CA2092730A1 - Method of producing three-dimensionally surface-structured linings for wall and floor surfaces and structure paste therefor - Google Patents
Method of producing three-dimensionally surface-structured linings for wall and floor surfaces and structure paste thereforInfo
- Publication number
- CA2092730A1 CA2092730A1 CA002092730A CA2092730A CA2092730A1 CA 2092730 A1 CA2092730 A1 CA 2092730A1 CA 002092730 A CA002092730 A CA 002092730A CA 2092730 A CA2092730 A CA 2092730A CA 2092730 A1 CA2092730 A1 CA 2092730A1
- Authority
- CA
- Canada
- Prior art keywords
- structure paste
- paste according
- dispersion
- paste
- micropearls
- 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.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000006188 syrup Substances 0.000 claims abstract description 11
- 235000020357 syrup Nutrition 0.000 claims abstract description 11
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims abstract description 9
- 239000011256 inorganic filler Substances 0.000 claims abstract description 9
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011325 microbead Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000004815 dispersion polymer Substances 0.000 claims abstract description 5
- 239000012188 paraffin wax Substances 0.000 claims abstract description 5
- 229920001577 copolymer Polymers 0.000 claims abstract description 4
- 239000012766 organic filler Substances 0.000 claims abstract 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 19
- 229920002472 Starch Polymers 0.000 claims description 17
- 239000008107 starch Substances 0.000 claims description 17
- 235000019698 starch Nutrition 0.000 claims description 17
- 239000000945 filler Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 5
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910001679 gibbsite Inorganic materials 0.000 claims description 4
- 235000010216 calcium carbonate Nutrition 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 3
- 239000003139 biocide Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000010021 flat screen printing Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims 3
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 claims 1
- 229920001038 ethylene copolymer Polymers 0.000 claims 1
- 238000005189 flocculation Methods 0.000 claims 1
- 230000016615 flocculation Effects 0.000 claims 1
- 238000010422 painting Methods 0.000 claims 1
- 239000000049 pigment Substances 0.000 claims 1
- 238000010022 rotary screen printing Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 239000004890 Hydrophobing Agent Substances 0.000 abstract 1
- 239000003340 retarding agent Substances 0.000 abstract 1
- 229920001944 Plastisol Polymers 0.000 description 6
- 239000004999 plastisol Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 241000428533 Rhis Species 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011049 pearl Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 101100285518 Drosophila melanogaster how gene Proteins 0.000 description 1
- 101100456896 Drosophila melanogaster metl gene Proteins 0.000 description 1
- 101100536354 Drosophila melanogaster tant gene Proteins 0.000 description 1
- DYYVHMHEXGIRFA-CFYXSCKTSA-N acetic acid;dibutyl (z)-but-2-enedioate Chemical compound CC(O)=O.CCCCOC(=O)\C=C/C(=O)OCCCC DYYVHMHEXGIRFA-CFYXSCKTSA-N 0.000 description 1
- ACOGMWBDRJJKNB-UHFFFAOYSA-N acetic acid;ethene Chemical group C=C.CC(O)=O ACOGMWBDRJJKNB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- CYKDLUMZOVATFT-UHFFFAOYSA-N ethenyl acetate;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=O)OC=C CYKDLUMZOVATFT-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
-
- 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
- C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- 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
- D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
- D06N7/0002—Wallpaper or wall covering on textile basis
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Paper (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Abstract A method is described for producing structured wallpapers in which a PVC-free and plasticizer-free structure paste on The basis or inorganic and/or organic fillers and a polymer dispersion of a vinyl acetate copolymer is used. Non-crystallizing sorbite syrup or ethylene glycol as processing retarding agents, paraffin dispersion as hydrophobing agent and micropearls and/or hollow microbeads for increasing the specific volume may also be added to the structure composition.
Description
2~9273~
~ t~ L ~ii`(Jd~l('lrl(3 t;~lr~:e-~irl~t~ll.sionallv .~ rfa-!e-9truct ~ JS for l~all dnCI Lloor sult~cl?6 and structure paste tller ef or rhe inv~ntion relates to a methc~d of produciny three-dimensiorlally surface-structured coverlngs or linings for wall and floor su~faces, in parti~ular for producing structured wallpaper according to the preamble of claim 1.
The invention further relates to a structure paste for use in this prodùctic~r Floor lininys, wall lini.llgs and in particular wallpapers having a str~ctuIed r-elief~ e surface are known. For producin-~ the relief-li~e structures, in known methods e]ther hlc)winy-a~ent-free corrlpact plastisvls or hlowing-agen~-(ontairliny foam plasti,l-~ls are usecl, in each case on tll~ ~)d~iC of pc~lyvinyl chlc~rid~ (PVC:).
~eperl(ling Oll the type ()~ ,trl.l(1tllre t(~ be .Eormed, t;he plclsti.L;(ll ~)a~te :is a~)lie(1 b~ kllowrl appl:icatioll metllocl~, .ir parti(.~u1ar printillg metl1l~)ds, tc) a su.ilable sllbstrate web W}1iCh may cOl'ltiSt oE var.ious InclteL-i.alc;, ill particul~:r plasti( m-lter:i.als, but in the ~ase (>f strllctured wallpaper i) uL;Ilally a raw wallpapeL. ~uitable methods of applic~tion are the rotary .screen printlng method, the flat screen printing method, the rotocJravure method, the squeeze rotogravure method, l.etterpress printing method, coating methods and spraying methods.
After their solidification 011 the substrate web PVC
plastisol pastes have properties which have led them to be genera~ly used for the purpose in question here. The~ have 7 ~ ~
a clc-od resistallce tc, 'licJ'IIt, dl e hiCJ]lly r e>lstc-lllt to ~.~sllirl~, sclatc~ Lesi~tant, and e~en in the solidified s~ate remain adequately soft ancd flexib].e, can be worked to ~elatively lightweight .structures by employing blowing aaentC;~ are resistant to wear and also flame-resistant.
rhe PVC pla6tisc,1s however also have some disadvantages.
Thus, for the aelatiol1 and foaming they require relatively higll processing temperatures in the range of 180C to 2~0C
and furthermc)re thev reduce the breathing activity of the walls ancl are sensitive to ~licotine (discolouring).
However, the greatest disadvantaae of PVC plastisols is theiL^ chenlical origin because they are chlorinated compollnds which can lead to envirc)nmental problems. The polyvin~1 cl~lorid~s are e.ssentially rc,t proof and consequentl.y can gellerally c)llly be disposed c,f by burning. ~.
~'hen this is dolle the~ gi~e off harmful hvdrochlori~ acid va~ours, which by the wav alsc) OCCULS in the ca~e of fire, and carl become a collsiderable hdzard to hurnalls.
Furthermore PVC plastisols fundamentallv contain plasticizers, substantially phthalates, wh:ich are part:ially liherated during processincJ and requ:ire experlsive collection and combllsti(~n appar.atuses.
The invent:iorl is basec3 on the problelll of prc)vicling a Tnelhod of procluc:ing thr.~ee~ ellsi.c)na~l.].v ~;urface-struetured lin:ings or cover:incls for wa'l.'L, ceilirlcJ and floc)r ~urEaces in which structlJring paste~ are u.~ed which are essentially free from PVC and plasticizers, can be worked by the hitherto usual apE~licatiol~l n~eth~.-33 withollt any problems and lead to high product quality. The oh-iective of the inventiorl is also to mdke available a particular substantia~lv PVC--free alld ~last:icizer-free structure paste for producing suLface-~tructured linil~g:~.
2~273~
~ re~lard:; the metl~od, thi~s problem i7 solvec~5 according tc, the invention fullcdamentallv bv the cllaracterizing features :,f ~laim 1. A suitable structurr~ paste is characterized fundamentally by clairsl 8, For silnplicit~, hereillarter the irlvention wi]l be de6cribecl C)nly il3 it~ ap~c)lication to the production of structured wallpapers: it ivill be clear t-> tlle per~on skilled in the art that the productic,n method described can be applied li~ewise to (ither structured articles ancl thus in particular is ;uitak)1e also for ~rodilcirlc,J other ~all and rloor coverin~cs an(i lininc!cs. Al~so, the substrate is in no way restricted tc- the raw wallpaper usually employed wherl ma~ing strue~tllrec's -~allpaper. The s~l~strate may consist c)f a csreat variet~- of Illaterials, in F~articular raw wallpapers pre~oated in suitable manner mav al~cso be employed for F)ro~sucins ~tructured wallpaper~.
It l~as been found in e~teilsi~-e tests that hiclh-qualitv structured surfaces can be obtainecl usincl structure pastes basecl on pc):Lymer disperAc5:ion5 of villvl acetate copolvmex 5 and containinc suitable fillers and pigsnents in an aqueous s~stem. Th~ aqueou~s ~s~stem ha-s the advarlta~Je th-lt l:he C;tructlsre pastecs can k)e so~ic]ifiec] hy silnple (,lryinc~ or evapora~.ic)n alld 110 llarnlfl,ll vapc)llr~; are formed. The clryincJ
may take place at temperatufes kletween ~l() anc's 200''C ancl thi~--s is another aclvantage c~c)lnparecl wit11 the use of PVC
,c l~stic:c)ls .
Tl1e st,rllcture paste accorc]illg to the invention Mav also be wor~ed l,lsirl~ the a~ )lication methc)ds ïllentic)ned at the becinnillg hitllert,~ usual for PVC plastisols. A further -urface finisnin~ oi; the solidified structures, for exanlple by irliprinr,ing, pain~,illg, flocclllatioll or the like, is readily possihle.
7~ ~
pc~lymer disF)ersion orl the basis c,f a viny~ acetate-ethylene copolylller (EVA) av~ilc-l~)le as a 5~ to ~)5 b p]astici~er-free dispersion of said copolymer in water has ~een founcl particularly suita~)le for the structure paste accordill~ to the inventivn. rhis dispersic)n ]eads to good flc~w propeJties of the structure paste and ensures an adl-cllldte t>irldillg ot the otiler corllpollerlt~s ot the paste ~-ith resiJect to each other; it exhibits ac)od adhec;ion to the s7lbstrate all(3 arter drvirly leads to a permanently flexible structure.
Other polvmer dispersions have been follnd suitable for example on the basis of vinvl acetate maleic acid di-n-butyl ester and vinyl acetate-acrylic acid ester.
A fundamental composition of the structure preparation accc)rdinc3 tc> the invelltioll May reside in that it contains 0.8 - 2.0 parts by weight of a 50 - 55 % polymer dispersion tor 1 part by weight islorganic and/or orgallic fillers.
As orgclrlic tiller for the ~tructure paste, principally ullc~latirlized ~tarch call be uc;ed preerably pOtcltc) starch.
The un~lat~ izeti or non-ac~(~lutirlated starcilila~ a clood fi-LLin(J ~)OW8r Wi~llOUI; tlle ~t;rll(-ture composition becomirlg heavier b~lcallc)e the star-lJ i~ llc-lhter than the inor~allic riller.s. Furttlel~more it is bic)lo-~icall~- easily and completely decom~osible and this has a positive effect on th~ decompc)sibility of the structure paste. Since the un~elatinizs(3 starch foral~ a unit with the inorc~anic tillers irre.spective of whether the inorganic fillers are calcium carbonates or aluminiuln hydroxides it can be re~arded as a partial substitute for inorganic fillers.
2~992~
or~)ver iile lir~ ati~ d starch is in.s(JIIlbLe in cold ~ tt~i ar~ 3 t(~ 3~3(:~1ve ~ .V Witll riging temperature.
r~lis prop~Lrv ha> pr(~ u~ti~ll tecl~ al advalltag~s. ~he (iryiny temE)erat~r~ arl(l th~ dryillg dllratiorl C~lll be chosen so t}lat the starch particl~s at t~leir surface are sli~htly i~-itiall~ dissolved by the tempe~ature and the moisture of the nlixture and conl~ine with each other and with the other fillers to form a Ullit. This gives a better strength of the structure composition.
In addition, the starch binds a considerable proportion of the water and liberates the latter slowly during drying.
This prevents rapid evaporation, which could lead to formation of bubhles.
i;h(?n u~sillcl starcil the total fillers contain expediently at least 10 % hy weight, ~)referably however 25 - 40 % by weight, ungelatillized starch as or~allic filler. The unqe~atinized starch is ~Ireserlt in powder form, preferably with a graill si~e of L0 - 100 Ilm.
Pc)s~ible illc~r~arlic filLers for the structure compositic,n are primaril~- aluminium llydrc)xide iAl(VII)3) ancl calcillm ca~i)onate ~a~03). However, a certain acldition O~e titarliuln dioxicl~-3 (rri.o2~ II)aV also he a(lvantayeous as adcl:it:iorlal white pi(Jmerlt. Tlle amollrll ol l::itdnil~ dioxide~ u3ecl mdy be up to ln '~ by wei~lht of the total irlc)ryan:ic and/or oryanic fillers.
Tlle aluminium hydroxide as filler is preferably used with a ~rain size of 20 - 25 um. The calcium carbo~ate preferably has a grain size distribution of 5 - 30 ~m and an oil numbeL of 15. In the case of titanium dioxide, preferably tile rutile M(~dification is emplc)ved. Deviations from the filler specificatic)ns above are however possible.
20~2 73 D
It has further been Eoulld extrernely ac]vantacJeol~s to add to the systerll a certairl amount of an organic processing retarder. It has been found that the addition of 1 - 8 %
by weig}lt rJon-crystallizing sorbite syrup, with respect tc>
the total paste is ver~ advantageous for the working thereof because in addition to the working retardation the viscosity of the structure paste is also positively influenced.
The non-crystallizirlc~ sorbi.te syrup may possibl~ be replaced by ethylene glvcc)l or other organic solvents with correspondin~ properties. Thus it has been found that the ad(3ition of l - 5 ~6 by weight ethylene glycol with respect to the total paste i.s also advantageolls for the working therec)f in certain ca.se-;.
It may also be advantageous to add hyclrophobiny agents to the struct~re paste to impart to the structured wallpaper to be made a water-repellent character to a certain exten-t.
It has been fourld that this can also be achieved hy ad~lition of 1 - 3 % by weiyht para~Efin dispersion with respect tc the total paste.
To reduce the speci.~:ie weight oE the dried structure paste and to -irltensify the structure forlllation tllereoE during drying as w~ll, appropriate adclitives may be added to the ~tructure p~te in relatively srnall amounts hy weig}lt.
To enable the specific volume of the structure paste to be inc-rea~ed during the processing in particular during -the dryiny it has been found advanta~eous to add to the total paste abou-t I - 8 ''6 hy wei~ht c~f so-called rllicropearls.
~lier(lpearls are m1(crocapsll1es WiliCh are filled with a blowirlg agellt and have a diameter of about 10 - 20 um, 2 ~ 3 ~
~onsisting of therrnoplastic plast:ic, and at 120 - 140C
they expand to several times their volume. These micrc-pearls have for example polyrller shells on the basis of meth~lmethacr~late or also an acrylonitrile copolyrrler.
Prefera~)ly, forllls are used which have arl expan6ion ratio of abollt 20. In the structllre paste accorc3ing to the irlventioll thec:e micropearls partially perfortn the function of the ~-lowillg ac~el~t ill the collventi(,)nal PVC plastisols.
e(lver-, ro redlic1e tlle ~;~)ecific weic!llt c,f the fillers or Increas~ tilt3 s~ecific v(~lume of the dried ~aste, a prc)~ )rtioJ1 of abc)~t l - 5 -~ by weight sc) called hollo~-microbea~.s may be added to the total paste. These are ex~anded hc)llc~w polymef headq, in the surface of which inor~allic fillers are advanta~ec)uqly embedded. The diameter of such hc~llow microbeads is preferably in the range of 10 - ~0 ~m and their specific volume is about 0.15 g/cm~. Due to the polylller material of the microbead walls and the inorganic filler particles attached thereto, the hollow Illicrc~beads are practically a mixed or,cJanic-irlc)r~allic filler of very high specific vol~lme. The person skilled in the art i~c; fal~liliar Wit~l the viscosity which a strllcture paste mllst a~ roxirllately hav~ l;o perrllit work:lng ~5 ill a s~ecific a~1icatic)rllllethc)cl. 'rhis vic:cc,c~ity can be re~!lllate-l wirl~ tlle l~aste accoLel:ill~J tc) t:lle inverltioll by appropriate ad(lit:ic)ll c,f water.
i'~f ((~urse, col(~llr pigrllell-ts or dyes may for example also be adde(3 tc, the-3 structllIe paste accc)rdill~ to the invention to influellce tlle ol~ter appearance thereof. It may also be neces.qary for the workin~ to acld to the cornposition small amollllts o~ biocides or a defoamer, should this prove neces~C;ary. The person skilled in the art is farniliar with such additives.
~27~
Iwo ~referrecl compositic,rl t~pes of the structure paste acc~rdinq to the invention are as follows, in parts bv wei~h t:
~ t~ L ~ii`(Jd~l('lrl(3 t;~lr~:e-~irl~t~ll.sionallv .~ rfa-!e-9truct ~ JS for l~all dnCI Lloor sult~cl?6 and structure paste tller ef or rhe inv~ntion relates to a methc~d of produciny three-dimensiorlally surface-structured coverlngs or linings for wall and floor su~faces, in parti~ular for producing structured wallpaper according to the preamble of claim 1.
The invention further relates to a structure paste for use in this prodùctic~r Floor lininys, wall lini.llgs and in particular wallpapers having a str~ctuIed r-elief~ e surface are known. For producin-~ the relief-li~e structures, in known methods e]ther hlc)winy-a~ent-free corrlpact plastisvls or hlowing-agen~-(ontairliny foam plasti,l-~ls are usecl, in each case on tll~ ~)d~iC of pc~lyvinyl chlc~rid~ (PVC:).
~eperl(ling Oll the type ()~ ,trl.l(1tllre t(~ be .Eormed, t;he plclsti.L;(ll ~)a~te :is a~)lie(1 b~ kllowrl appl:icatioll metllocl~, .ir parti(.~u1ar printillg metl1l~)ds, tc) a su.ilable sllbstrate web W}1iCh may cOl'ltiSt oE var.ious InclteL-i.alc;, ill particul~:r plasti( m-lter:i.als, but in the ~ase (>f strllctured wallpaper i) uL;Ilally a raw wallpapeL. ~uitable methods of applic~tion are the rotary .screen printlng method, the flat screen printing method, the rotocJravure method, the squeeze rotogravure method, l.etterpress printing method, coating methods and spraying methods.
After their solidification 011 the substrate web PVC
plastisol pastes have properties which have led them to be genera~ly used for the purpose in question here. The~ have 7 ~ ~
a clc-od resistallce tc, 'licJ'IIt, dl e hiCJ]lly r e>lstc-lllt to ~.~sllirl~, sclatc~ Lesi~tant, and e~en in the solidified s~ate remain adequately soft ancd flexib].e, can be worked to ~elatively lightweight .structures by employing blowing aaentC;~ are resistant to wear and also flame-resistant.
rhe PVC pla6tisc,1s however also have some disadvantages.
Thus, for the aelatiol1 and foaming they require relatively higll processing temperatures in the range of 180C to 2~0C
and furthermc)re thev reduce the breathing activity of the walls ancl are sensitive to ~licotine (discolouring).
However, the greatest disadvantaae of PVC plastisols is theiL^ chenlical origin because they are chlorinated compollnds which can lead to envirc)nmental problems. The polyvin~1 cl~lorid~s are e.ssentially rc,t proof and consequentl.y can gellerally c)llly be disposed c,f by burning. ~.
~'hen this is dolle the~ gi~e off harmful hvdrochlori~ acid va~ours, which by the wav alsc) OCCULS in the ca~e of fire, and carl become a collsiderable hdzard to hurnalls.
Furthermore PVC plastisols fundamentallv contain plasticizers, substantially phthalates, wh:ich are part:ially liherated during processincJ and requ:ire experlsive collection and combllsti(~n appar.atuses.
The invent:iorl is basec3 on the problelll of prc)vicling a Tnelhod of procluc:ing thr.~ee~ ellsi.c)na~l.].v ~;urface-struetured lin:ings or cover:incls for wa'l.'L, ceilirlcJ and floc)r ~urEaces in which structlJring paste~ are u.~ed which are essentially free from PVC and plasticizers, can be worked by the hitherto usual apE~licatiol~l n~eth~.-33 withollt any problems and lead to high product quality. The oh-iective of the inventiorl is also to mdke available a particular substantia~lv PVC--free alld ~last:icizer-free structure paste for producing suLface-~tructured linil~g:~.
2~273~
~ re~lard:; the metl~od, thi~s problem i7 solvec~5 according tc, the invention fullcdamentallv bv the cllaracterizing features :,f ~laim 1. A suitable structurr~ paste is characterized fundamentally by clairsl 8, For silnplicit~, hereillarter the irlvention wi]l be de6cribecl C)nly il3 it~ ap~c)lication to the production of structured wallpapers: it ivill be clear t-> tlle per~on skilled in the art that the productic,n method described can be applied li~ewise to (ither structured articles ancl thus in particular is ;uitak)1e also for ~rodilcirlc,J other ~all and rloor coverin~cs an(i lininc!cs. Al~so, the substrate is in no way restricted tc- the raw wallpaper usually employed wherl ma~ing strue~tllrec's -~allpaper. The s~l~strate may consist c)f a csreat variet~- of Illaterials, in F~articular raw wallpapers pre~oated in suitable manner mav al~cso be employed for F)ro~sucins ~tructured wallpaper~.
It l~as been found in e~teilsi~-e tests that hiclh-qualitv structured surfaces can be obtainecl usincl structure pastes basecl on pc):Lymer disperAc5:ion5 of villvl acetate copolvmex 5 and containinc suitable fillers and pigsnents in an aqueous s~stem. Th~ aqueou~s ~s~stem ha-s the advarlta~Je th-lt l:he C;tructlsre pastecs can k)e so~ic]ifiec] hy silnple (,lryinc~ or evapora~.ic)n alld 110 llarnlfl,ll vapc)llr~; are formed. The clryincJ
may take place at temperatufes kletween ~l() anc's 200''C ancl thi~--s is another aclvantage c~c)lnparecl wit11 the use of PVC
,c l~stic:c)ls .
Tl1e st,rllcture paste accorc]illg to the invention Mav also be wor~ed l,lsirl~ the a~ )lication methc)ds ïllentic)ned at the becinnillg hitllert,~ usual for PVC plastisols. A further -urface finisnin~ oi; the solidified structures, for exanlple by irliprinr,ing, pain~,illg, flocclllatioll or the like, is readily possihle.
7~ ~
pc~lymer disF)ersion orl the basis c,f a viny~ acetate-ethylene copolylller (EVA) av~ilc-l~)le as a 5~ to ~)5 b p]astici~er-free dispersion of said copolymer in water has ~een founcl particularly suita~)le for the structure paste accordill~ to the inventivn. rhis dispersic)n ]eads to good flc~w propeJties of the structure paste and ensures an adl-cllldte t>irldillg ot the otiler corllpollerlt~s ot the paste ~-ith resiJect to each other; it exhibits ac)od adhec;ion to the s7lbstrate all(3 arter drvirly leads to a permanently flexible structure.
Other polvmer dispersions have been follnd suitable for example on the basis of vinvl acetate maleic acid di-n-butyl ester and vinyl acetate-acrylic acid ester.
A fundamental composition of the structure preparation accc)rdinc3 tc> the invelltioll May reside in that it contains 0.8 - 2.0 parts by weight of a 50 - 55 % polymer dispersion tor 1 part by weight islorganic and/or orgallic fillers.
As orgclrlic tiller for the ~tructure paste, principally ullc~latirlized ~tarch call be uc;ed preerably pOtcltc) starch.
The un~lat~ izeti or non-ac~(~lutirlated starcilila~ a clood fi-LLin(J ~)OW8r Wi~llOUI; tlle ~t;rll(-ture composition becomirlg heavier b~lcallc)e the star-lJ i~ llc-lhter than the inor~allic riller.s. Furttlel~more it is bic)lo-~icall~- easily and completely decom~osible and this has a positive effect on th~ decompc)sibility of the structure paste. Since the un~elatinizs(3 starch foral~ a unit with the inorc~anic tillers irre.spective of whether the inorganic fillers are calcium carbonates or aluminiuln hydroxides it can be re~arded as a partial substitute for inorganic fillers.
2~992~
or~)ver iile lir~ ati~ d starch is in.s(JIIlbLe in cold ~ tt~i ar~ 3 t(~ 3~3(:~1ve ~ .V Witll riging temperature.
r~lis prop~Lrv ha> pr(~ u~ti~ll tecl~ al advalltag~s. ~he (iryiny temE)erat~r~ arl(l th~ dryillg dllratiorl C~lll be chosen so t}lat the starch particl~s at t~leir surface are sli~htly i~-itiall~ dissolved by the tempe~ature and the moisture of the nlixture and conl~ine with each other and with the other fillers to form a Ullit. This gives a better strength of the structure composition.
In addition, the starch binds a considerable proportion of the water and liberates the latter slowly during drying.
This prevents rapid evaporation, which could lead to formation of bubhles.
i;h(?n u~sillcl starcil the total fillers contain expediently at least 10 % hy weight, ~)referably however 25 - 40 % by weight, ungelatillized starch as or~allic filler. The unqe~atinized starch is ~Ireserlt in powder form, preferably with a graill si~e of L0 - 100 Ilm.
Pc)s~ible illc~r~arlic filLers for the structure compositic,n are primaril~- aluminium llydrc)xide iAl(VII)3) ancl calcillm ca~i)onate ~a~03). However, a certain acldition O~e titarliuln dioxicl~-3 (rri.o2~ II)aV also he a(lvantayeous as adcl:it:iorlal white pi(Jmerlt. Tlle amollrll ol l::itdnil~ dioxide~ u3ecl mdy be up to ln '~ by wei~lht of the total irlc)ryan:ic and/or oryanic fillers.
Tlle aluminium hydroxide as filler is preferably used with a ~rain size of 20 - 25 um. The calcium carbo~ate preferably has a grain size distribution of 5 - 30 ~m and an oil numbeL of 15. In the case of titanium dioxide, preferably tile rutile M(~dification is emplc)ved. Deviations from the filler specificatic)ns above are however possible.
20~2 73 D
It has further been Eoulld extrernely ac]vantacJeol~s to add to the systerll a certairl amount of an organic processing retarder. It has been found that the addition of 1 - 8 %
by weig}lt rJon-crystallizing sorbite syrup, with respect tc>
the total paste is ver~ advantageous for the working thereof because in addition to the working retardation the viscosity of the structure paste is also positively influenced.
The non-crystallizirlc~ sorbi.te syrup may possibl~ be replaced by ethylene glvcc)l or other organic solvents with correspondin~ properties. Thus it has been found that the ad(3ition of l - 5 ~6 by weight ethylene glycol with respect to the total paste i.s also advantageolls for the working therec)f in certain ca.se-;.
It may also be advantageous to add hyclrophobiny agents to the struct~re paste to impart to the structured wallpaper to be made a water-repellent character to a certain exten-t.
It has been fourld that this can also be achieved hy ad~lition of 1 - 3 % by weiyht para~Efin dispersion with respect tc the total paste.
To reduce the speci.~:ie weight oE the dried structure paste and to -irltensify the structure forlllation tllereoE during drying as w~ll, appropriate adclitives may be added to the ~tructure p~te in relatively srnall amounts hy weig}lt.
To enable the specific volume of the structure paste to be inc-rea~ed during the processing in particular during -the dryiny it has been found advanta~eous to add to the total paste abou-t I - 8 ''6 hy wei~ht c~f so-called rllicropearls.
~lier(lpearls are m1(crocapsll1es WiliCh are filled with a blowirlg agellt and have a diameter of about 10 - 20 um, 2 ~ 3 ~
~onsisting of therrnoplastic plast:ic, and at 120 - 140C
they expand to several times their volume. These micrc-pearls have for example polyrller shells on the basis of meth~lmethacr~late or also an acrylonitrile copolyrrler.
Prefera~)ly, forllls are used which have arl expan6ion ratio of abollt 20. In the structllre paste accorc3ing to the irlventioll thec:e micropearls partially perfortn the function of the ~-lowillg ac~el~t ill the collventi(,)nal PVC plastisols.
e(lver-, ro redlic1e tlle ~;~)ecific weic!llt c,f the fillers or Increas~ tilt3 s~ecific v(~lume of the dried ~aste, a prc)~ )rtioJ1 of abc)~t l - 5 -~ by weight sc) called hollo~-microbea~.s may be added to the total paste. These are ex~anded hc)llc~w polymef headq, in the surface of which inor~allic fillers are advanta~ec)uqly embedded. The diameter of such hc~llow microbeads is preferably in the range of 10 - ~0 ~m and their specific volume is about 0.15 g/cm~. Due to the polylller material of the microbead walls and the inorganic filler particles attached thereto, the hollow Illicrc~beads are practically a mixed or,cJanic-irlc)r~allic filler of very high specific vol~lme. The person skilled in the art i~c; fal~liliar Wit~l the viscosity which a strllcture paste mllst a~ roxirllately hav~ l;o perrllit work:lng ~5 ill a s~ecific a~1icatic)rllllethc)cl. 'rhis vic:cc,c~ity can be re~!lllate-l wirl~ tlle l~aste accoLel:ill~J tc) t:lle inverltioll by appropriate ad(lit:ic)ll c,f water.
i'~f ((~urse, col(~llr pigrllell-ts or dyes may for example also be adde(3 tc, the-3 structllIe paste accc)rdill~ to the invention to influellce tlle ol~ter appearance thereof. It may also be neces.qary for the workin~ to acld to the cornposition small amollllts o~ biocides or a defoamer, should this prove neces~C;ary. The person skilled in the art is farniliar with such additives.
~27~
Iwo ~referrecl compositic,rl t~pes of the structure paste acc~rdinq to the invention are as follows, in parts bv wei~h t:
3~;~ p . b. W . o~ a 5;i-55 ~ plasticizer-free EVA dispersion F~_ 50 p.h.w. l10l~-crvstalli Zil1~1 sorhite syrup l~- 5~ p.b.w. mic~opearls ~ p.b.w. Al~OH)3 and ungelatillized starch ~- 35 p.~.~. watef as viscosity adiustincl agent.
1 ~'` ;
~ u p.b.~. o~ a 5~-55 ~ plasticizer-free EV~ dispersion 6- ~ p.b.~. ethylene c11ycol ~- 30 p.b.w. m3.crc)pearls ~ p.b.-w. AllOH)3 and/or t'aC03 6- 30 p.b.w. hc)llow microbeads 25- 30 p.b.w. -~ater as viscosity adjusting agent.
Up to 30 % by weight titani~ dioxide of the rutile type may also be added to these comp(:)sitions. In addition, the compositions, as rnentiorled abcjve, may aLso be supplemelltetl b~ colour pi~ments, dyes, defoarrlers, b.ioc-ides and clirnllar additives tc~ he uc:ecl in slnall amollrlts.
A structllLe paste o~ the compositions set forth above meets all the demclrlds macle on it. It has a goc)d res:istance to ~ ht, i.s hi~h1~ washpro(:)f, scratch-proof, hardwearing, relllains soft and flexi~le, anci i.l1 addition can be made with Lelati~el-~ light ~eight. In addi.tion, it i.s hardly inflalllrllable, thi~ bein~ due to the relativel~ high content ~)f alull~ iurl~ h~dro.Yide. Compared with the conventional PVC
plastisol structures it has the additiona1 advantages that it is free from PVC and plasticizer, has a good ~ater vapour permeabilit~ and is insensitive to llicotine, and on 7 ~ ~
cc)lnl~ll-~,t:lc,ll CiOe3 nc,t c~ e otI~ al'lV chlc,rllle cc)nt.airlirJq corllpc)ullds, in part~cular 11(J ll~cir~cilloric ac:id vapours.
Fil3th~more, it do~s l~(Jt colltain any solutivlls which are i;r-~ Jles(:,rl,e dl~ w-Jrkill~ ~r ;vollld llave tv be collected arld nlay be solicllfied at relat~ ely lc)-w temperatureC;~
I ea(iinCI 011 1;51~ w~ e to a ~vi~g ill energ~ duril~q working.
Finallv, the structure pa;te accc)fdincl tc, the invention i~s dl:.O ea3il~ i3iolocl~(all-v- decompo3lble.
Exanlples 03-_E~Ibodilne3lt ~xanlr~le 1:
A structure paste was mixed togetller frorn the starting materials in the amounts give3l below:
28i) p.b.-w. 03 a 5i~-55 ~O plasticizer-free E~'A dispersion 2i-~ p.h.~. Al(i)H)3 having a cJrain size distributioll of 20-25 ~3m lOG p.b.n. of an urlcielcltinized starcl 20 p.b.w. ri()~ ot~ rutile tvpe 37.5 P~IJ~W. rnicr(:,E~eari~
~5 p.l).w. of a nol,-cryc;tAllille :olbite syrup 2l, ~.b.~ arar:E:in di 13iJe 3,~;i l:J~1 and ).C).l~. wat,l-!r c~11 ~ 'C);ity acl iu't:LI'lg agerlt.
rlle EVA di.3~ersi(~l, tlle noll-ctr~6tallizillcl sor~ite svrup ancd tlle water were placed in arl agitating vessel and slowl~
agitated. Durlnq tile a-~itatiol-l tlle -~sngelatinizes~ starch, the nlicrc)peaLls, the aluminiu~ ydrc)xide, the titaniunl dioxide and the paraffin di.spersion were slowly added in succes-:siorl. After about ~ mirl. agitatincf tiïne the paste was readv to use.
20~2730 L [~
(~11 a L)(~ n~ WI~-V~I1 f dL,i-iC dS ~liL`)StL`a te havillcJ c-l weight peL' Ulli t aL~a of 50 ~n~ a -widti~ ~f lL0 ~m a wallpaper ~CLUC~UL~ Wd~ a~liecl witi, t~ paste ln the ~cr~en pri1lting me~.in~-l at a Iate ()f -10 inilllin. rhis structllle ~a~ dried at a~)()ut 150'C fol 35 sec. The structured wallpaper thus procluced met a.Ll the derlldn~s made c~n it.
Fxam~le ~:
.~ strLIcture paste was mi.Yed togetl-ler from the startinc~
materials in the amoul-lts given belc)h-:
3~0 p.b.w. VL a 50-55 ~ plasticizer-free ~VA dispersion 200 p.b.-w. Al(OH)3 havillq a g-rain si~e ~lstribution of 20-25 um 00 ~ .h . {)f an unge]atillized starch 15 p.b.~. micropearl.s 0 L).b.-W. of a noll-crystallil-Je sorbite syrup 7.5 L~.l).w. pal~a~fln cli.5E~t~rsioll al~d ~5 U.~).w. water dS v~.9cC)Si t~- adiustirlc~ agent.
Tlle E~t~ persloll. the no~ rystaili~ing sorbite .~yrup and the wdter were placed ~.n arl ac~itcltillcl vessel arlcl slowl~
agitated. Durlng the ag:itatioll the un(Jelatil-lized starc~l tl~le Illicr~Jp~arlc;, the all3lrl-irl:iunl hyclro~:icle and the paraff-LI~
di3peL~siol-l were ~lowly ad<-~ed in successl~n. ~fter abollt 3 mill. agitating tiïme the paste was ready to u~e.
On a polymer non-wovell fabric as substrate having a weight per unit area of 50 g/m2 and a width of 110 cnl a wallpaper structure was applied witll the paste in the gravure method at a rate of ~0 nl/min. This structure was dried at abc,ut 150~ for 35 se(. rhe stru(tured wallpaper thlls produced met all the del,larld~ made Oll it.
2~9273~
E~am~le 3:
A structure paste was mi~ed together frorll the starting materials in the amounts c7iven ~elc~w:
300 p.b.w. of a 50-55 ~ plasticizer-free EVA dispersion 30 p.b.~. water L0~ p.b.w. etllylelle glycol 107 p.h w. mic:rop~ar]~s having a grairl diameter of 10 -~() um and an expansion ratio of 20 13() p.b.h. Al~)H)3 havil-JcJ a qrain size cli.stribution of 20-25 um 100 p.b.w. CaC03 havincJ a c!rain size distribution of 5-30 ~m 7.5 p.b.w. TiO2 of rutile type L2 p.b.w. hollow microbead.s having a diameter of 10-8 0 ~1III .
The EVA dispersion the ethylene cllycol and water were placed in an agitating vessel and slowly agitated. During the aJitati~n the rmicro~arls the aluminium hyd:roxic3e the calcium carbc~nate the titaniunl dioxicle ancl the hc):l.low microbeacd.s w~re slowly a(1ded in sllcce~.si-)n. A:f ter about 30 mill. aaitatil1c! tilne Lhe paste wa~ read~ to use.
011 J polyrner n~ wovell f.Jbr:Lc as ~ubstrate havincJ a weight per Ullit. ar~a of 50 g/m2 and a w:idth of 110 cm a wallpaper StrUC`tllre WclS applied witll the paste in the rotary screen printinc7 metll()d at a rate of gO m/min. This structure was dried at ab(~llt l5n(~ for 35 sec. The structured wallpaper thus produced met all the demands made on it.
1 ~'` ;
~ u p.b.~. o~ a 5~-55 ~ plasticizer-free EV~ dispersion 6- ~ p.b.~. ethylene c11ycol ~- 30 p.b.w. m3.crc)pearls ~ p.b.-w. AllOH)3 and/or t'aC03 6- 30 p.b.w. hc)llow microbeads 25- 30 p.b.w. -~ater as viscosity adjusting agent.
Up to 30 % by weight titani~ dioxide of the rutile type may also be added to these comp(:)sitions. In addition, the compositions, as rnentiorled abcjve, may aLso be supplemelltetl b~ colour pi~ments, dyes, defoarrlers, b.ioc-ides and clirnllar additives tc~ he uc:ecl in slnall amollrlts.
A structllLe paste o~ the compositions set forth above meets all the demclrlds macle on it. It has a goc)d res:istance to ~ ht, i.s hi~h1~ washpro(:)f, scratch-proof, hardwearing, relllains soft and flexi~le, anci i.l1 addition can be made with Lelati~el-~ light ~eight. In addi.tion, it i.s hardly inflalllrllable, thi~ bein~ due to the relativel~ high content ~)f alull~ iurl~ h~dro.Yide. Compared with the conventional PVC
plastisol structures it has the additiona1 advantages that it is free from PVC and plasticizer, has a good ~ater vapour permeabilit~ and is insensitive to llicotine, and on 7 ~ ~
cc)lnl~ll-~,t:lc,ll CiOe3 nc,t c~ e otI~ al'lV chlc,rllle cc)nt.airlirJq corllpc)ullds, in part~cular 11(J ll~cir~cilloric ac:id vapours.
Fil3th~more, it do~s l~(Jt colltain any solutivlls which are i;r-~ Jles(:,rl,e dl~ w-Jrkill~ ~r ;vollld llave tv be collected arld nlay be solicllfied at relat~ ely lc)-w temperatureC;~
I ea(iinCI 011 1;51~ w~ e to a ~vi~g ill energ~ duril~q working.
Finallv, the structure pa;te accc)fdincl tc, the invention i~s dl:.O ea3il~ i3iolocl~(all-v- decompo3lble.
Exanlples 03-_E~Ibodilne3lt ~xanlr~le 1:
A structure paste was mixed togetller frorn the starting materials in the amounts give3l below:
28i) p.b.-w. 03 a 5i~-55 ~O plasticizer-free E~'A dispersion 2i-~ p.h.~. Al(i)H)3 having a cJrain size distributioll of 20-25 ~3m lOG p.b.n. of an urlcielcltinized starcl 20 p.b.w. ri()~ ot~ rutile tvpe 37.5 P~IJ~W. rnicr(:,E~eari~
~5 p.l).w. of a nol,-cryc;tAllille :olbite syrup 2l, ~.b.~ arar:E:in di 13iJe 3,~;i l:J~1 and ).C).l~. wat,l-!r c~11 ~ 'C);ity acl iu't:LI'lg agerlt.
rlle EVA di.3~ersi(~l, tlle noll-ctr~6tallizillcl sor~ite svrup ancd tlle water were placed in arl agitating vessel and slowl~
agitated. Durlnq tile a-~itatiol-l tlle -~sngelatinizes~ starch, the nlicrc)peaLls, the aluminiu~ ydrc)xide, the titaniunl dioxide and the paraffin di.spersion were slowly added in succes-:siorl. After about ~ mirl. agitatincf tiïne the paste was readv to use.
20~2730 L [~
(~11 a L)(~ n~ WI~-V~I1 f dL,i-iC dS ~liL`)StL`a te havillcJ c-l weight peL' Ulli t aL~a of 50 ~n~ a -widti~ ~f lL0 ~m a wallpaper ~CLUC~UL~ Wd~ a~liecl witi, t~ paste ln the ~cr~en pri1lting me~.in~-l at a Iate ()f -10 inilllin. rhis structllle ~a~ dried at a~)()ut 150'C fol 35 sec. The structured wallpaper thus procluced met a.Ll the derlldn~s made c~n it.
Fxam~le ~:
.~ strLIcture paste was mi.Yed togetl-ler from the startinc~
materials in the amoul-lts given belc)h-:
3~0 p.b.w. VL a 50-55 ~ plasticizer-free ~VA dispersion 200 p.b.-w. Al(OH)3 havillq a g-rain si~e ~lstribution of 20-25 um 00 ~ .h . {)f an unge]atillized starch 15 p.b.~. micropearl.s 0 L).b.-W. of a noll-crystallil-Je sorbite syrup 7.5 L~.l).w. pal~a~fln cli.5E~t~rsioll al~d ~5 U.~).w. water dS v~.9cC)Si t~- adiustirlc~ agent.
Tlle E~t~ persloll. the no~ rystaili~ing sorbite .~yrup and the wdter were placed ~.n arl ac~itcltillcl vessel arlcl slowl~
agitated. Durlng the ag:itatioll the un(Jelatil-lized starc~l tl~le Illicr~Jp~arlc;, the all3lrl-irl:iunl hyclro~:icle and the paraff-LI~
di3peL~siol-l were ~lowly ad<-~ed in successl~n. ~fter abollt 3 mill. agitating tiïme the paste was ready to u~e.
On a polymer non-wovell fabric as substrate having a weight per unit area of 50 g/m2 and a width of 110 cnl a wallpaper structure was applied witll the paste in the gravure method at a rate of ~0 nl/min. This structure was dried at abc,ut 150~ for 35 se(. rhe stru(tured wallpaper thlls produced met all the del,larld~ made Oll it.
2~9273~
E~am~le 3:
A structure paste was mi~ed together frorll the starting materials in the amounts c7iven ~elc~w:
300 p.b.w. of a 50-55 ~ plasticizer-free EVA dispersion 30 p.b.~. water L0~ p.b.w. etllylelle glycol 107 p.h w. mic:rop~ar]~s having a grairl diameter of 10 -~() um and an expansion ratio of 20 13() p.b.h. Al~)H)3 havil-JcJ a qrain size cli.stribution of 20-25 um 100 p.b.w. CaC03 havincJ a c!rain size distribution of 5-30 ~m 7.5 p.b.w. TiO2 of rutile type L2 p.b.w. hollow microbead.s having a diameter of 10-8 0 ~1III .
The EVA dispersion the ethylene cllycol and water were placed in an agitating vessel and slowly agitated. During the aJitati~n the rmicro~arls the aluminium hyd:roxic3e the calcium carbc~nate the titaniunl dioxicle ancl the hc):l.low microbeacd.s w~re slowly a(1ded in sllcce~.si-)n. A:f ter about 30 mill. aaitatil1c! tilne Lhe paste wa~ read~ to use.
011 J polyrner n~ wovell f.Jbr:Lc as ~ubstrate havincJ a weight per Ullit. ar~a of 50 g/m2 and a w:idth of 110 cm a wallpaper StrUC`tllre WclS applied witll the paste in the rotary screen printinc7 metll()d at a rate of gO m/min. This structure was dried at ab(~llt l5n(~ for 35 sec. The structured wallpaper thus produced met all the demands made on it.
Claims (28)
1. Method of producing three-dimensionally surface-structured linings for wall and floor surfaces, in particular structured wallpapers in which a structure paste is applied by means of a suitable application method in desired structure to a sub-strate web and then solidified on the substrate web, characterized in that structure paste is used on the basis of a vinyl acetate-copolymer dispersion which contains inorganic and/or organic fillers and if necessary diluting agents.
2. Method according to claim 1, characterized in that a structure paste is used of which the total fillers contain a proportion of at least 10% by weight un-gelatinized starch as organic filler.
3. Method according to claim 1 or 2, characterized in that as diluting agent water is employed, with which the structure paste is adjusted to a suitable working viscosity.
4. Method according to at least one of claims 1 to 3, characterized in that the application of the structure paste to the substrate path is carried out by the rotary screen printing method, the flat screen printing method, the rotogravure method, the squeeze gravure method the letterpress method, a coating method or a spraying method.
5. Method according to at least one of claims 1 to 4, characterized in that the structure paste is solidified on the substrate web by drying.
6. Method according to claim 5, characterized in that the drying takes place at temperatures of 40°C to 200°C.
7. Method according to at least one of claims 1 to 6, characterized in that the solidified structure paste is subjected to a further surface finishing, in particular an imprinting painting and/or flocculation.
8. Structure paste for producing three-dimensionally surface-structured linings for wall and floor surfaces, in particular structured wallpapers, characterized by a mixture containing a polymer dis-persion on the basis of a vinyl acetate copolymer, inorganic and/or organic fillers and if necessary solvents and/or diluents.
9. Structure paste according to claim 8, characterized in that the polymer dispersion is a plasticizer-free dispersion of a vinyl acetate-ethylene copolymer (EVA).
10. Structure paste according to claim 8 or 9, characterized in that it contains ungelatinized starch as organic filler.
11. Structure paste according to at least one of claims 8 to 10, characterized in that the inorganic fillers are substantially A1(OH)3 and/or CaC03.
12. Structure paste according to at least one of claims 8 to 11, characterized in that the fillers include up to 10 % by weight TiO2.
13. Structure paste according to at least one of claims 8 to 12, characterized in that it contains 0.8 to 2.0 parts by weight of a 50-55 % polymer dispersion for 1 part by weight inorganic and/or organic fillers.
14. Structure paste according to at least one of claims 10 to 13, characterized in that the total filler contains 25-40 % by weight ungelatinized starch as organic filler and as residual filler substantially Al(OH)3 as inorganic filler.
15. Structure paste according to at least one of claims 8 to 14, characterized in that it contains as processing retardation agent non-crystallizing sorbite syrup or ethylene glycol.
16. Structure paste according to claim 15, characterized in that it contains sorbite syrup in an amount of 1 to 8 % by weight with respect to the total paste.
17. Structure paste according to at least one of claims 8 to 16, characterized in that as expansion agent it contains micropearls.
18. Structure paste according to claim 16, characterized in that the amount of micropearls is 1 to 8 % by weight with respect to the total paste.
19. Structure paste according to claim 9, containing substantially:
240-360 p.b.w. of a 50-55 % plasticizer-free EVA
dispersion 5- 50 p.b.w. non-crystallizing sorbite syrup 10- 50 p.b.w. micropearls 300 p.b.w. A1(OH)3 and ungelatinized starch 5- 30 p.b.w. water as viscosity adjusting agent.
240-360 p.b.w. of a 50-55 % plasticizer-free EVA
dispersion 5- 50 p.b.w. non-crystallizing sorbite syrup 10- 50 p.b.w. micropearls 300 p.b.w. A1(OH)3 and ungelatinized starch 5- 30 p.b.w. water as viscosity adjusting agent.
20. Structure paste according to claim 19, characterized in that it contains 100 p.b.w. ungelatinized starch.
21. Structure paste according to claim 9, containing substantially:
240-360 p.b.w. of a 50-55 % plasticizer-free EVA
dispersion 6- 30 p.b.w. ethylene glycol 6- 30 p.b.w. micropearls 230 p.b.w. A1(OH)3 and/or CaCO3 6- 30 p.b.w. hollow microbeads 25- 35 p.b.w. water as viscosity adjusting agent.
240-360 p.b.w. of a 50-55 % plasticizer-free EVA
dispersion 6- 30 p.b.w. ethylene glycol 6- 30 p.b.w. micropearls 230 p.b.w. A1(OH)3 and/or CaCO3 6- 30 p.b.w. hollow microbeads 25- 35 p.b.w. water as viscosity adjusting agent.
22. Structure according to claim 19, 20 or 21, characterized in that it contains 5-25 p.b.w. paraffin dispersion.
23. Structure paste according to claim 19, 20, 21 or 22, characterized in that it additionally contains 5-30 p.b.w. TiO2 of the rutile type.
24. Structure paste according to claims 19, 20, 22 and 2 containing substantially:
280 p.b.w. of a 50-55 % plasticizer-free EVA
dispersion 200 p.b.w. Al(OH)3 having a grain size distribution of 20-25 µm 100 p.b.w. of an ungelatinized starch 20 p.b.w. TiO2 of rutile type 37.5 p.b.w. micropearls having a grain diameter of 10-20 µm and an expansion ratio of 45 p.b.w. of a non-crystallizing sorbite syrup 20 p.b.w. paraffin dispersion and 10 p.b.w. water as viscosity adjusting agent.
280 p.b.w. of a 50-55 % plasticizer-free EVA
dispersion 200 p.b.w. Al(OH)3 having a grain size distribution of 20-25 µm 100 p.b.w. of an ungelatinized starch 20 p.b.w. TiO2 of rutile type 37.5 p.b.w. micropearls having a grain diameter of 10-20 µm and an expansion ratio of 45 p.b.w. of a non-crystallizing sorbite syrup 20 p.b.w. paraffin dispersion and 10 p.b.w. water as viscosity adjusting agent.
25. Structure paste according to claims 19, 20 and 22, containing substantially:
320 p.b.w. of a 50-55 % plasticizer-free EVA
dispersion 200 p.b.w. Al(OH)3 having a grain size distribution of 20-25 µm 100 p.b.w. of an ungelatinized starch 15 p.b.w. micropearls having a grain diameter of 10-20 µm and an expansion ratio of 20 10 p.b.w. of a non-crystalline sorbite syrup 7.5 p.b.w. paraffin dispersion and 25 p.b.w. water as viscosity adjusting agent.
320 p.b.w. of a 50-55 % plasticizer-free EVA
dispersion 200 p.b.w. Al(OH)3 having a grain size distribution of 20-25 µm 100 p.b.w. of an ungelatinized starch 15 p.b.w. micropearls having a grain diameter of 10-20 µm and an expansion ratio of 20 10 p.b.w. of a non-crystalline sorbite syrup 7.5 p.b.w. paraffin dispersion and 25 p.b.w. water as viscosity adjusting agent.
26. Structure paste according to claims 21 and 23, containing substantially:
300 p.b.w. of a 50-55 % plasticizer-free EVA
dispersion 30 p.b.w. water 10 p.b.w. ethylene glycol 7 p.b.w. micropearls having a grain diameter of 10-20 µm and an expansion ratio of 20 130 p.b.w. A1(OH)3 having a grain size distribution of 20-25 µm 100 p.b.w. CaCO3 having a grain size distribution of 5-30 µm 7.5 p.b.w. TiO2 of rutile type 12 p.b.w. hollow microbeads having a diameter of 10-80 µm.
300 p.b.w. of a 50-55 % plasticizer-free EVA
dispersion 30 p.b.w. water 10 p.b.w. ethylene glycol 7 p.b.w. micropearls having a grain diameter of 10-20 µm and an expansion ratio of 20 130 p.b.w. A1(OH)3 having a grain size distribution of 20-25 µm 100 p.b.w. CaCO3 having a grain size distribution of 5-30 µm 7.5 p.b.w. TiO2 of rutile type 12 p.b.w. hollow microbeads having a diameter of 10-80 µm.
27. Structure paste according to at least one of claims 8 to 26, characterized in that it additionally contains dyes, colour pigments, biocides and/or defoamers.
28. Use of a structure paste according to at least one of claims 8 to 27 for producing structured wallpapers.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP4210922.1-43 | 1992-04-02 | ||
DE4210922A DE4210922A1 (en) | 1992-04-02 | 1992-04-02 | Process for the production of three-dimensional surface-structured coverings for wall and floor surfaces and structural paste therefor |
EP92121757A EP0564712B2 (en) | 1992-04-02 | 1992-12-22 | Process for the preparation of three-dimensional structured surface coatings for wall and floor areas and paste therefor |
EP92121757.6 | 1992-12-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2092730A1 true CA2092730A1 (en) | 1993-10-03 |
Family
ID=25913531
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002092730A Abandoned CA2092730A1 (en) | 1992-04-02 | 1993-03-26 | Method of producing three-dimensionally surface-structured linings for wall and floor surfaces and structure paste therefor |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0563977A2 (en) |
JP (1) | JPH0757848B2 (en) |
CA (1) | CA2092730A1 (en) |
HU (1) | HUT68632A (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5431960A (en) * | 1994-08-29 | 1995-07-11 | Watts; Charles E. | Anti-slip floor coating composition |
JPH11200300A (en) * | 1997-12-26 | 1999-07-27 | Okamoto Ind Inc | Biodegradable wall paper having excellent application |
KR100533806B1 (en) | 2003-07-10 | 2005-12-06 | 한국바이린주식회사 | Wallpaper for automobile and manufacturing method |
DE102021126981A1 (en) * | 2021-10-18 | 2023-04-20 | Marburger Tapetenfabrik J. B. Schaefer Gmbh & Co Kg | Wallpaper with a mineral surface and method for its manufacture |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1157040A (en) * | 1967-11-15 | 1969-07-02 | Scott Bader Co | Coating Composition for Wallpaper |
GB1325338A (en) * | 1969-07-28 | 1973-08-01 | Cpc International Inc | Sizing and coating compositions for paper |
JPS5135486A (en) * | 1974-09-20 | 1976-03-25 | Shionogi Seiyaku Kk | 22 keto ll guronsan no seizohoho |
CA1043193A (en) * | 1975-02-14 | 1978-11-28 | Douglas C. Edwards | Coating of paper |
JPS5282937A (en) * | 1975-12-29 | 1977-07-11 | Kuraray Co Ltd | Emulsified composition for thick coating |
SU1288238A1 (en) * | 1985-09-25 | 1987-02-07 | Центральный научно-исследовательский институт бумаги | Aqueous composition for coating wallpaper |
JPH01118581A (en) * | 1987-10-30 | 1989-05-11 | Kikusui Kagaku Kogyo Kk | Composition for forming tile pattern by troweling |
JPH026682A (en) * | 1987-12-01 | 1990-01-10 | Honshu Paper Co Ltd | Starch-filled paper |
DE3841199A1 (en) * | 1988-12-07 | 1990-06-13 | Feldmuehle Ag | PRINTED PAPER, METHOD FOR ITS MANUFACTURE AND ITS USE |
JPH02303573A (en) * | 1989-05-17 | 1990-12-17 | Sumitomo Metal Ind Ltd | Formation of coated film having rugged pattern |
JPH0321671A (en) * | 1989-06-19 | 1991-01-30 | Suzuka Toryo Kk | Coating material for thick film to form uneven pattern |
-
1993
- 1993-01-07 JP JP5001168A patent/JPH0757848B2/en not_active Expired - Fee Related
- 1993-03-26 CA CA002092730A patent/CA2092730A1/en not_active Abandoned
- 1993-03-31 HU HU9300934A patent/HUT68632A/en unknown
- 1993-04-02 EP EP93105457A patent/EP0563977A2/en not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
JPH0757848B2 (en) | 1995-06-21 |
HUT68632A (en) | 1995-07-28 |
EP0563977A3 (en) | 1994-04-13 |
HU9300934D0 (en) | 1993-11-29 |
JPH06101199A (en) | 1994-04-12 |
EP0563977A2 (en) | 1993-10-06 |
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