RU2538580C1 - Polymer composition, method of performing direct part marking with polymer composition and direct mark - Google Patents

Polymer composition, method of performing direct part marking with polymer composition and direct mark Download PDF

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RU2538580C1
RU2538580C1 RU2013132807/05A RU2013132807A RU2538580C1 RU 2538580 C1 RU2538580 C1 RU 2538580C1 RU 2013132807/05 A RU2013132807/05 A RU 2013132807/05A RU 2013132807 A RU2013132807 A RU 2013132807A RU 2538580 C1 RU2538580 C1 RU 2538580C1
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surface
marked
composition
film
label
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RU2013132807A (en
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Алексей Васильевич Лежнев
Александр Леонидович Рощин
Александр Евгеньевич Жедулов
Галина Николаевна Дорожкина
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Закрытое акционерное общество "ТехМаркинг" (ЗАО "ТехМаркинг")
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Abstract

FIELD: chemistry.
SUBSTANCE: invention relates to polymer compositions for direct part marking (DPM). Invention is aimed at creation of planarising polymer composition, solidified by drying, photo- or thermo- polymerisation, and formation of DPM by layer-by-layer application on the surface to be marked of planarising and fluorescent polymer compositions. Planarising composition includes polymerisation or polycondensation polymer from the group of urethane, alkide, acryl film-generating, at least two solvents from the series: acetone, toluene, ethylacetate, cellosolve, diethyl ether, butylacetate additive-filler, siccative and additive. Direct part marking includes application of said planarising polymer composition on the surface to be marked with formation on the surface to be marked of coating layer, gluing mechanically strong film with limited adhesion on coating layer, formation of holes in glued film and hollows in the surface to be marked by dot-peen method, filling them with fluorescent (F) composition, absorbing light radiation at wavelengths of UV visible and nearest UR ranges and irradiating in range of wavelengths 600-700 nm, and removal of said mechanically strong film.
EFFECT: reduction of geometrical inhomogeneities of the surface to be marked in range of dimensions, close to geometrical dimensions of information elements of marking, and simplification of technology of manufacturing and further decoding of 2D FDPM.
5 cl, 6 dwg, 6 ex

Description

The present invention relates to chemical polymer compositions for marking various objects, to polymer compositions applying directly to a marked object direct labeling (MLN - "Direct Part Marking" - DPM), in particular, to methods of applying MPN using compositions containing fluorescent substances and / or particles (FMPN).

A photosensitive polymer-containing composition is known (WO 03-022594, G03C 1/053, 2003) based on a resin for laser engraving of a printing plate to prevent the formation of fragments during laser engraving, which reduces sticking on the surface of the mold and protects against contamination, which is closest to the claimed composition.

The technical result is the simplification of technology and overcoming the difficulties encountered in the manufacture and subsequent decoding of 2D PSF on rough, contaminated or coated with loose deposits surfaces (which is typical, for example, for surfaces obtained by casting).

The technical result is that the preliminary application of the polymer (planarizing) composition on the marked surface reduces the geometric heterogeneity of the marked surface in a range of sizes close to the geometric dimensions of the information marking elements, as a result of which it becomes possible to manufacture and subsequently decode 2D PSF on surfaces, the nature of the geometric the heterogeneities of which are close in size to the size of the information elements of the labels (such heterogeneities thorns in particular obtained by molding surfaces).

The technical result is achieved by a group of inventions.

A planarizing polymer composition cured by drying, photo- or thermopolymerization, for forming a direct application label, includes a polymerization or polycondensation two-component polymer selected from the group consisting of urethane, alkyd, acrylic, as a film-forming, at least two solvents selected from a series including acetone, toluene, ethyl acetate, cellosolve, diethyl ether, butyl acetate, at least one filler additive from the range of chalk, titanium dioxide, microparticles glass, barium sulfate, carbon black, desiccant and an additive selected from the range including anti-flotation additives, adhesives, wetting agents, thickeners, biocides, corrosion inhibitors, in the following ratio, wt.h .:

specified film-forming up to 80 specified solvent 30-50 specified filler additive 25-30 desiccant no more than 5 specified additive no more than 1

A method of manufacturing a direct-applied label includes applying the indicated planarizing polymer composition onto the marked surface with its subsequent curing and forming a coating layer on the marked surface, gluing a mechanically strong film with limited adhesion to it, forming holes in the glued film and depressions in the marked surface using the needle-shock method filling them with a fluorescent composition that absorbs light at wavelengths of the UV, visible and near infrared ranges and radiating in the wavelength range of 600-700 nm, and the removal of the specified mechanically strong film.

The application of a planarizing and fluorescent composition can be carried out using a roller, swab, brush, squeegee or spray, for example by aerosol spray.

To protect the information elements of direct application labels from external influences during operation, an additional protective layer is applied on the surface of the label in the form of a transparent varnish on an organosilicon or polyurethane or alkyd base, which has high adhesion to the indicated planarizing composition, or a protective film is applied that is transparent in the visible range wavelengths and readable label information elements of direct application.

The fluorescent composition contains a mixture of organic solvents with different boiling points, a mixture of polymers capable of polymerizing monomers, a fluorescent pigment or dye and additives in an amount of not more than 1 wt.h.

A mechanically strong film is adhered to the surface of an additional layer of planarizing polymer composition, having limited adhesion to the layer of planarizing composition and to the marked surface; Then, holes are formed in the glued film and recesses in the marked surface by the needle-like method, which are filled with the fluorescent composition, and after filling the formed information elements of the direct application mark with the fluorescent composition, the mechanically strong film with limited adhesion to the planarizing composition layer and the marked surface is removed.

The fluorescent and / or planarizing composition is applied to the surface to be marked with a roller, swab, brush, doctor blade or spray (for example, by aerosol spray).

When applying the fluorescent composition and / or planarizing composition by an aerosol method, a propellant is introduced into the composition — a mixture of isobutane, propane, and diethyl ether.

Drying and / or polymerization of the fluorescent and / or planarizing composition is carried out.

Drying and / or polymerization can be carried out using heating and / or UV and / or IR radiation.

To protect the information elements of the direct application label from external influences during operation, an additional protective layer is applied on it in the form of a transparent varnish on an organosilicon or polyurethane or alkyd or other basis, which has high adhesion to the planarizing composition, and / or a protective film is glued, which can be transparent in the visible wavelength range and allow the reading of information elements of direct label labels.

The essence of the invention lies in the fact that in the manufacture of the device - tags - three different compositions can be used, each of which can be, in particular, photosensitive or heat-sensitive, and each can be applied in a number of ways, some of which are defined in the text of the proposed patent formula.

The first in the order of application composition - planarizing - is applied with the main goal of reducing the geometric heterogeneity of the marked surface and, at the same time, with additional goals of increasing the resistance of the marked surface to mechanical stress and / or changing its adhesive properties and / or increasing the optical contrast of subsequently formed information elements tags.

A typical composition of such compositions is a polymer solution (varnish) of, for example, latex or modified alkyd resins or styrene or PF-060 or organosilicon polymers with a polymer mass fraction of 30-50% in a mixture of solvents containing, for example, acetone, toluene, ethyl acetate, cellosolve , diethyl ether, butyl acetate - only 30-50%; fillers, for example chalk, titanium dioxide, glass microparticles, barium sulfate, carbon black (P-803, K-354) with a mass fraction of up to 30%; desiccants (e.g. ZhK-1, NF-1) up to 5%, anti-flotation additives, adhesives, film formers, wetting agents, corrosion inhibitors, rust converters and other special additives with a mass fraction of less than a percent.

The second composition is applied locally and forms the label information elements.

It contains:

- a fluorescent substance with a maximum radiation in the wavelength range of 600-700 nm when excited in the wavelength region of 450-500 nm in an amount of 18-23% of the total weight of the composition;

- a mixture of organic solvents (37-72% high-boiling, 17-21% with medium boiling points, 11-42% easy-boiling) in an amount of 14-23% of the total weight of the composition;

- a mixture of polymers (for example, acrylic) in an amount of 5-55% of the total weight of the composition;

- special additives with a mass fraction of less than a percent. When applying the composition by an aerosol method, propellant (a mixture of isobutane, propane, diethyl ether) is added in an amount of 55-60% of the total weight of the composition. The third composition - protective - is applied if necessary and is the usual transparent varnish on an organosilicon, polyurethane, alkyd or other basis.

The invention is illustrated by drawings.

Figures 1-6 use the following notation:

1 - a fluorescent composition that absorbs light at wavelengths of UV, visible and near infrared ranges and emits in the range of wavelengths of the passband of the input filter of the reader;

2 is a composition that reduces the geometric heterogeneity of the marked surface, and / or increases its resistance to mechanical stress, and / or changes its adhesive properties, and / or increases the optical contrast of the generated information elements of the label;

3 - a marked part with indentations (information elements) applied during marking (for example, needle-impact);

4 - film with holes formed after acupuncture (or other) marking;

5 - protective varnish, transparent in the visible wavelength range and absorbing in the short-wave part of the UV wavelength range.

Figure 1 shows a direct-application label device consisting of information elements formed by changing the surface of the marked part (3) by creating recesses during needle-marking, followed by applying to the part a fluorescent composition (1) that absorbs light radiation at UV wavelengths, visible and near infrared ranges and the passband of the input filter of the reader emitting in the wavelength range until the fluorescent composition is removed from the surface of the part between the recesses. Before the formation of the information elements of the label on the marked surface, a composition (2) is applied, which reduces the geometric heterogeneities of the marked surface and / or increases its resistance to mechanical stress and / or changes its adhesive properties and / or increases the optical contrast of the subsequently formed information elements of the label.

Figure 2 shows a direct-application label device consisting of information elements formed by changing the surface of the marked part (3) by creating recesses when marking (for example, needle-impact) with subsequent application of the fluorescent composition (1) to the part after removal of the fluorescent composition from the surface details between the recesses. Before the formation of the information elements of the label, a planarizing composition (2) is applied to the marked surface.

Figure 3 shows a device for direct application of a fluorescent protective information label obtained by needle impact marking with filling of information elements with a fluorescent composition (1) through a film (4) pre-glued onto the surface of the part (3), the holes on which are formed during the process of needle impact marking. Before the formation of the information elements of the label, a planarizing composition (2) is applied to the marked surface.

Figure 4 shows the method of forming a direct application mark by carrying out the process of photopolymerization of a fluorescent composition (1) of a label using UV radiation after filling with the composition information elements formed by changing the surface of the marked part (3) by creating recesses during needle marking. Before the formation of the information elements of the label, a planarizing composition (2) is applied to the marked surface.

Fig. 5 shows a method for forming a direct application mark by drying the fluorescent composition (1) of the mark with infrared radiation after filling in the information elements formed by changing the surface of the marked part (3) by creating recesses during needle marking. Before the formation of the information elements of the label, a planarizing composition (2) is applied to the marked surface.

Fig. 6 shows a method of manufacturing a direct-applied label, consisting of information elements formed by changing the surface of the marked part (3) by creating recesses during needle marking, followed by applying a fluorescent composition (1) to the part, characterized in that the applied label is coated with a protective varnish (5), transparent in the visible and absorbing in the short-wave part of the UV wavelength range. Before the formation of the information elements of the label, a planarizing composition (2) is applied to the marked surface.

Companies and enterprises whose activities are associated with high and / or costly risks are required to provide legal evidence of a causal relationship of losses (and often human casualties) and product failure (parts, assemblies), which allows to make the responsibility for the consequences of product failure to its manufacturer (to dealer, supplier). Therefore, direct application labels are used in industries characterized by increased requirements for authenticity, certification and reliability of parts, assemblies and products.

Unlike marks applied by paint or glued onto a controlled object, direct application marks consist of information elements formed by changing the surface of the marked part in one way or another, for example by applying recesses during needle marking or creating surface areas with microcracks and roughnesses during laser irradiation, electrospark treatment or electrochemical etching. MPN can only be removed together with the material of the surface of the marked part, thus being a reliable way to control the entire life cycle of an object up to its disposal.

When applying MPN, as a rule, two-dimensional (2D) encoding is used, which has high information capacity and noise immunity (2D MPN). In terms of the amount of stored information, the capacity of a 2D code can be hundreds of times greater than the capacity of a one-dimensional one (for example, it can store several pages of text). If an external computer database is required when working with one-dimensional code, the use of a 2D code allows in many cases to abandon such a database, since the code capacity is sufficient to store the necessary information about the object. The use of 2D codes is preferred, for example, in stand-alone identification systems or, if necessary, storing characters from languages such as Japanese or Chinese. In addition, almost all modern technologies of 2D codes, unlike one-dimensional ones, contain error correction tools and, therefore, guarantee greater reliability of data safety.

2D codes have a predominantly matrix form and do not use traditional strokes / spaces to encode information. Instead of the standard technology for determining the stroke width, matrix codes are used to encode information of a yes-no or unit-zero structure (ie, on / off - design). There are many varieties of 2D codes (e.g. PDF417, MaxiCode, DataMatrix).

2D-code readers, unlike barcode scanners, first capture the image, then analyze the resulting image and only then extract it from it and decode the information. In this regard, the reading and decoding of 2D MPN is associated with technological difficulties in terms of hardware solutions and the development of the necessary software. When reading a 2D MPN, the main problem is to obtain a label image with a quality sufficient for reliable decoding of the information contained in it, regardless of the ambient lighting and the state of the surface on which the label is applied. In terms of software, the problem is to increase the decoding ability in the analysis of heterogeneous (“blurry”) images.

The source [patent application adopted by Rospatent on October 23, 2009, No. 2009139034] proposed an effective way to solve the problem of reading 2D MPN by using compositions containing fluorescent substances and / or particles (2D FMPN – 2D FDPM) in the manufacture of labels. This leads to a significant improvement in the image quality of the label when it is read, in particular its contrast, and reduces the dependence of the decoding reliability of the label on the nature of the surface on which the 2D MPN is applied. This solution allows you to read tags as a conventional reader (reader), and a special one that registers a fluorescent image. Using this solution allows you to expand the range of applicability and reduce the cost of using shock-dot marking.

However, the authors of the known solutions were not able to overcome the significant difficulties that arise during the application and subsequent decoding of 2D MPN and 2D FMN on surfaces:

- the microrelief of which is close in size to the size of the information elements of the labels (such heterogeneities are characteristic, in particular, for surfaces obtained by casting);

- covered with loose deposits (for example, rust, scale);

- on which heterogeneous, mechanically fragile or poorly adhesion coatings are applied (for example, some varieties of paints, thermal protective or anticorrosive coatings).

Reducing the influence on the result of the application of MPN of geometric characteristics (microroughnesses, roughness) of the surface on which MPN is applied can be achieved by planarizing it by preliminary applying varnish, putty, lubricant or other coating to this surface that reduces the geometric heterogeneity of the surface in a size range close to the geometric dimensions of the labeling information elements. This can also be achieved by using a composition having the properties listed above and pre-applied to a film having sufficient mechanical strength and high adhesion to the composition layer. It is advisable that the layer of the composition has a thickness exceeding the geometric inhomogeneities of the marked surface, and a gel-like consistency, which allows pressing (rolling, lapping, pressing) the film with the composition to the marked surface to reduce its geometric inhomogeneities. As a result of applying such a layer, it becomes possible to form information elements of the 2D FMPN, and the film with the composition after marking, due to the limited adhesion of the composition layer to the marked surface, can be removed without damaging the information elements of the marking.

In some cases, the application of MPN is complicated by the mechanical properties of the marked surface. The surface may be coated with rust or scale (in particular, formed during the manufacture of marked parts by casting), painted with heat-resistant or other paints having insufficient adhesion to the surface and / or mechanical strength, subjected to electrochemical or other processing. Reducing the influence of the mechanical properties of the marked surface on the result of the MPN deposition process can be achieved by applying a composition to it, which makes it possible to obtain a surface layer with hardness, ductility, abrasion resistance, and adhesion to the marked surface, sufficient for the manufacture and subsequent operation of 2D FMN.

Each of the above compositions can be further modified to improve the optical properties of the marking. For this, particles absorbing light, reflecting light, scattering light and / or re-emitting light are introduced into the composition.

Modified formulations require adequate application methods.

The compositions can be applied to a surface prepared for marking with a roller, swab, brush, doctor blade or spray, after which drying and / or polymerization, if necessary, is carried out, in particular using heat, UV and / or IR radiation.

Compositions can be prepared for application in the form of a layer on a substrate having limited adhesion to this substrate and increased adhesion to the marked surface, as a result of which, during the pressing process (knurling, lapping, pressing), the corresponding composition is transferred to the surface prepared for marking and fixed on her. To fix the compositions, if necessary, drying and / or polymerization is carried out, in particular using heat, UV and / or IR radiation.

Liquid compositions containing photo- or thermosensitive curing agents (for example, phthalocyanine or porphyrin dyes) which, when illuminated with actinic light (for example, a laser beam with an appropriate wavelength) or when heated, induce formation on the surface to be marked, can be preliminarily applied to the surface to be marked. a film (layer, coating) having the necessary mechanical properties and good adhesion to this surface.

The following examples illustrate but do not limit the present invention.

Example 1. UV-polymerizable curing planarizing composition contains a mixture of organic solvents in an amount of 30 parts by weight, while the solvent mixture contains 72% high boiling point - ethyl cellosolve, 17% toluene - with an average boiling point, 11% acetone - low boiling point; capable of polymerization 30 wt.h. ethyl methacrylate and 20 parts by weight methyl acrylate; filler chalk in an amount of 30 parts by weight; desiccant in an amount of 1 wt.h .; thickener - sodium alginate 0.5 wt.h, biocide 2,2-dibromo-3-nitrilopropionamide 0.3 wt.%.

The polymerization curable planarizing composition may contain film-forming polymers containing units of ethylenically unsaturated monomers capable of radical polymerization, preferably units of a monomer selected from the group consisting of acrylic acid, methacrylic acid, esters of acrylic acid and esters of methacrylic acid.

Example 2. Drying curable planarizing composition contains polyoxypropylene triol with MM = 3000-5000 cu - Laprol-5003 - 30 parts by weight, N, N-tetrapropanol-ethylenediamine - 3.0 parts by weight, 4,4'-diphenylmethanediisocyanate - 25.0 parts by weight, filler titanium dioxide - 25 parts by weight; desiccant in the amount of 3 parts by weight; anti-flotation additive sodium carbonate - 0.7 wt.h, as an organic solvent - ethyl acetate and toluene up to 100 wt.h.

Example 3. The heat-curing planarizing composition contains an oligomeric carboxyl-containing butadiene nitrile rubber SKN-26-1A - 28.1 parts by weight, epoxy diane oligomer ED-22 - 7.0 parts by weight, filler: carbon black - 3 parts by weight. barium sulfate - 8 parts by weight, glass microparticles - 15 parts by weight; desiccant in the amount of 4 parts by weight; rust converter - phosphoric acid (85%) - 0.8 wt.h, and 48 wt.h. a solvent containing 70 wt.% ethyl cellosolve and 30 wt.% diethyl ether.

Example 4. The formulation of the fluorescent composition (PMI-R):

a fluorescent substance with a maximum radiation at a wavelength of λ = 630 nm when excited in the wavelength region of 450-500 nm in an amount of 22-23 parts by weight;

23 parts by weight mixtures of organic solvents containing 72 wt.% high boiling ethyl cellosolve; 17 wt.% Butyl acetate; 11 wt.% Diethyl ether;

55 parts by weight capable of polymerizing a mixture of 30 parts by weight ethyl methacrylate and 25 parts by weight methyl acrylate providing adhesive properties of the composition and mechanical stability of the finished label.

Example 5. The formulation of the fluorescent composition (PMI-A) for aerosol application:

21 parts by weight a fluorescent substance with a maximum radiation at a wavelength of λ = 606 nm when excited in the wavelength region of 450-500 nm;

23 parts by weight mixtures of organic solvents containing 37 wt.% ethyl cellosolve; 21 wt.% Butyl acetate; 42% acetone;

12 parts by weight acrylic binder, providing adhesive properties of the composition and mechanical stability of the finished label;

60 parts by weight propellant - a mixture of isobutane, propane, diethyl ether.

Example 6. The composition of the protective varnish:

55 parts by weight a mixture of organic solvents consisting of 72 wt.% methylcellosolve; 17 wt.% Butyl acetate; 11 wt.% Acetone; capable of polymerization 30 wt.h. ethyl methacrylate and 20 parts by weight methyl acrylate, 2.0 parts by weight coalescent - butyl glycol acetate, 0.2 wt.h. thickener - sodium alginate, 0.15 parts by weight 2,2-dibromo-3-nitrilopropionamide biocide.

Regardless of the properties of the compositions used, the methods of their application and the manufacturing methods of 2D FMPS for protecting the information elements of 2D FMPS from external influences during its operation, after manufacturing of the 2D FMPS, a protective coating (varnish) may be applied to it or a protective film may be glued. The varnish and film can be transparent in the visible wavelength range and allow the reading of 2D PSF without removing them.

Claims (5)

1. Planarizing polymer composition, cured by drying, photo or thermopolymerization to form a direct application label, comprising a polymerization or polycondensation two-component polymer selected from the group comprising urethane, alkyd, acrylic, as a film-forming at least two solvents selected from the series, including acetone, toluene, ethyl acetate, cellosolve, diethyl ether, butyl acetate, at least one filler additive from the series comprising chalk, titanium dioxide, micropart gical glass, barium sulfate, carbon black, siccative and an additive selected from the group consisting of antiflotatsionnye additives, adhesives, wetting agents, corrosion inhibitors, rust converters, with the following component ratio, mass parts .:
specified film-forming up to 80 specified solvent 30-50 specified filler additive 25-30 desiccant no more than 5 specified additive no more than 1
2. A method of manufacturing a direct application label, comprising applying to the surface to be marked the planarizing polymer composition according to claim 1, followed by curing it and forming a coating layer on the surface to be marked by gluing a mechanically strong film with limited adhesion to it, forming holes in the glued film by the impact method and recesses in the marked surface, filling them with a fluorescent composition that absorbs light at wavelengths of UV, visible and near infrared ranges and radiating in the wavelength range of 600-700 nm and the removal of the specified mechanically strong film.
3. The method according to claim 2, characterized in that the planarizing and fluorescent composition is applied using a roller, swab, brush, squeegee or spray, for example by aerosol spray.
4. The method according to claim 2, characterized in that to protect the information elements of the label direct application from external influences during operation, an additional protective layer is applied to the surface of the label in the form of a transparent varnish on an organosilicon, or polyurethane, or alkyd base, which has high adhesion to the planarizing composition according to claim 1, or a protective film is glued that is transparent in the visible wavelength range and allows the reading of information elements of direct application labels.
5. Direct application label obtained by the method according to any one of claims 2 to 4.
RU2013132807/05A 2013-07-16 2013-07-16 Polymer composition, method of performing direct part marking with polymer composition and direct mark RU2538580C1 (en)

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RU2637041C2 (en) * 2015-05-15 2017-11-29 Общество с ограниченной ответственностью "Флуоресцентные информационные технологии" (ООО "Флуринтек") Method for manufacturing marking of direct application (mda)

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RU2377134C2 (en) * 2004-02-16 2009-12-27 Хуек Фолиен Гез.М.Б.Х. Counterfeit-protected symbol with variable-colour effect
RU96269U1 (en) * 2008-07-11 2010-07-20 ЗАО "Констеллейшн 3Ди Восток" Combined brand
RU2405679C2 (en) * 2005-01-14 2010-12-10 Кабот Корпорейшн Protection property, its use, and methods of manufacturing
RU2425722C2 (en) * 2006-03-21 2011-08-10 Акцо Нобель Коатингс Интернэшнл Б.В. Method of applying pattern on substrate
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Publication number Priority date Publication date Assignee Title
RU2000124346A (en) * 1998-03-18 2002-09-20 Омд Девайсиз Ллс Production of optical recording medium having a plurality of fluorescent recording layers, the recording layer by embossing
RU2377134C2 (en) * 2004-02-16 2009-12-27 Хуек Фолиен Гез.М.Б.Х. Counterfeit-protected symbol with variable-colour effect
RU2405679C2 (en) * 2005-01-14 2010-12-10 Кабот Корпорейшн Protection property, its use, and methods of manufacturing
RU2425722C2 (en) * 2006-03-21 2011-08-10 Акцо Нобель Коатингс Интернэшнл Б.В. Method of applying pattern on substrate
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RU2472627C2 (en) * 2007-12-11 2013-01-20 Гизеке Унд Девриент Гмбх Protective element with variable optical properties
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2637041C2 (en) * 2015-05-15 2017-11-29 Общество с ограниченной ответственностью "Флуоресцентные информационные технологии" (ООО "Флуринтек") Method for manufacturing marking of direct application (mda)

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