CA1098386A - Stone surface treatment - Google Patents
Stone surface treatmentInfo
- Publication number
- CA1098386A CA1098386A CA257,956A CA257956A CA1098386A CA 1098386 A CA1098386 A CA 1098386A CA 257956 A CA257956 A CA 257956A CA 1098386 A CA1098386 A CA 1098386A
- Authority
- CA
- Canada
- Prior art keywords
- stone
- agent
- dipping
- gaps
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
Abstract
ABSTRACT OF THE DISCLOSURE
Surface treatment of stones such as marbles, granites and the like by means of impregnating the stone with a liquid protector agent which may be a monomer such as styrene, methyl methacrylate and the like for forming the acrylic resin or a lower polymer thereof so as to penetrate in crystal grain gaps of the stone, and then heating the stone for polymerizing or copolymerizing of the impregnated agent, whereby the stone is efficiently protected from being soiled, faded, discolored, weathered and eroded. According to another aspect, said liquid protector agent is a solution of paraffin, nitrocellulose, lacquer and the like of which solvent is evaporated so that the solidified solute is left in the grain gaps. When impregnating the stone with solution or dispersion of a coloring agent which may be usual pigment or dyestuff and then applying said pro-tector agent or when impregnating the stone with the coloring agent in the protector agent, it is possible to produce durable and desired coloring of marbles, granites and the like stone no less better than the naturally colored and expensive stones.
Surface treatment of stones such as marbles, granites and the like by means of impregnating the stone with a liquid protector agent which may be a monomer such as styrene, methyl methacrylate and the like for forming the acrylic resin or a lower polymer thereof so as to penetrate in crystal grain gaps of the stone, and then heating the stone for polymerizing or copolymerizing of the impregnated agent, whereby the stone is efficiently protected from being soiled, faded, discolored, weathered and eroded. According to another aspect, said liquid protector agent is a solution of paraffin, nitrocellulose, lacquer and the like of which solvent is evaporated so that the solidified solute is left in the grain gaps. When impregnating the stone with solution or dispersion of a coloring agent which may be usual pigment or dyestuff and then applying said pro-tector agent or when impregnating the stone with the coloring agent in the protector agent, it is possible to produce durable and desired coloring of marbles, granites and the like stone no less better than the naturally colored and expensive stones.
Description
~83~6 1 The present invention relates to surface treatment of ~tones, and more partlcularly to a method for protectin~ the stone surface from being soiled, faded, discolored, weathered and erorled by means of particularly applying a particular protector a~ent, and so treated stones. According to another aspect of the invention, it relates further to a method for coloring the stone surface by adding a coloring agent to said surface protector agent, and ~o treated stones.
Various natural stones have been used with various purposeq for a very long time. Above all, marbles, ~ranites and the like stoneq have been used for interior and exterîor building materials s~ch as flooring, outer and inner wall materials, furnitures such as de~ks, mantelpiece~, bath tubsJ benche~, monumentq, tombs and the like, in view of respectively beautiful colors and patterns, good sence of touch, hi~h strength and durability and other preferable propertie~.
Such stones have crystal ~rains and consequently fine gaps or chin~s between ad~acent cr-g~tal ~rain the dimension of s~id ~ap bein~ varied from ~e~eral microns to ~everal tens of microns and the total volume of ~aid ~ap~ being arran~ed frorn C.l~ to G.7~ Or the totai volume Or the stone, so that various alien matters are apt to penetrate into ~uch ~aps which cau~es soil, fadin~ and discolorir,~l. Thi3 is particularly stri~ing in the case of ~Jround and polished stone surrace, which may be observed for instar~ce on the cor-idor floor covered with marble stone plates. ~aid cr-yst~l ~rain gaps can be a cause also of weatherin~ and ero~ior~ of the stone during the lapRe of a long time above all whe~ such gtones are used for outdoor str,~ct~res, which na~- be ob e,ved for 3~ instance on the old bench maae o~ C~ranite stone bloc~ in the parK.
Hitherto wax or any su;table s~nthetic reC ~^. ha^ beeY
_ " _ 10~8386 1 used for applying on the stone surface to form a transparent protection coatinp;. This treatment, however, has been found un~atl~ractory in that not only the coatin~; is readily wiped ~way or the coated film i9 apt to be partly peeled off but also such coating or film adversely affects on the desired properties Or marbleQ, graniteQ etc. such as reqpectively- characteri~tic lu~trous color and sence of touch.
'~he inventor has ~ucceeded in fairly complete protection of the stone surface by treating ~uch stones of crystal ~rains and consequently havin~ chin~s or gaps therebetween with a specific agent in the liquid phase for impregnation which is then solidiried so as to fill up every cryQtal grain gap open at the stone surface. Arrangement of the crystal grain~ and consequently of the gaps are complex and not uniform, but it can be ~aid that each of saia gaps may not only extend sub-~tantially vertically so as to be exposed at the ~tone surface at one end thereof but also be connected with saps substantially transversely extendin~ at the rear o~ the crystal grains, and mutually connected gaps ma~3 extend often intG fairly deep inner portion. ~en a colorin~ a~ent is applied about the time of applying said filling-up esent, thu~, not only durable but also natural coloring is attainable.
There have been produced natural ~tones of varlous beautirul colors and patterns. For instance marbles whicn cGnsi~t al~ost of crysta] li~e~tone or calcite and fall under the categvr-y of metamorphite derived from limestone may cGrtain a small amount of minerals ~uch as carbonaceous subata;~ces, irori oxide, an~ite or pyroxene, horr.blende, chlorite, clay ard the lii~e which give the marbles various color~ such as ~reerl, red, purple and blue as well as patterns. Althoug~ there are pro~luced T~rhite or grey marbles in large quar.titie_, but cGlored beautif~l marbleS are hardly obtainable an~ ery expers;-Je. As fGr ~ran1ter, 10!~8386 l these con~ist mainly o~ quarz and feldspar and contain a small ;
amount of minerals such as black and white mica, hornblende and the like whi¢h impart gives colors Or black, red and blue. ;
Whlte-black granites such as called "Inada-i¢hi" or 1'Inada-Mikage" and produced in the Kanto Distric of Japan, white-black^
red granites such as called "Mannari-ishi" and produced in the Chyugoku ~istrict of Japan are common and produced in large quQntities. However red-bla¢k granites Juch as oalled "~mperial Red" and blue-black granite~ such as called "B1ue Pearl"~ ar~e r~re ~d expensive.
The inventor has found it can attaln durable and natural coloration of marble~, granites and tho li~e stone to apply a coloring agent in addition to application of said filling-up ugent in liquid state to be made solld thereafter.
A principal ob~ect o~ the present lnvention i~, thus, to provide a method for stone surrace treatment which can obviate and o~srcome the do~ect~ re~erred to abov~.
A particular obJ~ct o~ the invention i~ to provide a method for protecting the stone ~urface for a considerably long time without adversely a~ecting on the deslred properties o~ th~ respective stone such as colors and ~nce of touch.
The other obJect i~ to provide a method for coloring the stone 3urface durably and in the color tone li~e as naturally colored stone.
me still other ob~ect is to provide the stone surface treatment as referred to above to be readily combined with the conventional stone grinding and polishing treatments.
Various advantage~ and obiects other than the above o~
the invention will be readily appreciated by studyine more detailed explanation and sxamples of the invention to be given hereinafter wh-ch ~hall be made not ~or re~tricting it thereto but merely for making the invention more readily and correctly 1Q98386 ~
',:
1 under~tandable. -~
According to one aspect of the invention, the liquid agent !
with which the mater~al stone i8 impregnated to be ~olidified later in the cry~tal grain gaps existing at the vicinity of and opened at the stone surface may be any monomer or lower polymer to be readily penetratable such gaps and polymerizable when heating at a fairly low temperature ~o a~ not to adversely affect on the stone structure and properties to form a transparent, fairly hard and compact polymer or copolymer. It has been found pref-erable, however, to use above all styrene monomer and variou~monomers to form ths so-called acrylic resin, among which methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, a-methylcyanoacrylate and a-ethglcyanoacrylate are more preferable.
The lower polymer of the above o~ which polymerization degree i8 le~s than 30~ may al~o be used.
According to another aspect of the invention, said liquid agent for filling-up gaps i~ a ~olution of paraffin, nitro-cellulose lacquer, poly~inyl chloride, vinylacetate resin or the like of which sol~ent is evaporated after impregnation so that the solidified solute is left in the crgstal grein gaps.
As for the coloring agent, every organic and inorganic pigment and every dyestuff may be used. Two or more pigments and/or dyes can be used a~ mixture. They may be di~solved or dispersed in inorganic solvent such as water and carbon di~ul-fide; or~anic solvent such as the alcoholic inclu~ive of methanol, ethanol, the ~etonic inclu~ive of methyli~obutyl-ketone, butylisobutylketone, the esteric inclusive of methylacetate, ethylacetate, dibutylphthalate, dioctylphthalate, and the benzenic inclusive of benzene, toluene. Among the inor~anic pigments, preferably u~ed are chromimm oxide, Cadmium ~ellow, Chrome Yellow, Pru~sian Blue, Ultramarine Blue and Cadmium Red. As for the organic pigment~, preferably u~ed are 1~983~36 1 phthalocyanine, Green ~old, Lithol Red and Hansa 'Yellow. Among .
t'he dye~, there are preferably water soluble direct dyes ~uch as Dirr.~e~ Yello~r, the Zapon series such as Zapon Red, Zapon Green~
and the Orasol series such as Orasol Red, Orasol ~lue respec-tively soluble to the above qo]vents. A fillin~-up agent such as methyl methacrylate itself may be used as solvent for some colorin~ agent such as Orasol Red.
Impre~nation of the stone with the filling-up agent and/or the colorin~ a~ent is preferably carried. out by soaking the stone piece or plate in the bath of said liquld agent or mixture of said two agr~7nts, although it is posqible by any other mea.ns for instance by spraying. Applying the filling-up agent and the coloring agent may be done ~r7parately, in which the latter is preferably done first.
Example 1 A plate of white marble produce~ in Forrnosa and of 4.G cm by 20 cm with 10 rnm thlckness of which one si~le surface had been ~r~round and polished was soaked in the filling-up a~ent bath consistin~; of methyl methacr~Jlate added with 0.1 mol~
2C benzoyl peroxide as poly~erization initiator at thç room temperature for 6 hcurs, anr~ then at a tern~eratu-re of oC5 rOr 20 minutes for proceedin~ with prelirninar~ pol~.rnerization. The stone plate was then taKen out of said 'bath to be i~e~t ;n the air of 100C for 6 hours7 fo. completing ~ol~.erizatirJrl Or the fillin~-up agent.
The surface Or the trrated mar'cle Ljlate wa~ ore l~strou~.
than and water repellent in co!~parison ~I tr. ~ne ~treated similar marble plate a~7 the crjr!tro' The t,.o ~la5e~, one treated an~ the other untreates, were laid _ -le b~ .eide in front of the laborator-r office entrarce a.n~ o.p~e~l e~-.S7r-~ ~JaJ
for one mo~th. '~he treatel rQarble piese wa~ a rno.~t sarrle ~itr, the fresh marble ctone plate but the -~n~reatf~i Grle -~as f'airlJ
"
a83~6 .,~,iled so that said two were clearly distingui shed according to th~ b'lin(~l p~nel test.
~xr~rn~ le The marble e,tone ~)late as used ir. :Example 1 was soaked in the bath of 5 wei~ht~O Ora~cl Rea as the colori.n( agent di s solved in methyl methacrylate, to which further 20 mol7~
rnethyl acrylate ~las added, for 3C minutes at the room ternpera.-ture, and then take-n out ther eof to be dried at the surface .
This treatment was repeated ~ times. ~rhe stone plate was then soaL~ed in said bath to which azobisisobutylnitrile was ad-led as the pol,ymerization initiator at the room te-,~peratur e for 30 minutes, and then at a temperature of ~GC for 15 minutes.
Ilhe test piece was taken out of thei bath to be xept in the air of' lGOC for 6 hour~ for completing poly7rlerizat ion of methyl meth~crylate .
The surface of the treated mar~le etone ~>late ~,ras colored in vivid and l.ustrou~ red rio less better th~.n tne rlatu.ral.ly colored marble.
~ample 3 A piece of ~-,rar~ite called "Inada-ishl" pro~ ec~ lrl the Kanto District, Japan an~ of' 3G c-r. by 30 c~,. bl ~,0 CJn of w'hich every side was rou~hly grourl(~ waC soaKer3 i rl the bath of' solution of 5 wei~,ht,~b Orasol Red ln methJl eth~l ,retGrle a~ t'ne colorirl~- al~er;t to be ~:lfficiently imp-re,gr,ate~J.. ~4f te- ~7ryin~J, the stone ~iece was eoa~.ed in the 7cath of half-an~l-half rnixture of st~,rrene and rrlethyl rr.e-thacr,~late ar/~r'e ~,;ith 0.1 mol~O
benzo~l r7eroxide at the roor~ territ,erat7l,~e fc,r ri hours. Ths graIlite piece was t~en out there~f to be ~e&t irl the alr of 110~ to proceed with copol,-,rmerization o~ s 1i~7 ~.orJorr!erc 30 contalninF the col.orir.,, a ent. O-rie s~ide of~ t,r,e s;,or? r"a-, sll~htly "rc7~n~l and poli~e'ner~.
The red-blac~ ,-.ra.nlte ~jf li n ~ ter re ~e ~e~ a~, ,bt 1 to be suitable for the building material.
~xample 4 The ~ranite stone piece as used in Example 3 was soaked in the bath of the mixture of styrene and acrylonitrile in : 2 mol ratio added with 0.1% benzoyl peroxide at the room temperature for 1 hour, and then at a temperature of 80C for 15 minute~ for proceeding with preliminary copolymerization.
The test piece was ta~en out o~ ~aid bath to be kept in the air of 100C for 6 hours to complete copolymerization.
mere wa~ observed lu~tre and substantially complete water repellency at the surface in comparison with the untreated stone piece.
Exam~le 5 The filling-up agent was prepared by dilutin~, Acryl Sirup which is a trade mark of about 30~0 lower polymer Or acrylic acid with the ~&me amount of methyl methacrylate. A piece of gran,ite stone called "Mannari-ishi" produced in the Chyugo~u District, Japan of 30 cm by 90 cm by 120 cm was put into a polymerization vessel which was .~ealed and air-evacuated by means of a vacuum purnp. Into said ves~el was fed said filling-up agent and filled nitrGgen gas so as to be ~ept at 5 Kk;r/cm2 by gauge pres~ure for ~ hour~ for impregnatini; the st,one piece with ~aid lig,uid agent. The lia,uid agerlt was tnen excluded ~nd the stone piece impregnated with the liouid a~ent was heated in inert atmo~phere at a temperature of 85C for 6 hour~i for completing copol,ymerizatiorl.
When the stone surrace was sli~htl~J .-Jround ara poli3hed, the characteristic pattern of sald stone wa~s obser-~ed beautiful a~ if wetted.
hxample 6 The marble stone plate as used in ~xample 1 ~la.-, .,oa~e~
in the bath of suspension of l wei~Jht~ Cadmil~.m Yello,J in -,~ater lQ~838~
1 for 1 hour, and then taken out thereo~ to be dried. The stone plate was soaked in the bath of the lacquer dissolved in the thinn~r for 30 mlnutes and taXen out thereof to be dried, which treatment wa~ repeated 4 times.
Thf treated marble plate was tinted in light yellow and crystal grain ?gaps were completely filled up with the lacf~uer so that the stone c2urface was lustrous and beautiful no less better than the naturally 50 colored marble.
~x~mple 7 The marble plate a~ use~ in ~x~mple 1 was soa~ed in the bath o~ 10 gr. Zapon Fa~t Green di?3solved in 1,000 cc. methanol for 1 hour and ta~en out to be dried. l'he 3tone plate was soa~ed in the bath of the lacquer solution in the thinner for 30 minutes which treatment was repeated 3 times.
The treated marble stone was tinted in li~ht green and ?showed beautiful color tone no less better thr~r. the natural green marble.
~xample 8 The stone plate clit a~ in ~xample 1 but not of marble but Or "Pocheon Granite" prodljced in ~orea wasl soa~ed in the bath of 100 ct~r. Ora?2ol ~ed and 30 gr. Orasol ~rown d;s~olved in 1,000 cc. methanol as the color-in~r age..t at the rtjom temper~ture for 30 minutes, arl-~ ta~en out frorrl the bath to be dried, which treatment was repeated 3 times. The yranite stone plate was so&~ed ir~ the bath of nitrocellJlo e disc,olved in methyl acetate as the filling-up aC?~ent at t~.e roor?l temperature for 1 hour and taken out thereof to be dried ~7hitr. treatment was repeated 3 times.
The granite stone treated a~2 a~o-~re was rJo e-_ better thari the red granite called Imperial ~e?~ pro?~ute~ wef3en. il?hte crystal grain C7~aps were -~?el] filled u? ,~ith thC age..t.
5xam~1e '3 lQ~8386 1 The plate Or 3.2 m by 8 m and 5 cm thic~ness of white marble produced in Formosa was ~round and polished at one ~ide thereo~. It was ;ntended to form a mural painting of "A~afuji" or "~ed Mount Fuji" by Ukiyoe Artist, Hokusai on said marble plate. With covering the mountain portion of the marble plate by means of a plastic material sheet, the solution of Ora~ol Blue in ~ethanol was applied by 3praying for coloring the s~y portion. The solution of Orasol Red in the solvent was similarly applied for coloring the mountain portion and then the ~olution of Orasol Green was applied at the left lower portion on the marble plate. The marble plate was then impreg-nated with the solution of the lacquer in methyl acetate for filling-up the crystal grain gaps and driecl. The color tone was not ~o gaudy but placid. Owing to that the coloring agent was carried by the filling-up agent in e~ery crystal grain gap~, the colors are to be durable for a long time.
-- . C
Various natural stones have been used with various purposeq for a very long time. Above all, marbles, ~ranites and the like stoneq have been used for interior and exterîor building materials s~ch as flooring, outer and inner wall materials, furnitures such as de~ks, mantelpiece~, bath tubsJ benche~, monumentq, tombs and the like, in view of respectively beautiful colors and patterns, good sence of touch, hi~h strength and durability and other preferable propertie~.
Such stones have crystal ~rains and consequently fine gaps or chin~s between ad~acent cr-g~tal ~rain the dimension of s~id ~ap bein~ varied from ~e~eral microns to ~everal tens of microns and the total volume of ~aid ~ap~ being arran~ed frorn C.l~ to G.7~ Or the totai volume Or the stone, so that various alien matters are apt to penetrate into ~uch ~aps which cau~es soil, fadin~ and discolorir,~l. Thi3 is particularly stri~ing in the case of ~Jround and polished stone surrace, which may be observed for instar~ce on the cor-idor floor covered with marble stone plates. ~aid cr-yst~l ~rain gaps can be a cause also of weatherin~ and ero~ior~ of the stone during the lapRe of a long time above all whe~ such gtones are used for outdoor str,~ct~res, which na~- be ob e,ved for 3~ instance on the old bench maae o~ C~ranite stone bloc~ in the parK.
Hitherto wax or any su;table s~nthetic reC ~^. ha^ beeY
_ " _ 10~8386 1 used for applying on the stone surface to form a transparent protection coatinp;. This treatment, however, has been found un~atl~ractory in that not only the coatin~; is readily wiped ~way or the coated film i9 apt to be partly peeled off but also such coating or film adversely affects on the desired properties Or marbleQ, graniteQ etc. such as reqpectively- characteri~tic lu~trous color and sence of touch.
'~he inventor has ~ucceeded in fairly complete protection of the stone surface by treating ~uch stones of crystal ~rains and consequently havin~ chin~s or gaps therebetween with a specific agent in the liquid phase for impregnation which is then solidiried so as to fill up every cryQtal grain gap open at the stone surface. Arrangement of the crystal grain~ and consequently of the gaps are complex and not uniform, but it can be ~aid that each of saia gaps may not only extend sub-~tantially vertically so as to be exposed at the ~tone surface at one end thereof but also be connected with saps substantially transversely extendin~ at the rear o~ the crystal grains, and mutually connected gaps ma~3 extend often intG fairly deep inner portion. ~en a colorin~ a~ent is applied about the time of applying said filling-up esent, thu~, not only durable but also natural coloring is attainable.
There have been produced natural ~tones of varlous beautirul colors and patterns. For instance marbles whicn cGnsi~t al~ost of crysta] li~e~tone or calcite and fall under the categvr-y of metamorphite derived from limestone may cGrtain a small amount of minerals ~uch as carbonaceous subata;~ces, irori oxide, an~ite or pyroxene, horr.blende, chlorite, clay ard the lii~e which give the marbles various color~ such as ~reerl, red, purple and blue as well as patterns. Althoug~ there are pro~luced T~rhite or grey marbles in large quar.titie_, but cGlored beautif~l marbleS are hardly obtainable an~ ery expers;-Je. As fGr ~ran1ter, 10!~8386 l these con~ist mainly o~ quarz and feldspar and contain a small ;
amount of minerals such as black and white mica, hornblende and the like whi¢h impart gives colors Or black, red and blue. ;
Whlte-black granites such as called "Inada-i¢hi" or 1'Inada-Mikage" and produced in the Kanto Distric of Japan, white-black^
red granites such as called "Mannari-ishi" and produced in the Chyugoku ~istrict of Japan are common and produced in large quQntities. However red-bla¢k granites Juch as oalled "~mperial Red" and blue-black granite~ such as called "B1ue Pearl"~ ar~e r~re ~d expensive.
The inventor has found it can attaln durable and natural coloration of marble~, granites and tho li~e stone to apply a coloring agent in addition to application of said filling-up ugent in liquid state to be made solld thereafter.
A principal ob~ect o~ the present lnvention i~, thus, to provide a method for stone surrace treatment which can obviate and o~srcome the do~ect~ re~erred to abov~.
A particular obJ~ct o~ the invention i~ to provide a method for protecting the stone ~urface for a considerably long time without adversely a~ecting on the deslred properties o~ th~ respective stone such as colors and ~nce of touch.
The other obJect i~ to provide a method for coloring the stone 3urface durably and in the color tone li~e as naturally colored stone.
me still other ob~ect is to provide the stone surface treatment as referred to above to be readily combined with the conventional stone grinding and polishing treatments.
Various advantage~ and obiects other than the above o~
the invention will be readily appreciated by studyine more detailed explanation and sxamples of the invention to be given hereinafter wh-ch ~hall be made not ~or re~tricting it thereto but merely for making the invention more readily and correctly 1Q98386 ~
',:
1 under~tandable. -~
According to one aspect of the invention, the liquid agent !
with which the mater~al stone i8 impregnated to be ~olidified later in the cry~tal grain gaps existing at the vicinity of and opened at the stone surface may be any monomer or lower polymer to be readily penetratable such gaps and polymerizable when heating at a fairly low temperature ~o a~ not to adversely affect on the stone structure and properties to form a transparent, fairly hard and compact polymer or copolymer. It has been found pref-erable, however, to use above all styrene monomer and variou~monomers to form ths so-called acrylic resin, among which methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, a-methylcyanoacrylate and a-ethglcyanoacrylate are more preferable.
The lower polymer of the above o~ which polymerization degree i8 le~s than 30~ may al~o be used.
According to another aspect of the invention, said liquid agent for filling-up gaps i~ a ~olution of paraffin, nitro-cellulose lacquer, poly~inyl chloride, vinylacetate resin or the like of which sol~ent is evaporated after impregnation so that the solidified solute is left in the crgstal grein gaps.
As for the coloring agent, every organic and inorganic pigment and every dyestuff may be used. Two or more pigments and/or dyes can be used a~ mixture. They may be di~solved or dispersed in inorganic solvent such as water and carbon di~ul-fide; or~anic solvent such as the alcoholic inclu~ive of methanol, ethanol, the ~etonic inclu~ive of methyli~obutyl-ketone, butylisobutylketone, the esteric inclusive of methylacetate, ethylacetate, dibutylphthalate, dioctylphthalate, and the benzenic inclusive of benzene, toluene. Among the inor~anic pigments, preferably u~ed are chromimm oxide, Cadmium ~ellow, Chrome Yellow, Pru~sian Blue, Ultramarine Blue and Cadmium Red. As for the organic pigment~, preferably u~ed are 1~983~36 1 phthalocyanine, Green ~old, Lithol Red and Hansa 'Yellow. Among .
t'he dye~, there are preferably water soluble direct dyes ~uch as Dirr.~e~ Yello~r, the Zapon series such as Zapon Red, Zapon Green~
and the Orasol series such as Orasol Red, Orasol ~lue respec-tively soluble to the above qo]vents. A fillin~-up agent such as methyl methacrylate itself may be used as solvent for some colorin~ agent such as Orasol Red.
Impre~nation of the stone with the filling-up agent and/or the colorin~ a~ent is preferably carried. out by soaking the stone piece or plate in the bath of said liquld agent or mixture of said two agr~7nts, although it is posqible by any other mea.ns for instance by spraying. Applying the filling-up agent and the coloring agent may be done ~r7parately, in which the latter is preferably done first.
Example 1 A plate of white marble produce~ in Forrnosa and of 4.G cm by 20 cm with 10 rnm thlckness of which one si~le surface had been ~r~round and polished was soaked in the filling-up a~ent bath consistin~; of methyl methacr~Jlate added with 0.1 mol~
2C benzoyl peroxide as poly~erization initiator at thç room temperature for 6 hcurs, anr~ then at a tern~eratu-re of oC5 rOr 20 minutes for proceedin~ with prelirninar~ pol~.rnerization. The stone plate was then taKen out of said 'bath to be i~e~t ;n the air of 100C for 6 hours7 fo. completing ~ol~.erizatirJrl Or the fillin~-up agent.
The surface Or the trrated mar'cle Ljlate wa~ ore l~strou~.
than and water repellent in co!~parison ~I tr. ~ne ~treated similar marble plate a~7 the crjr!tro' The t,.o ~la5e~, one treated an~ the other untreates, were laid _ -le b~ .eide in front of the laborator-r office entrarce a.n~ o.p~e~l e~-.S7r-~ ~JaJ
for one mo~th. '~he treatel rQarble piese wa~ a rno.~t sarrle ~itr, the fresh marble ctone plate but the -~n~reatf~i Grle -~as f'airlJ
"
a83~6 .,~,iled so that said two were clearly distingui shed according to th~ b'lin(~l p~nel test.
~xr~rn~ le The marble e,tone ~)late as used ir. :Example 1 was soaked in the bath of 5 wei~ht~O Ora~cl Rea as the colori.n( agent di s solved in methyl methacrylate, to which further 20 mol7~
rnethyl acrylate ~las added, for 3C minutes at the room ternpera.-ture, and then take-n out ther eof to be dried at the surface .
This treatment was repeated ~ times. ~rhe stone plate was then soaL~ed in said bath to which azobisisobutylnitrile was ad-led as the pol,ymerization initiator at the room te-,~peratur e for 30 minutes, and then at a temperature of ~GC for 15 minutes.
Ilhe test piece was taken out of thei bath to be xept in the air of' lGOC for 6 hour~ for completing poly7rlerizat ion of methyl meth~crylate .
The surface of the treated mar~le etone ~>late ~,ras colored in vivid and l.ustrou~ red rio less better th~.n tne rlatu.ral.ly colored marble.
~ample 3 A piece of ~-,rar~ite called "Inada-ishl" pro~ ec~ lrl the Kanto District, Japan an~ of' 3G c-r. by 30 c~,. bl ~,0 CJn of w'hich every side was rou~hly grourl(~ waC soaKer3 i rl the bath of' solution of 5 wei~,ht,~b Orasol Red ln methJl eth~l ,retGrle a~ t'ne colorirl~- al~er;t to be ~:lfficiently imp-re,gr,ate~J.. ~4f te- ~7ryin~J, the stone ~iece was eoa~.ed in the 7cath of half-an~l-half rnixture of st~,rrene and rrlethyl rr.e-thacr,~late ar/~r'e ~,;ith 0.1 mol~O
benzo~l r7eroxide at the roor~ territ,erat7l,~e fc,r ri hours. Ths graIlite piece was t~en out there~f to be ~e&t irl the alr of 110~ to proceed with copol,-,rmerization o~ s 1i~7 ~.orJorr!erc 30 contalninF the col.orir.,, a ent. O-rie s~ide of~ t,r,e s;,or? r"a-, sll~htly "rc7~n~l and poli~e'ner~.
The red-blac~ ,-.ra.nlte ~jf li n ~ ter re ~e ~e~ a~, ,bt 1 to be suitable for the building material.
~xample 4 The ~ranite stone piece as used in Example 3 was soaked in the bath of the mixture of styrene and acrylonitrile in : 2 mol ratio added with 0.1% benzoyl peroxide at the room temperature for 1 hour, and then at a temperature of 80C for 15 minute~ for proceeding with preliminary copolymerization.
The test piece was ta~en out o~ ~aid bath to be kept in the air of 100C for 6 hours to complete copolymerization.
mere wa~ observed lu~tre and substantially complete water repellency at the surface in comparison with the untreated stone piece.
Exam~le 5 The filling-up agent was prepared by dilutin~, Acryl Sirup which is a trade mark of about 30~0 lower polymer Or acrylic acid with the ~&me amount of methyl methacrylate. A piece of gran,ite stone called "Mannari-ishi" produced in the Chyugo~u District, Japan of 30 cm by 90 cm by 120 cm was put into a polymerization vessel which was .~ealed and air-evacuated by means of a vacuum purnp. Into said ves~el was fed said filling-up agent and filled nitrGgen gas so as to be ~ept at 5 Kk;r/cm2 by gauge pres~ure for ~ hour~ for impregnatini; the st,one piece with ~aid lig,uid agent. The lia,uid agerlt was tnen excluded ~nd the stone piece impregnated with the liouid a~ent was heated in inert atmo~phere at a temperature of 85C for 6 hour~i for completing copol,ymerizatiorl.
When the stone surrace was sli~htl~J .-Jround ara poli3hed, the characteristic pattern of sald stone wa~s obser-~ed beautiful a~ if wetted.
hxample 6 The marble stone plate as used in ~xample 1 ~la.-, .,oa~e~
in the bath of suspension of l wei~Jht~ Cadmil~.m Yello,J in -,~ater lQ~838~
1 for 1 hour, and then taken out thereo~ to be dried. The stone plate was soaked in the bath of the lacquer dissolved in the thinn~r for 30 mlnutes and taXen out thereof to be dried, which treatment wa~ repeated 4 times.
Thf treated marble plate was tinted in light yellow and crystal grain ?gaps were completely filled up with the lacf~uer so that the stone c2urface was lustrous and beautiful no less better than the naturally 50 colored marble.
~x~mple 7 The marble plate a~ use~ in ~x~mple 1 was soa~ed in the bath o~ 10 gr. Zapon Fa~t Green di?3solved in 1,000 cc. methanol for 1 hour and ta~en out to be dried. l'he 3tone plate was soa~ed in the bath of the lacquer solution in the thinner for 30 minutes which treatment was repeated 3 times.
The treated marble stone was tinted in li~ht green and ?showed beautiful color tone no less better thr~r. the natural green marble.
~xample 8 The stone plate clit a~ in ~xample 1 but not of marble but Or "Pocheon Granite" prodljced in ~orea wasl soa~ed in the bath of 100 ct~r. Ora?2ol ~ed and 30 gr. Orasol ~rown d;s~olved in 1,000 cc. methanol as the color-in~r age..t at the rtjom temper~ture for 30 minutes, arl-~ ta~en out frorrl the bath to be dried, which treatment was repeated 3 times. The yranite stone plate was so&~ed ir~ the bath of nitrocellJlo e disc,olved in methyl acetate as the filling-up aC?~ent at t~.e roor?l temperature for 1 hour and taken out thereof to be dried ~7hitr. treatment was repeated 3 times.
The granite stone treated a~2 a~o-~re was rJo e-_ better thari the red granite called Imperial ~e?~ pro?~ute~ wef3en. il?hte crystal grain C7~aps were -~?el] filled u? ,~ith thC age..t.
5xam~1e '3 lQ~8386 1 The plate Or 3.2 m by 8 m and 5 cm thic~ness of white marble produced in Formosa was ~round and polished at one ~ide thereo~. It was ;ntended to form a mural painting of "A~afuji" or "~ed Mount Fuji" by Ukiyoe Artist, Hokusai on said marble plate. With covering the mountain portion of the marble plate by means of a plastic material sheet, the solution of Ora~ol Blue in ~ethanol was applied by 3praying for coloring the s~y portion. The solution of Orasol Red in the solvent was similarly applied for coloring the mountain portion and then the ~olution of Orasol Green was applied at the left lower portion on the marble plate. The marble plate was then impreg-nated with the solution of the lacquer in methyl acetate for filling-up the crystal grain gaps and driecl. The color tone was not ~o gaudy but placid. Owing to that the coloring agent was carried by the filling-up agent in e~ery crystal grain gap~, the colors are to be durable for a long time.
-- . C
Claims (4)
1. A method for producing a durably colored stone slab which comprises the steps of dipping a raw material stone slab having crystal grains therein and consequently gaps existing in and interconnecting with the outer surface of said stone slab in a a solution of coloring agent in a monomer or a lower polymer having polymerization degree of less than 30% and being selected from at least one member of the group consisting of styrene methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate,?-methylcyanoacrylate and d-ethylcyanoacrylate, repeating said dipping runs with drying period after each dipping run, and heating the resulting stone slab, whereby the monomer or lower polymer is polymerized or copolymerized to cause solidi-fication thereof together with said coloring agent within the crystal grain gaps.
2. A method as claimed in Claim 1, wherein said monomer or lower polymer further contains a polymerization initiator.
3. A method as claimed in Claim 1, wherein the dipping is conducted under pressure,
4. A method as claimed in Claim 1, wherein the dipping is carried out by soaking,
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5300376A JPS52135882A (en) | 1976-05-10 | 1976-05-10 | Surfaceetreated stone material |
| JP53003/76 | 1976-05-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1098386A true CA1098386A (en) | 1981-03-31 |
Family
ID=12930731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA257,956A Expired CA1098386A (en) | 1976-05-10 | 1976-07-28 | Stone surface treatment |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS52135882A (en) |
| BR (1) | BR7605686A (en) |
| CA (1) | CA1098386A (en) |
| DE (1) | DE2639752C3 (en) |
| IN (1) | IN145705B (en) |
| IT (1) | IT1065079B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5449727A (en) * | 1983-07-02 | 1995-09-12 | Rohm Gmbh | Acrylate resins as binders for color concentrates |
| WO1997024234A1 (en) * | 1995-12-29 | 1997-07-10 | Eduardo Huarte Erro | Process for coating alabaster plates for ornamental purposes |
| CN102515839A (en) * | 2011-12-12 | 2012-06-27 | 杭州市园林绿化工程有限公司 | Antique finish method of stone |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54155217A (en) * | 1978-05-30 | 1979-12-07 | Sumitomo Cement Co | Coloring lime stone based natural stones |
| EP0053874B1 (en) * | 1980-12-06 | 1985-07-10 | Cole Polymers Limited | Preservation of structures |
| JPH02275787A (en) * | 1989-04-17 | 1990-11-09 | Inax Corp | Production of colored ceramic product |
| DE4035406A1 (en) * | 1990-11-07 | 1992-05-14 | Schmid Rene P | METHOD FOR PROTECTING POROESIC CONSTRUCTION MATERIALS AGAINST DEALING AGENTS |
| DE4041607C2 (en) * | 1990-12-22 | 1994-02-17 | Florenz Cotto Ton Handels Gmbh | Process for the protective treatment of a floor covering |
| IT1293153B1 (en) * | 1997-02-04 | 1999-02-12 | Dario Toncelli | PROCEDURE FOR THE RECOVERY OF CRACKED SHEETS. |
| DE202007007508U1 (en) * | 2007-03-22 | 2007-10-04 | Dronia, Damian | CARPETS |
| DE102009006342A1 (en) * | 2009-01-27 | 2010-07-29 | Hoyer, Manfred | Colored stones, preferably natural stones, lacquered with a water-based lacquer having a ground base made of aqueous dispersion based on acrylates, in which a desired pigmentation is brought, useful for food packaging and children's toys |
-
1976
- 1976-05-10 JP JP5300376A patent/JPS52135882A/en active Pending
- 1976-07-27 IN IN1340/CAL/76A patent/IN145705B/en unknown
- 1976-07-28 CA CA257,956A patent/CA1098386A/en not_active Expired
- 1976-08-03 IT IT25952/76A patent/IT1065079B/en active
- 1976-08-30 BR BR7605686A patent/BR7605686A/en unknown
- 1976-09-03 DE DE2639752A patent/DE2639752C3/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5449727A (en) * | 1983-07-02 | 1995-09-12 | Rohm Gmbh | Acrylate resins as binders for color concentrates |
| WO1997024234A1 (en) * | 1995-12-29 | 1997-07-10 | Eduardo Huarte Erro | Process for coating alabaster plates for ornamental purposes |
| ES2102331A1 (en) * | 1995-12-29 | 1997-07-16 | Erro Eduardo Huarte | Process for coating alabaster plates for ornamental purposes |
| CN102515839A (en) * | 2011-12-12 | 2012-06-27 | 杭州市园林绿化工程有限公司 | Antique finish method of stone |
Also Published As
| Publication number | Publication date |
|---|---|
| IT1065079B (en) | 1985-02-25 |
| BR7605686A (en) | 1978-03-28 |
| JPS52135882A (en) | 1977-11-14 |
| DE2639752C3 (en) | 1979-10-11 |
| DE2639752A1 (en) | 1977-11-17 |
| DE2639752B2 (en) | 1979-02-15 |
| IN145705B (en) | 1985-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1098386A (en) | Stone surface treatment | |
| CA1128227A (en) | Ceramic coated quartz particles | |
| EP1546064B1 (en) | Method for the decoration of porous ceramic materials and in particular polished porcelain stoneware | |
| KR100854488B1 (en) | Thermal insulation for building structure of construction method and the structure | |
| CA2181622A1 (en) | Method for producing efflorescence resistant coating on cementitious substrate | |
| JP7428749B2 (en) | Method of forming decorative coating surface | |
| Sabatini et al. | Stearyl methacrylate co-polymers: Towards new polymer coatings for mortars protection | |
| CN108624126B (en) | Bi-component silk-screen glass printing ink and preparation and use methods thereof | |
| CN102092229B (en) | Manufacturing process of clay ornaments | |
| CN111620563A (en) | Preparation method of high-gray black ink-jet ceramic tile and preparation method of modified glaze slip | |
| US6268410B1 (en) | Colored concrete roofing tiles and a method for producing colored concrete bodies such as colored concrete roofing tiles | |
| RU2749259C2 (en) | Light-coloured fiber-cement items and methods of manufacture thereof | |
| US3949044A (en) | Process for forming decorated sheets of acrylic resin | |
| US4452604A (en) | Decorative sheets and coverings comprising polyvinyl chloride and cationic dyestuffs | |
| Bera et al. | Recent developments in synthetic marble processing | |
| Alessandrini et al. | Partially fluorinated acrylic copolymers as coatings for calcareous stone materials | |
| JPS5896664A (en) | Covering composition for forming natural stone pattern | |
| JP2893044B2 (en) | Multiple coating materials and coatings obtained using them | |
| RU2765443C1 (en) | Decorative coating imitating natural stone, and method for production thereof | |
| RU2745624C1 (en) | Painting method using glaze painting material composition with bz-effect | |
| JP2932767B2 (en) | Coating method for ceramic products | |
| CN116656169A (en) | Method for preparing novel powder pigment | |
| GB1593043A (en) | Cast article containing ceramic coated quartz particles | |
| CN113666696A (en) | Colored pervious concrete and preparation method thereof | |
| CN115091886A (en) | Building water purple pottery colored mud pile-carving process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |