Pigments and compositions for use in laser marking

FIELD: marking materials.

SUBSTANCE: invention relates to pigmentation and compositions for use in laser marking, in particular UV absorbing pigment at least partly covered with synergist having general formula [Rm(SiOn)]pR'q wherein m=1-3, n=1-3, p is a number equal to at least 1, q=0-3, and at least one of R or R' represents substituent. When pyrolized, pigment forms black material appropriate to form label. Such pigments are suitable for fluoropolymers serving to insulate wire conductors and cables.

EFFECT: expanded marking possibilities.

20 cl, 6 tbl, 38 ex

 

Cross-reference to proposals related to this invention

This application is an application under section 35, United States Code (35 U.S.C.) 111(a) and claims the priority of an application under 35 USC 119 from provisional application with registration No. 60/252286, filed November 21, 2000 under 35 USC 111(b). The description of this prior application is incorporated herein by reference.

BACKGROUND of INVENTION

The scope of the invention

This invention relates to pigments and compositions containing such pigments, especially the compositions of fluorocarbon polymers, and their use in laser marking substrates.

Introduction to the invention of

Polymers, such as fluoropolymers, are usually used as insulation materials for such substrates as wire and cable. For such use the fluoropolymer usually surrounds the Central wire or forms a wrapper around one or more insulated wires. To identify specific wires, it is often necessary to mark the insulation material or shell numbers, letters, or other trademarks. Laser marking is one preferred method of marking, as it can ensure the formation of relatively stable, very clear markings on the surface of the insulation and does not cause mechanical damage or not requires good and is GeSHi dye to the polymer.

In the laser marking is often used ultraviolet (UV) laser such as an excimer laser. Since the fluorocarbon polymers are transparent to ultraviolet radiation, usually to the fluoropolymer you want to add absorbing UV rays, connection or pigment, to form a label. Commonly used additive is titanium dioxide (TiO2). When the laser is aimed at containing the additive polymer composition, photosensitive TiO2changes the color of the result caused by the laser recovery Ti4+(colorless) in Ti3+(blue-black) in the crystal lattice TiO2. The use of TiO2in the fluorocarbon resin is described in U.S. patent No. 5560845 and 5789466 (both Birmingham et al.), which provide details on laser marking pigmented processed in the melt fluoropolymer substrates, which is used as a pigment of titanium dioxide-coated organosilanes. These documents assure that organosilane improves the dispersibility of the pigment TiO2while reducing the number of agglomerates TiO2and improving the quality of the label. In the described compositions organosilane is present in amount of from about 0.1 to about 5 weight percent based on the number of organosilane and pigment.

SUMMARY of the INVENTION

The inventors of naruhina, laser tag with enhanced contrast can be obtained if the pigment is covered with a synergist or is in close proximity to the synergist, which includes the Deputy that when the pyrolysis generates a black material such as carbon black, providing education labels. Such pigments can be used in the compositions, which are subjected to the action of excimer laser radiation, for example, insulation for wires and cables. Different types of synergists can be adapted for different treatments and use of the different States of the polymer. In particular, the authors found that laser marks formed using pigments of the present invention and compositions comprising them, to keep a good contrast in terms of thermal aging.

In the first aspect of this invention relates to a colorless UV-devouring the pigment at least partially coated with a synergist having the formula

[Rm(SiOn)]pR'q,

where

(a) m is 1-3, n is 1-3, p is the number that, at least, is 1, and q is 0-3,

(b) at least one of R or R' represents a Deputy, who during pyrolysis produces a black material suitable for the formation of the label.

In the second aspect of the invention is a composition suitable for laser marking when in the action of radiation from an excimer laser, moreover, this composition includes

(1) a fluoropolymer having processing temperatures Tp,

(2) from 0.1 to 25 wt.% composition colorless UV-absorbing pigment, and

(3) the synergist in accordance with the first aspect of the invention, with the specified synergist (i) is present in amount of at least 10 wt.% from the amount of pigment present in the composition of the polymer (ii) is heat-resistant at a temperature of at least Tpand (iii) is in physical proximity to the pigment.

Particularly preferred are compositions in which the synergist and the pigment used polytetrafluoroethylene (PTFE). Therefore, in the third aspect, the invention provides a composition suitable for laser marking when exposed to radiation from an excimer laser, and the specified composition includes

(1) polytetrafluoroethylene,

(2) from 0.1 to 50 wt.% composition colorless UV-absorbing pigment, and

(3) the synergist having the formula

[Rm(SiOn)]pR'q

where

(a) m is 1-3, n is 1-3, p is the number that, at least, is 1, and q is 0-3 and

(b) at least one of R or R' represents a Deputy, who during pyrolysis produces a black material suitable for the formation of the label,

moreover, the specified synergist (i) is present in amount less the th least 0.1 wt.% from the amount of pigment present in the composition of the polymer (ii) is heat-resistant at a temperature of, at least, Tr, and (iii) is in physical proximity to the pigment.

Pigments and compositions of the invention are particularly suitable for insulating materials. Therefore, in the fourth aspect, the invention provides an isolated conductor, which includes

(A) an elongated wire and

(C) an insulating layer surrounding the specified wire and the layer comprises a composition according to the second aspect of the invention.

DETAILED description of the INVENTION

The pigments of the invention absorb UV radiation, i.e. radiation having less than approximately 400 nm. They are, preferably, essentially colorless. For the purposes of this description of "white" means the absence of color and, therefore, white pigments are colorless. Suitable pigments include titanium dioxide (TiO2), zinc oxide (ZnO) and zinc sulfide (ZnS). Especially preferred due to its non-transparency, high refractive index and susceptibility to UV radiation is a crystalline TiO2. You can use forms of TiO2either rutile or anatase. Preferably, the average particle size of the pigment was less than 1 μm, preferably less than 0.5 μm, the company and less than 0.4 μm, especially less than 0.3 microns.

Pimento, at least partially covered or in contact with a synergist (here called coating)having the formula

[Rm(SiOn)]pR'q(I)

in which m is 1-3, n is 1-3, p is the number that, at least, is 1, and q is 0-3. At least one of R and R' represents a Deputy that during pyrolysis, for example, UV radiation, forms a large amount of black material such as carbon black, silicon carbide, oxycarbide silicon or mixtures thereof. If R is greater than 1 element, the elements of R may be the same or different; when R' is greater than 1 element, the elements of R' may be the same or different; R' may be absent, depending on the choice of m, n and R. for Example, if m=1, n=1.5, and R represents a very large number, then R' is essentially absent. For cyclic analogues (I) R' is missing. R and R' may be the same or different substituents. For R or R' are preferred aryl groups, or substituted or unsubstituted. The synergist, preferably, is essentially colorless and must be heat-resistant (i.e. should not decompose) and non-volatile to remain relatively unchanged throughout the processing and subsequent conditions of product use.

Heat for pyrolysis t is aetsa a result of absorption excimer laser light pigment. Therefore, it is important that the synergist was directly in contact with the pigment or close enough to it, usually in physical proximity, so that was easily achieved by heat transfer. The synergist should be applied to the pigment or should be able to migrate to the surface during processing of the polymer to form a coating, which remains in close proximity to the surface of the pigment throughout the treatment and conditions of use of the product. If the synergist is applied to the pigment synergist may partially cover the pigment, for example, the coating is at least 25% of the surface area of the pigment, or may completely cover the pigment.

Preferred synergists are silsesquioxane and polyhedral oligomeric silsesquioxane (POSS). The POSS materials have the General structure (RSiO1,5)nwhere R can be any organic residue, but preferably is an aromatic group such as phenyl or naphthyl, and n may be equal to 8, 10, 12 or more. In addition, suitable additives are various oligomeric and polymeric silicones of the structure R-(SiO[R1,R2]2)n-R - suitable additives, where R, R1and R2may be the same or different. One of the substituents R, R1or R2preferably represents phenyl which must be present as a significant substituent, moreover, a typical example of it is silicone, which contains a large number of phenyl groups (one or two per atom of silicon). Suitable phenyl-POSS-connections include Octafinal-POSS, dodecaphony-POSS and polyphenyl-POSS (available from Hybrid Plastics under the Molecular Silica™ brand, product numbers MS0380, MS0802 and PM1270 respectively). Dodecaphony-POSS, which has the structure [(C6H5)SiO1,5]12has the lattice structure. Heat treatment, for example, at 200°C for 1.5 hours to remove any clathration the solvent used for obtaining dodecaphony-POSS; such a solvent may have an adverse effect on the stability of each composition, with which is mixed a synergist. Although the connection phenyl-POSS not known as additives for laser marking or as additives for perftoralkil, they have significant advantages that are (1) stable at the processing temperatures that are higher than 360°, or equal to 360°and which are necessary for the treatment of certain polymers, including parfocality, and (2) colorless in visible light.

Suitable for use are also generalcondition, such as phenyltrimethoxysilane, such as silane, available from Sivento Inc. called SRO. Materials, such as phenyl-POSS, and phenylsilane are stable at high is the temperature.

The synergist is usually present in quantities greater than 5 wt.% from the total amount of synergist and pigment, preferably at least 10 wt.%, in particular, at least 20 wt.%, particularly, at least 30 wt.%, and may be present in much higher percentages, such as 50% or more. These quantities are particularly suitable for the processing in the melt polymers (as described below)containing vinylsilane or silicone. However, to be processed in the melt of polymers, including silsesquioxane or POSS as synergists, or for not being handled in the melt of the polymer, including any of these synergists, the amount present of the synergist may be much lower, for example at least 0.1 wt.% the total number of synergist and pigment, preferably at least 0.5 wt.%, particularly, at least 1 wt.%.

The pigments described above can be used to improve laser marking compositions, comprising any suitable polymer, including polyolefins such as polyethylene and polypropylene. However, of particular interest, especially for wires in aircraft structures are fluoropolymers. They include processed in the melt fluoropolymers, such as a copolymer of ethylene and tetrafluoroethylene (ETFE), and processed in the melt parfocality, of would each hydrogen, directly attached to the carbon atom substituted by fluorine. Suitable processed in the melt parfocality include a copolymer of tetrafluoroethylene and hexaferrite (FEP), a copolymer of tetrafluoroethylene and propilenovomu ether (PFA) and a copolymer of tetrafluoroethylene and methylvinylether ether (MFA). Such polymers can be processed in the melt, using suitable equipment, for example, equipment for extrusion. You can also use polytetrafluoroethylene (PTFE), which is not processed in the melt. Compositions comprising PTFE, can handle plunger extrusion with subsequent sintering. Processing or processed in the melt, or not processed in a melt of polymers can be alternative ways, for example, electrostatic coating or dispersion coating, in which the composition is applied onto a substrate and then subjected to heat treatment. The polymer composition has a processing temperatures Tpwhich is defined as the highest temperature to which the composition is subjected during normal processing of the composition. For crystalline polymers Tpusually higher than the melting temperature Tmwhich is defined as the peak ectothermy on the curve recorder differential scanning calorimetry (DSC).

PERFLUORO alimera high purity are particularly preferred for use, because they provide maximum contrast for a given concentration of pigment and coatings. Having high purity PFAs are completely substituted on the ends of fluorine polymers having less than six non-fluorinated end groups per million carbon atoms. Such polymers are described in U.S. patent No. 4743658 (Imbalzano et al.), the description of which is incorporated herein by reference.

Compositions of the present invention include essentially colorless UV-absorbing pigment, i.e. TiO2in the amount of from 0.1 to 70 wt.% of the total composition, preferably from 0.1 to 50%, in particular from 0.1 to 25%, especially from 0.1 to 10%. There is also a synergist, as described above. The synergist is selected so that it was thermostable at a temperature of at least Tp. He may be in direct physical contact with the pigment, for example, made with pigment to be added to the polymer. In the alternative case, it may migrate close enough to the pigment during processing, with the result that he has sufficient proximity required for heat transfer during UV radiation.

The inventors discovered that the addition of the synergist and pigment to the molten polymer may have an impact on the final contrast. In General, if the synergist added after the pigment, it preferably covers part of the s pigment with high energy surface. However, if the synergist added after the pigment, it can be dispersed in the polymer is homogeneous and is not suitable for coating of pigment, resulting in a lower contrast. In addition, the contrast of the final composition can influence the temperature of the mix, and lower processing temperatures often give a better contrast. In particular, a very high temperature processing perftoralkil can generate hydrofluoric acid (HF), which may have an adverse effect on the structure of the synergist. If the synergist melt processing at a temperature higher than its melting range, can provide better contrast for pigment. For example, DPOSS detects the ranges of melting at temperatures up to approximately 375°so that the treatment above this temperature gives the synergist ability to melt and cover the pigment.

Especially preferred for use with PTFE is polyphenylsilsesquioxane (PPSQ), available from Gelest under the name SST-R). PPSQ has a ladder structure. The inventors have discovered that this material can be sewn, so that when it is applied to the pigment, he formed a coating that remains on the pigment and is resistant to some types of solvents used in gaining the tape PTFE. One suitable stapling procedure described below in example 15.

Compositions of the present invention are, in particular, are suitable for use on an isolated conductor in which an elongated element such as a wire, cable or bundle of wires, is surrounded at least partially with an insulating layer, including this song. The composition can also be used to surround the elongated element, such as a fiber optic cable. If the composition is based on processable in the melt of the polymer, the composition may be extruded on top of the item. Alternatively, if the composition includes not processed in the melt of the polymer, for example PTFE, it is possible to cause the plunger extrusion or you can wrap the ribbon on top of the item. Between the wire or cable and layer compositions may contain one or more layers of different or the same thickness and/or composition. Such layers can include a strip of mica, such as described in application for U.S. patent No. 09/587229 (Nyberg et al.) and publication of International patent application no WO 00/74075 (Tuco Electronics Corporation et al.), the description of which is incorporated herein by reference. In General, the contrast is increased when the thickness of the insulating layer containing the pigment and the synergist is raised.

The conductor may include an outer layer of polymer, to whom that does not contain a pigment or a synergist. This layer should be sufficiently thin, for example less than 0.1 mm, to allow the laser radiation to penetrate through it to mark below the pigmented layer. This outer layer can improve the abrasion resistance of the conductor at the same time providing the Explorer acceptable contrast.

The contrast expressed in percent, is the difference between the reflectivity of the label and the basics, which is applied to the label. The contrast obtained with the use of pigments and compositions of the present invention is at least 70%, preferably at least 75%, in particular at least 80% and remains at a high level, even after thermal ageing at an elevated temperature for 24 hours or more.

As a General rule, unable to melt polymers (e.g., PTFE), the precursors of thermosetting plastics or polar thermoplastics (for example, polyethylene terephthalate, polybutylene terephthalate, polyvinylidene fluoride or polyvinyl chloride), a synergist, preferably, is [C6H5SiO1,5]ndeposited on the pigment and sewn on it. For the less polar thermoplastic polymers (for example, PFA, FEP, polypropylene or polyethylene) as a synergist may be [C6H5SiO1,5]nor its low molecular weight, which can migrate to the pigment, dispergirovannom in the polymer matrix during processing of thermoplastic material with the formation of the coating on this pigment, which remains in place during use of the product. The preferred connection is dodekanissos [C6H5SiO1,5]12.

Compositions of the present invention, in particular, are suitable for the insulation of the wires for aircraft structures. For example, one commercial PTFE tape for wires for aircraft structures includes approximately 4% of TiO2. When the tape is treated with an excimer laser at 308 nm, it provides approximately 60 to 70% of the contrast of the laser mark. Examples of PTFE compositions of the invention possess by contrast, more than 75%.

Although the invention is in General described in terms of synergists on the basis of silicon, a more General description is that the synergist has the formula

[RsX]t(ii)

where R has the above values (i.e. the Deputy, which is selected to ensure that during pyrolysis of a large number of black mass), X is a structural unit that includes one or more elements, s is represented by the remaining valences of X and t is equal to at least 1. Examples of synergist II are aryl-substituted siloxanes, silanes, silsesquioxane is s, oxides of phosphorus, phosphonates, phosphazene and their oligomers or polymers.

The present invention also includes a method of forming a mark on a polymer substrate, and the method includes (1) a composition of the invention and (2) the processing composition excimer laser pyrolysis Deputy synergist and education of the black material for marking.

The invention is illustrated in the following examples, in which examples 20, 23, 31, 32 and 33 are comparative examples.

Processed in the melt composition: examples from 1 to 30

The compositions shown in table I, were obtained and were granulated or alloy preformed using the ingredients described in table II (in which "MFR" means the rate of flow of the melt as determined by the manufacturer), III and IV, and the following procedures below. Table I lists the total % cover as a percentage of the amount of pigment as determined by [wt.% cover/(wt.% cover + wt.% pigment)], as well as the total amount of pigment present in the composition according to the weight of the total composition.

Example 1. The polymer is introduced into the container for mixing Brabender 250 cm3heated to approximately 350°and melt. To the polymer type DPOSS, and the mixture is stirred, then add pigment TiO2and the mixture is stirred. The composition is then removed from the container d is I mix, cool and granularit. Granulated composition is then ekstragiruyut at a temperature of about 375-385°using 25.4 mm extruder having a ratio of length/diameter 24:1, over conductor wire of copper 19, Nickel-plated 20 AWG, getting a wall thickness of approximately 0.20 mm (0.008 inches). Samples each obtained by extrusion of the wire is then marked with a laser. All laser marking conduct Spectrum Technologies PLC (UK) using an excimer laser Capris 100 XeCl at a wavelength of 308 nm with an intensity of 800 MJ/cm2. Measuring the contrast also conduct Spectrum using Capris CMS2. The contrast is expressed as a percentage, represents the difference between the reflectivity of the sign and the basics, which is applied to the token.

Example 2. Used the procedure of example 1, except that after the polymer is melted, then add TiO2then add DPOSS. Data comparison-contrast examples 1 and 2 showed that the addition of the coating material after pigment provide higher contrast.

Example 3. Dodecaphony-POSS heated at 385°C for one hour to become infusible and more soluble in toluene material. This material is then dissolved in toluene. Two parts of TiO2Kronos 2078 and 1 part DPOSS mixed in solution DPOSS/toluene is stirred; the toluene is removed by heating above its boiling point. The resulting coated TiO2grind to a size of 200 mesh sieve, added to the molten polymer and mixed, cooled and granularit. The composition is then xtraceroute as in example 1.

Example 4. The procedure of example 3, TiO2covered DPOSS, obtained when the ratio of 4 parts of TiO21 part DPOSS. Then apply the procedure of example 1.

Example 5. The procedure of example 3, TiO2covered DPOSS, obtained when the ratio of 8 parts of TiO21 part DPOSS. Then apply the procedure of example 1.

Example 6. The procedure of example 3, TiO2covered DPOSS, obtained when the ratio of 16 parts of TiO21 part DPOSS. Then apply the procedure of example 1.

Examples 7 to 12. The procedure of example 2, TiO2add to the melted polymer and then adding DPOSS. Then use the procedure of example 1 except that the extrusion is carried out at approximately 400°C.

Example 13. Used 100 parts of TiO2Kronos 2078 and 25 parts of phenyltrimethoxysilane (SRO). Phenyltrimethoxysilane pre-hydrolized by adding 3 mol of water per mole of silane. Then add HCl to reach pH 2. With vigorous stirring the mixture ethanol prior to the formation of one phase. A mixture of closed and stirred for 3 hours. Receive a suspension of TiO2 in the water, and add a pre-hydrolyzed silane and the mixture well stirred. The mixture is heated at 100°C in an oven with forced air supply until then, until it becomes dry, then dried, treated TiO2break into small pieces and ground in a jet mill to an average particle size of approximately 8.5 μm and then crushed in cryogenic conditions to 1.75 wt.% milled pigment is added to the molten polymer and mixed (at approximately 370°C)granularit and ekstragiruyut (at approximately 400° (C)as in example 1.

Example 14. The procedure of example 13 is used to produce coated phenyltrimethoxysilane TiO2except that dried, the treated pigment grind before passing through a sieve of 200 mesh. Ground pigment mixed with 360°and then granularit and ekstragiruyut (385° (C)as in example 1.

Example 15. TiO2Kronos 2078 cover polyphenylsilsesquioxane (PPSQ) Gelest SST-3P01, with a ratio of 4:1 TiO2:PPSQ in the following way. Round bottom 3-necked flask of 5 liters supply with a mechanical stirrer, addition funnel, two thermometers, distillation through a trap and an electric heater casing mounted on the lifting device. The reaction system continuously rinsed with nitrogen. The reactor zag is ujaut 1200 ml of deionized water and begin stirring at room temperature, add 300 g of TiO 2. The suspension is stirred at room temperature for 2 hours. Separately 75 g PPSQ dissolve approximately 175 ml of toluene. This solution is added through the addition funnel in a well-mixed suspension of TiO2for 20 minutes; the residual quantity of PPSQ drip funnel rinse approximately 20 ml of toluene. The formed suspension-emulsion was stirred at room temperature for about 2 hours, then the temperature was raised to around 90°for the distillation of the azeotropic mixture of toluene/water (80/20 wt./wt.) (nominal boiling point 85°). To minimize the formation of foam is used, a relatively large unused volume of the reactor and almost at the end of the azeotropic distillation add approximately 5 ml of deionized water (which, to some extent, inhibits the formation of foam). In addition, the trap prevents foam in the distillation item. The increased flow of nitrogen at the end of the distillation and the temperature of the flask at or below 90°accelerates the removal of residual toluene. Then add a 1.75 g of concentrated ammonia, dissolved in approximately 30 ml of deionized water to catalyze the crosslinking PPSQ-coating on the particles of titanium dioxide and to minimize agglomeration during subsequent drying of the product is. The heating is stopped while continuing the mixing until then, while the reaction suspension to cool to room temperature. The suspension is centrifuged at 10000 rpm./min for 0.5 hour and opaque supernatant liquid decanted from the pellet of the centrifugation, which is then dried for >1 hour at 100°thus the plastic powder. This powder is then dried at 150°200°With (complete linkage) for one hour at each temperature by injecting nitrogen, while receiving 357 g of the product. Scanning electron microscopy showed evenly covered with the powder. The powder is then milled in a jet mill to obtain fine particles, and add it to the melted polymer, and the mixture is stirred, granularit and ekstragiruyut (385° (C)as in example 1.

Example 16. TiO2Kronos 2078 in the amount of 8.7 and 8.7 grams grams polyphenyl-POSS (Hybrid Plastics PM 1270) dissolved in 500 ml of toluene. The toluene is removed by heating and the resulting material is dried in a vacuum oven at 200°C for one hour. The dried material is ground using a mortar and pestle, while receiving relatively coarse powder having a ratio of 1:1 TiO2:PPOSS. Covered PPOSS TiO2add to the melted polymer, mixed (with 365°C)granularit and sextrader the Ute (375° (C)as in example 1.

Example 17. The procedure of example 13 100 parts of TiO2Kronos 2078 and 10 parts of triphenylsilane (SR) is used to produce processed TiO2that is ground to pass through a sieve of 200 mesh. Then molten polymer type 1.1 wt.% milled pigment and the mixture is stirred (at approximately 350°C)granularit and xtraceroute as in example 1.

Example 18. The procedure of example 13 100 parts of TiO2Kronos 2078 and 20 parts of triphenylsilane (SR) is used to produce processed TiO2that is ground to pass through a sieve of 200 mesh. Then molten polymer added to 1.2 wt.% milled pigment and the mixture is stirred (at approximately 350°C)granularit and ekstragiruyut as in example 1.

Example 19. The procedure of example 2, TiO2add to the melted polymer and then adding DPOSS. Then use the procedure of example 1 except that the extrusion is carried out at approximately 400°C.

Example 20 (comparative). TiO2Kronos 2078 in the amount of 25 wt.% and 75 wt.% Dyneon PFA 8502 UHP served together in 27 mm rotating twin screw extruder Leistritz, heated to approximately 380°and mixed/tabletirujut education masterbatches (Royal mix 1). Uterine mixture in an amount of 4 wt.% and 96 wt.% Dyneon PFA 8502 UHP smesi the Ute in the dry state and ekstragiruyut at 400° With, as in example 1.

Example 21. Uterine mixture 1 of example 20 in number 93,02 wt.% loaded into the extruder Leistritz together from 6.98 wt.% DPOSS and mix/tabletirujut education masterbatches 2. Uterine mixture in an amount of 4.3 wt.% and to 95.7 wt.% Dyneon PFA 8502 UHP mixed in a dry state and ekstragiruyut at 400°S, as in example 1.

Example 22. Use the same procedure as for example 21, except that mixed in the dry state, the material ekstragiruyut at 400°With over a core wire made of copper 19, Nickel-plated 24 AWG, getting a wall thickness of approximately 0.20 mm (0,008 inch).

Example 23 (comparative). TiO2add to the melted polymer and the mixture is stirred (at 370°C)granularit and ekstragiruyut as in example 1.

Examples 24 to 27. Before mixing DPOSS subjected to heat treatment at 200°C for 1.5 hours to remove solvent. The procedure of example 2, TiO2add to the melted polymer and then adding the heat-treated DPOSS. The mixture was then stirred, cooled, granularit and ekstragiruyut as in example 1.

Example 28. The procedure of example 2, TiO2add to the melted polymer and then adding DPOSS and then to 0.75% concentrate blue pigment FEP Wilson. The mixture is stirred, granularit and ekstragiruyut as in example 1.

Examples 29 and 30. Procedure note the RA 2 TiO 2add to the melted polymer and then adding DPOSS and the mixture is stirred, granularit and ekstragiruyut as in example 1. The use of FEP with normal purity, instead of FEP with high purity results in a lower contrast.

98,0
Table 1
ExamplePolymerFloorPigment% Cover% PigmentContrast
Type%Type%Type%%
1PFA198,0DPOSS11TiO21150181,4
2PFA198,0DPOSS11TiO21150187,7
3PFA198,5DPOSS10,5TiO22133,1to 89.5
PFA198,8DPOSS10,24TiO230,96200,9687,2
5PFA198,87DPOSS10,13TiO24111182,3
6PFA198,94DPOSS10,06TiO2515,9181,5
7PFA298,3DPOSS10,2TiO211,511,81,583
8PFA2of 98.2DPOSS10,3TiO211,516,71,585
9PFA298,1DPOSS10,4TiO211,5211,586
10PFA297,7DPOSS10,3TiO212,013282
11PFA2of 98.2DPOSS10,3TiO261,516,71,584
12PFA2of 98.2DPOSS10,3TiO271,516,71,575
13PFA398,25PhS0,35TiO281,4201,476
14PFA498,8PhS0,24TiO280,96200,9671
15PFA298,33PPSQ0,33TiO29of 1.3420of 1.3477
16PFA198,0PPOSS1TiO210150179
17PFA1the 98.9PhS0,1TiO21119,1178
PFA198,8PhS0,2TiO212116,7180
19PFA598,3DPOSS10,5TiO211,229,41,288
20PFA399,0-0TiO2110153
21PFA398,7DPOSS10,3TiO21123176
22PFA398,7DPOSS10,3TiO21123174
23FEP199,0-0TiO2110156
24FEP298,0DPOSS21TiO21150189
25FEP3DPOSS21TiO21150181
26FEP198,0DPOSS21TiO21150182
27FEP198,4DPOSS20,6TiO21137,5177
28FEP197,25DPOSS21TiO21150180
29FEP498,4DPOSS20,6TiO21137,5163
30FEP497,4DPOSS20,6TiO21223,1262

Table II
ComponentDesignationManufacturerNotes
Perftrack ismale
PFA1PFA 440 NRWDuPontHigh purity fluorine in limit positions; MFR 14
PFA2PFA 445 HPDuPontHigh purity fluorine in limit positions; MFR 5
PFA38502 UHPDyneonHigh purity fluorine in limit positions; MFR 2
PFA4PFA 340DuPontNormal purity; MFR 14
PFA5PFA 950 HPDuPontHigh purity fluorine in the limit positions, comonomer PEVE, MFR of 1.7 to 3.0
Fluorinated copolymers of ethylene and propylene
FEP1FEP 5100JDuPontHigh purity fluorine in the limit positions, MFR 22
FEP2FEP 100JDuPontHigh purity fluorine in the limit positions, MFR of 6.6
FEP3FEP 100DuPontNormal purity; MFR of 6.6
FEP4FEP 5100DuPontNormal purity, MFR 22

Table III
ComponentDesignationManufacturerNotes
DPOSS1MS0802Hybrid PlasticsPolyhedral oligomeric dodekanissos; the structure of the lattice; the initial particle size of about 120 microns; (C6H5SiO1,5)12
DPOSS2DPOSS1, heat-treated at 200°C for 1.5 hours to remove solvent
PhSSRSivento Inc.Phenyltrimethoxysilane
PPSQSST-3P01GelestPolyphenylsilsesquioxane; ladder
PPOSSPM1270Hybrid PlasticsPolyhedral oligomeric Polyphenylsilsesquioxane; the lattice structure in the polymer chain; primary particle size of ˜40 μm;

Table IV
ComponentDesignationManufacturerNotes
TiO2
TiO212078KronosRutile; uncoated; particle size ˜0,27 mcm
TiO222:12:1 Kronos 2078:DPOSS1
TiO234:141 Kronos 2078:DPOSS1
TiO248:18:1 Kronos 2078:DPOSS1
TiO2516:116:1 Kronos 2078:DPOSS1
TiO26AHR-FHuntsmanThe anatase; some amount of organic coating; the size of the crystals ˜0.13
TiO27TiPure R103DuPontRutile; 0,25% organic treatment; 3.2% of aluminum oxide; particle size ˜0,23 mcm
TiO284:14:1 Kronos 2078:PhS (SR)
TiO294:14:1 Kronos 2078:XLPPSQ
TiO2101:11:1 Kronos 2078:finaltime-toxicity
TiO21110:110:1 Kronos 2078:PhS (SR)
TiO2125:15:1 Kronos 2078:PhS (SR)
TiO213TiPure R100DuPontRutile; 0,2% organic treatment; 1.7% of aluminum oxide; particle size ˜0,32 mcm
TiO214Tiona RCL-4Millennium Inorganic ChemicalsRutile; at least 97% of TiO2; aluminium oxide and organic coating; size cha is TIC ˜ of 0.27 μm
TiO2152:12:1 Kronos 2078:XLPPSQ

Samples wrapped with PTFE tape (examples 31 to 38)

Respectiely tape PTFE receive the following way: the specified pigment TiO2as shown in table V, grind on jet mill to reduce particle size and then add to PTFE (61, available from DuPont) way of mixing with low shear force, followed by the method of mixing with a high shear force to improve the dispersion of pigment. To a mixture of PTFE/pigment add oil in terms of mixing with low shear force. Receive a preformed billet greased with a mixture of PTFE/pigment with further aging, plunger extrusion in the form of a tape and calandrinia to the desired thickness. The grease is then removed by heat treatment at a temperature below 250°and the tape is cut to obtain a desired width.

One or more respectice tapes PTFE wound on top of the wire material Nickel-copper, which is wrapped with mica tape using a wrapping tape device EJR. Tape mica receive, as described in example 4 of patent application U.S. No. 09/587229 (Nyberg et al.) and publication of International patent application no WO 00/74075 (Tuco Electronics Corporation et al.), the description of which is incorporated herein by reference. From the calculations, the PTFE material is sintered at a temperature of from 380 to 400° With over a period of approximately 1 minute. The outer diameter of the finished wire, and the contrast measured as described in example 1 are shown in table V. Percentage of coverage and pigment in table V apply only to the extreme layer of the conductor, if there is more than one polymer layer.

0,33
Table V
ExampleFloorPigmentWireOuter diameterContrast
Type%Type%(AWG)(mm)%
31-0TiO2134201,4269,6
32-0TiO2144201,4560,2
33-aboutTiO2144241,2266,0
34PPSQ0,33TiO215of 1.34241,2486,0
35PPSQTiO215of 1.34241,2386,0
36PPSQ0,24TiO290,96241,2376,0
37PPSQ0,33TiO215of 1.34201,3377
38PPSQ0,33TiO215of 1.34201,4781

Example 31 (comparative). Wire wrapped with mica tape with 50% overlap. Two layers 0,051 mm (0.002 inch) thick commercial PTFE tape (DuPont 613 (A), containing 4% of TiO2TiPure R100 wrapped with 52% overlap.

Example 32 (comparative). Wire wrapped with mica tape with 50% overlap. Three layers of 0.038 mm (0.0015 inch) thick commercial PTFE tape (DuPont 613 (A), containing 4% of TiO2RCL-4 wrapped with an overlap of 52%.

Example 33 (comparative). Wire wrapped with mica tape with 50% overlap. Two layers of 0.076 mm (0.003 to inch) thick commercial PTFE tape (DuPont 613 (A), containing 4% of TiO2RCL-4 wrapped with an overlap of 52%.

Example 34. Using the procedure described in example 15, TiO2Kronos 2078 covered by polyphenylsilsesquioxane (PPSQ) Gelest SST-3P01 in the ratio 2:1 TiO2:XLPPSQ. This paragraph shall gment coated used for nespereira 0.076 mm (0.003 to inch) thick PTFE tape, containing 2 wt.% pigment coated, as described above. The conductor was obtained by wrapping wire mica tape with 50% overlap. The first layer of nespereira PTFE tape wrapped with an overlap of 52% and a second identical respectueuse PTFE tape was placed on top of the first layer of PTFE and blocked by 52%.

Example 35.

Wire wrapped mica tape with 50% overlap. The first layer is 0.076 mm (0.003 to inch) thick commercial PTFE tape (DuPont 613 (A), containing 4% of TiO2RCL-4, wrapped with an overlap of 52% and this layer is covered with a layer of 0.076 mm (0.003 to inch) PTFE tape, containing 2 wt.% coated pigment described in example 34, with 52% overlap.

Example 36. Pigment Kronos 2078 covered by polyphenylsilsesquioxane (PPSQ) Gelest SST-3P01 in the ratio 4:1 TiO2:XLPPSQ as described in example 15, and 1.25 wt.% pigment coated mixed with PTFE for nespereira 0.076 mm (0.003 to inch) thick PTFE tape. The conductor was obtained by wrapping wire mica tape with 50% overlap. Tape mica covered the first and second layers of nespereira 0.076 mm (0.003 to inch) thick PTFE tape, in each case, with 52% overlap.

Example 37. Wire wrapped mica tape with 50% overlap. It is then covered with one layer of 0.076 mm (0.003 to inch) PTFE tape, containing 2 wt.% pigment coated as described in example 34, with overlapping of 52%. The contrast was lower with one layer of PTFE tape than with DV the two layers, as indicated in example 35.

Example 38. Wire wrapped mica tape with 50% overlap. Then it was covered with one layer of 0.076 mm (0.003 to inch) PTFE tape, containing 2 wt.% pigment coated as described in example 34, with overlapping of 69%. Increased wall thickness (resulting from increased overlap) gives a higher contrast, as shown by comparison of examples 37 and 38.

Thermal aging of labeled samples

Thermal aging was performed on labeled laser samples at a temperature and for a time specified in table VI. Examples 31 and 32 are comparative examples. Even after heat aging the composition of the present invention was found high contrast.

Table VI
ExampleInitial contrast (%)T aging (°)The ageing time (hours)Contrast after aging (%)
11833102482
12753102472
13763102468
19 88310390
310689
3101286
3102483
317029016865
29033665
26067765
326029016840
29067837
26067837
35863102473
37773102469
38813102475

1. Colorless UV-absorbing pigment, hence, is her least partially covered with a synergist having the formula

[Rm(SiOn)]pR'q,

where (a) m is 1-3, n is 1-3, p is the number that, at least, is 1, and q is 0-3 and

(b) at least one of R or R' represents a Deputy, who during pyrolysis produces a black material containing carbon black, silicon carbide, oxycarbide silicon or mixtures thereof and suitable for education labels.

2. The pigment according to claim 1, wherein m is 2 or 3 and all R are the same substituents.

3. The pigment according to claim 1, wherein m is 2 or 3, and R are all different substituents.

4. The pigment according to claim 1, characterized in that at least one R is the same as R'.

5. The pigment according to claim 1, characterized in that at least one of R and R' contains an aryl group.

6. The pigment according to claim 1, characterized in that it includes TiO2, ZnO or ZnS.

7. The composition is suitable for laser marking when exposed to radiation from an excimer laser, and the specified composition includes

(1) a fluoropolymer having processing temperatures Tp,

(2) 0.1 to 50 wt.% composition colorless UV-absorbing pigment and

(3) the synergist having the formula

[Rm(SiOn)]pR'q,

where (a) m is 1-3, n is -3, p is the number that, at least, is 1, and q is 0-3 and

(b) at least one of R or R' represents a Deputy, who during pyrolysis produces a black material containing carbon black, silicon carbide, oxycarbide silicon or mixtures thereof and suitable for education labels

moreover, the specified synergist (i) is present in amount of at least 10 wt.% from the amount of pigment present in the composition of the polymer (ii) is heat-resistant at a temperature of at least Tpand (iii) is in physical proximity to the pigment.

8. The composition according to claim 7, characterized in that the polymer is processed in the melt the fluoropolymer.

9. The composition of claim 8, wherein the fluoropolymer contains PFA (copolymer of tetrafluoroethylene and propilenovomu ether), MFA (copolymer of tetrafluoroethylene and methylvinylether ether), ETFE (copolymer of ethylene and tetrafluoroethylene) or FEP (copolymer of tetrafluoroethylene and hexaferrite).

10. The composition according to claim 7, wherein the fluoropolymer contains PTFE (polytetrafluoroethylene).

11. The composition according to claim 7, wherein the synergist contains silsesquioxane or polyhedral oligomer of silsesquioxanes (POSS).

12. The composition according to claim 11, wherein the synergist contains dodekafonicheskogo.

13. The composition according to claim 7, otlichayushiesya, the synergist is present in amount of at least 20 wt.% the pigment.

14. The composition according to claim 7, characterized in that the pigment contains TiO2, ZnO or ZnS.

15. The composition is suitable for laser marking when exposed to radiation from an excimer laser, and the specified composition includes

(1) polytetrafluoroethylene,

(2) 0.1 to 50 wt.% composition colorless UV-absorbing pigment and

(3) the synergist having the formula

[Rm(SiOn)]pR'q,

where (a) m is 1-3, n is 1-3, p is the number that, at least, is 1, and q is 0-3 and

(b) at least one of R or R' represents a Deputy, who during pyrolysis produces a black material containing carbon black, silicon carbide, oxycarbide silicon or mixtures thereof and suitable for education labels

moreover, the specified synergist (i) is present in amount of at least 0.1 wt.% from the amount of pigment present in the composition of the polymer (ii) is heat-resistant at a temperature of at least Tpand (iii) is in physical proximity to the pigment.

16. The insulated wire containing an elongated wire and the insulation layer surrounding the specified wire and the layer comprises a composition containing

(1) a polymer having the speaker the processing temperatures T p,

(2) 0.1 to 25 wt.% composition colorless UV-absorbing pigment and

(3) the synergist having the formula

[Rm(SiOn)]pR'q,

where (a) m is 1-3, n is 1-3, p is the number that, at least, is 1, and q is 0-3 and

(b) at least one of R or R' represents a Deputy, who during pyrolysis produces a black material containing carbon black, silicon carbide, oxycarbide silicon or mixtures thereof and suitable for education labels

moreover, the specified synergist (i) is present in amount of at least 10 wt.% from the amount of pigment present in the composition of the polymer (ii) is heat-resistant at a temperature of at least the Tr and (iii) is in physical proximity to the pigment.

17. Guide to item 16, characterized in that the composition includes performalite.

18. Guide to 17, characterized in that performalite is a polytetrafluoroethylene.

19. Guide to p, wherein the synergist is dodekanissos.

20. Guide to item 16, characterized in that it is under the influence of excimer laser at a wavelength of 308 nm and the intensity of 800 MJ/cm2creates a label with a contrast of at least 70%.



 

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25 cl, 5 tbl, 13 ex

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