CA1183627A - Improving algae or micro-organism anti-fouling of materials - Google Patents
Improving algae or micro-organism anti-fouling of materialsInfo
- Publication number
- CA1183627A CA1183627A CA000375610A CA375610A CA1183627A CA 1183627 A CA1183627 A CA 1183627A CA 000375610 A CA000375610 A CA 000375610A CA 375610 A CA375610 A CA 375610A CA 1183627 A CA1183627 A CA 1183627A
- Authority
- CA
- Canada
- Prior art keywords
- tin
- radical
- fouling
- compounds
- octyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
- A01N55/02—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing metal atoms
- A01N55/04—Tin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Pest Control & Pesticides (AREA)
- Environmental Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Sealing Material Composition (AREA)
- Glass Compositions (AREA)
- Moulding By Coating Moulds (AREA)
- Paints Or Removers (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
<<Improving algae or micro-organism anti-fouling of materials>>
A method of reducing the susceptibility of materials to fouling by algae or microorganisms comprises treating the material with an anti-fouling agent selected from certain tin compounds. The compounds which may be used are selected from inorganic divalent tin salts, monoorgano tin compounds of formula R Sn X3 and diorgano tin compounds of formula R2SnX2, in which R represents a hydrocarbon radical and X represents inorganic radicals or an organic radical other than hydrocarbon. The compounds are particularly suitable for treating soft PVC materials by mixing in with the moulding compositions. They are generally of lower toxicity than hitherto used anti-fouling agents, and give good results in the prevention of algae deposit on, for example, swimming pool sheeting.
<<Improving algae or micro-organism anti-fouling of materials>>
A method of reducing the susceptibility of materials to fouling by algae or microorganisms comprises treating the material with an anti-fouling agent selected from certain tin compounds. The compounds which may be used are selected from inorganic divalent tin salts, monoorgano tin compounds of formula R Sn X3 and diorgano tin compounds of formula R2SnX2, in which R represents a hydrocarbon radical and X represents inorganic radicals or an organic radical other than hydrocarbon. The compounds are particularly suitable for treating soft PVC materials by mixing in with the moulding compositions. They are generally of lower toxicity than hitherto used anti-fouling agents, and give good results in the prevention of algae deposit on, for example, swimming pool sheeting.
Description
Improving algae or micro-organism anti-foulins of materials This invention relates to a method of reducing the susceptibility of materials to fouling by algae and 5 microorganisms by theuse of inorganic tin salts or certain monoorgano or diorgano tin compounds.
It is known to include bio-stabilisers in certain materials, the function of the bio-stabilisers being to resist biological attack on the material. Such 10 biological attack may occur in different ways, for example by mould, algae, fungi, bacteria, rodents, fouling and slime-formation,or sea-water parasites.
The general requirements of suitable bio-stablisers may be summarised in general as follows:
broad spectrum of anti microbial activity; no negative influence on the material to be protected (for example no discolouration, or deterioration in heat-stability or light-stability); compatibility with plasticisers and other additives (such as stabilisers, lubricants or anti-oxidants); no negative secondary properties (such as corrosivity, skin irritation or ~dour); thermal resistance and low volatility und~r proc~æ~ing conditions;
storage stability; simplicity o~ application; durability in use;
and low toxicity in warm-blooded animals.
It is known to use the following practically important substances as bio-stabilisers with biocidal effect:
10,10' oxy-bis-phenoxyarsine, N-(trihalomethylthio)-phthalimide, diphenyl antimony-2-ethyl hexanoate, and copper 8-hydroxy quinoline. They are generally used in initial concentrations of form 0.3% (when used as pure substance) to 5% (when used in solutions)~ as may be seen ~'';~ '~
..~. . ~
by reference to G~ch-ter/MUller, Plastic-additive, Carl Hanser-Verlag, Munich 1979, page 456 and Polymer ~ngineering and Science, July 1970, Vol 10, No. 4, page 241 to 246. Of these bio-stabilisers, copper-8-hydroxy quinoline and N-(trihalomethyltll:lo)-pl~thalimi~e have proved themselves particularly useful as biocides in soft-PVC products. According to German Offenlegungsschrift (DE-OS) 2 929 756 there may be used as anti~fouling materials in underwater coating agents, special dihalophenyl-~-chloro ethyl sulphone derivativ~s.
Triorgano tin compounds of the R3SnX type, where R is an organic radical, form a further group o.f bio-stabilisers which are known and used for their extraordinary effectiveness against the most varied types of micro organisms such as fungi, bacteria and algae. The effectiveness of such compounds depends substantially on the chain lengrth O:e the hydrocarbon radicals R
connected to the tin atom. Thus with trialkyl tin compounds best results have bee~n achieved when the to-tal number o~ car~)on ~torns :In the al~y~ ~rr~up~
is from 9 to 12, that is with tripropyl- and tributyl-tin compounds. Of the aryl compounds, the triphenyl compounds have an effect whichis comparable with the trialkyl compounds. The triorgano tin compounds are used for example as textile protective agents having a biocidal effect against fungi and bacteria, or as wood protective agents, for example in combatting wood-destroying fungi or ship's bore worms. As anti-fouling coatingsto prevent the underwater fouling of objects in seas,rivers or lakes, apart from Cu20, mercury compounds and also triorgano tin compounds, in particular tributyl- and triphenyl tin compounds have been used;
~3--3 6;~
in general composi.tions containing from 10 to 20%
of these active materials, based on the dried anti-fouling coatings7 are considered necessary. In addition, trihutyl tin compounds in particular have been used in bi.ocide coatings to preyent attack or ~ouling by microorgani.sms for example in damp areas. A further known use of triorgano tin compounds such as tributyl tin oxide, is to provide biocidal properties for plastics materials, and in particular plasticiser-containing plastics such as soft PVC. On the one hand the tri.organo tin compound functions as a fungus-preventative, in particular -~or theplasticisers, and on the other hand it functions as a fouling preventative against mi.cro organisms which positively attack the plastics material. However, since tributyl tin oxide,which is preferably used, is not light-resistant, so-called stabilised tributyl tin oxide has to be used. In addition it is known to use tributyl tin compounds as insecticides and as mollu~cicid~s, disinfectant agents and ~li.m~-~ombat~ln~ ag~nt.
in the paper industry In contrast to the lsnown use o~ triorgano tin compounds against a wide variety ol types of biologrical attack, hitherto inorganic tin compounds J diorgano tin compounds o~ the R2SnX2 type and mono organo tin compounds of the RSnX3 type have been considered to be practically useless in this biocidal area. In this regard reference is made to the technical specification pamphlet of Schering AG, Industrial Chemists J "Technical Production and Use of Organo tin compounds" by Dr. A.
Boghans and Dr. H. Plum,of March 1975.
Some diorgano tin compounds and some mono organo tin compounds are known, however J for their PVC
stabilising effect; in particular they serve to prevent decomposition reactions induced by heat, light or oxidation in PVC, and accordingly the compounds are used as stabilisers. However since they do not generally have good properties with respect to light fastness, waterproofness, lasting e~fect, heat s-tability and workability, they are usually not used alone, but rather in combination with other stabilisers.
~or example, dibu-tyl tin dilaur~te shows a good light-stabilising effect but a relatively poor heat-stability, and is thereIore usually only used in combination with other tin stabilisers which are better in their heat effect. Also, dibutyl tin maleate is agood stabiliser against the adverse ef~ects of heat, but as a ,polymer compound it is insoluble in PVC and so presents difficulties in working and has a tendency to plate-out.
In general the best heat stabilisers, which may be used in the high-temperature working of hard PVC tv form :eOx e~ample plates, sheets and bott~e~, ar~ ~:iorgan~h~o tin compounds which hav~ a dl,rec-t tin-~ùlphur bond such as dialkyl tin diiso octyl thioglycolate~s. These compounds have the disadvantage though that they do not keep for long in free weathering conditions, which leads to damage of the hard PVC. The same disadvantage applies to dioctyl tin compounds. However because of their non-toxicity, these compounds are used for the stabilising of PVC which is used for example in the packaging of foodstuffs. Poor weathering resistance is also a proper-ty of the toxically harmless mono organo tin compounds .
~. .
~ -5-~ ~ ~3 3 ~ ~2 7 such as polymeric monoalkyl tin oxides or-sulphides, which again are used to stabilise PVC against the ef-fect of heat and light in the field of foodstuff packaging.
Thus although certain organo tin compounds are used as stabilisers for PVC, their weather resistance is not sufficiently high for many areas of usage. In particular they are not generally good with regard to long-terrn colour stability, low water absorption, and decomposition, properties which are particularly required of, for example, window profiles, facade profiles and plates, roof sheeting, agricultural sheeting, swimming pool sheeting and covers for air halls. Hence in these and other areas o~ usage, in addition to the tin compounds which stablise PVC against decomposition through the effect of heat, light and oxidation, it is necessary to incorporate other stabilisers which are eIfective against weathering. According to the current state o~ development in the art, barium-cadmium stabilisers are thought to be superio~ ~o all o~h@r ~ab~ er~ and systems in this respe~c~. Thu~ ror the purpose~ o~
weather-resistance, organo tin compounds are not used alone as stabilisers since they show cléar damage after a short weathering time, see for example PLAST VERARBEITER, 30th Vol, 1979, No. 112, page 747 - 751 "Barium/Cadmium forthe stabilising of PVC,by Dr. P Bredereck and Dr. H.
Endriss".
A particularly rlifficult application of soft PVC
isin the manufacture of sheeting for use in swimming pools.
These require high weather-resistance and colour- and light ~astness, and also resistance to biological -6- .
attack by micro organisms and algae. It is known that swimming pool sheets of soft PVC tend -to deposit a slimy surface co~ting because the sur~ace roughness of the sheet acts as an adhesive base for micro organisms. This effect is made worse by the penetration ofmicro organisms, with the aid of water as a carrier, into the relatively soft material.
Because of the high requirements of swirnming pool coatings with regard to water-, weathering- and colour stability, the sheetings used are stabilised predominantly with barium-cadmium compounds. The problem of the slimy coating formation is generally indirectly solved by -the addition to the pool water of so-called water-maintenance agents such as chlorine- or bromine preparations having a strong oxidising effect. As a direct measure it has been known to use tributyl tin oxide as a so-called bio-stabiliser for the prevention of fouling in swimming pool sheeting. Tributyl tin oxide, as well as other known trialkyl tin compounds are however, very toxic, and more particularly they have a strong inhalation toxicity which leads ~o con~:LdQrabl~ probl@m~
for example dllr:ln~ t}le pto~luct:Lon o~ llle ~3heeting at high processing temperatures.
As is mentioned above, the stabilising ef~ect of diorgano- and mono organo tin compounds against the decomposition of PVC by the effect of light, heat and oxidation has been known ~or a long time. It has now surprisingly been discovered that in addition such compounds, and also certain tin salts, which until now have been considered biocidally ineffective against a wide ~3~
variety of microorganisms such as fungi, bacteria and algae, have a good effectiveness as anti-fouling agents i.e. agents which counter the settling or deposition of algae, micro-organisms and the like onto surfaces.
According to the present invention there is provided a plastic material which comprises plasticised polyvinyl chloride and an anti-fouling agent selected from inorganic divalent tin salts~ monovrgano-tin compounds of formula RSnX3 and diorgano tin compounds of formula R2SnX2 in which formulae the radicals R each represent a hydrocarbon radical, and either (i) each radical X represents an inorganic radical or an organic radical other than a hydrocarbon radical, or (ii~ two radicals X together represent an organic radical other than a hydrocarbon radical and any remaining radical X represents an inorganic radical or an organic radical other than a hydrocarbon radical, and wherein the anti-fouling agent is present in an amount so as to give the plastic material a tin content of from 0.05 to 1.2~ by weight.
In accordance w:ith anoth~r asp~t the present lnven-tion provides a method for preparing a sheet or foil of plas-ticised polyvinyl chloride having reduced susceptibility to fouling by algae or microorganisms, which comprises providing a plastic material which comprises plasticised polyvinyl chloride and an anti-fouling agent and moulding said plastic material into a sheet or foil thereof, the anti-fouling agent being selected from inorganic divalent tin salts, monoorgano-tin compounds of formula RSnX3 and diorgano tin compounds offormula R2SnX2 in which formulae the radicals R each represent a hydrocarbon radical, and either ~ ,. ~ ~
~ 8 -.. . ,.~ .
(i) each radical X represents an inorganic radical or an organic radical other than a hydrocarbon radical, or (ii) two radicals ~ together represent an organic radical other than a hydrocarbon radical and any remaining radical X represents an inorganic radical or an organic radical other than a hydrocarbon radical, and wherein the plastic material contains from 0.05~ to 1.2%
by weight of tin calculated from the specified anti-fouling agent.
The present invention particularly provides a method for preparing a sheet or foil of plasticised polyvinyl chloride, having reduced susceptibility to fouling by algae or microorganisms, which comprises admixing in the presence of one or more plasticisers, polyvinyl chloride with an anti-fouling agent and moulding the obtained plastic material into a sheet or foil, the anti-fouling agent being selected from inorganic divalent tin salts, monoorgano-tin compounds of formula RSnX3 and diorgano tin compounds of formula R2SnX2 in which formulae th~ radicals R each represent a hydrocarbon radical, and either (i) each radical X reprcsents an inorganic radical or an organic radical other than a hydrocarbon radical, or (ii) two radicals X together represent an organic radical other than a hydrocarbon radical and any xemaining radical X represents an inorganic radical or an organic radical other than a hydrocarbon radical, and wherein the plastic material which is formed by the admixing step contains from 0.05 to 1.2% by weight of tin calculated from the specified anti-fouling agent.
The use of the specified tin compounds in accordance ~-'A`' ~ - 8a -., !f with the invention yie`lds compositions having properties which have low toxicity or no toxicity at all, and which are therefore as harmless as possible to the environment. The material, for example soft PVC (polyvinyl chloride~ which may contain stabilisers such as barrium- cadmium compounds or calcium-zinc compounds to give light-, weather- and heat-resistance is preferably treated in accordance with the invention by admixing it with the anti-fouling agent to form a composition having anti-fouling properties. The composition formed by carrying out the method of the invention can contain from 0.05 (0.005) to 1.2% by weight/ more preferably from 0.1 to 0.5% by weight of tin calculated from the amount of /
~ 8b -~ ~3~
fou]ing agent used.
The hydrocarbon radicals R of the monoorgano and diorgano tin compounds are preferably alkyl groups such as methyl, bu-tyl or octyl. The radicals X may be for example halogen, preferably chlorine, sulphur or oxygen When X is an organic radical other than a hydrocarbon then it may be for example an alkoxide.or an ester radical of a saturated and/or unsaturated carboxylic acid such as a laurate or a maleate.
It is particularly preferred to use dialkyl tin compounds as anti-fouling agents accord:ing to the invention. By way of examp~ethere may be mentioned dibutyl tin dilaurate, dibutyl tin maleate, dioc-tyl tin dilaureate, or dioctyl tin maleate. It will be appreciated that in the general formula R2SnX2, the two radicals ~ may simply represent a divalent group such as maleate. Other useful dialkyl compounds which may be mentioned are di-n-but 1 tin dichloride, di-n-octyl tin dichloride, dibutyl tin oxide, dimethyl- or dibutyl tin sulphid~ and dialkyl tin oxid~$. ~ o proven to hav~ be~n ~'eec~iv@ :in accordance with the invention are dialkyl tin alkoxides in which one or both alkoxide groups have been replaced by dicarboxylic acid semi esters or thio carboxylic acld esters such as dibutyl tin methoxy maleic acid-rnethyl ester, di-n-octyl tin diiso octyl-thioglycolate or -maleate, dimethyl tin-diiso-octyI-thioglycolate and di-n-butyl tin diiso octyl thio glycolate. ~ feature of the invention is the fact that the predominant number of diorgano tin compounds used are toxically harmless, in contrast to the _9_ predominant number of triorgano tin compounds formerly used for these purposes.
Mono organo tin compounds may be used to treat materials in accordance with the invention. There are preferably used mono alkyl tin compounds or their polymeric form, or mono alkyl compounds in which the radicals X represent inorganic radicals such as halogens, sulphur or oxygen, for example n-butyl tin trichloride, monobutyl tin oxide or monobutyl tin sulphide. As 10 with the diorgano compounds~ X may be alkoxide, or instead one, two or three of the alkoxy groups may bé replaced by dicarboxylic acid semi esters and/or thio carboxylic acid esters and/or carboxylic acids, as in n-octyl tin tri iso octyl thioglycolate or n-octyl tin-bis-iso vctyl thioglycolate -laureate.
Of the inorganic tin salts which also surprisingly can be used as anti-fouling agents, particular menticnis made of tin chloride and tin sulpha-te. However a certain water-solubility in the tin salts can be disadvantag~ous insofar as it can lead, ~or examplc, to an ~ncr~as:lng roughness in the sur~ace o~ a coating.
With conventional bio-s~abili.sers it is normal to use from 0.3 to 5% by weight based on the material to be treated. However in accordance with the invention the tin compounds may be used to treat the material at starting concentrations of from 0.05 to 1.2.
preferably Ool to 0.5% tin calculated from the tin compounds added. Such proportions have been found to be sufficient as anti-fouling agents, although this depends on the field or area of usage and the requirements of this field. A preferred field of usage for the invention are --10-- .
~3~
weather-resistant products :Eormed from moulding materials based on so~t PVC treated by the method of the invention and optionally containing stabilisers for light-, weather~
and heat-resistance, and if necessary conventional additives such as colouring agents, fillers and lubricants.
The treating of such materials with from 0.05 -to 1.2, preferably 0.1 to 0.5% by weight of tin calculated -rom the tin compounds added for anti-f'ouling, based on 100%
by weight of the moulding material, is generally sufficient to achieve the desired effect.
The weater-resistant products based on soft PVC
treated in accordance with the invention have the advantage of' a good light-, weather- and heat-resistance through the use of' suitable stabilisers, preferably based on barium-cadmium compounds or calcium-zinc compounds or in combination wi-th other stabilisers, and at the same time they reduce or prevent the settling or deposition of' fouling, like algae or micro organisms.
Surprisingly, neither the light resistance, nor the weather-resistance, nor the h~at-r~s:Lstan~e, no~ th~
workability c~P the mould:ing material or products, is adversely a~fected by the tin compounds used according to t~ invention. On t~ contrary, the organo tin compounds used according to the invention generally have as a su'bsidiary eff'ect, an unexpected improvement in the Ba-Cd- or Cd-Zn basic stabilisation. In addition the selected tin compounds are for the most part toxically inactive, the majority o-i them being toxicologically harmless and even released for use by the health authorities.
`~` -1 1-As mentioned above, the preferred area of use of the invention is in the treatment of soft PVC materials.
These contain plasticisers, and require particular stability against bio~ogical attack on the plastic~sers.
Here it is particularly surprising that the tin compounds as de~ined, which were thought of until now as useless against biological attack, display an anti-fouling ef~ect. Applications of products based on soft PVC
are for example as sealing sheeting for coating or lining swimming pools, damp areas or cooling-water tanks, and as agricultural sheeting. The plasticisers which may be included in the PVC material are pre~erably esters o~ polybasic acids with monovalent alcohols, such as phthalates, es-ters of adipic acid and sebacic acid, trimellitic acid esters, or para~fin-sulphonic acid phenyl/cresyl esters. Preferab1y from 15 to 50%
by weight of plasticiser is used based upon the total weight o~ the composition.
PVC is not usually plasticised merely by th~
addition of low molccular w~ h~t pla~;t~ r~; u~ually high polymer plasticising additives such as ethylene vinyl acetate, ethylene vinyl acetate copolymers or chlorinated polyethylene are included. The moulding materials which are treated by the method of the invention preferably contain from 20 to 8~/o by weight of high polymer plasticising additives based on 100%
by weight of moulding material. It is pre~erred, though, that the plasticisexs and high polymer additives together do not amount to more than 80% by weight of the moulding material.
Materials treated by the method of the invention may be moulded into furnished products such as sealing sheeting based OD soft PVC, ~or the coating of water-containing receptacles or the like.
As may be seen ~rom the ~ollowing Examples very good results have been achièved in accordance with the invention. Thus the protective e~fect of the prevention o~ fouling for example in swimming pool sheeting and the prevention of formation of slimy surface coatings was practically as good as that o~
the known triorgano tin compounds, in particular of the hitherto preferably used trialkyl tin compounds. However, the anti-fouling agents of the invention have the advantage over hitherto used biostabilisers that they are substantially less toxic or not at all toxic. In addition because of the required extreme light- and weathering-resistance and the low water absorption, sealing sheeting which comes into contact constantly with water, is stabilised predominantly with barium-cadmium compounds or calcium-zinc compounds or i~ necessary combinations o~
these with ~urther stabili~ers. It i~ also surprl~ng that the anti~ouling agents o~' th0 invention d:l~play a par-ticularly good e~fectiveness on PVC moulding materials with a very high content of plasticiser.
A iurther feature of sealing sheet based on a material treated according to the invention which is used as swimming pool sheeting, is that a low concentration o~ maintenance additive is required to keep the water clean. In contrast,normally a speci~ic amount o~ maintenance agent is necessary to keep the water clean 3~ and clearland in swimming pools with little water movement a coating inevitably forms on the sheeting. In order to avoid this, the maintenance agents are o~ten added in excess. In addition to the strong annoying smells, this may be harmful to the skin and in particular for the eyes, and also harmful to the sheeting itself which may age prematurely.
'~F
Thé inven-tion is illustrated by the following Examples.
Comparison Example 1 A soft PVC sheet was produced by calendering (extruding) a mixture of the following: 100 parts by weight ofs(suspension)PVC, 62 parts by weight of a C8-C10 alkyl phthalate plasticiser, 3.3 parts by weight of epoxidised soya oil, 4 parts by weight of a commercial,liquid Ba/Cd stabiliser containing 6%
by weight of cadmium, and 7.8 parts by weight of conventional anti-oxidants, screening agents and dye (colour) pigments. The sheet thus produced was stored at room temperature in tap water, and after 7 days it was found that a slimy coating had ~ormed on the surface of the sheet. This coating consisted of micro organisms sticking to the sheet, and corresponded in the practical case o swimming pools to the starting point or origin of a progressive deterioration in the quality of the water as the micro organisms increased correspondingly. In :~ct th~ coat~.ng gr~w s~ron~r on further storage of the sh~et in tap wat~r, and after 60 days formed a layer thickness o~ about 0.5 mrn. The coating -itsel~ was slippery-slimy, and had an unpleasant i'eel.
C'omparison Example 2 The procedure of Comparison ~xample 1 was repeated, except that the composition used to form the sheeting additionally included 1.2 parts by weight of tributyl tin oxide No coating had been formed on the surface of the sheet after storage in tap water at room temperature for 14 days. In fact not until 60 days storage in tap water at room temperature did a barely perceptible slippery thin coating form on the surface of the sbeet;
this slightly strengthened during the next 30 days storage. Aftcr further stora~e there again occurred the formation of a coating which grew thicker. The disadvantage of this known biocidal material is its high toxicity, which greatly restricts its application possibilities.
Example 3 A composition was prepared as in Comparison Example 1 except that there was additionally included 2.43 parts by weight of a commercial dibutyl-tin-dithio glycolate;
this proportion corresponded to 0.4 parts by weight of -tin (0.23~ by weight of tin based on the composition as a whole). From this composition, as in Comparison Example 1, a sheet was produced which was tested in the same way.
After 14 days storage in water the sheet was still completely coating-free and after 60 days a barely perceptible coating had formed.
Example 4 A composition was prepared as in Comparison Example 1 except that there was additionally included 0.5 parts by weight oi thelinorganic Sn-salt, SnC12, corresponding to 0.31 parts by weigh-t Sn (0.17% by weight of Sn based on the composition as a whole). ~rom this composition, as in Comparison Example 1, a sheet was produced and tested under the same conditions. After 14 days storage the sheet was still completely coating free. After 60 days the sheet showed a slimy coating which was still less substan-tial than the sheet of Comparison Example 1 had shown .
~3~
after 7 days.
Example 5 The procedure of Comparison Example 1 was repeated except that the composition included 1 part by weight of a liquid dibutyl tin maleic acid ester, which corresponds to 0.19 parts by weight of Sn (0.11% by weight of Sn based on the composition as a whole). The sheet produced was tested under the same conditions as in Comparison Example 1 and showed the same be.haviour as the sheet according to Example 3.
Comparison Example 6 A sheet was produced by extrusion from a composition cons:isting of 100 parts by weigJht o~
PVC, 96 parts by weight of ethylene vinyl acetate copolymer, 6 parts by weight of epoxidised soya oil, 6 parts by weight of a liquid barium-cadmium stabiliser (with 6% by weight o~ cadmium) and 9.8 parts by weight of conventional anti-oxidants, screening agents and colour (dye~ pigments. The sheet was tes~ed under th~ same conditions as in Comparison Examp:lo 1, ~nd ~;howcd very similar behaviour ln its coating l'ormation to the sheet according to Compari.son Example 1.
Example 7 A composi-tion was -~ormed as in Comparison Example 6, except that there was included 1 part by weight o~ liquid dibutyl tin maleic acid ester, which corresponds tu 0.19 parts by weight of Sn (0.09% by weight of Sn based on the composition as a whole). A sheet was produced ~rom this composition as in Example 5, and on testing showed the same behaviour as the sheet of Example 4 with respect to coating formation, i.e. settling of micro organisms.
Example 8 The procedure o-.f ~xample 7 was repeated except that 2 parts by weight of the liquid dibutyl tin maleic acid ester were incorporated. On testing it was found that the sheet produced was even less prone to coating ~ormation after 60 days storage in water than the sheet of Example 7, i.e. it was still practically coating-free and was hardly slippery. From this it rnay be concluded that a higher content of active su~stance according to the invention shows a better and longer lasting e~ectiveness ~or the prevention of fouling, i.e. ~or preventing the formation of' slimy/slippe~ coa-tings on the sheet.
Example g To a composition according to Comparison Example 1 were added 3.5 parts by weight of n-butyl-tin- tri iso octyl thio glycolate, which corresponds to 0.53 parts by weight of tin (0.29% by weight of tin based on the composition as a whole). A shec~t w~s produ~ nd t~.Jt~d under the same conditi.ons as i.n Compari~on Ii,xarnple 1. This behaved similarly in its coating formation as the ~heet according to Example 7.
The following Table summaris~ the coating ~orrnation properties of the sheets according to the Examples over a period of up to 90 days. The code numbers 0-4 as used in the Table correspond to the following results:
O no coating 1 hardly perceptible coati.ng
It is known to include bio-stabilisers in certain materials, the function of the bio-stabilisers being to resist biological attack on the material. Such 10 biological attack may occur in different ways, for example by mould, algae, fungi, bacteria, rodents, fouling and slime-formation,or sea-water parasites.
The general requirements of suitable bio-stablisers may be summarised in general as follows:
broad spectrum of anti microbial activity; no negative influence on the material to be protected (for example no discolouration, or deterioration in heat-stability or light-stability); compatibility with plasticisers and other additives (such as stabilisers, lubricants or anti-oxidants); no negative secondary properties (such as corrosivity, skin irritation or ~dour); thermal resistance and low volatility und~r proc~æ~ing conditions;
storage stability; simplicity o~ application; durability in use;
and low toxicity in warm-blooded animals.
It is known to use the following practically important substances as bio-stabilisers with biocidal effect:
10,10' oxy-bis-phenoxyarsine, N-(trihalomethylthio)-phthalimide, diphenyl antimony-2-ethyl hexanoate, and copper 8-hydroxy quinoline. They are generally used in initial concentrations of form 0.3% (when used as pure substance) to 5% (when used in solutions)~ as may be seen ~'';~ '~
..~. . ~
by reference to G~ch-ter/MUller, Plastic-additive, Carl Hanser-Verlag, Munich 1979, page 456 and Polymer ~ngineering and Science, July 1970, Vol 10, No. 4, page 241 to 246. Of these bio-stabilisers, copper-8-hydroxy quinoline and N-(trihalomethyltll:lo)-pl~thalimi~e have proved themselves particularly useful as biocides in soft-PVC products. According to German Offenlegungsschrift (DE-OS) 2 929 756 there may be used as anti~fouling materials in underwater coating agents, special dihalophenyl-~-chloro ethyl sulphone derivativ~s.
Triorgano tin compounds of the R3SnX type, where R is an organic radical, form a further group o.f bio-stabilisers which are known and used for their extraordinary effectiveness against the most varied types of micro organisms such as fungi, bacteria and algae. The effectiveness of such compounds depends substantially on the chain lengrth O:e the hydrocarbon radicals R
connected to the tin atom. Thus with trialkyl tin compounds best results have bee~n achieved when the to-tal number o~ car~)on ~torns :In the al~y~ ~rr~up~
is from 9 to 12, that is with tripropyl- and tributyl-tin compounds. Of the aryl compounds, the triphenyl compounds have an effect whichis comparable with the trialkyl compounds. The triorgano tin compounds are used for example as textile protective agents having a biocidal effect against fungi and bacteria, or as wood protective agents, for example in combatting wood-destroying fungi or ship's bore worms. As anti-fouling coatingsto prevent the underwater fouling of objects in seas,rivers or lakes, apart from Cu20, mercury compounds and also triorgano tin compounds, in particular tributyl- and triphenyl tin compounds have been used;
~3--3 6;~
in general composi.tions containing from 10 to 20%
of these active materials, based on the dried anti-fouling coatings7 are considered necessary. In addition, trihutyl tin compounds in particular have been used in bi.ocide coatings to preyent attack or ~ouling by microorgani.sms for example in damp areas. A further known use of triorgano tin compounds such as tributyl tin oxide, is to provide biocidal properties for plastics materials, and in particular plasticiser-containing plastics such as soft PVC. On the one hand the tri.organo tin compound functions as a fungus-preventative, in particular -~or theplasticisers, and on the other hand it functions as a fouling preventative against mi.cro organisms which positively attack the plastics material. However, since tributyl tin oxide,which is preferably used, is not light-resistant, so-called stabilised tributyl tin oxide has to be used. In addition it is known to use tributyl tin compounds as insecticides and as mollu~cicid~s, disinfectant agents and ~li.m~-~ombat~ln~ ag~nt.
in the paper industry In contrast to the lsnown use o~ triorgano tin compounds against a wide variety ol types of biologrical attack, hitherto inorganic tin compounds J diorgano tin compounds o~ the R2SnX2 type and mono organo tin compounds of the RSnX3 type have been considered to be practically useless in this biocidal area. In this regard reference is made to the technical specification pamphlet of Schering AG, Industrial Chemists J "Technical Production and Use of Organo tin compounds" by Dr. A.
Boghans and Dr. H. Plum,of March 1975.
Some diorgano tin compounds and some mono organo tin compounds are known, however J for their PVC
stabilising effect; in particular they serve to prevent decomposition reactions induced by heat, light or oxidation in PVC, and accordingly the compounds are used as stabilisers. However since they do not generally have good properties with respect to light fastness, waterproofness, lasting e~fect, heat s-tability and workability, they are usually not used alone, but rather in combination with other stabilisers.
~or example, dibu-tyl tin dilaur~te shows a good light-stabilising effect but a relatively poor heat-stability, and is thereIore usually only used in combination with other tin stabilisers which are better in their heat effect. Also, dibutyl tin maleate is agood stabiliser against the adverse ef~ects of heat, but as a ,polymer compound it is insoluble in PVC and so presents difficulties in working and has a tendency to plate-out.
In general the best heat stabilisers, which may be used in the high-temperature working of hard PVC tv form :eOx e~ample plates, sheets and bott~e~, ar~ ~:iorgan~h~o tin compounds which hav~ a dl,rec-t tin-~ùlphur bond such as dialkyl tin diiso octyl thioglycolate~s. These compounds have the disadvantage though that they do not keep for long in free weathering conditions, which leads to damage of the hard PVC. The same disadvantage applies to dioctyl tin compounds. However because of their non-toxicity, these compounds are used for the stabilising of PVC which is used for example in the packaging of foodstuffs. Poor weathering resistance is also a proper-ty of the toxically harmless mono organo tin compounds .
~. .
~ -5-~ ~ ~3 3 ~ ~2 7 such as polymeric monoalkyl tin oxides or-sulphides, which again are used to stabilise PVC against the ef-fect of heat and light in the field of foodstuff packaging.
Thus although certain organo tin compounds are used as stabilisers for PVC, their weather resistance is not sufficiently high for many areas of usage. In particular they are not generally good with regard to long-terrn colour stability, low water absorption, and decomposition, properties which are particularly required of, for example, window profiles, facade profiles and plates, roof sheeting, agricultural sheeting, swimming pool sheeting and covers for air halls. Hence in these and other areas o~ usage, in addition to the tin compounds which stablise PVC against decomposition through the effect of heat, light and oxidation, it is necessary to incorporate other stabilisers which are eIfective against weathering. According to the current state o~ development in the art, barium-cadmium stabilisers are thought to be superio~ ~o all o~h@r ~ab~ er~ and systems in this respe~c~. Thu~ ror the purpose~ o~
weather-resistance, organo tin compounds are not used alone as stabilisers since they show cléar damage after a short weathering time, see for example PLAST VERARBEITER, 30th Vol, 1979, No. 112, page 747 - 751 "Barium/Cadmium forthe stabilising of PVC,by Dr. P Bredereck and Dr. H.
Endriss".
A particularly rlifficult application of soft PVC
isin the manufacture of sheeting for use in swimming pools.
These require high weather-resistance and colour- and light ~astness, and also resistance to biological -6- .
attack by micro organisms and algae. It is known that swimming pool sheets of soft PVC tend -to deposit a slimy surface co~ting because the sur~ace roughness of the sheet acts as an adhesive base for micro organisms. This effect is made worse by the penetration ofmicro organisms, with the aid of water as a carrier, into the relatively soft material.
Because of the high requirements of swirnming pool coatings with regard to water-, weathering- and colour stability, the sheetings used are stabilised predominantly with barium-cadmium compounds. The problem of the slimy coating formation is generally indirectly solved by -the addition to the pool water of so-called water-maintenance agents such as chlorine- or bromine preparations having a strong oxidising effect. As a direct measure it has been known to use tributyl tin oxide as a so-called bio-stabiliser for the prevention of fouling in swimming pool sheeting. Tributyl tin oxide, as well as other known trialkyl tin compounds are however, very toxic, and more particularly they have a strong inhalation toxicity which leads ~o con~:LdQrabl~ probl@m~
for example dllr:ln~ t}le pto~luct:Lon o~ llle ~3heeting at high processing temperatures.
As is mentioned above, the stabilising ef~ect of diorgano- and mono organo tin compounds against the decomposition of PVC by the effect of light, heat and oxidation has been known ~or a long time. It has now surprisingly been discovered that in addition such compounds, and also certain tin salts, which until now have been considered biocidally ineffective against a wide ~3~
variety of microorganisms such as fungi, bacteria and algae, have a good effectiveness as anti-fouling agents i.e. agents which counter the settling or deposition of algae, micro-organisms and the like onto surfaces.
According to the present invention there is provided a plastic material which comprises plasticised polyvinyl chloride and an anti-fouling agent selected from inorganic divalent tin salts~ monovrgano-tin compounds of formula RSnX3 and diorgano tin compounds of formula R2SnX2 in which formulae the radicals R each represent a hydrocarbon radical, and either (i) each radical X represents an inorganic radical or an organic radical other than a hydrocarbon radical, or (ii~ two radicals X together represent an organic radical other than a hydrocarbon radical and any remaining radical X represents an inorganic radical or an organic radical other than a hydrocarbon radical, and wherein the anti-fouling agent is present in an amount so as to give the plastic material a tin content of from 0.05 to 1.2~ by weight.
In accordance w:ith anoth~r asp~t the present lnven-tion provides a method for preparing a sheet or foil of plas-ticised polyvinyl chloride having reduced susceptibility to fouling by algae or microorganisms, which comprises providing a plastic material which comprises plasticised polyvinyl chloride and an anti-fouling agent and moulding said plastic material into a sheet or foil thereof, the anti-fouling agent being selected from inorganic divalent tin salts, monoorgano-tin compounds of formula RSnX3 and diorgano tin compounds offormula R2SnX2 in which formulae the radicals R each represent a hydrocarbon radical, and either ~ ,. ~ ~
~ 8 -.. . ,.~ .
(i) each radical X represents an inorganic radical or an organic radical other than a hydrocarbon radical, or (ii) two radicals ~ together represent an organic radical other than a hydrocarbon radical and any remaining radical X represents an inorganic radical or an organic radical other than a hydrocarbon radical, and wherein the plastic material contains from 0.05~ to 1.2%
by weight of tin calculated from the specified anti-fouling agent.
The present invention particularly provides a method for preparing a sheet or foil of plasticised polyvinyl chloride, having reduced susceptibility to fouling by algae or microorganisms, which comprises admixing in the presence of one or more plasticisers, polyvinyl chloride with an anti-fouling agent and moulding the obtained plastic material into a sheet or foil, the anti-fouling agent being selected from inorganic divalent tin salts, monoorgano-tin compounds of formula RSnX3 and diorgano tin compounds of formula R2SnX2 in which formulae th~ radicals R each represent a hydrocarbon radical, and either (i) each radical X reprcsents an inorganic radical or an organic radical other than a hydrocarbon radical, or (ii) two radicals X together represent an organic radical other than a hydrocarbon radical and any xemaining radical X represents an inorganic radical or an organic radical other than a hydrocarbon radical, and wherein the plastic material which is formed by the admixing step contains from 0.05 to 1.2% by weight of tin calculated from the specified anti-fouling agent.
The use of the specified tin compounds in accordance ~-'A`' ~ - 8a -., !f with the invention yie`lds compositions having properties which have low toxicity or no toxicity at all, and which are therefore as harmless as possible to the environment. The material, for example soft PVC (polyvinyl chloride~ which may contain stabilisers such as barrium- cadmium compounds or calcium-zinc compounds to give light-, weather- and heat-resistance is preferably treated in accordance with the invention by admixing it with the anti-fouling agent to form a composition having anti-fouling properties. The composition formed by carrying out the method of the invention can contain from 0.05 (0.005) to 1.2% by weight/ more preferably from 0.1 to 0.5% by weight of tin calculated from the amount of /
~ 8b -~ ~3~
fou]ing agent used.
The hydrocarbon radicals R of the monoorgano and diorgano tin compounds are preferably alkyl groups such as methyl, bu-tyl or octyl. The radicals X may be for example halogen, preferably chlorine, sulphur or oxygen When X is an organic radical other than a hydrocarbon then it may be for example an alkoxide.or an ester radical of a saturated and/or unsaturated carboxylic acid such as a laurate or a maleate.
It is particularly preferred to use dialkyl tin compounds as anti-fouling agents accord:ing to the invention. By way of examp~ethere may be mentioned dibutyl tin dilaurate, dibutyl tin maleate, dioc-tyl tin dilaureate, or dioctyl tin maleate. It will be appreciated that in the general formula R2SnX2, the two radicals ~ may simply represent a divalent group such as maleate. Other useful dialkyl compounds which may be mentioned are di-n-but 1 tin dichloride, di-n-octyl tin dichloride, dibutyl tin oxide, dimethyl- or dibutyl tin sulphid~ and dialkyl tin oxid~$. ~ o proven to hav~ be~n ~'eec~iv@ :in accordance with the invention are dialkyl tin alkoxides in which one or both alkoxide groups have been replaced by dicarboxylic acid semi esters or thio carboxylic acld esters such as dibutyl tin methoxy maleic acid-rnethyl ester, di-n-octyl tin diiso octyl-thioglycolate or -maleate, dimethyl tin-diiso-octyI-thioglycolate and di-n-butyl tin diiso octyl thio glycolate. ~ feature of the invention is the fact that the predominant number of diorgano tin compounds used are toxically harmless, in contrast to the _9_ predominant number of triorgano tin compounds formerly used for these purposes.
Mono organo tin compounds may be used to treat materials in accordance with the invention. There are preferably used mono alkyl tin compounds or their polymeric form, or mono alkyl compounds in which the radicals X represent inorganic radicals such as halogens, sulphur or oxygen, for example n-butyl tin trichloride, monobutyl tin oxide or monobutyl tin sulphide. As 10 with the diorgano compounds~ X may be alkoxide, or instead one, two or three of the alkoxy groups may bé replaced by dicarboxylic acid semi esters and/or thio carboxylic acid esters and/or carboxylic acids, as in n-octyl tin tri iso octyl thioglycolate or n-octyl tin-bis-iso vctyl thioglycolate -laureate.
Of the inorganic tin salts which also surprisingly can be used as anti-fouling agents, particular menticnis made of tin chloride and tin sulpha-te. However a certain water-solubility in the tin salts can be disadvantag~ous insofar as it can lead, ~or examplc, to an ~ncr~as:lng roughness in the sur~ace o~ a coating.
With conventional bio-s~abili.sers it is normal to use from 0.3 to 5% by weight based on the material to be treated. However in accordance with the invention the tin compounds may be used to treat the material at starting concentrations of from 0.05 to 1.2.
preferably Ool to 0.5% tin calculated from the tin compounds added. Such proportions have been found to be sufficient as anti-fouling agents, although this depends on the field or area of usage and the requirements of this field. A preferred field of usage for the invention are --10-- .
~3~
weather-resistant products :Eormed from moulding materials based on so~t PVC treated by the method of the invention and optionally containing stabilisers for light-, weather~
and heat-resistance, and if necessary conventional additives such as colouring agents, fillers and lubricants.
The treating of such materials with from 0.05 -to 1.2, preferably 0.1 to 0.5% by weight of tin calculated -rom the tin compounds added for anti-f'ouling, based on 100%
by weight of the moulding material, is generally sufficient to achieve the desired effect.
The weater-resistant products based on soft PVC
treated in accordance with the invention have the advantage of' a good light-, weather- and heat-resistance through the use of' suitable stabilisers, preferably based on barium-cadmium compounds or calcium-zinc compounds or in combination wi-th other stabilisers, and at the same time they reduce or prevent the settling or deposition of' fouling, like algae or micro organisms.
Surprisingly, neither the light resistance, nor the weather-resistance, nor the h~at-r~s:Lstan~e, no~ th~
workability c~P the mould:ing material or products, is adversely a~fected by the tin compounds used according to t~ invention. On t~ contrary, the organo tin compounds used according to the invention generally have as a su'bsidiary eff'ect, an unexpected improvement in the Ba-Cd- or Cd-Zn basic stabilisation. In addition the selected tin compounds are for the most part toxically inactive, the majority o-i them being toxicologically harmless and even released for use by the health authorities.
`~` -1 1-As mentioned above, the preferred area of use of the invention is in the treatment of soft PVC materials.
These contain plasticisers, and require particular stability against bio~ogical attack on the plastic~sers.
Here it is particularly surprising that the tin compounds as de~ined, which were thought of until now as useless against biological attack, display an anti-fouling ef~ect. Applications of products based on soft PVC
are for example as sealing sheeting for coating or lining swimming pools, damp areas or cooling-water tanks, and as agricultural sheeting. The plasticisers which may be included in the PVC material are pre~erably esters o~ polybasic acids with monovalent alcohols, such as phthalates, es-ters of adipic acid and sebacic acid, trimellitic acid esters, or para~fin-sulphonic acid phenyl/cresyl esters. Preferab1y from 15 to 50%
by weight of plasticiser is used based upon the total weight o~ the composition.
PVC is not usually plasticised merely by th~
addition of low molccular w~ h~t pla~;t~ r~; u~ually high polymer plasticising additives such as ethylene vinyl acetate, ethylene vinyl acetate copolymers or chlorinated polyethylene are included. The moulding materials which are treated by the method of the invention preferably contain from 20 to 8~/o by weight of high polymer plasticising additives based on 100%
by weight of moulding material. It is pre~erred, though, that the plasticisexs and high polymer additives together do not amount to more than 80% by weight of the moulding material.
Materials treated by the method of the invention may be moulded into furnished products such as sealing sheeting based OD soft PVC, ~or the coating of water-containing receptacles or the like.
As may be seen ~rom the ~ollowing Examples very good results have been achièved in accordance with the invention. Thus the protective e~fect of the prevention o~ fouling for example in swimming pool sheeting and the prevention of formation of slimy surface coatings was practically as good as that o~
the known triorgano tin compounds, in particular of the hitherto preferably used trialkyl tin compounds. However, the anti-fouling agents of the invention have the advantage over hitherto used biostabilisers that they are substantially less toxic or not at all toxic. In addition because of the required extreme light- and weathering-resistance and the low water absorption, sealing sheeting which comes into contact constantly with water, is stabilised predominantly with barium-cadmium compounds or calcium-zinc compounds or i~ necessary combinations o~
these with ~urther stabili~ers. It i~ also surprl~ng that the anti~ouling agents o~' th0 invention d:l~play a par-ticularly good e~fectiveness on PVC moulding materials with a very high content of plasticiser.
A iurther feature of sealing sheet based on a material treated according to the invention which is used as swimming pool sheeting, is that a low concentration o~ maintenance additive is required to keep the water clean. In contrast,normally a speci~ic amount o~ maintenance agent is necessary to keep the water clean 3~ and clearland in swimming pools with little water movement a coating inevitably forms on the sheeting. In order to avoid this, the maintenance agents are o~ten added in excess. In addition to the strong annoying smells, this may be harmful to the skin and in particular for the eyes, and also harmful to the sheeting itself which may age prematurely.
'~F
Thé inven-tion is illustrated by the following Examples.
Comparison Example 1 A soft PVC sheet was produced by calendering (extruding) a mixture of the following: 100 parts by weight ofs(suspension)PVC, 62 parts by weight of a C8-C10 alkyl phthalate plasticiser, 3.3 parts by weight of epoxidised soya oil, 4 parts by weight of a commercial,liquid Ba/Cd stabiliser containing 6%
by weight of cadmium, and 7.8 parts by weight of conventional anti-oxidants, screening agents and dye (colour) pigments. The sheet thus produced was stored at room temperature in tap water, and after 7 days it was found that a slimy coating had ~ormed on the surface of the sheet. This coating consisted of micro organisms sticking to the sheet, and corresponded in the practical case o swimming pools to the starting point or origin of a progressive deterioration in the quality of the water as the micro organisms increased correspondingly. In :~ct th~ coat~.ng gr~w s~ron~r on further storage of the sh~et in tap wat~r, and after 60 days formed a layer thickness o~ about 0.5 mrn. The coating -itsel~ was slippery-slimy, and had an unpleasant i'eel.
C'omparison Example 2 The procedure of Comparison ~xample 1 was repeated, except that the composition used to form the sheeting additionally included 1.2 parts by weight of tributyl tin oxide No coating had been formed on the surface of the sheet after storage in tap water at room temperature for 14 days. In fact not until 60 days storage in tap water at room temperature did a barely perceptible slippery thin coating form on the surface of the sbeet;
this slightly strengthened during the next 30 days storage. Aftcr further stora~e there again occurred the formation of a coating which grew thicker. The disadvantage of this known biocidal material is its high toxicity, which greatly restricts its application possibilities.
Example 3 A composition was prepared as in Comparison Example 1 except that there was additionally included 2.43 parts by weight of a commercial dibutyl-tin-dithio glycolate;
this proportion corresponded to 0.4 parts by weight of -tin (0.23~ by weight of tin based on the composition as a whole). From this composition, as in Comparison Example 1, a sheet was produced which was tested in the same way.
After 14 days storage in water the sheet was still completely coating-free and after 60 days a barely perceptible coating had formed.
Example 4 A composition was prepared as in Comparison Example 1 except that there was additionally included 0.5 parts by weight oi thelinorganic Sn-salt, SnC12, corresponding to 0.31 parts by weigh-t Sn (0.17% by weight of Sn based on the composition as a whole). ~rom this composition, as in Comparison Example 1, a sheet was produced and tested under the same conditions. After 14 days storage the sheet was still completely coating free. After 60 days the sheet showed a slimy coating which was still less substan-tial than the sheet of Comparison Example 1 had shown .
~3~
after 7 days.
Example 5 The procedure of Comparison Example 1 was repeated except that the composition included 1 part by weight of a liquid dibutyl tin maleic acid ester, which corresponds to 0.19 parts by weight of Sn (0.11% by weight of Sn based on the composition as a whole). The sheet produced was tested under the same conditions as in Comparison Example 1 and showed the same be.haviour as the sheet according to Example 3.
Comparison Example 6 A sheet was produced by extrusion from a composition cons:isting of 100 parts by weigJht o~
PVC, 96 parts by weight of ethylene vinyl acetate copolymer, 6 parts by weight of epoxidised soya oil, 6 parts by weight of a liquid barium-cadmium stabiliser (with 6% by weight o~ cadmium) and 9.8 parts by weight of conventional anti-oxidants, screening agents and colour (dye~ pigments. The sheet was tes~ed under th~ same conditions as in Comparison Examp:lo 1, ~nd ~;howcd very similar behaviour ln its coating l'ormation to the sheet according to Compari.son Example 1.
Example 7 A composi-tion was -~ormed as in Comparison Example 6, except that there was included 1 part by weight o~ liquid dibutyl tin maleic acid ester, which corresponds tu 0.19 parts by weight of Sn (0.09% by weight of Sn based on the composition as a whole). A sheet was produced ~rom this composition as in Example 5, and on testing showed the same behaviour as the sheet of Example 4 with respect to coating formation, i.e. settling of micro organisms.
Example 8 The procedure o-.f ~xample 7 was repeated except that 2 parts by weight of the liquid dibutyl tin maleic acid ester were incorporated. On testing it was found that the sheet produced was even less prone to coating ~ormation after 60 days storage in water than the sheet of Example 7, i.e. it was still practically coating-free and was hardly slippery. From this it rnay be concluded that a higher content of active su~stance according to the invention shows a better and longer lasting e~ectiveness ~or the prevention of fouling, i.e. ~or preventing the formation of' slimy/slippe~ coa-tings on the sheet.
Example g To a composition according to Comparison Example 1 were added 3.5 parts by weight of n-butyl-tin- tri iso octyl thio glycolate, which corresponds to 0.53 parts by weight of tin (0.29% by weight of tin based on the composition as a whole). A shec~t w~s produ~ nd t~.Jt~d under the same conditi.ons as i.n Compari~on Ii,xarnple 1. This behaved similarly in its coating formation as the ~heet according to Example 7.
The following Table summaris~ the coating ~orrnation properties of the sheets according to the Examples over a period of up to 90 days. The code numbers 0-4 as used in the Table correspond to the following results:
O no coating 1 hardly perceptible coati.ng
2 slight coating
3 slippery coating
4 thick slippery coating Example (coating value code) Duration o~ test 1 2 3 4 5 6 :7 8 9 (days) .. . 7 3 0 0 0 0 3 0 0 0 .. . .. ..
28 4. 0 0 1 0 4 1 0 4 1 1 2 1 ~ 2 1 2 A sheet is manufactured by extrusion from a formula tion of 100 parts by weight of sequence ethylene-propylene-polymer (buna*AP447 - Chemi~ch~ Werke l:luels), I.0 parts by weiyht of polyethylen~ 90 parts b~ w~i.ght of chalkt 10 parts by weight of epoxidized soybean oi.l, 0.3 parts by weight of a lubricant, 0-6 parts by weiyht o liyht protection ayent, 4 parts by weight of T102*and 0.5 parts by weight of color-ing pigments. The sheet is tested under the conditions described in Example 1. This sheet shows a very similar be-havior in plaque formation as the sheet of Example 1.
* Trademark ~ ~3~
-A foxmulation acco~din~ to Example 10 was co~bi~ed with 2 parts by weight o~ dibutylin oxide~ A sheet is produc-ed from this formulation as in Example 10, and tested~ This sheet shows a better behavior regarding prevention of plaque formations, I.E. establishment of microorganisms and first slight plaque is formed on the surface after 28 days of test-ing in tap water, same behavior as sheet of Example 3.
28 4. 0 0 1 0 4 1 0 4 1 1 2 1 ~ 2 1 2 A sheet is manufactured by extrusion from a formula tion of 100 parts by weight of sequence ethylene-propylene-polymer (buna*AP447 - Chemi~ch~ Werke l:luels), I.0 parts by weiyht of polyethylen~ 90 parts b~ w~i.ght of chalkt 10 parts by weight of epoxidized soybean oi.l, 0.3 parts by weight of a lubricant, 0-6 parts by weiyht o liyht protection ayent, 4 parts by weight of T102*and 0.5 parts by weight of color-ing pigments. The sheet is tested under the conditions described in Example 1. This sheet shows a very similar be-havior in plaque formation as the sheet of Example 1.
* Trademark ~ ~3~
-A foxmulation acco~din~ to Example 10 was co~bi~ed with 2 parts by weight o~ dibutylin oxide~ A sheet is produc-ed from this formulation as in Example 10, and tested~ This sheet shows a better behavior regarding prevention of plaque formations, I.E. establishment of microorganisms and first slight plaque is formed on the surface after 28 days of test-ing in tap water, same behavior as sheet of Example 3.
Claims
The embodiments of the invention in which an exclu-sive property or privilege is claimed are defined as follows:
1. A method for preparing a sheet or foil of plasti-cised polyvinyl chloride having reduced susceptibility to fouling by algae or microorganisms, which comprises providing a plastic material which comprises plasticised polyvinyl chlo-ride and an anti-fouling agent, and moulding said plastic mate-rial into a sheet or foil thereof, the anti-fouling agent being selected from inorganic divalent tin salts, mono organo-tin compounds of formula RSnX3 and diorgano tin compounds of formula R2SnX2 in which formulae the radicals R each represent a hydrocarbon radical, and either (i) each radical X represents an inorganic radical or an organic radical other than a hydrocarbon radical, or (ii) two radicals X together represent an organic radical other than a hydrocarbon radical and any remaining radical X represents an inorganic radical or an organic radical other than a hydrocarbon radical, and wherein the plastic material contains from 0.05% to 1,2% by weight of tin calculated from the specified anti-fouling agent.
2. A method for preparing a sheet or foil of plasti-cised polyvinyl chloride, having reduced susceptibility to fouling by algae or microorganisms, which comprises admixing in the presence of one or more plasticisers, polyvinyl chloride with an anti-fouling agent , and moulding the obtained plastic material into a sheet or foil, the anti-fouling agent being selected from inorganic divalent tin salts, mono organo-tin compounds of formula RSnX3 and diorgano tin compounds of formula R2SnX2 in which formulae the radicals R each represent a hydrocarbon radical, and either (i) each radical X represents an inorganic radical or an organic radical other than a hydrocarbon radical, or (ii) two radicals X together represent an organic radical other than a hydrocarbon radical and any remaining radical X represents an inorganic radical or an organic radical other than a hydrocarbon radical, and wherein the plastic material which is formed by the admixing step contains from 0.05 to 1.2% by weight of tin calculated from the specified anti-fouling agent.
3. A method according to claim 2 wherein for the formulae each radical R represents an alkyl group.
4. A method according to claim 3 wherein for the formulae, each radical R represents butyl, methyl or octyl.
5. A method according to claim 2 wherein each radical X represents halogen, sulphur or oxygen.
6. A method according to claim 2 wherein each radical X represents an alkoxide radical.
7. A method according to claim 2 wherein each radical X is an ester radical of a saturated or unsaturated carboxylic acid group.
8. A method according to claim 7 wherein each radical X represents a laurate group.
9. A method according to claim 2 wherein two radicals X together represent a maleate group.
10. A method according to claim 2 wherein each radical X represents an ester radical of a dicarboxylic acid semi-ester or a thiocarboxylic acid ester.
11. A method according to claim 10 wherein one or more of the radicals X represents a methyl maleic acid semi-ester radical, an isooctyl thioglycolate, or an isooctyl thiomaleate.
12. A method according to claim 2 wherein the anti-fouling agent is an inorganic divalent tin salt selected from the group consisting of tin chloride, tin sulphate and mixtures thereof.
13. A method according to claim 2 wherein the anti-fouling agent is a mono organo tin compound selected from the group consisting of n-butyl tin trichloride, mono-butyl tin oxide, monobutyl tin sulphide, a monoalkyl tin alkoxide, n-octyl tin triiso octyl thioglycolate, n-octyl tin bis-isooctyl thioglycolate-laurate and mixtures thereof.
14. A method according to claim 2 wherein the anti-fouling agent is a diorgano tin compounds selected from the group consisting of dibutyl tin dilaurate, dibutyl tin maleate, dioctyl tin dilaurate, dioctyl tin maleate, di-n-butyl tin chloride, di-n-octyl tin dichloride, dibutyl tin oxide, dimethyl tin sulphide, dibutyl tin sulphlde, a dialkyl tin alkoxide, dibutyl tin methoxy maleic acid methyl ester, di-n-octyl tin diiso octyl thioglycolate, di-n-octyl tin diiso octyl thiomaleate, dimethyl tin diiso octyl thio-glycolate, di-n-butyl tin diiso octyl thioglycolate and mixtures thereof.
15. A method according to claim 2 wherein the composition which is formed by the admixing step contains from 0.1 to 0.5% by weight of tin calculated from the specified anti-fouling agent .
16. A method according to claim 2 wherein the polyvinyl chloride and anti-fouling agent are admixed in the presence of a stabiliser for light, weather and heat resistance.
17. A method according to claim 16 wherein the stabiliser comprises barium-cadmium compounds.
18. A method according to claim 16 wherein the stabiliser comprises calcium-zinc compounds.
19. A method according to claim 2 wherein the plastic material obtained by said admixing contains from 15 to 50%
by weight of plasticiser, based on the weight of the plastic material.
20. A method according to claim 2 wherein the plasti-ciser is an ester of a polybasic acid and a monoalcohol.
21. A method according to claim 21 wherein the plas-ticiser is an ester of a polybasic acid and a monoalcohol.
22. A method according to claim 20 or 21 wherein the plasticiser is an ester of a phthalic acid, adipic acid, sebacic acid or trimellitic acid, or is a paraffin-sulphonic acid-phenyl/cresyl ester.
23. A method according to claim 2 wherein the admixing occurs in the presence of an additional high polymer plasticising additive.
24. A method according to claim 23 wherein the high polymer plasticising additive is an ethylene vinyl ace-tate copolymer or chlorinated polyethylene.
25. A method according to claim 23 wherein the amount of plasticiser and high polymer additive which is additionally includes stabilisers for light, weather and heat resistance , and/or conventional additives selected from colouring agents, fillers and lubricants.
31. A plastic material according to claim 28 when in the form of sheeting having anti-fouling properties.
1. A method for preparing a sheet or foil of plasti-cised polyvinyl chloride having reduced susceptibility to fouling by algae or microorganisms, which comprises providing a plastic material which comprises plasticised polyvinyl chlo-ride and an anti-fouling agent, and moulding said plastic mate-rial into a sheet or foil thereof, the anti-fouling agent being selected from inorganic divalent tin salts, mono organo-tin compounds of formula RSnX3 and diorgano tin compounds of formula R2SnX2 in which formulae the radicals R each represent a hydrocarbon radical, and either (i) each radical X represents an inorganic radical or an organic radical other than a hydrocarbon radical, or (ii) two radicals X together represent an organic radical other than a hydrocarbon radical and any remaining radical X represents an inorganic radical or an organic radical other than a hydrocarbon radical, and wherein the plastic material contains from 0.05% to 1,2% by weight of tin calculated from the specified anti-fouling agent.
2. A method for preparing a sheet or foil of plasti-cised polyvinyl chloride, having reduced susceptibility to fouling by algae or microorganisms, which comprises admixing in the presence of one or more plasticisers, polyvinyl chloride with an anti-fouling agent , and moulding the obtained plastic material into a sheet or foil, the anti-fouling agent being selected from inorganic divalent tin salts, mono organo-tin compounds of formula RSnX3 and diorgano tin compounds of formula R2SnX2 in which formulae the radicals R each represent a hydrocarbon radical, and either (i) each radical X represents an inorganic radical or an organic radical other than a hydrocarbon radical, or (ii) two radicals X together represent an organic radical other than a hydrocarbon radical and any remaining radical X represents an inorganic radical or an organic radical other than a hydrocarbon radical, and wherein the plastic material which is formed by the admixing step contains from 0.05 to 1.2% by weight of tin calculated from the specified anti-fouling agent.
3. A method according to claim 2 wherein for the formulae each radical R represents an alkyl group.
4. A method according to claim 3 wherein for the formulae, each radical R represents butyl, methyl or octyl.
5. A method according to claim 2 wherein each radical X represents halogen, sulphur or oxygen.
6. A method according to claim 2 wherein each radical X represents an alkoxide radical.
7. A method according to claim 2 wherein each radical X is an ester radical of a saturated or unsaturated carboxylic acid group.
8. A method according to claim 7 wherein each radical X represents a laurate group.
9. A method according to claim 2 wherein two radicals X together represent a maleate group.
10. A method according to claim 2 wherein each radical X represents an ester radical of a dicarboxylic acid semi-ester or a thiocarboxylic acid ester.
11. A method according to claim 10 wherein one or more of the radicals X represents a methyl maleic acid semi-ester radical, an isooctyl thioglycolate, or an isooctyl thiomaleate.
12. A method according to claim 2 wherein the anti-fouling agent is an inorganic divalent tin salt selected from the group consisting of tin chloride, tin sulphate and mixtures thereof.
13. A method according to claim 2 wherein the anti-fouling agent is a mono organo tin compound selected from the group consisting of n-butyl tin trichloride, mono-butyl tin oxide, monobutyl tin sulphide, a monoalkyl tin alkoxide, n-octyl tin triiso octyl thioglycolate, n-octyl tin bis-isooctyl thioglycolate-laurate and mixtures thereof.
14. A method according to claim 2 wherein the anti-fouling agent is a diorgano tin compounds selected from the group consisting of dibutyl tin dilaurate, dibutyl tin maleate, dioctyl tin dilaurate, dioctyl tin maleate, di-n-butyl tin chloride, di-n-octyl tin dichloride, dibutyl tin oxide, dimethyl tin sulphide, dibutyl tin sulphlde, a dialkyl tin alkoxide, dibutyl tin methoxy maleic acid methyl ester, di-n-octyl tin diiso octyl thioglycolate, di-n-octyl tin diiso octyl thiomaleate, dimethyl tin diiso octyl thio-glycolate, di-n-butyl tin diiso octyl thioglycolate and mixtures thereof.
15. A method according to claim 2 wherein the composition which is formed by the admixing step contains from 0.1 to 0.5% by weight of tin calculated from the specified anti-fouling agent .
16. A method according to claim 2 wherein the polyvinyl chloride and anti-fouling agent are admixed in the presence of a stabiliser for light, weather and heat resistance.
17. A method according to claim 16 wherein the stabiliser comprises barium-cadmium compounds.
18. A method according to claim 16 wherein the stabiliser comprises calcium-zinc compounds.
19. A method according to claim 2 wherein the plastic material obtained by said admixing contains from 15 to 50%
by weight of plasticiser, based on the weight of the plastic material.
20. A method according to claim 2 wherein the plasti-ciser is an ester of a polybasic acid and a monoalcohol.
21. A method according to claim 21 wherein the plas-ticiser is an ester of a polybasic acid and a monoalcohol.
22. A method according to claim 20 or 21 wherein the plasticiser is an ester of a phthalic acid, adipic acid, sebacic acid or trimellitic acid, or is a paraffin-sulphonic acid-phenyl/cresyl ester.
23. A method according to claim 2 wherein the admixing occurs in the presence of an additional high polymer plasticising additive.
24. A method according to claim 23 wherein the high polymer plasticising additive is an ethylene vinyl ace-tate copolymer or chlorinated polyethylene.
25. A method according to claim 23 wherein the amount of plasticiser and high polymer additive which is additionally includes stabilisers for light, weather and heat resistance , and/or conventional additives selected from colouring agents, fillers and lubricants.
31. A plastic material according to claim 28 when in the form of sheeting having anti-fouling properties.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3014291.7 | 1980-04-15 | ||
| DE3014291A DE3014291C2 (en) | 1980-04-15 | 1980-04-15 | Sealing membrane based on soft PVC |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1183627A true CA1183627A (en) | 1985-03-05 |
Family
ID=6099974
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000375610A Expired CA1183627A (en) | 1980-04-15 | 1981-04-15 | Improving algae or micro-organism anti-fouling of materials |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0038971B1 (en) |
| JP (1) | JPS56161305A (en) |
| AT (1) | ATE16676T1 (en) |
| AU (1) | AU549566B2 (en) |
| CA (1) | CA1183627A (en) |
| DD (1) | DD159548A5 (en) |
| DE (2) | DE3014291C2 (en) |
| ES (1) | ES501320A0 (en) |
| GR (1) | GR75622B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012116797A1 (en) * | 2011-03-03 | 2012-09-07 | Renolit Se | Method for applying an antifouling paint |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2307092A (en) * | 1940-11-09 | 1943-01-05 | Carbide & Carbon Chem Corp | Stabilized artificial resins |
| US2307157A (en) * | 1942-07-01 | 1943-01-05 | Carbide & Carbon Chem Corp | Stabilized vinyl resin |
| US2731484A (en) * | 1950-06-27 | 1956-01-17 | Firestone Tire & Rubber Co | Preparation of organotin mercaptides |
| US2746946A (en) * | 1952-01-11 | 1956-05-22 | Metal & Thermit Corp | Vinyl resins stabilized with organotin sulfides |
| NL87074C (en) * | 1954-11-08 | 1900-01-01 | ||
| US3067166A (en) * | 1959-09-17 | 1962-12-04 | Ferro Corp | Stabilized halogen containing vinyl resins |
| BE667359A (en) * | 1964-07-23 | |||
| US3391174A (en) * | 1965-02-16 | 1968-07-02 | M & T Chemicals Inc | Novel process for preparing bis (triorganotin) sulfates and bis (triorganotin) sulfites |
| US3644589A (en) * | 1969-03-13 | 1972-02-22 | Gen Tire & Rubber Co | Method of imparting self-extinguishing flame properties to impact-modified polyvinyl chloride |
| US4041014A (en) * | 1970-04-27 | 1977-08-09 | M&T Chemicals Inc. | Non-toxic stabilizer for vinyl chloride resins |
| BE791628A (en) * | 1971-11-19 | 1973-03-16 | Albright & Wilson | ORGANOETAN COMPOUNDS AND THEIR USE |
| CH588980A5 (en) * | 1974-01-17 | 1977-06-30 | Ciba Geigy Ag | |
| DD137312A3 (en) * | 1975-05-23 | 1979-08-29 | Christian Roehr | METHOD FOR STABILIZING POLYMERS AGAINST THERMOTO AND PHOTO-MXIDATIVE REMOVAL |
-
1980
- 1980-04-15 DE DE3014291A patent/DE3014291C2/en not_active Expired
-
1981
- 1981-04-03 GR GR64573A patent/GR75622B/el unknown
- 1981-04-09 EP EP81102689A patent/EP0038971B1/en not_active Expired
- 1981-04-09 DE DE8181102689T patent/DE3173048D1/en not_active Expired
- 1981-04-09 AT AT81102689T patent/ATE16676T1/en active
- 1981-04-14 ES ES501320A patent/ES501320A0/en active Granted
- 1981-04-15 CA CA000375610A patent/CA1183627A/en not_active Expired
- 1981-04-15 DD DD81229264A patent/DD159548A5/en unknown
- 1981-04-15 JP JP5573881A patent/JPS56161305A/en active Pending
- 1981-04-15 AU AU69582/81A patent/AU549566B2/en not_active Ceased
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012116797A1 (en) * | 2011-03-03 | 2012-09-07 | Renolit Se | Method for applying an antifouling paint |
Also Published As
| Publication number | Publication date |
|---|---|
| DD159548A5 (en) | 1983-03-16 |
| AU549566B2 (en) | 1986-01-30 |
| GR75622B (en) | 1984-08-01 |
| DE3173048D1 (en) | 1986-01-09 |
| AU6958281A (en) | 1981-10-22 |
| EP0038971B1 (en) | 1985-11-27 |
| ES8207550A1 (en) | 1982-09-16 |
| EP0038971A2 (en) | 1981-11-04 |
| ATE16676T1 (en) | 1985-12-15 |
| DE3014291A1 (en) | 1981-10-29 |
| EP0038971A3 (en) | 1982-04-21 |
| ES501320A0 (en) | 1982-09-16 |
| DE3014291C2 (en) | 1986-05-15 |
| JPS56161305A (en) | 1981-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU685234B2 (en) | Polyol ester PVC plasticizers | |
| CA1254377A (en) | Stabilizers for halogen-containing organic polymers comprising an organotin mercaptide and a diester of an unsaturated dicarboxylic acid | |
| CA1193373A (en) | Biocide material combination and its use in plastics moulding compositions | |
| EP0550010A1 (en) | Agricultural film | |
| US5102933A (en) | Polyvinylchloride composition and stabilizers therefor | |
| JP2008528726A (en) | Halogenated vinyl halide polymer composition and composite sheet | |
| CA1183627A (en) | Improving algae or micro-organism anti-fouling of materials | |
| US4617328A (en) | Biocidal agents for use in plastics, polymers and cellulosic materials | |
| DE2802531C2 (en) | ||
| CA1124503A (en) | Vinyl chloride polymers having improved stability | |
| CA1294775C (en) | Stabilizers for halogen-containing polymers comprising the product of a diorganotin oxide, an ethylenically unsaturated dicarboxylic acid ester and a mercaptan | |
| KR20000035650A (en) | Stabilizers For Improved Weatherability of Clear Polyvinyl Chloride Compositions | |
| US3533993A (en) | Vinyl chloride resins stabilized with 2 - mercaptopyridine - 1 - oxide and derivatives | |
| EP0165005B1 (en) | Process for protecting flora using stabilised polymer films | |
| CA1257440A (en) | Benzoate-stabilized rigid polyvinyl chloride compositions | |
| US5516821A (en) | Polymer stabilizer and polymer compositions stabilized therewith | |
| JPS57156408A (en) | Antifouling composition | |
| CA1333957C (en) | Compositions for stabilizing halogen-containing organic polymers | |
| JPS58125737A (en) | Vinyl chloride resin film for agricultural purpose | |
| JPH0639550B2 (en) | Agricultural polyethylene resin film | |
| JPH01202446A (en) | Agricultural laminated film | |
| US3943097A (en) | Polyvinyl chloride compositions containing trixylyl phospate and a second plasticizer | |
| CA1063792A (en) | Vinyl halide resin compositions | |
| JPS62122753A (en) | Agricultural laminated film having excellent transparent durability | |
| JPS5817505B2 (en) | Polyencabinyl cage resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |