GB1602980A - Process for the manufacture of plasticised polyvinyl chloride foam coatings having a relief surface on a substrate - Google Patents

Process for the manufacture of plasticised polyvinyl chloride foam coatings having a relief surface on a substrate Download PDF

Info

Publication number
GB1602980A
GB1602980A GB23918/78A GB2391878A GB1602980A GB 1602980 A GB1602980 A GB 1602980A GB 23918/78 A GB23918/78 A GB 23918/78A GB 2391878 A GB2391878 A GB 2391878A GB 1602980 A GB1602980 A GB 1602980A
Authority
GB
United Kingdom
Prior art keywords
paste
polyvinyl chloride
foam
substrate
process according
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
Application number
GB23918/78A
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.)
Huels AG
Original Assignee
Chemische Werke Huels AG
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 Chemische Werke Huels AG filed Critical Chemische Werke Huels AG
Publication of GB1602980A publication Critical patent/GB1602980A/en
Expired legal-status Critical Current

Links

Classifications

    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C09D127/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/28—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for wrinkle, crackle, orange-peel, or similar decorative effects
    • 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
    • D06N3/06—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 with polyvinylchloride or its copolymerisation products
    • 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
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride

Description

(54) PROCESS FOR THE MANUFACTURE OF PLASTICISED POLYVINYL CHLORIDE FOAM COATINGS HAVING A RELIEF SURFACE ON A SUBSTRATE (71) We, CHEMISCHE WERKE HOLS AKTIENGESELLSCHAFT, a German Company, of 4370 Marl, Federal Republic of Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The manufacture of wallpaper coated with polyvinyl chloride is increasingly gaining importance because of the numerous advantages of such wallpaper. For example, such wallpaper is washable and resistant to mechanical stress, can be painted over, and is light-resistant, easily hung and easily pulled off again, that is to say easily renewed.
Foam-coated wallpaper which, because of its structured surface, achieves a three-dimensional effect is of particular interest.
Such products possess, in addition to the numerous advantages of simple polyvinyl chloride wallpaper, a relief surface, which offers virtually inexhaustable scope for novel decorative effects.
Plasticised polyvinyl chloride foam coatings can be produced in the usual manner by the spreading process, optionally with subsequent embossing. In this process, a polyvinyl chloride paste is applied to the carrier, for example paper, by means of a doctor blade or reverse roll coater, and is gelled and foamed. The plasticised foam coating thus obtained can subsequently be embossed mechanically in the usual manner, on an embossing calender, and can thus be provided with a structured surface.
Relief surfaces without the process step of mechanical embossing are obtained if the polyvinyl chloride paste is applied by means of the rotary screen printing process (literature reference: Stdrk International, special publication for the manufacturers of wallpapers and the like, September 1976, Boxmeer/Holland).
Finished articles with plasticised polyvinyl chloride foam coatings, for example foamcoated wallpaper, are required by consumers to have a matt, non-smooth surface, since glossy and smooth wallpapers make an aesthetically less attractive impression. The matt surface can be achieved by adding matting agents, for example pyrogenic silica, or more preferably by adding fillers to the foamable polyvinyl chloride paste.
The non-smooth, "disturbed" surface can be achieved by mechanical embossing, a process step which must in any case be carried out when the structured foam coatings are manufactured by the spreading process. However, in the case of non-structured foam coatings, this method of production of a "disturbed" surface cannot be utilised.
Equally, the method is not applicable to the structured foam coatings obtained by rotary screen printing, since a subsequent mechanical embossing would again annul the substantial advantage of the considerably less expensive process of manufacture of the relief-like surface.
Accordingly, it would be desirable to achieve the desired "disturbance" of the surface in the manufacture of plasticised polyvinyl chloride foam coatings having a relief surface by the rotary screen printing process without introducing an additional process step, and to produce a "disturbed" surface in the manufacture of non-structured plasticised polyvinyl chloride foams.
According to the invention there is provided a process for the manufacture of a plasticised polyvinyl chloride foam coating having a relief surface on a substrate by applying a polyvinyl chloride paste containing a chemical blowing agent to the substrate, gelling and foaming, wherein the foamable paste contains 0.5 to 5 per cent by weight, based on the paste, of a monohydric alcohol of 2 to 5 carbon atoms.
Using the process of the invention it is possible to achieve a particular type of "disturbance" of the surface, namely a socalled "pockmark structure" with a plurality of small pockmarks.
It is possible to achieve a "pockmark structure" on the surface of polyvinyl chloride foam coatings by adding water to the foamable polyvinyl chloride paste. Admittedly, the desired "pockmark structure" is obtained in this way; however, the foam coating in question has low resistance to mechanical stress and thus has low performance in use. This is because in the case described the "pockmark structure" results from the formation of small blisters close under the surface, which can easily be torn open.
On the other hand, the "pockmark structure" obtained according to the invention consists of blisters which are on the underside of the foam coating, that is to say directly on the carrier. Their presence hardly impairs the resistance of the surface.
Examples of monohydric alcohols containing two to five carbon atoms which according to the invention are to be present in the foamable paste are: ethanol, n-propan-l-ol, n-butan-l-ol, n-pentan-l-ol, n-butan-2-ol, npentan-2-ol, isopropanol, isobutanol, isopentanol (isoamyl alcohol), diethylcarbinol and tert.-butyl alcohol. Alcohols with more than 5 carbon atoms give a less disturbed, smoother surface with increasing C-number.
The foamable paste must contain 0.5 to 5 per cent by weight, and preferably contains 1 to 3 per cent by weight, based on the paste, of the monohydric alochol with two to five carbon atoms. Amounts of alcohol in excess of 5 per cent by weight do not substantially improve the result. The alcohol can be added to the plasticiser or to the foamable paste.
Polyvinyl chloride pastes to be employed for the process according to the invention can be produced in the usual manner from pasteforming polyvinyl chloride powders, such as emulsion polymers and micro-suspension polymers, with or without addition of extender PVC, and from the appropriate proportions of customary plasticisers. Examples of plasticisers are dioctyl phthalate, dinonyl phthalate, didecyl phthalate, butyl decyl phthalate, dicapryl phthalate, butyl benzyl phthalate, dioctyl adipate, dioctyl sebacate, tricresyl phosphate, trioctyl phosphate and cresyl diphenyl phosphate. The pastes can be produced by the customary paste mixing process (see Gummi-Asbest-Kunststoffe, volume 23/1970, page 938). The weight ratio of polyvinyl chloride powder to plasticiser is preferably from 45:55 to 70:30.
Examples of chemical (i.e. chemically decomposable) blowing agents which can be employed are azodicarboxamide, toluenesulphonylhydrazide, N,N'-dinitroso-pentamethylenetetramine, benzene-1,3-disulpho- nylhydrazide, 5-morpholyl- 1 ,2,3,4-thiatriazole, diphenylsulphone-3,3'-disulphohydrazide and mixtures of two or more of these. In general, amounts of 0.5 to 8 per cent by weight, based on the polyvinyl chloride, are employed.
The paste can furthermore contain one or more customary constituents, such as fillers, pigments, viscosity regulators, thinners, heat stabilisers, light/UV stabilisers, flameproofing additives and, optionally, antistatic agents, fungicides, fluorescent colours and optical brighteners.
The foamable paste can be applied by the rotary screen printing process, as described, for example, in the Stork International special publication cited previously.
The gelling and foaming can be carried out in a customary gelling tunnel at 180 to 230"C, preferably 200 to 210"C, with residence times of 0.5 to 5 minutes, as is known from Paul Schmidt, Beschichten mit Kunststoffen (Coating with Plastics), Carl Hanser Verlag Munich 1967, page 77 to 80.
The Examples which follow are intended to illustrate the process. Parts and ratios are by weight.
Example I Wallpaper base paper weighing about 135 g/m2 was provided, by means of a reverse roll coater, with a compact PVC coating, at a coating weight of 80 g/m2. 300 g/m2 of a foam paste of the following composition were applied to this primed wallpaper base by means of a 40 mesh rotary screen printing stencil: 55 parts of paste polyvinyl chloride having a K value of 70 23 parts of diisodecyl phthalate 12 parts of benzyl butyl phthalate 3 parts of iso-octyl epoxystearate 1.5 parts of cadmium-zinc kicker/stabiliser 6.0 parts of azodicarboxamide masterbatch in dioctyl phthalate (1:1) 0.2 part of UV absorber 8.0 parts of titanium dioxide masterbatch in dioctyl phthalate (3:2) 1.5 parts of isopropanol.
After printing, the foam paste was heated at 200"C/1.3 minutes and was thereby gelled and foamed. A coating was obtained in which the raised foam pattern exhibited a "disturbed" surface, that is to say a "pockmark structure", Comparison Example 1 If the isopropanol was omitted from the paste formulation according to Example 1, and otherwise the same procedure was followed, a foam wallpaper was obtained in which the raised foam pattern had a smooth surface.
Example 2 The foam paste (containing isopropanol) described in Example 1 was coated onto paper by means of a doctor blade and then gelled and foamed in a tunnel oven (gelling tunnel) at 200"C with 2 minutes residence time. The coating weight was 250 g/m2. The resulting foam layer, having a foam density of about 0.15 to 0.25 g/cm3, had a "pockmark structure" on the surface, caused by extremely small blisters which had formed at the interface with the paper.
Comparison Example 2 If, in place of 1.5 parts of isopropanol, the same amount of water was used in the foam paste according to Example 2, a similar "pockmark structure" resulted, but this was formed by blisters immediately below the foam surface. The blisters could easily be torn open at this surface, which was not possible with the foam coating produced with isopropanol.
WHAT WE CLAIM IS: 1. A process for the manufacture of a plasticised polyvinyl chloride foam coating having a relief surface on a substrate by applying a polyvinyl chloride paste containing a chemical blowing agent to the substrate and gelling and foaming wherein the foamable paste contains from 0.5 to 5 per cent by weight. based on the paste, of a monohydric alcohol of 2 to 5 carbon atoms.
2. A process according to claim I, wherein the foamable paste contains l to 3 per cent by weight. based on the paste. of the alcohol.
3. A process according to claim I or 2, wherein the alcohol is isopropanol.
4. A process according to any of claims I to 3. wherein the paste contains polyvinyl chloride and plasticiser in a weight ratio of from 45:55 to 70:30. and from 0.5 to 8 per cent by weight of a chemical blowing agent.
based on the polyvinyl chloride.
5. A process according to any of claims I to 4. wherein the paste is applied to the substrate by a rotary screen printing process, and gelling and foaming is carried out at 180 to 230or for 0.5 to 5 minutes.
6. A process according to any of claims l to 5. wherein the substrate is a wallpaper base material.
7. A process for the manufacture of a plasticised polyvinyl chloride foam coating having a relief surface on a substrate carried out substantially as described in either of the foregoing Examples I and 2.
8. A composite comprising a substrate having thereon a plasticised polyvinyl chlo ride foam coating having a relief surface when manufactured by a process according to any of claims 1 to 7.
9. Wallpaper having a plasticised polyvinyl chloride foam coating with pockmark surface when manufactured by a process according to claim 6 or 7.
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (9)

**WARNING** start of CLMS field may overlap end of DESC **. Example 2 The foam paste (containing isopropanol) described in Example 1 was coated onto paper by means of a doctor blade and then gelled and foamed in a tunnel oven (gelling tunnel) at 200"C with 2 minutes residence time. The coating weight was 250 g/m2. The resulting foam layer, having a foam density of about 0.15 to 0.25 g/cm3, had a "pockmark structure" on the surface, caused by extremely small blisters which had formed at the interface with the paper. Comparison Example 2 If, in place of 1.5 parts of isopropanol, the same amount of water was used in the foam paste according to Example 2, a similar "pockmark structure" resulted, but this was formed by blisters immediately below the foam surface. The blisters could easily be torn open at this surface, which was not possible with the foam coating produced with isopropanol. WHAT WE CLAIM IS:
1. A process for the manufacture of a plasticised polyvinyl chloride foam coating having a relief surface on a substrate by applying a polyvinyl chloride paste containing a chemical blowing agent to the substrate and gelling and foaming wherein the foamable paste contains from 0.5 to 5 per cent by weight. based on the paste, of a monohydric alcohol of 2 to 5 carbon atoms.
2. A process according to claim I, wherein the foamable paste contains l to 3 per cent by weight. based on the paste. of the alcohol.
3. A process according to claim I or 2, wherein the alcohol is isopropanol.
4. A process according to any of claims I to 3. wherein the paste contains polyvinyl chloride and plasticiser in a weight ratio of from 45:55 to 70:30. and from 0.5 to 8 per cent by weight of a chemical blowing agent.
based on the polyvinyl chloride.
5. A process according to any of claims I to 4. wherein the paste is applied to the substrate by a rotary screen printing process, and gelling and foaming is carried out at 180 to 230or for 0.5 to 5 minutes.
6. A process according to any of claims l to 5. wherein the substrate is a wallpaper base material.
7. A process for the manufacture of a plasticised polyvinyl chloride foam coating having a relief surface on a substrate carried out substantially as described in either of the foregoing Examples I and 2.
8. A composite comprising a substrate having thereon a plasticised polyvinyl chlo ride foam coating having a relief surface when manufactured by a process according to any of claims 1 to 7.
9. Wallpaper having a plasticised polyvinyl chloride foam coating with pockmark surface when manufactured by a process according to claim 6 or 7.
GB23918/78A 1977-08-18 1978-05-30 Process for the manufacture of plasticised polyvinyl chloride foam coatings having a relief surface on a substrate Expired GB1602980A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2737242A DE2737242C3 (en) 1977-08-18 1977-08-18 Process for the production of relief-like structured polyvinyl chloride flexible foam coatings with special surface effects

Publications (1)

Publication Number Publication Date
GB1602980A true GB1602980A (en) 1981-11-18

Family

ID=6016720

Family Applications (1)

Application Number Title Priority Date Filing Date
GB23918/78A Expired GB1602980A (en) 1977-08-18 1978-05-30 Process for the manufacture of plasticised polyvinyl chloride foam coatings having a relief surface on a substrate

Country Status (6)

Country Link
BE (1) BE869801A (en)
DE (1) DE2737242C3 (en)
FR (1) FR2400542A1 (en)
GB (1) GB1602980A (en)
LU (1) LU80116A1 (en)
NL (1) NL186966C (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2933144C2 (en) * 1979-08-16 1983-01-13 Alfred Dr. phil. 5277 Kalsbach Schütz Process for the production of coatings from foamed polyvinyl chloride with a structured surface
DE4037961C2 (en) * 1990-11-29 1994-12-08 Erwin Fendrich Process for the plastic design of pictures and images
US5262444A (en) * 1992-11-30 1993-11-16 Borden, Inc. Porous plastic film product, useful as a breathable wall covering or filters
DE19502389A1 (en) * 1995-01-26 1996-08-01 Bausch Ag Prodn. of strong, abrasion-resistant decorative relief on substrate

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1621730C3 (en) * 1967-04-22 1975-09-18 Griffine-Marechal, Paris Process for the production of an object with a decorative, internal glitter effect
AU1011070A (en) * 1969-01-13 1971-07-08 Imperial Chemical Industries Limited Wall converings
JPS50155705A (en) * 1974-06-11 1975-12-16

Also Published As

Publication number Publication date
FR2400542B1 (en) 1985-02-15
NL186966C (en) 1991-04-16
DE2737242B2 (en) 1981-07-09
BE869801A (en) 1979-02-19
FR2400542A1 (en) 1979-03-16
LU80116A1 (en) 1979-01-19
NL7808540A (en) 1979-02-20
DE2737242C3 (en) 1982-04-22
DE2737242A1 (en) 1979-03-01

Similar Documents

Publication Publication Date Title
US3931429A (en) Surface covering materials
US3844814A (en) Foamed decorative covering material and method of manufacture
AT395560B (en) LAMINATE WITH DIRT-RESISTANT SURFACE, METHOD FOR PRODUCING IT AND ITS USE
CA1173982A (en) Printing ink compositions and use thereof for the production of textured foamed resin materials
US3574659A (en) Process of textured resinous sheet preparation
US3373072A (en) Chemical embossing method and product
GB1602980A (en) Process for the manufacture of plasticised polyvinyl chloride foam coatings having a relief surface on a substrate
US4579775A (en) Steering wheel for automobile
EP0304550B1 (en) Process for producing three-dimensional patterns or coatings on paper, textile or plastic foil substrates
US4259386A (en) Flexible wallcoverings
SE425091B (en) PROCEDURE FOR PREPARING RELIEFED STRUCTURED POLYVINYL CHLORIDE SOFT COATING
JP3864604B2 (en) Method for producing foamed decorative material
US4302489A (en) Process for producing a foam sheet having an embossed pattern
CA1086466A (en) Process for the manufacture of differentially expanded sheet
US4093686A (en) Sheet materials
GB2033395A (en) Production of Foamed Sheet Materials
JPH0624812B2 (en) Agricultural soft vinyl chloride resin film
DE1619210C (en)
JP2000158607A (en) Wall covering material produced by laminated polyvinyl chloride film
JPH0780979A (en) Decorative material
JPH09157427A (en) Paste-like composition and laminate having synthetic resin layer prepared by using the same
DE2747849A1 (en) PROCESS FOR THE PRODUCTION OF SOFT FOAM ON THE BASIS OF POLYVINYL CHLORIDE
CA1042619A (en) Chemically embossed sheet material
JPH04337345A (en) Gloss-controlling resin composition
JP6990526B2 (en) Foam wallpaper

Legal Events

Date Code Title Description
PS Patent sealed
PCNP Patent ceased through non-payment of renewal fee

Effective date: 19920530