GLASS WITH AN ADHESIVE COATING FILM, METHOD OF PRODUCTION THEREOF AND MODIFIED GLASS SUBSTRATE.

Abstract

An object of this disclosure is a film-coated glass in which a contact angle with an aqueous content is large, transparency is high, lubricating properties (gliding properties) are excellent, peeling (delamination) of a silica component in the glass is less likely to occur, elution of a glass-derived component (silicon, boron, sodium, potassium, and aluminum) with respect to the contents is less likely to occur, aggregation (adsorption) of a protein that is an active component of a medicinal product is less likely to occur when the film-coated glass fits a medical glass container, heat resistance is exhibited, and peeling of a film-coated glass is suppressed, a method of production therefor, and a modified glass substrate.The coated film-adhered glass (1) according to this disclosure includes a glass substrate (2) and a coating film (3) provided over at least a portion of a surface (2a) of the glass substrate (2), wherein a region of the surface (2a) of the glass substrate (2) on the side of the coating film (3) to a predetermined depth (d1) is a modified layer (4), and the modified layer (4) has a microcrystalline structure at least in part.

Description

GLASS WITH AN ADHESIVE COATING FILM, METHOD OF PRODUCTION THEREOF AND MODIFIED GLASS SUBSTRATE TECHNICAL FIELD The present invention relates to bonded film-coated glass, a method for producing such glass, and a modified glass substrate, and in particular to bonded film-coated glass on which a chemically, thermodynamically, and physically stable coating film is formed, and a method for producing such glass. A glass substrate for bonded film-coated glass, for example, includes glass in the form of a plate or tube, a glass container, a glass medical tool, and the like. TECHNICAL BACKGROUND In a stage of molding a glass container, a glass tube is processed to give it the shape of a container that includes a bottom portion and a mouth portion. In this process, the glass tube is heated to deform it at the bottom and mouth portions. When the glass tube is heated, an alkali or similar component contained in the glass volatilizes, and this volatilized alkali or similar component condenses and adheres to the inner wall of the glass container as the container cools. It is known that alkaline substances that exude or volatilize from glass form numerous small droplets on the inner wall of the glass container. These droplets condense and adhere, resulting in a degraded region, often appearing as a band, on the inner wall near the bottom. In glass containers used for liquid storage, the liquid is known to become alkaline due to an alkali or similar substance eluting from this degraded region. This is particularly problematic in medical glass containers, as the stability of the contained medicinal agent can be compromised by this alkalinization. Furthermore, it is also widely known that, in the region degraded by processing, the glass is hydrolyzed by contact with the water molecules that will be included in the contents, and therefore the glass itself is weakened, peeling (delamination) of a silica component occurs in the glass, and a component derived from the glass (silicon, boron, sodium, potassium, and aluminum) elutes into the contents. Therefore, an attempt has been made to reduce the elution of an alkali compound from a glass surface in contact with its contents using the related technique. Generally, this attempt is carried out by means of a treatment after the glass vessel has been molded. For example, a sulfur treatment method is known in which sodium sulfate (Na₂SO₄) is generated by a reaction between the alkali component present in the wall and the sulfur. Qezzzn / zznz / q / YiAi internal of the glass vessel and a sulfate salt or similar, and the sodium sulfate is removed by washing with water, or as a method to suppress the elution of the alkaline component of the internal wall of the glass vessel, it is known that the internal wall of the glass vessel is subjected to fire-blast treatment with an oxygen-gas flame from a spot burner while rotating the glass vessel formed from the glass tube to remove the degraded region by processing (e.g., see Patent Literature 1). Furthermore, as a method to suppress the hydrolyzability of the internal wall of the glass vessel, it is known that the internal wall is treated with a CO2 laser or similar while rotating the glass vessel formed from the glass tube to remove the degraded region by processing (e.g., see Patent Literature 2 or Patent Literature 3). On the other hand, a method is also known for isolating the contents of a glass surface by applying a coating film of an inorganic material such as silicon or an organic material to the glass surface, without reducing the absolute amount of the alkali component. This method involves forming a low-reactivity coating film on the glass surface (see, for example, Patent Literature 4). In this method, it is possible to provide additional value to the glass vessel after treatment by appropriately selecting the composition of the coating film. For example, it is possible to reduce the binding properties of a polar contents to the inner wall by forming a hydrophobic coating film, thereby decreasing the remaining properties of the vessel.This is an excellent advantage, particularly when it contains a rare and expensive medicinal agent such as a protein formulation, the demand for which has increased in recent years. List of appointments Patent literature Patent Literature 1: WO 2006 / 123621 A Patent literature 2: DE 10 2014 214 083 B4 Patent Literature 3: JP 2019-55896 A Patent Literature 4: JP 2007-076940 A BRIEF DESCRIPTION OF THE INVENTION Technical problem The methods in Patent Literatures 1 to 3 are effective in reducing the elution of the alkali compound, but they are required to provide added value, such as reducing the bonding properties of the contents to the glass container after processing. Therefore, a method for forming the film of Qezzzn / zznz / q / YiAi coating on the glass surface, as with Patent Literature 4. However, the following problems exist in the method for forming the coating film on the glass surface, as with Patent Literature 4. In general, it is known that the usual glass surface is an inorganic phase and, therefore, in many cases, the adhesion properties with respect to the coating film, which is an organic phase, are low, and the coating film is difficult to form. In particular, it is difficult to form the coating film that has low friction or hydrophobicity properties on the glass surface. Therefore, to form a stable coating film, a method is generally required to form the coating film after applying a primer that has affinity with both the glass layer and the coating film, such as a silane coupling agent forming on the glass surface. However, this not only increases the treatment man-hours, but also results in low thermal stability of the silane coupling agent, making this method unsuitable for medical containers exposed to high-temperature conditions such as dry heat sterilization and steam sterilization. Furthermore, even if the coating film forms on the glass surface, small holes (pores) easily develop in the coating film when its stability is low. If pores form in the coating film, it gradually detaches from the porous portions, resulting not only in the loss of the coating film but also in the introduction of foreign particles into the container's contents. Therefore, an object of this disclosure is a film-coated glass in which a contact angle with an aqueous content is large, transparency is high, lubricating properties (gliding properties) are excellent, peeling (delamination) of a silica component in the glass is less likely to occur, elution of a glass-derived component (silicon, boron, sodium, potassium, and aluminum) with respect to the content is less likely to occur, aggregation (adsorption) of protein that is an active component of a medicinal product is less likely to occur in a case where the film-coated glass fits a medical glass container, heat resistance is exhibited, and peeling of a film-coated glass is suppressed, a method of production therefor, and a modified glass substrate. Solution to the problem The present inventors have carried out intensive studies considering such Qezzzn / zznz / q / YiAi problems, have found that the problems are solved by modifying the glass surface on the glass substrate in advance and have completed the present invention. That is, the coated glass according to the present invention includes a glass substrate and a coating film provided on at least a portion of the surface of the glass substrate, wherein a region of the surface of the glass substrate on the side of the coating film to a predetermined depth is a modified layer, and the modified layer has a microcrystalline structure at least in part. The coated film glass according to the present invention includes a glass substrate and a coating film provided on at least a portion of the surface of the glass substrate, wherein a region from the surface of the glass substrate on the side of the coating film to a predetermined depth is a modified layer, the B2O3 content in the modified layer is less than in a region deeper than the modified layer, in mass % in terms of an oxide, and the Na2O content in the modified layer is less than in the region deeper than the modified layer, in mass % in terms of an oxide, the modified layer contains at least 1 to 8 mass % of B2O3, 1 to 6 mass % of Na2O and 80 mass % or more of S1O2, in terms of an oxide, and the region deeper than the modified layer contains at least 9 to 15 mass % of B2O3, 3 to 9 mass % of Na2O and 70 mass % or more of S1O2, in terms of an oxide. In the coated glass according to the present invention, it is preferable that the microcrystalline structure contain carbon. It is possible to further improve the adhesion to the coating film, in particular, with a coating film containing a carbon element in its composition. In glass with a coating film according to the present invention, it is preferable that the modified layer contains carbon. It is possible to further improve the adhesion to the coating film, in particular, with a coating film containing a carbon element in its composition. In the coated glass according to the present invention, it is preferable that the coating film be a silicon-free diamond-like carbon film, a silicon-containing diamond-like carbon film, a silicon oxide-based film, or an amorphous fluorine resin film. With such a coating film, the lubricating properties (gliding properties) are excellent, the contact angle with respect to the aqueous environment is large, and the suppression of aggregation (adsorption) of protein or similar active pharmaceutical ingredients is improved. Furthermore, a coating film with even greater transparency can be obtained using a silicon oxide-based film. The coated glass according to the present invention includes a Qezzzn / zznz / q / YiAi aspect in which the thickness of the coating film is from 1 to 70 nm. The glass with adhered coating film according to the present invention includes an aspect in which the glass substrate is borosilicic acid glass having a coefficient of expansion of 3.2 × 10'6 / K or more and 3.3 × 10'8 / K or less, or borosilicic acid glass having a coefficient of expansion of 4.8 × 10'8 / K or more and 5.6 × 10'6 / K or less. The coated film glass according to the present invention includes an aspect in which the glass substrate is a flask container, a syringe body, a needle-tipped syringe, an ampoule, or a cartridge-type syringe (also simply referred to as a cartridge). A production method for coating glass with an adhered film according to the present invention, wherein a coating film is formed on at least a portion of the surface of a glass substrate, includes a modification step consisting of attaching a region from the surface of the glass substrate on one side onto which the coating film is provided to a predetermined depth as a modified layer, and a film-forming step of forming the coating film onto the surface of the glass substrate onto which the modified layer is formed,wherein the modification step includes at least any of the steps of (i) a step of detonating a flame generated by burning low hydrocarbon gas in the presence of gaseous oxygen from a burner to apply a plasma-rich portion of the flame detonated from the burner to the surface of the glass substrate on the side where the coating film is provided, (ii) a step of performing a laser treatment with respect to the surface of the glass substrate on the side where the coating film is provided, and (iii) a step of performing a high-temperature gas treatment with respect to the surface of the glass substrate on the side where the coating film is provided. In the production method for coating glass with an adhered film according to the present invention, it is preferable that the film-forming step be a step of converting raw material gas containing at least one hydrocarbon gas into plasma to form an amorphous coating film containing at least one carbon element, such as a coating film, on the surface of the glass substrate on the side where the coating film is applied. The lubricating properties (gliding properties) are excellent, the contact angle with respect to the aqueous environment is large, and the suppression of aggregation (adsorption) of protein or similar active components of a medicinal product is improved by means of the coating film containing a carbon element in its composition. In the production method for coating glass with an adhered film according to the present invention, it is preferable that, in the modification stage, the temperature of a Qezzzn / zznz / q / YiAi The surface of the glass substrate on one side opposite the surface of the side where the coating film is applied, provided it is measured with a non-contact thermometer and the temperature being measured is within a specific temperature range. More reliable temperature control and adjustments can be made. A modified glass substrate according to the present invention includes a modified layer on at least a portion of the surface of a glass substrate, wherein the modified layer is a region from the surface of the glass substrate to a predetermined depth and has a microcrystalline structure, at least in part. Advantageous effects of the invention According to the present description, it is possible to provide film-coated glass in which a contact angle with an aqueous content is large, transparency is high, lubricating properties (gliding properties) are excellent, peeling (delamination) of a silica component in glass is less likely to occur, elution of a glass-derived component (silicon, boron, sodium, potassium, and aluminum) with respect to the content is less likely to occur, aggregation (adsorption) of protein that is an active component of a medicinal product is less likely to occur in a case where the film-coated glass fits a medical glass container, heat resistance is exhibited, and the detachment of a film coating is suppressed, a production method for this, and a modified glass substrate. BRIEF DESCRIPTION OF THE FIGURES Figure 1 is a schematic sectional view of glass with film coating adhered according to this modality. Figure 2 is a schematic sectional view of a glass substrate modified according to this modality. Figure 3 is a schematic view of a high-frequency internal surface film forming apparatus for a flask container. Figure 4(a) is a TEM image of a cross-sectional surface of a modified glass substrate after a modification step and before a film-forming step in Example 1. Figure 4(b) is an image in which Figure 4(a) is partially enlarged. Figure 5 is a TEM image of a cross-sectional glass surface with adhered film coating after the film-forming step in Example 1. Qezzzn / zznz / q / YiAi DESCRIPTION OF THE MODALITIES The present invention will now be described in detail based on one embodiment, but the present invention is not to be construed as being limited to the description of that embodiment. The embodiment may be modified in various ways, provided that the effects of the present invention are shown. Figure 1 is a schematic sectional view of bonded film-coated glass according to this embodiment. The film-coated glass 1 according to this embodiment includes a glass substrate 2 and a coating film 3 provided over at least a portion of the surface 2a of the glass substrate 2, wherein a region of the surface 2a of the glass substrate 2 on the side of the coating film 3 to a predetermined depth d1 is a modified layer 4, and the modified layer 4 has a microcrystalline structure at least in part. Furthermore, the coated glass film according to this embodiment includes the glass substrate 2 and the coating film 3 provided on at least a portion of the surface 2a of the glass substrate 2, wherein the region from the surface 2a of the glass substrate 2 on the side of the coating film 3 to the predetermined depth d1 is the modified layer 4, the B2O3 content in the modified layer 4 is less than in the region 5 deeper than the modified layer 4, in mass percent as an oxide, and the Na2O3 content in the modified layer 4 is less than in the region 5 deeper than the modified layer 4, in mass percent as an oxide, the modified layer 4 contains at least 1 to 8 mass percent of B2O3, 1 to 6 mass percent of Na2O3 and 80 mass percent or more of SiO2, in mass as an oxide, and the region 5 deeper than the modified layer 4 contains at least 9 to 15% by mass of B2O3,3 to 9 mass percent of Na₂O and 70 mass percent or more of SiO₂, in terms of oxide. It is preferable to include a case in which the modified layer 4 has a microcrystalline structure at least in part. (Glass substrate) In the coated film-adhered glass 1 according to this embodiment, it is preferable that the glass substrate 2 be borosilicic acid glass having a coefficient of expansion of 3.2 × 10⁻⁶ / K or more and 5.6 × 10⁻⁶ / K or less. The coated film-adhered glass 1 according to this embodiment includes an aspect in which the glass substrate 2 is borosilicic acid glass having a coefficient of expansion of 3.2 × 10⁻⁶ / K or more and 3.3 × 10⁻⁶ / K or less, or borosilicic acid glass having a coefficient of expansion of 4.8 × 10⁻⁶ / K or more and 5.6 × 10⁻⁶ / K or less. Such a glass substrate 2 is preferable because it has a small coefficient of expansion and low alkali elution properties. Specifically, examples of glass substrate 2 include NSV51 (manufactured by Qezzzn / zznz / q / YiAi Nipro PharmaPackaging Americas Corp.), W33 (manufactured by Nipro PharmaPackaging Americas Corp.), BS (manufactured by Nippon Electric Glass Co., Ltd.), FIOLAX (registered trademark) (manufactured by Schott AG), DURAN (registered trademark) (manufactured by Schott AG), and similar products. Table 1 shows a catalog value for the composition (% by mass) of each glass. In Table 1, for NSV51, the total Na₂O and K₂O content is shown as the Na₂O and K₂O content. The same applies to W33 and DURAN. Additionally, Table 1 indicates that the composition is not specified. Table 1: Qezzzn / zznz / q / YiAi Nsrsbrs of (% in jsasa) of exssessés í W'Vk· SW; ... ...............__________ saC s Meares 11.3 δ. θ g 3 3 * ( 2.3 3.3 32, 2 11.0 ?. 0 3.2 2.3 .....:..:.1.. '· ________ (Mares regssfedaii M y 2. & S, δ Λ V i... 5 - 233 3.2 3 3.7 2.2 4 Λ 01· ÁS.2IM________________ SSRAH (Seas rgqssraífe: 3% «i, 3 3. 0 3,3 4 δ It is preferable that the glass substrate 2 be borosilicic acid glass having a coefficient of expansion of 3.2 × 10⁻⁶ / K or more and 3.3 × 10⁻⁶ / K or less, and the surface 2a of the glass substrate 2, which is the interface with the coating film 3, contains at least 1 to 6% by mass of B₂O₃, 1 to 6% by mass of Na₂O, 1 to 2% by mass of Al₂O₃ and 80% by mass or more of SiO₂. Furthermore, it is preferable that the glass substrate 2 be borosilicic acid glass having a coefficient of expansion of 4.8 × 10'6 / K or more and 5.5 × 10-6 / K or less, and the surface 2a of the glass substrate 2, which is the interface with the coating film 3, contains at least 1 to 6% by mass of B2O3, 1 to 6% by mass of Na2O, 5 to 6.5% by mass of Al2O3 and 80% by mass or more of S1O2. It is preferable that the glass substrate 2 be transparent or amber in color, and have light transmittance, and specifically, a light transmittance at a wavelength of 590 to 610 nm or 290 to 450 nm is preferably 45% or more, and more preferably 60% or more. An evaluation method for a transparency test is based on the “Japanese Pharmacopoeia (17th edition) 7. Tests for Containers and Packaging Materials 7.01 Test for Glass Containers for Injections (5) Light transmission test for light-resistant containers.” Glass substrate 2, for example, includes plate or tube-shaped glass, a glass container, a glass medical tool, and the like. Film-coated glass 1 according to this embodiment includes an aspect in which the glass substrate is a flask container, a syringe body (a syringe), a needle-tipped syringe, an ampoule, or a cartridge-type syringe (also referred to simply as a cartridge). When the glass substrate 2 is the tube-shaped glass, the glass container, or the glass medical tool, it is preferable that at least a portion of the surface 2a of the glass substrate 2 (the surface of the glass substrate 2 on the film coating side 3), which is the surface on which the coating film 3 is formed, is the inner wall of the tube-shaped glass, the inner wall of the glass container, or the inner surface of the glass medical tool. Consequently, it is possible to reduce the bonding properties of a polar content with respect to the inner wall and, therefore, to decrease the remaining properties with respect to the container. Jar A flask is a container with an approximately cylindrical exterior shape and a sealed bottom. It includes a bottom portion, a side portion, a neck portion, a mouth portion, an inner portion, and an outer portion. The flask has an internal space and opens at one end of the mouth portion. The bottom portion is flat and disc-shaped, extending from the side portion at its edge. The side portion is cylindrical. This side portion is shaped so that the outer and inner diameters are constant along the axis. The neck portion extends from the side portion and tapers downwards. The neck portion is shaped so that the inner and outer diameters are narrower than those of the side portion.The mouth portion is adjacent to the neck portion and includes an opening divided by the rim portion. The mouth portion is shaped so that its inner and outer diameters are narrower than those of the side surface portion. The mouth portion is shaped so that its outer diameter is wider than the narrowest portion of the neck portion's outer diameter. The inner wall is a glass surface of the bottom portion, the side surface portion, the neck portion, and the mouth portion on the internal space side, and the outer wall is an outer surface facing the glass surface on the internal space side. (Production method for bottle) As an example, the bottle is molded by heating a glass tube that is held and rotated vertically, using a general vertical molding machine. The glass tube is softened by heating it with a burner flame. A portion of the glass tube softens and deforms. Qezzzn / zznz / q / YiAi and, therefore, the lower portion and the mouth portion of the flask are molded from the glass tube. When the lower portion is molded, an alkali borate salt or similar is volatilized from the borosilicic acid glass, which is a raw material for the glass tube. An alkaline component, such as the volatilized alkali borate salt, binds to the inner wall of the flask near the lower portion, causing a degraded area due to processing. (Modified glass substrate) The modified glass substrate 2 according to this modality includes the modified layer 4 over at least a portion of the surface of the glass substrate 2, and the modified layer 4 is the region from the surface 2a of the glass substrate to a predetermined depth d1 and has a microcrystalline structure, at least in part. (Modified layer) The glass substrate 2 includes the modified layer 4 and the region 5 deeper than the modified layer 4. The modified layer 4 is a region extending from the outermost surface to the predetermined depth d1, in addition to the outermost surface of the glass substrate 2 (in Figure 1, surface 2a on the coating film side). The predetermined depth d1 from the outermost surface is preferably 100 nm from the surface 2a of the glass substrate 2 in the depth direction D, more preferably 50 nm from the surface 2a of the glass substrate 2 in the depth direction D, even more preferably 20 nm from the surface 2a of the glass substrate 2 in the depth direction D, and still more preferably 10 nm from the surface 2a of the glass substrate 2 in the depth direction D.Here, the depth direction D is a direction from the surface 2a of the glass substrate 2 on the coating film side to a (non-polished) surface on the opposite side of the coating film. For example, if the glass substrate 2 is the flask container, the depth direction D is a direction from the inner wall surface to the outer wall surface. It is preferable that the modified layer 4 contains at least 1 to 8% by mass of B2O3, 1 to 6% by mass of Na2O, and 80% by mass or more of S1O2, in terms of oxide. It is more preferable that the modified layer 4 contains at least 2 to 6% by mass of B2O3, 2 to 4% by mass of Na2O, and 90% by mass or more of S1O2, in terms of oxide.The composition of modified layer 4, for example, is a mass % in terms of each atomic oxide of a surface composition (a percentage of atomic composition) to be analyzed by X-ray photoelectron spectroscopy (XPS). In glass with an adhered coating film 1 according to this embodiment, it is preferable that the modified layer 4 contain carbon. It is possible to further improve the adhesion with respect to the coating film 3, in particular, with a film of Qezzzn / zznz / q / YiAi coating containing a carbon element in a composition. The carbon content in the modified layer 4 is preferably from 1 to 15 atomic percent, more preferably from 1 to 11 atomic percent, even more preferably from 2 to 10 atomic percent, even more preferably from 3 to 8 atomic percent, and particularly preferably from 4 to 8 atomic percent. (Microcrystalline structure) For the microcrystalline structure, for example, the surface of the glass substrate section is observed using a transmission electron microscope (TEM). The microcrystalline structure is a subnanometer-sized matrix structure with an equal spacing. A portion having a microcrystalline structure is a portion in which crystalline particles are arranged that have a smaller particle diameter than a surrounding portion of the portion. In the microcrystalline structure, at least one glass component is assumed to be crystallized, and specifically, NaBCOs, KBCO3, (Na,K)AIBCO3, (Na,K)CO3, Na2CO3, Na2U, and similar compounds, containing Na as the main component and K, C, B, and similar components, are assumed to be crystallized. The average particle diameter of the crystalline particles in the microcrystalline structure is preferably 1 to 10 nm, and more preferably 1 to 5 nm. The average particle diameter is obtained by TEM observation and can be obtained by X-ray diffraction (XRD) or small-angle X-ray scattering (SAXS). In glass with a coating film adhered according to this embodiment, it is preferable that the microcrystalline structure contain carbon. Further improvement of adhesion to the coating film is possible, in particular, with a coating film containing a carbon element in its composition. (Region 5 deeper than modified layer 4) Region 5 deeper than modified layer 4 is a region that is consecutive to modified layer 4 in the depth direction D. Region 5 deeper than modified layer 4 may include the surface (not illustrated) of the glass substrate 2 on a side opposite the coating film side 3. There may be no boundary between modified layer 4 and region 5 deeper than modified layer 4, and, for example, a glass composition may be a gradient composition between modified layer 4 and region 5 deeper than modified layer 4. (Coating film) Coating film 3 includes an aspect in which the coating film 3 contains a carbon element in its composition. As an example, coating film 3 is a silicon-free diamond-like carbon film. Here, the diamond-like carbon film is also referred to as a diamond-like carbon film, or a film of Qezzzn / zznz / q / YiAi DLC and amorphous carbon film, and is a hydrogenated amorphous carbon film containing at least one carbon atom and one hydrogen atom. The coating film thickness is preferably from 1 to 70 nm, and more preferably from 2 to 60 nm. If the film thickness is less than 1 nm, it may be difficult to form a homogeneous coating film without defects, and if the film thickness is greater than 70 nm, flaking may occur or the coloration may exceed a permissible range. Here, the coating film, which is the silicon-free diamond-like carbon film, includes an aspect in which the coating film is a silicon-free, fluorinated, diamond-like carbon film (hereafter referred to as “F-DLC film”), or a silicon-free, fluorinated, diamond-like carbon film (hereafter referred to simply as “DLC film”). It should be noted that the fluorinated, diamond-like carbon film is also called a fluorinated amorphous carbon film. As an example, coating film 3 can be a diamond-like carbon film containing silicon. As an example, coating film 3 can be a silicon oxide-based film containing organic silane or siloxane as a raw material. The organic silane and siloxane are not particularly limited and include hexamethyl disiloxane, hexamethyl silazane, tetraethoxysilane, tetramethoxysilane, and tetramethylsilane. As an example, coating film 3 can be an amorphous fluorine resin film. The fluorine resin is not particularly limited and includes polytetrafluoroethylene and perfluoroalkoxyalkanes. It is preferable that the fluorine resin be an amorphous fluorine resin that is transparent across a broad range of wavelengths, including ultraviolet, visible, and near-infrared light. Specifically, the amorphous fluorine resin is CYTOP (registered trademark), obtained by cyclopolymerization of perfluoro(4-vinyloxy-1-butene). By providing the coating film 3 exemplified above, the lubricating properties (gliding properties) are excellent, the contact angle with respect to an aqueous content is large, and the suppression of the aggregation (adsorption) of protein or similar that is an active component of a drug is improved in the product. (Production method for coating glass with adhered film) As illustrated in Figure 1, a production method for coating glass with an adhered film 1 according to this embodiment, wherein the coating film 3 is formed on at least a portion of the surface 2a of the glass substrate 2, includes a region adjustment modification step from the surface 2a of the glass substrate 3 on one side where the coating film 3 is provided to a predetermined depth d1. Qezzzn / zznz / q / YiAi as the modified layer 4, and a film-forming step of forming the coating film 3 on the surface 2a of the glass substrate 2 on which the modified layer 4 is formed, wherein the modification step includes at least any one of the following steps: (i) detonating a flame generated by burning low hydrocarbon gas in the presence of gaseous oxygen from a burner to apply a plasma-rich portion of the flame detonated from the burner to the surface 2a of the glass substrate 2 on the side on which the coating film 3 is provided, (ii) performing a laser treatment with respect to the surface 2a of the glass substrate 2 on the side on which the coating film 3 is provided, and (iii) performing a high-temperature gas treatment with respect to the surface 2a of the glass substrate 2 on the side on which the coating film 3 is provided. (Modification step) A surface treatment in the modification step includes a plasma treatment or a heat treatment. In addition, the plasma treatment includes (i) a flame detonation treatment generated by burning the low hydrocarbon gas in the presence of oxygen gas from the burner to apply the plasma-rich portion of the flame to be detonated from the burner to the surface 2a of the glass substrate 2 on the side where the coating film 3 is provided (hereafter referred to as the modification step of (i)).The heat treatment includes (i) a laser treatment to be performed with respect to the surface 2a of the glass substrate 2 on the side where the coating film 3 is provided (hereinafter referred to as the modification step of (i)) and (iii) a high-temperature gas treatment to be performed with respect to the surface 2a of the glass substrate 2 on the side where the coating film 3 is provided (hereinafter referred to as the modification step of (!!!)). As an example, the modification step in (i) is a flame detonation step generated by burning the low-hydrocarbon gas in the presence of gaseous oxygen from the burner to apply the flame to the glass surface of the glass substrate 2. The low-hydrocarbon gas includes, for example, town gas, propane, butane, and natural gas. Furthermore, it is preferable that the plasma-rich portion of the flame, which is applied to the surface 2a of the glass substrate 2, be a hydronium ion-rich combustion flame, generated as a result of combustion. In the case that the glass substrate 2 is the glass container vial, it is preferable that in the modification step of (i), the flame is applied to the inner wall of the vial, preferably, the flame is applied to the vicinity of the lower portion of the inner wall of the vial (a portion that includes a region degraded by processing). In the production method for coating glass with adhered film 1 according to In this modality, it is preferable that during the modification step, the surface temperature of the glass substrate 2, on the side opposite surface 2a on the side where the coating film 3 is applied, be measured with a non-contact thermometer, and that the temperature being measured is within a specific temperature range. This allows for more reliable temperature control and more reliable modifications. It is preferable that the non-contact thermometer be a thermographic thermometer. Furthermore, if the glass substrate 2 is the bottle container, the surface opposite surface 2a is the outer surface of the bottle container, and, for example, the specific temperature range is preferably 650°C to 800°C, and more preferably 670°C to 780°C. Furthermore, as an example, in the laser treatment in the modification step of (i), laser light from a CO2 (carbon dioxide) laser, a trio aluminum (YAG) laser or an ultrafast (UF) laser is applied to the glass surface of the glass substrate 2. Furthermore, as an example, in the high-temperature gas treatment in the modification step of (iii), superheated steam from a superheated steam generator is applied to the surface of the glass substrate 2. In this mode, in the modification step, only one of the modification steps from (i), (ii), and (iii) can be performed, or two or more of them can be performed. A combination of two or more modification steps, for example, is a combination of (i) and (ii), a combination of (i) and (iii), a combination of (ii) and (iii), or a combination of (i), (ii), and (iii). (Film formation step) In the production method for coating glass with adhered film 1 according to this embodiment, it is preferable that the film-forming step be a step of converting raw material gas containing at least hydrocarbon gas into plasma to form an amorphous coating film containing at least carbon, such as coating film 3, on the surface 2a of the glass substrate 3 on the side where the coating film 3 is provided. Since the coating film 3 contains the element carbon in the composition, the lubricating properties (gliding properties) are excellent, the contact angle with respect to the aqueous content is large, and the suppression of the aggregation (adsorption) of protein or similar substances that are active components of a drug is improved in the product. In the film formation step, for example, it is preferable to form the amorphous carbon-containing coating film using a high-frequency film-forming apparatus. The amorphous carbon-containing coating film, for example, is the silicon-free diamond-like carbon film or the diamond-like carbon film. Qezzzn / zznz / q / YiAi containing silicon, as described above. When the cladding film 3 is a silicon-free diamond-like carbon film, the feed gas, for example, is acetylene, methane, ethylene, propane, benzene, hexafluoroethane, CeFiO(CF3)2, CeFe, tetrafluoromethane (CF4), and octafluoropropane (CsFs). Furthermore, when the cladding film 3 is a silicon-containing diamond-like carbon film, the feed gas, for example, is an organosilicon gas such as trimethylsilane (C1H2OSi) or tetramethylsilane (O4H2O1). The feed gas can be used alone, or two or more types can be used together. The following describes an example of the film-forming apparatus that can be used in the film-forming stage in the example where the glass substrate 2 is the flask container. Figure 3 illustrates a schematic view of a high-frequency internal surface film-forming apparatus for a flask container. A high-frequency internal surface film-forming apparatus 100 for a flask container, illustrated in Figure 3, includes raw material gas inlet systems 31, 32, and 33. Each of the raw material gas inlet systems includes a shut-off valve 34 and a gas flow meter 35, and is connected to a mixed gas pipe 36. Figure 3 illustrates an aspect in which there are three raw material gas inlet systems, and additional raw material gas inlet systems can be provided.Pipe 36 is connected to an internal electrode located in a vacuum chamber 38 and a conductive pipe 43a, which also serves as a gas inlet pipe. The vacuum chamber 38 is grounded, and a vacuum indicator 37 is connected to it. Within the vacuum chamber 38 are a flask container (glass substrate) 2, an external electrode 45 arranged to surround the lateral and lower surfaces of the flask container 2, a dielectric element 46 surrounding the external electrode 45, and an external housing 48 surrounding the dielectric element 46 and containing a conductive material for stably converting the feed gas into plasma. The vacuum chamber 38 is connected to the exhaust pipe 49. Furthermore, the external electrode 45 is connected to an automatic adaptation device 40 to prevent it from being electrically continuous with the vacuum chamber 38.The automatic matching device 40 is connected to a high-frequency power supply 41. A high frequency, for example, is from 1 to 100 MHz, and is preferably 13.56 MHz. The raw material gas expelled from the conducting tube 43a flows into the vial container 2 and is then discharged from the port at the tip of the vial container 2, passes through a space 48a provided on the upper side of the outer casing 48, and then reaches the internal space of the vacuum chamber 38. After that, it exits through the exhaust tube 49. Examples Qezzzn / zznz / q / YiAi The present invention will now be described in more detail, based on examples, but the present invention is not limited to such examples. (Preparing the Jar) A lower portion was molded from a BS borosilicic acid glass tube having an outer diameter of 15 mm and a wall thickness of 1.5 mm (manufactured by Nippon Electric Glass Co., Ltd.) using a vertical molding machine, and thus vials X1 and Y1 having an outer diameter of 15 mm, a height of 33 mm, an inner port diameter of 7.0 mm and a content of 2.0 ml. A lower portion was molded from a W33 borosilicic acid glass tube having an outer diameter of 15 mm and a wall thickness of 1.5 mm (manufactured by Nipro PharmaPackaging Americas Corp.) using a vertical molding machine, and thus the X2 and Y2 flasks having an outer diameter of 15 mm, a height of 33 mm, an inner port diameter of 7.0 mm and a content of 2.0 ml was prepared. (Modification step) Plasma treatment using the modification step in (i) was performed with respect to the inner wall of prepared flasks X1 and X2. (Modification Step Condition of (!)) The treatment was performed by igniting a flame from a spot burner into the flask's internal space while holding and rotating vials X1 and X2, and scanning the inner wall of the vial with the flame while applying a plasma-rich portion of the flame to the flask's inner wall. In this treatment, a spot burner with a 1.4 mm inner port diameter was used, in which a mixed gas flame (approximately 10 cm long) containing town gas (methane) and oxygen in a complete combustion ratio was ignited. Analysis of the composition of the glass surface The composition of the glass surface (approximately 3 to 5 mm from the lower portion) of the inner wall of the vial before and after plasma treatment was analyzed by XPS (AXIS-NOVA, manufactured by Kratos Analytical Ltd.). Analysis results of the compound composition on the surface of the vial before and after plasma treatment are shown in Table 2. Qezzzn / zznz / q / YiAi Table 2: Wssra Prspsrdás de csspssojn (¾ es Siús Ms-Os Ksú kgO 1 {SSj Phrases xl y... y 6.0 S.,3 1 A 0,0 . ...... Phrases xó ri. o 0.. l ; . 0 0.3 0 .i Ó .. ó 0.0 :Frasca n 1 (BS) : 01. 3 30.. 4 6.6 -Y * >.. : 1 . or 0.0 Ι^8 ^υο S8.7 % 3.0 1.7 «a 0.0 3.0' 0.0 Qezzzn / zznz / q / YiAi (Film Formation Step) One condition at the time of forming a film on the inner surface of the vial (X1, X2, Y1 and Y2) is the following. Device: a low-pressure plasma CVD device, illustrated in Figure 3 High frequency output: 100 W, 13.56 MHz Initial depressurization: 0.02 torr Film forming pressure: 2 torr Film formation time: as shown in Table 3 Mixed gas: as shown in Table 3. Here, a ratio indicates a volumetric flow mixing ratio. Pretreatment: none Table 3: taslra Ewpfc 1 pO; Capa ssás sxfema fTw D LO Tiesas fcrssKsófi «fe petóa (sj ΐ Cs-H ¡-Oí Fs 70 Ejsíspfc 2 -FOO} ΐ CqU-CjFs. Π:®; 30 1 (BS) F-OLO 00:3) í: 0 Stela ecmarasivo 2».....'................_ í Ο?®®.·®. 00:3) 30 The table shows... F-DLC indicates a diamond-like chestnut film containing fluorine and free of silicon.” [Steam sterilization treatment] Each flask was filled with water to 90% of its total capacity and subjected to high-pressure steam sterilization at 121°C for 1 h. In Examples 1 and 2, it was not possible to verify the detachment of F-DLC from the outermost layer, but in Comparative Examples 1 and 2, the detachment of F-DLC from the outermost layer was verified. [Microcrystalline structure] Figure 4(a) is a TEM image of the cross-sectional surface of a modified glass substrate after the modification step and before the film-forming step in Example 1, and Figure 4(b) is a partially enlarged image of Figure 4(a). In Figure 4(a) and Figure 4(b), a portion of the modified layer is a protective film provided for TEM analysis. As illustrated in Figure 4(a) and Figure 4(b), it was possible to verify that the modified layer has a microcrystalline structure, at least in part. In Figure 4(b), a dotted line was applied to a portion that is considered the boundary between the modified layer and a region deeper than the modified layer. Figure 5 is a TEM image of the cross-sectional surface of the glass with the bonded film coating after the film-forming step in Example 1. As illustrated in Figure 5, it was possible to verify that the glass bonded to the coating film includes the modified layer in the region from the surface of the glass substrate on the coating film side to a predetermined depth. The thickness of the modified layer was approximately 20 nm. The surface of the glass section bonded with coating film after the film-forming step in Example 1 was subjected to EDX analysis to verify a Si distribution image, an O distribution image, a C distribution image, an F distribution image, a Na distribution image, and a K distribution, and as a result, it was possible to verify at least Na and K in the modified layer.

Claims

1. A glass with an adhered film coating, characterized in that it comprises: a glass substrate; and a coating film provided on at least a portion of a surface of the glass substrate, wherein a region of the surface of the glass substrate on the side of the coating film at a predetermined depth is a modified layer, and the modified layer has a microcrystalline structure at least in part.

2. A glass with an adhered film coating, characterized in that it comprises: a glass substrate;and a coating film provided on at least a portion of a glass substrate surface, wherein a region of the glass substrate surface on the coating film side at a predetermined depth is a modified layer, the B2O3 content in the modified layer is less than that of the region deeper than the modified layer, by mass % in terms of an oxide, and the Na2U content in the modified layer is less than that of the region deeper than the modified layer, by mass % in terms of an oxide, the modified layer contains at least 1 to 8 mass % of B2O3, 1 to 6 mass % of Na2U and 80 mass % or more of SiO2, in terms of an oxide, and the region deeper than the modified layer contains at least 9 to 15 mass % of B2O3, 3 to 9 mass % of Na2U and 70 mass % or more of SiO2, in terms of an oxide.

3. Glass with an adhered coating film according to claim 1, characterized in that the microcrystalline structure contains carbon.

4. Glass with an adhered coating film according to claim 1 or 2, characterized in that the modified layer contains carbon.

5. Glass with an adhered coating film according to any of claims 1 to 4, characterized in that the coating film is a silicon-free diamond-like carbon film, a silicon-containing diamond-like carbon film, a silicon oxide-based film, or an amorphous fluorine resin film.

6. Glass with an adhered coating film according to any of claims 1 to 5, characterized in that the coating film thickness is from 1 to 70 nm. Qezzzn / zznz / q / YiAi 7. Glass with an adhered coating film according to any of claims 1 to 6, characterized in that the glass substrate is borosilicic acid glass having a coefficient of expansion of 3.2 × 10⁻⁶ / K or more and 3.3 × 10⁻⁶ / K or less, or borosilicic acid glass having a coefficient of expansion of 4.8 × 10⁻⁶ / K or more and 5.6 × 10⁻⁶ / K or less.

8. The glass with an adhered coating film according to any of claims 1 to 7, characterized in that the glass substrate is a flask container, a syringe body, a needle-tipped syringe, an ampoule, or a cartridge-type syringe.

9. A production method for coating glass with an adhered film in which a coating film is formed on at least a portion of a surface of a glass substrate, the method being characterized in that it comprises: a step of modifying the fit of a region of the surface of the glass substrate on one side in which the coating film is provided to a predetermined depth as a modified layer;and a film-forming step of applying a coating film onto the surface of the glass substrate on which the modified layer is formed, wherein the modification step includes at least one step of (i) detonating a flame generated by the combustion of low-hydrocarbon gas in the presence of oxygen gas from a burner to apply a plasma-rich portion of the flame to be detonated from the burner to the surface of the glass substrate on the side where the coating film is provided, (ii) performing a laser treatment with respect to the surface of the glass substrate on the side where the coating film is provided, and (ii) performing a high-temperature gas treatment with respect to the surface of the glass substrate on the side where the coating film is provided; 10. The production method for coating glass with an adhered film according to claim 9, characterized in that the film-forming step is a step of converting the feed gas containing at least hydrocarbon gas into plasma to form an amorphous coating film containing at least carbon, such as a coating film, on the surface of the glass substrate on the side on which the coating film is provided.

11. The production method for coating glass with an adhered film according to claim 9 or 10, characterized in that, in the modification step, a temperature of a surface of the glass substrate on a side opposite the surface of the side on which the coating film is applied is measured with a non-contact Qezzzn / zznz / q / YiAi type thermometer, and the temperature to be measured is within a specific temperature range.

12. A modified glass substrate, characterized in that it comprises: a modified layer on at least a portion of a surface of a glass substrate, wherein the modified layer is a region of the surface of the glass substrate at a predetermined depth and has a microcrystalline structure at least in part.