CN103180144B - For the compressible roller of printing machine - Google Patents

For the compressible roller of printing machine Download PDF

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Publication number
CN103180144B
CN103180144B CN201180051222.0A CN201180051222A CN103180144B CN 103180144 B CN103180144 B CN 103180144B CN 201180051222 A CN201180051222 A CN 201180051222A CN 103180144 B CN103180144 B CN 103180144B
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CN
China
Prior art keywords
roller
cylindrical die
compressible
compressible roller
organopolysiloxane composition
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Expired - Fee Related
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CN201180051222.0A
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Chinese (zh)
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CN103180144A (en
Inventor
D·布兰克
S·拉瓦迪尔
N·拉内力
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Elkem Silicones France SAS
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Bluestar Silicones France SAS
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N7/00—Shells for rollers of printing machines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41F—PRINTING MACHINES OR PRESSES
    • B41F13/00—Common details of rotary presses or machines
    • B41F13/08—Cylinders
    • B41F13/193—Transfer cylinders; Offset cylinders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41F—PRINTING MACHINES OR PRESSES
    • B41F17/00—Printing apparatus or machines of special types or for particular purposes, not otherwise provided for
    • B41F17/001—Pad printing apparatus or machines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N2207/00—Location or type of the layers in shells for rollers of printing machines
    • B41N2207/02—Top layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N2207/00—Location or type of the layers in shells for rollers of printing machines
    • B41N2207/04—Intermediate layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N2207/00—Location or type of the layers in shells for rollers of printing machines
    • B41N2207/14—Location or type of the layers in shells for rollers of printing machines characterised by macromolecular organic compounds
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C13/00—Rolls, drums, discs, or the like; Bearings or mountings therefor

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The present invention relates to compressible roller (1), it comprises: columniform rigidity roller core (2); Cover the intermediate layer (3) of being made up of Silicone foam of described roller core (2); And cover the skin (4) be made up of elastomer silicone in described intermediate layer (3).

Description

For the compressible roller of printing machine
Technical field
The present invention relates to new compressible roller, it can be used for printing or bat printing (tampographie) and comprise the flexible portion be made up of Silicone foam.
Background technology
Term " Silicone foam " represents the constituent polyorganosiloxane composition of foamed material (mousse) form.Silicone foam is well known in the art and its preparation is described in numerous patents.
In most of printing technology, print roller is used.In order to realize better printing repeatability, develop a large amount of flexible printing rollers.
Such as, patent US-A-3467009 describes the production of flexible printing roller, described flexible printing roller comprises roller core, the intermediate layer of polyurethane foamed material, natural rubber or neoprene and the compressible skin that at least one is prepared by the fibrous material being soaked with elastomer substances.
Patent EP-A-577920 describes a kind of compressible roller, it skin comprising roller core, the intermediate layer of being made up of nitrile/polyvinyl chloride foam material and comprise polyurethane seal fitting (joint).
But, unsatisfactory the printing application that the type of the foamed material adopted in the roller of these prior aries improves constantly for the requirement in the durability and printing quality of print roller.
Such as, the problem run in the production of these rollers relates to the production defect relevant with the not controlled foaming in foamed material intermediate layer, produce the defect relevant with the bubble that there is oversized dimensions and in expanded material, steep Size Distribution uneven, thus have impact on the mechanical performance of described roller.
And the foamed material used in the prior art no longer meets the restriction that new industrial process is brought.Such as, such as producing in the field of the roller being used for bat printing, usually use centrifugation technique, this results in new foaming restriction, thus this have impact on size and the Size Distribution of the bubble of expanded material, and this is key factor for printing roller.In fact, when these bubble oversize time and in expanded material, the distribution of the size of described bubble is large time, then can cause the anisotropy of the physical property of described roller.
Thus, for some application as bat printing (or roller printing), the particular characteristic of foamed material is sought.Bat printing is a kind of indirect printing technique.The pattern printed is carved on supporter in advance, is then attached in pad printer by printing forme; Then by ink deposition to the part of engraving with the liner by being made up of Silicone foam or roller by this design transfer on the object that will print.In order to realize high-quality engraving and printing, be necessary that the liner or roller be made up of Silicone foam is made up of undersized bubble and Size Distribution in this material of these bubbles are wanted, evenly with on the receiving layer making ink to deposit equably and to transfer to be supported by Silicone foam layer, to allow the accurate reproduction of described engraving simultaneously.Term " undersized bubble " refers to that its width (or diameter) is less than or equal to the bubble of about 1mm, term " middle-sized bubble " refers to the bubble that its width (or diameter) is 1-1.5mm, and for " large-sized bubble ", width (or diameter) is for being greater than 1.5mm.
Thus, for this application, the needs obtaining the foamed material with undersized bubble and uniform bubble Size Distribution are sought especially.
The preparation of the frothing part of flexible printing roller because of but the theme of special concern in print field.
Prior art describes the technology of multiple acquisition Silicone foam.The first technology adopts condensation reaction, release volatile byproducts.Be exactly particularly this situation for the system of the condensation reaction using SiH-SiOH type, this reaction release hydrogen, it then serves the effect of pore-foaming agent (agent porogene).Such as, French Patent (FRP) FR-A-2 589 872 describes the precursor composition of the Silicone foam comprising following component: comprise the organic silicon-containing polymer had with the siloxane unit of the oh group of silicon bonding, comprise the organic silicon-containing polymer had with the siloxane unit of the hydrogen atom of silicon bonding, catalyst as tin compound, and comprises the segmentation filler becoming hydrophobic silica through process.These compositions solidify via polycondensation reaction, although and it is satisfactory in many aspects, but the composition of the tin catalysis described in French Patent (FRP) FR-A-2 589 872 is considered to not satisfied owing to using tin catalyst, and tin catalyst can apply some undesirable toxic action.
Alternative Form described in US Patent No.-B-3 923 705 is that providing package contains the composition of the polydiorganosiloxanepolyurea with the hydrogen atom with silicon bonding, this hydrogen atom be used under the existence of platinum catalyst with the condensation reaction with the polydiorganosiloxanepolyurea of the hydroxyl (silanol) with silicon bonding.Therefore this reaction makes it possible to form network while generation Silicone foam forms necessary hydrogen.In this kind of preparaton, formation and the cross-linked speed of gas are proportional, and therefore the density refractory of gained foamed material is to control, thus explanation is being obtained the difficulty in low density foam material by this technology.These compositions can comprise the polydiorganosiloxanepolyurea with the vinyl with silicon bonding in addition, they are by being cross-linked with the polyaddition of the polydiorganosiloxanepolyurea with the hydrogen atom with silicon bonding simultaneously, thus participate in the structure of Silicone foam network.
According to the another kind of Alternative Form described in US Patent No.-B-4 189 545, Silicone foam is prepared: water by the composition comprising following component, with the polydiorganosiloxanepolyurea of the vinyl with silicon bonding, comprise with chain in and not only the unit of the end of the chain have with the hydrogen atom of silicon bonding the polydiorganosiloxanepolyurea of crosslinking agent can be served as.Water and the polysiloxanes comprising hydrogenation functional group react, thus produce hydrogen and silanol.Silanol then reacts via condensation reaction and the polydiorganosiloxanepolyurea comprising hydrogenation functional group, thus produce the second hydrogen molecule, and the polydiorganosiloxanepolyurea that another polydiorganosiloxanepolyurea with the vinyl with silicon bonding will comprise hydrogenation functional group via addition reaction and another reacts simultaneously, thus participate in the structure of Silicone foam network.The main contributions that this technology is made is to add silanol but adds a small amount of water and produces hydrogen.
In patent US-4 590 222, Silicone foam is prepared by the composition comprising following material: polydiorganosiloxanepolyurea, resin, platinum based catalyst, Organhydridosiloxaneresins, with the polysiloxane of oh group on end unit, filler and Organic Alcohol.
Such as, but the technical tendency utilizing silanol to originate as pore-foaming agent has the too high foamed material of numerous application density in generation, and those are intended for the application of transport industry.In addition, when obtaining the foamed material of intermediate density, this normally with mechanical performance (fracture strength, tearing strength etc.) for cost realizes.
Another technology is to be used in the pore-foaming agent or pore additive that add in silicone matrix, and it makes material expansion by following approach under heat effect:
-decompose release gas, particularly azo derivative is as the situation of Celogen Az, and it can make it possible to discharge nitrogen, carbon dioxide and ammonia.Although be widely used in other material, there is serious toxicity problem (discharging hydrazine) in this kind of pore-foaming agent,
The situation of-phase transformation (liquid is to gas), particularly low boiling point solvent.
Another example of the precursor composition of Silicone foam is described in bibliography WO-A-00/46282.Described composition comprises and (comprises the polysiloxane oil/Pt catalyst of the polysiloxane oil of ≡ SiH functional group/comprise ≡ SiVi functional group by the crosslinked silicone base material of polyaddition, wherein Vi=vinyl), comprise compound and the wollastonite (described example describes the composition with high filler content, is the filler of about 21 weight portions relative to the gross weight of composition) of hydroxy functional group.It should be noted that the viscosity (embodiment 1, table 2) of the composition prepared in an embodiment is all greater than 190 000mPas.As above-described, known (see US-B-4 418 157, the 2nd hurdle 13-24 is capable) this combination the viscosity of thing is larger, and the density of gained foamed material is lower.It should be noted that, from composition (the bibliography WO-A-00/46282 of most viscous, table 2,13rd page, composition [1-1], viscosity 274,000mPas) to minimum composition [1-3] (viscosity=198 of viscosity, 000mPas), the density of gained foamed material is increasing (from 0.20g/cm 3to 0.25g/cm 3), thus confirm the known teachings obtaining low density foam material difficulty about the composition by crosslinked low viscosity (viscosity is less than 30 000mPa.s) in the past.In fact, due to end user or use the producer of Silicone foam production line in the reason using these Composition Aspects to be optimized, importantly can have following such composition, said composition existed with the easy not too sticky form flowed in suitable apparatus before crosslinked.
Thus, in the preparation of print roller, importantly obtain low-density Silicone foam, to alleviate the weight of the equipment used in printing and transfer-print technology.
Thus can be summarized in the technology of seeking between technical specification in this problem considered to trade off, this is priori contradiction, seek the Silicone foam precursor composition that namely preparation low viscosity is less than 30 000mPa.s, and the precursor of Silicone foam, described Silicone foam has low-density, is namely less than 0.25g/cm 3density, there is good mechanical performance, be less than or equal to the bubble size of 1mm and steep Size Distribution uniformly in expanded material.In addition, sought foamed material no longer should have the problem relevant with the intervention of new technology as centrifugation technique in the commercial run of production print roller.
Summary of the invention
Thus object of the present invention is to provide the new compressible roller that can be used for printing, wherein namely frothing part is less than the organopolysiloxane composition preparation of the viscosity of 30 000mPa.s by low viscosity, and described composition can produce low-density and namely be less than 0.25g/em after being cross-linked and/or solidifying 3the Silicone foam of density, obtain the Silicone foam with good mechanical properties, it steeps size, and width or diameter are less than or equal to about 1mm and the uniform bubble Size Distribution in this material simultaneously.
Thus object of the present invention is to provide a kind of new compressible roller (1), and it comprises:
-columniform rigidity roller core (2),
-cover the intermediate layer (3) of being made up of Silicone foam of described roller core (2), and
-cover the skin (4) be made up of elastomer silicone in described intermediate layer (3),
The feature of described roller is that described intermediate layer (3) of being made up of Silicone foam is prepared by the crosslinked of organopolysiloxane composition X and/or solidification, and described organopolysiloxane composition X comprises:
-at least one polysiloxane A, has the viscosity of 10-300 000mPa.s and per molecule has the C that at least two are connected to silicon 2-C 6alkenyl group,
-at least one polysiloxane B, has the viscosity of 1-5000mPa.s and per molecule has at least two ≡ SiH unit and preferred at least three ≡ SiH unit,
At least one catalyst C of-catalytically effective amount, it is the compound of the metal belonging to platinum family derived from least one,
-at least one pore-foaming agent D, it is water or water-based emulsion,
-optionally, at least one its chain often hold by three organic siloxy units end-blockings diorganopolysiloxanecompositions oil E, its organic group be connected with silicon atom be selected from there is 1-8 the carbon atom comprising end value alkyl as methyl, ethyl, propyl group and 3,3,3-trifluoro propyl, cycloalkyl is as cyclohexyl, suberyl, ring octyl group, and aryl is as xylyl, tolyl and phenyl
-optionally, at least one metal and/or inorganic filler F,
-optionally, at least one additive G, and
-optionally, at least one polysiloxane resin H,
-other condition is, determines that the selection of described composition, kind and consumption are less than 30 000mPa.s to make the viscosity of described organopolysiloxane composition X, is more preferably less than 25 000mPa.s.
Applicant is unexpected and find unexpectedly, comprising to make it possible to obtain as the water of pore-foaming agent or the Efferescent compositions of the present invention of water-based emulsion has less to the print roller occurring the defect that bulla is relevant at its frothing part, thus improves the industrial reliability of the technique for the production of these rollers.
This new compressible roller has the advantage that the intermediate layer (3) of being made up of Silicone foam is formed, and the density of described Silicone foam is less than 0.25g/em 3, have good mechanical performance, the bubble size of its width or diameter is less than or equal to about 1mm and its bubble Size Distribution in material is uniform.
In addition, make it possible to avoid the problem relevant with the new restriction run in for the production of the method recently of these print roller for the preparation of the organopolysiloxane composition X in this intermediate layer, such as relevant with using centrifugation technique problem.In fact, in the foaming step of this layer for the preparation of this roller, organopolysiloxane composition X no longer produces and occurs with in some region of this layer the problem that bulla is relevant.
Pore-foaming agent D according to the present invention is water or water-based emulsion.It can be introduced with the form of the direct emulsion of oil-in-water organosilicon or Water-In-Oil organosilicon reversed-phase emulsion (it comprises organic silicone oil matter continuous phase, water-based phase and stabilizing agent).
Direct emulsion obtains by emulsifying process well known to those skilled in the art, this technique be comprise stabilizing agent as the water-based of surfactant mutually in the mixture of composition as described in emulsification.Then then O/w emulsion is obtained.Then can add remaining composition directly to (when water soluble ingredient) in emulsion or then add in the form of an emulsion (when organosilicon mutually in solvable composition).The granularity of the emulsion obtained can obtain by means of conventional method well known by persons skilled in the art, stirs the suitable time cycle especially by continuing in the reactor.
Organosilicon reversed-phase emulsion is made up of little the dropping in organic silicone oil continuous phase of water.They obtain by emulsifying process well known to those skilled in the art, and it relates to and mixes water-based phase and oil phase when not grinding or grind namely at Strong shear.This stabilizing agent is preferably selected from:
-nonionic, anion, cation or zwitterionic surfactant;
-organic silicon polyether;
-solid particle, the silica dioxide granule preferably optionally combined with at least one co-stabilizer, described co-stabilizer is preferably selected from nonionic, anion, cation or zwitterionic surfactant;
-and composition thereof.
Surfactant more generally base area HLB is selected.The hydrophily of polar group of term HLB (hydrophilic-lipophilic balance) presentation surface active agent molecule and the ratio of the hydrophobicity of their lipophilic portion.HLB value is especially recorded in various basic handbook, such as " Handbook des excipientspharmaceutiques (handbook of pharmaceutical excipients), The Pharmaceutical Press, London, 1994) ".Water/organic silicon emulsion is also by organic silicon polyether stabilisation (SiliconeSurfactants (organic silicon surfactant)-Surfactant Science Series V86 EdRandal M.Hill (1999)).
According to the specific embodiment of one, organopolysiloxane composition X is prepared by two Component System P, and the feature of described system P is
-it is present in two part P1 and P2 separated, and they are intended to be mixed to form described organopolysiloxane composition X and comprise composition A, B, C, D, E, F, G and H as above, and,
One of-part P1 or P2 comprises catalyst C and pore-foaming agent D and does not comprise polysiloxane B.
According to another embodiment of the present invention, the skin (4) be made up of elastomer silicone is by the crosslinked of organopolysiloxane composition X ' and/or solidification preparation, and described organopolysiloxane composition X ' comprises:
-at least one polysiloxane A ', per molecule has the C that at least two are connected to silicon 2-C 6alkenyl group,
-at least one polysiloxane B ', per molecule has at least two ≡ SiH unit and preferred at least three ≡ SiH unit,
At least one catalyst C of-catalytically effective amount, it is the compound of the metal belonging to platinum family derived from least one,
-optionally, at least one its chain often hold by three organic siloxy units end-blockings diorganopolysiloxanecompositions oil E, its organic group be connected with silicon atom be selected from there is 1-8 the carbon atom comprising end value alkyl as methyl, ethyl, propyl group and 3,3,3-trifluoro propyl, cycloalkyl is as cyclohexyl, suberyl, ring octyl group, and aryl is as xylyl, tolyl and phenyl
-optionally, at least one metal and/or inorganic filler F,
-optionally, at least one additive G, and
-optionally, at least one polysiloxane resin H.
Preferably, roller core (2) is made of metal.
According to the particularly advantageous embodiment of one, roller core (2) is columniform, rigidity, hollow, and comprises the network in hole, and wherein the diameter in each hole is 0.1-50mm and preferred 1-10mm.In the production process of roller according to the present invention, this structure of roller core to make it possible to said composition to be incorporated in hollow core and when applying centrifugal force, can make organopolysiloxane composition X or X ' through this some holes to form intermediate layer (3) or outer (4) after crosslinking.
According to the specific embodiment of one, the thickness of intermediate layer (3) is 1-100mm, preferred 1-50mm and more preferably 5-20mm.
According to the specific embodiment of another kind, the thickness of the skin be made up of elastomer silicone (4) is 0.1-10mm and preferred 0.5-5mm.
Polysiloxane A and A ' separately per molecule has the C that at least two are connected to silicon 2-C 6alkenyl group and have the viscosity of 10-300 000mPa.s, can be formed by following unit:
The siloxy units of-at least two following formulas:
Wherein:
-Y is C 2-C 6thiazolinyl, preferred vinyl,
-R is univalent hydrocarbyl group catalyst activity not being had to adverse effect, and its be usually selected from there is 1-8 the carbon atom comprising end value alkyl as methyl, ethyl, propyl group and 3,3,3-trifluoro propyl, cycloalkyl is as cyclohexyl, suberyl, ring octyl group, and aryl is as xylyl, tolyl and phenyl
-d=1 or 2, e=0,1 or 2 and d+e sum=1,2 or 3, and
-optionally, there is the siloxy units of following average formula:
Wherein R has identical meanings as above and f=0, and 1,2 or 3.
Following compound is the example of polysiloxane A and A ': the dimethyl polysiloxane with dimethylvinylsilyl end, there is (methyl ethylene) (dimethyl) polysiloxane copolymer of trimethylsilyl terminal, there is (methyl ethylene) (dimethyl) polysiloxane copolymer of dimethylvinylsilyl end.In the form of recommending most, polysiloxane A comprises terminal ethylenyl groups siloxy units.
Per molecule has at least two hydrogen atoms being connected to silicon and preferably at least three ≡ SiH unit and the example of the polysiloxane B or polysiloxane B ' with the viscosity of 1-5000mPa.s comprise with those of lower unit:
The siloxy units of-following formula:
Wherein:
-X is univalent hydrocarbyl group catalyst activity not being had to adverse effect, and its be usually selected from there is 1-8 the carbon atom comprising end value alkyl as methyl, ethyl, propyl group and 3,3,3-trifluoro propyl, cycloalkyl is as cyclohexyl, suberyl, ring octyl group, and aryl is as xylyl, tolyl and phenyl
-g=1 or 2, preferably equals 1, i=0, and 1 or 2, and g+i=1,2 or 3, and
-optionally, there is the siloxy units of following average formula:
Wherein X has identical meanings as above and j=0, and 1,2 or 3.
Suitable polysiloxane B or B ' is poly-methylhydrogensiloxane.
The catalyst C that the metal belonging to platinum family by least one forms also is known.Platinum group metal is called those of platinum metal, and platinum metal is also by term that ruthenium, rhodium, palladium, osmium and iridium are combined except platinum.Preferred use platinum and rhodium compound.The complex of patent US-A-3 159 601, US-A-3 159 602, US-A-3 220 972 and European patent EP-A-0 057 459, EP-A-0 188 978 and the platinum described in EP-A-0 190 530 and organic products can be used in especially, or the complex of platinum described in patent US-A-3 419 593 and vinylated organosiloxane.The general preferred platinum of catalyst.Preference is as the Karstedt complex described in US-A-3 775452 or solution.
Composition E is such as the linear polydimethylsiloxane-of nonfunctionalized, that is has formula (CH 3) 2siO 2/2repetitive and at its two ends, there is (CH 3) 3siO 1/2unit.
As inorganic filler F, can especially mention reinforcer and extending fillers.But the kind of this filler and consumption will be determined to obtain after mixing of all ingredients the viscosity of the composition being less than 30 000mPa.s.Thus, some filler is excluded because they have too high viscosity enhancing ability.These fillers can be the forms of the product segmented very much, and its average particulate diameter is less than 0.1 μm.In these fillers, especially can mention pyrogenic silica and precipitated silica; Their specific area is greater than 10m usually 2/ g, and be generally 20-300m 2/ g.These fillers can also be the forms that average particulate diameter is greater than the product of the more rough segmentation of 0.1 μm.As the example of these fillers, grinding quartz especially can be mentioned, diatomite, calcined clay, rutile-type titanium oxide, the oxide of iron, zinc, chromium, zirconium, magnesium, the aluminium oxide (hydration or unhydrated) of various form, boron nitride, lithopone, barium metaborate; Their specific area is less than 30m usually 2/ g.Filler can be surface modification, and this is undertaken by utilizing the various organic silicon-containing compound process being generally used for this object.Thus, these organic silicon-containing compounds can be organochlorosilane, two organocyclopolysiloxanes, six organic disiloxane, six organic disilazanes or two organic ring polysilazanes (French Patent (FRP) FR-A-1 126 884, FR-A-1 136 885, FR-A-1 236 505 and BP GB-A-1 024 234).As a rule, the filler processed comprises organic silicon-containing compound of the 3%-30% of their weight.Thus described filler can be processed before or after they are incorporated in preparaton.Described filler can be made up of the mixture of polytype varigrained filler.
The existence of metal packing F makes it possible to the anti-flammability improving foamed material.As metal packing F, can mention such as:
(a) based on platinum and the mixed oxide of iron or the additive of cerium-IV hopcalite, as described in patent application FR-A-2 757 869, especially following mixture:
-complex form or platinum compounds and FeO/Fe 2o 3the platinum mixture of the form of mixture;
-complex form or the platinum mixture of form of platinum compounds and cerium-IV oxide and/or hydroxide;
-complex form or platinum compounds and by cerium-IV oxide and/or hydroxide and titanium oxide TiO 2the platinum mixture of form of composition that forms of combination; And
-complex form or platinum compounds and by cerium-IV oxide and/or hydroxide, titanium oxide TiO 2and FeO/Fe 2o 3the platinum mixture of the form of the composition of the combination formation of compound;
(b) platinum and formula (FeO) x, (Fe 2o 3) mixture of Iron mixed oxide of y, wherein the ratio of x/y is 0.05/1 to 1/1, as described in patent application JP-A-76/035 501,
The mixture of (c) platinum and at least one rare earth oxide, especially platinum and cerium-IV oxide CeO 2mixture, as described in patent application FR-A-2 166 313, EP-A-0 347 349, FR-A-2 166 313 and EP-A-0 347 349,
(d) titanium oxide, such as by Degussa company with trade name product sold, such as product " tiO2 PF2 ", and
The oxide of the aluminium hydroxide of (e) hydration or non-hydrated, ferriferous oxide and cerium or hydroxide.
As additive G, catalyst-initiator can be introduced especially to make crosslinked slowing down.Organic amine, silazane, organic oxime, dicarboxylic diester, acetylenic ketone and alkynol (see such as FR-A-1 528 464,2 372 874 and 2 704 553) can be used especially.When using them for the moment, the additional proportion of this inhibitor can be 0.0001-5 weight portion for every 100 parts of polysiloxane A, preferred 0.001-3 weight portion.Phosphine, phosphite ester and phosphinate also belong to operable inhibitor in the present invention.The formula P (OR) described in patent US-B-6 300 455 can be mentioned especially 3compound.All these compounds it is known to the person skilled in the art that and can business obtain.Such as can mention following compound:
-be optionally the polysiloxane utilizing at least one thiazolinyl to replace of loop type, particularly preferably tetramethyl-ethylene base tetrasiloxane,
-pyridine,
-organic phosphite and phosphine,
-unsaturated amides,
-alkylating maleate, and
-there is the acetylene alcohol of following formula:
(R′)(R″)C(OH)-C≡CH
In the formula,
-R ' is linear or the alkyl of branching or phenyl;
-R " be alkyl or the phenyl of hydrogen atom or linear or branching; Radicals R ' and R " and optionally form ring relative to the carbon atom that triple bond is positioned at α position; And
-at R ' and R " in contained carbon atom add up at least 5, preferred 9-20.
For described acetylene alcohol, such as, can mention:
-1-acetenyl-1-cyclohexanol;
-3-methyl isophthalic acid-dodecyne-3-alcohol;
-3,7,11-trimethyl-1-dodecyne-3-alcohol;
-1,1-diphenyl-2-propine-1-alcohol;
-3-ethyl-6-ethyl-1-n-heptylacetylene-3-alcohol;
-2-methyl-3-butyne-2-alcohol;
-3-methyl isophthalic acid-ten five alkynes-3-alcohol, and
The derivative of-diallyl maleate or diallyl maleate.
These inhibitor add with the amount of the 1-50 000ppm relative to silicon composition gross weight, especially 10-10 000ppm and preferred 20-2000ppm.
Polysiloxane resin H is known commercially available branching organopolysiloxane oligomer or polymer.They provide in the form of a solution, preferred siloxane solution.As the example of branching organopolysiloxane oligomer or polymer, " MQ " resin, " MDQ " resin, " TD " resin and " MDT " resin can be mentioned, can by M, D and/or T siloxy units with alkenyl-functional groups.Person skilled in field of organic silicon uses the nomenclature of the following siloxy units of this expression usually:
R 3siO 1/2(M unit), RSiO 3/2(T unit), R 2siO 2/2(D unit) and SiO 4/2(Q unit).
Being particularly useful for polysiloxane resin H of the present invention is the organic siliconresin with " Si-thiazolinyl " functional group, namely has the resin of vinyl, pi-allyl and/or hexenyl functional group.A preferred embodiment of the invention, polysiloxane resin H is vinylated organic siliconresin.Advantageously, they comprise one or more alkenyl groups of 0.1%-20% weight in their structure.In these resins, alkenyl group can be positioned on siloxy units M, D or T.These resins can such as according to the method preparation described in patent US-A-2 676 182.Some in these resins can business obtain, and the most common is the form of solution.
Such as, polysiloxane resin H comprises:
-at least two kinds of different siloxy units, described unit is selected from following unit:
W aZ bSiO (4-(a+b))/2
(V)
Wherein:
-symbol W is identical or different, represents C separately 2-C 6alkenyl group;
-symbols Z is identical or different, and represent the monovalent hydrocarbon of non-hydrolysable catalyst activity not being had to adverse effect separately, it is optionally halogenation and it is preferably selected from alkyl group and is selected from aromatic yl group, and
-a is 1 or 2, and preferably 1, b is 0,1 or 2 and a+b sum equals 1,2 or 3 ,-and optionally, the unit of following formula:
Z cSiO (4-c)/2
(VI)
Wherein Z has identical meanings as above and c equals 0,1,2 or 3, and condition is unit (V) or (VI) is one of at least T or Q unit.
One of the present invention preferred embodiment in, polysiloxane resin H is following such resin, and this resin comprises Si-Vi unit (wherein " Vi " represents vinyl groups) and is selected from following organic siliconresin:
-MD viq, wherein vinyl groups is comprised in D unit,
-MD vitQ, wherein vinyl groups is comprised in D unit,
-MM viq, wherein vinyl groups is comprised in a part for M unit,
-MM vitQ, wherein vinyl groups is comprised in a part for M unit,
-MM vidD viq, wherein vinyl groups is comprised in M and D unit,
-and composition thereof,
Wherein:
-M=formula R 3siO 1/2siloxy units
-M vi=formula (R 2) (vinyl) SiO 1/2siloxy units
-D=formula R 2siO 2/2siloxy units
-D vi=formula (R) (vinyl) SiO 2/2siloxy units
-Q=formula SiO 4/2siloxy units;
-T=formula RSiO 3/2siloxy units, and
-R group is identical or different, is monovalent hydrocarbon, be selected from there is 1-8 the carbon atom comprising end value alkyl as methyl, ethyl, propyl group and 3,3,3-trifluoro propyl, and aromatic yl group is as xylyl, tolyl and phenyl.
The special embodiment of another kind according to the present invention, polysiloxane resin H is added in composition of the present invention with the form of the mixture at least one polysiloxane oil.
According to another embodiment of the invention, vinylated polysiloxane resin H before crosslinked with 25% weight at the most, preferably at the most 20% weight and more preferably the amount of 1%-20% weight be present in elastomer silicone composition, relative to the total weight of the present composition.
The amount of vinylated polysiloxane A or A ', polysiloxane resin H and polysiloxane B or B ' with hydrogenation functional group makes the mol ratio of ≡ SiH functional group and ≡ SiVi functional group between 0.5 and 10, preferably between 1 an 6.
The special embodiment of one according to the present invention, this organopolysiloxane composition X comprises:
(A) at least one polysiloxane A of 100 weight portions, has the viscosity of 10-300 000mPa.s and per molecule has the C that at least two are connected to silicon 2-C 6alkenyl group,
(B) at least one polysiloxane B of 0.5-50 weight portion, has the viscosity of 1-5000mPa.s and per molecule has at least two hydrogen atoms being connected to silicon and preferred at least three ≡ SiH unit,
(C) at least one catalyst C of catalytically effective amount, its metal belonging to platinum family by least one forms,
(D) at least one of 0.05-50 weight portion is according to pore-foaming agent D as above of the present invention,
(E) 0-50 weight portion at least one its chain often hold by three organic siloxy units end-blockings diorganopolysiloxanecompositions oil E, its organic group be connected with silicon atom be selected from there is 1-8 the carbon atom comprising end value alkyl as methyl, ethyl, propyl group and 3,3,3-trifluoro propyl, cycloalkyl is as cyclohexyl, suberyl, ring octyl group, and aryl is as xylyl, tolyl and phenyl
(F) at least one inorganic filler F of 0.5-50 part,
(G) at least one additive G of 0-10 weight portion, and
(H) the polysiloxane resin H of 0-70 weight portion,
-other condition is, determines that the selection of described composition, kind and consumption are less than 30 000mPa.s to make the viscosity of described composition.
Another object of the present invention relates to producing and can be used for the method for the compressible roller of the present invention (1) be defined as above of bat printing, and described method comprises and is following step:
A) roller core of the present invention (2) be defined as above is installed in the preferred cylindrical die be made up of stainless steel, to make main shaft be level,
B) in this mould, the organopolysiloxane composition X ' be defined as above is introduced by means of static mixer,
C) preferably by centrifugal action, force described cylindrical die round this main horizontal rotational shaft and heat cylindrical die to higher than 35 DEG C and preferably greater than or equal to the temperature of 40 DEG C, to be formed outer (4) on the inwall of described cylindrical die
D) in this mould, the organopolysiloxane composition X be defined as above being enough to the amount of filling this mould is introduced by means of dynamic mixer,
E) preferably by centrifugal action, force described cylindrical die round this main horizontal rotational shaft and heat cylindrical die to higher than 35 DEG C and preferably greater than or equal to the temperature of 40 DEG C, to form the intermediate layer (3) of being made up of Silicone foam, and
F) this cylindrical die is removed to reclaim compressible roller (1).
According to the particularly advantageous embodiment of one, method according to the present invention comprises and is following step:
A) the hollow roller core (2) of columniform rigidity is installed in the preferred cylindrical die be made up of stainless steel, be level to make main shaft, described roller core (2) comprises the network in hole, and wherein the diameter in each hole is 0.1-50mm and preferred 1-10mm
B) by means of static mixer, the organopolysiloxane composition X ' be defined as above is incorporated in the cavity of described roller core (2),
C) described cylindrical die is forced round this main horizontal rotational shaft to make this organopolysiloxane composition X ' through the hole of described roller core (2) and form uncrosslinked skin (4) on the inwall of described cylindrical die by centrifugal action
D) 35 DEG C are heated to above and preferably greater than or equal to the temperature of 40 DEG C to make the crosslinked and/or solidification of skin (4),
E) by means of dynamic mixer, the organopolysiloxane composition X be defined as above is incorporated in the cavity of described roller core (2),
F) described cylindrical die is forced round this main horizontal rotational shaft to make this organopolysiloxane composition X through the hole of described roller core (2) and to fill this cylindrical die by centrifugal action,
G) 35 DEG C are heated to above and preferably greater than or equal to the temperature of 40 DEG C to make this organopolysiloxane composition X foam and crosslinked, to form the intermediate layer (3) of being made up of Silicone foam, and
H) this cylindrical die is removed to reclaim compressible roller (1).
What look back is, in the static mixer of product being mainly used in relative flow, various composition presses together closely to mix via one group of baffle plate (chicanes), and in the dynamic mixer of product being generally used for more viscosity, various composition is introduced in mixing chamber, and the element of the such as pulpboard driven by stirring movement at this place performs mixing.
Static mixer and dynamic mixer are known and can business obtain.
Another object of the present invention relates to the compressible roller (1) obtained by the inventive method as above.
Finally, last object of the present invention relates to compressible roller of the present invention (1) as above for printing or the purposes of bat printing.
Accompanying drawing explanation
Appended single figure shows compressible roller (1), comprising:
The cylindrical roll core (2) of-rigidity,
-cover the intermediate layer (3) of being made up of Silicone foam of described roller core (2), and
-cover the skin (4) be made up of elastomer silicone in described intermediate layer (3).
Detailed description of the invention
All viscosity that this description relates to all correspond to the dynamic viscosity value measured at 25 DEG C by known method itself.Viscosity is measured according to the instruction of the standard A FNOR NFT 76 106 in May nineteen eighty-two with BROOKFIELD viscosimeter.These viscosity corresponds to what is called " newton " the dynamic viscosity value of 25 DEG C, that is by known method itself in dynamic viscosity that is enough low for surveyed viscosity thus that measure under the shear rate gradient had nothing to do with velocity gradient.
The embodiment that will be used as now non-limiting example describes the present invention in more detail.
Embodiment
Two component combine thing is prepared by following composition:
1) part P1:
- a: vinyl polysiloxane resin, comprises siloxy units M, D viwith Q (or " MD viq "), wherein Vi=vinyl groups, M:(CH 3) 3siO 1/2, Q:SiO 4/2, D vi: (CH 3) (Vi) SiO 2/2
- b1: dimethyl silicone polymer, with unit (CH 3) 2viSiO 1/2end-blocking and its viscosity is 3500mPa.s at 25 DEG C
- b2: dimethyl silicone polymer, with unit (CH 3) 2viSiO 1/2end-blocking and its viscosity is 10 000mPa.s at 25 DEG C
- b3: dimethyl silicone polymer, with unit (CH 3) 2viSiO 1/2end-blocking and its viscosity is 60 000mPa.s at 25 DEG C
- b4: polydimethyl siloxane oil, at its each end of the chain with unit Vi (CH 3) 2siO 1/2end-blocking, has the viscosity of 100 000mPa.s at 25 DEG C
- c1: with the pyrogenic silica of organic silicone oil process, the specific area had equals 30m 2/ g (BET), by trade name rY50 sells
- c2: diatomite, by CECA company with trade name fD sells
- d1: butanols, d2: organosilicon/aqueous emulsion, comprise 58.45% weight water or d3: water
- e: Karstedt platinum catalyst
- f: polydimethyl siloxane oil, at its each end of the chain with unit (CH 3) 3siO 1/2end-blocking and there is the viscosity of 1000mPa.s at 25 DEG C
- g: poly-(vinyl methyl) (dimethyl) silicone oil, has the cells D of 2% weight vithe unit M of content and 0.4% weight vicontent (there is the oil that side hangs vinylated group).
2) part P2:
- a: vinyl polysiloxane resin, comprises siloxy units M, D viwith Q (or " MD viq ")
- b1: dimethyl silicone polymer, with unit (CH 3) 2(Vi) SiO 1/2end-blocking and its viscosity is 3500mPa.s
- b3: dimethyl silicone polymer, with unit (CH 3) 2(Vi) SiO 1/2end-blocking and its viscosity is 25 DEG C of 60 000mPa.s
- b4: polydimethyl siloxane oil, at its each end of the chain with unit Vi (CH 3) 2siO 1/2end-blocking and there is the viscosity of 100 000mPa.s at 25 DEG C
- f: polydimethyl siloxane oil, at its each end of the chain with unit (CH 3) 3siO 1/2end-blocking and there is the viscosity of 1000mPa.s at 25 DEG C
- i: polydimethyl siloxane oil, at its each end of the chain with unit (CH 3) 2hSiO 1/2end-blocking
- h: poly-methylhydrogensiloxane oil, at each end of the chain with unit (CH 3) 3siO 1/2end-blocking
- j: by (CH 3) 2(Vi) SiO 1/2unit terminated and there is the solution comprising 1% ethynylcyclohexanol in the polydimethyl siloxane oil of the viscosity of 600mPa.s at 25 DEG C.
Following table 1 describes tested composition.
Table 1: composition-weight portion
3) for the preparation of the compressible roller of bat printing:
Added to by the part P2 of 50 parts by volume in the part P1 of 50 parts by volume, to prepare foamed material precursor organopolysiloxane composition X, it is tested in the following manner:
A) at stainless steel cylindrical die (long 132cm, overall diameter 46cm) the columniform rigid hollow roller core (2) of middle installation, to make main shaft be level, described roller core (2) comprises the network in hole, and wherein the diameter in each hole is about 4mm;
B) the organopolysiloxane composition X ' obtained by part A and the B (Rhodorsil or BlueSil by name applied for bat printing by Bluestar Silicones France company sells) of the poly-addition RTV-2 of mixing is introduced in the cavity of roller core (2) by means of static mixer
C) force cylindrical die around main horizontal rotational shaft by centrifugal action, to make organopolysiloxane composition X ' through the hole of roller core (2) and form uncrosslinked skin (4) on the inwall of cylindrical die,
D) by this mold heated to 40 DEG C, continue 1-4 minute, with make formed layer be cross-linked,
E) foamed material precursor organopolysiloxane composition X as above by means of dynamic mixing machine (the present invention, preparation path 1) or by means of static mixer (contrast preparation path 2)and be introduced in the cavity of roller core (2),
F) force cylindrical die around main horizontal rotational shaft by centrifugal action, to make organopolysiloxane composition X through the hole of roller core (2) and to fill this cylindrical die,
G) by system heating to higher than 40 DEG C, continue about 5 minutes, to foam to make organopolysiloxane composition X and crosslinked, to form the intermediate layer (3) of being made up of Silicone foam, and
H) cylindrical die is removed, to reclaim compressible roller (1).
4) result
According to preparation path 2 (contrast), also namely at the step e of said method) in use all foamed materials of preparing to introduce foamed material precursor silicon composition X of static mixer all to have defect, especially steep and the pachydermia on surface at foamed material owing to there is large scale on the outer surface of sponge layer.
When use preparation path 1 time, namely at the step e of said method) in use dynamic mixer (the present invention) to introduce foamed material precursor silicon composition X time, prepare roller by following embodiment:
A) embodiment 1 (contrast 1, butanols pore-foaming agent), has defect, especially there is the pachydermia on large scale bubble and the surface at foamed material owing to the outer surface at sponge layer;
B) embodiment 2,3 and 4, no longer has defect, and the bubble of middle sponge layer is uniform and has small size, and the skin on surface is much thinner than the skin obtained in embodiment 1.
Table 2:
As shown in table 2 go out, the foamed material being used as intermediate layer in roller prepared in accordance with the present invention really meet for print or bat printing compressible roller in the regulation requirement that uses.
In this manual:
-abbreviation " R/R " refers to the fracture strength according to standard A FNOR NF T 46002, represents with MPa,
-abbreviation hardness DS00 refers to Shore 00 hardness,
-abbreviation " A/R " refers to according to aforesaid standards in the elongation at break of %,
-abbreviation " R/d " refers to the tearing strength in units of N/mm.

Claims (33)

1. compressible roller (1), it comprises:
-columniform rigidity roller core (2),
-cover the intermediate layer (3) of being made up of Silicone foam of described roller core (2), and
-cover the skin (4) be made up of elastomer silicone in described intermediate layer (3),
The feature of described roller is that described intermediate layer (3) of being made up of Silicone foam is prepared by the crosslinked of organopolysiloxane composition X and/or solidification, and described organopolysiloxane composition X comprises following composition:
-at least one polysiloxane A, has the viscosity of 10-300000mPa.s and per molecule has the C that at least two are connected to silicon 2-C 6alkenyl group,
-at least one polysiloxane B, has the viscosity of 1-5000mPa.s and per molecule has at least two ≡ SiH unit,
At least one catalyst C of-catalytically effective amount, it is the compound of the metal belonging to platinum family derived from least one,
-at least one pore-foaming agent D, it is water or water-based emulsion,
-optionally, and at least one often holding by the diorganopolysiloxanecompositions oil E of three organic siloxy units end-blockings at its chain, its organic group be connected with silicon atom is selected from the alkyl with 1-8 the carbon atom comprising end value, cycloalkyl, and aryl,
-optionally, at least one metal and/or inorganic filler F,
-optionally, at least one additive G, and
-optionally, at least one polysiloxane resin H,
-other condition is, determines that the selection of described composition, kind and consumption are less than 30000mPa.s to make the viscosity of described organopolysiloxane composition X,
Wherein this Silicone foam has and is less than 0.25g/cm 3density.
2. the compressible roller (1) of claim 1, is characterized in that described polysiloxane B per molecule has at least three ≡ SiH unit.
3. the compressible roller (1) of claim 1, is characterized in that described alkyl is selected from methyl, ethyl, propyl group and 3,3,3-trifluoro propyl in described diorganopolysiloxanecompositions oil E.
4. the compressible roller (1) of claim 1, is characterized in that described cycloalkyl is selected from cyclohexyl, suberyl, ring octyl group in described diorganopolysiloxanecompositions oil E.
5. the compressible roller (1) of claim 1, is characterized in that described aryl is selected from xylyl, tolyl and phenyl in described diorganopolysiloxanecompositions oil E.
6. the compressible roller (1) of claim 1, is characterized in that the viscosity of described organopolysiloxane composition X is less than 25000mPa.s.
7. the compressible roller (1) of one of claim 1-6, it is characterized in that organopolysiloxane composition X is prepared by two Component System P, the feature of described system P is:
-it is present in two part P1 and P2 separated, and they are intended to be mixed to form described organopolysiloxane composition X and comprise composition A, B, C, D, E, F, G and the H as claim 1 limits, and,
One of-part P1 or P2 comprises catalyst C and pore-foaming agent D and does not comprise polysiloxane B.
8. the compressible roller (1) of one of claim 1-6, it is characterized in that the skin (4) be made up of elastomer silicone is by the crosslinked of organopolysiloxane composition X ' and/or solidification preparation, described organopolysiloxane composition X ' comprises:
-at least one polysiloxane A ', per molecule has the C that at least two are connected to silicon 2-C 6alkenyl group,
-at least one polysiloxane B ', per molecule has at least two ≡ SiH unit,
At least one catalyst C of-catalytically effective amount, it is the compound of the metal belonging to platinum family derived from least one,
-optionally, and at least one often holding by the diorganopolysiloxanecompositions oil E of three organic siloxy units end-blockings at its chain, its organic group be connected with silicon atom is selected from the alkyl with 1-8 the carbon atom comprising end value, cycloalkyl, and aryl,
-optionally, at least one inorganic filler F,
-optionally, at least one additive G, and
-optionally, at least one polysiloxane resin H.
9. the compressible roller (1) of claim 8, is characterized in that described polysiloxane B ' per molecule has at least three ≡ SiH unit.
10. the compressible roller (1) of claim 8, is characterized in that described alkyl is selected from methyl, ethyl, propyl group and 3,3,3-trifluoro propyl in described diorganopolysiloxanecompositions oil E.
The compressible roller (1) of 11. claims 8, is characterized in that described cycloalkyl is selected from cyclohexyl, suberyl, ring octyl group in described diorganopolysiloxanecompositions oil E.
The compressible roller (1) of 12. claims 8, is characterized in that described aryl is selected from xylyl, tolyl and phenyl in described diorganopolysiloxanecompositions oil E.
The compressible roller (1) of 13. claims 1, is characterized in that roller core (2) is made of metal.
The compressible roller (1) of one of 14. claim 1-6 and 13, it is characterized in that roller core (2) is columniform, rigidity, hollow, and comprise the network in hole, wherein the diameter in each hole is 0.1-50mm.
The compressible roller (1) of 15. claims 14, is characterized in that the diameter in each hole is 1-10mm.
The compressible roller (1) of one of 16. claim 1-6, is characterized in that the thickness in intermediate layer (3) is 1-100mm.
The compressible roller (1) of 17. claims 16, is characterized in that the thickness in intermediate layer (3) is 1-50mm.
The compressible roller (1) of 18. claims 16, is characterized in that the thickness in intermediate layer (3) is 5-20mm.
The compressible roller (1) of one of 19. claim 1-6, is characterized in that the thickness of the skin (4) be made up of elastomer silicone is 0.1-10mm.
The compressible roller (1) of 20. claims 19, is characterized in that the thickness of the skin (4) be made up of elastomer silicone is 0.5-5mm.
21. production methods that can be used for the compressible roller as any one of the claims (1) of bat printing, described method comprises following step:
Roller core (2) as claim 1-6, any one of 13-15 limit a) is installed in cylindrical die, to make that main shaft is level and to be thus referred to as main trunnion axis,
B) in this mould, the organopolysiloxane composition X ' as one of claim 8-12 limits is introduced by means of static mixer,
C) force described cylindrical die round this main horizontal rotational shaft and heat cylindrical die to higher than the temperature of 35 DEG C, to be formed outer (4) on the inwall of described cylindrical die,
D) in this mould, the organopolysiloxane composition X as claim 1 restriction being enough to the amount of filling this mould is introduced by means of dynamic mixer,
E) force described cylindrical die round this main horizontal rotational shaft and heat cylindrical die to higher than the temperature of 35 DEG C, to form the intermediate layer (3) of being made up of Silicone foam, and
F) this cylindrical die is removed to reclaim compressible roller (1).
The method of 22. claims 21, it is characterized in that described step a) in, described cylindrical die is made up of stainless steel.
The method of 23. claims 21, is characterized in that at described step c) in, force described cylindrical die round this main horizontal rotational shaft by centrifugal action.
The method of 24. claims 21, is characterized in that at described step c) in, described temperature is be more than or equal to the temperature of 40 DEG C.
The method of 25. claims 21, is characterized in that at described step e) in, force described cylindrical die round this main horizontal rotational shaft by centrifugal action.
The method of 26. claims 21, is characterized in that at described step e) in, described temperature is for being more than or equal to 40 DEG C.
27. as the production method of the compressible roller (1) that can be used for bat printing of one of claim 21-26, and described method comprises the following steps:
A) the hollow roller core (2) of columniform rigidity is installed in cylindrical die, to make that main shaft is level and to be thus referred to as main trunnion axis, described roller core (2) comprises the network in hole, and wherein the diameter in each hole is 0.1-50mm
B) by means of static mixer the organopolysiloxane composition X ' limited as one of claim 8-12 is incorporated into as described in roller core (2) cavity in,
C) described cylindrical die is forced round this main horizontal rotational shaft to make this organopolysiloxane composition X ' through the hole of described roller core (2) and form uncrosslinked skin (4) on the inwall of described cylindrical die by centrifugal action
D) temperature of 35 DEG C is heated to above to make skin (4) be cross-linked and/or solidification,
E) by means of dynamic mixer the organopolysiloxane composition X limited as one of claim 1-6 is incorporated into as described in roller core (2) cavity in,
F) described cylindrical die is forced round this main horizontal rotational shaft to make this organopolysiloxane composition X through the hole of described roller core (2) and to fill this cylindrical die by centrifugal action,
G) temperature being heated to above 35 DEG C to make this organopolysiloxane composition X foam and crosslinked, to form the intermediate layer (3) of being made up of Silicone foam, and
H) this cylindrical die is removed to reclaim compressible roller (1).
The method of 28. claims 27, it is characterized in that described step a) in, described cylindrical die is made up of stainless steel.
The method of 29. claims 27, it is characterized in that described step a) in, the diameter in described each hole is 1-10mm.
The method of 30. claims 27, is characterized in that in described steps d) in, described temperature is for being more than or equal to 40 DEG C.
The method of 31. claims 27, is characterized in that in described step g) in, described temperature is for being more than or equal to 40 DEG C.
32. compressible roller (1) obtained by the method for one of claim 21-31.
The compressible roller (1) limited any one of 33. claim 1-20 and 32 is for printing or the purposes of bat printing.
CN201180051222.0A 2010-09-06 2011-08-25 For the compressible roller of printing machine Expired - Fee Related CN103180144B (en)

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Families Citing this family (4)

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LU92573B1 (en) * 2014-10-16 2016-04-18 Windmöller & Hölscher Kg BASIC BODY FOR RECORDING A PRINT IMAGE STRUCTURE
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DE102018217261A1 (en) * 2017-11-09 2019-05-09 Heidelberger Druckmaschinen Aktiengesellschaft Printing process and sheet-fed printing machine
FR3099165A1 (en) * 2019-07-25 2021-01-29 Elkem Silicones France Sas SILICONE COMPOSITION FOR ELASTOMERIC FOAM.

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1313185A (en) * 1969-10-07 1973-04-11 Tokyo Serofan Kk Layer composition and a method of preparing it
EP0388740A2 (en) * 1989-03-18 1990-09-26 M.A.N.-ROLAND Druckmaschinen Aktiengesellschaft Shell for offset-cylinder for rotary machines
US5415612A (en) * 1992-06-12 1995-05-16 American Roller Company Compressible roller
US5645942A (en) * 1994-06-29 1997-07-08 Dow Corning Toray Silicone Co., Ltd. Foam coated rolls and method for preparing same
US6089848A (en) * 1994-03-08 2000-07-18 Syfal S.R.L. Apparatus for producing rollers with elastic silicone-based material layers
CN1296510A (en) * 1999-03-16 2001-05-23 三井化学株式会社 Crosslinkable rubber composition and use thereof
CN1659034A (en) * 2002-06-11 2005-08-24 曼·罗兰·德鲁克马辛伦公司 Application device for a printing/painting unit in a processing machine

Family Cites Families (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2676182A (en) 1950-09-13 1954-04-20 Dow Corning Copolymeric siloxanes and methods of preparing them
FR1126884A (en) 1954-10-02 1956-12-03 Teves Kg Alfred Pressure regulator for harmonic pressure distribution
FR1136885A (en) 1954-10-06 1957-05-21 Dow Corning Process for manufacturing hydrophobic pulverulent organosilicon products
BE556585A (en) 1956-04-11
US3159602A (en) 1962-06-07 1964-12-01 Olin Mathieson Preparation of polymeric phosphates
GB1024234A (en) 1962-06-27 1966-03-30 Midland Silicones Ltd Improvements in or relating to siloxane elastomers
US3159601A (en) 1962-07-02 1964-12-01 Gen Electric Platinum-olefin complex catalyzed addition of hydrogen- and alkenyl-substituted siloxanes
US3220972A (en) 1962-07-02 1965-11-30 Gen Electric Organosilicon process using a chloroplatinic acid reaction product as the catalyst
NL131800C (en) 1965-05-17
US3467009A (en) 1965-07-06 1969-09-16 Grace W R & Co Compressible printing roll
FR1528464A (en) 1966-06-23 1968-06-07 Dow Corning One-part curable organopolysiloxane compositions
US3775452A (en) 1971-04-28 1973-11-27 Gen Electric Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes
FR2166313A1 (en) 1972-01-07 1973-08-17 Rhone Poulenc Sa Fire resistant organopolysiloxane elastomer - by curing mixture of diorgano polysiloxane, filler, org peroxide, platinum and
JPS5135501A (en) 1974-09-19 1976-03-26 Maruyasu Doboku Kk SUKURYUOOGA
US3923705A (en) 1974-10-30 1975-12-02 Dow Corning Method of preparing fire retardant siloxane foams and foams prepared therefrom
DE2654893A1 (en) 1976-12-03 1978-06-15 Wacker Chemie Gmbh PROCESS FOR PRODUCING STICKY FABRIC REPELLENT COATING
US4189545A (en) 1978-03-13 1980-02-19 General Electric Company Silicone foam composition which has burn resistant properties
US4394317A (en) 1981-02-02 1983-07-19 Sws Silicones Corporation Platinum-styrene complexes which promote hydrosilation reactions
US4418157A (en) 1983-03-17 1983-11-29 General Electric Company Low density silicone foam compositions and method for making
FR2575085B1 (en) 1984-12-20 1987-02-20 Rhone Poulenc Spec Chim PLATINUM-TRIENE COMPLEX AS HYDROSILYLATION REACTION CATALYST AND PREPARATION METHOD THEREOF
FR2575086B1 (en) 1984-12-20 1987-02-20 Rhone Poulenc Spec Chim PLATINUM-ALCENYLCYCLOHEXENE COMPLEX AS HYDROSILYLATION REACTION CATALYST AND PROCESS FOR PREPARING THE SAME
US4590222A (en) 1985-10-16 1986-05-20 Dow Corning Corporation Lower density silicone elastomeric foam
FR2589872B1 (en) 1985-11-12 1988-06-10 Dow Corning Sa ORGANOSILOXANE FOAMS AND THEIR PREPARATION
FR2632961B1 (en) 1988-06-15 1992-03-13 Rhone Poulenc Chimie SILICONE ELASTOMERS, WITH IMPROVED FLAME RESISTANCE
US5206992A (en) 1992-06-12 1993-05-04 American Roller Company Compressible roller
FR2704553B1 (en) 1993-04-30 1995-06-09 Rhone Poulenc Chimie Long chain alpha-acetylenic alcohols as hydrosilylation reaction inhibitors, and their application for the preparation of stable curable silicone compositions.
ID22339A (en) 1996-12-30 1999-09-30 Ge Bayer Silicones Gmbh & Co MIXED MIXES CAN BE CONNECTED AND THE PROCESS OF MAKING IT
FR2757869B1 (en) 1996-12-31 1999-05-21 Rhodia Chimie Sa USE OF PT-BASED MIXTURES AND TRANSITIONAL METAL COMPOUNDS OTHER THAN PT TO IMPROVE ARC RESISTANCE PROPERTIES OF SILICON ELASTOMERS
US6084002A (en) 1999-02-02 2000-07-04 Dow Corning Corporation Flame retardant silicone foams
JP2002339949A (en) * 2001-05-14 2002-11-27 Shin Etsu Polymer Co Ltd Composite semiconductive silicone rubber roll
JP2008019337A (en) * 2006-07-12 2008-01-31 Canon Chemicals Inc Silicone rubber foam and silicone rubber expanded oa roll

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1313185A (en) * 1969-10-07 1973-04-11 Tokyo Serofan Kk Layer composition and a method of preparing it
EP0388740A2 (en) * 1989-03-18 1990-09-26 M.A.N.-ROLAND Druckmaschinen Aktiengesellschaft Shell for offset-cylinder for rotary machines
US5415612A (en) * 1992-06-12 1995-05-16 American Roller Company Compressible roller
US6089848A (en) * 1994-03-08 2000-07-18 Syfal S.R.L. Apparatus for producing rollers with elastic silicone-based material layers
US5645942A (en) * 1994-06-29 1997-07-08 Dow Corning Toray Silicone Co., Ltd. Foam coated rolls and method for preparing same
CN1296510A (en) * 1999-03-16 2001-05-23 三井化学株式会社 Crosslinkable rubber composition and use thereof
CN1659034A (en) * 2002-06-11 2005-08-24 曼·罗兰·德鲁克马辛伦公司 Application device for a printing/painting unit in a processing machine

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