Polymer composition for food containers

FIELD: chemistry.

SUBSTANCE: polymer composition contains polyethylene terephthalate, titanium oxide and iron oxide. The weight ratio of titanium oxide to iron oxide ranges from 150 to 250.

EFFECT: invention enables to obtain food containers with improved characteristics with respect to light absorption and reflection, improved light-protective properties.

8 dwg, 4 tbl

 

The technical field

Requirements for food containers is increasing. For example, significantly increases the awareness of consumers regarding aspects related to health. Thus, these health-related aspects should be heavily considered when choosing materials for food containers, also taking into account the changing national requirements. In addition, it is often necessary to ensure airtightness, to avoid, for example, the rapid oxidation of packaged food products or degassing carbonated drinks.

In addition, with regard, for example, dairy products, it is necessary to protect food from harmful exposure to light in the visible and ultraviolet (UV) region, respectively. Especially critical is visible light having a wavelength below 550 nm, which contributes to the photo-oxidation of vitamins such as Riboflavin, or amino acids such as methionine, and has a negative impact on the smell of dairy products. When using polymeric materials for food packaging conventional measure to achieve the best light shielding properties is added to the polymeric material reflective and/or light-absorbing agents such as inorganic pigments. One of the inorganic pigment is in, suitable in this respect is titanium oxide, as can be seen, for example, from WO 03/064267 A2, WO 01/55261 A2, JP 04173134 A, US 4051265 A, WO 03/076277 and EP 1737755 B1. These documents describe the fabrication of a single layer of containers made of polyester, in which the inorganic filler to ensure that it is lightproof use titanium oxide, using his reflection effect to reduce the transmittance of the obtained product.

In addition to titanium oxide is usually used and other pigments. For example, JP 04114057 And describes a composition based on a polyester, which is applicable to molded by blowing bottles and which contains light-reflecting pigment such as titanium white, light-absorbing agent such as carbon black, and the color corrector, such as iron oxide (Fe2O2). Assume that this combination of pigments ensures a good light shielding properties.

As for these light shielding properties of the polymer compositions intended for use in food containers, there is the additional possibility of improvement, particularly from the perspective of a good protective properties within the entire region of visible light and UV region.

In addition, you should also consider the color of the containers, because some of the ingredients commonly used to change light shielding properties, have the trend is to make the material of the container darker and sometimes in the polymeric matrix formed black spots. This darkening is an aesthetic disadvantage. Thus, it is desirable that the materials used were more white.

In addition, there is also a need to increase the degree of correspondence between the applied reflective/light-absorbing pigments and polymer matrix. This is because the pigments have an impact not only on the characteristics of the transmission, but also on the mechanical and chemical properties of the polymer matrix, and sometimes lead to its destruction.

In addition to the aspect of adequate protection from light for food containers are also important properties of the final product, as well as aspects of its manufacture. Namely, it is necessary to provide an acceptable balance between hardness and ductility, good properties processing AIDS used raw materials and appropriate technology, which allows quick and relatively cheap mass production, etc.

Accordingly, an objective of this invention is to provide polymer compositions that can be applied in the manufacture of food containers and which will provide the best performance in relation to the absorption and reflection of light for all relevant areas of wavelengths. In addition, at the same time, the Dol is but to be improved balance between stiffness and ductility, properties, processing AIDS and adaptability of this polymer composition. An additional objective of the invention is to improve the color of the polymer composition.

The invention

To solve the above problems in the present invention proposed polymer composition to obtain food containers, including polyethylene terephthalate, titanium oxide and Fe3O4, characterized in that:

the mass ratio of the specified titanium oxide and the Fe3O4is in the range from 150 to 250,

the contents of the specified titanium oxide is from 2 to 11% wt. calculated on the total weight of the composition, and

the contents of the specified Fe3O4is from 0.01 to 0.07 wt.%. calculated on the total weight of the composition.

In accordance with a preferred example of realization of the polymer composition is in the form of granules.

The polymer composition according to the invention mainly get through the polymerization process.

The present invention also proposed harvesting food container, preferably a bottle, which includes a polymer composition according to the invention.

Of the polymer of this invention can be obtained bottle, preferably a single-layer bottles, or other containers.

The application container, which includes polymers the Yu composition according to the invention, for packaging light-sensitive goods is particularly advantageous for food, especially milk or dairy products.

Thus, it is possible to manufacture the bottle containing the above polymer composition, which, when the wall thickness of 0.22 mm to 0.35 mm and a wavelength of 550 nm has a transmittance of light emitted ≤0,5%, when adjusting the dimension mode full sphere.

A method of obtaining a polymer composition to obtain food containers, including polyethylene terephthalate, titanium oxide and Fe3O4includes the following stages:

i) obtaining ester of terephthalic acid and ethylene glycol;

ii) adding titanium oxide and Fe3O4;

iii) carrying out the polymerization of the obtained reaction mixture;

iv) granulating the polymerized reaction mixture; and

v) increasing the molecular weight of the polymer obtained in the subsequent process of solid-phase polycondensation (TFPC).

Brief description of drawings

Figure 1 shows the comparison of the transmission coefficient for four different polymer compositions with a constant concentration of titanium oxide and increasing concentrations of Fe3O4.

Figure 2 shows the values of the transmittances for different concentrations of pigment and a constant mass ratio of TiO2/Fesub> 3O4=225, in the wavelength range from 400 to 700 nm.

Figure 3 shows a comparison of the transmittance at 550 nm for two different groups of samples, one of which contains only titanium oxide at various concentrations, and the other a combination of titanium oxide and iron oxide with a mass ratio of TiO2/Fe3O4=225, at different absolute concentrations of the pigments.

Figure 4 compares the transmittance of two samples: one with titanium oxide (7% wt.) and another with a combination of titanium oxide (4% wt.) and Fe3O4in the wavelength range from 400 to 700 nm.

Figure 5 shows the comparison of the transmission coefficient of two samples: one theoretical sample containing only titanium oxide (using equation 3), and another that contains a combination of titanium oxide and Fe3O4in the wavelength range from 400 to 700 nm.

Figure 6 shows a diagram of the technological process of obtaining a polymer composition according to this invention.

Figure 7 describes the obtaining of a suspension of titanium oxide in ethylene glycol.

On Fig described obtaining a suspension of iron oxide in ethylene glycol.

Description of the preferred implementation examples

As indicated above, this invention relates to a polymeric composition that includes polyethylene terephthalate, titanium oxide and iron oxide with a mass ratio of titanium oxide to iron oxide from 150 to 250.

In addition to the specific advantages of different signs and combinations of signs of the composition according to the invention, which are discussed in detail below, it should be noted that for the above composition was observed superior ability to disperse pigments and possible additives and no agglomeration or formation of clots in suspension.

The matrix resin composition essentially includes polyethylene terephthalate (PET). The reason for this is that the PET can easily be given the desired shape by means of molding, such as injection molding, blow blanks, injection-blow process, press molding, extrusion molding, etc. that provides excellent processability. The resulting containers are also acceptable balance between rigidity and flexibility.

At the same time PET allows you to enter the pigments of titanium oxide and iron oxide pigments in the desired amounts and ratios, while receiving improved dispersion of these pigments in the polymeric matrix, which is achieved homogeneous properties in terms of light transmission.

Accordingly, the present invention used polymer composition comprising PET. To change the chemical and mechanical properties of articles made from this composition, it is possible to add other polymers and copolymer is. Moreover, the PET may be chemically modified.

However, thanks to its very good compatibility with pigments used PET is the preferred basic ingredients in the polymeric composition. That is, the content of PET in the composition is preferably 88% wt. or more, more preferably 90 wt.%. or more. Depending on the amount of added pigments upper limit of the content of PET can be, for example, 95% wt. or even higher. However, it is possible, of course, higher and lower limits of the content of PET, if only implemented the ratio of the pigments according to the invention.

In this invention as one of the pigments, that is, as a reflective agent, used titanium oxide, preferably TiO2in the crystalline form of anatase or rutile. The titanium oxide is used because this pigment can easily adjust the white containers made of polymeric compositions. In addition, the titanium oxide has a high light shielding properties at short wavelengths (below 380 nm), high reflective properties and is safe in food applications. Moreover, the titanium oxide is very well dispersed in containing PET polymer matrix and does not interfere with polymerization processes.

In addition, the titanium oxide to the action of the t together with the second pigment iron oxide. This is because the scattering of light by the irradiation of light particles of titanium oxide can be used to achieve synergistic effects, when the light absorbing particles which are dispersed in the polymer matrix used in combination.

As the second pigment used iron oxide, which is selected from several possible absorbing agents (often used activated carbon or soot), and is made of the following reasons: it allows to obtain the corresponding chromaticity coordinate in a three-dimensional color space (the scale of the Cie-L*a*b*"), better than in the case, which makes the final appearance dark. In addition, it retains the ability to high specific light absorption at the critical wavelength of 550 nm. Experiments, using as the absorbing agent derived carbon, have demonstrated their abilities in relation to acquisitions, but also appeared and black spots due to agglomeration. There is a significant risk of degradation of the color L* (chromaticity coordinate, which indicates white color) and b* (chromaticity coordinate, which represents yellow color) with small changes to a final concentration C.

These shortcomings, especially related to absorbing agents based To overcome the sharing of the oxide yellow is for in addition to titanium oxide. In General, you can use dehydrated oxide FeIII(Fe2O3) and a mixed oxide of FeIIFeIII(Fe3O4).

However, it turned out that Fe3O4in the form of a mineral known as magnetite, shows much less tendency to agglomerate, so it is, therefore, leads to a better dispersion of the absorbing pigment in the matrix. As described above, a high degree of dispersion of the absorbent pigment leads to a synergistic effect when reflecting pigment is applied to the titanium oxide. In addition, Fe3O4absorbs more light in the visible light spectrum than other pigments based on iron oxides. In addition, Fe3O4better dispersed in the polymer matrix than, for example, carbon black, and does not form agglomerates during polymerization, while the carbon black has a significant tendency to agglomerate. Moreover, in the context of the use of this composition for food containers slightly yellowish tone, made of Fe3O4is preferred in comparison with a bluish tone, which gives the soot. The following Table 1 compares samples (real bottles) with two different combinations of pigments (titanium oxide/carbon black and titanium oxide/iron oxide). Measured transmittance at 550 nm for stink the x bottles with a thickness of 0.25 mm

Table 1
TiO2(% wt.)Soot (ppm)Fe3O4(ppm)T550 nm(%)Color L*/a*/b*
A194000,0888,8/-0,5/1,5
C191200,0888,7/-1,1/-0,2

As can be seen from Table 1, with comparable light shielding properties and color values L* Fe3O4has only a slight yellowish tone, while soot leads to the appearance of a bluish tone, which is indicated by a lower value of b* (preferred is yellowish tone corresponding to the positive coordinate b*).

Given the above, the most preferred absorbing pigment in this invention is a Fe3O4.

An additional reason for the preferred use of Fe3O4is its high absorption of radiation in the infrared region, more height is some, than the absorption in this region from other iron oxides. In the standard setting for the blower to heat the billets before blowing it uses infrared radiation. Procurement, referred to in this description can be heated and to inflate in a furnace, in which they are irradiated with IR light. Thus, if a pigment based on iron oxide in the polymeric composition is Fe3O4it is possible to shorten the heating time in the furnace, increasing, thus, the productivity of the manufacturing process and reducing energy consumption. It was also found that the distribution of heat, for example, in a heated infrared radiation to the workpiece is more uniform when using Fe3O4that eventually leads to a more uniform process of blowing and best product.

To reliably obtain improved light shielding properties of packaging materials made from compositions according to the invention, as well as their increased whiteness, the mass ratio of at least two pigments used in the compositions according to the invention, i.e. the mass ratio of the titanium oxide/iron oxide is in the range from 150 to 250.

The positive effects of this invention are achieved in a certain range, among other things, also for the following reasons. First, hydroxy what titanium is a pigment, reflective white color. With increase in the content of titanium oxide correspondingly increase as light shielding properties, and white compositions and made of it products, especially in the case of the above preforms and bottles. For such containers, which shall be made of a polymeric composition according to this invention, a high degree of whiteness desired for aesthetic reasons. On the other hand, the titanium oxide is relatively expensive, and its high content may cause the worst processability, for example, in the processes of injection and blowing.

Secondly, the iron oxide is a black light-absorbing pigment, and thus the increase in the content of this pigment provides a stronger light barrier, but also increases the dark song, or made of her container preforms, bottles and so on). Darkening is less desirable for the reasons mentioned above.

In principle, the addition of iron oxide reduces mass% of titanium oxide, at the same time keeping the same behavior in relation to the light barrier. However, a significant addition of iron oxide could reduce the whiteness of the composition to below an acceptable level. Practically, the composition and made of it the product should preferably have a value of L*≥88 and the value b*>0.

currently, it has been unexpectedly discovered, for polymeric composition containing PET, simultaneous optimization in relation to the light shielding properties and white compositions, as well as in relation to its manufacturability and cost can be achieved when the mass ratio of the titanium oxide/iron oxide in the range from 150 to 250.

Below is table 2, which presents the results for levels of light transmission at wavelengths of 550 nm and the coordinates in the three-dimensional color space for four actually made containers (bottles with wall thickness = 0.25 mm).

Table 2
TiO2(% wt.)Fe3O4(ppm)T550nm(%)Color L*/a*/b*
C2902,694,5/-1,3/3,7
C392001,1391,0/-1,0/2,8
A194000,0888,8/-0,5/1,5
the 4 97000,0686,5/-0,4/0,4

Table 2 shows the light shielding properties and color bottles with different content of iron oxide. Obviously, light shielding properties are improved by increasing the content of iron oxide, while at low contents of iron oxide properties against light transmittance are unsatisfactory. Color is also exposed to, i.e. the value of L* (white) decreases with increase in the content of iron oxide. Increased levels of iron oxide from 400 to 700 ppm does not result in additional significant improvement in light-protective properties, but leads to lower values of L* below an acceptable level 88, which is a disadvantage. In fact, the sample with the mass ratio of the pigments according to this invention (sample A1) gives the best balance of light shielding properties and color.

The results for a wavelength of 550 nm can be extended to the whole range of wavelengths from approximately 400 to 700 nm, as is evident from the measurements shown in figure 1.

The above mass ratio is preferably in the range from 155 to 245, more preferably in the range from 160 to 240, more preferably in the range from 165 to 235, and the effect of sootvetstvenno is increasing. Even better results are obtained with the more preferred mass ratios of from 170 to 230. The most preferred mass ratio is in the range from 222 to 228.

Below is a table 3, which compares light and color properties of two bottles (wall thickness = 0.25 mm), which have different concentrations of the pigments of titanium oxide and iron oxide, respectively, but which maintain the same mass ratio of the titanium oxide/iron oxide equal to 225.

Table 3
TiO2(% wt.)Fe3O4(ppm)T550nm(%)Color L*/a*/b*
A194000,0888,8/-0,5/1,5
C541782,3388,8/-0,5/1,8

The decrease in the concentration of these two pigments leads to a slightly lower light shielding properties, but the color does not change. This shows that the constant ratio dogpilecom within a particular this invention range enables to obtain an acceptable bottle with the most high light shielding properties with a minimum amount of titanium oxide. These examples are proof of the preferred balance of properties provided by the ratio of the pigments according to this invention.

The above results are supported by the data presented in figure 2 and 3. Figure 2 shows the impact of adding iron oxide to titanium oxide in the range of wavelengths from 400 to 700 nm for a constant mass ratio 225/1. In addition, figure 3 shows the dependence of the transmittance at 550 nm on the concentration of TiO2for a group of samples (bottles) using as a pigment only titanium dioxide (stars) and for the group of samples containing TiO2and Fe3O4(circles). Experimentally obtained points are approximated by exponential dependence, which is calculated by the equation shown in Figure 3. In this equation, y represents the transmittance at 550 nm, "x" represents the concentration of TiO2a R2 represents the correlation coefficient, which shows how well this line corresponds to the experimental points. At the chosen wavelength of 550 nm of the joint use of iron oxide in addition to titanium oxide, again when the mass ratio 225/1, leads to a sharp decrease in transmittance already at low concentrations of titanium oxide.

How about analog above, optimization of various properties of the polymer compositions according to the invention can basically be managed independently from the absolute contents of titanium oxide and iron oxide, respectively. However, for economic reasons and in order to provide improved manufacturability, is generally preferable content is low. Due to a synergistic effect against the best light shielding properties and balanced the colors are achieved with the combination of titanium oxide and iron oxide in the ratio according to this invention, it is possible to apply a sufficiently small quantities of these two pigments, at the same time still getting an excellent light shielding properties, which can further reduce costs. For example, this can be seen from the graphs shown in Figure 4. Adding only 180 ppm of iron oxide, which gives the mass ratio of the two pigments of about 222, you can save approximately 43% of titanium oxide, while achieving the same results in respect of the transmittance in the region of wavelengths from 400 to 700 nm.

If the titanium oxide and iron oxide are present in the above ratio, in addition to the significant improvement of the light protection properties are also observed an increased affinity between the applied pigments and polymer matrix.

Although the absolute content of the two main pigmentation treatment is now are not critical, excellent results are obtained already at relatively low concentrations of these pigments. To achieve significant reflecting the content of the titanium oxide preferably should be ≥2% wt. However, the introduction of a very large amount of this pigment could compromise the mechanical properties of the polymeric composition and could lead to worse affinity with the polymer matrix. Thus, as the upper limit of the content of titanium oxide is preferably ≤11% wt.

Similarly, the corresponding absorbing properties receive already at very low content of iron oxide, of order ≥0,01% wt., through his interaction with the pigment - titanium oxide. The high amount of iron oxide can cause low white, so the content of iron oxide should preferably be not greater than 0.07 wt.%, that is, preferably ≤0,07% wt.

As two specific examples of implementation should be mentioned a combination of 9% wt. titanium oxide with 0,040-0,045% wt. iron oxide, specifically, 9% wt. titanium oxide with 0,040% wt. iron oxide; and a combination of 3.9 wt.%. titanium oxide with 0,0185% wt. iron oxide, while the remainder of the corresponding composition is a PET. In both cases, it is preferable that TiO2used in combination with Fe3O4. For the case of 9% wt. oxide Titus is on and 0,040% wt. (400 ppm) iron oxide figure 5 shows that a very small amount of iron oxide used in addition to titanium oxide at a mass ratio of 225, leads to the same characteristics in respect of transmittance, which can be obtained in the case of a sample containing more than three times the amount of titanium oxide (since the actual test sample with 28% of TiO2we did not do that for this sample was calculated theoretical curve according to equation 3).

In addition, owing to the positive effect from the introduction of Fe3O4the composition according to this invention essentially does not contain activated carbon, carbon black or free carbon in other forms.

As mentioned above, a good light shielding properties is often necessary in order to protect packaged foods from decomposition caused by light. Thus, it is preferable that the wall of the container made from the polymer compositions according to the invention, for example, by a method of blowing, and the wall thickness of 0.29 mm and at a wavelength of 550 nm had a transmittance for light, which is irradiated (when measured in full sphere)of ≤0,5%. More preferably, the transmittance is ≤0,4%, even more preferably ≤0,3%, even more preferably ≤0,2%.

the Preferred examples of the container, made from polymer compositions according to this invention, are bottles, cans, barrels, packages, and boxes, as well as blanks for them. Preferred are bottles, especially single-layer bottles, as well as blanks for them.

Containers can be used for packaging light-sensitive goods, especially food products, including beverages. Therefore, preference is given to the use of containers containing polymer composition according to this invention, for packaging light-sensitive goods, particularly food and beverage products, such as dairy products.

Conducted some experiments that confirm good properties in this respect. Table 4 shows the results obtained with two different containers (1.5 l): A) single-layer bottle, 45 g, the wall thickness of 0.29 mm, with 9% of TiO2and C) single-layer bottle, 45 g, the wall thickness of 0.29 mm, on the basis of the present invention, with 9% of TiO2plus 400 ppm Fe3O4. In these experiments bottle of this composition were filled with pasteurized skim milk, and then they were kept in harsh conditions (climatic chamber at 25°C and 800 Lux lighting from the lamp cool white fluorescent light (OSRAM L18W10)). Were conducted sensory and chemical analysis at different values of the retention time. ensory test conducted by the group of experts on dairy products, which assessed the quality of the milk on a scale from 0 (poor quality) to 10 (best quality). In addition, there were several tests for vitamin B2 (Riboflavin).

Table 4
CompositionT, 550 nmThe sample of milk (5 weeks)Riboflavin (source)Riboflavin (2 weeks)Riboflavin (5 weeks)
Bottle And9% of TiO22,4%51500 ppm1131 ppm662 ppm
Bottle9% of TiO2+ 400 ppm Fe3O40,18%81500 ppm1446 ppm1286 ppm

The results of both sensory and chemical analyses show significantly better storage in bottles Century. the Light shielding barrier, which possess these bottles (the transmittance at 550 nm = 0,18%), provides effective protection organoleptic pitatelnyh properties of pasteurized milk.

The method including the following stages, results in a polymer composition from which further processing can easily get high quality billet container for food, and then himself such a container, especially a bottle:

- obtaining ester of terephthalic acid and ethylene glycol;

- adding titanium oxide and iron oxide;

- carrying out the polymerization of the obtained reaction mixture;

- granulation polymerized reaction mixture; and

- increase the molecular weight of the polymer obtained in the subsequent process of solid-phase polycondensation.

Next, with reference to Fig.6, described a specific example of the process of obtaining a polymer composition according to the invention.

In the first stage of terephthalic acid (TPA) and ethylene glycol (EG) served in the reactor continuous operation for carrying out the esterification. At this stage, the reaction temperature is usually maintained within the range from 250 to 260°C. the Reaction can be conducted at atmospheric pressure. Through distillation columns eye-catching water is removed from the reaction system.

In the second stage, the reaction mixture obtained in the first stage, served in the batch reactor, the pre-polymerization. In the batch reactor, the add-oxide slurry as is ESA in ethylene glycol, a suspension of titanium oxide in ethylene glycol and the catalyst. These two suspensions are described below. The reaction temperature in this second stage is usually somewhat higher than in the first stage, for example, from 260 to 270°C., while the pressure may be atmospheric.

The advantage is that the pigments and especially the titanium oxide added at this stage to even unpolymerized mixture (at this stage, usually the so-called degree of polymerization equal to 4), because the viscosity of the mixture is still very low compared to the viscosity, which is achieved at the end of the polycondensation process. This facilitates the dispersion in the mixture of pigments, primarily larger mass of titanium oxide, and allows you to avoid the formation of agglomerates. Thereby is achieved by optimizing the dispersion of pigments.

In an alternative example implementation, the suspension of titanium oxide with ethylene glycol and/or suspension of iron oxide in ethylene glycol, perhaps in conjunction with the catalyst added to the reactor with continuous action, which is used for the esterification, already at the first stage, because at this stage the viscosity of the mixture is low, which also provides improved dispersibility of pigments. However, in the first stage is terephthalic acid, therefore, the environment one is camping sour. Its acidity promotes the formation of aggregates, especially particles of titanium oxide, so it is preferable to add suspensions in the second stage, as described above.

In the third stage, the reaction mixture obtained in the second stage, served in one reactor periodic action where conduct the polymerization. In this case, you can optionally slightly increase the reaction temperature, for example, to a value of from 285 to 290°C. Preferably the reaction is continued at this stage under reduced pressure, and you can use vacuum of about 133 PA (1 Torr).

In the fourth stage of the obtained cured substance granularit in the system granulation. When granulating receive formless particles of polymer compositions which have a characteristic viscosity (HV) is about to 0.60 DL/g

At the fifth stage, the molecular weight of the cured resin increases through a continuing process of solid-phase polycondensation (TFPC). This stage of the process usually produces a final product with a characteristic viscosity of about to 0.80 DL/g in the Usual process parameters are a temperature of from 215 to 220°C and atmospheric pressure.

This method of polymerization results in a polymer composition with excellent performance, which indicates that additional benefits than the Oia with alternative possibilities of introduction of the ingredients, such as, for example, the use of mixtures or technology with the introduction of a concentrated mixture of ingredients ("master batches"). Namely, it is possible to introduce a large number of pigments (for example, above the content of titanium oxide 9% would be unusually high concentration to be added in the form of masterbatches) while achieving uniformity and a high degree of dispersion, while maintaining the integrity of the molecular chains.

Additional advantages of the described method in comparison with the technology introduction uterine mixtures are lower price and superior quality product. More specifically, for obtaining masterbatches PET resin melted in the extruder, double screw and to it add the pigment. Then, the resulting melt ekstragiruyut and cut to obtain a concentrated mixture of ingredients. If the workpiece is produced by injection, uterine mixture is again melted in the injection. On the contrary, if the workpiece is obtained using the resin obtained in the polymerization process, you need only one fusion, namely in the plant for injection. Thus, no additional hardware is required, such as an auxiliary dryer and dispensers that are required to obtain master batches.

As for quality, the distribution of pigment in Koh is anere, for example in the bottle, which is obtained in the polymerization process, as well as the dispersion of titanium oxide will be better in comparison with these characteristics a container obtained from a concentrated mixture of ingredients. The pigment concentration in the workpiece, and in the final container is very accurate because of its control during polymerization. In contrast, when using master batches for process injection concentration of pigment masterbatches is very high (typically 50-70%), and to obtain the necessary concentration of this mixture is mixed with a standard PET screw in the injection unit installation. The resulting mixture is not completely homogeneous, and sometimes there are changes in the concentration of the pigment in the blanks obtained in one working cycle (for example, 48; 72; 96 and 144 items). In addition, the uneven distribution of masterbatches in the polymer mixture leads to a significant tendency to delamination of the final products, especially ready-made bottles.

While the concentration of the pigment in the blanks obtained by a polymerization process, is exact in the continuous process, small fluctuations in the dosing device of the process of obtaining uterine mixtures over time, lead to significant differences in the concentrations of pigments in the blanks. Therefore clicks the zoom, at a later stage blowing is hard to control this stage of blowing, because you are changing the quality of the proposals submitted at this stage of preparations. In addition, if you want to guarantee some level of content of pigments in the final containers, it is necessary to apply an excessive amount of masterbatches to ensure that no blanks with less than the required pigment content.

In addition, the mechanical properties of the final containers affects the characteristic viscosity of the polymer. In accordance with the method of polymerization according to this invention is finite viscosity set about to 0.80 DL/g When it is injected using standard masterbatches, polymer viscosity, usually component to 0.80 DL/g, are mixed with the mother mixture viscosity, is usually component of less than 0.60 DL/g Thus, the characteristic viscosity in the workpiece and the target container is reduced, and the mechanical properties deteriorate (Fig.9).

Due to the above advantages of the workpiece according to the invention is produced by injection of a polymer obtained in the polymerization process, for example polymerization described above in the present description.

In addition, as can be seen from the described scheme of the production process, one of the characteristics of this process is the inclusion of all it is possible to light protection agents (pigments) already in the initial stages of the polymerization process.

The introduction of Ti and Fe is carried out by adding separate suspensions (suspensions) of these components in ethylene glycol at the stage of esterification of this process. The preparation of the suspensions described in Fig.7 and 8, respectively. In both cases, mix the metal oxide and ethylene glycol. Then spend the first treatment for dispersing, during which the suspension of metal oxides with particle sizes of approximately 5 μm (titanium oxide), or about 10 μm (iron oxide).

For the effective use of appropriate pigments and prevent clogging of filters, as well as to avoid the formation of agglomerates, which can adversely affect the final appearance, processability and final functional properties of the containers, preferably subsequent stage of grinding in which the particle size of pigments is reduced to about 3 microns, more preferably to below 3 microns, even more preferably to below 1 micron.

1. Polymer composition to obtain food containers, including polyethylene terephthalate, titanium oxide and Fe3O4, characterized in that:
the mass ratio of the specified titanium oxide and the Fe3O4is in the range from 150 to 250,
the contents of the specified titanium oxide is from 2 to 11 wt.% calculated on the total mass com is osili, and
the contents of the specified Fe3O4is from 0.01 to 0.07 wt.% calculated on the total weight of the composition.

2. Polymer composition according to claim 1, where the specified polymer composition is granulated.

3. Polymer composition according to claim 1 or 2, obtained by polymerization.



 

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FIELD: transport.

SUBSTANCE: invention relates to hybrid parts or low-weight parts with cavities consisting of cup-like base reinforced by thermoplastic materials. The latter contain 10-99.99 wt % of, at least, one partially crystalline thermoplastic polymer and 0.01-50 wt % of, at least, one olefin copolimerisate with one ether of methacrylic acid or ether of acrylic acid of aliphatic alcohol. Fluidity index of copolimerisate melt makes, at least, 100 g/10 min.

EFFECT: higher breaking strength, hardness and durability.

4 cl, 3 dwg, 4 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: composition contains at least one matrix polyester polymer and at least one filler. Said matrix polymer is obtained via polymerisation of a mixture containing a dicarboxylic acid and a diol. Characteristic viscosity of the matrix polymer at 30°C in a mixed solvent ranges from 0.7 to 0.9. The filler is selected from organoclay which exfoliate in polyamide, containing polymerised meta-xylene diamine links, and organoclay in form of nanoplates.

EFFECT: obtaining compositions used to mould containers, demonstrating improved gas-permeability characteristics.

38 cl, 1 tbl, 5 dwg, 12 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a thermoplastic moulding composition which is flame retardant and impact resistant. The thermoplastic moulding composition for making moulded articles contains aromatic polyester carbonate, polyalkylene terephthalate, graft copolymer having a nucleus-shell morphology, having a graft shell which contains polymerised alkyl(meth)acrylate, and a nucleus made from composite rubber which contains interpenetrating and inseparable polyorganosiloxane and poly(meth)alkyl acrylate components in form of particles having size from 0.05 to 5 mcm and glass transition temperature lower than 0°C, and where the weight ratio polyorganosiloxane/poly(meth)alkyl acrylate/hard shell equals 70-90/5-15/5-15, and a phosphorus-containing compound (IVa), where R1, R2, R3 and R4 denote phenyl, R5 denotes hydrogen, n equals 1, q ranges from 1 to 2, Y denotes C(CH3)2 and fluorinated polyolefin.

EFFECT: high resistance to inflammation and impact strength.

8 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to pigment compositions suitable for use as admix pigments. Disclosed is a solid pigment composition containing a pigment and a dispersant resin. Said composition contains at least 35 wt % of at least one pigment and not more than 65 wt % dispersant resin of the total weight of the pigment and dispersant resin. The dispersant resin contains a backbone polymer chain formed by esters containing an electron-depleted C=C double bond and having at least one side hydrophilic group of polyalkylene oxide monoalkyl ether. Said dispersant resin contains 30-80 wt % alkylene oxide links and has average molecular weight from 1000 to 150000. The invention also discloses a method of preparing said pigment composition, a method of obtaining a coloured coating composition and use of said dispersant resin to prepare admix pigment compositions.

EFFECT: invention provides pigment compositions compatible with various diluents and binders, suitable for use as admix pigments to obtain paint which is stable even when using pigments which are hard to disperse and stabilise.

12 cl, 4 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: composition contains polyether thermoplastic, olefin copolymers and a resin which contains aromatic fragments and hydroxyl groups.

EFFECT: composition provides a high level of physical and mechanical properties and increases chemical resistance to process fluids of spacers made from said composition.

7 tbl, 15 ex

FIELD: chemistry.

SUBSTANCE: composition contains the following in %: a) 35-78% aromatic polycarbonate, b) 6-55% thermoplastic polyester - polyethylene terephthalate, c) 5-15% halogenated acrylate, d) 3-15% impact resistance modifier, e) 2-15% phosphate-containing compound and f) 0.05-0.5% fluorinated polyolefin. The acrylate contains repeating structural units of the following formula: in which R1, R2, R3, R4 and R5 denote hydrogen, alkyl or aryl, n ranges from 0 to 5, m ranges from 10 to 10000, and R denotes halogen. The phosphate-containing compound is selected from a compound of formula (III) O-P-[-OCH2C(CH2Br)3]3 (III) and compounds of formula , in which R1, R2, R3 and R4 denote C1-C8-alkyl, C5-C6-cycloalkyl, C6-C20-aryl or C7-C12-aralkyl, unsubstituted or substituted with alkyl, n equals 0 or 1, N equals 0.1-30, X denotes a mono- or polycyclic aromatic residue with C6-C30 or a linear or branched aliphatic residue with C2-C30.

EFFECT: invention enables to obtain a composition with higher impact resistance and fire resistance.

3 cl, 1 tbl, 4 ex

FIELD: machine building industry.

SUBSTANCE: thermoplastic composition contains, in wt. parts: A) from 10 to 90 of aromatic polycarbonate; B) from 10 to 90 of, at least, one composition selected from a group consisting of: modified rubber of graft copolymer (B.1) or pre-compound or mixture from (B.1) with (co)polymer (B.2) free from rubber of, at least, one of monomer, selected from a group consisting of vinyl aromatic compositions, vinyl cyanides, alkyl ether (met)acryl acid with 1-8 carbon atoms in alkyls, unsaturated carboxylic acids and anhydrides and imides of unsaturated carboxylic acids; C) from 0.005 to 0.15 in terms of 100 weight parts of a combination of A and B components, of at least one aliphatic and/or carboxylic acid and D) at least, one additive. In addition, C component is either added to the melt containing A and B components, or pre-mixed up with B component at 180-260°C. This mixture is then mixed up with A component at compounding stage or B and C components mixture in a melted condition is mixed up with A component melt at 220-300°C, and all components are then dispersed.

EFFECT: invention ensures production of modified shock-resistant polycarbonate compositions, which are specific by their improved resistance to hydrolysis and light shade of raw product suitable for production of complicated molded items production.

16 cl, 2 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: composition contains the following, %: (A) 9.9-99.8 polycarbonate resin based on bisphenol A; (B) 0.1-90 polyethylene terephthalate, and (C) 0.1-30 grafted rubber, as well as 0.1 pts.wt heat stabiliser, 1 pts.wt dye and 0.7 pts.wt UV absorber. The grafted rubber consists of 30-80% substrate and 70-20% solid graft phase. The graft phase is obtained through copolymerisation of a monomer from a first group consisting of styrene, α-methylstyrene, styrene which is halogenated in the ring and styrene which is alkylated in the ring, and a monomer from a second group containing (meth)acrylonitrile and maleic anhydride, with the weight ratio of said monomers ranging from 90:10 to approximately 50:50. The substrate contains the following, %: (C1) 1-50 core of cross-linked polymerised vinyl monomer and (C2) 50-99 shell of cross-linked polymerised acrylate with glass transition point lower than 0°C.

EFFECT: invention enables to obtain articles characterised by intense lustre, high impact strength and absence of tiger stripes.

8 cl, 1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention includes polymer interlayers, applied in multi-layered glazing panels. Interlayers include thermoplastic polymer, plasticiser, tungsten oxide agent and stabilising agent which prevents tungsten oxide destruction.

EFFECT: interlayers possess improved characteristic of blocking ultraviolet light, support optic quality in the course of time.

7 cl, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a resin composition for making moulded articles, which efficiently block thermal radiation of sunlight and are excellent in terms of transparency, as well as articles moulded from said composition. The resin composition contains an aromatic polycarbonate resin (component A), particles of a hexaboride of at least one element selected from a group consisting of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sr and Ca, (component B-1) and at least another resin (component B-2) different from component A, and nitride particles. The other resin (component B-2) is selected from a group comprising acrylic resin, polyurethane resin, polyether resin and polyester resin. Total content of component B-1 and component B-2 ranges from 0.001 to 1 pts.wt per 100 pts.wt component A. The resin composition contains particles (1) formed from component B-1 and particles (2) formed from component B-1 and component B-2. Particles (1) and particles (2) are characterised by number-average diameter of secondary particles of 50 mcm or less, and maximum diameter of secondary particles of 300 mcm or less. The resin composition is obtained by mixing component B-1 and component B-2. A component B is obtained, which is mixed with component A. A mother batch is obtained, which is mixed with component A. An article is moulded from the resin composition.

EFFECT: resin composition for obtaining moulded articles which efficiently block thermal radiation of sunlight and are excellent in terms of transparency.

15 cl, 2 dwg, 2 tbl, 2 ex

FIELD: construction.

SUBSTANCE: asphalt-concrete mixture contains crushed stone, crushed stone siftings, sand and oil bitumen of grade BND 90/130. Besides, oil bitumen is modified with rubber crumb with size of 0.75 mm, mechanically activated jointly with magnesium nanospinel. The ratio of components in the modified bitumen is as follows: bitumen - 100%, rubber crumb - 7% from bitumen weight, magnesium nanospinel - 0.5% from bitumen weight.

EFFECT: improved complex of strength properties.

1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: polymer composite has a layered structure formed by layers of a polymer with nanosized thickness between layers of antipyrene-modified bentonite. The bentonite composition contains not less than 70-72% montmorillonite, with content of the latter in the composite not less than 5 vol. %.

EFFECT: composite is relatively cheap and has high fire-resistance.

2 cl, 2 dwg, 1 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention can be used in cosmetic industry when producing preparations which protect the skin from UV radiation. The finely dispersed titanium dioxide-based composite contains finely dispersed titanium dioxide particles which are combined with one or more polymers containing constituent monomers in form of carboxylic acid and/or a carboxylic acid derivative represented by the formula , where R is a C1-C15 alkenyl group, wherein hydrogen atoms can be substituted with a carboxyl group or a hydroxyl group; and X is a hydrogen atom or an alkali metal or a polyoxyethylene or polyoxypropylene group with 1-12 bonded moles. The average peak width of the maximum diffraction intensity assigned to titanium dioxide crystals is 2.0° or less in X-ray powder diffraction analysis.

EFFECT: invention increases transparency and stability of finely dispersed titanium dioxide-based composite, UV radiation absorption capacity thereof and re-dispersion capacity thereof.

11 cl, 9 tbl, 12 ex

Rubber mixture // 2461591

FIELD: chemistry.

SUBSTANCE: rubber mixture contains the following in pts.wt: isoprene rubber 30-70 combined with butadiene rubber 30-70, hydrocarbon resin 0.5-3.0 combined with colophony 0.5-3.0, silane-modified talc 5-20, petroleum oil 4-10. The rubber mixture also contains the following in pts.wt: sulphur 1.2-1.8; zinc oxide 5; stearic acid 1-2; protective wax 2; N-isopropyl-N'-phenyl-n-phenylene diamine 1-2; polymerised 2,2,4-trimethyl-1,2-dihydroquinoline 2; N-cyclohexylthiophthalimide 0.2-0.3; benzoic acid 0.2-0.3; N-cyclohexyl-2-benzthiazolylsulphenamide 0.8-1.2 and technical carbon 40-50.

EFFECT: invention increases dynamic endurance of rubber in conditions where an industrial rubber article operates under pressure.

2 tbl

FIELD: metallurgy.

SUBSTANCE: composition includes high pressure polyethylene, decabromodiphenyl oxide, maleic anhydride, as well as copolymer of ethylene and vinyl acetate, antimony trioxide, magnesium hydroxide modified with organosilanes and Penta®-1006 plastic modifying agent.

EFFECT: increasing thermal resistance of polymer composition for fabrication of products using extrusion, die casting and pressing methods at maintaining its compliance with burning resistance category.

2 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: composition contains liquid low-molecular weight siloxane rubber, ethyl silicate-40 or tetraethoxysilane as a structure-forming agent, tin dichloride dihydrate and calcium oxide as a catalyst, as well as a borosiloxane oligomer. Components of the composition are in the following ratio in pts.wt: liquid low-molecular weight siloxane rubber 100, structure-forming agent 10-20, tin dichloride dihydrate 2-4, calcium oxide 2-4, borosiloxane oligomer 10-20.

EFFECT: composition provides high binding strength of the coating made from said composition with synthetic fabric and significantly reduces rigidness of the obtained material.

1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: method of producing nanocomposites involves coating nanoparticles with mean particle size from 1 nm to 100 nm with dicarboxylic acid; mixing nanoparticles coated with dicarboxylic acid with a cross-linking agent to obtain a starting mixture; mixing the starting mixture with polyester to form a polyester-based nanocomposite.

EFFECT: low crystallisation temperature and high glass-transition temperature of the nanocomposite compared to polyester.

14 cl, 7 dwg, 2 ex

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