JPH03159935A - Glass bottle container for biological cosmetic or the like and production thereof - Google Patents

Abstract

PURPOSE:To prevent contents from coloring and maintain the quality of the contents by subjecting the inside of a glass bottle container to dealkalization processing treatment and simultaneously forming a film layer containing a colorant, etc., in a thermosetting type coating, etc., on the outside. CONSTITUTION:A glass bottle container for containing a cosmetic containing a biological ingredient, etc., is formed by mold blowing. In the aforementioned mold blowing process, the inside thereof is subjected to surface treatment with a dealkalizing agent. A coating blend containing an ultraviolet ray absorber, a matte agent and a colorant, etc., in a thermosetting type, two-liquid reaction type or ultraviolet curing type coating is prepared. The resultant coating blend is then used to form a film layer on the outside surface of the aforementioned container.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a glass bottle container for storing bio-cosmetics, etc., and a method for manufacturing the same, and particularly relates to a glass bottle container for storing bio-cosmetics, etc., which contains bio-related substances that are easily deteriorated by ultraviolet rays, alkalis, etc. The present invention relates to glass bottle containers for cosmetics, pharmaceuticals, etc., and methods for manufacturing the same.

[Conventional technology]

Traditionally, glass containers for cosmetics, pharmaceuticals, etc. have been given a matte finish to enhance their appearance and design, as well as to prevent the contents from deteriorating due to ultraviolet rays. It is required to block this. For these glass containers, metal oxides or inorganic substances such as cerium and chromium are added to the raw material of the glass and melted at high temperature to form colored glass, from which the bottle is shaped. There is a method of applying an inorganic or resinous paint mixed with a coloring agent or the like to form a film having ultraviolet blocking properties.
A glass product having a surface decorated with an ultraviolet curable paint or an electron beam curable paint containing an ultraviolet absorber or the like on the outer surface of a glass container body, as disclosed in Publication No. 24, etc., and a method for producing the same;
Furthermore, as disclosed in JP-A No. 61-190433, the surface of the glass bottle is coated with a hardened coating containing a photocurable resin, a photopolymerization initiator, an ultraviolet absorber, and a matting agent to provide ultraviolet blocking properties. Erased glass bottle, JP-A-63-1290
No. 38, etc., has proposed a method for manufacturing a bottle that blocks ultraviolet rays by containing an ultraviolet absorber in a thermosetting or two-component reaction type paint.

[Problem that the invention seeks to solve]

However, the above method has the following problems. The first point is that conventionally, cosmetics, pharmaceuticals, etc. that are packaged in glass bottles have the effect of blocking ultraviolet rays by simply applying an inorganic or resin paint mixed with a disinfectant and a coloring agent. : Methods such as applying a film with ultraviolet shielding properties as described in 1 on the surface of glass containers have been proposed, but for example, in the case of cosmetics, pharmaceuticals, etc. containing bio-related substances or enzyme-effective bases, etc. , ultraviolet rays, and depending on the contents, alkali emitted from the inner surface of the glass bottle may be a factor that promotes deterioration and decomposition. Issues such as ensuring ultraviolet shielding properties and preventing quality deterioration and deterioration of the contents due to alkaline elution have become issues. The second point is that when forming a coating film with conventional ultraviolet blocking or ultraviolet absorbing ability on the glass surface, it is necessary to ensure the necessary ultraviolet shielding properties and to prevent glass bottles from having complicated curved surfaces after being shaped. It has the disadvantage that it is difficult to ensure uniformity of the coating thickness because the coating is applied in a state in which the coating is applied. For this reason, even if the paint is applied, the condition of the paint is uneven, and therefore, depending on the contents that are particularly susceptible to ultraviolet rays, there is a problem that this may cause destruction of the precepts, deterioration, etc. It is required to ensure the uniformity of the coating film formed on glass bottles.

The present invention effectively solves the problems and difficulties of the prior art, and provides a glass bottle container suitable for storing cosmetics, pharmaceuticals, etc. containing so-called bio-related ingredients in recent years, and a method for manufacturing the same. 4 The purpose is to A second object of the present invention is to provide a glass bottle container having both such ultraviolet shielding properties and alkali elution prevention functions, which is stable in quality and industrially advantageous.

[Means for solving problems]

The present invention provides a glass bottle container for cosmetics and the like containing Paio-Ibun, etc. The inside of the container has a glass surface layer that has been surface-treated with a dealkalizing agent, and the outside has a thermosetting type, two-component reaction A glass bottle container for bio-cosmetics, etc., characterized in that a coating layer containing an ultraviolet absorber, a quenching agent, a coloring agent, etc. is formed on a mold or an ultraviolet curing type paint, etc.
In addition, in a method for manufacturing bottles and containers for cosmetics, etc. containing bio-based ingredients, the inner surface of the container is surface-treated with a dealkalizing agent in the blow-forming process, and then ultraviolet absorbers, quenching agents, coloring agents, etc. Thermosetting type, two-component reaction type, containing
Alternatively, the present invention relates to a method for manufacturing a glass bottle container for bio-cosmetics, etc., characterized in that a coating layer is formed on the outer surface of the container using an ultraviolet curable coating composition or the like.

5 As the ultraviolet absorber used in the present invention, 2-(-
2hydroxy-3,5-di(2,2-dimethylbenzine〉-phenyl)-2■benzotriazole, 2-(2'
-Hydroxy 31,5"D-t-7milphenyl) benzo-1-lyazole, henzophenone-based, acrylate-based, salicylate-based, dibenzoylmethane-based, etc.In addition, the point of high temperature storage resistance is Therefore, those with relatively low volatility are preferable.

These UV absorbers have relatively poor melting and dispersing properties, so
By dissolving it in an organic solvent such as xylene in advance and then mixing it with the paint, it can be uniformly dispersed in the paint. In addition, the mixing ratio of the ultraviolet absorber is required to be at least 0.5% or more based on the dry solid content of the paint, and preferably in the range of 1 to 10%. It can be selected as appropriate depending on its physical properties, such as being easily affected or having poor alkali resistance.

The paints used in the present invention include, for example, thermosetting paints such as acrylic resins and epoxy resins, two-component reaction paints such as 6 or epoxy resins, and polyurethane resins, as well as ultraviolet curable and electron beam curing paints. Any type of paint may be used as long as it is transparent or a coloring agent such as a dye or pigment that colors the entire paint can be mixed and dispersed uniformly in the paint.

In the present invention, the coating composition as described above may be applied by spray coating, dipping, electrostatic coating,
Furthermore, although a combination of these methods can be employed, electrostatic coating is suitable for the present invention.

Conventionally, when coating the outside of a glass bottle container, the non-uniformity of the coating film thickness has made UV shielding a problem, especially for products that are susceptible to ultraviolet rays. For this reason, in the present invention, in addition to normal painting, a two-step processing treatment using a base layer undercoat paint and an overcoat paint of the same or different compositions, or a thermosetting resin paint for the base layer and a coating layer for the coating layer, is applied. It is also possible to form an ultraviolet curable resin coating or the like. Furthermore, two or more stages of combination 7 In processing, selection or combination of UV absorbers to be blended, for example, differentiation of the amount of UV absorbers added in double coating, or combination of absorbers with different maximum absorption bands. This can be achieved by adopting a method that covers a wider absorption wavelength region.

In the structure of the present invention, in the process of dealkalizing the inner surface layer of the glass bottle container and in the formation of the coating layer laminated on the outer surface, especially in the latter, one or more stages of processing are performed as appropriate. However, in that case, it is necessary to ensure adhesion (prevention of peeling) of the base layer to the outer surface of the glass, and also to prevent so-called correlated peeling between the coating layers of the coating layer (overcoat). The coated Fi.Fi formed on the base layer in this way not only repairs unevenness on the surface of the base layer, but also secures the necessary coating thickness in order to add and blend the desired ultraviolet absorber. , thickness uniformity, smoothness, etc. In addition, in the coating film processing treatment that is formed on the outside of the bottle in the present invention, the ultraviolet absorber added and blended as described above can be adjusted depending on the contents to be stored. For example, by differentiating the amount of ultraviolet absorbers added, or by combining one or more types of ultraviolet absorbers with different absorption wavelength regions, the desired ultraviolet shielding effect can be achieved. It can solve technical problems.

In the case of the two-stage coating according to the present invention, the thickness of the coating formed on the outside of the bottle container after drying and baking is suitably 10 to 70μ, preferably 30 to 60μ.

[Effect]

In the glass bottle container according to the present invention, in order to extract and remove alkali components in the glass surface layer inside the container, a dealkalizing agent, such as ammonium sulfate, is used in the glass bottle, after blowing and shaping, before entering the slow cooling furnace. In the process, at a high temperature of 500 to 600 °C, ammonium sulfate (NH,)2S O4 crystal particles are appropriately added according to the capacity of the container, and the temperature is 60 to 120 °C.
The inside surface layer of the glass bottle was treated with dealkalization by decomposition gas at high temperature for a few seconds. In addition, in this process, it is necessary to uniformly contact and act on the inner surface of the bottle with the decomposed gas, and in some cases, such as in a wide-mouthed bottle, after ammonium sulfate crystal particles are introduced, the decomposed gas is quickly released from inside the bottle 9. To prevent volatilization and leakage, for example, a cover or a lid can be installed. Further, it is necessary to use an appropriate amount of the ammonium sulfate crystal particles; if the amount is too small, the dealkalization effect will be poor, and if the amount is too large, there will be problems such as the adhesion of residues.

Although the details of this mechanism are still unclear, for example, at a high temperature of at least 500°C, the ammonium sulfate crystal particles used as a dealkalizing agent decompose and form ammonium hydrogen sulfide (NH4) HS 04 scum and NH gas. It is presumed that a dealkalization effect is carried out to extract and remove alkaline components in the glass surface layer. and,
The inner surface layer shaped in this way has increased hardness and is considered to be less susceptible to scratches. In addition, these dealkalization treatments include the above-mentioned method in which an appropriate amount of ammonium sulfate crystal particles are directly introduced into the mouth of a glass bottle and subjected to gas decomposition treatment at high temperatures, as well as the method in which glass is decomposed using SO2 gas at a high temperature above the glass transition point. It is also possible to dealkalize the inner surface layer of the bottle.

In the present invention, the effect of the alkali elution prevention treatment 10 is determined using, for example, method 2 (surface method) of the general test methods of the Japanese Pharmacopoeia (11th revision) as an alkali elution test.
, or USP1 as an alkali dissolution test (inner surface method)
8, good test results were obtained using a sample with a consumption of 0.02N sulfuric acid in ml (m+).

Such alkali elution prevention treatment for the inner surface layer of glass bottles takes into account the physical properties of the contents of cosmetics, pharmaceuticals, etc. that are easily affected by alkalinity and/or heat, and is applied to It can be appropriately adopted as a simple processing treatment during the process.

Furthermore, regarding the coloring prevention effect when the contents are stored in the glass bottle container obtained according to the present invention and stored for a long period of time, for example, the change in color tone can be measured orally using a color difference meter in a constant temperature and humidity chamber at 45°C. The effect of suppressing color change due to heat can be determined by measuring and determining ΔE (color difference), or by placing the sample bottle containing the contents under sunlight exposure and measuring the oral color change using a color difference meter. The effect of suppressing color tone change against ultraviolet rays can be determined.

11 (Example> below,. The present invention will be explained in detail by way of examples.

Note that parts in the examples indicate parts by weight.

Example 1 [First step: Glass bottle inner surface layer treatment] The container glass raw material was melted in a melting tank at around 1500°C,
Clear glass bottle (cream 25g) shaped by an automatic shaping machine (press and blow type, IS machine)
After shaping in the manufacturing process of containers (containers), ammonium sulfate (
Approximately 1 g of N HJx S O+ crystal particles were put into the mouth of the glass bottle, gasified for 60 to 120 seconds, and adhered to the inner surface, thereby performing a dealkalization treatment on the inner surface of the glass. At this time, since the glass bottle had a wide mouth shape, a cover was attached to the mouth of the bottle to prevent early leakage of gas from inside the bottle after the crystal particles of ammonium sulfate were added.

Next, after applying surface corrosion treatment with hydrogen fluoride using a conventional method,
The outer and inner surface layers of the bottle were washed with water.

19 [Second step: Glass bottle outer surface layer treatment] First, a paint consisting of the following composition was created.

Eboxy IM resin paint 100 parts (GL Clear, Easy Chemical!!!) Diluent solvent
30 parts (xylene, butanol, isophorone mixed solvent) quenching agent. Silica powder 5
5 parts colorant (pigment titanium white 1.) Next, add ultraviolet absorber (Uvinal) to the above compounded paint.
400 BASF) 20 parts xylene solvent 100 parts
10 parts of the resulting dispersion were added with stirring.

In this case, since the ultraviolet absorber is difficult to dissolve and disperse, it was first dissolved in an organic solvent, xylene, and then mixed into the compounded paint to allow it to decompose uniformly.

Next, the degreased and cleaned transparent glass bottle was attached to a suitable jig, and electrostatic coating TA (disc type, manufactured by Landspag Co., Ltd.) was applied to coat the undercoat base layer to a coating thickness of 25 mm after drying.
Form a base layer on the side wall and bottom of the bottle excluding the bottle mouth for 30 to 60 seconds at room temperature so that the thickness is 80 to 1
Low temperature drying was performed at 00°C for 1013 minutes.

Next, using the above-mentioned mixed paint, it was similarly coated with an electrostatic coating agent at room temperature for 30 minutes so that the film thickness after heat curing would be 15 to 25 μm.
The coating was applied for 0 to 60 seconds, and then the glass bottle was placed in a heat drying oven and heat-cured at a temperature of 170'C for 30 minutes.

An alkali elution test was conducted on the glass bottle container obtained through the above steps in accordance with method 2 (surface method) of the general test methods of the Japanese Pharmacopoeia (11th revision).
At a sample consumption rate (ml) of 0.02N sulfuric acid, test results were obtained of 0.03 per 20 rrt for the sample treated with ammonium sulfate gas and 3.32 for the untreated sample.

A remarkable improvement in prevention of alkali elution was observed in the ammonium sulfate gas treated specimens.

In addition, a piece of glass (width IQm+m x length 30wn, thickness 3
．． 5), and the ultraviolet absorption rate of transmitted light was measured using a Shimadzu spectrophotometer UV-240 (manufactured by Shimadzu Corporation).The results were 100% at a wavelength of 370 nm and 8 at a wavelength of 380 nm.
It showed an ultraviolet absorption rate of 5% or more.

In contrast, as a comparative example, an untreated section with no coating layer formed on the surface of the glass bottle showed lO% at 370 nm, confirming that the product of Example 1 had excellent ultraviolet shielding properties.

Furthermore, the appearance of the obtained colored glass bottle was that of a uniform coating.Furthermore, after cross-casing, a cellophane tape peeling test was conducted, and similarly good results were obtained in all tests.

Next, a heat test was first conducted to determine the coloring prevention effect when the contents were placed in the glass bottle obtained in Example 1.

As Comparative Example 1, only the outer colored coating layer was formed under the same conditions as Example 1 without dealkalizing the inner layer, and as Comparative Example 2, a transparent glass candle bottle for chemical experiments,
A cosmetic cream product was placed in each of the glass bottle containers obtained in Example 1. Filled with 30 g of cream containing 1% kojic acid, placed in a constant temperature and humidity chamber at 45°C, and measured the oral color change using a color difference meter (210010P manufactured by Nippon Denshoku) to determine ΔE (color difference). It is as shown in Table 1.

15 As a result, in the bottle container of Example 1 in which the inner layer was subjected to dealkalization treatment, the increase in oral ΔE was suppressed, and the effect of suppressing coloring of the kojic acid-containing cream due to heat was obtained.

Furthermore, as a discoloration prevention effect, the effect against sunlight and ultraviolet rays was measured by filling 30 g of cream containing 1% kojic acid into each of the glass bottles of Example 1, Comparative Example 1, and Comparative Example 2, and exposing it to sunlight. and measure the change in color over time with a color difference meter (Z
-1001 Kano (manufactured by Nippon Denshoku) and the results of ΔE (color difference) are shown in Table 2.

The above results also show that the glass bottle container of Example 1 suppresses the rise in △E16, and the rise in △E is similarly suppressed in the case of Comparative Example 1, but the transparent glass candle bottle of Comparative Example 2 is not colored. △E is increasing. Thus, it is shown that the glass bottle container of Example 1 is effective in suppressing the coloration of kojic acid cream due to sunlight and ultraviolet rays.

Example 2 [First step: Glass bottle inner surface layer treatment] Under the same conditions as in Example 1, the glass bottle inner surface layer was treated with ammonium sulfate gas to perform a dealkalization process.

[Second step: Glass bottle outer surface layer treatment] A compounded paint consisting of the following composition was created.

Two-component paint, polyurethane resin [main ingredient] 40 parts (manufactured by EC Chemical) Hardening agent (manufactured by EC Chemical) IO part For 100 parts of the above paint, 7 parts of erasing agent (silica powder), colorant green smoke dye, Ciba Geigy Company-made 0.5
1 part and stirred to obtain a uniform dispersion. This compounded paint contains an ultraviolet absorber (Uvinal 400, manufactured by BASF).
2 parts of urethane resin 17 and 10 parts of a fat diluting solvent were added and stirred to obtain a dispersion.

Next, the degreased and cleaned transparent glass bottle was attached to a suitable jig, and as in Example 1, the side wall of the bottle except for the bottle mouth was coated with the above paint formulation using an electrostatic coating machine at room temperature for 30 to 60 seconds. After coating was applied to the top and bottom portions so that the film thickness after curing was 40 to 70 μm, the coating film was cured at a temperature of 140° C. for 25 minutes. With this two-component reaction type paint, even if it is not thermally cured, it can be left at room temperature for about 48 hours to form a coating film that can withstand use.

An alkali elution test was conducted on the glass bottle container obtained through the above process in accordance with the Japanese Pharmacopoeia (11th revision) General Test Methods Method 2 <Surface Method>.
Samples with 0.02 normal sulfuric acid consumption (ml), those treated with the above ammonium sulfate gas, 0.04 per 20 ml, untreated ones,
A test result of 3.26 was obtained. The samples treated with ammonium sulfate gas were found to be significantly more effective in preventing alkali elution than those not treated.

Next, the ultraviolet absorbance of transmitted light was measured using a Shimadzu spectrophotometric needle, Shimadzu-UV240, as in Example 1, and it was found that the normal wavelength was 36.
Approximately 100% absorption effect is observed below 0 nm region, but in Example 2, approximately 100% absorption effect is observed at wavelength 370nrn.
%, it showed an ultraviolet absorption effect of 80% at 380 nm, and it was recognized that the ultraviolet shielding property of the product of Example 2 was significantly improved.

In addition, the appearance of the glass bottle container obtained by the above process was uniformly painted in a faded dark green color, and after cross-cutting, a sellotape peeling I1t test was conducted, and it was equally good in all tests. The results were obtained.

Further, regarding the glass bottle container obtained in Example 2,
The same product as Comparative Example 1 and Comparative Example 2 in Example 1 was filled with a cream containing 1% kojic acid and placed in a constant temperature and humidity chamber at 45°C, and the oral color change was measured using a color difference meter. (Color difference)
As a result of calculating, in Example 2, 1.54 after 30 days,
After 50 days, a value of 2.76 was obtained. Furthermore, ΔE of kojic acid cream under sunlight exposure as in Example 1.
As a result of calculating 19, it was 0.33 after 30 days and 0.33 after 50 days.
A value of 47 was obtained.

Example 3 [First Process: Glass Bottle Inner Surface Layer Treatment] In the same manner as in Example 1, the glass bottle inner surface layer was treated with ammonium sulfate gas and dealkalized.

(Second step: Glass bottle outer surface layer treatment) Compound paint for base layer undercoat consisting of the following composition +
Created Ml.

Thermosetting acrylic paint 100 parts (GLA
Clear, manufactured by EC Chemical) Diluent solvent 30 parts Colorant,
Pigment carbon blank 10 parts Disinfectant
5 parts for 100 parts of the above paint,
3 parts of an ultraviolet absorber (Uvinal 400, manufactured by BASF) and 30 parts of a diluting solvent were added and stirred to obtain a dispersion.

Next, among the above components, ultraviolet absorber (Ubinal 400)
) was mixed to 2 parts by weight, and 10 parts of colorant pigment carbon blank was added to form a dispersion to prepare a compounded paint (b) for overcoat.

Next, attach the degreased and cleaned colored glass bottle to a jig,
First, using a spray paint machine (manufactured by Iwata Painting Co., Ltd.), use the base layer undercoat compound paint (a) to coat the side wall of the bottle, excluding the bottle mouth, to a coating thickness of 20 to 30 μm after heat curing. And a base layer was formed on the bottom.

Next, spray coating was applied using the above-mentioned spray coating machine using the above-mentioned overcoat paint (b) so that the film thickness after thermosetting was 15 to 25 μm. Thereafter, this glass bottle was placed in a heat drying oven, and heat curing treatment was performed at a temperature of 170° C. for 30 minutes.

An alkali elution test was conducted on the glass bottle container obtained through the above process in accordance with the Japanese Pharmacopoeia (11th revision) General Test Methods Method 2 (Surface Method).
The sample was treated with the above ammonium sulfate gas at a consumption of 0.02N sulfuric acid (+nl). The test results were 0.05 per 20 ml and 3.02 per 20 ml. It was observed that the samples treated with ammonium sulfate gas showed a remarkable improvement in prevention of alkali elution compared to the untreated sample 21.

In addition, a glass sample piece similar to that of Example 1 (horizontal 10
tm x length 30wm, thickness 3.5llm), and measured the UV absorption rate of transmitted light using Shimadzu-UV240 (manufactured by Shimadzu Corporation).
It was measured from Usually 36 by adding UV absorber.
Approximately 100% ultraviolet absorption effect is observed below 0 nm region, but in Example 3, 95% at wavelength 370 nm, 3
At 80 nm, the ultraviolet absorption rate was 80%. On the other hand, in the case of a comparative example of an untreated colorless glossy sake bottle container that does not have an outer coating layer, the ultraviolet absorption rate is 1 at a wavelength of 370 nm.
0%, and it was recognized that the product of Example 3 had excellent ultraviolet absorbency.

Further, the appearance of the obtained colored glass bottle was that of a uniformly painted state.Furthermore, a sellotape peeling test after cross-casing was conducted, and similarly good results were obtained in all tests.

Furthermore, regarding the glass bottle container 22 obtained in Example 3, 30 g of Koji #&1% cream was filled into the same glass bottle container as in Comparative Example 1 and Comparative Example 2 in Example 1, and the temperature was kept constant at 45°C. As a result of measuring the oral color change by placing it in a humidifier and determining △E (color difference), in Example 3, 30
A value of 1.68 was obtained after one day, and a value of 2.65 after 50 days. Furthermore, as in Example 1, the ΔE of the kojic acid cream under sunlight exposure was determined to be 0.4 after 30 days.
After 2.50 days, a value of 0.53 was obtained.

Example 4 [First step: Glass bottle inner surface layer treatment] In the same manner as in Example 1, the glass bottle inner surface layer was treated with ammonium sulfate gas and dealkalized.

[Second King's Degree: Glass bottle outer surface layer treatment] Compound paint (a) for base layer Undercoat 1, consisting of the following formulation and containing an ultraviolet absorber that has an ultraviolet absorbing effect in the wavelength region of 370 nm or more. was created.

Polyurethane resin paint 100 parts (Easy Kagaku gR) 23 Diluent (solvent for urethane) 30 parts Colorant (pigment carbon blank) 10 parts Matting agent (silica powder) 7 parts Ultraviolet absorber
Part 2 (Ubinal D49.BAS
(manufactured by Company F) Next, a dispersion liquid was prepared using the same paint composition as above, but with 3 parts of an ultraviolet absorber (Valsol 1789, manufactured by Givaudan) that exhibits an absorption effect in the wavelength region of 370 nm or less. Mixed paint for overcoat 1 (b)
I created l.

Next, the colored glass bottle, which had been degreased and cleaned in the same manner as in Example 3, was attached to a jig, and first, using an electrostatic coating machine (disk type, manufactured by Landsberg), a compound paint for the base layer undercoat (Al was used, and heated). A base layer was formed on the side wall and bottom of the bottle, excluding the bottle mouth, so that the coating thickness after curing was 25 to 35 μm.

Furthermore, so that the film thickness after thermosetting is 15 to 25μ,
Electrostatic coating was performed using the above-mentioned compounded paint for overcoat using the above-mentioned electrostatic coating machine. Thereafter, this glass bottle was placed in a heat drying oven, and heat curing treatment was performed at a temperature of 24 degrees Celsius and 170 degrees Celsius for 30 minutes.

An alkali elution test was conducted on the glass bottle container obtained through the above process in accordance with the Japanese Pharmacopoeia (11th revision) General Test Methods Method 2 (Surface Method).
Sample with 0.02 normal sulfuric acid consumption (ml>) treated with the above ammonium sulfate gas. 0.03 per 20 ml, untreated sample,
A test result of 3.32 was obtained. It was observed that the products treated with ammonium sulfate gas were significantly improved in preventing alkali elution compared to the non-treated products.

In addition, a glass sample piece similar to that of Example 1 (horizontal IQ
Shimadzu-UV240 (manufactured by Shimadzu Corporation) was used to measure the UV absorption rate of transmitted light using
It was measured by As a result, when adding and blending an ultraviolet absorber, approximately 100
% ultraviolet absorption effect is recognized, but for example, at wavelengths of 3 to 7%,
Although it was difficult to improve the shielding effect at wavelengths of 0 nm or more, in the case of Example 4, the UV absorption rate was 97% at 25 wavelengths of 370 nm and 85% at 380 nm. was recognized as being excellent.

Further, the appearance of the obtained colored glass bottle was that of a uniformly painted state.Furthermore, a sellotape peeling test after cross-casing was conducted, and similarly good results were obtained in all tests.

Next, regarding the glass bottle container obtained in Example 4,
In the same manner as in Example 1, 30 g of cream containing 1% kojic acid was filled into a glass bottle container, placed in a constant temperature and humidity chamber at 45°C, and the oral color change was measured by color dissection, and ΔE (color difference) was determined. As a result, values of 1.65 after 30 days and 2.70 after 50 days were obtained. Further, as in Example 1, the ΔE of the kojic acid cream under sunlight exposure was determined, and as a result, values of 0.35 after 30 days and 0.48 after 50 days were obtained.

<Effects of the Invention> As described above, in the present invention, the inner surface layer of the glass bottle container is subjected to a dealkalization treatment, and the outer surface layer is treated with a thermosetting type,
Since it is a two-component reactive type or UV-curing type 26 paint with a coating layer containing UV absorbers, quenching agents, coloring agents, etc., the heat generated during storage in a glass bottle container , under various conditions such as sunlight exposure, especially ultraviolet rays,
When storing contents such as cosmetics and medicines, including bio-cosmetics, which are susceptible to deterioration due to alkali elution inside the bottle, it is difficult to store contents such as cosmetics or pharmaceuticals, which are easily affected by alkali elution, etc. and prevents the contents from discoloring.
．． It has a remarkable effect in maintaining quality and ensuring long-term stability.

Claims (1)

[Scope of Claims] 1) A glass bottle container for cosmetics containing bio-based ingredients, etc., which has a glass surface layer surface-treated with a dealkalizing agent on the inside and a thermosetting type, A glass bottle container for bio-cosmetics, etc., characterized in that a coating layer containing an ultraviolet absorber, a quenching agent, a coloring agent, etc. is formed on a two-component reaction type or ultraviolet curing type paint. 2) In a method for manufacturing glass bottles for cosmetics and other products containing bio-based ingredients, the inside of the container is surface-treated with a dealkalizing agent during the blow-molding process, and then ultraviolet absorbers, quenching agents, coloring agents, etc. A method for manufacturing a glass bottle container for bio-cosmetics, etc., comprising forming a coating layer on the outer surface of the container using a thermosetting, two-component reaction, or ultraviolet curable coating composition containing the following.