JPH02302336A - Green glass and its utilization - Google Patents

Abstract

PURPOSE:To obtain green glass, containing respective prescribes amounts of Cr and Ni in soda-lime glass or borosilicate glass, having respective specific color tones and light transmittances and further color tones favorable to packaging and beautiful appearance for a soft drink. CONSTITUTION:Green glass, provided by containing Cr in an amount of 0.1 to 0.8wt.% expressed in terms of Cr2O3 and Ni in an amount of 0.08 to 0.15wt.% expressed in terms of NiO in soda-lime glass or borosilicate glass consisting of respective well-known compositions and satisfying the following requirements. That is the green glass has color tones expressed in terms of 4mm thickness according to the C.I.E indication method as follows. 15 to 50% lightness (Y), 565 to 575mmu main wavelength (lambdad) and 65 to 95% stimulation purity (Pe) as the aforementioned requirements. The abovementioned green glass must satisfy the requirements of <=45% transmittance of light at 550mmu wavelength expressed in terms of 4mm thickness. Since the aforementioned green glass substantially cuts off light at <=460mmu wavelength, the characteristics are especially beneficial if a soft drink is beer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Mushrooms of the Invention] Technical Field The present invention relates to a green glass excellent in blocking short-wavelength light and its use as a beer bottle. One specific form of this beer bottle is a state where it is filled with beer, and therefore, the present invention also relates to bottled beer filled in this beer bottle.

<Prior art> Glass bottles for packaging beer and other liquid beverages are
There is a need for blocking properties against ultraviolet rays and short wavelength rays in the near-ultraviolet region (hereinafter referred to as short wavelength rays including ultraviolet rays), which cause quality deterioration.

For example, in the case of beer, such short wavelength light,
It is known that when exposed to rays of less than about 550 mμ, a strange odor called so-called slag occurs. Therefore, in order to protect beer from such short wavelength rays, beer glass bottles are colored amber ( The so-called brown bottle is usually 2'.

However, since beer and other beverages that are consumed in large quantities often have a cooling sensation, the green color of the glass bottle as a container is attractive, and the variety of products, including packaging formats, is attractive. There is a lot of desire for green glass bottles from the perspective of commercialization as well.

From this point of view, green glass bottles for liquid beverages have been known for quite some time, but green glass for containers that has been around for a long time does not necessarily have the ability to block short wavelength light as described above. It wasn't enough.

Recently, as a solution to the drawbacks of green glass, 0.3 to 0.5% by weight of chromium oxide (calculated as Cr2O3) and 0.06% by weight of Fe2O3 in S102-Na20-CaO glass have been developed. % or less was proposed (Japanese Unexamined Patent Publication No. 185841/1983). As shown in the light transmittance curve in FIG. 1 of the same publication, this green glass is superior to conventional green glass for containers in its ability to block short wavelength light of 460 mμ or less. However, it is still not sufficient in blocking short wavelength light of about 550 mμ or less, which is necessary to prevent beer from tipping.

Chromium oxide is effective in reducing the transmittance of short wavelength light up to 550 mμ, but increasing the chromium oxide content leads to a decrease in the brightness (Y) of the glass, making it darker in color tone. This results in a green color, making the packaging aesthetically unacceptable. Therefore, from a technical point of view, it is considered to be quite difficult to block harmful rays using only chromium oxide.

[Summary of the invention]

Summary of the Invention The present invention aims to provide a solution to the above-mentioned problems, and attempts to achieve this purpose by using nickel in combination with chromium as a greening element.

Therefore, the green glass according to the present invention contains chromium oxide (C) in soda lime glass or borosilicate glass.
r203) converted to 0. 1 to 0.8% by weight and 0.08% of nickel in terms of nickel oxide (N i O)
It is characterized by containing ~0.15% by weight and satisfying the following requirements.

(a)C. I. E. 4-1 Thickness conversion color tone according to display method: brightness (Y) 15-50%, dominant wavelength (λd) 565-565%
575 μm, excitation purity (Pe) 65-95%.

(b) It has a thickness of 4 mm and has a transmittance of 45% or less for light with a wavelength of 550 mμ.

(c) 4-The transmittance of light having a wavelength of 460 mμ or less is substantially 0% in terms of thickness.

The invention also relates to the use of this green glass.

That is, the present invention relates to a beer bottle made of the above green glass.

The present invention also relates to bottled beer filled in a beer bottle made of the green glass described above.

Effects> The green glass according to the present invention not only has a color tone that is favorable for the aesthetic appearance of packaging for soft drinks, but also has a low transmittance for light with a wavelength of 550 mμ and substantially blocks light with a wavelength of 4601 nμ or less. . This property is particularly beneficial for those whose soft drink is beer.

[Detailed description of the invention]

Matrix glass> The matrix glass to be greened with a specific greening agent in the present invention is
Soda lime glass or borosilicate glass.

All of these are well known in the art, and their typical compositions are as follows.

(a) Soda lime glass component Weight 96S iO,2:
65-75N a20:
10~15Cab: 5~
15A 1203: 0-3 K20: 0-3 Fe20320-0.5 Mg0: O-5 Others:
0-2 (b) Borosilicate glass component Weight % 5in2: 60-75 NaO; 5-15 Cab: 5-15 Al 203: ・ 0-5K 20:
0 to 5 Fe203: 0 to 0.5 Mg0: 0 to 5 8203: 0 to 6 Other 2 0 to 2 - Such matrix glass is generally colorless, and the color tone when converted to 4 mm thickness is lightness. (Y) 88% or more, dominant wavelength (λd) 565-575 mμ, excitation purity (Pe) 2
% or less.

Greening> The greening agent according to the present invention is chromium oxide and nickel oxide, and the amorous glass according to the present invention converts chromium oxide into C'2
03 as 0.1 to 0.8 weight Q6, preferably 0.2
~0.6 mm%, nickel oxide as NiO 0.08
~0.15 weight 96, preferably 0.08 to 0.12 weight 96.

The content of these greening agents is closely related to the brightness, dominant wavelength, and excitation purity of the product glass, and therefore the specific combination of both contents should be selected to satisfy these color tone conditions of the product glass. Become. A preferred example of such a combination of both contents is shown in the attached graph. In the figure, the shaded area is the preferred content in the present invention.

Sources of chromium oxide include chromium oxide, chromic acid or dichromic acid, or salts of chromic acid or dichromic acid, such as potassium salts. Nickel oxide sources include nickel oxide, chromic acid or nickel dichromate, organic acid nickel salts or complex salts.

The chromium oxide and nickel oxide sources may be these compounds themselves or, if desired, may be added to the matrix glass in the form of a glass (i.e., a color frit) containing more than the final concentration of these compounds. good. A specific example of the latter case is Si0 45-50%, A I 2
03: Potassium dichromate and/or nickel oxide on a frit consisting of 1 to 29' o s2 ° Na O: 25 to 30%, 8203: 5 to 15%, and CaO: 5 to 10% (all weight 96) C "so that the 203 concentration is 3 to 10%,
Alternatively, add 0.5% to 2.5% Ni04 degree, heat and melt it, drop this melt into water and rapidly cool it, and finally make a color with a particle size of about 1 to 5 yen. - Obtain the frit and add it to the matrix glass.

Whether such colorants are added to the glass melting kiln or to the molten glass in a color feeder, the production of green glass according to the invention can be carried out by techniques well known in the art. . Therefore,
Specific examples of raw materials and manufacturing methods can be found in the textbook "Glass Engineering" by Naruse (December 1961, 151).
It would be permissible to defer to the description in P. Also, reference may be made to the above-mentioned publications.

The green glass according to the invention is made of C. I. E. The color tone calculated based on the display method at a thickness of 4 mm is as shown in the description below.

Lightness (Y): 15-50%, preferably 20-40%.

Main wavelength (λd): 5'65 to 575 mμ, preferably 567 to 573 mμ.

Stimulation purity (Pe): 65-95%, preferably 70-9
2%.

Moreover, the green glass according to the present invention has a thickness of 550 mm and a thickness of 4 mm.
The transmittance of light having a wavelength of mμ is 45% or more.

Utilization of dark green glass> The green glass according to the present invention as described above is preferably used for producing bottles for soft drinks because of its blocking properties against short wavelength light of 550 mμ or less and good color tone.

A typical example of such a soft drink is beer, which is easily affected by short-wavelength light, and can best enjoy the effects of the present invention, which suppresses the transmittance of light with a wavelength of 550 mμ.

Beer filled in a beer bottle made of green glass according to the present invention has significantly less sunlight than beer filled in a conventional green bottle.

The technology for manufacturing glass bottles is well known, and the beer bottles according to the present invention can be manufactured in other capacities such as 633 ml, 500 ml, and in any shape by conventional methods.

Experimental Examples Example 1 Silica sand, soda ash, limestone, and Glauber's salt were used as raw materials for container glass (base glass). For the seven-color agent, potassium dichromate (K2C "207") was used as chromium, and nickel oxide (NiO) was used as nickel.Batch preparation by mixing raw materials and glass melting were carried out by the usual method used in bottle factories. The final glass composition (% by weight) was as follows.

S i02 71.36, Al2O31, Q8, CaO
11,03, Mg0 0,20, Na 20 13.
28, K2O1,35, Fe2O30,04, Cr2O
30,60°NiO0,10, and other unavoidable components.

When the color tone of this glass was expressed in terms of 4 mm thickness, the brightness (Y) was 22.9%, the dominant wavelength (λd) was 567 mμ, and the excitation purity (Pe) was 91.8%.

Transmittance of light with a wavelength of 550 mμ (converted to a thickness of 411 m).

) was 30%. Also, the wavelength is 460 mμ
Transmittance of the following light rays (4ms thickness conversion)

) was zero.

Example 2 The composition of the container glass (base glass) is almost the same as in Example 1. The glass composition (% by weight) finally obtained is as follows.

Si0 71.45, Al2O32, (')O1Ca
0 11.20, MgOO,20, NaO13,2
9, K2O1,36, Fe00.04, C "2030.
12, NiOO, 10, and other unavoidable components.

When the color tone of this glass was expressed in terms of 4 Peng thickness, the brightness (Y) was 35.4%, the dominant wavelength (λd) was 572 mμ, and the excitation purity (Pe) was 73.1%.

The transmittance of light with a wavelength of 550 mμ is 37%, and the transmittance of light with a wavelength of 4
The transmittance of light rays below 60 mμ was zero.

Example 3 The container glass (base glass) composition is almost the same as in Example 1. The finally obtained glass composition (ball amount %) is as follows.

SiO71,35, A I 203 1,99, Ca
O11,03, Mg0 0.20, Na O13,2
g, K2O1,35, Fe2O30,04, Cr2O3
0.30, Ni0 0.10, and other unavoidable components.

When the color tone of this glass was expressed in terms of 4 m thickness, the brightness (Y) was 29.3%, the dominant wavelength (λd) was 57 (1 mμ), and the excitation purity (Pe) was 86.5%.

The transmittance of light with a wavelength of 550 mμ is 34%, and the transmittance of light with a wavelength of 4
The transmittance of light rays below 60 mμ was zero.

Comparative Example 1 (N i >0.15) The container glass (base glass) composition is almost the same as in Example 1. The glass composition (% by weight) finally obtained is as follows.

Si0 71.35, Al2O31,99, CaO1
1,03, MgO0,20, Na2O13128, K2,0 1.35, Fe00.
04, C "2030.30, NiOO, 20, and other unavoidable components.

When the color tone of this glass is expressed in terms of 41 thickness, the brightness (
Y) 13.4%, dominant wavelength (λd) 573 mμ, and stimulation purity 90.3%.

As is clear from the above results, this glass is 550m
Good blocking effect for short wavelength light below μ (550 μm = 1
6%, 460 mμ or less: zero 96), but the color tone was dark green and the brightness was 20 or less, which is not desirable from the viewpoint of packaging aesthetics.

Comparative Example 2 (Ni>0.15) The container glass (base glass) composition was the same as that of Example I! It is almost the same as A11. The final glass composition (Ffi
The amount 96) is as follows.

Si0 71.34, Al2O31,97, CaO1
0.72, Mg0 0.20, Na0 13.28
,K2O1,35,F,eoo,04,C"2030.
6, NIOo, 2, and other unavoidable components.

When the color tone of this glass was expressed in terms of 4■■ thickness, the brightness (Y) was 11.9%, the dominant wavelength (λd) was 570tnμ, and the excitation purity (Pe) was 92.8%.

As is clear from the above results, this glass is 550m
Good blocking effect for short wavelength light below μ (550 mμ: 1
5%, 460 mμ or less; 0%), but the color tone was dark green and the brightness was quite low at 11.9%, which is not desirable from the viewpoint of packaging aesthetics.

Comparative Example 3 (Ni=0) The container glass (base glass) composition is almost the same as in Example 1. Final glass composition (ifi m%)
is as follows.

Si0 71.34, A12031.97, Ca0
10.92, Mg0 0.20°Na O13,28
, K2O1,35, Fe00.04, C"2030.6
, and other unavoidable components.

When the color tone of this glass was expressed in terms of 4 liter thickness, the brightness (Y) was 48.7%, the main wave gc (λd) was 56'5 mμ, and the excitation purity (Pe) was 89.0%.

This glass is ordinary green glass with no Ni added as a colorant, and is called emerald green colored glass in the industry; Since the barrel transmits a considerable amount of light (550 mμ: 78%, 460 mμ or less: 0 Oo), it is not preferable when the contents of the bottle are beer.

Comparative Example 4 (Cr-0, Ni>0.15) The container glass (base glass) composition is almost the same as in Example]. The glass composition (% by weight) finally obtained is as follows.

Si0 71.34, Al2O31,97, CaO1
1,37, MgOO,20, NaO13,28, K2O1,35, Fe2O30
,04,Ni0 0.20. There were other unavoidable ingredients.

When the color tone of this glass was expressed in terms of 4as thickness, the brightness (Y) was 13.6%, the dominant wavelength (λd) was 582 mμ, and the excitation purity (Pe) was 43.0%.

゛Since Cr is not added to this glass as a colorant, it nominally transmits short wavelength light of 550 mμ or less (
550 mμ: 13%, 400 mμ = zero%). Furthermore, the dominant wavelength is 582 mμ, which can no longer be considered green in terms of color tone.

Example 4 For the above-mentioned various colored glasses, thick 4+o+s bottles were prototyped, filled with beer, and after being capped, the following weathering test was conducted. A sensory test was conducted by tasting beer by a panel of 51 people, and the following results were obtained.

Note l) Mosquito exposure test conditions are as above.

During clear weather in May (10:00 am to 11:00 am), 1 hour extra connection,
I placed beer and water on a concrete floor and let it cool under the sun's rays.

2) Degree of occurrence of day-to-day tools: 0 Not felt at all +1 Feels homey +2 Feels a little +3 Feels quite a bit +4 Significantly felt 3) The numerical values in the table are based on f=l'ldb of the five panelists. The average value is shown.

[Brief explanation of the drawing]

The drawing is a graph showing the content of chromium oxide and di-nokel oxide, and the shaded area is the preferred content. Applicant's representative Mr. Sato 0 0.51. ○ Figure 1

Claims (1)

[Claims] 1. Chromium in soda lime glass or borosilicate glass is 0.1 to 0 in terms of chromium oxide (Cr_2O_3).
．． 8% by weight and nickel oxide (NiO)
A green glass containing 0.08 to 0.15% by weight in terms of conversion and satisfying the following requirements. (a)C. I. E. The color tone converted to 4mm thickness according to the display method is brightness (Y) 15-50%, dominant wavelength (λd) 565-565%.
575 μm, excitation purity (Pe) 65-95%. (b) It has a thickness of 4 mm and has a transmittance of 45% or less for light with a wavelength of 550 mμ. (c) The thickness is 4 mm, and the transmittance of light with a wavelength of 460 mμ or less is substantially 0%.