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EP0733084A1 - Composition de plastisol - Google Patents

Composition de plastisol

Info

Publication number
EP0733084A1
EP0733084A1 EP95902111A EP95902111A EP0733084A1 EP 0733084 A1 EP0733084 A1 EP 0733084A1 EP 95902111 A EP95902111 A EP 95902111A EP 95902111 A EP95902111 A EP 95902111A EP 0733084 A1 EP0733084 A1 EP 0733084A1
Authority
EP
European Patent Office
Prior art keywords
composition according
plastisoi
polymer
weight
net
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.)
Ceased
Application number
EP95902111A
Other languages
German (de)
English (en)
Inventor
Michael Beck
Lutz Jeromin
Christiane Höltgen
Wolfgang Ritter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0733084A1 publication Critical patent/EP0733084A1/fr
Ceased legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/042—Acrylic polymers
    • 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
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/18—Plasticising macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/02—Inorganic compounds
    • C09K2200/0217—Salts
    • C09K2200/023—Sulfur-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0625—Polyacrylic esters or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0632—Polystyrenes

Definitions

  • the invention relates to a novel plastiso composition based on bead polymers, plasticizers and inorganic fillers and, if appropriate, other conventional additives.
  • Plastisols are generally understood to mean dispersions of organic plastics in plasticizers which gel when heated to a higher temperature and harden when cooled.
  • the plastisols which are still used in practice today contain predominantly fine-powdered polyvinyl chloride (PVC) which is dispersed in a liquid plasticizer and forms a paste.
  • PVC polyvinyl chloride
  • Such polyvinyl chloride plastisols are used for a wide variety of purposes.
  • sealing compounds e.g. used for seam seals in metal containers or as flanged seam adhesives in the metal industry, as corrosion protection coatings for metals (for example as underbody protection for motor vehicles), for impregnating and coating substrates made of textile materials (e.g. as carpet backing), as cable insulation etc. .
  • ERS ⁇ ZBL ⁇ T (RULE 26) are exposed. Residues of monomeric vinyl chloride in PVC could also be hazardous to health during further processing or for end users, although the content is generally only in the ppb range.
  • Coating compositions based on polyurethane or acrylate have already become known which, for. B. used in the automotive industry instead of PVC plastisols.
  • the volatility of the blocking agent can lead to the formation of bubbles in the case of thick layers; moreover, the applicable temperature range between 150 ° C. and 180 ° C. for the stoving conditions is often not to be kept.
  • aqueous PU dispersions do not fit into the usual production process.
  • Microencapsulated polyurethane systems lack shear stability, which leads to gelation in the pumps during application.
  • Acrylate plastisols as have become known from DE-B-24 54 235 and DE-B-25 29 732, largely meet the technical requirements mentioned at the outset, but the required acrylate polymers are also far more expensive than polyvinyl chloride, so that they are used Such acrylic plastisols have hitherto been limited to special fields of application, for example as spot welding pastes, in which PVC plastisols fail completely. Plastisols based on styrene / acrylonitrile copolymers according to EP-A-261 499 are also not yet a satisfactory solution because of inadequate abrasion resistance and / or storage stability.
  • DE-A-41 39382 proposes plastisols based on core / shell polymers, in which the core of the polymer particles is formed from a diene elastomer and the shell from a continuous layer from one
  • ERSATZBL ⁇ TT (REGEL26) Methyl methacrylate resin, an acrylonitrile resin or a vinyl chloride polymer.
  • the first two shell materials meet the requirement for a chlorine-free polymer
  • polymer particles with a high proportion of hard shell material are required for storage-stable plastisols. Since these polymer components are at least partially incompatible with the plasticizer, heterodisperse systems are formed after the gelling process, which systems do not allow optimum performance properties to be achieved.
  • Vinyl chloride polymer as the shell material reduces the chlorine content compared to pure PVC plastisols, but since these are not chlorine-free, these polymers represent only a less than satisfactory partial solution to the problem.
  • DE-A-40 34 725 describes that plastisol compositions with excellent application properties, in particular good storage stability, good adhesion to metals and high abrasion resistance and good mechanical properties, can be obtained if the organic polymer component can be prepared by emulsion polymerization Styrene copolymer powder uses which
  • styrene and / or ⁇ -methylstyrene and / or p-methylstyrene and b) 3 to 20% by weight (based on the copolymer) of methacrylic acid and / or acrylic acid and / or itaconic acid.
  • polymer particles with a very uniform average primary particle size of about 0.3 to 1.5 ⁇ m can be obtained, in which the polar carboxyl groups are essentially arranged on the outside and, as lipophobic residues, obviously for the stability of the dispersions of these particles in the plasticizer are responsible at room temperature.
  • These copolymers have a molecular weight of the order of 200,000 to 1,000,000.
  • aqueous polymer dispersions are usually dried by spray drying processes.
  • additional problems arise with chlorine-free polymers, since the very finely divided polymer powders tend to have dust explosions due to their very low minimal ignition energy.
  • the chlorine-free polymer dispersions have to be spray-dried under inert conditions, but this process makes the polymer production process considerably more expensive. The object was therefore to provide chlorine-free polymer powders for use in plastisols which do not need expensive spray drying processes under inert conditions.
  • plastisols can be prepared from certain bead polymers, which are suitable as adhesives, sealants and / or coating compositions.
  • Pearl polymerization often also called suspension polymerization, has long been known per se.
  • the organic monomer which is largely insoluble in water, is suspended in the aqueous phase with the aid of protective colloids and / or stabilizers as dispersion aids, and polymer particles of more or less size are formed.
  • Water-insoluble inorganic salts are often used as protective colloids and / or stabilizers. Usually, these inorganic salts are separated and removed from the polymer during workup, e.g. B. by treatment with acids.
  • the invention thus relates to plastisol compositions based on pearl polymers, which are filtered off from the aqueous phase after the polymerization without further processing and are then freed of the residual moisture in a conventional drying process.
  • the dispersing agents are selected so that they have at least no interfering influence in the plastiso composition, preferably they are at least in part normal components of the plastisol.
  • the inorganic constituent of these dispersing agents - also called Pickering emulsifier - is therefore preferably barium sulfate, calcium carbonate, magnesium carbonate, calcium silicate or an aluminosilicate.
  • ionic or nonionic emulsifiers are added in a minor amount, such as. B. sodium cetyl stearyl alcohol sulfate.
  • styrene-methacrylic acid or styrene-acrylic acid copolymers as described in DE-A-4034725 are preferably used according to the above processes polymerized and used in the plastisols according to the invention.
  • the monomers can either be initially charged or only the styrene is initially charged and the methacrylic acid or acrylic acid is metered in during the polymerization period. Due to the different solubility of the monomers in the polymer or water, a concentration gradient of the (meth) acrylic acid can be achieved over the particle cross section.
  • the particle size of the polymer can be varied within wide limits by suitable choice of the monomer concentration, the monomer / dispersant ratio and the stirrer speed and / or
  • the average particle size of the bead polymers for the plastisols according to the invention is between 1 ⁇ m and 150 ⁇ m, preferably between 5 ⁇ m and 60 ⁇ m.
  • the polymer formed can be separated from the water very easily by filtration and subsequent drying at 50 ° C. to 150 ° C., preferably at 60 ° C. to 100 ° C., and can be used directly for the production of plastisol, the inorganic residue remaining in the polymer Part of the dispersing agent serves as a filler which is necessary in the plastisol anyway. Since the above-mentioned drying process only serves to remove the residual moisture after the filtration, the less complex and therefore inexpensive belt drying processes or drying in a fluidized bed are suitable for this step. Surprisingly, the minimum ignition energy for these suspension polymers increases by a factor of about 1,000 in comparison to polymers which were produced according to DE-A-40 34 725 with the aid of the spray drying process. This is desirable because polymers with such a high minimum ignition energy can be handled safely without a great deal of inerting.
  • the plastiso composition according to the invention contains about 30 to 1,000 parts by weight of plasticizer per 100 parts by weight of the styrene copolymer.
  • plasticizers Conventional organic plasticizers are in themselves suitable as plasticizers (cf. Paul E. Bruins, Plasticizer Technology [Weinhold Publishing Corporation, New York], Volume 1, pages 228-232).
  • Alkyl phthalates such as dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate, dibenzyl phthalate and very particularly diisononyl phthalate (DINP) are preferred.
  • DINP diisononyl phthalate
  • the known ones are also suitable
  • SPARE BLADE (RULE 26) Plasticizers from the group of organic phosphates, adipates and sebacates or also benzyl benzoate or diphenyl ether.
  • the plastisols according to the invention may also contain additives which are customary in plastisol technology.
  • the plastisols according to the invention are particularly suitable in motor vehicle construction as underbody protection agents and also as adhesives for relining the hood, as masses for sill protection and as spot welding pastes, and other adhesive applications.
  • they can be used with advantage as sealants for container closures such as crown caps as well as seam sealants and seam seam adhesives for tin cans.
  • these plastisols can also be used for a variety of other technical applications, including: a. Coating aces for wallpaper, floor coverings, textile coating compositions, sheathing of panes, z. B. for Automob l- and other vehicle construction analogous to the method described in EP-B-333538, as an adhesive for the production of multi-pane safety gas.
  • the polymerization reaction takes place in a stirred tank (R) which is equipped with a stirrer consisting of three MIG stages and baffles.
  • the stirrer speed is infinitely adjustable.
  • a container (V) is used as a template.
  • the template is weighed and connected to the reactor R via a stainless steel line.
  • the dosing takes place automatically by preselecting the corresponding dosing rate.
  • the reactor R has various heating or cooling circuits.
  • the system can be operated in a temperature range from 15 ° C to 120 ° C via two separate temperature sensors (product temperature) installed in R. Nitrogen can be passed over to produce an inert atmosphere in the reactor R.
  • the metering of the methacrylic acid from template V into the reactor is controlled gravimetrically and takes place within the first three to four hours of the reaction.
  • the total reaction time is 7 to 8 hours.
  • the excess heat of reaction is removed by tempering the reactor with mixed water.
  • the present process is a simple radical copolymerization of styrene with methacrylic acid in an aqueous suspension with a water content of approx. 50%.
  • the polymerization is initiated by dibenzoyl peroxide or similar initiators which are poorly soluble in water by thermal radical formation.
  • ERSA ⁇ ZBLA ⁇ T (RULE 26) After the reaction has ended, the dispersion is cooled ( ⁇ 45 ° C.) and discharged through a belt filter. The residual moisture is removed by a downstream dryer. The powder obtained can be used directly for the production of plastisol; storage-stable plastisols are formed.
  • the reaction takes place analogously to Example 1 in a double-walled glass reactor, which is also equipped with a three-stage MIG stirrer (90% of the reactor inner diameter).
  • the stirrer speed corresponds to the same peripheral speed as with the 2 1 approach.
  • Aerosil 200 0.3 g 0.4%
  • the weighed-in SMA polymer consists of 79% polymer and 11% barium sulfate (according to the polymerization recipe)
  • the plastisol is made according to the above. Composition prepared in a beaker and homogenized.
  • REPLACEMENT BLA ⁇ (RULE 26) at 160 ° C) homogeneous, optically appealing and mechanically stable (visual assessment) coatings were obtained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Textile Engineering (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Sealing Material Composition (AREA)
  • Closures For Containers (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une composition de plastisol à base de polymères en perles. De préférence les polymères en perles ont une structure comprenant un noyau et une coquille et un diamètre moyen compris entre 1 et 150 νm. Les polymères en perles sont avantageusement exempts de chlore et sont constitués d'au moins (a) styrène, α-méthylstyrène et/ou p-méthylstyrène d'une part et de (b) 2 à 20 % en poids (par rapport au copolymère) d'acides carboxyliques oléfiniquement insaturés d'autre part. Cette composition de plastisol est utile pour produire des matériaux de revêtement, des matériaux d'étanchéité et des adhésifs.
EP95902111A 1993-12-10 1994-12-01 Composition de plastisol Ceased EP0733084A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4342098 1993-12-10
DE4342098A DE4342098A1 (de) 1993-12-10 1993-12-10 Plastisolzusammensetzung
PCT/EP1994/004000 WO1995015994A1 (fr) 1993-12-10 1994-12-01 Composition de plastisol

Publications (1)

Publication Number Publication Date
EP0733084A1 true EP0733084A1 (fr) 1996-09-25

Family

ID=6504628

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95902111A Ceased EP0733084A1 (fr) 1993-12-10 1994-12-01 Composition de plastisol

Country Status (8)

Country Link
EP (1) EP0733084A1 (fr)
JP (1) JPH09506643A (fr)
CA (1) CA2178726A1 (fr)
CZ (1) CZ166496A3 (fr)
DE (1) DE4342098A1 (fr)
HU (1) HU215239B (fr)
WO (1) WO1995015994A1 (fr)
ZA (1) ZA949841B (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19541923C2 (de) * 1995-11-10 2001-07-12 Sika Werke Gmbh Reaktiver thermoplastischer Heißschmelzklebstoff
DE19711022A1 (de) * 1997-03-17 1998-09-24 Basf Ag Verwendung eines Mehrstufenrührers zur Herstellung von Polymerisaten
EP1217037B1 (fr) * 1999-09-20 2016-10-19 Mitsubishi Rayon Co., Ltd. Particules de polymere fines pour plastisol, leur procede de production, composition plastisol exempte d'halogene et article fabrique avec celle-ci
DE10000940B4 (de) * 2000-01-12 2004-02-12 Silu Verwaltung Ag Einkomponentige Dichtmasse auf Basis einer Dispersion von Polyacrylaten, Verfahren zu deren Herstellung und System
JP3913444B2 (ja) * 2000-05-23 2007-05-09 アイシン化工株式会社 防音アンダーコート用アクリルゾル
JP2002155477A (ja) * 2000-11-16 2002-05-31 Okamoto Ind Inc アクリル系樹脂レザー
JP4633968B2 (ja) * 2001-06-21 2011-02-16 アキレス株式会社 アクリル系レザーの製造方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU630884B2 (en) * 1988-09-09 1992-11-12 B.F. Goodrich Company, The Polyvinyl chloride blends having improved physical properties
DE4034725A1 (de) * 1990-10-31 1992-05-07 Teroson Gmbh Plastisolzusammensetzung
CA2090262A1 (fr) * 1992-02-25 1993-08-26 Junji Oshima Polymere ame/gaine et plastisol obtenu a partir de ce polymere
EP0624606B2 (fr) * 1993-05-14 2003-08-27 Mitsui Takeda Chemicals, Inc. Polymère coeur-enveloppe et plastisol à partir de celui-ci

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9515994A1 *

Also Published As

Publication number Publication date
JPH09506643A (ja) 1997-06-30
CZ166496A3 (en) 1996-11-13
WO1995015994A1 (fr) 1995-06-15
DE4342098A1 (de) 1995-06-14
CA2178726A1 (fr) 1995-06-15
HUT75184A (en) 1997-04-28
HU9601596D0 (en) 1996-08-28
ZA949841B (en) 1995-06-13
HU215239B (hu) 1998-11-30

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