JP2016074182A - Glass-resin integrated member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass-resin integrated member in which a glass and a resin are joined without the use of an adhesive.SOLUTION: Provided is a glass-resin integrated member including a glass substrate having a first surface, and a resin installed on the first surface, and in the first surface, the maximum height roughness Rz is 100 nm or more, and the first surface has a convex shaped portion in which at least a portion of the root portion is constricted inwardly as compared to the tip portion.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a glass-resin integrated member that can be used, for example, for a protective member of a display device, for example, a front cover member of a smartphone.

  A glass-resin integrated member formed by integrating a glass part and a resin part is applied to a wide range of products such as a display surface of a portable electronic device. For example, a front cover member is usually disposed on the display surface of a portable electronic device such as a smartphone, and a glass-resin integrated member is used as the front cover member.

  Such a glass-resin integrated member can be manufactured, for example, by bonding a glass component and a resin component arranged around the glass component via an adhesive (Patent Document 1). ).

International Publication No. 2013/084550

  As described above, the glass-resin integrated member is configured by joining a glass component and a resin component via an adhesive.

  However, in the structure of the conventional glass-resin integrated member, since the process of arrange | positioning an adhesive agent between a glass component and a resin component is essential, there exists a problem that the manufacturing process of a member becomes complicated.

  Moreover, such an adhesive material may be a problem from the viewpoint of aesthetics. For example, when a glass-resin integrated member containing an adhesive is used for the front cover member of a smartphone, the adhesive in the member is easily visually recognized, thereby impairing the sense of quality of the smartphone, May be reduced.

  The present invention has been made in view of such a background, and an object of the present invention is to provide a glass-resin integrated member in which glass and resin are joined without using an adhesive. .

In the present invention, a glass-resin integrated member,
A glass substrate having a first surface; and a resin placed on the first surface;
In the first surface, the maximum height roughness Rz is 100 nm or more,
The first surface is provided with a glass-resin integrated member having a convex portion in which at least a part of a root portion is constricted inward compared to a tip portion.

  The present invention can provide a glass-resin integrated member in which glass and resin are bonded without using an adhesive.

It is the figure which showed typically the cross section of the glass substrate which can be applied to the glass-resin integrated member by one Embodiment of this invention. It is the enlarged view which showed typically the cross section of the glass-resin integrated member by one Embodiment of this invention. It is the flowchart which showed the manufacturing method of the 1st integrated member typically. It is the perspective view which showed typically the front cover member used for portable electronic devices like a smart phone. It is the figure which showed typically the cross section in the AA in FIG. It is the figure which showed typically the cross section of the laminated member which has a glass part and a resin part. 4 is a cross-sectional SEM photograph of the first surface of the concavo-convex substrate A used in Example 1. FIG. 4 is a surface SEM photograph of the first surface of the concavo-convex substrate A used in Example 1. FIG. 3 is a diagram schematically showing the form of an integrated sample A used in Example 1. 4 is a surface SEM photograph of the first surface of the concavo-convex substrate C used in Example 3. 10 is a cross-sectional SEM photograph of the first surface of the concavo-convex substrate D used in Example 4. 6 is a cross-sectional SEM photograph of an integrated sample D used in Example 4.

  Hereinafter, an embodiment of the present invention will be described.

  The glass-resin integrated member by one Embodiment of this invention has a glass substrate and resin installed in the 1st surface of this glass substrate. In the glass-resin integrated member according to one embodiment of the present invention, the first surface of the glass substrate has a large number of irregularities on the order of nanometers. More specifically, the first surface of the glass substrate has a maximum height roughness Rz of 100 nm or more and has a unique convex portion.

  Here, with reference to FIG. 1, the specific convex-shaped part formed in the 1st surface of a glass substrate and its effect are demonstrated. In FIG. 1, the cross section of the glass substrate which can be applied to the glass-resin integrated member by one Embodiment of this invention is shown typically.

  As shown in FIG. 1, this glass substrate 10 has the 1st surface 12 which has many convex-shaped parts 50 of nanometer order. And in these convex-shaped parts 50, a unique convex-shaped part is contained. The unique convex portion means a shape in which at least a part of the root portion of the convex portion 50 is constricted inward compared to the tip portion.

  For example, in the example shown in FIG. 1, two unique convex portions 51 and 52 are recognized. Among these, the unique convex portion 51 is narrowed inward on one side (right side) of the root portion. On the other hand, the unique convex portion 52 is narrowed inward on both sides of the root portion, and has a so-called neck portion 53. The neck portion 53 means a lower portion, that is, a so-called narrowed portion, whose cross section is smaller than that of the upper portion of the convex portion 50 formed on the first surface 12.

  In the present application, in order to distinguish the two unique convex portions 51 and 52, in particular, the unique convex portion 52 may be referred to as a convex portion having a neck portion 53.

  In addition, the presence or absence of the neck part 53 in a convex part can be judged as follows. That is, as shown in FIG. 1, the glass substrate 10 passes through a portion (point P) having the smallest diameter of one convex portion (for example, the unique convex portion 52) with respect to the glass substrate 10. A straight line L1 parallel to the thickness direction is drawn. When the straight line L1 intersects the singular convex portion 52 above the point P (in a direction further away from the first surface 12), it can be determined that the singular convex portion 52 has the neck portion 53.

  The first surface 12 having such unique convex portions 51 and 52 can be formed, for example, by etching the glass substrate 10 with a high-temperature hydrogen fluoride (HF) gas.

  When the resin is formed on the first surface 12 having the unique convex portions 51 and 52, the adhesion between the resin and the glass substrate 10 can be enhanced by the anchor effect. Therefore, in this case, it is not necessary to interpose an adhesive between the glass substrate 10 and the resin, and a glass-resin integrated member having no adhesive can be configured.

  In particular, when the resin is filled in the fine irregularities including the unique convex portions 51 and 52 formed on the first surface 12 without providing a space, an anchor effect is generated between the glass substrate 10 and the resin. It becomes noticeable and extremely good adhesion can be obtained.

  Thus, in the glass-resin integrated member according to an embodiment of the present invention, the presence of the first surface 12 having fine irregularities including the unique convex portions 51 and 52 does not require the use of an adhesive. In addition, significantly high adhesion due to the anchor effect can be obtained between the glass substrate 10 and the resin. In particular, when the first surface 12 has the unique convex portion 52 having the neck portion 53, the anchor effect becomes remarkable, and extremely good adhesion can be obtained between the glass substrate 10 and the resin.

(Glass-resin integrated member according to one embodiment of the present invention)
Next, an embodiment of the present invention will be described in detail with reference to FIG.

  In FIG. 2, the cross section of the glass-resin integrated member (henceforth "the 1st integrated member") by one Embodiment of this invention is shown typically.

  As shown in FIG. 2, the first integrated member 100 includes a glass substrate 110 and a resin 140.

  The glass substrate 110 has a first surface 112 and a second surface 114. The first surface 112 of the glass substrate 110 has a large number of irregularities on the order of nanometers, and among these, unique convex portions 151 and 152 are included.

  In the first surface 112 of the glass substrate 110, the maximum height roughness Rz is 100 nm or more. The maximum height roughness Rz can be measured based on 2001 JIS B0601. As the maximum height roughness Rz is larger, the anchor effect between the first surface 112 of the glass substrate 110 and the resin 140 becomes more prominent, and the adhesion is improved.

  In addition, on the first surface 112 of the glass substrate 110, the arithmetic average roughness Ra is preferably 10 nm or more. The arithmetic average roughness Ra can be measured based on 1994 JIS B0601.

  The maximum dimension of the cross section of the neck portion 153 in the direction perpendicular to the thickness direction of the glass substrate 110 is, for example, in the range of 50 nm to 400 nm.

  In the first integrated member 100, the resin 140 is directly disposed on the first surface 112 of the glass substrate 110. That is, no adhesive is installed between the glass substrate 110 and the resin 140. This is because good adhesion can be obtained between the glass substrate 110 and the resin 140 due to the presence of many irregularities in the order of nanometers on the first surface 112 without using an adhesive. . In addition, the adhesiveness between the glass substrate 110 and the resin 140 can be measured by a method as shown in the following Example 1 or Example 4, for example. In particular, the adhesion strength measured by the method of Example 1 is preferably 4 MPa or more.

  As described above, in the first integrated member 100, the manufacturing process can be simplified. Moreover, in the 1st integrated member 100, when this 1st integrated member 100 is applied to the front cover member of portable electronic devices, such as a smart phone, an adhesive material is visually recognized and design property worsens. This problem can be avoided significantly.

(Specifications of each component)
Next, the specifications of each member constituting the first integrated member 100 as shown in FIG. 2 will be described in detail.

(Glass substrate 110)
The dimensions and composition of the glass substrate 110 are not particularly limited. The glass substrate 110 may have a thickness of 0.05 mm to 10 mm, for example.

  The glass substrate 110 may be made of, for example, soda lime glass, aluminosilicate glass, borosilicate glass, alkali-free glass, or the like.

  As described above, the first surface 112 of the glass substrate 110 has a large number of fine irregularities. More specifically, the maximum height roughness Rz on the first surface 112 of the glass substrate 110 is 100 nm or more. For example, the maximum height roughness Rz is in the range of 100 nm to 500 nm, and may be in the range of 110 nm to 400 nm, for example.

  The arithmetic average roughness Ra is preferably 10 nm or more. For example, the arithmetic average roughness Ra is in the range of 10 nm to 50 nm, and may be in the range of 15 nm to 45 nm.

  Further, as described above, the first surface 112 of the glass substrate 110 has the unique convex portions 151 and 152.

  The glass substrate 110 having such a first surface 112 can be manufactured, for example, by etching the first surface 112 of the high-temperature glass substrate 110 with hydrogen fluoride (HF) gas.

  As will be described later, when the glass substrate 110 is etched with HF gas, columnar crystals may be generated on the first surface 112 in some cases.

  The columnar crystal has, for example, a total length in the range of 30 nm to 100 nm, a maximum width in the range of 1 nm to 50 nm, and an aspect ratio in the range of 1 to 10.

  This columnar crystal is composed of a glass component constituting the glass substrate 110, and the glass substrate 110 is subjected to relatively strong conditions (for example, an etching temperature of 500 ° C. or more and an HF gas concentration of 2 vol.) Using HF gas. %) Or the like). Therefore, the presence or absence of this columnar crystal can be used as a standard for determining the strength of the etching treatment conditions with HF gas. In addition, since the columnar precipitate is bonded to the first surface 112, the columnar precipitate itself has an effect of improving the adhesion as in the case of the unique convex portions 51 and 52.

  Note that the glass substrate 110 may be chemically strengthened. In a normal case, the chemical strengthening process is performed after the first surface 112 having the above-described characteristics is formed on the glass substrate 110.

  Here, “chemical strengthening treatment (method)” means that a glass substrate is immersed in a molten salt containing an alkali metal, and an alkali metal (ion) having a small atomic diameter present on the outermost surface of the glass substrate is dissolved in the molten salt. Is a generic term for technologies that replace alkali metals (ions) with large atomic diameters. In the “chemical strengthening treatment (method)”, an alkali metal (ion) having a larger atomic diameter than the original atoms before the treatment is disposed on the surface of the treated glass substrate. For this reason, a compressive stress layer can be formed on the surface of the glass substrate, thereby improving the strength of the glass substrate.

  For example, when the glass substrate contains sodium (Na), this sodium is replaced with, for example, potassium (K) in the molten salt (for example, nitrate) during the chemical strengthening treatment. Alternatively, for example, when the glass substrate contains lithium (Li), during the chemical strengthening treatment, the lithium is replaced with, for example, sodium (Na) and / or potassium (K) in a molten salt (for example, nitrate). Also good.

  Further, the glass substrate 110 may have a haze of 1% or less, for example, a haze of 0.9% or less. In this case, transparency is improved.

(Resin 140)
The type of the resin 140 included in the first integrated member 100 is not particularly limited. The resin 140 may be, for example, a thermoplastic resin or a curable resin.

  Among these, examples of the thermoplastic resin include polycarbonate resin, nylon resin, ABS resin, polyolefin resin, polyester resin, and polyacrylic resin. On the other hand, examples of the curable resin include acrylic resins, epoxy resins, and urethane resins.

  The method for installing the resin 140 on the glass substrate 110 is not particularly limited. For example, the resin 140 may be placed on the first surface 112 of the glass substrate 110 by an injection molding method, an injection compression molding method or a coating method, a laminating method, or a pressing method.

  In particular, in the injection compression molding method, the resin 140 can be sufficiently filled up to a minute space existing on the first surface 112 of the glass substrate 110, for example, around the neck portion 153 of the unique convex portion 152. In this case, the adhesion between the glass substrate 110 and the resin 140 is further improved.

(Method for producing a glass-resin integrated member according to an embodiment of the present invention)
Next, an example of the manufacturing method of the glass-resin integrated member by one Embodiment of this invention is demonstrated. Here, as an example, the manufacturing method of the first integrated member 100 as shown in FIG. 2 will be described. Therefore, when referring to each member, the reference numerals shown in FIG. 2 are used.

  In FIG. 3, the flow of the manufacturing method of the 1st integrated member 100 is shown typically.

As shown in FIG. 3, the manufacturing method of the first integrated member 100 is as follows.
(I) preparing a glass substrate (step S110);
(Ii) forming a first surface having a large number of irregularities on the order of nanometers on the glass substrate, including a unique convex part (step S120);
(Iii) a step of chemically strengthening the glass substrate (step S130);
(Iv) installing a resin on the first surface of the glass substrate (S140);
Have

  Note that step S130 is not an essential step and may be omitted.

  Hereinafter, each step will be described.

(Step S110)
First, a glass substrate 110 that serves as a glass portion of the first integrated member 100 is prepared.

  As described above, the composition of the glass substrate 110 is not particularly limited. Moreover, the dimension and shape of the glass substrate 110 are not particularly limited. For example, the thickness of the glass substrate 110 may be in the range of 0.05 mm to 10 mm.

(Step S120)
Next, the “first surface 112” having the above-described characteristics is formed on the glass substrate 110 prepared in step S110. Or the 1st surface of the glass substrate 110 prepared by step S110 is processed so that the above characteristics may be shown.

  The method for forming the first surface 112 is not particularly limited. For example, the first surface 112 having the above-described characteristics may be formed by etching the glass substrate 110 with high-temperature HF gas.

  In particular, in the case of etching treatment with HF gas, for example, HF gas concentration (for example, 0.1 vol% to 10 vol%), temperature of glass substrate 110 during etching (hereinafter referred to as etching temperature) (for example, 400 ° C. to 800 ° C.) By changing the etching conditions such as the etching time (for example, 1 second to several minutes), it is possible to control the size and form of the unevenness on the order of nanometers. In particular, by selecting relatively strong etching conditions (for example, an etching temperature of 500 ° C. or higher and an HF gas concentration of 2 vol% or higher), the existence probability of the unique convex portion 152 having the neck portion 153 is increased. be able to. In this case, the possibility that the above-described columnar crystal is generated is also increased.

(Step S130)
Next, the glass substrate 110 having the first surface 112 is chemically strengthened. Thereby, the strength of the glass substrate 110 is improved. However, this step is not an essential step and may be omitted. Further, this step may be performed before step S120.

  The conditions for the chemical strengthening treatment are not particularly limited, and general chemical strengthening treatment conditions may be applied.

  Examples of the molten salt used for the chemical strengthening treatment include alkali metal nitrates, alkali metal sulfates, and alkali metal chlorides such as sodium nitrate, potassium nitrate, sodium sulfate, potassium sulfate, sodium chloride, and potassium chloride. Examples include salt. These molten salts may be used alone or in combination of two or more.

  The chemical strengthening treatment temperature (molten salt temperature) varies depending on the type of molten salt used, but may be, for example, in the range of 350 ° C to 550 ° C.

  The chemical strengthening treatment may be performed, for example, by immersing the glass substrate 110 in a molten potassium nitrate salt at 350 ° C. to 550 ° C. for about 2 minutes to 20 hours. From an economical and practical viewpoint, it is preferably performed at 350 to 500 ° C. for 1 to 10 hours.

  In addition, for example, when application to the front cover member of a smart phone etc. is assumed, it is preferable that the haze of the glass substrate 110 prepared through steps S110 to S130 is 1% or less.

(Step S140)
Next, the resin 140 is placed on the first surface 112 of the glass substrate 110. The kind of the resin 140 to be installed is not particularly limited, and the resin 140 can be selected from, for example, a thermoplastic resin and a curable resin. Examples of the curable resin include a thermosetting resin, a photocurable resin, and a moisture curable resin. As the photocurable resin, an ultraviolet curable resin is preferable.

  The method for installing the resin 140 is not particularly limited. The resin 140 may be installed on the first surface 112 of the glass substrate 110 by, for example, an injection molding method or a coating method.

  In particular, in the injection molding method, the resin 140 can be sufficiently filled up to a minute space gap existing on the first surface 112 of the glass substrate 110, for example, around the neck portion 153 of the unique convex portion 152. Therefore, when the resin 140 is formed by this method, the adhesion between the glass substrate 110 and the resin 140 is further improved.

  Through the above steps, the first integrated member 100 as shown in FIG. 2 can be manufactured.

(Application example of glass-resin integrated member according to the present invention)
Next, an application example of the glass-resin integrated member according to the present invention having the above-described features will be described with reference to FIGS.

  FIG. 4 schematically shows a perspective view of a front cover member used in a portable electronic device such as a smartphone. FIG. 5 schematically shows a cross section taken along line AA in FIG.

  As shown in FIGS. 4 and 5, the front cover member 300 includes a glass substrate 310 and a frame-shaped member 341 formed in a frame shape around the glass substrate 310.

  The glass substrate 310 has a front surface 316, a back surface 317, and an end surface 318. The front surface 316 of the glass substrate 310 is the outer surface side of the front cover member 300 (that is, the side on which the user performs a touch operation). The back surface 317 of the glass substrate 310 is the inner surface side of the front cover member 300 (that is, the internal element side of the smartphone).

  The frame-shaped member 341 is made of resin and is formed on the outer surface side of the front cover member 300 so as to be level with the front surface 316 of the glass substrate 310. Further, the frame-shaped member 341 includes a support portion 344 having a substantially “L-shaped” cross section that supports the glass substrate 310 along the periphery of the glass substrate 310. The L-shaped support portion 344 substantially contacts a part (periphery) of the back surface 317 and the end surface 318 of the glass substrate 310.

  Here, in the conventional front cover member, an adhesive is disposed at a contact portion between the glass substrate and the frame-shaped member (that is, between the glass substrate and the support portion). Are joined.

  On the other hand, in the front cover member 300, the “first surface” having the above-described characteristics is formed on at least a part of the “contact portion” where the glass substrate 310 contacts the L-shaped support portion 344. Has been. That is, at least a part of the “contact portion” is configured to have an arithmetic average roughness Ra of 10 nm or more, a maximum height roughness Rz of 100 nm or more, and a large number of irregularities on the order of nanometers. In addition, among the many irregularities on the order of nanometers, unique convex portions are included.

  For example, in FIG. 5, a region in contact with the support portion 344 of the frame-shaped member 341 on the back surface 317 of the glass substrate 310 may have such a first surface. Or both the area | region which contacts the support part 344 of the frame-shaped member 341 of the back surface 317 of the glass substrate 310, and the end surface 318 of the glass substrate 310 may have such a 1st surface.

  In this case, good adhesiveness can be obtained between the glass substrate 310 and the frame-shaped member 341 without using an adhesive. As a result, it is possible to avoid deterioration of the aesthetic appearance of the front cover member due to the presence of the adhesive.

  When the entire back surface 317 of the glass substrate 310 is uneven, when the glass substrate 310 and the LCD panel (not shown) are joined with an optical adhesive (not shown), the glass substrate 310 and the optical adhesive are in close contact with each other. Improves.

(Another application example of the glass-resin integrated member according to the present invention)
Next, another application example of the glass-resin integrated member according to the present invention having the above-described features will be described with reference to FIG.

  In FIG. 6, sectional drawing of the laminated member which has a glass part and a resin part is shown typically.

  As shown in FIG. 6, the laminated member 500 is configured by laminating a glass layer 511 and a resin layer 542 with each other. The glass layer 511 has a main surface 512, and the resin layer 542 is formed in a layer shape on the main surface 512. “Main surface (512)” means the surface having the largest area among the surfaces of the glass layer 511.

  Here, the main surface 512 of the glass layer 511 has a “first surface” having the above-described characteristics. That is, at least a part of the main surface 512 of the glass layer 511 has an arithmetic average roughness Ra of 10 nm or more, a maximum height roughness Rz of 100 nm or more, and a large number of irregularities on the order of nanometers. Is done. In addition, among the many irregularities on the order of nanometers, unique convex portions are included.

  In this case, good adhesion can be obtained between the glass layer 511 and the resin layer 542 without using an adhesive. As a result, it is possible to avoid deterioration of aesthetics due to the presence of the adhesive.

  In the above, with reference to FIGS. 4-6, the two application examples of the glass-resin integrated member by this invention were demonstrated. However, it will be apparent to those skilled in the art that the glass-resin integrated member according to the present invention can be applied to other uses.

  Next, examples according to the present invention will be described.

(Example 1)
A sample in which glass and resin were joined was produced by the following method.

  First, an aluminosilicate glass substrate having dimensions of about 50 mm in length, about 12.5 mm in width, and about 0.5 mm in thickness was prepared. Next, an etching process using high-temperature HF gas was performed on one main surface (first surface) of the glass substrate. The temperature of the etching process was 580 ° C., and a mixed gas of nitrogen + 3.1 vol% HF was used as an etching gas. The etching time was 10 seconds.

  Next, this glass substrate was chemically strengthened. The chemical strengthening treatment was performed by immersing the entire glass substrate in 410 ° C. potassium nitrate molten salt. The processing time was 2 hours.

  As a result, a chemically strengthened glass substrate (hereinafter referred to as “uneven substrate A”) in which the first surface was etched was obtained.

  In FIG. 7, an example of the cross-sectional SEM photograph in the 1st surface of the uneven substrate A is shown. FIG. 8 shows a surface SEM photograph of the first surface of the concavo-convex substrate A. From these figures, it can be seen that a large number of fine irregularities are formed on the first surface of the irregular substrate A, and that many of the above-mentioned unique convex portions are included therein. In these figures, many columnar crystals having an aspect ratio in the range of 2 to 5 were also observed.

  In the obtained uneven substrate A, the surface roughness of the first surface was measured. The surface roughness Ra and Rz were measured based on JIS B0601 (2001) using a scanning probe microscope (SPI3800N: manufactured by SII Nano Technology). The measurement was carried out with the number of acquired data being 1024 × 1024 for a 2 μm square area of the cover glass. As a result of the measurement, the arithmetic average roughness Ra was 37 nm, and the maximum height roughness Rz was 330 nm.

  The haze (turbidity) of the concavo-convex substrate A was measured using a haze meter (HZ-2: manufactured by Suga Test Instruments Co., Ltd.). The haze was measured based on JIS K7361-1. A C light source was used as the light source. As a result of the measurement, the haze was 0.8%, and a sufficiently low value was obtained.

  Next, a sample (hereinafter referred to as “integrated sample A”) in which a resin was injection-molded on a part of the concavo-convex substrate A to join the glass and the resin was produced. As the resin, a glass-filled nylon thermoplastic resin (Leona 90G50: manufactured by Asahi Kasei Co., Ltd.) was used.

  In FIG. 9, the form of the integrated sample A is shown schematically.

  As shown in FIG. 9, the integrated sample A was formed by adhering a resin portion 640 to the tip portion of the first surface 612 of the concavo-convex substrate A (610). The dimensions of the resin portion 640 were about 50 mm long × about 12.5 mm wide × 2 mm thick. The width W of the portion where the concavo-convex substrate A (610) and the resin portion 640 overlap is about 13 mm.

  Using the obtained integrated sample A, the adhesion strength between the concavo-convex substrate A (610) and the resin portion 640 was measured. The adhesion strength is determined by pulling the outer end 619 of the concavo-convex substrate A (610) of the integrated sample A and the outer end 649 of the resin portion 640 opposite to each other (in the direction of the arrow in FIG. 9). It was carried out by measuring the strength at the time of breakage.

  As a result of the measurement, the adhesion strength was estimated to be 28 MPa.

  In the column of (Example 1) in Table 1 below, the etching treatment conditions of the uneven substrate A, the surface roughness of the first surface of the uneven substrate A, the haze of the uneven substrate A, and the adhesion strength test of the integrated sample A The results are summarized.

(Example 2)
A sample in which glass and resin were joined was produced in the same manner as in Example 1.

  However, in Example 2, conditions different from those in Example 1 were adopted as the glass substrate etching conditions. As a result, a glass substrate having a first surface different from that in Example 1 (hereinafter referred to as “uneven substrate B”) was obtained.

  Also in the concavo-convex substrate B, it was confirmed that a large number of fine irregularities were formed on the first surface, and that a large number of unique convex portions were included therein. However, in the concavo-convex substrate B, no columnar crystal was observed in the observation region.

  In the obtained uneven substrate B, the surface roughness of the first surface was measured. As a result of the measurement, the arithmetic average roughness Ra was 23 nm, and the maximum height roughness Rz was 230 nm.

  Moreover, the haze of the concavo-convex substrate B was 0.6%, and a sufficiently low value was obtained.

  Next, a sample (hereinafter referred to as “integrated sample B”) in which glass and a resin were joined was produced using the concavo-convex substrate B by the same method as in Example 1. Further, using this integrated sample B, the adhesion strength was measured.

  As a result of the measurement, the adhesion strength was estimated to be 4 MPa.

  In the column of (Example 2) in Table 1 above, the etching conditions of the concavo-convex substrate B, the surface roughness of the first surface of the concavo-convex substrate B, the haze of the concavo-convex substrate B, and the adhesion strength test of the integrated sample B The results are summarized.

(Example 3)
A sample in which glass and resin were joined was produced in the same manner as in Example 1.

  However, in Example 3, different conditions from those in Examples 1 and 2 were adopted as the etching conditions for the glass substrate. As a result, a glass substrate having a first surface different from those in Examples 1 and 2 (hereinafter referred to as “uneven substrate C”) was obtained.

  In FIG. 10, an example of the surface form (SEM photograph) in the 1st surface of the uneven substrate C is shown. From this figure, it was confirmed that on the first surface of the concavo-convex substrate C, almost no fine concavo-convex was observed, and many small pits were formed instead. That is, the first surface of the concavo-convex substrate C was in a relatively flat form.

  In the obtained uneven substrate C, the surface roughness of the first surface was measured. As a result of the measurement, the arithmetic average roughness Ra was 6 nm, and the maximum height roughness Rz was 90 nm.

  Moreover, the haze of the uneven substrate C was 0.5%.

  Next, a sample (hereinafter referred to as “integrated sample C”) in which glass and a resin were joined was produced using the uneven substrate C by the same method as in Example 1. Moreover, the adhesion strength was measured using the integrated sample C.

  As a result of the measurement, the adhesion strength was estimated to be less than 2 MPa.

  In the column of (Example 3) in Table 1 above, the etching processing conditions for the uneven substrate C, the surface roughness of the first surface of the uneven substrate C, the haze of the uneven substrate C, and the integrated sample C The adhesion strength test results are summarized.

  From the comparison of the adhesion strength test results in the integrated samples A to C, when the first surface of the concavo-convex substrate has a surface roughness that satisfies Ra ≧ 10 nm and Rz ≧ 100 nm, and has a specific convex portion, It was found that a relatively good adhesion can be obtained between the concavo-convex substrate and the resin portion.

(Example 4)
A sample in which glass and resin were joined was produced by the following method.

  First, a glass substrate made of soda lime having dimensions of about 50 mm long × about 50 mm wide × about 2 mm thick was prepared. Next, an etching process using high-temperature HF gas was performed on one main surface (first surface) of the glass substrate. The temperature of the etching process was 580 ° C., and a mixed gas of nitrogen + 1.9 vol% HF was used as an etching gas. The etching time was 10 seconds.

  Thereby, the glass substrate (henceforth "concavo-convex substrate D") by which the 1st surface was etched was obtained. In the uneven substrate D, no chemical strengthening treatment is performed.

  In FIG. 11, an example of the cross-sectional form (SEM photograph) in the 1st surface of the uneven substrate D is shown. From this figure, it can be seen that a large number of fine irregularities are formed on the first surface of the irregular substrate D, and that many of the above-mentioned specific convex portions are included therein.

  In the obtained uneven substrate D, the surface roughness of the first surface was measured. As a result of the measurement, the arithmetic average roughness Ra was 17 nm, and the maximum height roughness Rz was 140 nm.

  The haze of the concavo-convex substrate D was measured using a haze meter. As a result of the measurement, the haze was 0.5%, and a sufficiently low value was obtained.

  Next, resin was applied to the first surface of the concavo-convex substrate D, and a sample in which a resin layer was disposed on glass (hereinafter referred to as “integrated sample D”) was produced. As the resin, an acrylic UV curable resin was used. The resin layer (thickness 5 μm) was cured by exposing to ultraviolet light for 1 minute after application of the resin.

  In FIG. 12, an example of the cross-sectional form (SEM photograph) of the integrated sample D is shown. From this figure, the resin layer is arranged on the first surface of the concavo-convex substrate D without providing a space, and the fine concavo-convex portion including the unique convex portion existing on the first surface is sufficiently made of resin. It turns out that it is filled.

  An adhesion evaluation test was carried out using the obtained integrated sample D. The adhesion evaluation test was performed by a method based on JIS K5600-5-6. In this test, after the adhesive tape is pasted on the resin, the adhesive tape is peeled off at a stroke. And the adhesive force between the resin layer and the uneven | corrugated board | substrate D can be determined by evaluating whether the resin layer has adhered to the adhesive tape after a test.

  As a result of the adhesion evaluation test, it was found that the resin layer did not adhere to the adhesive tape side, and good adhesion was obtained between the resin layer and the uneven substrate D.

  In the column of (Example 4) in Table 2 below, etching conditions for the uneven substrate D, surface roughness of the first surface of the uneven substrate D, haze of the uneven substrate D, and adhesion evaluation of the integrated sample D The test results are summarized.

(Example 5)
A sample in which glass and resin were joined (hereinafter referred to as “integrated sample E”) was produced in the same manner as in Example 4. However, in this Example 5, the glass substrate prepared was not used, and the prepared glass substrate was used as it was.

  The arithmetic average roughness Ra on the first surface of the glass substrate was 0.2 nm, and the maximum height roughness Rz was 3 nm. Moreover, the haze of the glass substrate was 0.3%. The other manufacturing conditions are the same as in Example 4.

  Using the obtained integrated sample E, the above-described adhesion evaluation test was performed. As a result, it was found that the resin layer was easily peeled from the glass substrate, and good adhesion was not generated between them.

  In the column of (Example 5) in Table 2 above, the surface roughness of the first surface of the glass substrate in Example 5, the haze of the glass substrate, the adhesion evaluation test results of the integrated sample E, and the like are collectively shown. It was.

  From the comparison of the adhesion evaluation test results in Example 4 and Example 5, it was confirmed that in the integrated sample D in Example 4, good adhesion can be obtained between the glass and the resin without using an adhesive. It was.

  The present invention can be used for, for example, a protective member of a display device, for example, a front cover member of a smartphone.

DESCRIPTION OF SYMBOLS 10 Glass substrate 12 1st surface 50 Convex part 51 Singular convex part 52 Singular convex part 53 Neck part 100 1st integrated member 110 Glass substrate 112 1st surface 114 2nd surface 140 Resin 150 Convex shape Part 151 Unique convex part 152 Unique convex part 153 Neck part 300 Front cover member 310 Glass substrate 316 Front face 317 Rear face 318 End face 341 Frame member 344 L-shaped support part 500 Laminated member 511 Glass layer 512 Main surface 542 Resin layer 610 Uneven substrate A
612 First surface 619 Outer end portion of uneven substrate A 640 Resin portion 649 Outer end portion of resin portion

Claims (11)

A glass-resin integrated member,
A glass substrate having a first surface;
Having a resin installed on the first surface;
In the first surface, the maximum height roughness Rz is 100 nm or more,
The glass-resin integrated member, wherein the first surface has a convex portion in which at least a part of a root portion is constricted inward compared to a tip portion.   2. The glass-resin integrated member according to claim 1, wherein the first surface has an arithmetic average roughness Ra of 10 nm or more.   The glass-resin integrated member according to claim 1, wherein the convex portion has a neck portion.   The glass-resin integrated member according to any one of claims 1 to 3, wherein the glass substrate has a haze of 1% or less.   The glass-resin integrated member according to any one of claims 1 to 4, wherein the resin includes at least one resin selected from the group consisting of a thermoplastic resin and a curable resin.   The glass-resin integrated member according to any one of claims 1 to 5, wherein the glass substrate is aluminosilicate glass.   The glass-resin integrated member according to any one of claims 1 to 6, wherein the glass substrate is chemically strengthened.   The glass-resin integrated member according to any one of claims 1 to 7, wherein the first surface is formed by etching the glass substrate with hydrogen fluoride gas.   The glass-resin integration according to any one of claims 1 to 8, wherein the first surface has a columnar crystal having a total length in a range of 30 nm to 100 nm and a maximum width in a range of 1 nm to 50 nm. Element.   The glass-resin integrated member according to claim 1, wherein the resin is formed in a frame shape around the glass substrate.   The glass-resin integrated member according to any one of claims 1 to 9, wherein the resin is formed in a layered manner on the first surface of the glass substrate.