FORM 2
THE PATENTS ACT, 1970
(39 of 1970)
&
THE PATENTS RULES, 2003
COMPLETE SPECIFICATION
[See section 10, Rule 13]
COATING FILM-ATTACHED GLASS, PRODUCTION METHOD THEREFOR,
AND MODIFIED GLASS SUBSTRATE;
NIPRO CORPORATION, A CORPORATION ORGANISED AND EXISTING UNDER
THE LAWS OF JAPAN, WHOSE ADDRESS IS 3-9-3, HONJO-NISHI, KITA-KU,
OSAKA-SHI, OSAKA 5318510, JAPAN
THE FOLLOWING SPECIFICATION PARTICULARLY DESCRIBES THE INVENTION
AND THE MANNER IN WHICH IT IS TO BE PERFORMED.

2
DESCRIPTION
COATING FILM-ATTACHED GLASS, PRODUCTION METHOD THEREFOR,
AND MODIFIED GLASS SUBSTRATE
5 Technical Field
[0001]
The present invention relates to coating filmattached glass, a production method therefor, and a
modified glass substrate, and particularly relates to
10 coating film-attached glass on which a chemically,
thermodynamically, and physically stable coating film is
formed, and a production method therefor. A glass
substrate of the coating film-attached glass, for example,
includes plate-shaped or tube-shaped glass, a glass vessel,
15 a glass medical tool, and the like.
Background Art
[0002]
In a molding step of a glass vessel, a glass tube is
20 processed into the shape of a vessel including a bottom
portion and a mouth portion. In such a process, the glass
tube is heated to be deformed into the bottom portion and
the mouth portion. In a case where the glass tube is
heated, an alkaline component or the like contained in
25 glass is volatilized, and the volatilized alkaline
component or the like is condensed and attached to the
inner wall of the glass vessel while the glass vessel is
3
cooled.
[0003]
It is known that alkaline substances exuded or
volatilized from the glass are formed into a large number
5 of small droplets on the inner wall of the glass vessel and
are condensed and fixed, and thus, a processing-degraded
region is formed in the shape of a belt on the inner wall
close to the bottom portion. In particular, in the glass
vessel used for liquid storage, it is known that liquidity
10 is basic due to an alkali or the like eluted from the
processing-degraded region. This is serious particularly
in a medical glass vessel because the stability of a
medicinal agent to be contained may be impaired due to the
basification.
15 [0004]
In addition, it is also widely known that in the
processing-degraded region, the glass is hydrolyzed by the
contact of water molecules to be contained in the content,
and thus, the glass itself becomes weak, the peeling
20 (delamination) of a silica component in the glass occurs,
and a glass-derived component (silicon, boron, sodium,
potassium, and aluminum) is eluted to the content.
[0005]
Therefore, an attempt for reducing the elution of an
25 alkaline compound from a glass surface in contact with the
content has been made from the related art. It is general
that such an attempt is made by a treatment after molding
4
the glass vessel, and for example, a sulfur treatment
method is known in which sodium sulfate (Na2SO4) is
generated by a reaction between the alkaline component
existing on the inner wall of the glass vessel and a
5 sulfate salt or the like, and the sodium sulfate is removed
by being washed with water, or as a method of suppressing
the elution of the alkaline component from the inner wall
of the glass vessel, it is known that the inner wall of the
glass vessel is subjected to a fire blast treatment with an
10 oxygen-gas flame of a point burner while rotating the glass
vessel formed from the glass tube to remove the processingdegraded region (for example, refer to Patent Literature 1).
In addition, as a method of suppressing the hydrolyzability
of the inner wall of the glass vessel, it is known that the
15 inner wall is treated with CO2 laser or the like while
rotating the glass vessel formed from the glass tube to
remove the processing-degraded region (for example, refer
to Patent Literature 2 or Patent Literature 3).
[0006]
20 On the other hand, a method of insulating the content
from the glass surface by a coating film of an inorganic
material such as silicon or an organic material on the
glass surface, without reducing an absolute amount of the
alkaline component, such as a method of forming a low25 reactive coating film on the glass surface (for example,
refer to Patent Literature 4) is also known. In such a
method, it is possible to provide further added value to
5
the glass vessel after the treatment by suitably selecting
the composition of the coating film. For example, it is
possible to reduce attachment properties of a polar content
with respect to the inner wall by forming a hydrophobic
5 coating film, and thus, it is possible to decrease
remaining properties with respect to the vessel. This is
an excellent advantage particularly when containing a rare
and expensive medicinal agent such as a protein formulation,
of which the demand has increased in recent years.
10
Citation List
Patent Literature
[0007]
Patent Literature 1: WO 2006/123621 A
15 Patent Literature 2: DE 10 2014 214 083 B4
Patent Literature 3: JP 2019-55896 A
Patent Literature 4: JP 2007-076940 A
Summary of Invention
20 Technical Problem
[0008]
The methods in Patent Literatures 1 to 3 are
effective in reducing the elution of the alkaline compound,
but are required to provide added value such as the
25 reduction of attachment properties of the content to the
glass vessel after a processing treatment. Therefore, it
is considered to apply a method of forming the coating film
6
on the glass surface, as with Patent Literature 4. However,
there are the following problems in the method of forming
the coating film on the glass surface, as with Patent
Literature 4. It is generally known that the usual glass
5 surface is an inorganic phase, and thus, in many cases,
adhesion properties with respect to the coating film that
is an organic phase are low, and the coating film is
difficult to form. In particular, it is difficult to form
the coating film having low frictional properties or
10 hydrophobicity on the glass surface.
[0009]
Therefore, in order to form a stable coating film, in
general, a method of forming the coating film after
applying a primer having affinity with both of the glass
15 layer and the coating film, such as a silane coupling agent,
onto the glass surface is performed. However, not only do
treatment man-hours increase but also heat stability of the
silane coupling agent is low, and thus, such a method is
not suitable for a medical vessel exposed to a high
20 temperature condition such as dry-heat sterilization and
steam sterilization.
[0010]
In addition, even in a case where the coating film is
formed on the glass surface, small holes (pinholes) are
25 easily formed in the coating film when stability as the
coating film is low. In a case where the pinholes are
formed in the coating film, the coating film is gradually
7
peeled off from the pinhole portions, and thus, not only is
the coating film lost, but also foreign particles are mixed
in the vessel content.
[0011]
5 Therefore, an object of the present disclosure is to
provide coating film-attached glass in which a contact
angle with an aqueous content is large, transparency is
high, lubricating properties (sliding properties) are
excellent, the peeling (delamination) of a silica component
10 in glass is less likely to occur, the elution of a glassderived component (silicon, boron, sodium, potassium, and
aluminum) with respect to the content is less likely occur,
the aggregation (adsorption) of protein that is an active
component of a medicinal product is less likely occur in a
15 case where the coating film-attached glass is adjusted to a
medical glass vessel, heat resistance is exhibited, and the
peeling of a coating film is suppressed, a production
method therefor, and a modified glass substrate.
20 Solution to Problem
[0012]
The present inventors have conducted intensive
studies in consideration of such problems, found that the
problems are solved by modifying in advance the glass
25 surface on the glass substrate, and completed the present
invention. That is, coating film-attached glass according
to the present invention includes a glass substrate, and a
8
coating film provided on at least a part of a surface of
the glass substrate, in which a region from the surface of
the glass substrate on the coating film side to a
predetermined depth is a modified layer, and the modified
5 layer has a microcrystalline structure at least in part.
[0013]
Coating film-attached glass according to the present
invention includes a glass substrate, and a coating film
provided on at least a part of a surface of the glass
10 substrate, in which a region from the surface of the glass
substrate on the coating film side to a predetermined depth
is a modified layer, a content of B2O3 in the modified
layer is less than that in a region deeper than the
modified layer, by mass% in terms of an oxide, and a
15 content of Na2O in the modified layer is less than that in
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 Na2O, and 80 mass% or
more of SiO2, in terms of an oxide, and the region deeper
20 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 SiO2, in
terms of an oxide.
[0014]
In the coating film-attached glass according to the
25 present invention, it is preferable that the
microcrystalline structure contains carbon. It is possible
to further improve adhesiveness with respect to the coating
9
film, in particular, a coating film containing a carbon
element in a composition.
[0015]
In the coating film-attached glass according to the
5 present invention, it is preferable that the modified layer
contains carbon. It is possible to further improve
adhesiveness with respect to the coating film, in
particular, a coating film containing a carbon element in a
composition.
10 [0016]
In the coating film-attached glass according to the
present invention, it is preferable that the coating film
is a silicon-free diamond-like carbon film, a siliconcontaining diamond-like carbon film, a silicon oxide-based
15 film, or an amorphous fluorine resin film. According to
such a coating film, lubricating properties (sliding
properties) are excellent, a contact angle with respect to
an aqueous content is large, and the suppression of the
aggregation (adsorption) of protein or the like that is an
20 active component of a medicinal product is improved. In
addition, a coating film more excellent in transparency can
be obtained by a silicon oxide-based film.
[0017]
The coating film-attached glass according to the
25 present invention includes an aspect in which a film
thickness of the coating film is 1 to 70 nm.
[0018]
10
The coating film-attached glass according to the
present invention includes an aspect in which the glass
substrate is borosilicic acid glass having an expansion
coefficient of 3.2 × 10-6/K or more and 3.3 × 10-6/K or less,
5 or borosilicic acid glass having an expansion coefficient
of 4.8 × 10-6/K or more and 5.6 × 10-6/K or less.
[0019]
The coating film-attached glass according to the
present invention includes an aspect in which the glass
10 substrate is a vial container, a syringe barrel, a needletipped syringe, an ampule, or a cartridge type syringe
(also simply referred to as a cartridge).
[0020]
A production method for coating film-attached glass
15 according to the present invention in which a coating film
is formed on at least a part of a surface of a glass
substrate includes a modification step of setting a region
from the surface of the glass substrate on a side on which
the coating film is provided to a predetermined depth as a
20 modified layer, and a film formation step of forming the
coating film on the surface of the glass substrate on which
the modified layer is formed, in which the modification
step includes at least any one step of (i) a step of
blasting a flame generated by burning low hydrocarbon gas
25 in the presence of oxygen gas from a burner to apply a
portion rich in plasma in the flame to be blasted from the
burner to the surface of the glass substrate on the side on
11
which 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 on which the coating film
is provided, and (iii) a step of performing a high5 temperature gas treatment with respect to the surface of
the glass substrate on the side on which the coating film
is provided.
[0021]
In the production method for coating film-attached
10 glass according to the present invention, it is preferable
that the film formation step is a step of turning raw
material gas containing at least hydrocarbon-based gas into
plasma to form an amorphous coating film containing at
least carbon as the coating film on the surface of the
15 glass substrate on the side on which the coating film is
provided. Lubricating properties (sliding properties) are
excellent, a contact angle with respect to an aqueous
content is large, and the suppression of the aggregation
(adsorption) of protein or the like that is an active
20 component of a medicinal product is improved, by the
coating film containing a carbon element in a composition.
[0022]
In the production method for coating film-attached
glass according to the present invention, it is preferable
25 that in the modification step, a temperature of a surface
of the glass substrate on a side opposite to the surface on
the side on which the coating film is provided is measured
12
by a non-contact type thermometer, and the temperature to
be measured is in a specific temperature range. It is
possible to more reliably manage a temperature and to more
reliably perform modification.
5 [0023]
A modified glass substrate according to the present
invention includes a modified layer on at least a part of a
surface of a glass substrate, in which the modified layer
is a region from the surface of the glass substrate to a
10 predetermined depth and has a microcrystalline structure at
least in part.
Advantageous Effects of Invention
[0024]
15 According to the present disclosure, it is possible
to provide coating film-attached glass in which a contact
angle with an aqueous content is large, transparency is
high, lubricating properties (sliding properties) are
excellent, the peeling (delamination) of a silica component
20 in glass is less likely to occur, the elution of a glassderived component (silicon, boron, sodium, potassium, and
aluminum) with respect to the content is less likely occur,
the aggregation (adsorption) of protein that is an active
component of a medicinal product is less likely occur in a
25 case where the coating film-attached glass is adjusted to a
medical glass vessel, heat resistance is exhibited, and the
peeling of a coating film is suppressed, a production
13
method therefor, and a modified glass substrate.
Brief Description of Drawings
[0025]
5 FIG. 1 is a schematic sectional view of coating filmattached glass according to this embodiment.
FIG. 2 is a schematic sectional view of a modified
glass substrate according to this embodiment.
FIG. 3 is a schematic view of a high-frequency inner
10 surface film formation apparatus for a vial container.
FIG. 4(a) is a TEM image of a sectional surface of a
modified glass substrate after a modification step and
before a film formation step in Example 1.
FIG. 4(b) is an image in which FIG. 4(a) is partially
15 enlarged.
FIG. 5 is a TEM image of a sectional surface of
coating film-attached glass after the film formation step
in Example 1.
20 Description of Embodiments
[0026]
Hereinafter, the present invention will be described
in detail based on an embodiment, but the present invention
is not interpreted as being limited to the description
25 thereof. The embodiment may be modified in various forms
as long as effects of the present invention are exhibited.
[0027]
14
FIG. 1 is a schematic sectional view of coating filmattached glass according to this embodiment. Coating filmattached glass 1 according to this embodiment includes a
glass substrate 2, a coating film 3 provided on at least a
5 part of a surface 2a of the glass substrate 2, in which a
region from the surface 2a of the glass substrate 2 on the
coating film 3 side to a predetermined depth d1 is a
modified layer 4, and the modified layer 4 has a
microcrystalline structure at least in part.
10 [0028]
In addition, the coating film-attached glass 1
according to this embodiment includes the glass substrate 2,
and the coating film 3 provided on at least a part of the
surface 2a of the glass substrate 2, in which the region
15 from the surface 2a of the glass substrate 2 on the coating
film 3 side to the predetermined depth d1 is the modified
layer 4, the content of B2O3 in the modified layer 4 less
than that in a region 5 deeper than the modified layer 4,
by mass% in terms of an oxide, and the content of Na2O in
20 the modified layer 4 is less than that in the region 5
deeper than the modified layer 4, by mass% in terms of an
oxide, the modified layer 4 contains at least 1 to 8 mass%
of B2O3, 1 to 6 mass% of Na2O, and 80 mass% or more of SiO2,
in terms of an oxide, and the region 5 deeper than the
25 modified layer 4 contains at least 9 to 15 mass% of B2O3, 3
to 9 mass% of Na2O, and 70 mass% or more of SiO2, in terms
of an oxide. It is preferable to include a case in which
15
the modified layer 4 has a microcrystalline structure at
least in part.
[0029]
(Glass Substrate)
5 In the coating film-attached glass 1 according to
this embodiment, it is preferable that the glass substrate
2 is borosilicic acid glass having an expansion coefficient
of 3.2 × 10-6/K or more and 5.6 × 10-6/K or less. The
coating film-attached glass 1 according to this embodiment
10 includes an aspect in which the glass substrate 2 is
borosilicic acid glass having an expansion coefficient of
3.2 × 10-6/K or more and 3.3 × 10-6/K or less, or
borosilicic acid glass having an expansion coefficient of
4.8 × 10-6/K or more and 5.6 × 10-6/K or less. Such a glass
15 substrate 2 is preferable since the glass substrate 2 has a
small expansion coefficient and low alkaline elution
properties. Specifically, examples of the glass substrate
2 include NSV51 (manufactured by Nipro PharmaPackaging
Americas Corp.), W33 (manufactured by Nipro PharmaPackaging
20 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 the like. A catalog value of the
composition (mass%) of each glass is shown in Table 1. In
25 Table 1, in NSV51, the total content of Na2O and K2O is
shown as the content of Na2O and K2O. The same applies to
W33 or DURAN. In addition, in Table 1, “-” indicates that
16
the composition is not contained.
[0030]
[Table 1]
5 [0031]
It is preferable that the glass substrate 2 is
borosilicic acid glass having an expansion coefficient 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
10 with the coating film 3, contains at least 1 to 6 mass% of
B2O3, 1 to 6 mass% of Na2O, 1 to 2 mass% of Al2O3, and 80
mass% or more of SiO2.
[0032]
In addition, it is preferable that the glass
15 substrate 2 is borosilicic acid glass having an expansion
coefficient 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
mass% of B2O3, 1 to 6 mass% of Na2O, 5 to 6.5 mass% of Al2O3,
20 and 80 mass% or more of SiO2.
[0033]
17
It is preferable that the glass substrate 2 has a
transparent color or an amber color, and has light
transmittance, and specifically, a light transmissivity at
a wavelength of 590 to 610 nm or 290 to 450 nm is
5 preferably 45% or more, and is more preferably 60% or more.
An evaluation method for a transparency test is based on
“Japanese Pharmacopoeia (17th Edition) 7. Tests for
Containers and Packing Materials 7.01 Test for Glass
Containers for Injections (5) Light transmission test for
10 light-resistant containers”.
[0034]
The glass substrate 2, for example, includes plateshaped or tube-shaped glass, a glass vessel, a glass
medical tool, and the like. The coating film-attached
15 glass 1 according to this embodiment includes an aspect in
which the glass substrate 2 is a vial container, a syringe
barrel (a syringe), a needle-tipped syringe, an ampule, or
a cartridge type syringe (also simply referred to as a
cartridge).
20 [0035]
When the glass substrate 2 is the tube-shaped glass,
the glass vessel, or the glass medical tool, it is
preferable that at least a part of the surface 2a of the
glass substrate 2 (the surface of the glass substrate 2 on
25 the coating film 3 side), which is a surface on which the
coating film 3 is formed, is the inner wall of the tubeshaped glass, the inner wall of the glass vessel, or the
18
inner surface of the glass medical tool. Accordingly, it
is possible to reduce attachment properties of a polar
content with respect to the inner wall, and thus, it is
possible to decrease remaining properties with respect to
5 the vessel.
[0036]
(Vial)
A vial is a vessel having an approximately
cylindrical outer shape of which the bottom is sealed, and
10 includes a bottom portion, a lateral surface portion, a
neck portion, a mouth portion, an inner wall, and an outer
wall. The vial has an internal space and is opened to one
end of the mouth portion. The bottom portion is in the
shape of a flat disk and is consecutive to the lateral
15 surface portion on the edge of the bottom portion. The
lateral surface portion is in a cylindrical shape. The
lateral surface portion is molded such that an outer
diameter and an inner diameter are constant in an axis
direction. The neck portion is consecutive to the lateral
20 surface portion and is in a tapered shape from the lateral
surface portion. The neck portion is molded such that an
inner diameter and an outer diameter are narrower than that
of the lateral surface portion. The mouth portion is
consecutive to the neck portion and includes an opening
25 partitioned by the edge portion. The mouth portion is
molded such that an inner diameter and an outer diameter
are narrower than that of the lateral surface portion. The
19
mouth portion is molded such that the outer diameter is
wider than the narrowest portion of the outer diameter of
the neck portion. The inner wall is a glass surface of the
bottom portion, the lateral surface portion, the neck
5 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.
[0037]
(Production Method for Vial)
10 As an example, the vial is molded by heating a glass
tube that is vertically retained and rotated, using a
general vertical molding machine. The glass tube is
softened by being heated with a flame of a burner. A part
of the glass tube is softened and deformed, and thus, the
15 bottom portion and the mouth portion of the vial are molded
from the glass tube. When the bottom portion is molded, an
alkaline borate salt or the like is volatilized from
borosilicic acid glass that is a raw material of the glass
tube. An alkaline component such as the volatilized
20 alkaline borate salt is attached to the vicinity of the
bottom portion on the inner wall of the vial and causes a
processing-degraded region.
[0038]
(Modified Glass Substrate)
25 The modified glass substrate 2 according to this
embodiment includes the modified layer 4 on at least a part
of the surface of the glass substrate 2, and the modified
20
layer 4 is the region from the surface 2a of the glass
substrate 2 to the predetermined depth d1 and has a
microcrystalline structure at least in part.
[0039]
5 (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 from the outermost surface to
the predetermined depth d1, in addition to the outermost
10 surface of the glass substrate 2 (in FIG. 1, the surface 2a
on the coating film side). The predetermined depth d1 from
the outermost surface is preferably a depth of 100 nm from
the surface 2a of the glass substrate 2 in a depth
direction D, is more preferably a depth of 50 nm from the
15 surface 2a of the glass substrate 2 in the depth direction
D, is even more preferably a depth of 20 nm from the
surface 2a of the glass substrate 2 in the depth direction
D, and is still even more preferably a depth of 10 nm from
the surface 2a of the glass substrate 2 in the depth
20 direction D. Here, the depth direction D is a direction
from the surface 2a of the glass substrate 2 on the coating
film side toward a surface (not illustrated) on a side
opposite to the coating film side. For example, in a case
where the glass substrate 2 is the vial container, the
25 depth direction D is a direction from an inner wall surface
toward an outer wall surface. It is preferable that the
modified layer 4 contains at least 1 to 8 mass% of B2O3, 1
21
to 6 mass% of Na2O, and 80 mass% or more of SiO2, in terms
of an oxide. It is more preferable that the modified layer
4 contains at least, 2 to 6 mass% of B2O3, 2 to 4 mass% of
Na2O, and 90 mass% or more of SiO2, in terms of an oxide.
5 The composition of the modified layer 4, for example, is
mass% in terms of each atomic oxide of a surface
composition (an atomic composition percentage) to be
analyzed by an X-ray photoelectron spectroscopy (XPS).
[0040]
10 In the coating film-attached glass 1 according to
this embodiment, it is preferable that the modified layer 4
contains carbon. It is possible to further improve
adhesiveness with respect to the coating film 3, in
particular, a coating film containing a carbon element in a
15 composition. The content of carbon in the modified layer 4
is preferably 1 to 15 atomic%, is more preferably 1 to 11
atomic%, is even more preferably 2 to 10 atomic%, is still
even more preferably 3 to 8 atomic%, and is particularly
preferably 4 to 8 atomic%.
20 [0041]
(Microcrystalline Structure)
For the microcrystalline structure, for example, the
sectional surface of the glass substrate is observed by a
transmission electron microscope (TEM). The
25 microcrystalline structure is a sub-nanometer-sized array
structure having an equal interval.
[0042]
22
A portion having a microcrystalline structure is a
portion in which crystalline particles having a particle
diameter smaller than that in a surrounding portion of the
portion are arrayed. In the microcrystalline structure, it
5 is assumed that at least a glass component is crystallized,
and specifically, it is assumed that NaBCO3, KBCO3,
(Na,K)AlBCO3, (Na,K)CO3, Na2CO3, Na2O, and the like, which
contain Na as a main component and contain K, C, B, and the
like as a component, are crystallized. An average particle
10 diameter of the crystalline particles in the
microcrystalline structure is preferably 1 to 10 nm, and is
more preferably 1 to 5 nm. The average particle diameter
is obtained by the observation of TEM, and may be obtained
by X-ray diffraction (XRD) or small angle X-ray scattering
15 (SAXS).
[0043]
In the coating film-attached glass 1 according to
this embodiment, it is preferable that the microcrystalline
structure contain carbon. It is possible to further
20 improve adhesiveness with respect to the coating film, in
particular, a coating film containing a carbon element in a
composition.
[0044]
(Region 5 Deeper than Modified Layer 4)
25 The region 5 deeper than the modified layer 4 is a
region that is consecutive to the modified layer 4 in the
depth direction D. The region 5 deeper than the modified
23
layer 4 may include the surface (not illustrated) of the
glass substrate 2 on a side opposite to the coating film 3
side. There may be no boundary between the modified layer
4 and the region 5 deeper than the modified layer 4, and
5 for example, a glass composition may be a gradient
composition between the modified layer 4 and the region 5
deeper than the modified layer 4.
[0045]
(Coating Film)
10 [0046]
The coating film 3 includes an aspect in which the
coating film 3 contains a carbon element in a composition.
As an example, the coating film 3 is a silicon-free
diamond-like carbon film. Here, the diamond-like carbon
15 film is also referred to as a diamond-like carbon film, a
DLC film, and an amorphous carbon film, and is a
hydrogenated amorphous carbon film containing at least a
carbon atom and a hydrogen atom.
[0047]
20 A film thickness of the coating film is preferably 1
to 70 nm, and is more preferably 2 to 60 nm. In a case
where the film thickness is less than 1 nm, it may be
difficult to form a coating film homogeneously without any
defect, and in a case where the film thickness is greater
25 than 70 nm, peeling may occur, or coloring may exceed an
allowable range.
[0048]
24
Here, the coating film that is the silicon-free
diamond-like carbon film includes an aspect in which he
coating film is a silicon-free and fluorine-containing
diamond-like carbon film (hereinafter, may be referred to
5 as a “F-DLC film”), or a silicon-free and fluorine-free
diamond-like carbon film (hereinafter, may be simply
referred to as a “DLC film”). Note that, the fluorinecontaining diamond-like carbon film is also referred to as
a fluorinated amorphous carbon film.
10 [0049]
As an example, the coating film 3 may be a siliconcontaining diamond-like carbon film.
[0050]
As an example, the coating film 3 may be a silicon
15 oxide-based film containing organic silane or siloxane as a
raw material. The organic silane and the siloxane are not
particularly limited, and include hexamethyl disiloxane,
hexamethyl silazane, tetraethoxysilane, tetramethoxysilane,
and tetramethyl silane.
20 [0051]
As an example, the coating film 3 may be an amorphous
fluorine resin film. The fluorine resin is not
particularly limited, and includes polytetrafluoroethylene
and perfluoroalkoxyalkane. It is more preferable that the
25 fluorine resin is an amorphous fluorine resin having
transparency in a wide wavelength range of an ultraviolet
ray, a visible ray, and a near-infrared ray. Specifically,
25
the amorphous fluorine resin is CYTOP (Registered
Trademark) obtained by cyclopolymerizing perfluoro(4-vinyl
oxy-1-butene).
[0052]
5 By providing the coating film 3 exemplified above,
lubricating properties (sliding properties) are excellent,
a contact angle with respect to an aqueous content is large,
and the suppression of the aggregation (adsorption) of
protein or the like that is an active component of a
10 medicinal product is improved.
[0053]
(Production Method for Coating Film-Attached Glass)
As illustrated in FIG. 1, a production method for the
coating film-attached glass 1 according to this embodiment
15 in which the coating film 3 is formed on at least a part of
the surface 2a of the glass substrate 2 includes a
modification step of setting the region from the surface 2a
of the glass substrate 2 on a side on which the coating
film 3 is provided to the predetermined depth d1 as the
20 modified layer 4, and a film formation step of forming the
coating film 3 on the surface 2a of the glass substrate 2
on which the modified layer 4 is formed, in which the
modification step includes at least any one step of (i) a
step of blasting a flame generated by burning low
25 hydrocarbon gas in the presence of oxygen gas from a burner
to apply a portion rich in plasma in the flame to be
blasted from the burner to the surface 2a of the glass
26
substrate 2 on the side on which the coating film 3 is
provided, (ii) a step of 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) a
5 step of 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.
[0054]
(Modification Step)
10 A surface treatment in the modification step includes
a plasma treatment or a heating treatment. Further, the
plasma treatment includes (i) a treatment of blasting the
flame generated by burning the low hydrocarbon gas in the
presence of oxygen gas from the burner to apply the portion
15 rich in plasma in the flame to be blasted from the burner
to the surface 2a of the glass substrate 2 on the side on
which the coating film 3 is provided (hereinafter, may be
referred to as a modification step of (i)). The heating
treatment includes (ii) a laser treatment to be performed
20 with respect to the surface 2a of the glass substrate 2 on
the side on which the coating film 3 is provided
(hereinafter, may be referred to as a modification step of
(ii).) and (iii) a high-temperature gas treatment to be
performed with respect to the surface 2a of the glass
25 substrate 2 on the side on which the coating film 3 is
provided (hereinafter, may be referred to as a modification
step of (iii)).
27
[0055]
As an example, the modification step of (i) is a step
of blasting the flame generated by burning the low
hydrocarbon gas in the presence of oxygen gas from the
5 burner to apply the flame to the glass surface of the glass
substrate 2. The low hydrocarbon gas, for example, town
gas, propane, butane, and natural gas. In addition, it is
preferable that the portion rich in plasma in the flame,
which is applied to the surface 2a of the glass substrate 2,
10 is combustion flame rich in hydronium ions, which is
generated as a result of burning.
[0056]
In a case where the glass substrate 2 is the vial of
the glass vessel, it is preferable that in the modification
15 step of (i), the flame is applied to the inner wall of the
vial, preferably, the flame is applied to the vicinity of
the bottom portion of the inner wall of the vial (a portion
including a processing-degraded region).
[0057]
20 In the production method for the coating filmattached glass 1 according to this embodiment, it is
preferable that in the modification step, the temperature
of the surface of the glass substrate 2 on a side opposite
to the surface 2a on the side on which the coating film 3
25 is provided is measured by a non-contact type thermometer,
and the temperature to be measured is in a specific
temperature range. It is possible to more reliably manage
28
a temperature and to more reliably perform modification.
It is preferable that the non-contact type thermometer is a
thermography type thermometer. In addition, in a case
where the glass substrate 2 is the vial container, the
5 surface on the side opposite to the surface 2a is the outer
surface of the vial container, and for example, the
specific temperature range is preferably a range of 650°C
to 800°C, and is more preferably a range of 670 to 780°C.
[0058]
10 Further, as an example, in the laser treatment in the
modification step of (ii), laser light of a CO2 (carbon
dioxide) laser, an yttrium aluminium gernet (YAG) laser, or
an ultra fast (UF) laser is applied to the glass surface of
the glass substrate 2.
15 [0059]
Further, as an example, in the high-temperature gas
treatment in the modification step of (iii), overheated
steam of an overheated steam generator is applied to the
surface of the glass substrate 2.
20 [0060]
In this embodiment, in the modification step, only
one of the modification step of (i), the modification step
of (ii), and the modification step of (iii) may be
performed, or two or more thereof may be performed. A
25 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
29
(i), (ii), and (iii).
[0061]
(Film Formation Step)
In the production method for the coating film5 attached glass 1 according to this embodiment, it is
preferable that the film formation step is a step of
turning raw material gas containing at least hydrocarbonbased gas into plasma to form an amorphous coating film
containing at least carbon as the coating film 3 on the
10 surface 2a of the glass substrate 2 on the side on which
the coating film 3 is provided. By the coating film 3
containing the carbon element in the composition, the
lubricating properties (sliding properties) are excellent,
the contact angle with respect to the aqueous content is
15 large, and the suppression of the aggregation (adsorption)
of protein or the like that is the active component of the
medicinal product is improved.
[0062]
In the film formation step, for example, it is
20 preferable to form the amorphous coating film containing
carbon by using a high-frequency film formation apparatus.
The amorphous coating film containing carbon, for example,
is the silicon-free diamond-like carbon film or the
silicon-containing diamond-like carbon film, described
25 above. When the coating film 3 is the silicon-free
diamond-like carbon film, the raw material gas, for example,
is acetylene, methane, ethylene, propane, benzene,
30
hexafluoroethane, C6F10(CF3)2, C6F6, tetrafluoromethane (CF4),
and octafluoropropane (C3F8). In addition, when the coating
film 3 is the silicon-containing diamond-like carbon film,
the raw material gas, for example, is organic silicon gas
5 such as trimethyl silane (C3H10Si) or tetramethyl silane
(C4H12Si). The raw material gas may be used alone, or two
or more types thereof may be used together.
[0063]
Next, an example of the film formation apparatus that
10 can be used in the film formation step in the example in
which the glass substrate 2 is the vial container will be
described. FIG. 3 illustrates a schematic view of a highfrequency inner surface film formation apparatus for a vial
container. A high-frequency inner surface film formation
15 apparatus 100 for a vial container, illustrated in FIG. 3,
includes raw material gas input systems 31, 32, and 33.
Each of the raw material gas input systems includes a stop
valve 34 and a gas flow meter 35, and is connected to one
pipe 36 for mixed gas. In FIG. 3, an aspect is illustrated
20 in which there are three raw material gas input systems,
and more raw material gas input systems may be provided.
The pipe 36 is connected to an internal electrode that is
arranged in a vacuum chamber 38 and a conductive pipe 43a
that also functions as a gas introduction pipe. The vacuum
25 chamber 38 is grounded, and a vacuum gauge 37 is connected
to the vacuum chamber 38. In addition, in the vacuum
chamber 38, the vial container (glass substrate) 2, an
31
external electrode 45 arranged to surround the lateral
surface and the bottom surface of the vial container 2, a
dielectric member 46 arranged to surround the external
electrode 45, and an external case 48 that surrounds the
5 dielectric member 46 and contains a conductive material for
stably turning the raw material gas into plasma are
arranged. The vacuum chamber 38 is connected to the
exhaust pipe 49. In addition, the external electrode 45 is
connected to an automatic matching device 40 not to be
10 electrically continuous with the vacuum chamber 38. The
automatic matching device 40 is connected to a highfrequency power source 41. A high frequency, for example,
is 1 to 100 MHz, and is preferably 13.56 MHz. The raw
material gas blown off from the conductive pipe 43a flows
15 into the vial container 2, and then, is discharged from the
tip port of the vial container 2, passes through a space
48a provided on the upper side in the external case 48, and
then, reaches the internal space of the vacuum chamber 38.
After that, is exhausted from the exhaust pipe 49.
20 Examples
[0064]
Hereinafter, the present invention will be described
in more detail, on the basis of Examples, but the present
invention is not limited to such Examples.
25 [0065]
(Preparation of Vial)
A bottom portion was molded from a borosilicic acid
32
glass tube BS having an outer diameter of 15 mm and a wall
thickness of 1.5 mm manufactured by Nippon Electric Glass
Co., Ltd.) by a vertical molding machine, and thus, vials
X1 and Y1 having an outer diameter of 15 mm, a height of 33
5 mm, a port inner diameter of 7.0 mm, and a content of 2.0
mL were prepared.
A bottom portion was molded from a borosilicic acid
glass tube W33 having an outer diameter 15 mm and a wall
thickness of 1.5 mm (manufactured by Nipro PharmaPackaging
10 Americas Corp.) by a vertical molding machine, and thus,
vials X2 and Y2 having an outer diameter of 15 mm, a height
of 33 mm, a port inner diameter of 7.0 mm, and a content of
2.0 mL were prepared.
[0066]
15 (Modification Step)
The plasma treatment using the modification step of
(i) was performed with respect to the inner wall of the
prepared vials X1 and X2.
[0067]
20 (Condition of Modification Step of (i))
The treatment was performed by blasting a flame of a
point burner into the internal space of the vial while
retaining and rotating the vials X1 and X2, and by scanning
the inner wall of the vial with the flame while applying a
25 portion rich in plasma in the flame to the inner wall of
the vial. In such a treatment, the point burner having a
port inner diameter of 1.4 mm was used in which a mixed gas
33
flame (a length of approximately 10 cm) containing town gas
(methane) and oxygen at a complete combustion ratio was
blown off.
[0068]
5 (Composition Analysis of Glass Surface)
The composition of the glass surface (in the vicinity
of 3 to 5 mm from the bottom portion) of the inner wall of
the vial before and after the plasma treatment was analyzed
by XPS (AXIS-NOVA, manufactured by Kratos Analytical Ltd.)
10 Analysis results of the compound composition on the vial
surface before and after the plasma treatment are shown in
Table 2.
[0069]
[Table 2]
15
[0070]
(Film Formation Step)
A condition at the time of forming a film on the
inner surface of the vial (X1, X2, Y1, and Y2) is as
20 follows.
Device: a low-pressure plasma CVD device, illustrated
in FIG. 3
34
High-Frequency Output: 100 W, 13.56 MHz
Initial Depressurization: 0.02 torr
Film Formation Pressure: 2 torr
Film Formation Time: as shown in Table 3
5 Mixed Gas: as shown in Table 3 Here, a ratio
indicates a volumetric flow mixing ratio.
Pretreatment: none
[0071]
[Table 3]
10
[0072]
[Steam Sterilization Treatment]
Each of the vials was filled with water of 90% of the
full content and was subjected to a high-pressure steam
15 sterilization treatment at 121°C for 1 h. In Examples 1
and 2, it was not possible to check the peeling of F-DLC of
the outermost layer, but in Comparative Examples 1 and 2,
the peeling of F-DLC of the outermost layer was checked.
[0073]
20 [Microcrystalline Structure]
FIG. 4(a) is a TEM image of the sectional surface of
35
a modified glass substrate after the modification step and
before the film formation step in Example 1, and FIG. 4(b)
is an image in which FIG. 4(a) is partially enlarged. In
FIG. 4(a) and FIG. 4(b), a portion on the modified layer is
5 a protective film that is provided for TEM analysis. As
illustrated in FIG. 4(a) and FIG. 4(b), it was possible to
check that the modified layer has a microcrystalline
structure at least in part. In FIG. 4(b), a dotted line
was applied to a part that is regarded as the boundary
10 between the modified layer and a region deeper than the
modified layer.
[0074]
FIG. 5 is a TEM image of the sectional surface of
coating film-attached glass after the film formation step
15 in Example 1. As illustrated in FIG. 5, it was possible to
check that the coating film-attached glass 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.
20 [0075]
The sectional surface of the coating film-attached
glass after the film formation step in Example 1 was
subjected to EDX analysis to check a Si distribution image,
an O distribution image, a C distribution image, a F
25 distribution image, a Na distribution image, and a K
distribution, and as a result thereof, it was possible to
check at least Na and K in the modified layer.
36
We Claim :
1. Coating film-attached glass, comprising: a glass
substrate; and a coating film provided on at least a part
of a surface of the glass substrate,
5 wherein a region from the surface of the glass
substrate on the coating film side to a predetermined depth
is a modified layer, and
the modified layer has a microcrystalline structure
at least in part.
10 2. Coating film-attached glass, comprising: a glass
substrate; and a coating film provided on at least a part
of a surface of the glass substrate,
wherein a region from the surface of the glass
substrate on the coating film side to a predetermined depth
15 is a modified layer,
a content of B2O3 in the modified layer is less than
that in a region deeper than the modified layer, by mass%
in terms of an oxide, and a content of Na2O in the modified
layer is less than that in the region deeper than the
20 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 Na2O, and 80 mass% or more of SiO2, in
terms of an oxide, and
the region deeper than the modified layer contains at
25 least 9 to 15 mass% of B2O3, 3 to 9 mass% of Na2O, and 70
mass% or more of SiO2, in terms of an oxide.
3. The coating film-attached glass according to claim 1,

wherein the microcrystalline structure contains carbon.
4. The coating film-attached glass according to claim 1
or 2, wherein the modified layer contains carbon.
5. The coating film-attached glass according to any one
5 of claims 1 to 4, wherein the coating film is a siliconfree diamond-like carbon film, a silicon-containing
diamond-like carbon film, a silicon oxide-based film, or an
amorphous fluorine resin film.
6. The coating film-attached glass according to any one
10 of claims 1 to 5, wherein a film thickness of the coating
film is 1 to 70 nm.
7. The coating film-attached glass according to any one
of claims 1 to 6, wherein the glass substrate is
borosilicic acid glass having an expansion coefficient of
3.2 × 10-6/K or more and 3.3 × 10-6 15 /K or less, or
borosilicic acid glass having an expansion coefficient of
4.8 × 10-6/K or more and 5.6 × 10-6/K or less.
8. The coating film-attached glass according to any one
of claims 1 to 7, wherein the glass substrate is a vial
20 container, a syringe barrel, a needle-tipped syringe, an
ampule, or a cartridge type syringe.
9. A production method for coating film-attached glass
in which a coating film is formed on at least a part of a
surface of a glass substrate, the method comprising:
25 a modification step of setting a region from the
surface of the glass substrate on a side on which the
coating film is provided to a predetermined depth as a
38
modified layer; and
a film formation step of forming the coating film on
the surface of the glass substrate on which the modified
layer is formed,
5 wherein the modification step includes at least any
one step of (i) a step of blasting a flame generated by
burning low hydrocarbon gas in the presence of oxygen gas
from a burner to apply a portion rich in plasma in the
flame to be blasted from the burner to the surface of the
10 glass substrate on the side on which 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
on which the coating film is provided, and (iii) a step of
performing a high-temperature gas treatment with respect to
15 the surface of the glass substrate on the side on which the
coating film is provided.
10. The production method for coating film-attached glass
according to claim 9, wherein the film formation step is a
step of turning raw material gas containing at least
20 hydrocarbon-based gas into plasma to form an amorphous
coating film containing at least carbon as the 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 film-attached glass
25 according to claim 9 or 10, wherein in the modification
step, a temperature of a surface of the glass substrate on
a side opposite to the surface on the side on which the
39
coating film is provided is measured by a non-contact type
thermometer, and the temperature to be measured is in a
specific temperature range.
12. A modified glass substrate, comprising: a modified
5 layer on at least a part of a 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.