CN1337426A - Painting material containing colouring resin sheet, water paint composition containing resin sheet, and painting material for forming colourful grains - Google Patents
Painting material containing colouring resin sheet, water paint composition containing resin sheet, and painting material for forming colourful grains Download PDFInfo
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- CN1337426A CN1337426A CN 01104549 CN01104549A CN1337426A CN 1337426 A CN1337426 A CN 1337426A CN 01104549 CN01104549 CN 01104549 CN 01104549 A CN01104549 A CN 01104549A CN 1337426 A CN1337426 A CN 1337426A
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Abstract
Provided is painting material which has excellent performances such as light in weight, operationality, drying ability and has a colouring pattern similar to natural stone. The painting material comprises a colouring resin sheet which containing particles with a prescribed maxthickness, maxlength, and particle flat rate. Also disclosed is an aqueous painting composition has a quickly drying ability even containing a colouring resin sheet, a flexible sheet shaped surface decoration material containing flat colouring resin sheet and is not turnup even the sheet is deformed.
Description
The present invention relates to a kind of water-based paint compositions, multicolour pattern that contains the coating material of pigmentary resin thin slice, resinous thin slice forms with coating material and flexible sheet surface decoration material.
Recently, the needs to the coating material of painted aggregates such as the fragment that contains glass and ceramic ware etc. or natural stone particle enlarge.By these coating materials of application, can show the coarse grain decorative pattern that exactly likes very much in for example being called as the natural stone of " light andesite " or " grouan " in Japan attractive in appearancely.
In addition, these coating materials are under the occasion of water-based paint compositions, compare with the oil paint composition, and it is dangerous and to the detrimentally affect of environment to reduce fire etc.Further, these coating materials are coated with install on the flexible substrate and constitute flexible sheet surface decoration material, the curved wall (for example periphery) that is suitable for most at buildings is gone up the occasion of construction, even the occasion of constructing on the smooth wall of buildings also can tolerate wall distortion or bending that the long-time back of earthquake and process forms.
But, because the ratio of painted aggregates such as glass fragment, ceramic ware fragment, natural stone particle is great, if use for example above big particles of aggregates of diameter 5mm, the sedimentation in coating material of then painted aggregate, be difficult to blending equably, and coating material itself also becomes very heavy, therefore is unsuitable for forming thick coating layer.Consider from this reason,, then can not show the big coarse grain decorative pattern of natural stone if only use the particles of aggregates of minor diameter.Further, the flat blocky-shaped particle of the general right and wrong of these painted aggregates, so under the thin occasion of coating material layer, therefore surperficial outstanding from this coating material layer, be difficult to entirely form the surface of coating material layer.
But,, consider that from the proportion of resin flat pattern little and thin slice there do not have to be as described above unfavorable if use the resin flake of painted flat pattern to replace painted aggregate as described above.Therefore, even for example in very thin coating material layer, also can use the width of major diameter part to reach the resin flake of 70mm, can show the big coarse grain decorative pattern of natural stone.
On the other hand, the coating material that contains this flats resin flake is under the occasion of water-based paint compositions, produces new problem shown in Figure 1.That is, when on coated base 1, being coated with water-based paint compositions 2, evaporate from the coating material laminar surface in order to make water molecules 3 as dispersion medium, shown in dotted line such, must get around most flats resin flakes 4 and mobile very long distance.Therefore, originally be exactly in the easy water-based paint compositions that postpones of application after drying, dry further delay.
Secondly, make and contain in the coating material when forming decorative pattern with the flats resin flake of several colour colorings, resin flake exactly likes the multicolour pattern that has the concavo-convex coarse grain decorative pattern of natural stone for having concavo-convex flat pattern at surface and inner face, can forming.In addition, equitant part forms factitious being uneven between the resin flake, is not preferred, therefore wishes to find the countermeasure of this problem.
Further, if will contain the coating material of flats resin flake is coated with to install on the flexible strip shape substrate and forms flexible sheet surface decoration material, when the deflection of then flexible sheet surface decoration material generation expection and distortion, at the pack portion of resin flake, sometimes crackle can partly take place or peel off in the coating material layer.Its reason and softish coating material layer follow that the distortion of plate shape substrates is irrelevant, and this is because the pigmentary resin thin slice is the hardened resin material, can not be along with distortion, and owing to be flat pattern, stick up from the coating material layer.
In order to solve above-mentioned problem, the formation of the 1st invention of the present invention (invention of record in the claim 1) is a kind of coating material that contains the pigmentary resin thin slice, it is a kind of coating material that contains the pigmentary resin thin slice of several colors with flexibility, the thickness X of above-mentioned pigmentary resin thin slice is 0.2～7mm, the width Y of major diameter part is 2～70mm, and particle flat ratio Y ÷ X is more than 4.
In order to solve above-mentioned problem, the formation of the 2nd invention of the present invention (invention of record in the claim 2) is a kind of water-based paint compositions that contains resin flake, it be a kind of contain have flexibility, non-coloring or with the water-based paint compositions of the resin flake of several colour colorings, the thickness X of above-mentioned resin flake is 0.2～7mm, the width Y of major diameter part is 2～70mm, particle flat ratio Y ÷ X is more than 4, and contains following A～C or A～D component in the above-mentioned water-based paint compositions.
A. anionic property synthetic resin emulsion
B. contain the amine functional group polymer of monomers with the monomer constituent ratio more than the prescribed value
C. above-mentioned amine functional group is remained the volatile alkali of the q.s of nonionic state
D. use above-mentioned volatile alkali neutral anionic property pigment dispersing agent and pigment
In order to solve above-mentioned problem, the formation of the 3rd invention of the present invention (invention of record in the claim 3) is a kind of multicolour pattern formation coating material, it be a kind of by several colors with flexibility the pigmentary resin thin slice and when dry or when curing be roughly the mixing multicolour pattern that forms of water white jointing material and form and use coating material, the thickness X of above-mentioned pigmentary resin thin slice is 0.2～7mm, the width Y of major diameter part is 2～70mm, particle flat ratio Y ÷ X is more than 4, and the shape of each thin slice is random, thin and thick is irregular, and has the periphery of outside edge thinning.
In order to solve above-mentioned problem, the formation of the 4th invention of the present invention (invention of record in the claim 4) is a kind of flexible sheet surface decoration material, it possesses the coating material layer that shows any decorative pattern that has the flexible plate shape substrates and form on this plate shape substrates, meet the condition of following (1)～(3).
(1) contain at least in the above-mentioned coating material layer tackiness agent with resin and this tackiness agent with that sneak in the resin and the flats pigmentary resin thin slice relevant with showing above-mentioned decorative pattern;
(2) above-mentioned tackiness agent is with in the resin, and selection can be followed the resin material according to the flexibility material of the predefined flexible deformation's amount of the purposes of above-mentioned flexible sheet surface decoration material;
(3) to select thickness X be 0.2～7mm for above-mentioned pigmentary resin thin slice, and the width Y of major diameter part is 2～70mm, and particle flat ratio Y ÷ X is more than 4, and material is than above-mentioned coating material layer softish resin material more.
The coating material that contains the pigmentary resin thin slice of the 1st invention owing to contain the pigmentary resin thin slice of several colors, can show the coarse grain decorative pattern of similar " light andesite " or natural stones such as " grouan " attractive in appearancely.
And, because the proportion of pigmentary resin thin slice is little, therefore not sedimentation in coating material, blending equably easily because coating material itself is not overweight, therefore forms thick coating layer easily.Because the thickness X of pigmentary resin thin slice is 0.2～7mm, the width Y of major diameter part is 2～70mm, can show the big coarse grain decorative pattern or the little coarse grain decorative pattern of natural stone with admixture freely.In addition, because the pigmentary resin thin slice has particle flat ratio Y ÷ X at the big flat ratio more than 4, even in very thin coating material layer, also can be arranged in parallel in the coating material layer, and can be not outstanding from the surface, can entirely form the surface of coating material layer.
The water-based paint compositions that contains resin flake of the 2nd invention contains non-coloring or with the flat-section resin flake of several colour colorings, but owing to contain the moiety of above-mentioned A～C or A～D, has following effect and effect.
That is, volatile alkali C is encapsulant (blocker), water-based paint compositions enclosed container during can not volatilize, the pH value of water-based paint compositions is remained on to a certain degree above (for example more than the pH5 or more than the pH7).Therefore, the amine functional group in the polymer B is retained as nonionic state (closed state), can not combine with the anionic property synthetic resins of latex A.
But in a single day water-based paint compositions is coated arbitrarily on the base material, then volatile alkali C volatilization, and the pH value reduction of water-based paint compositions, the closed state of the amine functional group in the polymer B is disengaged.Its result, polymer B combines in whole coating material layer with the anionic property synthetic resins of latex A, tightens the coating material layer powerfully.Its result even contain the resin flake of many flats in the coating material layer, also can be forced to and promptly be expressed into the outside of coating material layer as the water of solvent.
Should illustrate that because the suitable tensio-active agent that is used as pigment dispersing agent is metal-salts such as sodium salt, sylvite, the pH value that has therefore hindered above-mentioned water-based paint compositions reduces.But, if use in the 2nd invention with volatile alkali neutral anionic property pigment dispersing agent, then the alkali of pigment dispersing agent itself also volatilizees, and impels the pH value reduction of water-based paint compositions, therefore, can further improve the rapid-drying properties of water-based paint compositions.
The multicolour pattern of the 3rd invention forms with in the coating material, because the pigmentary resin thin slice of several colors is erose, and thin and thick is irregular, can form the concavo-convex multicolour pattern that has that exactly likes natural stone coarse grain decorative pattern.In addition, because these pigmentary resin thin slices have the periphery of outside edge thinning, equitant part can not form factitious being uneven between the resin flake.
In the flexible sheet surface decoration material of the 4th invention, with in the resin, cooperate material at the tackiness agent that can follow the predefined flexible deformation's amount of purposes according to flexible sheet surface decoration material than the coating material layer flats pigmentary resin thin slice that constitutes of the resin material of softish more with flexibility.Therefore, when the deflection of flexible sheet surface decoration material generation expection and distortion, the pigmentary resin thin slice also will flexibly be out of shape than coating material layer, therefore, the pigmentary resin thin slice can not take place to stick up from the coating material layer, or the pack portion that causes thus at resin flake, the phenomenon that coating material layer segment ground crackle occurs and peels off.
In addition, because the particle flat ratio Y ÷ X of pigmentary resin thin slice is the big flat ratio more than 4, from this point, deflection and distortion take place easily also, it is above-mentioned unfavorable to be difficult to further to cause.
Below the relevant coating material that contains the pigmentary resin thin slice, the water-based paint compositions of resinous thin slice, multicolour pattern forms the embodiment with coating and flexible sheet surface decoration material in explanation the 1st invention of the present invention～the 4 invention.Resin flake
The resin flake that uses in the 1st invention～the 4 invention, for non-coloring or with the resin flake of several colour colorings, thickness X is 0.2～7mm, the width Y of major diameter part is 2～70mm, particle flat ratio Y ÷ X is more than 4.More preferably, thickness X is 0.2～0.5mm, and the width Y of major diameter part is 5～30mm, and particle flat ratio Y ÷ X is more than 10.
Above-mentioned " thickness X " is that part of thickness the thickest in the flats resin flake.Above-mentioned " major diameter width Y partly " is the longest that part of length that passes through in the flats resin flake.Color kind under the occasion of use pigmentary resin thin slice can at random be selected according to application target, without any qualification.
The kind of the resin of formation resin flake is also unqualified, but preferred general soft material, the more preferably material of excellent propertys such as weathering resistance, water tolerance, alkali resistance, cold-resistant flexible.For example preferably can enumerate resins such as acrylic acid series, chloroprene-based, ethylene-acrylic acid copolymerization system, vinylformic acid-butadiene-based, flexibel polyurethane system, soft silicone resin system.
In the 4th invention, the resin that constitutes resin flake is preferably than coating material layer softish material more, can select according to for example following the 1st～the 5th benchmark.
The 1st benchmark: make test film of above-mentioned coating material layer with certain width, length and thickness.In addition, make same test film with the resin material that constitutes above-mentioned pigmentary resin thin slice.With these test horses between two fulcrums that are provided with keeping at a certain distance away, will have manometric polishing head ride on two middle positions between fulcrum to test film from the top contact, pressurize.Loading value when then, mensuration is pressurizeed the deflection that makes test film generation certain amplitude.The mensuration loading value of test film that uses the coating material layer is during as a, as long as the mensuration loading value of test film that uses the resin material that constitutes the pigmentary resin thin slice is below 0.9a.
The 2nd benchmark: as long as the tackiness agent resin is acrylic resin, the pigmentary resin thin slice of comparison hard is more soft acrylic resin.Can enumerate as object lesson, the tackiness agent resin is that vinylformic acid styrene resin, pigmentary resin thin slice are the occasion of ethyl propenoate resin.
The 3rd benchmark: as long as the tackiness agent resin is that the higher acrylic resin of second-order transition temperature, pigmentary resin thin slice are the lower acrylic resin of second-order transition temperature.Can enumerate as object lesson, it is the occasion of same combination that tackiness agent is used resin and pigmentary resin thin slice and above-mentioned " the 2nd benchmark ", and also having the tackiness agent resin is that acrylonitrile resin, pigmentary resin thin slice are the occasion of butyl acrylate resin.
The 4th benchmark: if the tackiness agent resin for to contain a large amount of comparison hard be monomeric acrylic resin, pigmentary resin thin slice for contain a large amount of more soft be monomeric acrylic resin.Can enumerate as object lesson, tackiness agent is the occasion of 2 kind combinations identical with the occasion of above-mentioned " the 3rd benchmark " with resin and pigmentary resin thin slice.
The 5th benchmark: as long as the tackiness agent resin is that styrene resin, pigmentary resin thin slice are vinyl acetate resin.
Resin flake can only be made of resin material as described above, also can cooperate natural aggregate such as limestone, silicon sand, mica with the amount of the sort of degree of obstruction resin flake flexibility within reason and make various additives such as the pigment of its painted various artificial aggregates and various colors and defoamer, frostproofer, sanitas with coating lining natural aggregate.
The shape of resin flake as long as width Y, the particle flat ratio Y ÷ X of its thickness X, major diameter part satisfy above-mentioned condition, just can be a shape arbitrarily.For example, planeform is circular, square, various elongated shape or random chip shape, also can be that surface and inner face are smooth fine sheet.But, in the 3rd invention, make being shaped as of each thin slice random and thin and thick is irregular and have the shape of the periphery of outside edge thinning.The formation method of resin flake
There is no particular limitation for the formation method of non-coloring resin flake or pigmentary resin thin slice, can adopt known any means.For example can will with the state forming that contains or do not contain aggregate be thickness non-coloring or the painted fine fragmentation of resin film slightly uniformly.
Especially, the formation method as the 3rd pigmentary resin thin slice of inventing preferably can adopt following method.That is, the painted composition material that resin flake is formed usefulness is adjusted into high viscosity when wanting to form average thick resin flake, be adjusted into low viscosity when wanting to form on average thin resin flake.Then, the tabular surface of demoulding processing is passed through on the surface or have little concavo-convex surface, use the suitable nozzle diameter and the spray gun of form, spray above-mentioned painted composition material, so that its formation is independently granular as being coated panel.Then, make the painted composition material dry solidification of spraying after, strip down recovery from being coated panel, the thin slice classification that breaks away from predetermined size is removed.When wanting to form the pigmentary resin thin slice of several colors, the pigmentary resin thin slice that every kind of color can be carried out the various colors of above operation and recovery respectively mixes use.The coating material of the 1st invention, the 3rd invention and the 4th invention
The kind that contains the coating material of resin flake, unqualified for the 1st invention, the 3rd invention and the 4th invention, can be the water-based coating material, also can be the oiliness coating material.As the type of coating material, do not comprise emulsion-type, solution-type, reaction-curable, no-solvent type etc. with limiting.As the tackiness agent (jointing material) of these coating materials, the emulsion-type jointing material can be enumerated for example acrylic resin, the styrene copolymerized system of vinylformic acid, vinyl acetate between to for plastic copolymerization system, various synthetic rubber latex, urethane resin system, epoxy resin.Also can use urethane resin, Resins, epoxy, silicone resin of solvent-free system etc.
Can at random contain the various gradation compositions beyond above-mentioned in these coating materials, the pigment of for example natural or artificial aggregate, various colors, defoamer, frostproofer, sanitas etc.The water-based paint compositions of the 2nd invention
Anionic property synthetic resin emulsion A must make anionic property stable.Anionic property synthetic resins is the insoluble polymer that can adopt polymerization technique commonly used such as for example letex polymerization to make, but also can use the polymkeric substance of the such complicated form of core-shell particle.
As the general method that in the anionic property synthetic resin emulsion, obtains anionic property, can enumerate the method for for example when letex polymerization, utilizing the anionic surfactant, also can in emulsion, add this tensio-active agent after the polymerization.Nonionic surfactant also can or be present in the synthetic resin emulsion after the polymerization in the polymerization of the synthetic resin emulsion that anionic property has been stabilized.
As tensio-active agent, can use the tensio-active agent of any suitable, but, can enumerate salt, sulfosuccinate, senior alkyl sulfosuccinate of the carboxylic acid polyalcohol of condensation product, wetting ability-lipophilicity proper equilibrium of cycloalkanes sulfonic acid and lower molecular weight formaldehyde and senior alkyl-sulphate such as multipolymer, Sodium Lauryl Sulphate BP/USP, alkylaryl sulfonate, isopropyl benzene sulfonic acid etc. etc. as useful especially tensio-active agent.
As the other types of anionic property synthetic resin emulsion, also have as the emulsion that makes the result's acquisition that contains a small amount of acidic-group (toxilic acid, vinyl sulfonic acid, Ba Dousuan, vinylformic acid etc.) in the polymkeric substance.Acidic-group can be an alkali metal salts or ammonium salt.Another kind of type as the anionic property synthetic resin emulsion contains the alkaline monomeric latex polymer that acrylamide, Methacrylamide etc. are neutralized in addition.
The anionic property synthetic resin emulsion can adopt known any means to make.When making, can use polymkeric substance or the multipolymer for example made: the vinyl acetate of methyl acrylate, ethyl propenoate, butyl acrylate, ethyl acrylate, decyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, branched chain fatty acid (バ-サ テ ィ ッ Network acid) etc., vinylchlorid, vinylidene chloride, vinyl cyanide, methacrylic acid, chloroprene etc. by following monomer class.
The Tg of anionic property synthetic resin emulsion is preferably 0 ℃～70 ℃ scope.Water-based paint compositions of the present invention comprises by containing more than the certain value, being specially the water-soluble or aqueous dispersion polymers that the monomer mixture that contains 20 weight % amine functional groups at least forms.
Contain first type of amine functional group polymer of monomers B, be aminoalkyl vinyl ether or identical thioether, wherein, alkyl can be a straight chain type, can be branched chain type also, has 2～3 carbon atoms, nitrogen can be uncle's nitrogen, secondary nitrogen, uncle's nitrogen any.As specific examples, can enumerate β-aminoethyl vinyl ether, β-aminoethyl vinyl thioether, N-monomethyl-β-aminoethyl vinyl ether, N-monomethyl-β-aminoethyl vinyl thioether, N-monomethyl-3-aminopropyl vinyl ether, N-monomethyl-3-aminopropyl vinyl thioether etc.
Contain second type of amine functional group polymer of monomers B, be acrylamide or acrylate, for example, dimethylaminoethyl acrylate, dimethylaminoethyl (methacrylic ester), β-aminoethyl acrylate, β-aminoethyl (methacrylic ester), N-β-aminoethyl acrylamide, N-β-aminoethyl (Methacrylamide), N-(monomethyl aminoethyl)-acrylamide, N-(monomethyl aminoethyl)-Methacrylamide etc.
The third type that contains amine functional group polymer of monomers B, be N-acryloxyalkyl-oxazolidines, N-acryloxyalkyl tetrahydrochysene-1, the substituent that 3-oxazine, Zhe Xie oxazolidine He the alkyl bond in the oxazine are replaced by alkoxyalkyl and poly-(alkoxyalkyl) etc.
Contain the 4th type of amine functional group polymer of monomers B, for containing the polymkeric substance that becomes the monomer (for example acryloxy-ketoimine, acryloxy-aldimine) of amine to constitute by facile hydrolysis.As its example, can enumerate 2-[4-(2, the inferior heptyl of 6-dimethyl)-amino]-ethyl (methacrylic ester), 3-[2-(the inferior heptyl of 4-methyl)-amino]-propyl group (methacrylic ester), β-(benzylidene amino)-ethyl (methacrylic ester), 12-(cyclopentylidene-amino)-dodecyl (methacrylic ester), N-(1,3-dimethyl butylidene)-2-(2-methacryloxy oxyethyl group)-ethamine etc.
Above-mentioned any that contains at least 20 weight % contains the monomeric amine-containing polymer of amine functional group, exists with ... desired specific polymkeric substance, can adopt solution polymerization to obtain in neutrality, alkalescence or tart aqueous medium.This polymerization generally is to carry out in the aqueous medium that contains a small amount of organic acid or mineral acid.
The type of volatile alkali C and consumption, must be when the amine functional group of amine-containing polymer reaches nonionic, the pH value of water-based paint compositions of the present invention risen to be generally pH5, more preferably be pH7～9, with avoid fully with composition in the negatively charged ion synthetic resin emulsion or other anionic property interaction between component that have been stabilized.As concrete example, can use ammonia, morpholine, alkylamine, 2-dimethylaminoethanol, N-methylmorpholine, quadrol or their mixture.The equivalence ratio of the acid in amine and the synthetic resin emulsion is preferably amine/acid=0.5～1.0.
Anionic property pigment dispersing agent D, promptly anionic surfactant's content so long as be enough to make the amount of colo(u)rant dispersion to get final product, is generally 0.2～1.0 weight % of pigment.Common can hinder the pH of the water-based paint compositions after the application to reduce with neutral tensio-active agents such as sodium and potassium, protonated the beginning of amine functional group postponed, its result makes dry the delay, so is not preferred.As with volatile alkali neutral anionic surfactant, can enumerate trade(brand)name " オ ロ Application 901 (Rhom﹠amp; Hass company produces) " and trade(brand)name " Port イ ズ 532A (Hua Wangshe system) ".
In addition, water-based paint compositions of the present invention preferably contains the nonionic surfactant of the higher fatty acid amides condensation system of 0.5～3.0 weight %.It plays a part wetting agent, can improve the storage stability of water-borne coatings and make stability.
As pigment, can be separately or arbitrary combination ground for example use titanium dioxide, lime carbonate, clay as white pigment; As the ferric oxide of tinting pigment and various organic system pigment etc.The pigment volume concentration (PVC) of water-based paint compositions of the present invention (PVC) is preferably below 30%, and total solid concentration is preferably 40～80 weight %.PVC more preferably 10～25%, and total solid concentration is 50～65 weight % more preferably.Pigment is the occasion of titanium dioxide, and with lime carbonate and time spent, rapid-drying properties is good during than independent use titanium dioxide.The preferred blending ratio of the two is titanium dioxide: lime carbonate=95: 7～70: 30.
The water-based paint compositions of the 2nd invention can at random contain the various gradation compositions beyond above-mentioned, the pigment of for example natural or artificial aggregate, various colors, defoamer, frostproofer, sanitas etc.
Embodiment 1
Present embodiment is and the 1st invention and the relevant embodiment of the 2nd invention.As can satisfy and relevant above-mentioned A, the B of the 2nd invention, the composition of each composition of C, use contain 50 weight % as the acrylate copolymer of A composition, 2 weight % as B composition De Ju oxazolidinyl ethyl (methacrylic acid) ester, 2 weight % composition as the ammonia of C composition.In addition, as composition, use above-mentioned Port イ ズ 532A (containing the poly-carbonic acid of 40 weight % is tensio-active agent) with respect to above-mentioned D composition.
As solid composition, use resin flake a, resin flake b, these three kinds of solid substances of plastic flakes.Resin flake a and resin flake b all with the coating that contains 32 weight % acrylic acid series synthetic resin emulsions, 40 weight % natural aggregates, 10 weight % artificial aggregates, 10 weight % pigment extenders, 3 weight % additives and 5 weight % water as raw material, following steps for manufacturing forms.
At first,, above-mentioned coating is added in the spray gun of nozzle diameter 6mm, air nozzle bore 1.5mm, facing to the smooth coated plate of coating releasing agent, with 3.5kgf/m for resin flake a
2Spray pressure, adopt the method for grit blast application to carry out spray-coating.This painting object after the forced drying, is peeled off from coated plate in 50 ℃ thermostatic chamber, obtain resin flake a.The form of resin flake a is indefinite form, random size, has the periphery of outside edge thinning, even in 1, per 1 middle thin and thick is also inhomogeneous, and maximum ga(u)ge is about 1.2mm, and major diameter is about 15mm.
Secondly, for resin flake b, adopt the similar technology of occasion with above-mentioned resin flake a, but after above-mentioned grit blast application, before forced drying, additional such operation:, make the homogeneous film thickness about grit blast shape painting object formation 0.5mm with having the plastics roller applying light application face of coating with thinner.After the forced drying, peel off, obtain resin flake b from coated plate.The form of resin flake b is indefinite form, random size, and thin and thick is roughly even, and maximum ga(u)ge is about 1.0mm, and major diameter is about 15mm.
For plastic flakes, be the fragment that the polyvinyl resin film of 0.6mm cuts into indefinite form and the random size in following ranges with thickness, modulation.The form of plastic flakes is indefinite form, random size, and thin and thick is roughly even, and maximum ga(u)ge is about 1.0mm, and major diameter is about 15mm, is translucent polyvinyl resin film fragments.
Table 1 illustrates embodiment 1-1～embodiment 1-4 relevant with present embodiment and the coating prescription of comparative example 1-1～comparative example 1-4.In the table 1, " M4000 " is the tackifier of chemical industry society of SHIN-ETSU HANTOTAI system, " M75 " is the natural lubricant of same and カ Le Off ア イ Application society system for the trade(brand)name モ PVC ニ-Le M75 (synthetic resin emulsion that does not contain polyfunctional amine) of the synthetic society of ヘ キ ス ト system, " KD-1 ".In each example, make the total weight % of natural aggregate and resin flake a, resin flake b or plastic flakes consistent.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| ?E-2706 | ??25 | ??25 | ????25 | ?????25 | ???25 | ??- | ???- | ??25 |
| ?M75 | ??- | ???- | ???- | ?????- | ???- | ??25 | ??25 | ??- |
| デヒドラン1620 | ??0.2 | ??0.2 | ???0.2 | ????0.2 | ???0.2 | ??0.2 | ??0.2 | ??0.2 |
| テキサ-ル | ??2.8 | ??2.8 | ???2.8 | ????2.8 | ???2.8 | ??2.8 | ??2.8 | ??2.8 |
| ポイズ532A | ??- | ???- | ???- | ????0.2 | ???- | ??- | ???- | ??0.2 |
| Resin flake (a) | ??- | ???30 | ???- | ?????- | ???- | ??- | ???- | ??- |
| Resin flake (b) | ??- | ???- | ???30 | ????30 | ???- | ??30 | ???- | ??- |
| Plastic flakes | ??30 | ???- | ???- | ?????- | ???- | ??- | ???- | ??- |
| ?KD-1 | ??30 | ???30 | ???30 | ????30 | ??60 | ??30 | ???60 | ??60 |
| Water | ??11 | ???11 | ???11 | ????11 | ??11 | ??11 | ???11 | ??11 |
| ?M4000 | ??1 | ???1 | ???1 | ????1 | ??1 | ??1 | ???1 | ??1 |
| Add up to | ??100 | ???100 | ???100 | ???100.2 | ??100 | ??100 | ???100 | ??100.2 |
Embodiment 1-1～embodiment the 1-4 of composition and the water-based paint compositions among comparative example 1-1～comparative example 1-4 shown in the above-mentioned table 1 are all constructed by following main points.That is, water-based paint compositions is added in the spray gun of nozzle diameter 12mm, air nozzle bore 1.5mm, with 3.5kgf/m
2Spray pressure, carrying out in advance on the flexible sheet of handling as the protective layer of surface preparation, with 4.0kg/m
2Glue spread carry out spray-coating.
After the spray-coating, be stained with the desired quantity of coating material thinner on pushing with roller, the nappy part of applying light thin slice intactly is placed in the constant temperature and humidity cabinet of 20 ℃ of temperature, humidity 65%, estimates the time of drying of coating.Even be to be dried to the coating that is dried under the condition in above-mentioned constant temperature and humidity cabinet to flood in water 15 minutes this time of drying, the needed time in the time of also unusual degree can taking place in the coating the earliest, represent with hours.It the results are shown in the table 2.
Table 2
| Embodiment 1 | | | | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Time of drying | ????25 | ????22 | ????23 | ????16 | ????12 | ????32 | ????20 | ????10 |
Can find out that from table 1 and table 2 comparative example 1-4 drying is the fastest.This is because comparative example 1-4 has the whole components of above-mentioned A～D, and does not contain flats resin flake or the plastic flakes that constitutes obstruction moisture diffusion major reason.Secondly, be equivalent to from comparative example 1-4, remove the comparative example 1-1 fast drying of D component.Therefore, can be understood as, have the component of A～C, more preferably have the rapidly dry of A～D component, consolidate the dry slow of shape component and contain flats.
On the other hand, with respect to containing the solid shape component of flats but do not contain the comparative example 1-2 of A～D component, the drying of embodiment 1-1～embodiment 1-4 with the solid shape component of flats and A～C or A～D component is fast significantly.And, embodiment 1-1～embodiment 1-4 all 25 hours with interior (roughly in the diel) complete drying, therefore we can say that be significant time of drying in construction.
Also to emphasize following 3 points.The 1st, the result of embodiment 1-4 with A～D component is far short of what is expected unlike comparative example 1-1, comparative example 1-4.The 2nd, to compare with the comparative example 1-3 that does not contain the solid shape component of flat-section, the drying of embodiment 1-1～embodiment 1-4 that contains the solid shape component of flat-section is fast on the contrary.The 3rd, use the embodiment 1-2 of resin flake a and embodiment 1-3 and the embodiment 1-4 that uses resin flake b, when outward appearance is compared in dry back, do not see evident difference.Embodiment 2
Present embodiment is and the 1st invention and the relevant embodiment of the 3rd invention.At first, adopt the above-mentioned manufacture method relevant to form the pigmentary resin thin slice with the 3rd invention.The part by weight of composition material is shown in as follows in the resin flake of all kinds.In every kind of tone of resin flake, thickness difference according to resin flake, be divided into scumble with (maximum ga(u)ge 1.2mm) and thick coating with (maximum ga(u)ge 2mm) two kinds, according to the difference of the major diameter of resin flake, be divided into the standard decorative pattern with (major diameter 15mm), big-pattern with (major diameter 20mm), little decorative pattern with (major diameter 10mm) three kinds.1. the occasion of white feldspathic tone
Acrylic resin latex (solid substance 55%) 32%
Natural aggregate (white, particle diameter 0.05～0.5mm) 40%
Artificial aggregate (white, particle diameter 0.05～0.5mm) 10%
Pigment extender (white, particle diameter is below 0.05) 10%
Water 5%
The occasion that adds up to 100%2. pink feldspathic tones
Acrylic resin latex (solid substance 55%) 32%
Natural aggregate (white, particle diameter 0.05～0.5mm) 40%
Artificial aggregate (white, particle diameter 0.05～0.5mm) 5%
Artificial aggregate (black tea look, particle diameter 0.05～1mm) 10%
Pigment extender (white, particle diameter 0.05mm is following) 5%
Water 5%
The occasion that adds up to 100%3. black tea look feldspathic tones
Acrylic resin latex (solid substance 55%) 32%
Natural aggregate (white, particle diameter 0.05～0.5mm) 20%
Artificial aggregate (tea ash look, particle diameter 0.1～2mm) 5%
Artificial aggregate (black tea look, particle diameter 0.05～1mm) 35%
Water 5%
The occasion that adds up to 100%4. grey quartzose tones
Acrylic resin latex (solid substance 55%) 32%
Natural aggregate (white, particle diameter 0.05～0.5mm) 40%
Natural aggregate (grey, particle diameter 0.1～2mm) 10%
Artificial aggregate (grey, particle diameter 0.1～2mm) 10%
Water 5%
The occasion that adds up to 100%5. tea ash colored stone English mass tones
Acrylic resin latex (solid substance 55%) 32%
Natural aggregate (white, particle diameter 0.05～0.5mm) 35%
Natural aggregate (tea ash look, particle diameter 0.1～2mm) 10%
Artificial aggregate (tea ash look, particle diameter 0.1～2mm) 15%
Water 5%
The occasion that adds up to 100%6. color mineral tones
Acrylic resin latex (solid substance 55%) 32%
Natural aggregate (white, particle diameter 0.05～0.5mm) 30%
Artificial aggregate (tea ash look, particle diameter 0.1～2mm) 5%
Artificial aggregate (black, particle diameter 0.05～1mm is following) 25%
Water 5%
Add up to 100%
Below, select the color more than 3 kinds in the resin flake that is classified aptly, allotment can form the coating material of any grouan decorative pattern in similar white grouan tone, pink grouan tone, the red grouan tone.The part by weight of compounding ingredient is shown in as follows in these coating materials.1. the coating material (standard decorative pattern, desired being coated with about thickness 2mm) of white grouan tone
1) resin flake
White feldspathic (scumble with the about 1.2mm of maximum ga(u)ge,
The standard decorative pattern is with the about 15mm of major diameter) 25%
The grey quartzose (scumble with the about 1.2mm of maximum ga(u)ge,
The standard decorative pattern is with the about 15mm of major diameter) 8%
The black color mineral (scumble with the about 1.2mm of maximum ga(u)ge,
Little decorative pattern is with the about 10mm of major diameter) 7%
2) jointing material (Emulsion acrylic resin, solid substance 50%) 45%
3) white translucent aggregate (the limestone particle of particle diameter 0.05～0.25mm) 15%
The coating material (big-pattern is about desired coating thickness 3.5mm) that adds up to 100%2. pink grouan tones
1) resin flake
The pink feldspathic (thick coating with the about 2mm of maximum ga(u)ge,
Big-pattern is with the about 20mm of major diameter) 8%
White feldspathic (scumble with the about 1.2mm of maximum ga(u)ge,
The standard decorative pattern is with the about 15mm of major diameter) 26%
Tea. the grey quartzose (thick coating with the about 2mm of maximum ga(u)ge,
Big-pattern is with the about 20mm of major diameter) 10%
The black color mineral (scumble with the about 1.2mm of maximum ga(u)ge,
Little decorative pattern is with the about 10mm of major diameter) 4%
2) jointing material (Emulsion acrylic resin, solid substance 50%) 52%
The coating material (the standard decorative pattern is about desired coating thickness 2mm) that adds up to 100%3. red grouan tones
1) resin flake
Black tea look feldspathic (scumble with the about 1.2mm of maximum ga(u)ge,
The standard decorative pattern is with the about 15mm of major diameter) 25%
Tea ash look quartzose (scumble with the about 1.2mm of maximum ga(u)ge,
Little decorative pattern is with the about 10mm of major diameter) 6%
The black color mineral (scumble with the about 1.2mm of maximum ga(u)ge,
The standard decorative pattern is with the about 15mm of major diameter) 9%
2) jointing material (Emulsion acrylic resin, solid substance 50%) 50%
3) white translucent aggregate (the limestone particle of particle diameter 0.05～0.25mm) 10%
Add up to 100% construction example 1
The spray gun of materials used jetting nozzle bore 12mm, jet bore 2mm is to carrying out the concrete decoration wall that quality is adjusted in advance, with the white grouan tone of the ratio spray-coating coating material of per 1 square metre of 3.5kg.Under the undried state of coating material,, make its drying with pushing with behind the roller applying light surface.
Its result can obtain to spray evenly, have filming of mild male and fomale(M﹠F), and it is color patterned that it has having of the normal size that exactly likes very much natural white grouan, and thickness is about 1.5～2.5mm.Construction example 2
The coating material of pink grouan tone is being carried out on the mortar wall that quality adjusts in advance, with the ratio of per 1 square metre of 6kg floating after, make its drying.Its result can obtain level and smooth, coating and film uniformly, and it has exactly like very much the red grouan of natural powder big has color patterned.Further, after this fully curing of filming, coating silicone acrylic copolymer is the solution resin, forms transparent top coat.Its result can make the surface of filming realize beautiful gloss.Construction example 3
With the coating material of red grouan and above-mentioned construction example 1 similarly spray-coating decorate on the wall to concrete, under the undried state of coating material, after pushing usefulness roller applying light surface, make its drying.
Its result can obtain to spray evenly, have filming of mild male and fomale(M﹠F), and it is color patterned that it has having of the normal size that exactly likes very much neutral red grouan.Further, make this film fully solidify after, similarly form transparent top coat with construction example 2, can make the surface of filming realize beautiful gloss.Embodiment 3
Present embodiment is and the 1st invention and the relevant embodiment of the 4th invention.The coating material Production Example
The coating material (suitable is coated with about thickness 3mm) of coating material (suitable is coated with about thickness 2mm) the and Flos Carthami hilllock rock tone of the white grouan tone of the following narration of preparation.
White grouan tone coating material: the Emulsion acrylic resin 45 weight % of softish acrylic resin (solid substance 50%) that will use second-order transition temperature-5 ℃ are as jointing material, to wherein fitting into white translucent aggregate (the limestone particle of particle diameter 0.05～0.25mm) 15 weight %, fit into 3 kinds of resin flakes again.3 kinds of resin flakes are white feldspathic resin flake (about 1.2mm of maximum ga(u)ge, the about 15mm of major diameter) 25 weight %, grey quartzose resin flake (the about 1.2mm of maximum ga(u)ge, the about 15mm of major diameter) 8 weight % and black color mineral matter resin flake (the about 1.2mm of maximum ga(u)ge, the about 10mm of major diameter) 7 weight %.Constitute the resin material of the base material of these resin flakes, be the acrylic resin of second-order transition temperature-25 ℃.
Red grouan tone coating material: the Emulsion acrylic resin 50 weight % of softish acrylic resin (solid substance 50%) that will use second-order transition temperature-5 ℃ are as jointing material, to wherein fitting into white translucent aggregate (the limestone particle of particle diameter 0.05～0.25mm) 10 weight %, fit into 3 kinds of resin flakes again.3 kinds of resin flakes are black tea look feldspathic resin flake (about 1.2mm of maximum ga(u)ge, the about 15mm of major diameter) 25 weight %, tea ash look quartzose resin flake (the about 1.2mm of maximum ga(u)ge, the about 10mm of major diameter) 6 weight % and black color mineral matter resin flake (the about 1.2mm of maximum ga(u)ge, the about 15mm of major diameter) 9 weight %.Constitute the resin material of the base material of these resin flakes, be the acrylic resin of second-order transition temperature-40 ℃.Coating material construction example 1
For the plasticity plate shape substrates, use suitable spray gun, with the above-mentioned white grouan tone coating material of the ratio spray-coating of per 1 square metre of 3.5kg.Then, under the undried state of coating material, behind roller applying light surface, make its drying.
Its result, can obtain spraying evenly, have a concavo-convex sheet surface decoration material, it has, and to exactly like very much having of natural white grouan color patterned, thickness is 1.5～2.5mm.The cylinder plate of the inner face of this sheet material being close to diameter 10mm around, bend to 90 °, do not observe on the outer circumferential side coated surface that resin flake peels off and based on the coated surface crackle that peels off.Coating material construction example 2
For the plasticity plate shape substrates, use suitable spray gun, with the above-mentioned red grouan tone coating material of the ratio spray-coating of per 1 square metre of 3.5kg.Then, under the undried state of coating material, behind roller applying light surface, make its drying.
Its result, can obtain spraying evenly, have a concavo-convex sheet surface decoration material, it has, and to exactly like very much having of neutral red grouan color patterned, thickness is 1.5～2.5mm.After this was filmed and fully solidifies, coating silicone acrylic copolymer system solution resin formed transparent top coat.Its result can make the surface of filming realize beautiful gloss.
The cylinder plate of the inner face of this sheet material being close to diameter 10mm around, bend to 90 °, do not observe on the outer circumferential side coated surface that resin flake peels off and based on the coated surface crackle that peels off.Comparative example 1
Except being that 40 ℃ quite hard acrylic resin is as the constituent material of resin flake with second-order transition temperature, modulate coating material in the same manner with the red grouan tone coating material of embodiment 1, then, similarly the plasticity plate shape substrates is carried out spray-coating with coating material construction example 2, formation is filmed.But, because bumping against on the plate shape substrates, resin flake rebounds, be difficult to attached on the application face, therefore can not form slick filming.Under the undried state of coating material,, can not compress into being coated with the resin flake that sticks up in the rete with roller applying light surface.The cylinder plate of the inner face of this sheet material being close to diameter 10mm around, when bending to 90 °, observe on the outer circumferential side coated surface that resin flake peels off and based on the coated surface crackle that peels off, further observe significant resin flake crackle.Comparative example 2
Except being that 10 ℃ hard slightly acrylic resin is as the constituent material of resin flake with second-order transition temperature, modulate coating material in the same manner with the white grouan tone coating material of embodiment 1, then, similarly the plasticity plate shape substrates is carried out spray-coating with coating material construction example 1, formation is filmed.Resin flake bumps against on the plate shape substrates and rebounds seldom, be attached on the application face, but many resin flakes is to adhere to the state that warps, and therefore can not form slick filming.Under the undried state of coating material,, can not fully compress into being coated with the resin flake that warps in the rete with roller applying light surface.The cylinder plate of the inner face of this sheet material being close to diameter 10mm around, when bending to 90 °, the crackle of observing resin flake is few, but resin flake peels off and a lot of based on the coated surface crackle that peels off.Comparative example 3
Except with second-order transition temperature be-5 ℃ (promptly, identical with second-order transition temperature as the acrylic resin of jointing material solid substance) acrylic resin as beyond the constituent material of resin flake, modulate coating material in the same manner with the white grouan tone coating material of embodiment 1, then, similarly the plasticity plate shape substrates is carried out spray-coating with coating material construction example 1, formation is filmed.Resin flake with roller applying light surface, can form slick application face well attached on the application face.But in the drying process of filming, resin flake sticks up from be coated with rete.In addition, after the drying, the cylinder plate of the inner face of this sheet material being close to diameter 10mm around, when bending to 90 °, do not observe the crackle of resin flake, but observe to a certain extent that resin flake peels off and based on the coated surface crackle that peels off.
The simple declaration of accompanying drawing
Fig. 1 evaporates the explanatory view of delay situation for water molecules in containing the coating material layer of flats particle.Nomenclature
1 coated base
2 water-based paint compositions
3 water moleculess
The resin flake of 4 flat patterns
Claims (4)
1. coating material that contains the pigmentary resin thin slice, it is a kind of coating material that contains the pigmentary resin thin slice of several colors with flexibility, it is characterized in that,
The thickness X of above-mentioned pigmentary resin thin slice is 0.2～7mm, and the width Y of major diameter part is 2～70mm, and particle flat ratio Y ÷ X is more than 4.
2. water-based paint compositions that contains resin flake, it be a kind of contain have flexibility, non-coloring or with the water-based paint compositions of the resin flake of several colour colorings, it is characterized in that,
The thickness X of above-mentioned resin flake is 0.2～7mm, and the width Y of major diameter part is 2～70mm, and particle flat ratio Y ÷ X is more than 4, and contains following A～C or A～D component in the above-mentioned water-based paint compositions,
A. anionic property synthetic resin emulsion
B. contain the amine functional group polymer of monomers with the monomer constituent ratio more than the prescribed value
C. above-mentioned amine functional group is remained the volatile alkali of the q.s of nonionic state
D. use volatile alkali neutral anionic property pigment dispersing agent and pigment.
3. a multicolour pattern forms and use coating material, it be a kind of by several colors with flexibility the pigmentary resin thin slice and be roughly the mixing multicolour pattern that forms of water white jointing material when dry or during curing and form and use coating material, it is characterized in that,
The thickness X of above-mentioned pigmentary resin thin slice is 0.2～7mm, and the width Y of major diameter part is 2～70mm, and particle flat ratio Y ÷ X is more than 4, and the shape of each thin slice is irregular, and thin and thick is irregular, and has the periphery of outside edge thinning.
4. flexible sheet surface decoration material, it possesses the coating material layer that shows any decorative pattern that has the flexible plate shape substrates and form on this plate shape substrates, it is characterized in that, meets the condition of following (1)～(3),
(1) contain at least in the above-mentioned coating material layer tackiness agent with resin and this tackiness agent with that sneak in the resin and the flats pigmentary resin thin slice relevant with showing above-mentioned decorative pattern;
(2) above-mentioned tackiness agent is with in the resin, and selection can be followed the resin material according to the flexibility material of the predefined flexible deformation's amount of the purposes of above-mentioned flexible sheet surface decoration material;
(3) to select thickness X be 0.2～7mm for above-mentioned pigmentary resin thin slice, and the width Y of major diameter part is 2～70mm, and particle flat ratio Y ÷ X is more than 4, and material is than above-mentioned coating material layer softish resin material more.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000240393 | 2000-08-03 | ||
| JP240393/00 | 2000-08-03 |
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| CN1337426A true CN1337426A (en) | 2002-02-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01104549 Pending CN1337426A (en) | 2000-08-03 | 2001-02-15 | Painting material containing colouring resin sheet, water paint composition containing resin sheet, and painting material for forming colourful grains |
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| CN (1) | CN1337426A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105714996A (en) * | 2016-03-07 | 2016-06-29 | 刘新宇 | Ultra-weather resistant building outer wall paint film wall cloth and manufacturing process thereof |
| CN109338595A (en) * | 2013-10-01 | 2019-02-15 | 精工爱普生株式会社 | Sheet producing device and complex |
| CN115636625A (en) * | 2021-07-19 | 2023-01-24 | 青岛海之润涂料制造有限公司 | Method for manufacturing molding material by using liquid granite coating |
| CN115637083A (en) * | 2021-07-19 | 2023-01-24 | 青岛海之润涂料制造有限公司 | Granite coating and preparation method thereof |
-
2001
- 2001-02-15 CN CN 01104549 patent/CN1337426A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109338595A (en) * | 2013-10-01 | 2019-02-15 | 精工爱普生株式会社 | Sheet producing device and complex |
| CN109338595B (en) * | 2013-10-01 | 2021-07-16 | 精工爱普生株式会社 | Sheet manufacturing apparatus and composite |
| CN105714996A (en) * | 2016-03-07 | 2016-06-29 | 刘新宇 | Ultra-weather resistant building outer wall paint film wall cloth and manufacturing process thereof |
| CN105714996B (en) * | 2016-03-07 | 2018-11-02 | 刘新宇 | Super-weathering resistance external wall paint film wall cloth and its manufacture craft |
| CN115636625A (en) * | 2021-07-19 | 2023-01-24 | 青岛海之润涂料制造有限公司 | Method for manufacturing molding material by using liquid granite coating |
| CN115637083A (en) * | 2021-07-19 | 2023-01-24 | 青岛海之润涂料制造有限公司 | Granite coating and preparation method thereof |
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