CN1247376C - Method for mfg. colored rubber sheet - Google Patents

Abstract

The present invention provides a method of preparing a colored rubber sheet, which comprises the following steps: at least a material formed by a leather diaphragm with pigment and 10 to 100 shares (by weight) of polyurethane resin with the single component property or the double component property, which is solidified from the liquid state to the gelling state for 60 seconds, are added to 100 shares (by weight) of vulcanized rubber sheets with the particle diameter of 1 to 10MM or fibrous rubber sheets with the fiber length of less than 30MM, and then stirred and mixed; after the polyurethane resin starts to gel and the rubber sheets start to solidify, the polyurethane resin and the rubber sheets are continuously stirred and mixed so as to cancel the solidification of the rubber sheets. The present invention does not need complicated steps, and can be used for preparing thick colored leather diaphragms and angular pyramidal colored rubber sheets with the advantage of excellent color stability, the shape of which is similar to that of the ground colored rubber sheets.

Description

The manufacture method of tinted rubber sheet

Technical field

The present invention relates to can be used as the manufacture method of the preferred tinted rubber sheet of elasticity pavement material, in more detail, relate to the method that on the outer surface of vulcanized rubber sheet, forms the flexible painted epithelium of thick film.

Background technology

At present, manufacture method as painted elasticity pavement material, as everyone knows, carry out bonding with polyurethane binder the crushing rubber of discarded vulcanized rubber, the method that is coated with coating from the teeth outwards after the curing, and with the crushing rubber sheet with adhesive bonding the time, add pigment and inorganic powder and carry out method of colouring.Yet, for painted elasticity pavement material with these method gained, under the former situation because of under the wearing and tearing of coating, the latter's the situation because of the wearing and tearing of adhesive epithelium, can expose the ground of black rubber sheet soon, so the problem of color retentivity difference is arranged.

As solution of the above problems, in the fair 7-119284 communique of spy, disclose and use polymer solution or emulsion and pigment, on the outer surface of vulcanized rubber sheet, form the method for painted epithelium, in the method, there is following problem.

1. for the sheet rubber of manufacturing is not condensed, sheet rubber for 100 weight portions, can only use following polymer solution of 12 weight portions or emulsion (actual solid constituent is with in the majority below 50%), so thickness extremely thin (tens of μ m degree) of painted epithelium, with this with the bonding elastic layer of adhesive, will soon wear and tear, cause the color retentivity poor.

2. under the situation of with an organic solvent polymer solution, in the subsequent drying step, dangerous property during solvent evaporates, and harmful.Under the situation of using emulsion, then need drying steps, complex procedures and cost height if water management is bad, mix with the situation of making elastic layer thereafter with adhesive under, can cause the bad and poor durability of cementability.

3. emulsion is originally not good for the cementability of vulcanized rubber sheet, so the painted epithelium that applies is easy to peel off, makes the durability of elastic layer of this sheet rubber curing gained poor with adhesive yet.

And, open in the flat 7-292238 communique the spy, disclose and use waterborne polyurethane resin and pigment, on the sheet rubber outer surface, form the method for painted epithelium, but in the method, have following problem.

1. when the sheet rubber that make to apply, same with said method for preventing cohesion, can't use the polyurethane emulsion of volume.Make the thicker more emulsion that uses for making to film, then sheet rubber can be condensed into bulk, and sheet rubber is discrete to come and can't make.

2. need the drying steps of driving moisture out of, complex procedures and cost height if water management is bad, mix with the situation of making elastic layer thereafter with adhesive under, can cause the bad and poor durability of cementability.

3. emulsion is originally not good for the cementability of vulcanized rubber sheet, so the painted epithelium that applies is easy to peel off, makes the durability of elastic layer of this sheet rubber curing gained poor with adhesive yet.

On the other hand, the synthetic rubber of EPDM etc. is painted, bonding by adhesive, will make the method for elastic layer through the sheet rubber of pulverizing again, be the most general, still, it need be pulverized expensive virgin material rubber and use, can't utilize recovery article, can't do the resources effective utilization, be its problem points.

Summary of the invention

Problem in view of above-mentioned existence, the object of the present invention is to provide a kind of manufacture method of tinted rubber sheet, this method does not need complicated step, can form thick painted epithelium, color retentivity excellence and the close pyramidal tinted rubber sheet that corner angle are arranged of shape can make at an easy rate and pulverize the time.

For solving above-mentioned problem, be surprised to find that after present inventor's further investigation: the vulcanized rubber sheet that needs is formed thick epithelium, even use the polyurethane resin of the volume that reaches the cohesion degree, beginning gel, sheet rubber by polyurethane resin begin also to continue to be mixed after the cohesion, just can remove this cohesion.Therefore the present invention is accomplished.

Promptly, the manufacture method of tinted rubber sheet of the present invention, it is characterized in that, contain following step: in the vulcanized rubber sheet of particle diameter 1～10mm or fibrous sheet rubber 100 weight portions below the long 30mm of fiber, add through forming material by the aqueous epithelium that needs polyurethane resin 10～100 weight portions of the one pack system that solidify with interior process in 60 minutes more than 60 seconds or bi-component and contain pigment to gel, mixed, begin gel at polyurethane resin, this sheet rubber begins also to continue to mix after the cohesion, remove the cohesion of above-mentioned sheet rubber, when no longer cohesion taking place after making the monomer of described sheet rubber be separated, stop to stir.

The specific embodiment

Below, just the present invention is explained.

The manufacture method of tinted rubber sheet of the present invention, contain following step: in the vulcanized rubber sheet of particle diameter 1～10mm or fibrous sheet rubber 100 weight portions below the long 30mm of fiber, at least add through needing the process more than 60 seconds and polyurethane resin 10～100 weight portions of the one pack system of solidifying or bi-component and the epithelium that contains pigment form material to gel by aqueous, mixed, begin gel, this sheet rubber at this polyurethane resin and begin also to continue to mix after the cohesion, remove the cohesion of above-mentioned sheet rubber.

Add the epithelium that contains sheet rubber, polyurethane resin, pigment and other inserts and form material, mix, then the most at the beginning, be flow regime because viscosity is low, along with and airborne moisture between the carrying out of reaction, viscosity rises gradually, and the difficulty gradually that flows is carried out gel inchmeal, resin becomes and is the jelly shape, all begin cohesion, under the state of large crumb, become inadequate flowable state.Continue to be mixed again then to resolve into several medium-sized agglomerates gradually, adherence is gradually little, and last, sheet rubber is dissociated into monomer, breaks the state that comes for discrete, and therefore, mixer stops revolution.

The deciliter collecting and distributing of sheet rubber carried out repeatedly, remove cohesion at short notice and stop to stir, therefore, the epithelium on sheet rubber surface is for relatively evenly, and sheet rubber has the pyramidal feature of the corner angle similar with the shape when the pulverizing.

Thereafter, if continue to stir, then the epithelium that covered of the corner angle of sheet rubber part can be worn totally, undermines the uniformity of leather film thickness, so inadvisable.

By polyurethane resin by aqueous the carrying out that becomes the cross-linking reaction between the elastomer to the end, process: gel state → dry to touch state that mobile liquid → viscosity increase → flowability disappears → appearance curing →, reach last solid state through elastomeric process.Polyurethane resin interpolation pigment and continuation to sheet rubber and epithelium formation resin mix, and then can increase viscosity, begin gel soon and become the jelly shape, and all begin simultaneously to condense.Under the state of big agglomerate cohesion, proceed to mix, even jelly shape then, also become hard crisp state gradually, reduce along with adhesive, make sheet rubber superimposition situation also begin to be separated from each other because of state of resin in surface coverage, last, all sheet rubbers become the discrete monomer that comes eventually.

It is generally acknowledged: because when being separated into monomer, the interparticle covering epithelium of sheet rubber is reciprocally the time or be integrated, the time or separate, and simultaneously via the carrying out of solidifying, can independently become monomer at a certain time point, this moment is if promptly stop the revolution of mixer, the epithelium of comparison uniform thickness can be obtained, and the sheet rubber of pyramid shape can be obtained.

Changing condition to the coating epithelium is confirmed via experiment.Promptly, in the environment of 25 ℃ * 50%RH (relative humidity), (sand cuts down nurse (サ one Off ァ system) F-9, Yokohama Rubber (thigh) system to polyurethane resin, expediting setting type single-component mist-solidifying type polyurethane prepolymer), add curing accelerator (DABCO33LV, Air Products (thigh) system, 3 grades of amine catalysts) 1 weight %, after evenly stirring, coating 0.8mm thickness is observed it along with the state variation that the time carries out on corrosion resistant plate, and the result is as shown in table 1.

Table 1

Step	Elapsed time	State
			A	0 minute	Mixing coating finishes.
B	10 minutes	Also in flowing, self planarization is arranged.
			C	12 minutes	The surface forms epithelium, does not have flowability, the beginning gel.
D	14 minutes	Soft jelly shape.
			E	17 minutes	Hard slightly jelly shape, surperficial toughness, coating powder are then not sticking.
F	19 minutes	The surface becomes non-sticky, and is not bonding to polyethylene film, presses then distortion with finger.
			G	22 minutes	The surface is a non-sticky, presses also indeformable with finger.
H	25 minutes	Do not have scratch with the pocket knife pressure yet.
			I	32 minutes	Become real epithelium, begin to occur rerum natura.
J	38 minutes	Become the epithelium of flexible, extensibility, intensity.

According to table 1, in the E stage, all cohesions become big agglomerate, when continuing to be mixed again, diminish at F stage agglomerate, become the monomer of sheet rubber to the end and separate, and remove the state of cohesion.Thereby, by the short more thickness epithelium uniformly that can obtain more of the time of stage F → stage G.The monomer of sheet rubber becomes Abherent each other fully, and can not condense again, for caution's sake, but the also a spot of powder of spreading.Epithelium through covering is increased strength promptly also, and epithelium can not cut again and decrease or destroy soon.

And, as described later, for beginning moment that gel, sheet rubber begin to condense at polyurethane resin, adding situation inorganic or organic dust and done research.Promptly adding inorganic or organic dust in the incipient moment of gel, then all before becoming the strong state of aggregation of unusual thickness, can more early remove state of aggregation, make mixer reduce load, is its advantage.

According to table 1, if add the organic or inorganic powder between stage D～E, when then beginning, powder is gone in the polyurethane resin epithelium by mixing, when becoming hard gel state, then is difficult to enter in the film again, and becomes the lip-deep state that covers.At this moment, the sheet rubber agglomerate in the cohesion tendency is suddenly discrete to come, become between the monomer of sheet rubber to be Abherent mutually, and no longer cohesion.Epithelium through covering is increased strength promptly also, and epithelium can not cut again and decrease or destroy soon.Powder is under some excessive tendencies, can not adhere to and residual with powder state originally, even so, because can be mixing with adhesive when elastomer forms, so do not have obstruction fully.

Even the stage before stage D adds powder, do not continue to append powder up to the moment that has crossed stage E, then can't remove the cohesion situation, cause in the epithelium powder can sneak into too much, and the epithelium rerum natura is become fragile, inadvisable.

As vulcanized rubber sheet used in the present invention, be tire, conveyer belt, window frame joint filling thing etc., be that the vulcanized rubber of natural rubber, SBR, BR etc., polyurethane rubber etc. are carried out the cracked gained of physics under normal temperature or freezing state particle diameter is the sheet rubber of 1～10mm, usually with the most normal being used of sliver of damaged tire.And the fibre length that is produced when tyre rebuilding is that the fibrous sheet rubber (sheep dwell dish shape sheet rubber) below the 30mm also can use.

As the polyurethane resin of one pack system or bi-component, so long as by aqueous need through more than 60 seconds just the process of gel solidify, be that employed adhesive in the elasticity pavement material, polyether polyols with reduced unsaturation, elastomer all can use with resin at sheet rubber at present.

The time that reaches gel is more than 60 seconds, is the scope that can form epithelium, if than 60 seconds weak points, the yield of then removing cohesion can reduce, and causes the productivity variation.In addition, if the time that reaches gel of polyurethane resin is long, then because the non-persistent intermediateness under the gel state is also elongated, so the agglomerate at sheet rubber is diffusing after disintegration, if stop mixer, have the misgivings of cohesion once again or the processing time is elongated, and cover after the possibility of how many variation of shape.Thereby, reach in preferred 60 minutes of the appropriate time of gel, and more preferably 10～60 minutes.If under the situation outside this scope, can be by heating, cool off or regulating via adjusting, water and other the interpolation of catalytic amount.

As one pack system based polyurethane resin, for example can enumerate: to the polypropylene glycol of the polyurethane prepolymer of moisture-curable, poly-tetramethyl glycol, the polyalcohols of polybutadiene polyol etc., with excessive toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, polymethylene polyphenyl isocyanate, the isocyanates of hexamethylene diisocyanate etc., or these polyurethane-modified body, what the modified isocyanate of carbodiimides modification body etc. reacted gained is aqueous polyurethane prepolymer at room temperature, and the containing ratio that wherein can exemplify its isocyanate group is 3～15%.

In order to promote to solidify, the organic metal salt of 3 grades of amine, lead, tin etc. that preferably uses trimethylamine, triethylamine, N-methylmorpholine etc. is as catalyst.In addition, in as two amines of the curing agent of isocyanate group, can add reactivity faster, for example: 4,4 '-diaminodiphenyl-methane, 1,3-and 1,4-penylene diamines, 2,4-and 2,6-diaminotoluene etc.

And, as described later, in order to promote gel, under the situation of spraying with spray water before gel, water can react with isocyanate group, in order to substitute this reaction, also can be for example be added into the potentiality curing agent of Ju oxazolidine ring in the adhesive in advance, when spreading water,, react with isocyanate group by amine and alcohol radical and to reach gel, curing with the open loop of water reaction Shi oxazolidine ring.

As bi-component based polyurethane resin, for example: host can be used the polyurethane prepolymer of above-mentioned one pack system, as curing agent, can use the polyalcohols and above-mentioned two amines of PPG, polybutadiene polyol etc., uses or use its mixture separately.In order to promote to solidify, the preferred organic metal salt of lead, tin etc. that uses is as catalyst.But, as described later, in order to promote gel, under the situation of before gel, spraying with spray water and since can with the isocyanate group reaction of part, so that the amount of curing agent should be set is more a small amount of.

Polyurethane resin for vulcanized rubber sheet 100 weight portions, should use 10～100 weight portions, and be preferably 20～40 weight portions.Under the situation of the sheet rubber of 1～3mm of practicality, cladding thickness is necessary for more than the 0.1mm, and be preferably the degree of 0.2～0.3mm, and if the particle diameter of sheet rubber is different, and surface area also can be different, then amount of resin need take in (if particle diameter is big, then amount of resin is less gets final product, and particle diameter is little, then needs more amount of resin), so wish to get required leather film thickness, preferred above-mentioned scope.

Amount of resin is as if less than 10 weight portions, and leather film thickness meeting attenuation if use as elastic layer, can wear away than more quickly when then wearing and tearing, and causes color retentivity variation.In addition, if amount of resin surpasses 100 weight portions, then when covering the sheet rubber manufacturing, state by cohesion can be had any problem to all disassembling, be separated into the sheet rubber monomer, it is residual to cause having part to fail the segregator, and yield is variation terrifically, causes the setting of the creating conditions difficulty that becomes.In addition, fail to make whole resins all to become epithelium, the paddle etc. that is subjected to mixer cuts, and can be attached to the surface by the epithelium resin under cutting, and becomes the sheet rubber of shape defect.

As pigment, though different according to color, for example: under the situation of brick-red, brown, yellow, can use the oxide of iron; Under the situation of green, can use chromium oxide, phthalocyanine is organic pigment; Under the situation of black, can use carbon black; Under the situation of white, can use titanium dioxide; Or with the adjustable shades of colour of allotting of other pigment combinations.

Form in the material at epithelium of the present invention, in case of necessity, also can contain other compounding ingredient.

For example, desire further to improve weatherability, ozone resistance, resistance to water, hear resistance, can add the phenol system of Irganox1010 (Ciba-Geigy corporate system), Yoshinox BHT (Ji Fu drugmaker system) etc., the BTA system of Tinuvin P-327 etc., the age resister of the ultra-violet absorber of the benzophenone series of Tomisorb 800 grades etc.

In addition, according to purposes, it is dispersed in the suitable plasticizer in advance, can add antibiotic, the mould inhibitor of mercaptopyridine zinc (ジ Application Network ピ リ チ オ Application), 2-mercaptopyridine-1-zinc oxide (ジ Application Network 2-ピ リ ジ Application チ オ-Le-1 オ キ サ ィ De) etc., to suppress the generation of bacterium, mould.

And, according to purposes, require under the situation of firmer rerum natura, before dropping into polyurethane resin in the sheet rubber, the solution of the polypropylene glycol of the solution of the polybutadiene of the available OH of containing base, the solution that contains the isoamyl propylene of OH base, alkyd etc. carries out surface treatment.

The step of releasing among the present invention cohesion promptly, is added epithelium and is formed material and mixed, and begins gel, vulcanized rubber sheet at polyurethane resin and also continues the step that mixes after beginning to condense, repeatedly to be advisable.Cover number of processes by increasing, promptly be divided into covering for several times thinly, can cover more homogeneous thickness.

And the inorganic or organic dust of moment interpolation by just having removed in cohesion makes separated sheet rubber not have adherence, can not condense again even then stop to mix yet, and be desirable.

And, in the beginning gel of polyurethane resin, the moment that sheet rubber begins to condense, promptly, along with the viscosity of carrying out of reacting rises gradually, begin from a certain moment, be accompanied by the gel sheet rubber and begin to condense and become the crumby moment than the initial stage (just having begun to form the moment of agglomerate), it is also passable to add inorganic or organic powder.Begin to drop into the powder of organic or inorganic, continuously to drop into one by one on a small quantity, then the rubber grain that was condensing in tens of seconds can become the discrete state that comes suddenly.

But in the case, if stirring efficiency, the mixing speed of mixer are not cautiously studied with regard to cooperating output each time, then cohesion can be difficult to remove, and the possibility that can reduce yield is arranged.In addition, the covering of the corner angle of sheet rubber part is because the meeting attenuation becomes the possibility that slightly becomes the shape of circle so have.

The powder of organic or inorganic is not in order to the reinforcement rerum natura, but is main purpose with the cohesion that prevents to adhere, remove sheet rubber, therefore, is good with the low person of cost as far as possible, can use the organic-inorganic powder of the silica sand of the silica flour of ultra-micro powder of 10 μ m and even 1mm.As organic powder, can enumerate for example powder of rubber, plastics; As inorganic powder, for example can enumerate: the powder of the inanimate matter of calcium carbonate, talcum powder, silica, clay, kaolin etc. etc. be often used as powder for the inserts of rubber, plastics.In addition, the particle diameter of the powder of organic or inorganic is preferably 0.5～50 μ m.

And, before the gel of polyurethane resin, preferably spray with vaporific water.By before gel, carrying out a spot of spraying with vaporific water, can significantly shorten time of reaching gel, and from gel to time that superficiality is solidified, therefore, during a small amount of stirring after the cohesion of sheet rubber is removed, to cover into the epithelium of uniform thickness as possible, it contacts with the particle friction or with the blade of mixer and caves in or the situation of being cut damage can reduce, and can obtain more uniform epithelium.

As long as the spraying of water is a small amount of gel that promptly fully promotes polyurethane resin.Particularly, the about 30～40% promptly enough of equivalent arranged,, epithelium then can take place innerly bubble, drying steps must be arranged for removing excessive moisture if too much, inadvisable.Thereby if the NCO amount is 10% prepolymer, every 1kg serves as an amount of with 7g～9g.If the size of droplet littler, can have bigger contact area with polyurethane resin, is desirable.

And, form in the material at epithelium, preferably contain the shot-like particle that particle diameter is 0.2～0.8mm.By shot-like particle being disposed in the epithelium on the sheet rubber outer surface, during a small amount of stirring after removing cohesion, even friction is arranged or contact with the blade of mixer, its depression, the situation of being out of shape can tail off, and therefore, can obtain more uniform epithelium.

Shot-like particle is for the thickness that makes epithelium evenly adds, therefore, so long as moisture, heat, cementability, and other durability aspect no problem organic and inorganic shot-like particle arbitrarily all can.Particularly, under organic situation, can use the powder of rubber, plastics, under inorganic situation, can use silica sand, calcium carbonate, silica flour, and other incinerated matter powder etc., or the white sand of hollow sphere (shilasu) hollow sphere, phyllite, glass hollow sphere etc.

And particle diameter is good about with the thickness of epithelium, all can not reach purpose too big or too for a short time.The leather film thickness of situation of the present invention is a maximum limit with about 0.8mm, so particle diameter also is advisable according to this, if too little, then leather film thickness can irregular differing, if too big, then to have particle outstanding in the outside of epithelium.Projection a little still can, big projection can make the bond area of sheet rubber reduce, and causes that rerum natura is had harmful effect, so inadvisable.

As the mixer that uses among the present invention, be preferably mixer with the scraper of the attachment that can scrape stirring vane and container bottoms and wall.The speed of gyration of stirring vane, be preferably unlikely epithelium scratch of will be as yet fully solidifying or the degree peeled off than low velocity.

And, for the top of agitator, but be preferably opening-wide state and Visual Confirmation gel state, and can drop into the spraying of water, the powder of organic or inorganic.The viscosity of material, the affirmation of gel can be under also with quantitative assay methods, carry out with visual, for example if variation, device torque meter by electric current wait and measure, then can be made into the mixer of closed.And,, can heat at peripheral logical steam of container or warm water in order to regulate hardening time (gel time).

Embodiment

Below, be described in more detail with regard to the present invention according to embodiment.And ' part ' among the embodiment is meant weight portion.

(use material)

Sheet rubber: ' sheet rubber 800H ', three pools (Misawa) Japan (thigh) corporate system are the cracked vulcanized rubber sheet of damaged tire, particle diameter 1～3mm

Polyurethane resin: ' Sha cuts down nurse F-9 ', Yokohama Rubber (thigh) corporate system, expediting setting type one pack system moisture-curable polyurethane prepolymer

Solidify and promote catalyst: ' DABCO33LV ', Air Products (thigh) corporate system, 3 grades of amine catalysts

Pigment: iron oxide red, field, family industry (thigh) corporate system, the red pigment of iron oxide

Polyurethane binder: ' SBU adhesive 0621S ', Sumitomo Bayer polyurethane (thigh) corporate system, single-component mist-solidifying type sheet rubber adhesive

Inorganic powder: calcium carbonate powder, ball tail calcium (thigh) corporate system, precipitated calcium carbonate, particle diameter 0.5 μ m

Inorganic hollow spheroid: ' syracuse PB-09L ' syracuse 5 (thigh) corporate system, white sand (shilasu) hollow sphere, particle diameter 50～300 μ m

Polyurethane emulsion: ' speed despot Fu Liekesi 750 ', the first industrial pharmacy (thigh) corporate system, anion system, solid content 40%

Synthetic rubber tinted rubber sheet: ' tinted rubber sheet 3010-R2 ', three damp Japan (thigh) corporate systems, EPDM rubber substrate tinted rubber

＜embodiment 1 〉

In stirred vessel, drop into 100 parts of sheet rubbers, rotate stirring vane on one side, drop into 30 parts of polyurethane resins, 6 parts of the pigment that is pre-mixed 1.5% catalyst on one side, approximately through 13 minutes, polyurethane resin is tackify gradually at normal temperatures, the beginning gel, all condense, proceed to mix, Ning Ju agglomerate begins to resolve into fritter soon, through 18 minutes, particle agglomerated together finally loose and leaves.Also have adherence a little, stirring when stopping, it is some overlapping and condense to worry that sheet rubber in the container bottom has, and therefore adds 1 part calcium carbonate powder, and then fully no longer adhesion just stops stirring.

So make easily that sheet rubber fully becomes monomer and separate the pyramidal and painted covering sheet rubber of the corner angle close with the shape when pulverizing is arranged.

＜embodiment 2 〉

1) primary covering step

In stirred vessel, drop into 100 parts of sheet rubbers, rotate stirring vane on one side, drop into 15 parts of polyurethane resins, 3 parts of the pigment that is pre-mixed 1.5% catalyst on one side, approximately through 13 minutes, polyurethane resin is tackify gradually at normal temperatures, the beginning gel, all condense, proceed to mix, Ning Ju agglomerate begins to resolve into fritter soon, through 18 minutes, particle agglomerated together finally loose and leaves.Owing to also have adherence a little, therefore add 1 part calcium carbonate powder, make it complete inadhesion, just stop to stir.Under this state, placed 20 minutes.

2) secondary covering step

With above-mentioned material once more under stirring on one side, drop into 15 parts of polyurethane resins, 3 parts of the pigment that is pre-mixed 1.5% catalyst on one side, at normal temperatures approximately through 13 minutes, polyurethane resin is tackify gradually, and the beginning gel is all condensed, proceed to mix, soon Ning Ju agglomerate begins to resolve into fritter, and through 18 minutes, particle agglomerated together finally loose and leaves.Owing to also have adherence a little, therefore add 1 part calcium carbonate powder, make it complete inadhesion, just stop to stir.

Sheet rubber fully becomes monomer and separates, so can make pyramidal easily and have the painted covering sheet rubber of the corner angle close with the shape when pulverizing.Obtaining outward appearance and embodiment 1 does not almost have the painted covering sheet rubber of difference.

＜embodiment 3 〉

In stirred vessel, drop into 100 parts of sheet rubbers, rotate stirring vane on one side, drop into 6 parts of 30 parts of polyurethane resins, pigment, 10 parts of the hollow spheres that is pre-mixed 4.5% catalyst on one side, approximately through 120 seconds, polyurethane resin is tackify gradually at normal temperatures, the beginning gel, bonding all cohesions hastily, proceed to mix, begin to resolve into fritter through the agglomerate of cohesion in 4 minutes, particle agglomerated together looses and leaves.Though adherence is a little arranged, compared little a lot with embodiment 1, therefore do not add calcium carbonate powder, promptly stop to stir.

Obducent being shaped as is bordering on pyramidally, owing to contain the hollow sphere of shot-like particle, becoming edges and corners has attenuation to become the painted covering sheet rubber of circle slightly, can easily separate obtaining monomer.

＜embodiment 4 〉

In stirred vessel, drop into 100 parts of sheet rubbers, rotate stirring vane on one side, drop into 80 parts of polyurethane resins, 6 parts of the pigment that is pre-mixed 1.5% catalyst on one side, at normal temperatures approximately through 16 minutes, polyurethane resin is tackify gradually, the beginning gel, and integral body is the very large cohesion agglomerate of toughness, proceed to mix, Ning Ju agglomerate begins to resolve into fritter soon.Owing to also have the residual situation of little agglomerate, again through 30 minutes, finally little condensation product also decomposes and is separated into monomer.Owing to also have adherence a little, adds 2 parts of calcium carbonate powders, what make does not have adherence fully, just stops stirring.

Sheet rubber is separated into monomer and approaches pyramidally, because final stage needs the long time to stir, edges and corners become the outward appearance of justifying slightly.

＜embodiment 5 〉

In stirred vessel, drop into sheet rubber 100 weight portions, rotate stirring vane on one side, drop into 30 parts of polyurethane resins, 6 parts of the pigment that is pre-mixed 0.5% catalyst on one side, at normal temperatures approximately through 120 minutes, polyurethane resin is tackify gradually, under change point is not obvious, begin gel, all condense lentamente, proceed to mix.After 3 hours, promote even thick place is arranged, also to obtain the good emulsion sheet of pyramidal shape under the gel in edges and corners to heating around the mixer.

＜comparative example 1 〉

In stirred vessel, drop into 100 parts of sheet rubbers, Yi Bian rotate stirring vane, Yi Bian drop into 120 parts of polyurethane resins, 6 parts of the pigment that is pre-mixed 1.5% catalyst, approximately through 22 minutes, polyurethane resin is tackify gradually at normal temperatures, the beginning gel, all condense, proceed to mix.Yet whole viscosity is very big, and agglomerate is difficult for decomposing.Though continue to stir gel is carried out, had any problem, after 35 minutes, add 20 parts of calcium carbonate powders,, have 20% degree to fail to separate approximately though there are some degree to resolve into the sheet rubber monomer because the load that mixer bears causes too greatly stirring.In addition, have many epitheliums by the fractionlet of the polyurethane resin cutting under this moment, and this surface that equals epithelium has much reins in ditch and adhere on it, and the surface is as the upright state on it of feather, and shape is expansion not, is undesirable condition.And though amount of resin is many, leather film thickness is thin.Like this, even amount of resin increases,, still can remove coacervation as long as shape changes to some extent.

＜comparative example 2 〉

In stirred vessel, drop into 100 parts of sheet rubbers, rotate stirring vane on one side, drop into 6 parts of 30 parts of polyurethane resins, pigment, 20 parts of the calcium carbonate powders that is pre-mixed 6.0% catalyst on one side, at normal temperatures approximately through 40 seconds, polyurethane resin is tackify gradually, the beginning gel, bonding all cohesions are hastily proceeded to mix, and diminish and begin through 120 seconds agglomerates and decompose, at last, even through 5 minutes, about 1/3 degree of cohesion does not still become discrete particle, in addition, residual have spherical condensation product to continue to solidify, and can't all remove.

＜comparative example 3 〉

In stirred vessel, drop into 100 parts of sheet rubbers, rotate stirring vane on one side, drop into 12 parts of polyurethane resin emulsions, 6 parts of pigment on one side, at normal temperatures through 20 minutes, moisture has volatilization slightly, and system's viscosity rises, and becomes the situation of approximate gel, when all beginning to become big agglomerate, with 6 parts of a little addings of gradation of calcium carbonate powder.Agglomerate diminishes, and in the relatively shorter time, can make powder on the covering resin surface coverage, and the sheet rubber of cohesion is then discrete to come.

Because covering does not have thickness, so same sharp keen, covering sheet rubber that outward appearance is good when obtaining corner angle with pulverizing.

(evaluation method)

According to following method, estimate with regard to the sheet rubber characteristic of embodiment 1～5, comparative example 1～3.The result is shown in table 2 and table 3.

(1) cladding thickness

Select 3 on bigger particle, amplify 75 times of mensuration with micrometer (wheat Kroes Kui Er (thigh) corporate system).Measure at 5 and get maximum and minimum of a value.

Table 2

		Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4
						The covering of sheet rubber	Sheet rubber (part)	800H 100	800H 100	800H 100	800H 100
Covering resin (part)	Mono-component polyurethane 30	Mono-component polyurethane adds up to 30	Mono-component polyurethane 30	Mono-component polyurethane 30
					Degree of covering		1 time	2 times	1 time	1 time
Gel time	13 minutes	13 minutes	120 seconds	16 minutes
					Pigment (part)		6	Add up to 6	6	6
Shot-like particle	Do not have	Do not have	Have	Do not have
					Inorganic powder (part)		1	Add up to 2	-	2
Covering performance	Overwrite job	Well	Well	Well							Roughly good
					Yield (%)	100	100	100	About 100
	Cladding thickness (mm)	0.2～0.3	0.2～0.3	0.3～0.5						0.3～0.6
					Thickness evenness	Well (containing corner angle portion is roughly uniformly)	Well (containing corner angle portion is roughly uniformly)	Well (corner angle portion is thin slightly to be roughly uniformly)	Well (corner angle portion is thin slightly to be roughly uniformly)
	The shape outward appearance that covers	Pyramidal good	Pyramidal good	Corner angle portion circle slightly is roughly pyramidal, good						Corner angle portion circle slightly is roughly pyramidal, good

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Can learn as follows by table 2, table 3.

1) overwrite job. yield

' well ' expression efficient is good, can easily remove cohesion, and yield is also good, almost makes the covering sheet rubber with 100% yield, and embodiment 1～3 belongs to this type of, even the efficient of mixer is poor slightly, also can easily make.4 of embodiment condense the more time of palpus so remove, but there is no special problem because amount of resin is many.Embodiment 5 there is no special problem except mixing time is very long.The epithelium amount of resin of comparative example 1 is too many, and comparative example is too fast 2 hardening times, and both all are difficult to cohesion 100% is removed.Add powder before 3 bone dries in mixing of comparative example,, also can easily obtain covering sheet rubber even under the situation of emulsion.

2) cladding thickness, thickness evenness, shape outward appearance

The difference of embodiment 1 and the degree of covering of embodiment 2 is also non-key, even only cover 1 time, it is irregular few also can to obtain comprising corner angle part integral thickness, and the pyramidal excellent in shape when pulverizing.Embodiment 3, use hollow sphere, and cladding thickness is thick slightly, and it is thin slightly slightly round that corner angle partly become, and still can keep pyramid shape.Embodiment 4,5 is close to identical.

＜embodiment 6 〉

100 parts of the painted covering sheet rubbers that embodiment 1 is made, add 25 parts in polyurethane resin adhesive, use mixer stir about 3 minutes with sheet rubber, on model (mold) basal disc, grind thick with hot-rolling and trowel (trowel), making it thickness is 10mm, even, placed 10 days down at 25 ℃ * 50%RH (relative humidity), be cured health, make rubber lamella (elastic layer).

＜embodiment 7 〉

Except using the painted covering sheet rubber that embodiment 3 makes, all the other make elastic layer with similarly to Example 6 the practice.

＜embodiment 8 〉

Except using the painted covering sheet rubber that embodiment 4 makes, all the other make elastic layer with similarly to Example 6 the practice.

＜embodiment 9 〉

Except using the painted covering sheet rubber that embodiment 5 makes, all the other make elastic layer with similarly to Example 6 the practice.

＜comparative example 4 〉

Except using the painted covering sheet rubber that comparative example 3 makes, all the other make elastic layer with similarly to Example 6 the practice.

(evaluation method)

With following method, estimate with regard to the characteristic of the rubber lamella (elastic layer) of embodiment 6～9, comparative example 4.The result is as shown in table 4.

(1) outward appearance

Estimate with following benchmark.

Zero: good.Can see the state that the PYR sheet rubber of the pulverized shape of rubber manifests side by side on the surface.

*: bad.Can see round slightly sheet rubber side by side on the surface.

△: poor slightly.Above-mentioned zero with * the state of centre.

(2) proportion

Measure according to JIS Z 8807 (sample mass/volume).

(3) hot strength, percentage elongation

Measure according to JIS K 6301.And observe its state of rupture.

(4) wearability

With the pyramidal abrasion tester of JIS K 7204, load onto friction bands CS-17, hang up weight above 1kg, make its rotation 1000 times, the appearance during surface abrasion is estimated with following benchmark.

Zero: ground that can't see black fully.

△: the ground that can how much see black.

*: the black part can be seen a lot of.

(5) weatherability

Expose appearance in 1000 hours with daylight weather resistance test machine, estimate with following benchmark.

Zero: ground that can't see black fully.

△: the ground that can how much see black.

*: the black part can be seen a lot of.

Table 4

	Embodiment 6	Embodiment 7	Embodiment 8	Embodiment 9	Comparative example 9
						Outward appearance	○	○	○	△～○	○
Proportion	0.84	0.81	0.86	0.83	0.77
						Hot strength (kgf/cm 2)	14.7	13.2	14.3	14.1	5.2
Percentage elongation (%)	88	76	93	85	52
						State of rupture	The material of cover layer or bonding agent is destroyed	The material of cover layer or bonding agent is destroyed	The material of cover layer or bonding agent is destroyed	The material of cover layer or bonding agent is destroyed	Interface peel between cover layer and sheet rubber
Wearability	○	○	○	○	×
						Weatherability	○	○	○	○	△

By table 4, can learn as follows.

1) outward appearance

Embodiment 6～8, although thick painted epithelium is arranged, can the pyramidal sheet rubber of pulverized shape of seeing rubber on the surface side by side situation, be good surface appearance.Embodiment 9 is the round slightly particles of corner angle, and for good slightly, 4 of comparative examples are good.

2) hot strength, percentage elongation

Embodiment 6～9, because the bonding force of coverlay and adhesive is strong, so intensity is arranged, state of rupture also is the material destruction of painted cover layer or adhesive, peels off at sheet rubber and tectal interface.But embodiment 7, owing to there is the big slightly hollow sphere of particle diameter to contain into wherein, so hot strength, percentage elongation are all low slightly.

Comparative example 4 owing to be the epithelium of aqueous polyurethane, so and the cementability between sheet rubber poor, hot strength also a little less than, the situation that causes the interface one-tenth on sheet rubber surface to be peeled off.

3) wearability

Be formed with the embodiment 6～9 of polyurethane epithelium on the sheet rubber surface, for well, and the comparative example 4 of aqueous polyurethane epithelium, then because epithelium is thin, so bad.

4) weatherability

Be formed with the embodiment 6～9 of polyurethane epithelium on the sheet rubber surface, for well, and the comparative example 4 of aqueous polyurethane epithelium, then because epithelium is thin, so bad.

＜embodiment 10 〉

1) sheet rubber being carried out painted epithelium covers

In stirred vessel, drop into 100 parts of sheet rubbers, rotate stirring vane on one side, drop into 30 parts of polyurethane resins, 6 parts of the pigment that is pre-mixed 1.5% catalyst on one side, at normal temperatures approximately through 13 minutes, polyurethane resin is tackify gradually, the beginning gel adds 30 parts of inorganic powders in the cohesion one by one on a small quantity all beginning.Inorganic powder spreads on the outer surface that is overlying on sheet rubber, and the particle that is condensing looses suddenly and leaves, and through confirming to be separated into one one state fully, just stops to stir.

2) rubber lamella (elastic layer) makes

To 100 parts of above-mentioned tinted rubber sheets, add 25 parts of polyurethane binder, use mixer stir about 3 minutes with sheet rubber, on model (mold) basal disc, grind thick, pave with hot-rolling and trowel, making it thickness is 10mm.

＜embodiment 11 〉

1) sheet rubber being carried out painted epithelium covers

In stirred vessel, drop into sheet rubber 100 weight portions, rotate stirring vane on one side, drop into 30 parts of polyurethane resins, 6 parts of the pigment that is pre-mixed 1.5% catalyst on one side, at normal temperatures approximately through 10 minutes, have slightly in the tackify at polyurethane resin, the running water of minute quantity is sprayed into fine mist sprays.Tackify and begin gel hastily between 2～3 minutes adds inorganic powder for 20 parts in the cohesion one by one on a small quantity all beginning.Inorganic powder spreads on the outer surface that is overlying on sheet rubber, and the particle of cohesion looses suddenly and leaves, and through confirming to be separated into one one state fully, just stops to stir.

2) rubber lamella (elastic layer) makes

To 100 parts of above-mentioned tinted rubber sheets, add 25 parts of polyurethane binder, use mixer stir about 3 minutes with sheet rubber, on model (mold) basal disc, grind thick, pave with hot-rolling and trowel, making it thickness is 10mm.

＜comparative example 5 〉

Making of rubber lamella (elastic layer)

To 100 parts of sheet rubbers, add 25 parts of polyurethane binder, 6 parts of pigment, use mixer stir about 3 minutes with sheet rubber, on model (mold) basal disc, grind thick, pave with hot-rolling and trowel, making it thickness is 10mm.

＜comparative example 6 〉

1) sheet rubber being carried out painted epithelium covers

In stirred vessel, drop into 100 parts of sheet rubbers, rotate stirring vane on one side, drop into 8 parts of polyurethane resins, 4 parts of the pigment that is pre-mixed 1% catalyst on one side, at normal temperatures approximately through 13 minutes, polyurethane resin is tackify gradually, the beginning gel adds 15 parts of inorganic powders in the cohesion one by one on a small quantity all beginning.Inorganic powder spreads on the outer surface that is overlying on sheet rubber, and the particle that is condensing looses suddenly and leaves, and through confirming to be separated into one one state fully, just stops to stir.

2) rubber lamella (elastic layer) makes

To 100 parts of above-mentioned tinted rubber sheets, add 25 parts of polyurethane binder, use mixer stir about 3 minutes with sheet rubber, on model (mold) basal disc, grind thick, pave with hot-rolling and trowel, making it thickness is 10mm.

＜comparative example 7 〉

Making of rubber lamella (elastic layer)

To 100 parts of above-mentioned tinted rubber sheets, add 25 parts of polyurethane binder, use mixer stir about 3 minutes with sheet rubber, on model (mold) basal disc, grind thick, pave with hot-rolling and trowel, making it thickness is 10mm.

(evaluation method)

Estimate with the method identical with the evaluation method of the sheet rubber of embodiment 1～9, comparative example 1～4 and rubber lamella (elastic layer).The result is shown in table 5 and table 6.

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Table 6

	Embodiment 10	Embodiment 11	Comparative example 5	Comparative example 6	Comparative example 7
						Outward appearance	△～○	△～○	○	○	○
Proportion	0.83	0.84	0.74	0.77	0.84
						Hot strength (kgf/cm 2)	14.4	14.2	6.5	10.8	9.5
Percentage elongation (%)	82	79	60	72	92
						State of rupture	The material of cover layer or bonding agent is destroyed	The material of cover layer or bonding agent is destroyed	Interface peel between bonding agent and sheet rubber	The material of cover layer or bonding agent is destroyed	Interface peel between bonding agent and sheet rubber
Wearability	○	○	×	△	○
						Weatherability	○	○	×	△～○	○

Can learn as follows by table 5.

1) overwrite job. yield

Embodiment 10,11, comparative example 6 are all well, and yield might as well.

2) cladding thickness, thickness evenness, shape outward appearance

The leather film thickness of embodiment 10,11 is average except the corner angle top ends, because the corner angle top ends is thin than central portion, so become round slightly outward appearance.Comparative example 6, because amount of resin is few, leather film thickness is quite thin, so be shaped as pyramid.

Can learn as follows by table 6.

1) outward appearance

Being shaped as after the covering of embodiment 10,11 is round slightly, so good slightly, 5～7 of comparative examples are good.

2) hot strength, percentage elongation

Embodiment 10,11, because the bonding force of coverlay and sheet rubber is strong, so intensity is arranged, state of rupture also is the material destruction of painted cover layer or adhesive, peels off at sheet rubber and cover layer interface.

And comparative example 5, because the bonding force of sheet rubber and bonding agent is not too strong, so intensity is low.

3) mar proof

Embodiment 10,11 is excellent, and comparative example 5 is bad, and comparative example 6 is because leather film thickness is thin, so bad, comparative example 7 is not owing to cover sheet rubber, and institute thinks zero.

4) weatherability

Embodiment 10,11, because leather film thickness is thick, thus good, comparative example 5, owing to there is not epithelium, so bad, comparative example 6 is because leather film thickness is thin, so poor slightly.

As mentioned above, can obtain following effect according to the present invention.

1) can obtain on the outer surface of vulcanized rubber sheet that the thickness of the thick degree of 0.1～0.8mm is more uniform a chromatic colorant epithelium, this epithelium can be followed the elastic force of sheet rubber. It is solidified with polyurethane binder, use as the elasticity pavement material, then can aspect the color confining force durability arranged.

2) there is the thick cured film of the good polyurethane rubber of cementability to be covered with on the outer surface of sheet rubber, make it solidify the elastic layer of gained with polyurethane binder of one species, physical property is strong, can anti-land sports ground, running and the walking of the spikes of golf course etc., and can the road of anti-the golf court management, the vehicle to run in road, garden, park etc.

3) when cohesion is removed, even use the slightly poor mixer of stirring efficiency, it is also very good to remove efficient, so few covering process number of times of showing greatly 1 time can obtain the covering of uniform thickness, and can obtain with sheet rubber pulverize the time roughly the same corner angle pyramid shape, elastic layer so that bonding agent solidifies can obtain the good outward appearance similar to the painted synthetic rubber sheet pavement material of present type.

4) because epithelium has thickness, the hardness by changing employed polyurethane resin or change the powder that adds, the amount of shot-like particle can freely be adjusted the hardness of particle, thereby, can obtain conforming with the elastic layer of the hardness of application target.

5) be used to the polyurethane resin that applies, because the solid composition is 100%, do not contain organic solvent, so even heating, in the problem that does not have on the operation on the safety, and it is not because moisture, do not need to carry out drying, and can reduce operation, make at short notice with other step, therefore, manufacturing expense is very cheap.

6) immediately with the granular white sheet rubber pack of making, even the fastest storehouse etc. that packed after 20 minutes thereafter, sheet rubber bears some weight, and its cover layer also can not be out of shape, and efficient is good on operation is carried out.

7) be effective recovery technology of damaged tire and other scrap rubber, compare with the situation of the virgin material rubber that uses EPDM etc., with low cost.

Claims (5)

1. the manufacture method of a tinted rubber sheet is characterized in that:

Include following step: at particle diameter is that the vulcanized rubber sheet of 1～10mm or fiber are long in fibrous sheet rubber 100 weight portions below the 30mm, add through forming material by the aqueous epithelium that needs polyurethane resin 10～100 weight portions of the one pack system that solidify with interior process in 60 minutes more than 60 seconds or bi-component and contain pigment to gel, mixed, begin gel at this polyurethane resin, this sheet rubber begins also to continue to mix after the cohesion, remove the cohesion of above-mentioned sheet rubber, when no longer cohesion taking place after making the monomer of described sheet rubber be separated, stop to stir.

2. the manufacture method of tinted rubber sheet as claimed in claim 1 is characterized in that:

Include repeatedly following step: add described epithelium and form material and mix, beginning gel, sheet rubber at this polyurethane resin begins also to continue to mix after the cohesion, should condense releasing again, in when, no longer cohesion taking place after making the monomer of described sheet rubber be separated, the step that stops to stir.

3. the manufacture method of tinted rubber sheet as claimed in claim 1 or 2 is characterized in that: before described gel, spray vaporific water.

4. the manufacture method of tinted rubber sheet as claimed in claim 1 or 2 is characterized in that: containing the particle diameter that is selected from silica sand, calcium carbonate, silica flour, white sand hollow sphere, phyllite, glass hollow sphere in described epithelium formation material is the shot-like particle of 0.2～0.8mm.

5. the manufacture method of tinted rubber sheet as claimed in claim 3 is characterized in that: containing the particle diameter that is selected from silica sand, calcium carbonate, silica flour, white sand hollow sphere, phyllite, glass hollow sphere in described epithelium formation material is the shot-like particle of 0.2～0.8mm.