JPH0764349B2 - Stretch blow molding bottle with acrylonitrile resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a transparent brown molding bottle obtained by using an acrylonitrile resin composition.

[Prior Art] A molding bottle body obtained by stretch blow molding using an acrylonitrile-based resin is known to have excellent effects on gas barrier properties and transparency.
Since it also exhibits an excellent effect on stability against many solvents, it has characteristics as a container for filling foods, chemicals, cosmetics, etc., as well as carbonated gas-containing beverages and the like.

In particular, as an acrylonitrile-based resin composition for molding a molding bottle body having a property of blocking visible light and ultraviolet rays required for a container for filling beer, certain pharmaceuticals, or the like, JP-A-62-20548. Japanese Patent Laid-Open Publication No. 2003-242242 discloses a resin composition in which 0.001 to 1.0 parts by weight of iron oxide having a particle size of 0.03 μm or less is added to 100 parts by weight of the acrylonitrile resin in the molding composition of the acrylonitrile resin molding bottle. Is proposed.

[Problems to be Solved by the Invention] By the way, the resin composition for color molding bottle molding to which the iron oxide is added has poor dispersibility of the iron oxide added to the composition, In order to improve the dispersibility of this product, the resin composition must be processed to impart a high shearing force, and the acrylonitrile resin is decomposed during the process.

On the other hand, the present invention efficiently blocks visible light and ultraviolet rays without impairing the gas barrier properties, chemical stability, transparency, etc. originally possessed by the stretch-blow molding bottle made of acrylonitrile resin. The bottle is a bottle, and the dispersibility of the coloring agent as an additive and the ultraviolet absorber in the resin composition used for molding the stretch blow molded bottle is very good, and the color tone is comparable to that of a brown glass bottle. The present invention provides a stretch blow molded bottle body which has transparency, gloss, gas barrier property and the like and can be used mainly as a container for beer filling.

[Means for Solving Problems] The stretch blow molding bottle made of the acrylonitrile-based resin of the present invention has a polymer component in which the raw material for forming the stretch blow molding bottle has an acrylonitrile polymer as a polymer main component. For 100 parts by weight, 0.02 to 0.1 parts by weight of perinone red dye, 0.06 to 0.3 parts by weight of quinophthalone yellow dye, 0.004 to 0.02 parts by weight of anthraquinone green dye, and 0.0008 to 0.004 parts by weight. An acrylonitrile resin composition comprising a colorant component comprising an anthraquinone dyeing dye and 0.05 to 0.2 part by weight of a benzotriazole UV absorber, wherein the colorant component is a perinone red dye 1 2.7 to 3.3 parts by weight of quinophthalone yellow dye, 0.18 to 0.22 parts by weight of anthraquinone green dye, 0.036 of anthraquinone purple dye, based on parts by weight.
The resin composition is mixed at a ratio of about 0.044 parts by weight. And, the stretch blow molded bottle of the present invention, the thinnest part in the bottle has a thickness of 0.4 mm or more, the thickest part is 1.4 mm or less, and has an average wall thickness of 0.7 to 1.10 mm. Moreover, the product of the average wall thickness (mm) and the amount of the colorant component (parts by weight) relative to 100 parts by weight of the acrylonitrile polymer in the raw material for molding is 0.15 to 0.18 (mm · parts by weight), , The product of the average wall thickness (mm) and the amount of benzotriazole-based UV absorber (parts by weight) relative to 100 parts by weight of the acrylonitrile-based polymer in the raw material for molding is within the range of 0.08 to 0.10 (mm · parts by weight) There is something.

The polymer main component in the acrylonitrile-based resin composition as a raw material for molding in the stretch-blow molding bottle of the present invention is, of course, composed of an acrylonitrile-based polymer, but in the resin composition, As a minor component of the polymer, synthetic rubber such as natural rubber, butadiene polymer, isoprene polymer, neoprene polymer, nitrile rubber, acrylate rubber, acrylonitrile-butadiene copolymer, ethylene-propylene copolymer, chlorinated rubber, etc., is used as a total component of the polymer. It has been confirmed that the content of the stretch-blow molded bottle obtained can be enhanced by blending it in an amount of 25% by weight or less. As the polymer component, a composition containing an acrylonitrile polymer component and a rubber component is, for example, a copolymer obtained by directly polymerizing monomers, a copolymer obtained by grafting a nitrile monomer on the rubber component skeleton, Examples thereof include those obtained by polymer blending a rubber graft polymer and a matrix polymer.

The acrylonitrile-based polymer that is the main polymer component in the acrylonitrile-based resin composition is such that the stretch blow molded bottle obtained by the acrylonitrile-based resin composition can exhibit excellent gas barrier properties against oxygen gas and carbon dioxide gas. , 55 to 85% by weight of the total weight of the polymer is a nitrile monomer unit component calculated as acrylonitrile, and examples of the nitrile monomer component include acrylonitrile, methacrylonitrile,
A material comprising one or more of ethacrylonitrile, propacrylonitrile, glutaronitrile, methylylene glutaronitrile, and furomanitrile is used. Incidentally, when the monomer unit component is methacrylonitrile, excellent gas barrier properties can be obtained when the monomer unit component is 70 to 98% by weight. This is a nitrile monomer calculated as acrylonitrile. An amount corresponding to about 55 to 78% by weight of the unit component. Suitable monomers to be copolymerized with these monomer unit components include aromatic monomers such as styrene and α-methylstyrene, and 2 to 6 carbon atoms such as ethylene, propylene, butylene and isobutylene. Lower α-
Acrylic acids such as olefins, acrylic acid, methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate and their derivatives, vinyl esters such as vinyl acetate, ethyl vinyl ether One or more such as alkyl vinyl ethers with alkyl groups having 1 to 4 carbon atoms are utilized, most commonly acrylonitrile-methacrylonitrile-styrene copolymers, acrylonitrile-styrene-methyl vinyl ether copolymers, acrylonitrile-styrene- An acrylonitrile polymer composed of ethyl vinyl ether copolymer or the like is used.

The acrylonitrile-based resin composition contains a colorant component composed of a combination of the dyes described above and a benzotriazole-based UV absorber as an essential component, but in addition to these essential components, A dispersant for improving the dispersibility of an additive component, an antioxidant that prevents or suppresses the action of oxygen in the presence of light or heat, a release agent, a lubricant, and a stretch blow obtained by an acrylonitrile resin composition. As a matter of course, a formaldehyde compound or the like is appropriately contained in an amount sufficient to reduce the content of extractable hydrogen cyanide in the bottle as a molded body.

A preferred specific example of the dispersant for improving the dispersibility of the additive component in the resin composition is an ester of glycerol or sorbitan and a C _{12 to} C ₂₈ saturated fatty acid, and a poly of C _{12 to} C ₂₈ saturated fatty acid. It is composed of a mixture with oxyethylene sorbitan ester. Examples of the C _{12 to} C ₂₈ saturated fatty acid include lauric acid, tridecylic acid, myristines, pentadecyl acid, palmitic acid, margaric acid, stearic acid, nondecyl acid, arachidic acid, behenic acid,
There are lignoceric acid, cerotic acid, montanic acid and the like, and glyceryl ester or sorbitan ester consisting of a partial or complete esterification product with glycerol or sorbitan is used. On the other hand, as the polyoxyethylene sorbitan ester, a partially or completely esterified product of polyoxyethylene sorbitan having 4 to 30 oxyethylene units and the above-mentioned C _{12 to} C ₂₈ saturated fatty acid is used. The dispersant consisting of a mixture of glyceryl ester or sorbitan ester and polyoxyethylene sorbitan ester has a weight ratio of both of 80.
/ 20 to 20/80 is preferable, especially 70/30 to 30 /
Those in the range of 70 are preferred. Further, the dispersant composed of these mixtures has a content of 0.01 to 1.0 of the polymer component in the composition.
It may be about wt%, and the range of 0.01 to 0.1 wt% is most preferable. Further, it goes without saying that a dispersant such as the above-mentioned metal salt of C _{12 to} C ₂₈ saturated fatty acid or amide may be used.

Preferable specific examples of the antioxidant include, for example, dibutyloxytoluene, butyloxyanisole, ethyl protocatechuate, isoamyl gallate, propyl gallate,
Guayak butter, nordihydroguaiaretic acid, etc. are used.

Further, the formaldehyde compound added to reduce the content of extractable hydrogen cyanide in the resulting molded bottle may be, for example, free or unreacted formaldehyde, a homopolymer of formaldehyde, or formaldehyde upon heating or processing. Alternatively, it may be formaldehyde in the presence of a nitrile polymer or other compound that behaves as a formaldehyde donor, such as cyclic polymers such as trioxane and tetraoxane and linear polymers of formaldehyde consisting of polyoxymethylene glycol and their derivatives. Formaldehyde homopolymer, alkali metal formaldehyde bisulfite, alkali metal formaldehyde sulfoxylate, etc. eg sodium formaldehyde bisulfite, potassium Formaldehyde compounds such as lumaldehyde bisulfite, sodium formaldehyde sulfoxylate, and potassium formaldehyde sulfoxylate that produce formaldehyde, hexamethylenetetramine, 2-nitro-2-methyl-1,3-propanediol, tris (hydroxymethyl) ) Nitromethane and adducts of formaldehyde with at least one other compound and condensates prepared therefrom: eg phenol-formaldehyde, urea-formaldehyde condensates including dimethylolurea and their cyclic derivatives such as ethylene urea. -Produces formaldehyde during heating or processing consisting of formaldehyde condensate and uron resin, or as formaldehyde or formaldehyde feeder Formaldehyde compounds that behave as such are used, but formaldehyde compounds such as formaldehyde, paraformaldehyde, trioxane, tetraoxane, dimethylolurea, and para-toluenesulfonamide formaldehyde condensate are particularly preferable. Incidentally, the extractable hydrogen cyanide in the stretch blow hollow molded article obtained by the acrylonitrile resin composition is an extremely small amount,
For example, the amount is lower than that contained in foods and drinks such as cereals, cocoa, ham, bacon, sausages, etc., and there is no problem for health, but it depends on the type of filling material filled in the hollow molded body. Is the case where the taste of the inner filler may be impaired by the extractable hydrogen cyanide, and the aldehyde compound is used when it is used as a hollow molding bottle for packaging the inner filler which may cause such a risk. The aldehyde compound is added in an amount of about 0.005 to 2.0% by weight of the nitrile polymer.

[Examples] Hereinafter, specific configurations of stretch-blow molded bottles made of the acrylonitrile-based resin of the present invention are shown in Examples, and the physical properties of the molded bottles are also shown.

Example 1 Acrylonitrile-styrene copolymer [acrylonitrile monomer unit component 68.0% by weight, manufactured by Monsanto Co., Ltd .: L-
600] With respect to 100 parts by weight, after obtaining an acrylonitrile resin composition for stretch blow molding containing an additive component indicated in a predetermined column of Table 1 below, the composition is used to form a bottomed cylindrical shape. Parison [body diameter approx. 30 mm, wall thickness approx. 4.4 mm,
A total height of about 160 mm] was molded by the injection molding method.

Then, the parison was irradiated with an electron beam of 0.15 Mrad by an electron beam irradiation device with an acceleration voltage of 3 MeV, and immediately after the irradiation treatment.
Heat treatment was performed at 80 to 120 ° C.

Further, the parison after the heat treatment is stretched at a temperature of 130 to 150 ° C.
Then, biaxial stretch blow molding was carried out to obtain a stretch blow molding bottle [I] having a capacity of 600 ml, which was an example of the present invention.

Example 2 Acrylonitrile-styrene copolymer [acrylonitrile monomer unit component 68.0% by weight, manufactured by Monsanto Co., Ltd .: L-
600] 100 parts by weight, chip-shaped color pellets made of a resin composition containing an additive component shown in a predetermined column of Table 1 below were molded by an extrusion molding method.

Then, using the obtained color pellets, a molding bottle body [II] comprising a biaxially stretched blow molded body was obtained in accordance with the method described in Example 1 below.

Example 3 Acrylonitrile-styrene copolymer [acrylonitrile monomer unit component 68.0% by weight, manufactured by Monsanto Co., Ltd .: L-
600] 100 parts by weight of the dispersant (Aldosperse TS-4
0] 0.05 parts by weight and p-toluene sulfonamide formaldehyde resin [Santolite MHP] 0.15 parts by weight,
Natural pellet-shaped pellets [A] made of a resin composition containing 0.14 parts by weight of 2,6-di-t-butyl-P-cresol [BHT] were molded by an extrusion molding method.

In addition, acrylonitrile-styrene copolymer [acrylonitrile monomer unit component 68.0 wt%, Monsanto Co., Ltd.
Made: L-600] 100 parts by weight, quinophthalone yellow dye 1.2 parts by weight, anthraquinone green dye 0.1 part by weight, anthraquinone purple dye 0.02 part by weight, benzotriazole ultraviolet absorber 1.0 part by weight, dispersion Agent [Aldosperse TS-
40] 0.05 parts by weight, paratoluene sulfonamide formaldehyde resin [Santolite MHP] 0.15 parts by weight, 2,6-
Chip-shaped colored masterbatch pellets [B] made of a resin composition containing 0.14 parts by weight of di-t-butyl-P-cresol [BHT] were molded by an extrusion molding method.

Thereafter, a mixed composition of 90 parts by weight of the natural pellets [A] and 10 parts by weight of the colored masterbatch pellets [B] was used, and a biaxially stretched blow-molded article was produced according to the method described in Example 1 below. A molded bottle body [III] was obtained.

Average wall thickness, light transmittance, turbidity, color difference of molded bottles [I] to [III] obtained in each of the above examples, gas barrier property per molded bottle, acrylonitrile monomer in the same material And the amount of cyanide ion eluted are summarized in Table 2.

Comparative Example 1 Acrylonitrile-styrene copolymer [acrylonitrile monomer unit component 68.0% by weight, manufactured by Monsanto Co., Ltd .: L-
600] to 100 parts by weight of dispersant [Aldosperse TS-4
0] 0.05 parts by weight and p-toluene sulfonamide formaldehyde resin [Santolite MHP] 0.15 parts by weight,
After obtaining a resin composition in which 0.14 parts by weight of 2,6.di.t.butyl.P.cresol [BHT] is blended, the resin composition is used and the method described in Example 1 is followed. Then, a molded bottle body [i] for comparison was obtained.

Comparative Example 2 50 parts by weight of perylene red pigment [Pigment Red 178] and 50 parts by weight of zinc stearate were dry-colored by an atomizer to dry color the perylene red pigment and disazo yellow pigment [Pigment Yellow 83] 50 parts by weight. And 50 parts by weight of zinc stearate in a dry color with an atomizer, a dry color of a disazo yellow pigment, 50 parts by weight of carbon black [Pigment Black 7] and 50 parts by weight of zinc stearate in a dry color with an atomizer. The dry color of the black pigment was prepared.

Next, with respect to 100 parts by weight of an acrylonitrile-styrene copolymer [acrylonitrile monomer unit component 68.0% by weight, Monsanto Co., Ltd .: L-600], a dispersant [Aldosp
erse TS-40] 0.05 parts by weight and paratoluene sulfonamide formaldehyde resin [Santolite MHP] 0.09
Parts by weight and 2,6 di-t-butyl P. cresol [BHT]
0.14 parts by weight and dry color of the perylene red pigment
0.024 parts by weight, dry color of disazo yellow pigment 0.07
After obtaining a resin composition in which 1 part by weight and 0.01 part by weight of a dry color of carbon black are mixed, a molding bottle for comparison is prepared using the composition according to the method described in Example 1 below. I got a body [ii].

Comparative Example 3 Instead of the acrylonitrile resin composition for stretch blow molding in Example 1, a resin composition of the composition component obtained by removing the anthraquinone green dye from the resin composition was used. By the same method as the method,
A molded bottle body [iii] was obtained for comparison.

Comparative Example 4 Instead of the acrylonitrile-based resin composition for stretch blow molding in Example 1, a resin composition having a composition component in which an ultraviolet absorber was removed from the resin composition,
By the same method as that of Example 1, a molded bottle body [iv] for comparison was obtained.

Average wall thickness, light transmittance, turbidity, color difference of molded bottles [i] to [iv] obtained in each of the above examples, gas barrier property per molded bottle, acrylonitrile monomer in the same material And the amount of cyanide ion eluted are summarized in Table 2.

[Operations and Effects of the Invention] The stretch-blow molding bottle made of the acrylonitrile resin of the present invention has 0.02 to 0.1 parts by weight of a perinone red dye with respect to 100 parts by weight of a polymer component containing an acrylonitrile polymer as a polymer main component. And a colorant component consisting of 0.06 to 0.3 parts by weight of a quinophthalone yellow dye, 0.004 to 0.02 parts by weight of anthraquinone green dye, and 0.0008 to 0.004 parts by weight of anthraquinone purple dye, and 0.05 to 0.2 parts by weight. Part of a benzotriazole-based ultraviolet absorber, and the colorant component is a perinone-based red dye 1
With respect to parts by weight, quinophthalone-based yellow dye 2.7 to 3.3 parts by weight, anthraquinone-based green dye 0.18 to 0.22 parts by weight, anthraquinone-based purple dye 0.036 to 0.044 parts by weight acrylonitrile-based resin composition mixed in the ratio. A stretch blow molded bottle body as a raw material for molding, wherein the stretch blow molded bottle body has a thinnest portion of the bottle having a thickness of 0.4 mm or more and a thickest portion of 1.4 mm or less, and an average meat thickness. Thickness 0.7-1.
10 mm, and the product of the average wall thickness (mm) and the amount of the colorant component (parts by weight) relative to 100 parts by weight of the acrylonitrile polymer in the raw material for molding is 0.15 to 0.18.
(Mm / part by weight), and the average wall thickness (mm) and the amount of benzotriazole-based UV absorber (parts by weight) based on 100 parts by weight of the acrylonitrile-based polymer in the molding raw material.
The product of and is in the range of 0.08 to 0.10 (mm / part by weight).

However, the colorant component in the acrylonitrile-based resin composition, which is the raw material for molding the stretch blow molded bottle of the present invention, has the property of excellent chemical stability, and thus is decomposed at the molding stage of the resin composition. Since it does not reduce the gloss of the surface of the molded product, or does not elute on the surface of the molded product to be obtained, the dispersibility at the processing temperature applied to the acrylonitrile resin composition It has excellent properties.

Further, the ultraviolet absorber in the acrylonitrile-based resin composition described above has a property of excellent dispersibility at a molding processing temperature applied to a general acrylonitrile-based resin, and a small addition amount is good. It is effective and does not adversely affect the transparency and gloss of the resulting molded bottle. On the other hand, the molded bottle body [i], which is a comparative example product made of a resin composition in which the acrylonitrile-based resin composition does not contain a colorant and an ultraviolet absorber, adversely affects the contents in the molded bottle body. It has a very high light transmittance in the ultraviolet, which is easy to do. Also, in the case of a comparatively molded product bottle [ii] made of a resin composition containing a pigment as a colorant component, the dispersibility of the above-mentioned pigment is poor. , Its turbidity is about 20% and its transparency is poor,
Does not work as a colored transparent bottle. Further, in the case of the molding bottle [iii] which is a comparative example when the colorant component is different from that specified in the present invention, a color tone greatly different from the color tone of the commercially available brown glass bottle comes out, In addition, in the case of the molded bottle [iv], which is a comparative example product to which the colorant is added but the ultraviolet absorber is not added, the light transmittance is as high as 1% or more particularly near 370 nm where the energy level is high. Therefore, it has a drawback that the shelf life of the filling material inside the molding bottle becomes short.

However, the stretch-blow molding bottle made of the acrylonitrile-based resin of the present invention has no deterioration in gas barrier property, transparency and gloss originally possessed by the stretch-blow molding bottle using the acrylonitrile-based resin, and has a color tone of a brown glass bottle. And exhibits an excellent action of blocking ultraviolet rays and visible rays.

The color tone, transparency, gloss and the like of the above-mentioned brown glass bottle in the stretch-blown hollow molding bottle of the present invention are determined from acrylonitrile resin as a raw material for molding and a specific combination of dyes added to the resin. Which is obtained by the action of a colorant component and an ultraviolet absorber, the stretch-blow molding bottle of the present invention has an oxygen gas barrier property, transparency, chemical stability, etc. It is a brown container that also has a blocking property, and has the same color tone, transparency, gloss, and blocking property against visible light and ultraviolet rays as the conventional glass brown container, and it is also light in weight and far superior in mechanical strength. It exerts an action and an effect.

Furthermore, in the acrylonitrile resin composition as a raw material for molding the stretch blow molded bottle of the present invention, a coloring agent or an ultraviolet absorber having poor dispersibility at the molding temperature applied to the acrylonitrile resin is added. Since there is no, it is not necessary to perform a process of imparting a high shearing force to the additive to uniformly disperse the additive, and it is possible to avoid such a problem that the acrylonitrile resin in the composition decomposes. The stretch-blow molding bottle of the present invention exhibits a stable color tone without color unevenness, increase in turbidity, change in color difference, and the like, and moreover, the amount of acrylonitrile monomer in the material of the molding bottle and cyan ion It also has the action and effect of avoiding an increase in the elution amount.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 33/20 LJL (72) Inventor Hideo Kushida 3-2-6 Oshima, Koto-ku, Tokyo Stockholders' Association Inside the company Yoshino Industry

Claims (5)

[Claims] 1. To 100 parts by weight of a polymer component containing an acrylonitrile polymer as a main component, 0.02 to 0.1 part by weight of a perinone red dye, 0.06 to 0.3 part by weight of a quinophthalone yellow dye, and 0.004 to Colorant component consisting of 0.02 parts by weight of anthraquinone green dye and 0.0008 to 0.004 parts by weight of anthraquinone purple dye, 0.05 to 0.2
Benzotriazole-based UV absorber in an amount of 1 part by weight of the perinone red dye, and the quinophthalone-based yellow dye 2.7 to 3.3 parts by weight.
Parts by weight, anthraquinone green dye 0.18 to 0.22 parts by weight,
An anthraquinone-based purple dye 0.036 to 0.044 parts by weight stretch blow molding bottle using the acrylonitrile resin composition mixed as a raw material for molding, the stretch blow molding bottle body, in the bottle The thinnest part is 0.4 mm
Above, the thickest part is 1.4 mm or less, and the average wall thickness is 0.7-1.10.
mm, and the product of the average wall thickness (mm) and the amount of the colorant component (parts by weight) relative to 100 parts by weight of the acrylonitrile polymer in the raw material for molding is 0.15 to 0.18 (mm
-Part by weight), and the product of the average wall thickness (mm) and the amount of benzotriazole-based UV absorber (parts by weight) relative to 100 parts by weight of the acrylonitrile-based polymer in the raw material for molding is 0.08 to 0.10 ( (mm · part by weight) Stretch blow molding bottle made of acrylonitrile resin. 2. A stretch-blow molding bottle made of an acrylonitrile resin according to claim 1, wherein the acrylonitrile resin composition is a composition containing a dispersant. 3. A stretch blow molding bottle made of an acrylonitrile resin according to claim 1 or 2, wherein the acrylonitrile resin composition is a composition containing an antioxidant. 4. An acrylonitrile-based resin composition is a composition containing a formaldehyde compound in an amount sufficient to reduce the content of extractable hydrogen cyanide in a stretch-blow molded bottle obtained by the composition. A stretch blow molding bottle made of the acrylonitrile resin according to any one of claims 1 to 3. 5. Acrylonitrile-based polymer is a nitrile monomer unit component 55 to 85 calculated as acrylonitrile.
A stretch-blow molding bottle made of an acrylonitrile-based resin according to claim 1, which is a polymer in a weight percentage.