CA1050683A - Acrylic polymer plastisols - Google Patents
Acrylic polymer plastisolsInfo
- Publication number
- CA1050683A CA1050683A CA239,683A CA239683A CA1050683A CA 1050683 A CA1050683 A CA 1050683A CA 239683 A CA239683 A CA 239683A CA 1050683 A CA1050683 A CA 1050683A
- Authority
- CA
- Canada
- Prior art keywords
- plastisol
- polymer
- weight
- parts
- plasticiser
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
Abstract
ABSTRACT OF THE DISCLOSURE
PVC-plastisols are well known in many industrial processes.
However, it is now know that vinyl chloride per so presents a health hazard.
known plastisols of PVC have a disadvantage in that they tend to release vinyl chloride during processing. The present invention seeks to overcome this drawback of the prior art by providing a plastisol, in which solid particles of an organic polymer component (a) are dispersed in an organic liquid compo-ment (b), which serves as a compatible plasticiser for the organic polymer, in a proportion effective to form a viscous dispersion having a liquid or past-like appearance capable of being gelled by heating, the improvement in which the organic polymer component consists substantially of units derived from (i) at least one monomer selected from: t-butly acrylate, a C1-4 alkyl methacrylate and cyclohexyl methacrylate, or (ii) at least one of the above monomers and at least one comonomer selected from: methacrylates of aliphatic C2 to C10 alcohols, acrylates of aliphatic C1-C10 alcohols, styrene and alpha-styrene, the polymer having a glass transition temperature of above 35°C and an average degree of poly-merization of more than 400, and the average particle size of the polymer in the plastisol being from 0.1 to 500 microns; said plasticiser being present in an amount of from 30 to 1000 parts per 100 parts by weight of said polymer and being sufficiently compatible that at least 8 days after the gelling of said plastisol, the plasticiser does not exude from said plastisol, said plasticiser moreover being effective to provide the plastisol with a viscosity index V8/0 of less than 3Ø
PVC-plastisols are well known in many industrial processes.
However, it is now know that vinyl chloride per so presents a health hazard.
known plastisols of PVC have a disadvantage in that they tend to release vinyl chloride during processing. The present invention seeks to overcome this drawback of the prior art by providing a plastisol, in which solid particles of an organic polymer component (a) are dispersed in an organic liquid compo-ment (b), which serves as a compatible plasticiser for the organic polymer, in a proportion effective to form a viscous dispersion having a liquid or past-like appearance capable of being gelled by heating, the improvement in which the organic polymer component consists substantially of units derived from (i) at least one monomer selected from: t-butly acrylate, a C1-4 alkyl methacrylate and cyclohexyl methacrylate, or (ii) at least one of the above monomers and at least one comonomer selected from: methacrylates of aliphatic C2 to C10 alcohols, acrylates of aliphatic C1-C10 alcohols, styrene and alpha-styrene, the polymer having a glass transition temperature of above 35°C and an average degree of poly-merization of more than 400, and the average particle size of the polymer in the plastisol being from 0.1 to 500 microns; said plasticiser being present in an amount of from 30 to 1000 parts per 100 parts by weight of said polymer and being sufficiently compatible that at least 8 days after the gelling of said plastisol, the plasticiser does not exude from said plastisol, said plasticiser moreover being effective to provide the plastisol with a viscosity index V8/0 of less than 3Ø
Description
~5D6~3 The invention relates to novel plastisols based on acrylate polymers and orga~ic plasticisersO
Plastisols are generally understood to mean dispersions of organic plastics in plasticisers, which are gelled on heating to an elevated temperature. The presently conventional plastisols generally comprise pulverulent polyvinyl-chloride dispersed in a compatible liquid plasticiser w~ich forms a pasteO Polyvinyl-chloride plastisols are used for numerous different purposes, particularly as sealing compounds, as anti-corrosive coatings for metals, for impregnating and coating textile substrates, as cable insulations, etc.
However, several serious problems occur in the production and use of PVC-plastisolsO In fact, the production of PVC itself represents a problem because persons working in the production area may be exposed to a health risk by the vinyl chloride. Of late this has led to the closing of a large number of PVC factories.
Residual momomer in the PVC could also endanger people during processing, and possibly even~the final consumer if the plastigel 1- comes into contact with foodstuffs. -` When using PVC-plastisols, it is disadvantageous that PVC
- 20 is both sensitive to light and heat and tends to split off hydrogen chloride, me splitting off of hydrogen chloride represents a particularly serious problem because during use the plastisol must be heated to an elevated temperature, and any hydrogen ~-~
chloride liberated ~mder these conditions has a corrosive effect and, for example, corrodes metal substrates. Attempts have been made to counteract thermal decomposition by adding heat stabilisers, ., ' ~,,'~'''' , ;. . .: ~',
Plastisols are generally understood to mean dispersions of organic plastics in plasticisers, which are gelled on heating to an elevated temperature. The presently conventional plastisols generally comprise pulverulent polyvinyl-chloride dispersed in a compatible liquid plasticiser w~ich forms a pasteO Polyvinyl-chloride plastisols are used for numerous different purposes, particularly as sealing compounds, as anti-corrosive coatings for metals, for impregnating and coating textile substrates, as cable insulations, etc.
However, several serious problems occur in the production and use of PVC-plastisolsO In fact, the production of PVC itself represents a problem because persons working in the production area may be exposed to a health risk by the vinyl chloride. Of late this has led to the closing of a large number of PVC factories.
Residual momomer in the PVC could also endanger people during processing, and possibly even~the final consumer if the plastigel 1- comes into contact with foodstuffs. -` When using PVC-plastisols, it is disadvantageous that PVC
- 20 is both sensitive to light and heat and tends to split off hydrogen chloride, me splitting off of hydrogen chloride represents a particularly serious problem because during use the plastisol must be heated to an elevated temperature, and any hydrogen ~-~
chloride liberated ~mder these conditions has a corrosive effect and, for example, corrodes metal substrates. Attempts have been made to counteract thermal decomposition by adding heat stabilisers, ., ' ~,,'~'''' , ;. . .: ~',
- 2 _ ' `
~5~3 but these compounds are frequently toxic so that they cannot be used where the plastisol comes in~o contact with foodstuffs. The above-indicated problems are further exacerbated in that in certain special cases PVC-plastisols require relatively high baking temperatures in order to obtain very short gelling times so tha~ the danger of PVC-decomposition is urther increased.
It is the object of the invention to develop novel plastisols which also have the excellen* processing and product characteristics of PVC-plastlsols but which gel at lower temperatures and are also chlorine-free so that there can be no splitting off of chlorine or hydrogen chloride. It has surprisingly been found that this problem can be solved in that for the production of the plastisols particular acrylic polymers are used and pro-cessed with plasticisers.
According to the present invention an improvement is provided in a plastisol, in which solid particles of an organic polymer component ~a) are dispersed in an organic liquid component ~b), which serves as a compatible plasticiser for the organic polymer, in a proportion effective to form a ;, viscous dispersion having a liquid or paste-like appearance capable of being gelled by heating, the improvement in which the organic polymer compone~t consists substantially of units derived from ~i) at least one monomer selected from: t-butyl acrylate, a Cl 4 alkyl methacrylate and cyclohexyl methacrylate, or `
~ii) at least one of the above monomers and at least one comonomer selected from: methacrylates of aliphatic C2 to C10 alcohols, acrylates of aliphatic Cl-C10 alcohols, styrene and alpha~methyl styrene, the polymer ;~
having a glass transition temperature of above 35C and an average degree of - polymerization of more than 400, and the average particle size of the polymer in the plastisol being from 0.1 to 500 microns; said plasticiser being present in an amount of from 30 to 1000 parts per 100 parts by weight of said polymer and being sufficiently compatible that at least 8 days after the gelling of said plastisol, the plasticiser does not exude from said plastlsol, said plasticiser moreover being effective to pro~ide the plastisol with a viscosity index V8/o of less than 3Ø
~k .
~ ~ 3 ~ . ,..: .~
~05~83 The present inven-tion also provides a plastiso:L comprising ~a) 100 weight parts of solid particles of an organic polymer selected from t-butylacrylate or methyl, ethyl, n-propyl, isopropyl, isobutylJ sec-butyl, t-butyl or cyclohexylmethacrylate homopolymers, and copolymers of at least one said monomer with at least one comonomer selected from methacryla~es of aliphatic C2 to C10 alcoholsJ acrylates of Cl to C10 alcohols, styrene and a-methyl-styrene~ whereby the polymer has an average parti~le size of 0.1 to 500 microns~ a glass transition temperature above 35C and an average degree of polymerization of more than 400, and (b) 30 to 1000 parts of an organic ~ 10 liquid plasticiser which is sufficiently compatible with the polymer that at :~ least 8 days after gelling of said plastisol the plasticiser does not exude from said plastisolJ said plasticiser further being effective to provide the plastisol with a viscosity index V8/o of less than 3.0; the average particle size of polymer ~a) being related to its glass transition temperature so as to lie with m the triangle XYZ of the accompanying drawing, said plastisol further being in the form of a liquid or paste-like dispersion of polymer -.
particles (a) in plasticiser ~b) capable of being gelled by heating to a temperature between about 70 and 240C.
There is also provided in accordance with the present invention a homogeneousJ elasticJ solid gel formed by heating to a temperature between about 70 and 240C a plastisol comprising solid particles of average particle size 0.1 to 500 microns of an organic polymer having a glass transition temperature above 35C and consisting of 40-100% of units derived from methyl methacrylateJ 0-60% o~ units derived from a first comonomer selected from alkyl acrylates having 1-4 carbon atoms in the alkyl portion and alkyl meth-acrylates having 2-4 carbon atoms in the alkyl portionJ 0-3% of units derived from a second comonomer selected from methacrylic and acrylic compounds having at least one hydroxylJ epoxyJ amino or carboxylic acid groupJ and 0-10% of units derived from a third comonomer which is a heterocyclic vinyl compound of the general formula -3a-, . . ~ .............. : .
,, :- . . . ~`' '' ~ ': , : .
lalS/~ 3 C~12= C- ~C~12)n R2 in which n is 0 or 1, Rl is selected from hydrogen, alkyl of 1 to 4 carbon atoms and phenyl and R2 is selected from -C-OR3, -COR3 and -R3 in which R3 is o a heterocyclic group having at least one ring containing a nitrogen atom, all percentages being by weight, the degree of polymerization of the polymer being more than 400, based on methyl methacrylate and the first comonomer when used dispersed in (b) an amount of compatible organic liquid plasticiser effective to form a viscous plastisol the viscosity of which does not increase by more than 300% within 3 days of preparation; said amount being in the range of from 30 to 1000 parts per 100 parts by weight of said polymer, said plasticiser being sufficiently compatible that at least 8 days after ~he gelling of said plastisol, the plasticiser does not exude from said plastisol.
~' '' ' `' ' '.
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, ~:
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~ -3b-,j ~, The average particle s~ e of the polymer used is preferably increased proportionally with the decrease of its glass transition temperature Tg. The glass transition temperature is preferably above 60 C.
To obtain usable resultsg the degree o~ polymerisation ; of the polymer used must be at least about 400.
Advantageously the degree of polymerisation is between 400 and 20,000~ corresponding to an average molecular weight of about 40,000 to 2,000,000.
The preferred polymer component consists substantially wholly of one kind of units derived from t-butyl acrylate, methyl~ ethyl~ n-propyl~ isopropyl~ n-butyl, sec-butyl or t-butyl methacrylate or cyclohexyl me~hacrylate~ i.e. is ; essentially a homopolymer. Methyl methacrylate is preferred. The alcohol acrylate or methacrylate comonomers ` preferably have an alkanol alcohol component, i.e. are unsubstituted and saturated~ and the type (i) monomers, i.e. those listed above~ will generally predominate over those of type (ii). The preferred copolymers are those in which one of the monomers is methyl methacrylate and constitutes at least 40%, preferably at least 5U~ by weight of the total monomer units, and the other component is a C2 4 alkyl methacrylate, especially n-butyl methacrylate, ~-or a Cl 4 alkyl acrylate~
However, within the scope of the present invention only those copolymers can be used whose glass transitiOn or solidification temperature is above about 35C. The glass transition te~perature T of a particular copolymer can be calculated beforehand by the Fox formula (T.G. Fox, Bull~ Am. Phys~ Soc., vol. 1~ 123 (1956)):
~ - 4 -31~05~6~3 ,:
i 1 Wl W2 n Co Tl T2 T
wherein Wl represents the weight por~ion of monomer 1, ~2 the weight portion of monomer 2~ Tl the glass transition temperature of the polymerised monomer 1 in K~ T2 the glass transition temperature of the polymerised monomer 2 in K3 TC the glass transition temperat~e of the copolymer in ~0 . , ; ~
' . ' j - 4a - .
;83 The aYerage particle size of the polymer used must be between about 0.1 pm and 500 ~m~ preferably between 0.3 and 200 ~m. If too large a particle size is used, the plastisol obtained ~rill not have ~n adequate internal bond, and no complete gelling of the polymer occurs. If the particle size is too small, the storage stability is inadequate~ i.e. gelling occurs even when the polymer is left to stand.
As will be explained relative to the attached dra~ing, when using a plastisol there is an interdependence ~etween the average particle size of the polymer used and its glass transition temperature Tg- The graph shows the logarithm of the average particle size in pm versus the glass transition temperature Tg in CO The polymers most suitable ~or the plastisols according to the invention substantially ~ -occur within a triangle formed by the two coordinates as well as ~ -the connecting line between the minimum particle size and the minimum glass transition temperature. It can also be seen that the higher the glass transition temperature of the polymer~ the lower can be its average particle size. However, extremely fine-grained polymers with a low glass transition temperature are not suitable. ~ ~
. ~:
It is also possible within the scope of the present invention ~;;
to use two polymers having dif~erent average particle sizes~
As a result of using a mixture of a fine-grained and a coarse-grained polymer~ it is possible to control within certain limits the flow characteristics and plasticiser requirements (cf~ e.g. ;
German Patent 934~ 498~o Both suspension-polymerized and emulsion-polymeried acrylic polymers are suitable for the plastisols according to the i~vention. In the case of suspension-polymerisation, the desired ~ Qs~6s3 particle size can be controlled by the 3tirring rate, and in the ca~e of emulsion-polymerisation by the quantity and type of emulsifier. The particle size of the polymer I is determined in conventional manner, e.g. by means of A~ 5 a Coulter counter.
- Preferably 65 to 800 parts by weight of plasticiser are used per 100 parts by weight of polymer.
~ he plasticiser selected must of course be completely compatible with the particular acrylic polymer. A useful simple test of compatibility in that at least 8 days after the gelling of he plastisol, the plasticiser does ~ot e~ ~J cl e.
~da, as Ahown by a completely dry and non-tacky surface.
Naturally, the compatibility is dependent both on the type of acrylic pol~mer and on the type of plasticiser. For exa~plel dibutyl-phthalate is not a suitable plasticiser for ;pol~methyl~methacrylate because compatibility is inadequate. Howevex; the same plasticiser can be used for copolymers of methyl-methacrylate and approximately 5 to 25% of butylmethacrylate;
A further important criterion for selecting suitable plasticisers is the storage stability of the pla~tisol.
This can be quantitatively defined by the viscosity number (based e~gO on a 1:1 polymer/plasticiser mixture~ in the following manner:
Trc~ rk , _ 6 _ ~, ' . ~ , ' .
, ~ ~ ,. . .
;~ . .
~L~5~683 8/0 = 8d ~ .
wherein V8!0 represents the viscosity number, ~ the initial viscosity of the plastisol, and ''? 8d the plastisol viscosity after standing for 8 days, ¦
The viscosity is determined by means of conventional methods of determination, e, g. with a rotar~ viscosimeter (Drage).
According to the definition indicated hereinbefore, the viscosity number must be below 3. 0 for the plasticisers usable according to the inVentiOn, i. e. the viscosity may not rise more than three time~ ~ ~
within a peri~d of 8 days, Such a plasti~ol would still not : :
- : necessarily always be adequately stable, but this can easi1y be reme~ied, eOg. by increasing the plasticiser content or adding fillers or other ad~itives. . ;
. ,. . - . . . :: -The selection of themost appropriate plastici~er can again be explained relative to the drav~ing. Within the triangle XYZ which encloses ~.
.
`~ the suitable acrrlic polymers, ther0 is a smaller triangle for each usable plasticiser within which are located those acryllc polymers which can be combined with a particuiar plasticizser to give a usable , .
plastisol, The zones for the indivldual plastici~ers are limited'to 20 the left by the compatibility with the polymer, and upwards (hypotenuse . .
of the triangle) ~y the viscosity number (storage stability). For each plasticisex these limits can be deterrnined by simple experiments.
As examples, the drawings show the zones GYH, DEF and AB~ for dimethoxy-ethyl-phthalate (~MEP3, dibutyl-phthalate (DBP) and 25 dioctyl-phthalate (DOP). :~
Plasticisers having at least two aromatic rings and/or two ether groups in the molecule have proved particu.larly .
uitable for ~e~ k ~ 7~
polymethylmethacrylate homopolymers. The first group includes, : for example9 butylbenzyl-phthalate, dibenzyl-toluene~ dibenzyl-phthalate~ diphenyloctyl~phosphate, triphenyl~phosphate, tricresol-- phosphate~ dibenzyl-benzoate, and diphenylether. The second group includes~ among others~ dimethoxy-ethyl-phthalateg diethoxyethyl-phthalate~ dibuto~yethyl-phthalate and methylphthalyethyl-glycollate Both criteria are satisPiedsby diethyleneglycol-diben~oate and dipropyleneglycol-dibenzoate. A further preferred plasticiser is acetyl tributyl citrate.
When methacrylic copolymers are used~ generally the compat-ibility with plasticisers increased, but in many cases there is a ` viscosity number above 3.0, i.e. an inadequate stability. For example~ for a copolymer of 15% n-butyl-methacrylate and 85%
~ methylmethacrylate with an average particle size of 100 ~ dibutyl - phthalate~ diisobutyl phthalate and diamyl phthalate are also suitable ;
in addition to the above-indicated plasticisers. However, if in the case of these polymers the particle size is reduced to 2 ~m~ the j viscosity number for most of the indicated plasticisers rises to above 3~0O However~ tricresol phosphate and diben~yl toluene still remain suitable as plasticisers.
Conventional plasticisers such as dioctyl phthalate, dinonyl phthalate and other~s require a still higher comonomer content in the copolymer in order to obtain an adequate compatibility.
In the case of a copolymer consisting of 50 parts by weight of ~ ~ `
butylmethacrylate and 50 parts by weight of methylmethacrylate and having an average particle si~e of 50 ~, even if the necessary compatibility exists, it is impossible to obtain an adequate storage stability with most of the above-indicated plasticisers. However~
dioctyl phthalate~ dinonyl phthcilate~ didecyl phthalate3 butyl cyclo-hexyl phthalate and the like remain suitable as plasticisers in such cases. Thus~ with an increasing comonomer cont~nt in the polymer~
the aliphatic groups in the phthalate may proportionally become longer.
While pure aliphatic plasticisers such as adipates or sebacates are unsuitable it is then possible to use higher boiling aromatic hydro-carbons with aliphatic groups. For example, Ingralur 839 ~(hydro-carbon mixture containing more than 40% aromaticsg produced by the Fuchs Company, Mannheim) has proved suitable for the latter ~ -~
copolymers. In the case of a comonomer content of 70% butyl -methacrylate very coarse particles are required~ but phthalates cannot be used due to the too limited storage stability. Plasticisers such as Ingralur 839, ~ polymerol (naphthenic hydrocarbons produced by Shell) ~-and tri-(ethylhexyl)-mellitate and high boiling aromatic oils remain suitable.
Many plasticisers which have a good storage stability but poor compatîbility with the particular polymers making them unsuitable per se for plastisol formation can~ in certain circumstances~ be used as so-called extenders to replace up to about 25% by weight of the main plasticiserO These extenders particularly include plasticisers which are alone only compatible in the case o~ a high comonomer content.
Finally~ it is also possbile to use so-called polymer plasticisers if they are compatible with the particular acrylic polymer used. In this connection the plastisol viscosity is substantially - ?
dependent on the viscosity of the polymer plasticiser~ which is always significantly higher than that of the monomeric plasticisers. Suitable polymer plasticisers are e.g. ortho_ and para-phthalate-based polyesters.
* Trademark , . ~
_ 9 _ ~-J
If differcnt plasticisers can be used for thc compounding of a plastisol from a speci~ic acrylic polymer or co-polymer, the choice ; will ultimately depend on the end use of the plastisol, Thus, polymethyl methacrylate can advantageously be used together with acetyl tributyl c;trate or food applications (container gaskets) while other technically ,feasible plasticisers would not be suita'ble for this purpose.
In addition to acrylic polymers and plasticisers, the plastisols according to the invention can contain up to 700, preferably up to 400 parts by weight of inert fillers per 100 parts by weight of polymer, The fillers mainly eerve to increase the viscosity as well as to improve the I brasion resistance. They also permit a cost saving. Suitable fillers ?re chalks which can, e. g. be ground, precipitated or coated, barite, kaolin, highly dispersed silica, talc, bentonite, glass powder, sand, .: aluminium oxide and hydroxide, antimony triox;de, titanium dioxide, carbon black, metal soaps, such as zinc or calcium stearate, dyes, pigments and corrosion inhibitors may also be added to the plastisols.
In addition, the plastisols can contain con~entional additives, for exampie viscosity regulators suFh as emulsifiers and silicones, further oxidation, light and heat stabilisers, as well as epoxide softeners. It - 20 is also possible to add foaming agents, for example azo-compounds which decompose during gelling and lead to a foamed plastigel. ;
It is finally particularly important to ensure the adhesion of the plastisols-according to the invention on the particular substrate to be treated, e. g. steel (greased, de-grèased, phosphatised, primed), alu-25 minium, textiles, papers and others. For this purpose are used suitable adhesion promoters such-as triethyleneglycol dimethacrylate, trimethylol f trimethacrylate combined Wit}l peroxides which decompose at the gelling temperature, and initiate a radical polymerisation of the adhesiveO
.
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- ~()5~33 ` ~
Liquid or sc>lid phenol or resorcinol resins with a low -formaldehyde content are also suitable, It i5 also possible to use epoxide resins with heat-reacting hardeners such as acetoguanamine or dicyano-diamide, as well as amino-silanes, The adhesion promoter content can be 0, l to 50, preferably 1 to 5 parts by weight to 100 parts by weight of polymer, The adhesion can also be improved by co-polymerising :~
a small quant~ty (based on the polymer and/or copolymer) o:E
an acrylate or methacrylate monomer with free functlonal 10,\~ groups or of one or more copolymerizable monomers having :
a heterocyclic group with at least one nitrogen atom in the ring with the acrylic or methacrylic polymer, The proportion of, ,. . .
such comonomers is generally up to about 3% by weight. . ~ .
Acrylate and/or methacrylate monomers with free carboxyl, ~ .
~ ~ 15 hydro~l, epoxy or amino.groups are particularly suitable, . In particular, It is therefore possible to use free acrylic acid or methacrylic acid as well as esters thereof with lower aliphatic oxy, epoxy or amino alcohols. -' - : - . Excellent adhesion properties are obtained If the ~nome~ of the ~- . 20 ~ol~ner: ' are co-polymerized with small amounts of certain ~;~
. . heterocyclic compounds. Preferably, a heterocyclic vinyl compound of the general formula ., ' -R
CH2 = C-(CH2)n R2 is used as comonomer for the co-polymerisation in which n is ~.
equal to O or 1 and in which Rl is a hydrogen atom, a'linear or branched alkyl group with 1 to 4 carbon atoms or a phenyl group , - - I 1 - .
, 8~
o while R2 is a group of the formulae -C-OR3, -COR3, or -R3 in which R3 is a heterocyclic group having one or several rings with a least one nitrogen atom in the ring.
Pre~erably, the amount of the heterocyclic compound is about 0.1 to 3%, preferably 0.2 to 3%, by weight (based on the polymer and/or copolymer or monomer/s to be polymerised) since excellent resul~s have been obtained with amounts in this range. Optionally, however, the amount can be increased, e.g. to up to 5% and in special cases even to 10% by weight.
Suitable monomers are, for example N- or C-vinyl or N- or C-allyl compounds of imidazole, imidazoline, imidazolidine, ben~imidazole, triazole, pyrrole, pyrazole, oxyzole, pyridine, chinoline, diazine as well as other heterocyclic compounds with at least one nitrogen atom in the ring system.
N-vinyl imidazole is particularly preferred. Furthermore, vinyl and allyl ethers and acrylic or methacrylic acid esters of the heterocyclic compounds are useful.
The adhesion properties of the plastisols can be further improved by adding additisnal cross-linking agents which react with the heterocyclic group of the co-polymerised monomer. The cross-linking agent may be added to the plastisol in an amount equal to the amount of heterocyclic compound pre-sent. The plastisol may thus also contain a cross-linking agent in an amount of 0.1 to 3.0% by weight which is effective to react with the heterocyclic groups of said comonomer. Epoxy resins were found suitable; apart from the commercial epoxy resins a polym~r can also be used which, according to the present invention has been co-polymerised with a small amount of acrylate and/or methacrylate monomer with epoxy groups. Furthermore, polybasic car-boxylic acids, e.g. benzene tricarboxylic acid, adipic acidg maleic acid and itaconic acid, have proved to be suitable and to effect a further improvement B
. . . . . .. . .. .. . .
,: ~ , ! , . . ' .
`' ' ' ' ' '`' ',~ "' ' ' ', '' ,:,; ~ ' ' ~ ; ' ' . . .
5t;~!33 of tho ~dhesion propcrtics, Preparation of the plastisols according to the present invention can also be effected in that two or more acrylate or methacrylate polymers which meet the requirements of the invention are blended with each other, For example, a methylmethacrylate homopolymer can be blended with a methyl-methacrylate copolymer or with a copolymer which ~as been further modified by co-polymerisation with a heterocyclic compound, In this manner, particularly favourable rheological properties can be obtained. ~
It is also possible to blend copolymers containirg groups - which react with each other. The above-described combination of copolymers with epoxy groups and of copolymers with hetero-- cyclic groups is one example for this method.
The plastisols according to the invention can be processed in conventional manner dependent on the particular viscosity, for example by applying with a float, coating with a brush, applying with a paint gun, spraying with an atomiser and air, spraying by - high pressure (without air), scraping on, calendering, pouring ;
or immersing.
Finally, to form the plastigel the plastisols must be gelled. -For this purpose temperatures between about 70 and 240 C are used, dependent on the plastisol composition and the particular working conditions. The necessary gelling time is between two ;
minutes and two hours, The necessary heating can take place, for example, by hot air, metal pipes, infra-red rays, }iigh -.
frequency heating, etc. ~
. '' , . ..
~ 13 -The plastisols acco~i g @ the invelltion arc particularly suitablc as abrasion and corrosion inhibitors for steel sheets, for example as underbody-protection for auto-mobiles, trucks and buses. The plastisols can also be used for seam seals for levelling out folding systems, as metal adhesr~es, coating compounds, spot welding cc)rnpounds, expanding pastes, sealing agents for spot welded sheets and for sealing double-flanged seams. They can also be used for impregnating and coating textiles and similar substrates such as tarpaulins, artificial leather, floor coverings, carpet backings, packaging materials, conveyor belts and driving belts. Using the immersion ~ ~
, process, it is possible to produce hollow bodies, gloves, boots, finger stalls etc The plastisols are also suitable as seals for - bottle caps and folding seams, as plastic seals for air and ollfilters, for extrusion and injection mould~ng highly elastic sections and items such as sealing strips and packaging cords, trays, technical components and for rolling foils and strips. If appro-priate plasticisers and additives are used, the plastisols according , to the invention are also suitable for packing foodstuffs because ~. - .
there are no~ob~ections to methylmethacrylate.
- - The following examples are provided to illustrate the invention, All formulations are given in parts by weight unless otherwise stated, .~
''~
( . . .
r~ . .
~5~3 but these compounds are frequently toxic so that they cannot be used where the plastisol comes in~o contact with foodstuffs. The above-indicated problems are further exacerbated in that in certain special cases PVC-plastisols require relatively high baking temperatures in order to obtain very short gelling times so tha~ the danger of PVC-decomposition is urther increased.
It is the object of the invention to develop novel plastisols which also have the excellen* processing and product characteristics of PVC-plastlsols but which gel at lower temperatures and are also chlorine-free so that there can be no splitting off of chlorine or hydrogen chloride. It has surprisingly been found that this problem can be solved in that for the production of the plastisols particular acrylic polymers are used and pro-cessed with plasticisers.
According to the present invention an improvement is provided in a plastisol, in which solid particles of an organic polymer component ~a) are dispersed in an organic liquid component ~b), which serves as a compatible plasticiser for the organic polymer, in a proportion effective to form a ;, viscous dispersion having a liquid or paste-like appearance capable of being gelled by heating, the improvement in which the organic polymer compone~t consists substantially of units derived from ~i) at least one monomer selected from: t-butyl acrylate, a Cl 4 alkyl methacrylate and cyclohexyl methacrylate, or `
~ii) at least one of the above monomers and at least one comonomer selected from: methacrylates of aliphatic C2 to C10 alcohols, acrylates of aliphatic Cl-C10 alcohols, styrene and alpha~methyl styrene, the polymer ;~
having a glass transition temperature of above 35C and an average degree of - polymerization of more than 400, and the average particle size of the polymer in the plastisol being from 0.1 to 500 microns; said plasticiser being present in an amount of from 30 to 1000 parts per 100 parts by weight of said polymer and being sufficiently compatible that at least 8 days after the gelling of said plastisol, the plasticiser does not exude from said plastlsol, said plasticiser moreover being effective to pro~ide the plastisol with a viscosity index V8/o of less than 3Ø
~k .
~ ~ 3 ~ . ,..: .~
~05~83 The present inven-tion also provides a plastiso:L comprising ~a) 100 weight parts of solid particles of an organic polymer selected from t-butylacrylate or methyl, ethyl, n-propyl, isopropyl, isobutylJ sec-butyl, t-butyl or cyclohexylmethacrylate homopolymers, and copolymers of at least one said monomer with at least one comonomer selected from methacryla~es of aliphatic C2 to C10 alcoholsJ acrylates of Cl to C10 alcohols, styrene and a-methyl-styrene~ whereby the polymer has an average parti~le size of 0.1 to 500 microns~ a glass transition temperature above 35C and an average degree of polymerization of more than 400, and (b) 30 to 1000 parts of an organic ~ 10 liquid plasticiser which is sufficiently compatible with the polymer that at :~ least 8 days after gelling of said plastisol the plasticiser does not exude from said plastisolJ said plasticiser further being effective to provide the plastisol with a viscosity index V8/o of less than 3.0; the average particle size of polymer ~a) being related to its glass transition temperature so as to lie with m the triangle XYZ of the accompanying drawing, said plastisol further being in the form of a liquid or paste-like dispersion of polymer -.
particles (a) in plasticiser ~b) capable of being gelled by heating to a temperature between about 70 and 240C.
There is also provided in accordance with the present invention a homogeneousJ elasticJ solid gel formed by heating to a temperature between about 70 and 240C a plastisol comprising solid particles of average particle size 0.1 to 500 microns of an organic polymer having a glass transition temperature above 35C and consisting of 40-100% of units derived from methyl methacrylateJ 0-60% o~ units derived from a first comonomer selected from alkyl acrylates having 1-4 carbon atoms in the alkyl portion and alkyl meth-acrylates having 2-4 carbon atoms in the alkyl portionJ 0-3% of units derived from a second comonomer selected from methacrylic and acrylic compounds having at least one hydroxylJ epoxyJ amino or carboxylic acid groupJ and 0-10% of units derived from a third comonomer which is a heterocyclic vinyl compound of the general formula -3a-, . . ~ .............. : .
,, :- . . . ~`' '' ~ ': , : .
lalS/~ 3 C~12= C- ~C~12)n R2 in which n is 0 or 1, Rl is selected from hydrogen, alkyl of 1 to 4 carbon atoms and phenyl and R2 is selected from -C-OR3, -COR3 and -R3 in which R3 is o a heterocyclic group having at least one ring containing a nitrogen atom, all percentages being by weight, the degree of polymerization of the polymer being more than 400, based on methyl methacrylate and the first comonomer when used dispersed in (b) an amount of compatible organic liquid plasticiser effective to form a viscous plastisol the viscosity of which does not increase by more than 300% within 3 days of preparation; said amount being in the range of from 30 to 1000 parts per 100 parts by weight of said polymer, said plasticiser being sufficiently compatible that at least 8 days after ~he gelling of said plastisol, the plasticiser does not exude from said plastisol.
~' '' ' `' ' '.
.1 :
, ~:
.~
',~ ~ .~ .
~ -3b-,j ~, The average particle s~ e of the polymer used is preferably increased proportionally with the decrease of its glass transition temperature Tg. The glass transition temperature is preferably above 60 C.
To obtain usable resultsg the degree o~ polymerisation ; of the polymer used must be at least about 400.
Advantageously the degree of polymerisation is between 400 and 20,000~ corresponding to an average molecular weight of about 40,000 to 2,000,000.
The preferred polymer component consists substantially wholly of one kind of units derived from t-butyl acrylate, methyl~ ethyl~ n-propyl~ isopropyl~ n-butyl, sec-butyl or t-butyl methacrylate or cyclohexyl me~hacrylate~ i.e. is ; essentially a homopolymer. Methyl methacrylate is preferred. The alcohol acrylate or methacrylate comonomers ` preferably have an alkanol alcohol component, i.e. are unsubstituted and saturated~ and the type (i) monomers, i.e. those listed above~ will generally predominate over those of type (ii). The preferred copolymers are those in which one of the monomers is methyl methacrylate and constitutes at least 40%, preferably at least 5U~ by weight of the total monomer units, and the other component is a C2 4 alkyl methacrylate, especially n-butyl methacrylate, ~-or a Cl 4 alkyl acrylate~
However, within the scope of the present invention only those copolymers can be used whose glass transitiOn or solidification temperature is above about 35C. The glass transition te~perature T of a particular copolymer can be calculated beforehand by the Fox formula (T.G. Fox, Bull~ Am. Phys~ Soc., vol. 1~ 123 (1956)):
~ - 4 -31~05~6~3 ,:
i 1 Wl W2 n Co Tl T2 T
wherein Wl represents the weight por~ion of monomer 1, ~2 the weight portion of monomer 2~ Tl the glass transition temperature of the polymerised monomer 1 in K~ T2 the glass transition temperature of the polymerised monomer 2 in K3 TC the glass transition temperat~e of the copolymer in ~0 . , ; ~
' . ' j - 4a - .
;83 The aYerage particle size of the polymer used must be between about 0.1 pm and 500 ~m~ preferably between 0.3 and 200 ~m. If too large a particle size is used, the plastisol obtained ~rill not have ~n adequate internal bond, and no complete gelling of the polymer occurs. If the particle size is too small, the storage stability is inadequate~ i.e. gelling occurs even when the polymer is left to stand.
As will be explained relative to the attached dra~ing, when using a plastisol there is an interdependence ~etween the average particle size of the polymer used and its glass transition temperature Tg- The graph shows the logarithm of the average particle size in pm versus the glass transition temperature Tg in CO The polymers most suitable ~or the plastisols according to the invention substantially ~ -occur within a triangle formed by the two coordinates as well as ~ -the connecting line between the minimum particle size and the minimum glass transition temperature. It can also be seen that the higher the glass transition temperature of the polymer~ the lower can be its average particle size. However, extremely fine-grained polymers with a low glass transition temperature are not suitable. ~ ~
. ~:
It is also possible within the scope of the present invention ~;;
to use two polymers having dif~erent average particle sizes~
As a result of using a mixture of a fine-grained and a coarse-grained polymer~ it is possible to control within certain limits the flow characteristics and plasticiser requirements (cf~ e.g. ;
German Patent 934~ 498~o Both suspension-polymerized and emulsion-polymeried acrylic polymers are suitable for the plastisols according to the i~vention. In the case of suspension-polymerisation, the desired ~ Qs~6s3 particle size can be controlled by the 3tirring rate, and in the ca~e of emulsion-polymerisation by the quantity and type of emulsifier. The particle size of the polymer I is determined in conventional manner, e.g. by means of A~ 5 a Coulter counter.
- Preferably 65 to 800 parts by weight of plasticiser are used per 100 parts by weight of polymer.
~ he plasticiser selected must of course be completely compatible with the particular acrylic polymer. A useful simple test of compatibility in that at least 8 days after the gelling of he plastisol, the plasticiser does ~ot e~ ~J cl e.
~da, as Ahown by a completely dry and non-tacky surface.
Naturally, the compatibility is dependent both on the type of acrylic pol~mer and on the type of plasticiser. For exa~plel dibutyl-phthalate is not a suitable plasticiser for ;pol~methyl~methacrylate because compatibility is inadequate. Howevex; the same plasticiser can be used for copolymers of methyl-methacrylate and approximately 5 to 25% of butylmethacrylate;
A further important criterion for selecting suitable plasticisers is the storage stability of the pla~tisol.
This can be quantitatively defined by the viscosity number (based e~gO on a 1:1 polymer/plasticiser mixture~ in the following manner:
Trc~ rk , _ 6 _ ~, ' . ~ , ' .
, ~ ~ ,. . .
;~ . .
~L~5~683 8/0 = 8d ~ .
wherein V8!0 represents the viscosity number, ~ the initial viscosity of the plastisol, and ''? 8d the plastisol viscosity after standing for 8 days, ¦
The viscosity is determined by means of conventional methods of determination, e, g. with a rotar~ viscosimeter (Drage).
According to the definition indicated hereinbefore, the viscosity number must be below 3. 0 for the plasticisers usable according to the inVentiOn, i. e. the viscosity may not rise more than three time~ ~ ~
within a peri~d of 8 days, Such a plasti~ol would still not : :
- : necessarily always be adequately stable, but this can easi1y be reme~ied, eOg. by increasing the plasticiser content or adding fillers or other ad~itives. . ;
. ,. . - . . . :: -The selection of themost appropriate plastici~er can again be explained relative to the drav~ing. Within the triangle XYZ which encloses ~.
.
`~ the suitable acrrlic polymers, ther0 is a smaller triangle for each usable plasticiser within which are located those acryllc polymers which can be combined with a particuiar plasticizser to give a usable , .
plastisol, The zones for the indivldual plastici~ers are limited'to 20 the left by the compatibility with the polymer, and upwards (hypotenuse . .
of the triangle) ~y the viscosity number (storage stability). For each plasticisex these limits can be deterrnined by simple experiments.
As examples, the drawings show the zones GYH, DEF and AB~ for dimethoxy-ethyl-phthalate (~MEP3, dibutyl-phthalate (DBP) and 25 dioctyl-phthalate (DOP). :~
Plasticisers having at least two aromatic rings and/or two ether groups in the molecule have proved particu.larly .
uitable for ~e~ k ~ 7~
polymethylmethacrylate homopolymers. The first group includes, : for example9 butylbenzyl-phthalate, dibenzyl-toluene~ dibenzyl-phthalate~ diphenyloctyl~phosphate, triphenyl~phosphate, tricresol-- phosphate~ dibenzyl-benzoate, and diphenylether. The second group includes~ among others~ dimethoxy-ethyl-phthalateg diethoxyethyl-phthalate~ dibuto~yethyl-phthalate and methylphthalyethyl-glycollate Both criteria are satisPiedsby diethyleneglycol-diben~oate and dipropyleneglycol-dibenzoate. A further preferred plasticiser is acetyl tributyl citrate.
When methacrylic copolymers are used~ generally the compat-ibility with plasticisers increased, but in many cases there is a ` viscosity number above 3.0, i.e. an inadequate stability. For example~ for a copolymer of 15% n-butyl-methacrylate and 85%
~ methylmethacrylate with an average particle size of 100 ~ dibutyl - phthalate~ diisobutyl phthalate and diamyl phthalate are also suitable ;
in addition to the above-indicated plasticisers. However, if in the case of these polymers the particle size is reduced to 2 ~m~ the j viscosity number for most of the indicated plasticisers rises to above 3~0O However~ tricresol phosphate and diben~yl toluene still remain suitable as plasticisers.
Conventional plasticisers such as dioctyl phthalate, dinonyl phthalate and other~s require a still higher comonomer content in the copolymer in order to obtain an adequate compatibility.
In the case of a copolymer consisting of 50 parts by weight of ~ ~ `
butylmethacrylate and 50 parts by weight of methylmethacrylate and having an average particle si~e of 50 ~, even if the necessary compatibility exists, it is impossible to obtain an adequate storage stability with most of the above-indicated plasticisers. However~
dioctyl phthalate~ dinonyl phthcilate~ didecyl phthalate3 butyl cyclo-hexyl phthalate and the like remain suitable as plasticisers in such cases. Thus~ with an increasing comonomer cont~nt in the polymer~
the aliphatic groups in the phthalate may proportionally become longer.
While pure aliphatic plasticisers such as adipates or sebacates are unsuitable it is then possible to use higher boiling aromatic hydro-carbons with aliphatic groups. For example, Ingralur 839 ~(hydro-carbon mixture containing more than 40% aromaticsg produced by the Fuchs Company, Mannheim) has proved suitable for the latter ~ -~
copolymers. In the case of a comonomer content of 70% butyl -methacrylate very coarse particles are required~ but phthalates cannot be used due to the too limited storage stability. Plasticisers such as Ingralur 839, ~ polymerol (naphthenic hydrocarbons produced by Shell) ~-and tri-(ethylhexyl)-mellitate and high boiling aromatic oils remain suitable.
Many plasticisers which have a good storage stability but poor compatîbility with the particular polymers making them unsuitable per se for plastisol formation can~ in certain circumstances~ be used as so-called extenders to replace up to about 25% by weight of the main plasticiserO These extenders particularly include plasticisers which are alone only compatible in the case o~ a high comonomer content.
Finally~ it is also possbile to use so-called polymer plasticisers if they are compatible with the particular acrylic polymer used. In this connection the plastisol viscosity is substantially - ?
dependent on the viscosity of the polymer plasticiser~ which is always significantly higher than that of the monomeric plasticisers. Suitable polymer plasticisers are e.g. ortho_ and para-phthalate-based polyesters.
* Trademark , . ~
_ 9 _ ~-J
If differcnt plasticisers can be used for thc compounding of a plastisol from a speci~ic acrylic polymer or co-polymer, the choice ; will ultimately depend on the end use of the plastisol, Thus, polymethyl methacrylate can advantageously be used together with acetyl tributyl c;trate or food applications (container gaskets) while other technically ,feasible plasticisers would not be suita'ble for this purpose.
In addition to acrylic polymers and plasticisers, the plastisols according to the invention can contain up to 700, preferably up to 400 parts by weight of inert fillers per 100 parts by weight of polymer, The fillers mainly eerve to increase the viscosity as well as to improve the I brasion resistance. They also permit a cost saving. Suitable fillers ?re chalks which can, e. g. be ground, precipitated or coated, barite, kaolin, highly dispersed silica, talc, bentonite, glass powder, sand, .: aluminium oxide and hydroxide, antimony triox;de, titanium dioxide, carbon black, metal soaps, such as zinc or calcium stearate, dyes, pigments and corrosion inhibitors may also be added to the plastisols.
In addition, the plastisols can contain con~entional additives, for exampie viscosity regulators suFh as emulsifiers and silicones, further oxidation, light and heat stabilisers, as well as epoxide softeners. It - 20 is also possible to add foaming agents, for example azo-compounds which decompose during gelling and lead to a foamed plastigel. ;
It is finally particularly important to ensure the adhesion of the plastisols-according to the invention on the particular substrate to be treated, e. g. steel (greased, de-grèased, phosphatised, primed), alu-25 minium, textiles, papers and others. For this purpose are used suitable adhesion promoters such-as triethyleneglycol dimethacrylate, trimethylol f trimethacrylate combined Wit}l peroxides which decompose at the gelling temperature, and initiate a radical polymerisation of the adhesiveO
.
, ~ .
.: -, .. .... . , . -.
: . ,, :
- ~()5~33 ` ~
Liquid or sc>lid phenol or resorcinol resins with a low -formaldehyde content are also suitable, It i5 also possible to use epoxide resins with heat-reacting hardeners such as acetoguanamine or dicyano-diamide, as well as amino-silanes, The adhesion promoter content can be 0, l to 50, preferably 1 to 5 parts by weight to 100 parts by weight of polymer, The adhesion can also be improved by co-polymerising :~
a small quant~ty (based on the polymer and/or copolymer) o:E
an acrylate or methacrylate monomer with free functlonal 10,\~ groups or of one or more copolymerizable monomers having :
a heterocyclic group with at least one nitrogen atom in the ring with the acrylic or methacrylic polymer, The proportion of, ,. . .
such comonomers is generally up to about 3% by weight. . ~ .
Acrylate and/or methacrylate monomers with free carboxyl, ~ .
~ ~ 15 hydro~l, epoxy or amino.groups are particularly suitable, . In particular, It is therefore possible to use free acrylic acid or methacrylic acid as well as esters thereof with lower aliphatic oxy, epoxy or amino alcohols. -' - : - . Excellent adhesion properties are obtained If the ~nome~ of the ~- . 20 ~ol~ner: ' are co-polymerized with small amounts of certain ~;~
. . heterocyclic compounds. Preferably, a heterocyclic vinyl compound of the general formula ., ' -R
CH2 = C-(CH2)n R2 is used as comonomer for the co-polymerisation in which n is ~.
equal to O or 1 and in which Rl is a hydrogen atom, a'linear or branched alkyl group with 1 to 4 carbon atoms or a phenyl group , - - I 1 - .
, 8~
o while R2 is a group of the formulae -C-OR3, -COR3, or -R3 in which R3 is a heterocyclic group having one or several rings with a least one nitrogen atom in the ring.
Pre~erably, the amount of the heterocyclic compound is about 0.1 to 3%, preferably 0.2 to 3%, by weight (based on the polymer and/or copolymer or monomer/s to be polymerised) since excellent resul~s have been obtained with amounts in this range. Optionally, however, the amount can be increased, e.g. to up to 5% and in special cases even to 10% by weight.
Suitable monomers are, for example N- or C-vinyl or N- or C-allyl compounds of imidazole, imidazoline, imidazolidine, ben~imidazole, triazole, pyrrole, pyrazole, oxyzole, pyridine, chinoline, diazine as well as other heterocyclic compounds with at least one nitrogen atom in the ring system.
N-vinyl imidazole is particularly preferred. Furthermore, vinyl and allyl ethers and acrylic or methacrylic acid esters of the heterocyclic compounds are useful.
The adhesion properties of the plastisols can be further improved by adding additisnal cross-linking agents which react with the heterocyclic group of the co-polymerised monomer. The cross-linking agent may be added to the plastisol in an amount equal to the amount of heterocyclic compound pre-sent. The plastisol may thus also contain a cross-linking agent in an amount of 0.1 to 3.0% by weight which is effective to react with the heterocyclic groups of said comonomer. Epoxy resins were found suitable; apart from the commercial epoxy resins a polym~r can also be used which, according to the present invention has been co-polymerised with a small amount of acrylate and/or methacrylate monomer with epoxy groups. Furthermore, polybasic car-boxylic acids, e.g. benzene tricarboxylic acid, adipic acidg maleic acid and itaconic acid, have proved to be suitable and to effect a further improvement B
. . . . . .. . .. .. . .
,: ~ , ! , . . ' .
`' ' ' ' ' '`' ',~ "' ' ' ', '' ,:,; ~ ' ' ~ ; ' ' . . .
5t;~!33 of tho ~dhesion propcrtics, Preparation of the plastisols according to the present invention can also be effected in that two or more acrylate or methacrylate polymers which meet the requirements of the invention are blended with each other, For example, a methylmethacrylate homopolymer can be blended with a methyl-methacrylate copolymer or with a copolymer which ~as been further modified by co-polymerisation with a heterocyclic compound, In this manner, particularly favourable rheological properties can be obtained. ~
It is also possible to blend copolymers containirg groups - which react with each other. The above-described combination of copolymers with epoxy groups and of copolymers with hetero-- cyclic groups is one example for this method.
The plastisols according to the invention can be processed in conventional manner dependent on the particular viscosity, for example by applying with a float, coating with a brush, applying with a paint gun, spraying with an atomiser and air, spraying by - high pressure (without air), scraping on, calendering, pouring ;
or immersing.
Finally, to form the plastigel the plastisols must be gelled. -For this purpose temperatures between about 70 and 240 C are used, dependent on the plastisol composition and the particular working conditions. The necessary gelling time is between two ;
minutes and two hours, The necessary heating can take place, for example, by hot air, metal pipes, infra-red rays, }iigh -.
frequency heating, etc. ~
. '' , . ..
~ 13 -The plastisols acco~i g @ the invelltion arc particularly suitablc as abrasion and corrosion inhibitors for steel sheets, for example as underbody-protection for auto-mobiles, trucks and buses. The plastisols can also be used for seam seals for levelling out folding systems, as metal adhesr~es, coating compounds, spot welding cc)rnpounds, expanding pastes, sealing agents for spot welded sheets and for sealing double-flanged seams. They can also be used for impregnating and coating textiles and similar substrates such as tarpaulins, artificial leather, floor coverings, carpet backings, packaging materials, conveyor belts and driving belts. Using the immersion ~ ~
, process, it is possible to produce hollow bodies, gloves, boots, finger stalls etc The plastisols are also suitable as seals for - bottle caps and folding seams, as plastic seals for air and ollfilters, for extrusion and injection mould~ng highly elastic sections and items such as sealing strips and packaging cords, trays, technical components and for rolling foils and strips. If appro-priate plasticisers and additives are used, the plastisols according , to the invention are also suitable for packing foodstuffs because ~. - .
there are no~ob~ections to methylmethacrylate.
- - The following examples are provided to illustrate the invention, All formulations are given in parts by weight unless otherwise stated, .~
''~
( . . .
r~ . .
3~0~ 3 l~xamplcs I ~:o 15 .
Table I gives the results of 15 :E~xamples. In Examples 1, 2, 7, 11 and 12 the plasticiser used was unsuitable for the particular polymer due to inadecluate compatibility In Examples 5, 9, 13 and 5 , 14 the value of 3. 0 for the viscosity rlumber was exceeded when using the indicated plasticiser, so that these combinations are also `
unsuitable, However, excellent results were obtained with the polymer/plasticiser combinations of Examples 3, 4, 6, 8,~10 and 15, wherein the plasticiser satisfied both criteria, i. e. it was completely compatible with the polymer and led to a viscosity number V8/0 of - ,¦ less than 3, 0, ~ .
.~;
` ` ' . ~ . ' `' , . - ` : ~
- ~:
. ` ` ~ ' , ~; .
. ' .
_ 15 -:, .
.''. ' . ~`, ,:
'' . , ` .
~5~8~3 .,, d O O O O O O --' ~ O
~ 8 ga1 ~8 ~ o a~ o d O C~ 8 O t:~ ~ ~r-l N r-l CJl O a~ O r`
--I O~O ~0 8 ~ ~ 8 ~ ~ 8 8 1~
r~ I ~ N r~l N N N O O
d I ~ o o o rl 8 o o r1 ~rl 8 o o o .,~ o o Lt~ ~1 0 0 d ~ --I
00i~ 1~ r~l O t~ 00 0 Il~ G'' t~) O O '::t cd ot) a- ~ o ~ o ~ r) N ~ Ul U~
~rl ~ ~1 ~ ~ U~ N
r r l N ~ Il) O It'~ ~ O 8 In g 1l~ 8 u) ~ C~ 3~ 0~ 0 00 CO N Cl~ r-l ~ N ~ r~l ~rl ~ r~
a~ N
~r~
,~ ~ ~ ~ ~ ~ ~ h ~ ~ ~ h h ~ ~ ~1 cd o o o o o I:J o o o ~cl '1 ~ 0 0 0 ~ O
0 g0 ~0 b4 E~ g0 g0 ~ ~ ~ ~0 g g4 ~ ~ h ;~
E-' h h ~
O P~) O~r~ ~ ~
~ o H ,~, H X O a I H O ;~ U.i 1--1 0 U.7 b4 ~d Cl C~ E-- Cl ~ E-l Q 3 Cl C:l C ~ E-' C~ a E~ :Q
r~ O O O O O O O O O O O O O O O C~
D~ 3 ~ u~ ~ a ~, . ~~ ~
a.l h ~r ~ O ~ ~ ~ N ~ ~ ~ O ~ ~ ~ O _- ~
rl ::
, . .. ~
~ ~ ' ~1 O ~ - oo _ _ _ ~ _ O
~bl . O r-l ~ t-d td ~ h ~
o ~o- - ~
~d 3 O O ~ O ~ O ~ ~ D h ,~ O _I-rl.rl I r~ O-rl ~ ~ ~4 rQ l l ~ l I
~ ~ o ~ ~
~Ll r-~ ~ r1 r-~ r~ ~ ~ ~ ~ H ~ . .
~.
`:, : ,; , . : . . . : ~ , ~0~i~33 Example 16 The following mixture is homogenised with a stirrer and applied with a doctor blade to a degreased steel sheet:
30 parts P~A (30 ~m) 30 parts but~lbenzyl-phthalate 36 parts chalk 3 parts triethyleneglycol-dimethacrylate 0.3 parts tert.-butylperbenzoate If this mixture is gelled for 20 minutes at 170C, a tough strongly adhering film is obtained which has good anti-corrosive properties. `~
Example 17 30 parts copolymer (MMA/BMA 50/50) (50 ~m) 30 parts dinonyl-phthalate ~
40 parts chalk -~ -5 parts resorcinol resin (Rousselot* RH-74-01) This mixture was tested as a metal adhesive by gelling it at 170C between two metal plates of ~a) steel and ~b) aluminium.
The subsequent tearing test revealed a tensile strength of ~a) 52kg/cm2 ~
and Cb) 42 kg/cm2 (5 cm2 bonding area and 0.3 mm coating thickness).- i -However, if in place of the 50 ~m copolymer, a copolymer with an average particle si~e of 500 ~m is used, a tearing value of only 3 kg/cm2 is obtained.
Example 18 24 parts MMA/BMA 85/15 (2 ~m) 33 parts diben~yl-toluene 40 parts chalk 3 parts azodicarbonamide *Trademark .
.
S~68;~
This mixture gclled in IS minutes ~t 170 C and formed a highly elastic solid foam with 100% foam expansion.
Exampl e 19 .
20 parts PMMA(100%)(particle 5iZ~: 30/um) S 1 30 parts butylben~yl-phthalate 45 parts chalk .
5 parts resorcinol resin (Rouss~lot RH 74-01) This highly viscous substance was suitable as a sealmg compound fo~ metal welding seams in the automobile and .`10 ~ r~frigerator industry. After baking at 180 C for 15 minutes the :
substance adhered well to polished m~tal sheets and can be easily ` . ~ lacquer~d. ` `; . ::
, .. . . .
E:xample 20 ~ ~:
~ . If a polymer plasticiser ~urea/~ormald~ehyde plasticiser resin .
-. 1 601d as Plastige~; is used the following comparison is obtained .
with a polymer: plasticiser mixing ratio of 1: 1, - : . . ~
- -: - Tab1e 2 ~ ~ ~:
: ~ ~ Particle ~ c~
~, immed~y after --., ~, . .~. - , ..
- . - . . . ~.
100% PMMA 30 22000 16000 good hard ,. .. A/BMA . ...... ~ ~ .
85/15 . 2 1630Q0 218000 good hard~ to~gh :~
-. ~A/BMA
50~50 60 23250 22250 good elastic - ~d:U~i ' " '' ' ' . ' ' Table 3 sho-~ls the thermal stability of all acrylic plastisol .
. as compare~ with a PVC-plastisol with a bakin~ cy~le of 30 minutes at 150C.
., . ' /ro~é~ - 18 - . . . : :
- . - , . ....
' - ' ' ~ '' '.
-,.:. ... . . . . , . : , Tabl 3 Emulsion PVC, K-value 74 t2 ~m) . 20 PMMA (30 ~m) 20 Ch~lk 4S 45 . Butylbenzylphthalate 35 35 S Viscosity immediately 36000 52500 - . in cP . ater 10 days 21000 18000 Vlo/O 0.58 0~3 Cold elasticity -40~C
Discolouration 120C sligh~ sligh~
-.10 after 14 ~ays at 150C black slight . , . . . . . . . ~
- . Abrasion ~mm/min~ ramb.temp. . - 0~01~ 0.045 - `~ ater 14 days 1120C 0.039 0.390 : : storage at ~150C 1.280 0.220 ~ . . . - - - ~ . . , : -The Table shows that after 14 days at 150C the PVC~
15 ~ plastigel had completely discoloured.(decomposed? and tha~ `~
- ~- the abrasion values in a sand-blasting device ~with corundum -~
: : -. in place o~ sand) rose 80~ in the case of PVC, whereas in the . . , - . -~ case of the acrylic plastigel the:abrasion values, although . - not originally especially good, only rose by a maximum of ~ 25 tîmes.
, . . . . . . .......... . .. . . . .
On omp~ring the followîng mixtures~
. ~.- - . -: 25 parts PVC ~paste type, emulsion-polymerised~
K valu 74g 2 ~m) ~5 - .. ; . 40 parts chalk ., . . ;, . . . . . . .
, -`: 5 parts iron oxide (magn.) .
- ` ~7 parts DOP
! - - , - - 3 parts triethyleneglycol-dimethacrylate - - 0.3 parts ~ert-butylperbenzoate and the s~me mixture with . -25 parts copolymer ~A/BMA 50/50) (50 ~m par~ticle diamete~
n place ol ~VC by coating them between t~o overlapping ste~l , .
..... .. .
.. , ,, . ; . .
105~D6 8 sheets and then joining the two sheets by spot welding, in the case of the PVC decomposition and hydrogen chlo~ide formation occurs, whilst ~hen :Left standing in air there `
is pronounced corrosion at the points where PVC-decomposition S too~ place. This was not observed in the case of the - methacrylate plastlsol, . ~n gellin~ ~our plastisols - a) 60 parts ~VC (as in b) 60 paxts PVC (as in . Example 22 Example 22 ~:
; -I~\ 40 parts DOP 40 parts DBP .
c~ 60 parts ~MMA/BMA 50~50 d) 60 parts PMMA(30 ~m~
40 parts DBP -~ 40 parts DOP -- -.. . . . : , , . . . .
or lO minutes at 200C they gelled ~o ~onm a transparent -: ~ilm, but the ~VC ;s always discoloured yellow to brown, ~i :- whereas the ac~ylic resin remains colourless. ~ .
- ~31YsL-: 2~_~e~æ~12eD) `
On gelling together the ollowing components 2~ ; - a) 30 parts PVC (as in Example 22~ . :
` 30 par~s DOP : - :
-.~ - . . . 20 parts chalk ~ : .
~ 20 parts bari~e - b) 30 par~s ~MA/BMA 85/lS S2 ~m) in place of PVC
.:~ - otherw~se as a~ -~ ~or 30 minutes at 700C, in the case o~ a) a crumbly substance 't` . ' ''' iS obtained and in the case of b3 a solid tough film.
.; . - .
- ~ .
..
:; . , ., '' . ' ' ' - ZO -.. . . . .
iv ' '' ~ ' . . . .
... . . . .
,,~ . ~. .. .
o 28 For the preparation of the following plastisols in each case a copolymer was used which Wc18 polymerised with 1% , by weight of a rnethacrylate monomer with a functional group. ~
The plastisols obtained in this mannler were tested for their .
adhesion properties using the method described in E~ample 17, The results compiled in the attached table 4 show that excellent f ~dhesion values were obtained. - I
- 1:
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(a) A plastisol was prepared from 50 parts by weight of a copolymer from methy~tethacrylate an.d n-butylmethacrylate (MMA/B~ 85:15; particle size appro~imately 2 ~n~ and S parts of dibenzyl toluene.
This plastisol was tested as metal-to-metal adhesire by applying it to two degreased metal sheets (bonding area 5 cm and 0.3 mm layer thickness) and gelli.ng it for 30 minutes at 180C.
The subsequent tear-off test (tearing speed: 100 mm per minute). ~.
did not yield a bonding strength value.
(b~ The test was repeated using 50 parts by weight of a terpolymer which was copolymerised with 1 part by weight of `;~
; N-vinyl imidazole (MMA/~MA~Yinyl imidazole 84 15:1). Under otherwise unaltered conditions a bonding strength value of 13-kg/cm ~
was now obtained~ ~ -When.the above plastisol, with a content of N-vinyl imidazole, . according to the invention was used for the bonding of test sheets which has been electro-coated with a di.p primer as it is used in the automotive industry a bonding strength ~alue of 28 kg/cm was obtained.
Exam~le 30 A further plastisol was prepared ~rom 20 parts by weight o~
copolymer (-~MA/BMA/N-vinyl imidazole 84:15~ 35 parts by ::i! weight of chalk and 45 parts by weight of dibenzyl toluene. Upongelling ~or 30 minutes at 180& on an EC primed metal sheet a bonding strength value of 11 kg~cm was obtained ' ~ - 23 - :;
.' ,, .
.. . . . . . ..
~56i 6~3 The same pla~tisol surprisingly yielded bonding strength ~
~I values of 14 and 12 kg/cm, respectively, when applied to degreased or slightly greasy metal sheetsO
If, for comparative purposes, a methylmethacrylate homo-polymer or a methylmethacrylate/butylmethacrylate copolymer I ~
.~, is used which was not copolymerised with an adhesion promoter~ -- no bonding strength value was obtained.
.... : . : .
Example 31 , - - A plastisol was prepar~d from 50 parts by weight of a - 10 copolymer (MMA/N-vinyl imidazole 99:1), 30 parts by weight of chalk and 45 parts by weight of butylbenzyl-phthalate. Upon gelling for 30 mirlutes at 90 C the plastisol coating on the primed metal - 6heet could ~ot be removed.
- . . ::
- - If, however, the imidazole group is left out of ~the polymer ;ilO adh~sion is obtained.
Examk~le 32 - Following Example 29 ~b) a plastisol was prepared to which 1% by weight of one of the polybasic carbo~lic acid~ listed below was added. The results show that the adhesion was . 20 ~ ~ ConBiderably improved.
........ .
Table 5 . , , ,-, . ~
, - , , , , ~ :
id Bonding Strength Values in kg/crn~ -: a~ter Gelling for 30 Minutes at - ~ - 120 160 . "
. None 1 1 ~ 5 ; 20 ~ :
Benzene tri- , .
car~oxylic ac.id 20.2 28.o ~;
Adipic acid . 22 . 3 . 19 . 6 Maleic acid . 34 . 2 30 . 7 - I~aconic acid 27 . 8 . . . .. 25 . 3 - . . ~ 24 ~
. . .. . . . .
, . .
~: ~ : : - :
~S~83 Ex~nple 33 A plastisol was prepared f'rom the following ingredients: ;
100 parts poly~methyl methacrylate)~ -100 85 parts acetyl tributyl citrate - 5 parts titanium dioxide 5 parts zinc stearate The plastisol thus prepared was lined into the peripheral annular channel of lug caps by means of conventional lining machinery and the lined material was fluxed for one minute at o 350 F (177 C)-` The resulting gasketed lug caps were tested for sealing ability - by deter~ining their vacuum retention performance with the following procedure: A jar is filled with boiling water to one half inch from its top. A lug cap is sealed on with 35 inch pound (0.40 mkg) torqueO The resulting assembly is cooled to room temperature and kept for one week. A Yacuum reading is then obtained by means of a vacuum gauge. After removal of the cap, the compressed gasket thickness is measured.
All jars tested with lug caps gasketed with the above composition held a Yac~um satisfactorily. Gasket thicknesses ranging from 20 to 35 mils (0.5 to 0.9 mm) were acceptable. ~
: ., A plastisol was prepared with the following ingredients~
100 parts poly(methyl methacrylate)~ 100% ~ -120 parts acetyl tributyl citrate 5 parts titanium dioxide 5 parts zinc stearate
Table I gives the results of 15 :E~xamples. In Examples 1, 2, 7, 11 and 12 the plasticiser used was unsuitable for the particular polymer due to inadecluate compatibility In Examples 5, 9, 13 and 5 , 14 the value of 3. 0 for the viscosity rlumber was exceeded when using the indicated plasticiser, so that these combinations are also `
unsuitable, However, excellent results were obtained with the polymer/plasticiser combinations of Examples 3, 4, 6, 8,~10 and 15, wherein the plasticiser satisfied both criteria, i. e. it was completely compatible with the polymer and led to a viscosity number V8/0 of - ,¦ less than 3, 0, ~ .
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~.
`:, : ,; , . : . . . : ~ , ~0~i~33 Example 16 The following mixture is homogenised with a stirrer and applied with a doctor blade to a degreased steel sheet:
30 parts P~A (30 ~m) 30 parts but~lbenzyl-phthalate 36 parts chalk 3 parts triethyleneglycol-dimethacrylate 0.3 parts tert.-butylperbenzoate If this mixture is gelled for 20 minutes at 170C, a tough strongly adhering film is obtained which has good anti-corrosive properties. `~
Example 17 30 parts copolymer (MMA/BMA 50/50) (50 ~m) 30 parts dinonyl-phthalate ~
40 parts chalk -~ -5 parts resorcinol resin (Rousselot* RH-74-01) This mixture was tested as a metal adhesive by gelling it at 170C between two metal plates of ~a) steel and ~b) aluminium.
The subsequent tearing test revealed a tensile strength of ~a) 52kg/cm2 ~
and Cb) 42 kg/cm2 (5 cm2 bonding area and 0.3 mm coating thickness).- i -However, if in place of the 50 ~m copolymer, a copolymer with an average particle si~e of 500 ~m is used, a tearing value of only 3 kg/cm2 is obtained.
Example 18 24 parts MMA/BMA 85/15 (2 ~m) 33 parts diben~yl-toluene 40 parts chalk 3 parts azodicarbonamide *Trademark .
.
S~68;~
This mixture gclled in IS minutes ~t 170 C and formed a highly elastic solid foam with 100% foam expansion.
Exampl e 19 .
20 parts PMMA(100%)(particle 5iZ~: 30/um) S 1 30 parts butylben~yl-phthalate 45 parts chalk .
5 parts resorcinol resin (Rouss~lot RH 74-01) This highly viscous substance was suitable as a sealmg compound fo~ metal welding seams in the automobile and .`10 ~ r~frigerator industry. After baking at 180 C for 15 minutes the :
substance adhered well to polished m~tal sheets and can be easily ` . ~ lacquer~d. ` `; . ::
, .. . . .
E:xample 20 ~ ~:
~ . If a polymer plasticiser ~urea/~ormald~ehyde plasticiser resin .
-. 1 601d as Plastige~; is used the following comparison is obtained .
with a polymer: plasticiser mixing ratio of 1: 1, - : . . ~
- -: - Tab1e 2 ~ ~ ~:
: ~ ~ Particle ~ c~
~, immed~y after --., ~, . .~. - , ..
- . - . . . ~.
100% PMMA 30 22000 16000 good hard ,. .. A/BMA . ...... ~ ~ .
85/15 . 2 1630Q0 218000 good hard~ to~gh :~
-. ~A/BMA
50~50 60 23250 22250 good elastic - ~d:U~i ' " '' ' ' . ' ' Table 3 sho-~ls the thermal stability of all acrylic plastisol .
. as compare~ with a PVC-plastisol with a bakin~ cy~le of 30 minutes at 150C.
., . ' /ro~é~ - 18 - . . . : :
- . - , . ....
' - ' ' ~ '' '.
-,.:. ... . . . . , . : , Tabl 3 Emulsion PVC, K-value 74 t2 ~m) . 20 PMMA (30 ~m) 20 Ch~lk 4S 45 . Butylbenzylphthalate 35 35 S Viscosity immediately 36000 52500 - . in cP . ater 10 days 21000 18000 Vlo/O 0.58 0~3 Cold elasticity -40~C
Discolouration 120C sligh~ sligh~
-.10 after 14 ~ays at 150C black slight . , . . . . . . . ~
- . Abrasion ~mm/min~ ramb.temp. . - 0~01~ 0.045 - `~ ater 14 days 1120C 0.039 0.390 : : storage at ~150C 1.280 0.220 ~ . . . - - - ~ . . , : -The Table shows that after 14 days at 150C the PVC~
15 ~ plastigel had completely discoloured.(decomposed? and tha~ `~
- ~- the abrasion values in a sand-blasting device ~with corundum -~
: : -. in place o~ sand) rose 80~ in the case of PVC, whereas in the . . , - . -~ case of the acrylic plastigel the:abrasion values, although . - not originally especially good, only rose by a maximum of ~ 25 tîmes.
, . . . . . . .......... . .. . . . .
On omp~ring the followîng mixtures~
. ~.- - . -: 25 parts PVC ~paste type, emulsion-polymerised~
K valu 74g 2 ~m) ~5 - .. ; . 40 parts chalk ., . . ;, . . . . . . .
, -`: 5 parts iron oxide (magn.) .
- ` ~7 parts DOP
! - - , - - 3 parts triethyleneglycol-dimethacrylate - - 0.3 parts ~ert-butylperbenzoate and the s~me mixture with . -25 parts copolymer ~A/BMA 50/50) (50 ~m par~ticle diamete~
n place ol ~VC by coating them between t~o overlapping ste~l , .
..... .. .
.. , ,, . ; . .
105~D6 8 sheets and then joining the two sheets by spot welding, in the case of the PVC decomposition and hydrogen chlo~ide formation occurs, whilst ~hen :Left standing in air there `
is pronounced corrosion at the points where PVC-decomposition S too~ place. This was not observed in the case of the - methacrylate plastlsol, . ~n gellin~ ~our plastisols - a) 60 parts ~VC (as in b) 60 paxts PVC (as in . Example 22 Example 22 ~:
; -I~\ 40 parts DOP 40 parts DBP .
c~ 60 parts ~MMA/BMA 50~50 d) 60 parts PMMA(30 ~m~
40 parts DBP -~ 40 parts DOP -- -.. . . . : , , . . . .
or lO minutes at 200C they gelled ~o ~onm a transparent -: ~ilm, but the ~VC ;s always discoloured yellow to brown, ~i :- whereas the ac~ylic resin remains colourless. ~ .
- ~31YsL-: 2~_~e~æ~12eD) `
On gelling together the ollowing components 2~ ; - a) 30 parts PVC (as in Example 22~ . :
` 30 par~s DOP : - :
-.~ - . . . 20 parts chalk ~ : .
~ 20 parts bari~e - b) 30 par~s ~MA/BMA 85/lS S2 ~m) in place of PVC
.:~ - otherw~se as a~ -~ ~or 30 minutes at 700C, in the case o~ a) a crumbly substance 't` . ' ''' iS obtained and in the case of b3 a solid tough film.
.; . - .
- ~ .
..
:; . , ., '' . ' ' ' - ZO -.. . . . .
iv ' '' ~ ' . . . .
... . . . .
,,~ . ~. .. .
o 28 For the preparation of the following plastisols in each case a copolymer was used which Wc18 polymerised with 1% , by weight of a rnethacrylate monomer with a functional group. ~
The plastisols obtained in this mannler were tested for their .
adhesion properties using the method described in E~ample 17, The results compiled in the attached table 4 show that excellent f ~dhesion values were obtained. - I
- 1:
- , . "
.
'`.:
., , . . ' ' ` . '`' . ';
:
: ` j , ' ~ ,.:~
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....
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. . .
., ~ ~, , .
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. ~ ' i ' ~ ' Q
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(a) A plastisol was prepared from 50 parts by weight of a copolymer from methy~tethacrylate an.d n-butylmethacrylate (MMA/B~ 85:15; particle size appro~imately 2 ~n~ and S parts of dibenzyl toluene.
This plastisol was tested as metal-to-metal adhesire by applying it to two degreased metal sheets (bonding area 5 cm and 0.3 mm layer thickness) and gelli.ng it for 30 minutes at 180C.
The subsequent tear-off test (tearing speed: 100 mm per minute). ~.
did not yield a bonding strength value.
(b~ The test was repeated using 50 parts by weight of a terpolymer which was copolymerised with 1 part by weight of `;~
; N-vinyl imidazole (MMA/~MA~Yinyl imidazole 84 15:1). Under otherwise unaltered conditions a bonding strength value of 13-kg/cm ~
was now obtained~ ~ -When.the above plastisol, with a content of N-vinyl imidazole, . according to the invention was used for the bonding of test sheets which has been electro-coated with a di.p primer as it is used in the automotive industry a bonding strength ~alue of 28 kg/cm was obtained.
Exam~le 30 A further plastisol was prepared ~rom 20 parts by weight o~
copolymer (-~MA/BMA/N-vinyl imidazole 84:15~ 35 parts by ::i! weight of chalk and 45 parts by weight of dibenzyl toluene. Upongelling ~or 30 minutes at 180& on an EC primed metal sheet a bonding strength value of 11 kg~cm was obtained ' ~ - 23 - :;
.' ,, .
.. . . . . . ..
~56i 6~3 The same pla~tisol surprisingly yielded bonding strength ~
~I values of 14 and 12 kg/cm, respectively, when applied to degreased or slightly greasy metal sheetsO
If, for comparative purposes, a methylmethacrylate homo-polymer or a methylmethacrylate/butylmethacrylate copolymer I ~
.~, is used which was not copolymerised with an adhesion promoter~ -- no bonding strength value was obtained.
.... : . : .
Example 31 , - - A plastisol was prepar~d from 50 parts by weight of a - 10 copolymer (MMA/N-vinyl imidazole 99:1), 30 parts by weight of chalk and 45 parts by weight of butylbenzyl-phthalate. Upon gelling for 30 mirlutes at 90 C the plastisol coating on the primed metal - 6heet could ~ot be removed.
- . . ::
- - If, however, the imidazole group is left out of ~the polymer ;ilO adh~sion is obtained.
Examk~le 32 - Following Example 29 ~b) a plastisol was prepared to which 1% by weight of one of the polybasic carbo~lic acid~ listed below was added. The results show that the adhesion was . 20 ~ ~ ConBiderably improved.
........ .
Table 5 . , , ,-, . ~
, - , , , , ~ :
id Bonding Strength Values in kg/crn~ -: a~ter Gelling for 30 Minutes at - ~ - 120 160 . "
. None 1 1 ~ 5 ; 20 ~ :
Benzene tri- , .
car~oxylic ac.id 20.2 28.o ~;
Adipic acid . 22 . 3 . 19 . 6 Maleic acid . 34 . 2 30 . 7 - I~aconic acid 27 . 8 . . . .. 25 . 3 - . . ~ 24 ~
. . .. . . . .
, . .
~: ~ : : - :
~S~83 Ex~nple 33 A plastisol was prepared f'rom the following ingredients: ;
100 parts poly~methyl methacrylate)~ -100 85 parts acetyl tributyl citrate - 5 parts titanium dioxide 5 parts zinc stearate The plastisol thus prepared was lined into the peripheral annular channel of lug caps by means of conventional lining machinery and the lined material was fluxed for one minute at o 350 F (177 C)-` The resulting gasketed lug caps were tested for sealing ability - by deter~ining their vacuum retention performance with the following procedure: A jar is filled with boiling water to one half inch from its top. A lug cap is sealed on with 35 inch pound (0.40 mkg) torqueO The resulting assembly is cooled to room temperature and kept for one week. A Yacuum reading is then obtained by means of a vacuum gauge. After removal of the cap, the compressed gasket thickness is measured.
All jars tested with lug caps gasketed with the above composition held a Yac~um satisfactorily. Gasket thicknesses ranging from 20 to 35 mils (0.5 to 0.9 mm) were acceptable. ~
: ., A plastisol was prepared with the following ingredients~
100 parts poly(methyl methacrylate)~ 100% ~ -120 parts acetyl tributyl citrate 5 parts titanium dioxide 5 parts zinc stearate
4 parts azobisformamide 1.5 parts Light weight silica (Cab-0-Sil( )) ~50~;~33 This composition wa~ lincd into a wide-mouth jar closure ~:
(83 mm diameter) by conventional means. The lining was 1uxed for 1, 5 minute at 350 F (177~C).
` . The caps thus obtained were applied to jars with a 32 inch S pound (O. 36 mkg) torque and kept at room temperature for 24 hours, - They were then placed on a stacker itor one week, being subjected in the process to a net load of 128 lbs (57 kg) on each cap and jar . ' . - ., . ' . ' ' a~embly, ` The jars were then removed, kept at room temperature - ' . ' !
for 24 hours and placed in a cold room for two days. Vacuum was -- - .. . 10: determined at 40 F (4 G) by means of a gauge. Nine out of ten jar~ tested held 40 mmHg, an acceptable performance;
.. , , . . . . ... ~ . . . . .
. - - : , ~ . - - . -: ^- -: , - . , :. .
' . ' ' ' .; . -' . '' ,. ..' ' '''.'' ' ~, ~ , ^ : : - : - . , . ; .:
' .'~ ' '` . ' ' ~ ' .
.` ' ' ' ' '~.
.
.: . ~ : ~ ;....................................... : ~
(83 mm diameter) by conventional means. The lining was 1uxed for 1, 5 minute at 350 F (177~C).
` . The caps thus obtained were applied to jars with a 32 inch S pound (O. 36 mkg) torque and kept at room temperature for 24 hours, - They were then placed on a stacker itor one week, being subjected in the process to a net load of 128 lbs (57 kg) on each cap and jar . ' . - ., . ' . ' ' a~embly, ` The jars were then removed, kept at room temperature - ' . ' !
for 24 hours and placed in a cold room for two days. Vacuum was -- - .. . 10: determined at 40 F (4 G) by means of a gauge. Nine out of ten jar~ tested held 40 mmHg, an acceptable performance;
.. , , . . . . ... ~ . . . . .
. - - : , ~ . - - . -: ^- -: , - . , :. .
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Claims (24)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In a plastisol, in which solid particles of an organic polymer component (a) are dispersed in an organic liquid component (b), which serves as a compatible plasticiser for the organic polymer, in a proportion effective to form a viscous dispersion having a liquid or paste-like appearance capable of being gelled by heating, the improvement in which the organic polymer component consists substantially of units derived from (i) at least one monomer selected from: t-butyl acrylate, a C1-4 alkyl methacrylate and cyclohexyl methacrylate, or (ii) at least one of the above monomers and at least one comonomer selected from: methacrylates of aliphatic C2 to C10 alcohols, acrylates of aliphatic C1-10 alcohols, styrene and alpha-methyl styrene, the polymer having a glass transition temperature of above 35°C and an average degree of polymerization of more than 400, and the average particle size of the polymer in the plastisol being from 0.1 to 500 microns; said plasticiser being present in an amount of from 30 to 1000 parts per 100 parts by weight of said polymer and being sufficiently compatible that at least 8 days after the gelling of said plastisol, the plasticiser does not exude from said plastisol, said plasticiser moreover being effective to provide the plastisol with a viscosity index V8/0 of less than 3Ø
2. A plastisol according to claim 1 wherein the average particle size of the polymer is related to its glass transition temperature so as to lie within the triangle XYZ of the accompanying drawing.
3. A plastisol according to claim 2 wherein the plasticiser is dioctyl phthalate, dibutyl phthalate or di(2-methoxyethyl)phthalate and the average particle size of the polymer is related to its glass transition temperature so as to lie within the triangle ABC, DEF or GYH, respectively, of the accompanying drawing.
4. A plastisol according to claim 1 wherein the organic polymer component consists substantially of units derived from methyl methacrylate.
5. A plastisol according to claim 1 wherein the organic polymer consists substantially of units derived from at least 40% by weight of methyl methacrylate and substantially all the balance a monomer selected from C2 4 alkyl methacrylates and G1-4 alkyl acrylates.
6. A plastisol according to claim 5 wherein the proportion of methyl methacrylate units is at least 50%
but less than 100%.
but less than 100%.
7. A plastisol according to claim 1 which contains also 0.1 to 50 parts by weight of an adhesion promoter, per 100 weight parts of polymer component.
8. A plastisol according to claim 1 wherein the polymer contains also up to 3% by weight, based on the polymer, of units derived from a monomer selected from acrylate and methacrylate monomers possessing a group selected from hydroxyl, epoxy, amino and free carboxyl groups.
9. A plastisol according to claim 1 wherein the polymer contains also up to 10% by weight of units derived from at least one comonomer containing a heterocyclic group having at least one nitrogen atom in a heterocyclic ring.
10. A plastisol according to claim 9 wherein the heterocyclic group-containing comonomer is a heterocyclic vinyl compound of the general formula in which n is equal to 0 or 1, R1 is selected from the group consisting of hydrogen atoms, linear alkyl groups with 1 to 4 carbon atoms and branched alkyl groups with 1 to 4 carbon atoms and phenyl groups, and R2 is selected from groups of the formulae:-, -COR3, and -R3 in which R3 is a heterocyclic group having at least one ring, at least one nitrogen atom being present in at least one ring.
11. A plastisol according to claim 9 containing 0.2 to 3.0% by weight of the heterocyclic group-containing comonomer.
12. A plastisol according to claim 10, which contains also a cross-linking agent in an amount of 0.1 to 3.0%
by weight which is effective to react with the heterocyclic groups of said comonomer.
by weight which is effective to react with the heterocyclic groups of said comonomer.
13. A plastisol according to claim 12, wherein the cross-linking agent is a polyepoxide and/or a polybasic carboxylic acid.
14. A container closure containing therein a plastisol claimed in claim 1 in an amount effective to provide a sealing gasket for said closure.
15. An article comprising a metal substrate coated with a plastisol claimed in claim 1.
16. A solid elastic gel formed from a plastisol according to claim 1 by heating said plastisol to a temperature between about 70 and 240°C.
17. A homogeneous, elastic, solid gel formed by heating to a tempera-ture between about 70 and 240°C a plastisol comprising solid particles of average particle size 0.1 to 500 microns of an organic polymer having a glass transition temperature above 35°C and consisting of 40-100% of units derived from methyl methacrylate, 0-60% of units derived from a first comonomer selected from alkyl acrylates having 1-4 carbon atoms in the alkyl portion and alkyl methacrylates having 2-4 carbon atoms in the alkyl portion, 0-3% of units derived from a second comonomer selected from methacrylic and acrylic compounds having at least one hydroxyl, expoxy, amino or carboxylic acid group, and 0-10% of units derived from a third comonomer which is a heterocyclic vinyl compound of the general formula in which n is 0 or 1, R1 is selected from hydrogen, alkyl of 1 to 4 carbon atoms and phenyl and R2 is selected from , -COR3 and -R3 in which R3 is a heterocyclic group having at least one ring containing a nitrogen atom, all percentages being by weight, the degree of polymerization of the polymer being more than 400, based on methyl methacrylate and the first comonomer when used dispersed in (b) an amount of compatible organic liquid plasticiser effective to form a viscous plastisol the viscosity of which does not increase by more than 300% within 8 days of preparation; said amount being in the range of from 30 to 1000 parts per 100 parts by weight of said polymer, said plasticiser being sufficiently compatible that at least 8 days after the gelling of said plastisol, the plasticiser does not exude from said plastisol.
18 An article according to claim 17 in the form of a container closure sealing gasket.
19. A plastisol comprising (a) 100 weight parts of solid particles of an organic polymer selected from t-butylacrylate or methyl, ethyl, n-propyl, isopropyl, isobutyl, sec-butyl, t-butyl or cyclohexylmethacrylate homopoly-mers, and copolymers of at least one said monomer with at least one comonomer selected from methacrylates of aliphatic C2 to C10 alcohols, acrylates of C1 to C10 alcohols, styrene and .alpha.-methyl-styrene, whereby the polymer has an average particle size of 0.1 to 500 microns, a glass transition temperature above 35°C and an average degree of polymerization of more than 400, and (b) 30 to 1000 parts of an organic liquid plasticiser which is sufficiently compatible with the polymer that at least 8 days after gelling of said plastisol the plasticiser does not exude from said plastisol) said plasticiser further being effective to provide the plastisol with a viscosity index V8/o of less than 3.0; the average particle size of polymer (a) being related to its glass transition temperature so as to lie within the triangle XYZ of the accompanying drawing, said plastisol further being in the form of a liquid or paste-like dispersion of polymer particles (a) in plasticiser (b) capable of being gelled by heating to a temperature between about 70 and 240°C.
20. A plastisol composition according to claim 8, comprising 50 parts by weight of a polymer of methmethacrylate, n-butylmethacrylate and methacrylic acid in a weight ratio of 84:15:1 and 50 parts by weight of dibenzyl-toluene.
21. A plastisol composition according to claim 8, comprising 20 parts by weight of a polymer of methmethacrylate, n-butylmethacrylate and methacrylic acid in a weight ratio of 84:15:1; 45 parts by weight of dibenzyl-toluene and 35 parts by weight of chalk.
22, A plastisol composition according to claim 9 or 10 comprising 50 parts by weight of a polymer of methmethacrylate, n-butylmethacrylate and N-vinyl imidazole in a weight ratio of 84:15:1 and 50 parts by weight of dibenzyl-toluene,
23, A plastisol composition according to claim 9 or 10 comprising 20 parts by weight of a polymer of methmethacrylate, n.butylmethacrylate and N-vinyl imidazole in a weight ratio of 84:15:1; 45 parts by weight of di-benzyl toluene and 35 parts by weight of chalk.
24, A plastisol composition according to claim 1 comprising 50 parts by weight of a polymer of methmethacrylate and N-vinyl imidazole in a weight ratio of 99:1; 45 parts by weight of butylbenzyl-phthalate and 30 parts by weight of chalk.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19742454235 DE2454235C3 (en) | 1974-11-15 | 1974-11-15 | Plastisols based on acrylate polymers |
| DE19752529732 DE2529732C3 (en) | 1975-07-03 | 1975-07-03 | Plastisols based on acrylate polymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1050683A true CA1050683A (en) | 1979-03-13 |
Family
ID=25767971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA239,683A Expired CA1050683A (en) | 1974-11-15 | 1975-11-14 | Acrylic polymer plastisols |
Country Status (14)
| Country | Link |
|---|---|
| JP (1) | JPS5171344A (en) |
| AU (1) | AU504142B2 (en) |
| BG (1) | BG27911A3 (en) |
| BR (1) | BR7507547A (en) |
| CA (1) | CA1050683A (en) |
| ES (1) | ES442631A1 (en) |
| FR (1) | FR2291248A1 (en) |
| GB (1) | GB1516510A (en) |
| HU (1) | HU177765B (en) |
| IT (1) | IT1054391B (en) |
| NL (1) | NL175423C (en) |
| PL (1) | PL106055B1 (en) |
| RO (1) | RO70308A (en) |
| SE (1) | SE414036C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4309331A (en) | 1977-03-22 | 1982-01-05 | E. I. Du Pont De Nemours And Company | Surfactant-free acrylic plastisols and organosols compositions |
| US4421619A (en) | 1978-10-18 | 1983-12-20 | E. I. Du Pont De Nemours & Co. | Acrylic plastisols and organosols and photosensitive compositions and elements made therefrom |
| US6559213B2 (en) | 1995-03-16 | 2003-05-06 | Henkel-Teroson Gmbh | Plastisol composition |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2529732C3 (en) * | 1975-07-03 | 1982-11-04 | Teroson Gmbh, 6900 Heidelberg | Plastisols based on acrylate polymers |
| DE3139090C1 (en) * | 1981-10-01 | 1983-07-28 | Röhm GmbH, 6100 Darmstadt | Plastisols made from copolymers of methyl methacrylate with improved adhesive strength and their use |
| DE3308925A1 (en) * | 1983-03-12 | 1984-09-13 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING STORAGE-STABLE PLASTISOLS AND ORGANOSOLS |
| DE3442646C2 (en) * | 1984-11-22 | 1986-10-23 | Dr. Alois Stankiewicz GmbH, 3101 Adelheidsdorf | Polyvinyl chloride free plastisol and its uses |
| DE3523480C1 (en) * | 1985-07-01 | 1987-01-22 | Teroson Gmbh | Metal adhesive |
| DE4008980C2 (en) * | 1990-03-21 | 1996-03-28 | Staedtler Fa J S | Plastic mass for kneading, modeling, handicrafts and decorating and processes for their production |
| GB2252267A (en) * | 1991-01-31 | 1992-08-05 | Grace W R & Co | Curing of plastisol liner material in thermoplastic closure |
| DE19542746A1 (en) | 1995-11-16 | 1997-05-22 | Roehm Gmbh | Plastisols based on polymer masses softened by the addition of plasticizers |
| FR2791353B1 (en) | 1999-03-23 | 2001-05-25 | Chavanoz Ind | FLAME RETARDANT PLASTIC COMPOSITION, WIRE AND TEXTILE STRUCTURE COATED WITH THE SAME |
| JP4384286B2 (en) * | 1999-03-30 | 2009-12-16 | ガンツ化成株式会社 | Injection molding method of acrylic resin plastisol composition for injection molding |
| DE19928352A1 (en) | 1999-06-21 | 2000-12-28 | Roehm Gmbh | Plastisol use for mould articles, comprises (meth)acrylate (co)polymer(s) with bimodal or multi-modal prim. particle distribution prepared from methyl methacrylate, (meth) acrylate, vinyl monomer and adhesion aiding monomers |
| DE10227898A1 (en) | 2002-06-21 | 2004-01-15 | Röhm GmbH & Co. KG | Process for the preparation of spray-dried poly (meth) acrylate polymers, their use as polymer component for plastisols and plastisols prepared therewith |
| CN1324054C (en) * | 2002-07-23 | 2007-07-04 | 可隆株式会社 | Preparation of acrylic polymer sol for coating |
| CN100427543C (en) | 2003-01-21 | 2008-10-22 | 株式会社可乐丽 | Acrylic acid polymer powder, acrylic acid sol and forming article |
| DE102004030404A1 (en) * | 2004-06-23 | 2006-01-19 | Röhm GmbH & Co. KG | Plastisols based on a methyl methacrylate copolymer |
| KR101379051B1 (en) | 2006-02-23 | 2014-03-28 | 미츠비시 레이온 가부시키가이샤 | (meth)acrylic polymer particle, process for production of the particle, plastisol, and article |
| CN101688082B (en) * | 2007-07-10 | 2013-07-17 | 三菱丽阳株式会社 | Thermal-flowability regulator for powder coating compositio, process for producing the same, and powder coating |
| GB2495776A (en) * | 2011-10-21 | 2013-04-24 | Henkel Ag & Co Kgaa | Plastisol composition for sealing and automotive coating |
| JP5965824B2 (en) * | 2012-11-26 | 2016-08-10 | 積水化学工業株式会社 | Post-curing tape and joining member joining method |
| WO2017161101A1 (en) * | 2016-03-17 | 2017-09-21 | Crop Enhancement, Inc. | Plastisol-coated agrochemical formulations and methods of use |
-
1975
- 1975-10-31 GB GB45385/75A patent/GB1516510A/en not_active Expired
- 1975-11-03 SE SE7512297A patent/SE414036C/en not_active IP Right Cessation
- 1975-11-10 AU AU86477/75A patent/AU504142B2/en not_active Expired
- 1975-11-11 BG BG7531459A patent/BG27911A3/en unknown
- 1975-11-12 JP JP50135244A patent/JPS5171344A/en active Granted
- 1975-11-13 HU HU75TE845A patent/HU177765B/en unknown
- 1975-11-14 RO RO7583915A patent/RO70308A/en unknown
- 1975-11-14 ES ES442631A patent/ES442631A1/en not_active Expired
- 1975-11-14 NL NLAANVRAGE7513337,A patent/NL175423C/en not_active IP Right Cessation
- 1975-11-14 CA CA239,683A patent/CA1050683A/en not_active Expired
- 1975-11-14 BR BR7507547*A patent/BR7507547A/en unknown
- 1975-11-14 IT IT29316/75A patent/IT1054391B/en active
- 1975-11-14 FR FR7534895A patent/FR2291248A1/en active Granted
- 1975-11-15 PL PL1975184779A patent/PL106055B1/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4309331A (en) | 1977-03-22 | 1982-01-05 | E. I. Du Pont De Nemours And Company | Surfactant-free acrylic plastisols and organosols compositions |
| US4421619A (en) | 1978-10-18 | 1983-12-20 | E. I. Du Pont De Nemours & Co. | Acrylic plastisols and organosols and photosensitive compositions and elements made therefrom |
| US6559213B2 (en) | 1995-03-16 | 2003-05-06 | Henkel-Teroson Gmbh | Plastisol composition |
Also Published As
| Publication number | Publication date |
|---|---|
| NL7513337A (en) | 1976-05-18 |
| AU504142B2 (en) | 1979-10-04 |
| RO70308A (en) | 1982-05-10 |
| HU177765B (en) | 1981-12-28 |
| JPS5171344A (en) | 1976-06-21 |
| NL175423B (en) | 1984-06-01 |
| IT1054391B (en) | 1981-11-10 |
| SE414036C (en) | 1984-07-10 |
| NL175423C (en) | 1984-11-01 |
| GB1516510A (en) | 1978-07-05 |
| SE7512297L (en) | 1976-05-16 |
| AU8647775A (en) | 1977-05-19 |
| SE414036B (en) | 1980-07-07 |
| JPS5516177B2 (en) | 1980-04-30 |
| BR7507547A (en) | 1976-08-10 |
| FR2291248B1 (en) | 1979-07-06 |
| BG27911A3 (en) | 1980-01-15 |
| PL106055B1 (en) | 1979-11-30 |
| FR2291248A1 (en) | 1976-06-11 |
| ES442631A1 (en) | 1977-04-16 |
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