JPS6250356A - Transparent polyvinyl chloride product and composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION BACKGROUND OF THE INVENTION Polyvinyl chloride (PVC') has had many commercial successes as a material that can be formed into useful products. In that case, it can be molded, extruded, rolled or formed and its low cost has contributed to this good result. However, these vinyl chloride polymers are particularly susceptible to decomposition by heat due to the high temperatures at which these polymers are processed to be manufactured into useful products, protecting these vinyl chloride polymers from thermal decomposition To do this, materials commonly known as stabilizers are added.

PVC itself is not thermostable. It would be impossible to process it on industrial machinery without using stabilizers. During processing at high temperatures (approximately 200° C.), this instability leads to loss of hydrochloric acid and color formation.

These two phenomena can be explained by the following reaction: Thermosensitive Site New Thermosensitive Site CI CI . Hydrochloric acid is released from the heat sensitive site, which is allyl chlorine. If hydrochloric acid is released,
A double bond and a new active site are formed. Decomposition continues with successive releases of large amounts of hydrochloric acid and the creation of long sequences of double bonds that interact for color. This dechlorination reaction is catalyzed by the presence of bases, acids and certain salts.

Hydrochloric acid and zinc chloride are particularly bad and their presence should be limited.

The most commonly used heat stabilizers to prevent this decomposition are metal salts, such as organic salts of tin, calcium and zinc. In many cases, colorants are added to polyvinyl chloride to produce colored products, but for some applications a transparent product is desired.Products for the market, such as bottles, packaging and films, are , requiring high transparency.

To achieve high clarity, tin stabilizers are usually mixed into the vinyl polymer. However, tin stabilizers are known to impart undesirable taste and odor to the contents of tin-stabilized PVC products. For example, when stabilizing a PVC water bottle, within a very short time,
The water will have an undesirable odor and taste.

For products where taste and odor are important, calcium/zinc stabilizer systems are usually used. The calcium/zinc stabilizer acts by neutralizing the hydrochloric acid that is formed and stopping the production reaction. Zinc compounds are II
Reacts with cN to form zinc chloride. Zinc chloride is also
It is a catalyst for decomposition. This is because calcium stabilizers are used. The calcium reacts with zinc chloride to form calcium chloride, which has no catalytic effect on decomposition. The zinc salt limits the initial development of color by reacting with hydrochloric acid, but causes sudden decomposition. The calcium salt slows decomposition but allows for early development of color.

These opposing effects should be overcome.

Calcium/zinc stabilizer systems do not impart unpleasant tastes and odors. However, other problems exist with calcium/zinc stabilizer systems. One is the clarity of the product, for example the bottle, and it does not impart the same clarity as tin stabilizers.

Also, previously known calcium/zinc stabilizer systems develop "brushing", where the walls of the bottle become cloudy upon exposure to alcohol and water.

Its calcium/zinc stabilizer system is approved by the U.S. Food and Drug Administration (U.S.) for use in contact with food and beverages.
Food and Drug Administrator
ion). Other materials known as co-stabilizers are typically used with the calcium/zinc stabilizer system. The most widely used P
The calcium/zinc stabilizer system for VC is a combination of at least four components: zinc soap, calcium soap, epoxidized fatty ester, and non-toxic organophosphite ester. The above stabilizer system provides short color stability times with good yellowness or initial color. It is then necessary to use further co-stabilizers to enhance thermal stability while retaining low yellowness and good processability of the bottle composition. Generally, alcohols are added to increase thermal stability, but they cause "brushing." Brushing problems arise when the bottle contains an alcoholic solution, e.g. in the case of an intraluminal irrigation bottle.
This is especially important.

The technology of PVC formulation is very complex as many components interact with each other. This complexity means that the levels of ingredients and types of ingredients should vary to yield a product that is useful for a given application. It is not as simple as adding one component that improves a particular property but does not affect other important properties.

Calcium/zinc stabilized PVC products, such as bottles (which will have high clarity and low brushing), and substantially no tin stabilizer, which will not impart taste and odor to the product's content. Or it is highly desirable to not include it completely.

It would also be desirable to improve the calcium/zinc stabilizer system to provide the system with thermal degradation resistance.

In the margin below [Summary of the Invention] PVC products have the following characteristics: (a) When measured according to ASTM D-1746, by the following formula: % Light Transmission = 100 - (460 x thickness in inches) (b) high transparency as defined by having a higher % light transmission than stated;
Measured according to ASTM D-1003-61 and with the following formula: % Haze = % Haze of value lower than stated by thickness at 184.6 x inches; (c) 50150 for 48 hours at 50°C Brushing less than 30% at 0.065 inch thickness after exposure to ethanol/water solution; (d) 200°C according to ASTM D-1925.
and (e) the property of not imparting an unpleasant taste and odor to other materials when they are brought into contact with the PVC product.

PVC products as characterized above may be
(c) and further the following properties.

(f) For uncolored compounds, ASTM
Yellowness index less than 13% at 0.065 inch thickness when measured according to D-1925; (g) 8 STM at 200°C according to D-1925;
(h) the composition is substantially free of tin stabilizers; and (h) the composition is substantially free of tin stabilizers.
A preferred feature is the absence of tin stabilizers.

The composition contains at least one compound selected from the group consisting of compounds of the following formula: %Formula %. X in the above formula has 2 to about 20 oxygen atoms, preferably 2 to 10 and more preferably 2 to 6
A straight chain, branched or cyclic group having 5 oxygen atoms.

At least one of said oxygen atoms should form an ether bond, and the remainder may form ether, epoxy or hydroxy bonds or mixtures thereof.

X also has from about 4 to about 60, preferably from 6 to 30°, more preferably from 6 to 20 carbon atoms.

R is about 5 to about 40. Preferably it is a straight chain group having 12 to 20 carbon atoms.

[Specific explanation]

The new and highly transparent PVC products of the present invention include bottles,
Including products such as jars, packaging materials and the like.

The products will include products that are liquid or solid. Particularly useful products of the invention are PVC bottles, in particular these should be transparent and impart no taste or odor to the contents of the bottle. The products most sensitive to taste or odor are, of course, those intended for human consumption, such as mouthwashes, water, beverages, and the like. Products referred to herein are also packaging materials, including solid products.

Sometimes only part of the packaging material is transparent PVC, and the rest can be other materials, such as paper, metal or other materials. An example of the invention would be a vacuum formed blister package, where the top would be clear PVC and the bottom would be cardboard.

The invention will be described with respect to a clear PVC bottle to illustrate embodiments, but those skilled in the art will readily be able to apply the invention to other products.

The new high clarity bottle is manufactured from a polymer composition consisting of a vinyl polymer and other essential formulation ingredients.

PvC, vinyl polymers or vinyl polymer materials as used in the present invention relate to homopolymers and copolymers of vinyl halides and vinylidene halides, such as vinyl chloride, vinyl bromide, vinylidene chloride, and the like. Vinyl halides and vinylidene halides can be copolymerized with each other or with one or more polymerizable olefinic monomers having at least one terminal @C11,=C group. Examples of such olefinic monomers include α5β-olefinically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, α-
Cyanoacrylic acid and the like; esters of acrylic acid, such as methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, cyanoethyl acrylate and the like; esters of methacrylic acid, such as methyl methacrylate, butyl methacrylate, and the like. Litriles, such as acrylonitrile, methacrylaterile and the like; Acrylic 7mides, such as methylacrylamide, N-methylolacrylamide, N-butyoxymethacrylamide and the like; Vinyl ethers, such as ethyl vinyl ether, chloroethyl vinyl ether and the like. ; vinyl ketone; styrene and styrene derivatives;
For example, methylstyrene, vinyltoluene, chlorostyrene and the like; vinylnaphthalene, allyl and vinylchloroacetate vinyl acetate, vinylpyridine, methylvinyl ketone; diolefins such as butadiene, isoprene, chloroprene and the like; and those skilled in the art There are other polymerizable olefinic monomers known in the art.

The present invention is based on the weight of a homopolymer and a heptamer mixture obtained by polymerizing only vinyl chloride or vinylidene chloride,
l which can be copolymerized with them in amounts up to about 20% by weight.
or to copolymers produced by mixing with multiple polymerizable olefinic monomers. Copolymers tend to reduce the clarity of the product and therefore their amount should be minimized. The most preferred vinyl polymer or resin is polyvinyl chloride (PVC), which is produced by bulk polymerization methods, and for simplicity and convenience, the present invention will be described herein with:
And it will be understood that this is merely intended to be illustrative and not restrictive. The bulk polymerization method produces resins that lack the pericellular membranes present in resins produced by suspension polymerization methods. The products of the invention may be manufactured from suspension or bulk resins.

The high clarity bottle of the present invention has, in addition to the vinyl polymer described above, an essential stabilizer system.

A common stabilizer system used in conventional transparent PVC bottles is a tin stabilizer system. Tin stabilizers cause unpleasant tastes and odors in products such as mouthwashes, bottled water, beverages, and the like. Since the bottles of the present invention do not impart taste and odor to the bottle contents, tin stabilizers should be substantially avoided, and preferably avoided completely. The level of tin stabilizer should be less than about 0.1 parts by weight per 100 parts by weight of vinyl polymer.

To achieve the necessary high degree of stability, a calcium/zinc stabilizer system may be used in the polymer composition used to make the bottles of the invention. At least one calcium soap and one zinc soap may each be used at a level of about 0.005 to about 1.0, preferably about 0.03 to about 0.3 parts by weight per 100 parts by weight of vinyl polymer. Preferably, the level of zinc soap is higher than the level of calcium stone M. The level of calcium soap may be very low or not present at all in the present invention. In the most preferred embodiment, the zinc soap is about twice the level of calcium soap.

Examples of suitable calcium soaps are calcium stearate, calcium laurate, calcium oleate, calcium valmitate, calcium octoate and calcium benzoate. Calcium stearate is the most preferred calcium soap. Examples of suitable zinc soaps are zinc stearate, zinc laurate, zinc valmitate, zinc 2-ethylhexanate, zinc octoate,
Zinc oleate and zinc benzoate. Zinc stearate is the most preferred zinc soap.

In addition to the calcium/zinc stabilizer system, the polymer composition includes co-stabilizers. Further, the stabilizer that functions as a lubricant in the present invention is at least one compound selected from the group consisting of compounds of the following formula: % Formula %. X in the above formula is a straight chain, branched or cyclic group having from 2 to about 20, preferably from 2 to 10 and more preferably from 2 to 6 oxygen atoms. at least one of said oxygen atoms should form an ether bond;
and the remainder will form ether, epoxy or hydroxy bonds or mixtures thereof. X also has about 4 to about 60 carbon atoms, preferably 6 to 30 and more preferably 6 to 20 carbon atoms. R is about 5 to about 40
, preferably 12 to 20 carbon atoms.

Compounds according to the above formula may be prepared by reacting glycerol, such as triglycerol or hexaglycerol, with a fatty acid, such as stearic acid.

The term fatty acid as used herein tends to mean that one purified fatty acid may be used or a mixture of fatty acids may be used. Glycerol can be reacted with a hydroxy fatty acid, such as 12-hydroxystearic acid, to form one costabilizer of the present invention. Glycerol can also be reacted with long chain alcohols such as dodecyl alcohol. These co-stabilizers can also be prepared by using glycerol, such as ethylene glycol or propylene glycol, and by reacting these glycerols with fatty acids, hydroxy fatty acids or long chain alcohols.

The costabilizers of the invention according to the above formula can also be prepared from mixed glycols, which can be synthesized by etherification of glycerin with propylene glycol or ethylene glycol or other glycols. The synthesized mixed glycols can then be reacted with fatty acids, hydroxy fatty acids or long chain alcohols to produce the novel co-stabilizers of the present invention. In addition, polyhydroxy alcohols are
During glycerol synthesis, it can be used in the presence of glycerin. Suitable polyhydroxy alcohols include trimethylolpropane, ditrimethylolpropane, pentaerythritol and dipentaerythritol.

Polyhydroxy alcohols such as ditrimethylolpropane and dipentaerythritol are reacted directly with fatty acids, hydroxy fatty acids or long chain alcohols to produce the novel stabilizers of the present invention.

In the above formula, R is a straight chain group of about 5 to about 40 carbon atoms. Its long R linear chain is important for producing high clarity products due to its miscibility with PvC.

R may be substituted, for example with hydroxy or chlorine. The substitution should be kept to a minimum so as not to affect the compatibility with PVc and therefore the clarity of the product.

R forms a bond with X, and it forms an ester (X
-0-C---) or x-chill (X-0-C---)
It is a combination. Ester bonds are formed when fatty acids are used in making costabilizers, and ether bonds are the result of long chain alcohols.

The novel co-stabilizers of the present invention are rarely pure compounds but mixtures. This mixture occurs due to the impure nature of the reactants and the course of the reaction. for example,
Triglycerol monostearate includes some distearates and tristearates. The glycerol portion of the compound is also composed of different glycerols that are linear, branched or cyclic.

The hydroxy end group in the above formula, 0H-X-0-H, may be replaced by a -0-R group, thus giving the above-obtained formula, R-0-X-0-R. This formula represents materials such as hexaglycerol distearate.

Preferably, the costabilizers of the present invention have the following formula;
n is from 2 to 20, preferably from 2 to 10 and more preferably from 2 to 6, and R is as defined above. The oligo-glycerols are linear, branched or cyclic. Preferred oligos
Glycerol is an ester of oligo-glycerol and fatty acid (where the ratio of glycerol units to fatty acid units is 1:
1, preferably higher than 2:l).

Readily commercially available esters include triglycerol monostearate, hexaglycerol monostearate and hexaglycerol distearate. l
:1 ratio of esters, such as glycerol monostearate, do not work satisfactorily, esters with a ratio of glycerol units:fatty acid units higher than 1:1 act as co-stabilizers to form bottles of high transparency. Surprisingly, it was discovered that it would.

The co-stabilizer can be an oligo-propylene glycol of the following formula: where n and R are as defined above. Examples of oligo-propylene glycol co-stabilizers include tripropylene glycol monostearate, hexapropylene glycol monostearate and tripropylene glycol monolaurate.

The costabilizer can also be an oligo-ethylene glycol of the following formula: where n and R are as defined above. Oligo
Examples of ethylene glycol costabilizers include triethylene glycol monostearate, hexaethylene glycol monostearate, and triethylene glycol monolaurate.

The incorporation level of this new co-stabilizer used is from about 0.2 to about 3.0 parts by weight per 100 parts by weight of vinyl polymer. Preferably, the amount used is vinyl polymer 1
from about 0.4 to about 1.5 parts by weight per 00 parts by weight. Mixtures of several of these co-stabilizers can be used.

For the novel co-stabilizers of the present invention, the calcium soap is reduced to very low levels or completely eliminated;
Therefore, it provides improved initial color retention. This feature is
This is very surprising and leads to the suspicion that the co-stabilizers of the present invention form complexes with zinc chloride and thus supplement the function of calcium soaps.

Besides the novel costabilizers described above, other costabilizers used are costabilizers known to those skilled in the art, such as phosphite stabilizers, polymeric phosphites, β-
diketones and the like. Epoxidized soybean oil also exhibits a dual role as costabilizer and plasticizer. A particularly preferred lubricant that works very well with the esters disclosed above is polyglycerol di- and trioleate.

The composition can also include other ingredients, such as impact modifiers and lubricants that aid in processing the polymer composition into the final product. A small amount of blue pigment can be mixed into the composition to slightly color the product and still retain clarity.

The components of the composition are mixed in parts to form a compound before being formed into the desired product. Mixing can be carried out by any of the conventional methods known to those skilled in the art, such as Banbury mixers, Henschel mixers, mills or other mixers.

The compositions are formed into useful high clarity products by different methods depending on the desired end product. Standard techniques are used to form the product. Suitable methods for manufacturing PVC bottles include extrusion blow molding, injection blow molding and stretch blow molding. The bottle was formed by the extrusion-stretch process disclosed in U.S. Pat. No. 3,980,192, incorporated herein by reference. The film is formed by a rolling method.

PVC bottles are usually about 0.005 inch to about 0.10 inch
It has a wall thickness of 0 inches. The film usually has a thickness of about 0.
0.001 inch to about 0,000 inches thick.

Products made from the compositions described above have unusual and surprising properties. One such property is transparency. Transparency can be measured by the percent transmission of light through the product.

% Light Transmission is measured according to ASTM D4746 on typically 0.065 inch thick samples.

The higher the percent transmittance, the more transparent the sample. A bottle product of the present invention having a thickness of 0.065 inches will have a % light transmission greater than about 70%. Light transmission changes as the thickness changes. The % light transmittance for the products of the invention is the following formula:
% light transmittance = 100-(460X inch thickness)
would be higher than the transmittance explained by. Preferably, the % light transmittance is calculated using the following formula: 2% light transmittance = 10
The transmittance would be higher than that described by 0-(thickness in 400 x inches).

Another important property that the products of the invention should have is low haze. Haze is AST? for a 0.065 inch thick sample. Measured according to I 01003-61. For a 0.065 inch thick sample, the product of the present invention will have a haze level of less than about 12%. As the thickness increases, the % haze will increase. The % haze for the products of this invention will be less than that expressed by the following formula: % haze = 184.6 x thickness in inches.

Preferably, the % meeting degree is calculated by the following formula: % Haze - Thickness in 100 x inches would be lower than that represented by .

Products of the invention should also have good color stability. Color stability is determined by ASTM D after being subjected to high temperatures.
-1925 by measuring the yellowness index at different times. The product of the present invention comprises 20
It should have a black (color change time) of about 16 minutes or more at 0° C. Preferably, the color change time is about 21 minutes or more.

For products containing alcoholic solutions, as in the case of bottles containing mouthwash, the bottle should have one more
One feature is low brushing. Brushing was performed using a 50150 ethanol/water blend at 50°C.
Defined as % haze after 8 hours aging. If the bottle is sensitive to alcohol solutions, it will initially be clear, but will soon begin to cloud. One cause of brushing is that alcohol appears to hydrolyze certain components in the composition. Physical absorption of alcohol or water is another cause of brushing.
After aging in a 50° C. ethanol/water solution for 48 hours at 50° C., it has a % brushing of less than 30% when measured on a 0.065 inch sample.

The products of the invention should also not impart taste and odor to the product's contents. This is best accomplished by using ingredients that do not form soluble compounds with unpleasant tastes and odors. Tin stabilizers should be kept to a minimum or preferably avoided altogether. Tin stabilizer is
During processing of the product, dioctyltin dichloride is formed, which dissolves in water and causes taste and odor.

The novel compositions used to make the products of the present invention have properties of clarity, haze, brushability and low taste/odor, as well as other measurable and necessary properties.

One such property that the compositions should have is that they should have a low yellowness index. PvC
The composition should be processed at a temperature of about 200°C.

At these high temperatures, Pvc compositions tend to turn more yellow the longer they are held at high temperatures. With increasing time at high temperatures, the yellow color changes to amber, then dark amber and finally black. The composition has an uncolored sample of about 1
Provides a low yellowness index of 3 or less and a time to darken of 20 minutes or more. A stabilization time of about 4 minutes will normally be used during processing of the composition into a useful product.

This is because the composition will require a time of about 20 minutes or more before turning black, whereas the final product will have a stability of about 16 minutes or more before turning black. .

Compositions for low taste may also include vinyl polymer 100
It should contain less than about 0.1 part by weight of tin stabilizer, and preferably the composition is free of tin stabilizer.

If clarity is not a desired property, any of the other stabilizers well known in the art may be used with the stabilizers of the present invention. These known stabilizers include tin, zinc and calcium stabilizers, and phosphite and phenol stabilizers. For applications that normally require calcium and zinc soap stabilizer systems, the stabilizers of the present invention can be used and calcium soap levels can be reduced or even eliminated.

The stability of the compositions of the present invention is easily determined according to ASTM D-1925 by measuring the time to black at 202°C.

Compositions of the invention may be prepared by mixing together the ingredients that form the composition. The mixing may be carried out by conventional methods known to those skilled in the art, such as a Banbury mixer,
It can be carried out either in a Henschel mixer, mill or other mixer.

The following examples are presented to more fully illustrate the invention.

In these examples, 24 pvcMi compositions are evaluated for their stability for producing high clarity products, such as PVc bottles. The entire composition was mixed using a two-roll mill mixer, followed by an intensive powder mixer, a Banbury mixer, and conventional mixing methods well known to those skilled in the art. The mixing method is as follows:
Powder mixing at 200@F, Banbury mixing at 300°F, and two-roll milling for 2 minutes at a mill roll temperature of 310'F.

The recipe for the composition being evaluated is as shown in Table 1. Amounts of all ingredients are given in parts by weight based on 100 parts by weight of chloride and nil polymer.

A discussion of the data presented below in the margin Examples 1-24. Example 1 shows a control compound using a tin stabilizer. The color stability time (30 minutes) is good, but the haze is too high and the light transmission is slightly low. Also, because the composition has a tin stabilizer, the composition will impart taste and odor to the contents of bottles made from the composition.

Example 2 shows a previously known good quality PVcMi composition for bottles based on a calcium/zinc stabilizer system. When compared with the tin stabilizer system of Example 1, the haze is lower, but the color stabilization time is greatly shortened.

Examples 3 and 4 compare the effects of epixidized soybean oil. When compared to Example 3 (19 to 5), Example 4 shows a much improved color stability time. Adding epoxidized soybean oil also reduces haze, increases light transmission (and reduces yellowness).

Example 5 is the same as Example 4. However, phosphite was added. The initial color was improved (yellowness), but the color stability was reduced.

In Example 6, a mixture of β-diketones was added which improved the yellowness while keeping the color stability constant.

Example 7 shows that if part of the lubricant system is replaced by triethylene glycol, the color stability is greatly improved, but the brushing is very poor. Glycerol appears to be very poor for brushing because, when in contact with alcohol and water, it absorbs the alcohol and water and clouds the composition.

Example 8 shows that when a new ingredient, triglycerol monostearate, is used and part of the lubricant system is replaced, the brushing is improved over Example 7 using triethylene glycol, and the stability is improved over Example 6 using triethylene glycol. The above shows that it has been greatly improved.

In Example 9, the phosphite was removed.

Long-term color stability was improved, but yellowness was high.

Example 10 is the same as Example 9. However, the triglycerol monostearate was replaced by polyglycerol di- and trioleate as the lubricant and the phosphite was added back. Haze was high, light transmission was low, and color stability was lower.

In Example 11, hexaglycerol distearate was used as a lubricant in place of the polyglycerol of Example 10. Improved color stability.

In Example 12, the level of calcium stearate was reduced to 0.1 part. Haze, light transmission, yellowness and brushing were improved.

However, calcium stearate acts as a stabilizer and therefore 10 minutes of color stability is too low for satisfactory results.

To improve the stability of Example 12, triethylene glycol was added in Example 13. Stability was improved, but brushing became dramatically worse (higher).

Example 14 shows that by adding triglycerol monostearate, stability was further improved and brushing was improved, but yellowness, haze and light transmission were reduced.

Example 15 shows that when glycerol monostearate is removed from Example 14, haze, light transmission, yellowness, and blushing are all improved.

In Example 16, some of the 1-liglycerol monostearate was replaced with polyglycerol di- and trioleate. Although the results were directed toward an undesired outcome, no significant impact was demonstrated.

When Example 17 is compared to Example 15, it is seen that triglycerol monostearate provides improvements over polyglycerol di- and trioleate.

Example 18 shows that hexaglycerol distearate is also
It is shown to be more effective than the polyglycerol of Example 17 in terms of stability, consistency and light transmission.

Example 19 shows that a blend of triglycerol monostearate and hexaglycerol distearate provides superior stability over polyglycerol di- and trioleate.

Example 20 increased processing aids, decreased β-diketone,
A polymer phosphite was then added for the phosphite in the previous example. The result meets all the requirements of an outstanding bottle compound.

Example 21 removed the small amount of polyglycerol in Example 20 and added a small amount of triglycerol monostearate. Again, an excellent formulation was obtained.

In Example 22, triglycerol monostearate and triethylene glycol were exchanged.

Stability and brushing were unfavorable.

When compared to Example 21, Example 23 shows that the polymeric phosphite of Example 21 provides improved stability over the phosphite node in Example 23.

Example 24 shows that hexaglycerol distearate provides improved stability over triglycerol monostearate, but also results in higher yellowness and lower light transmission.

Of the 24 different compositions illustrated by example, example 2
Only 0, 21 and 23 give the most suitable combination of results for PVC bottle compositions.

PVC, H acid formulation is a very complex technique, and many components interact with each other to give different results depending on the levels and nature of the rest of the composition.

The compositions of Examples 20, 21 and 23 provide compositions that, when processed into products such as bottles, containers and films, will yield products hitherto unknown in the art. The product has a high degree of clarity, does not cloud excessively when exposed to alcohol, and has excellent initial color (yellowness) and excellent color stability.

1) This example is provided to demonstrate another critical feature of the bottle of the present invention. It is characterized by the fact that it imparts no odor or taste to the contents of the bottle.

Bottles were made from the compositions of Examples 1 and 21.

Distilled water was placed in each bottle and aged at 50°C for 12 weeks. After 3 days, the water was taste tested and odor tested by 6 judges. The water in the bottle made from the composition of Example 1 had a very noticeable malodor. The judges were unable to distinguish between the water in the bottle made from the composition of Example 21 and fresh distilled water in terms of taste and odor. Aging continued for 12 weeks, and the water in the bottles made from the composition of Example 21 was indistinguishable from fresh distilled water.

This example shows that the malodor and taste problems associated with tin stabilizers are independent of the calcium/zinc stabilizer used in this invention.

The product of the invention has the best of both properties. That is, they have the clarity and stability of tin-stabilized products and the taste and odor characteristics of calcium/zinc-stabilized products.

The products of the invention are useful for containing beverages or other products as well as for films where high clarity is required.

This example is provided to demonstrate the effectiveness of the novel stabilizers of the present invention. Sample 1 is a PVC homopolymer stabilized with a large amount of a known tin stabilizer. Sample 2 is the same compound as Sample 1. However, PVC100
0 parts by weight of solitriglycerol monostearate is added to the formulation. As shown in Table 1, the oven stability is further improved by the addition of triglycerol monostearate with a large amount of tin stabilizer (2.5 parts).

The recipe used and the oven stability results are shown in Table 1, where the ingredients are given in parts by weight per 100 parts by weight of vinyl polymer.

Below are the margins - Table 1 P V C Nemo Polymer - 1oo, oo too
,o.

Tin stabilizer 2,50 2.5
0 Epoxidized oil 1,50 1.
50 Processing aids 2,25 2
,25 Lubricant 1,
05 1,05 triglycerol monostearate) -0,502
Topun stability (min) at 0.2°C 4553 As seen from the example, the stability of sample 2 is
shows an improvement over the stability of Example 1 even though it has a large amount of tin stabilizer.

The new stabilizer used in this example, triglycerol monostearate, is a permitted food additive and therefore represents an outstanding choice as a stabilizer when used for the food industry.

The stabilized resins of the invention are suitable for many applications. They are mixed with fillers, colorants, lubricants, other stabilizers and the like to form vinyl chloride resin compositions. They are extruded and melted and made into pipes, house siding, windows, bottles and the like. They can also be rolled into sheet form for use as films and the like.

Claims (1)

[Claims] 1. A polyvinyl chloride product having the following characteristics: (a) A
When measured according to STM D-1746, as defined by having a % light transmission higher than stated by the following formula: % light transmission = 100 - (460 x thickness in inches) High transparency; (b) ASTM
D-1003-61 and with the following formula: % Haze = % Haze = 184.6 x % Haze of value lower than stated by thickness in inches; (c)5
Brushing less than 30% at 0.065 inch thickness after exposure to a 50/50 ethanol/water solution for 48 hours at 0°C; and (d) aging at 200°C according to ASTM D-1925. and (e) does not impart an unpleasant taste and odor to other materials when brought into contact with the PVC product. products to do. 2. The product of claim 1, wherein said product is substantially free of tin stabilizers. 3. The product of claim 2, wherein the product is selected from the group consisting of bottles and films. 4. A polyvinyl chloride composition having the following properties: (a)
When measured according to ASTM D-1746, as defined by having a % light transmittance higher than stated by the following formula: % Light Transmittance = 100 - (460 x thickness in inches) High transparency; (b) ASTM
D-1003-61 and with the following formula: % Haze = % Haze = 184.6 x % Haze of value lower than stated by thickness in inches; (c)5
Brushing less than 30% at a thickness of 0.065 inch after exposure to a 50/50 ethanol/water solution for 48 hours at 0°C; (d) ASTM D for uncolored compounds;
- a yellowness index of less than 13% at a thickness of 0.065 inches when measured in accordance with ASTM D-1925; and (e) a color that turns black in 20 minutes or more when aged at 200°C in accordance with ASTM D-1925. and (f) does not impart taste or odor to other materials when they are brought into contact with the composition. 5. A method for manufacturing transparent polyvinyl chloride products having the following characteristics: (a) When measured according to ASTM D-1746, the following formula: % light transmission = 100 - (460 x (b) greater clarity than stated by thickness in inches); (b) as measured according to ASTM D-1003-61 and with the following formula: % Haze = 184.6 x thickness in inches; % haze of low value; (c)5
Brushing less than 30% at a thickness of 0.065 inch after exposure to a 50/50 ethanol/water solution for 48 hours at 0°C; (d) ASTM D for uncolored compounds;
- a yellowness index of less than 13% at a thickness of 0.065 inches when measured in accordance with ASTM D-1925; and (e) a color that turns black in 20 minutes or more when aged at 200°C in accordance with ASTM D-1925. shaping a polyvinyl chloride composition having a stability of rolling,
A method characterized in that it is carried out by extrusion or pressurization. 6. A stabilized halogenated vinyl resin composition having the following formulas: OH-X-O-R and R-O-X-O-R [wherein, X is (a) 2-20 or (b) 4 to is a straight chain, branched or cyclic group having 60 carbon atoms, and R is
a straight chain group of 5 to 40 carbon atoms. 7. Contains at least one stabilizer compound selected from the group consisting of oligo-glycerol, oligo-propylene glycol and oligo-ethylene glycol, and the oligo-glycerol has the following formula: ▲ The mathematical formula, chemical formula, table, etc. ▼ where n is 2 to 20 and R is a straight chain group having 5 to 40 carbon atoms, and a straight chain,
branched or cyclic; the oligo-propylene glycol has the following formula: ▲ formula;
There are chemical formulas, tables, etc. ▼ having [where n and R are as defined above];
and the stabilization according to claim 6, wherein said oligo-ethylene glycol has the following formula: ▲ which may be a mathematical formula, a chemical formula, a table, etc. ▼ where n and R are as defined above. halogenated vinyl resin composition. 8. Claim 7, wherein the oligo-glycerol is an ester of oligo-glycerol and a fatty acid, wherein the glycerol:fatty acid ratio is greater than 1:1.
Compositions as described in Section. 9. The composition of claim 8, wherein the ester of oligo-glycerol and fatty acid is selected from the group consisting of triglycerol monostearate, hexaglycerol monostearate and hexaglycerol distearate. 10. A method for stabilizing a halogenated vinyl resin, comprising the following formulas: OH-X-O-R and R-O-X-O-R [wherein, X is (a) 2 to 20 of oxygen atoms, where at least one of the oxygen atoms forms an ether bond and the remainder form bonds selected from the group consisting of ether, epoxy and hydroxy; or (b) 4 to 60 straight chain, branched or cyclic group having 5 carbon atoms, and R is 5
a straight chain group of ~40 carbon atoms. 11. Adding to the resin an effective amount of at least one stabilizer compound selected from the group consisting of oligo-glycerol, oligo-propylene glycol, and oligo-ethylene glycol, and wherein the oligo-glycerol has the following formula: , chemical formulas, tables, etc. ▼ [wherein n is 2 to 20 and R is a straight chain group having 5 to 30 carbon atoms], and a straight chain,
branched or cyclic; the oligo-propylene glycol has the following formula: ▲ formula;
There are chemical formulas, tables, etc. ▼ having [where n and R are as defined above];
and the oligo-ethylene glycol has the following formula: ▲ where n and R are as defined above. 12. The method of claim 11, wherein the oligo-glycerol is an ester of oligo-glycerol and a fatty acid, wherein the glycerol:fatty acid ratio is greater than 1:1. 13. The ester of oligo-glycerol and fatty acid is selected from the group consisting of triglycerol monostearate, hexaglycerol monostearate, and hexaglycerol distearate.
The method described in section. 14. The method of claim 13, wherein the level of said ester is from 0.2 to 3.0 parts by weight per 100 parts by weight of vinyl polymer. 15. A shaped article having the following formula; OX-X-O-R and R-O-X-O-R [wherein, X is (a) 2 to 20 oxygen atoms (where (at least one of the oxygen atoms forms an ether bond and the remainder form bonds selected from the group consisting of ether, epoxy and hydroxy); or (b) a straight line having from 4 to 60 carbon atoms. chain, branched or cyclic group, and R is 5
A shaped article comprising at least one stabilizer selected from the group consisting of compounds consisting of a linear group of ~40 carbon atoms and at least one fused vinyl halide resin.