavelength range of 243 nm or less; The apparatus for manufacturing a resin glass is characterized in that the light source irradiates the hard coat layer with ultraviolet light at an integrated light amount such that the ratio of inorganic glass components in the modified region is 40% to 50%.

6. a memory unit that stores an integrated light amount that causes the ratio of the inorganic glass component in the modified region to be 40% to 50%; The resin glass manufacturing apparatus according to claim 5 , further comprising a control unit that controls a lighting operation of the light source based on the integrated light amount stored in the memory unit.

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