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Method for laser engraving flexographic printing articles based on millable polyurethanes

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Title: Method for laser engraving flexographic printing articles based on millable polyurethanes.
Abstract: A flexographic printing sleeve or plate is made by a method that includes providing a millable polyurethane, crosslinking the millable polyurethane, and forming a relief by at least laser engraving the crosslinked millable polyurethane. For example, crosslinking may be accomplished by a peroxide-based process or by a vulcanization process using sulfur. A relief in one example is formed by extruding the millable polyurethane, thermally crosslinking the polyurethane after the extrusion step and laser engraving the crosslinked millable polyurethane. A printing article is formed into the shape of a flat printing plate or a continuous in-the-round printing sleeve. ...


Inventor: Rustom S. Kanga
USPTO Applicaton #: #20120043701 - Class: 264400 (USPTO) - 02/23/12 - Class 264 
Plastic And Nonmetallic Article Shaping Or Treating: Processes > Laser Ablative Shaping Or Piercing (i.e., Nonetching, Devoid Of Chemical Agent Other Than Air)



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The Patent Description & Claims data below is from USPTO Patent Application 20120043701, Method for laser engraving flexographic printing articles based on millable polyurethanes.

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CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of priority and is a Divisional of U.S. Non-Provisional Application Patent Application Ser. No. 12/356,330, filed Jan. 20, 2009, by Kanga and entitled “Laser Engravable Flexographic Printing Articles Based on Millable Polyurethanes, and Method”. The Non-Provisional Patent Application Ser. No. 12/356,330 is a Continuation-in-Part (CIP) of U.S. Non-Provisional Patent Application Ser. No. 11/813,612, filed Jul. 10, 2007, by Kanga and entitled “Laser Engravable Flexographic Printing Article.” The Non-Provisional Patent Application Ser. No. 11/813,612 is a U.S. national stage application of International Application No. PCT/US07/72246, filed Jun. 27, 2007, by Kanga and entitled “Laser Engraveable Flexographic Printing Article.” The International Application No. PCT/US2007/072246 claims the benefit of priority of U.S. Provisional Patent Application No. 60/816,786, filed Jul. 27, 2006, by Kanga. This application also claims priority to U.S. Provisional Patent Application No. 61/083,327, filed Jul. 24, 2008, by Kanga and entitled “Laser Engravable Flexographic Printing Article Based on Millable Polyurethanes.” The contents of the above-referenced applications are incorporated by reference herein.

TECHNICAL

FIELD OF THE INVENTION

The invention relates to an article for use in flexographic printing, such as a plate or sleeve, and a method for laser engraving the printing article to form a relief such that the article can be used in flexographic printing. The present invention also provides a method of crosslinking a Polyurethane Elastomer for making a directly laser engravable flexographic printing article by the use of commercially available Millable Polyurethanes (MPU). The printing article could be either a flat printing plate or a continuous in-the-round printing sleeve. Commercially available MPUs can be compounded either in an extruder or a compounder such as a Brabender using various crosslinking and laser sensitive additives. The compounded MPU is then extruded either on a flat carrier or a round sleeve, crosslinked either during extrusion or thereafter using thermal energy. The extruded and crosslinked MPU is ground or machined to the dimension required for the printing process and is ready for laser engraving. In one embodiment of the invention, the article does not require further processing, and as such can be used in a “direct-to-plate” laser engraving system.

BACKGROUND OF THE INVENTION

Printing plates are well known for use in flexographic printing, particularly on surfaces which are corrugated or smooth, such as packaging materials like cardboard, plastic films, etc. Typically, flexographic printing plates are manufactured using photopolymers which are exposed through a negative, processed using a solvent to remove the non-crosslinked areas to create a relief, which is post-crosslinked and detackified. This is typically a very lengthy and involved process. Recently, flexographic plates have been manufactured using digital imaging of an in situ mask layer which obviates the need for a negative or a photomask to make the plate, and which has other performance benefits as well.

Recently, it has been possible to laser engrave a rubber element directly to provide the desired relief surface necessary for flexographic printing. Laser engraving has provided a wide variety of opportunities for rubber printing plates. Highly concentrated and controllable energy lasers can engrave very fine details in rubber. The relief of the printing plate can be varied in many ways. Very steep as well as gently decreasing relief slopes can be engraved so as to influence the dot gain of such plates. Ethylene propylene diene monomer (EPDM) rubber can be laser engraved to form flexographic printing plates.

The directly engraved type of flexographic printing plate is made from vulcanized rubber. Commercial rubbers can be natural or synthetic, such as EPDM elastomers. Lasers can develop sufficient power densities to ablate certain materials. For example, high-power carbon dioxide (CO2) lasers can ablate many materials such as wood, plastic and rubber and even metals and ceramics. Once the output from a laser is focused at a particular point on a substrate with a suitable power density, it is possible to remove material to a desired depth to create a relief. Areas not struck by the laser beam are not removed. Thus, the use of the laser offers the potential of producing very intricate engravings in a desired material with substantial savings.

U.S. Pat. No. 3,459,733 to Caddell describes a method for producing polymer printing plates. The printing plate is made by exposing a layer of the polymeric material to a controlled laser beam of sufficient intensity to ablate the polymer and form depressions on the surface.

U.S. Pat. Nos. 5,798,202 and 5,804,353 to Cushner et al. disclose processes for making a flexographic printing plate by laser engraving a reinforced elastomeric layer on a flexible support. The process disclosed in U.S. Pat. No. 5,798,202 involves first reinforcing and then laser engraving a single-layer flexographic printing element having a reinforced elastomeric layer on a flexible support. The elastomeric layer may be reinforced mechanically, thermochemically, photochemically or with combinations of these processes. Mechanical reinforcement is provided by incorporating reinforcing agents, such as finely divided particulate material, into the elastomeric layer. Photochemical reinforcement is accomplished by incorporating photohardenable materials into the elastomeric layer and exposing the layer to actinic radiation. Photohardenable materials include photo-crosslinkable and photo-polymerizable systems having a photo-initiator or photo-initiator system.

The process disclosed in U.S. Pat. No. 5,804,353 is similar to U.S. Pat. No. 5,798,202, except that the process involves reinforcing and laser engraving a multilayer flexographic printing element having a reinforced elastomeric top layer, and an intermediate elastomeric layer on a flexible support. The elastomeric layer is reinforced mechanically, thermochemically, photochemically or combinations thereof. Mechanical and photochemical reinforcement is accomplished in the same manner as described by U.S. Pat. No. 5,798,202. The intermediate elastomeric layer may be reinforced as well.

A problem associated with elastomeric elements that are reinforced both mechanically and photochemically is that laser engraving does not efficiently remove the elastomeric material to provide desired relief quality, and ultimately, printing quality. It is desirable to use an additive in the elastomeric layer that is sensitive to infrared light in ordeff to enhance the engraving efficiency of the element. Photo-chemically reinforcing the element provides the desired properties for engraving as well as in its end-use as a printing plate. However, the presence of the additive as particulate or other absorbing material tends to reduce the penetration of the ultraviolet radiation required to photo-chemically reinforce the element. If the elastomeric layer is insufficiently crosslinked during photochemical reinforcement, the laser radiation cannot effectively remove the material and poor relief quality of the engraved area results. Further, the debris resulting from laser engraving tends to be tacky and difficult to completely remove from the engraved element. Additionally, if the element is not sufficiently photo-chemically reinforced, the required end-use properties as a printing plate are not properly achieved. These problems tend to be exacerbated with increasing concentration of the additive that enhances engraving efficacy.

U.S. Pat. No. 6,627,385 teaches the use of graft copolymers for laser engraving. U.S. Pat. No. 6,511,784, U.S. Pat. No. 6,737,216 and U.S. Pat. No. 6,935,236 teach the use of elastomeric copolymers for laser engraving using various infrared (IR) additives.

Many patents in the field teach the use of typical styrenic thermoplastic elastomers (TPEs) that have been used for photo-crosslinking applications. One problem associated with these non-polar TPEs is that they have limited sensitivity to laser engraving because of their hydrocarbon backbone nature. The use of polar TPEs such as thermoplastic polyurethanes (TPUs) thermoplastic polyester elastomers (TPPE) and thermoplastic polyamide elastomers (TPAE) as both laser engravable systems and as printing elements would be desirable. However, most of the above polar TPEs on the market would not be effective either as laser engravable systems, or as printing plates because they are not crosslinked.

The crosslinking of the above TPEs and especially TPUs has not been done before in flexography, and thus, TPUs have not been used in flexography. However, polyurethanes for flexography have been well known, particularly for liquid photopolymers. By definition, a TPU is solid at room temperature and can be extruded, and is workable at higher temperatures. This characteristic is due to the presence of hard and soft segments that form a network at room temperature, and is thus solid.

This network structure also differentiates TPUs from traditional polyurethanes in its outstanding physical attributes and thus offers an attractive system to be used in flexo applications. However, most elastomers used in Flexo need to be crosslinked to withstand the rigors of the printing process and to minimize swells in the inks used for printing. Additionally, the elastomers used in laser engraving have to be crosslinked. Traditional flexo photopolymers have unsaturation in the backbone, which allows the crosslinking with acrylate monomers and UV photo-initiators. The TPUs on the market today do not have unsaturation. Hence, the difficulty in UV crosslinking these for flexo applications. Additionally, laser engraving of elastomers with lasers lasing in the Near IR wavelengths need to be doped with highly absorptive laser additives. This does not allow UV crosslinking as a viable option to crosslink such elastomers. Thermal crosslinking or vulcanization is the only feasible approach in such applications. Millable Polyurethanes (MPUs) are a special category of TPUs. Millable Polyurethanes, as the name suggests, could be processed in the same way as rubber elastomers, including the use of compounding and extrusion methods. MPUs can be thermally crosslinked in a subsequent crosslink and post-crosslink step.

SUMMARY

OF THE INVENTION

Therefore, an object of the present invention is to provide a method for making a laser engravable flexographic printing article.

Another object of the present invention is to provide a reliable method for making a printing plate from crosslinking of Millable Polyurethanes (MPUs).

These and other objects of the present invention can be achieved in the preferred embodiments of the invention described below.

One preferred embodiment of the invention includes a method for making a flexographic printing article including the steps of providing a millable polyurethane, and crosslinking the polyurethane whereby the article can be used in a direct laser engraving flexographic process.

According to another preferred embodiment of the invention, the crosslinked millable polyurethane can be used in the direct laser engraving flexographic process and in flexographic printing without further processing.

According to another preferred embodiment of the invention, the printing article is laser engraved by infrared laser radiation to form a relief such that the article can be used in flexographic printing.

According to another preferred embodiment of the invention, the printing article can be a plate or a sleeve.

According to another preferred embodiment of the invention, the binder is a high performance polyester-based polyurethane processed as a millable polyurethane.

According to another preferred embodiment of the invention, the binder is a high performance polyether-based polyurethane processed as a millable polyurethane.

According to another preferred embodiment of the invention, the millable polyurethane is extruded and thermally crosslinked during extrusion.

According to another preferred embodiment of the invention, the millable polyurethane is compounded in a compounder and thermally crosslinked in a hot press.

According to another preferred embodiment of the invention, the millable polyurethane is milled on a 2-roll mill and thermally crosslinked in a hot press.

According to another preferred embodiment of the invention, at least one crosslinking additive for inducing the thermal crosslinking of the millable polyurethane is provided.

According to another preferred embodiment of the invention, at least one laser additive comprising such as carbon black, kaolin clay, mica, antimony tin oxide, or copper oxide is provided.

According to another preferred embodiment of the invention, the millable polyurethane is thermally crosslinked after extrusion.

According to another preferred embodiment of the invention, the millable polyurethane is crosslinked for about 15-30 minutes at about 240 to 350° F., and the polyurethane is crosslinked during the crosslinking.

According to another preferred embodiment of the invention, the mllable polyurethane is post-crosslinked for about 8 to 12 hours at about 180-240° F.

According to another preferred embodiment of the invention, the millable polyurethane is crosslinked during crosslinking with electron beam radiation.

According to another preferred embodiment of the invention, the printing article is hot-pressed to a desired dimension.

According to another preferred embodiment of the invention, the printing article is machined to a desired dimension.

According to another preferred embodiment of the invention, the binder is millable polyurethane/rubber blend.

According to another preferred embodiment of the invention, the binder is millable polyurethane/Energetic TPE blend.

According to another preferred embodiment of the invention, at least one additive for dissipating heat such as metal-based nanoparticles and/or metal oxide based nanoparticles or combination of Graphite/Carbon Black pigment are provided.

According to another preferred embodiment of the invention, at least one burn-rate modifier for increasing the rate of mass transfer during laser engraving such as oxidizers, burn rate catalysts such as Iron Oxides, Copper oxides, Copper Chromates or burn rate accelerators such as nano aluminum, boron and magnesium powders are provided.

According to another preferred embodiment of the invention, microspheres for decreasing the density of the millable polyurethane and increasing the rate of mass transfer during laser engraving of the article are provided.

According to another preferred embodiment of the invention, a method for laser engraving a flexographic printing article includes the steps of providing a millable polyurethane, crosslinking the polyurethane to form a laser engravable article, machined to precise dimension and laser engraving the article to form a relief such that the article can be used in flexographic printing.

According to another preferred embodiment of the invention, the article is engraved with a far infrared radiation laser, such as a carbon dioxide laser (10,600 NM).

According to another preferred embodiment of the invention, the article is engraved with a near infrared radiation laser, such as a Yttrium-based fiber laser (1100 NM), a neodymium doped yttrium aluminum garnet (ND-YAG) laser (1060 NM) and/or a diode array laser (830 NM).

According to another preferred embodiment of the invention, a method for making a flexographic printing article includes the steps of providing a binder such as a thermoplastic elastomer from a millable polyurethane system crosslinking the polyurethane such that the article can be used in a direct laser engraving flexographic process and in flexographic printing without further processing.

In at least one embodiment of the invention, a method of making a flexographic printing article includes providing a millable polyurethane, crosslinking the millable polyurethane to provide a laser-engravable element, and forming a relief in the element by at least laser engraving the crosslinked millable polyurethane. In at least one example, the millable polyurethane is crosslinked by a peroxide-based process. In at least one other example, the millable polyurethane is crosslinked by a vulcanization process using sulfur. The relief may be formed by lasing the element using laser radiation having a wavelength between approximately 830 nanometers and approximately 10,600 nanometers, for example the wavelength may be between approximately 830 nanometers and approximately 1100 nanometers. In at least one example, the article is formed as a flat printing plate, and in another example, the article is formed as a continuous in-the-round printing sleeve.

An additive may be added for increasing laser absorptivity of the element. For example, an additive may be selected from nanomaterials, mica, carbon black, kaolin clay, antimony tin oxide, and copper oxide.

An additive may be added for increasing heat dissipation in the element. For example, an additive may be selected from metal-based nanoparticles, metal-oxide based nanoparticles, carbotherm boron nitride platelets, carbon black, and graphite.

An additive may be added for reducing density of the element. For example, an additive may be selected from microspheres, borosilicate glass bubbles, spherical porous silica, crosslinked microspheres, and unexpanded microspheres containing liquid hydrocarbon.

An additive may be added for decreasing the pyrolysis temperature of the element. For example, an additive may be selected from ammonium perchlorate, ammonium nitrate, potassium nitrate, iron oxide, copper oxide, copper chromate, chrome oxide, manganese oxide, ferrocene, aluminum, boron, magnesium powder, oxetane group energetic thermoplastic elastomers, and azide group energetic thermoplastic elastomers.

In another embodiment of the invention, a flexographic printing article includes a substrate, and an outer layer of a laser-engravable cross-linked millable polyurethane applied to the substrate. The outer layer may be crosslinked, for example, by a peroxide-based process, or by a vulcanization process using sulfur. The outer layer may be absorptive of laser radiation having a wavelength between approximately 830 nanometers and approximately 10,600 nanometers, for example the wavelength may be between approximately 830 nanometers and approximately 1100 nanometers. In at least one example, the article is formed as a flat printing plate, and in another example, the article is formed as a continuous in-the-round printing sleeve.

The outer layer may include an additive for increasing laser absorptivity of the element. For example, an additive may be selected from nanomaterials, mica, carbon black, kaolin clay, antimony tin oxide, and copper oxide.

The outer layer may include an additive for increasing heat dissipation in the element. For example, an additive may be selected from metal-based nanoparticles, metal-oxide based nanoparticles, carbotherm boron nitride platelets, carbon black, and graphite.

The outer layer may include an additive for reducing density of the element. For example, an additive may be selected from microspheres, borosilicate glass bubbles, spherical porous silica, crosslinked microspheres, and unexpanded microspheres containing liquid hydrocarbon.

The outer layer may include an additive for decreasing the pyrolysis temperature of the element. For example, an additive may be selected from ammonium perchlorate, ammonium nitrate, potassium nitrate, iron oxide, copper oxide, copper chromate, chrome oxide, manganese oxide, ferrocene, aluminum, boron, magnesium powder, oxetane group energetic thermoplastic elastomers, and azide group energetic thermoplastic elastomers.

BRIEF DESCRIPTION OF THE DRAWINGS

The subject matter that is regarded as the invention may be best understood by reference to the following description taken in conjunction with the accompanying drawing figures in which:

FIG. 1 provides Table 1, which lists tested MPU and MPU blends;

FIG. 2 provides Table 2, which lists typical flexographic printing plate physicals;

FIG. 3 provides Table 3, which lists samples used in engraving tests with an Yttrium-based laser;

FIG. 4 provides Table 4, which lists process conditions, and physical properties of the sample sets of Table 3;

FIG. 5 provides Table 5, which lists results of the Yttrium-based laser engraving test of the sample sets of Table 3;

FIG. 6 provides Table 6, which lists test results of an engraving test on MPU and MPU/Rubber blends using a CO2 laser;

FIG. 7 provides Table 7, which lists physical properties and test results of cast polyurethanes used for an engraving test using a CO2 laser;

FIG. 8 provides Table 8, which lists PHR values for thermal crosslinking of TPUs during extrusion;

FIG. 9 provides Table 9, which lists a formulation for crosslinking an MPU by peroxide and sulfur cure systems;

FIG. 10 is a graph for illustrating the theoretical concept of balancing the physical properties and laser sensitivity;

FIGS. 11A-11F provide digital photographic images from an engraving test on MPU and MPU/Rubber blends using an Yttrium-base fiber laser; and

FIG. 12 is a perspective view of an engraving article.

DETAILED DESCRIPTION

OF THE PREFERRED EMBODIMENTS AND BEST MODE

According to a preferred embodiment of the invention, laser engraving provides a true “direct-to-plate” technology for flexography. The method is applied and practiced without the need for complicated processing steps during manufacturing, resulting in a substantial gain in productivity from laser engraving. Also, the plates are relatively inexpensive to manufacture, obviating the need for a sophisticated mask coating as is needed for digitally imaged plates. Recently, there has been a decrease in flexo reliefs with the use of thin plates (˜45 mil) becoming more common. This trend is very attractive and well-suited for the laser engraving of flexo plates.

However, for laser engraving plates in the market thus far, the image fidelity is not as good as current digitally imaged (laser ablation of a mask) or even conventional flexo plates. This relegates laser engraving to a niche market. Additionally, the productivity so far has not been good. Thus, there is a market need to improve both the two main deficiencies of engraving, compared with mask ablation-image quality and plate making productivity.

A laser engraving article according to a preferred embodiment of the invention comprises a flat engravable plate which is mounted on a round cylinder during the printing step, or a continuous “in the round” engravable sleeve. Either system comprises a carrier on which there may be one or more binder layers that are laser engravable.

The carrier for the laser engraving article depends on the end product. For the flat plates a heat stabilized polyethylene terephthalate (PET) of 5-7 mils thickness is preferred. The PET may be corona treated to improve adhesion, and may also be primer and adhesive coated.

For the sleeves the carrier may be a metal sleeve, typically nickel based or a composite sleeve. The sleeve is further primer and/or adhesive coated for improved adhesion. Often, the sleeve is further coated with a polyurethane foam which acts as the in situ cushion layer.

The choice of binder system for the engraving system is governed by a combination of its performance as a printing plate and sensitivity to or behavior in laser engraving. It is believed that a crosslinked millable polyurethane elastomer would provide the best performance attribute both for its printing performance and as an engravable system.

Millable Polyurethanes

Polyurethane elastomers for direct laser engraving applications can be divided in 3 broad classes:

1) Thermoplastic Polyurethanes (TPU)

2) Castable Polyurethanes (CPU) and,

3) Millable Polyurethanes (MPU)

All of the above have been tested in direct engraving applications but with very mixed results. Crosslinking of the elastomer is a requirement for the material to be used as an engravable elastomer. It was found that both the TPU and CPU resulted in a direct laser engraving (DLE) system that was unacceptable. The thermoplastic character in both resulted in undesirable melting artifacts and unacceptable imaging. Only the MPU showed acceptable engraving characteristics (clean engraving without melting artifacts).

Usually, TPU elastomers are typically produced in a single step with a slight excess of isocyanate (NCO). CPU elastomers are made by reacting polyol with a surplus of isocyanate in order to be in a liquid state during processing. Then, during final processing, the material is mixed with chain extenders to reach stoichiometric equivalence versus the combined OH number of polyol and chain extender. MPU elastomers on the other hand are produced with a final stoichiometric deficiency of isocyanates in order to obtain the necessary millable state.

MPU rubbers can be classified in accordance to either the chemical backbone or the type of vulcanization. As polyols, either polytetramethylene ether glycol ethers based on polytetrahydrofuran) or polyester. adipates (based on adipic acid and diols like ethandiol, butanediol, methylpropanediol, hexanediol, neopentylglycol, cyclohexanedimethanol, etc.) can be used. The careful selection of diol/glycol. and the molar ratio of glycol-blends influence the final properties of the MPU rubber. The right molar ratio of glycol blends is also important. The diisocyanate component is either aromatic diisocyanates like methylene diphenyl diisocyanate (MDI) and toluene diisocyanate (TDI) or aliphatic diisocyanate like dicyclohexylmethane diisocyanates or TMXDI (tetramethylxylene diisocyanate), which is a light stable isocyanate where the methylene groups separate the isocyanate groups from the aromatic ring. Aromatic diisocyanates provide excellent mechanical strength, whereas aliphatic diisocyanates give better heat and hydrolysis resistance. Aliphatic diisocyanates are also necessary if a light and color stable MPU is intended to be produced. Chain extenders are of low molecular weight like ethylene glycol, 1,4-butanediol, hydro quinone bis(2-hydroxy-ethyl)ether, glycerolmonoallylether, trimethylolpropane-monoallylether or water.

All polyurethane rubbers provide outstanding mechanical strengths and a high chemical resistance. Generally, ether-based polyurethane rubber provides excellent hydrolysis resistance, but poorer heat resistance, while ester based polyurethanes are typical for their outstanding oil and fuel resistance. Millable urethanes are polymers that are known for their excellent abrasion and strength properties, while being able to be processed on conventional rubber equipment. Existing millable urethanes are primarily used in applications that take advantage of these properties.

Polyurethane rubber is a specialty rubber that finds use in many common rubber articles such as skate wheels, conveyor belts, rubber covered rolls and other applications where urethane is used because of its properties. Urethane rubber compounds possess a unique combination of excellent abrasion resistance, excellent solvent and oil resistance, high tensile and tear properties, good resistance to ozone and oxygen, and good low temperature properties.

Peroxide Versus Sulfur Crosslinking of MPU

The vulcanization of polyurethane rubber leads to crosslinking between molecular chains, which result in a network structure. This resembles the concept of other vulcanized rubbers, but compared to other polyurethane elastomers, to a smaller number of urethane groups. These urethane groups form hydrogen bonds and contribute substantially to improved mechanical strength. For this reason, most polyurethane rubbers require the addition of active fillers like carbon blacks or silicas, which reinforce polyurethane rubbers in the same manner as with other rubbers. As will be seen later, the function of the reinforcing filler (carbon black) is also to increase the absorbance of the MPU to the lasing wavelength and additionally act as thermally dissipative additive.

Sulfur vulcanization requires unsaturated components to be built into the structure of polyurethane rubbers. This is done by using OH functional compounds with a double bond as chain extenders, for example glycerolmonoallylether (GAE) or trimethylpropane-monoallylether (TMPMAE). Of all isocyanates, only MDI hard segments are suitable co-reactants for peroxide crosslinking. With MDI we get stabilized diphenylmethane radical formation through the central methylene group which then results in crosslinking of the MPU. MPUs based on other isocyanates, i.e., aliphatic isocyanates, require unsaturation for peroxide crosslinking. Unlike sulfur vulcanization, only small amounts of unsaturation are sufficient.



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stats Patent Info
Application #
US 20120043701 A1
Publish Date
02/23/2012
Document #
13268196
File Date
10/07/2011
USPTO Class
264400
Other USPTO Classes
International Class
29C35/08
Drawings
18


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Plastic And Nonmetallic Article Shaping Or Treating: Processes   Laser Ablative Shaping Or Piercing (i.e., Nonetching, Devoid Of Chemical Agent Other Than Air)