TW386999B - Marking composition, moldings thereof and marking method - Google Patents

Abstract

The present invention relates to a marking composition capable of developing a vivid white color on application of laser beams, which composition comprises a thermoplastic resin having no fluidity at a temperature of 50 DEG C and at least one inorganic material selected from talc, calcium carbonate, alumina, clay, magnesium oxide, aluminum hydroxide, silica, magnesium carbonate and magnesium hydroxide, wherein the inorganic material is blended in a ratio of 1-300 w/w% to the thermoplastic material. The invention also provides the resin moldings and a marking method using the composition.

Description

Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (1) The present invention relates to a composition suitable for marking (hereinafter referred to as a composition for marking), a molded article obtained therefrom And marking methods. More specifically, the present invention is related to the manner in which the illuminated area appears clear white by irradiation with a laser beam, forming a clear mark on the thermoplastic resin molded article by the marked composition, the present invention is also about. A resin molded article obtained from the composition and a marking method. BACKGROUND OF THE INVENTION Recently, it is used to put the name of the manufacturer, the name of the product, the date of manufacture, etc. in different goods (such as: electronic parts (such as: I c, resistors, capacitors, inductors, etc ...) , Power parts (such as: relays, switch connectors, printed circuit boards, etc.), housings of power equipment, automotive parts, mechanical parts, cables, boards, filler boards, sheets, various containers for food and medicine, containers Cover ... etc.) The method of marking on the surface, because using the laser beam (laser marking) to mark has several advantages, such as: no contact with each other during operation, fast marking speed, easy Automation and program management are easy ... etc., so this method is becoming more and more popular. In the method of marking with a laser beam, the laser beam is directly used on the surface of an object made of a large molecular weight organic material, metal or other material that can cause thermal decomposition or evaporation of the surface portion of the object. Therefore, the state of the surface is changed or the irradiated area is discolored or discolored, and a mark is formed by using such a change. However, this marking method has some disadvantages in practical applications. For example, when a thermoplastic resin is used as the base material for marking, laser light will penetrate the resin and will not form a marking on it. · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ) —A — (Please read the notes on the back before filling this page) Order 1Π- Printed by the Consumers Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 5. Description of the invention (2) Or, even if the laser beam is properly absorbed, As a result of the corrosion, the resin almost melts, so a clear mark cannot be formed. On the other hand, even if a colorant is used, a strong color cannot be formed. Therefore, even if a laser mark is made on a thermoplastic resin as a substrate, The need for a clear, white marked composition is increasing. SUMMARY OF THE INVENTION The present inventors have devoted themselves to research in order to overcome the problems described above, and thus completed the present invention. Basically, the present invention intends to propose: (1) The composition for marking includes a thermoplastic resin having no fluidity at 50 ° C and at least one inorganic material selected from the group consisting of talc, calcium carbonate, alumina, For clay, magnesium oxide, aluminum hydroxide, silica, magnesium carbonate, and magnesium hydroxide, the content of the one or more inorganic materials is 1 to 300% by weight based on the weight of the thermoplastic resin. (2) The composition for marking as described in (1) above, wherein the thermoplastic resin is polypropylene or polyethylene "(3) The composition for marking as described in (1) above, wherein The inorganic material is talc, calcium carbonate or aluminum hydroxide. (4) The composition for marking as described in (1) above, wherein the thermoplastic resin is polyethylene, the inorganic material is aluminum hydroxide, and the content of aluminum hydroxide is 1 to 1 5 by weight of polyethylene weight%. (5) The composition for marking as described in (4) above, wherein the content of aluminum hydroxide is 1 to 10% by weight based on the weight of polyethylene. (6) The composition for marking as described in (4) above, in which the paper size applies to the Chinese national standard (CNS> A4 specification (2 丨 0X297 mm) (Please read the precautions on the back before filling (This page) Order A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (3) The content of aluminum hydroxide is 2 to 5% by weight based on the weight of polyethylene. (7) As mentioned above (1) The composition for marking described in the above, wherein the thermoplastic resin is polypropylene and the inorganic material is talc or calcium carbonate, and the content of the inorganic material is 5 to 250% by weight based on the weight of the polypropylene. (8) Such as The labeled composition described in (7) above, wherein the content of talc or calcium carbonate is 10 to 100% by weight. (9) The labeled composition described in (1) above, wherein The thermoplastic resin is polypropylene, the inorganic material is aluminum hydroxide, and the content of aluminum hydroxide is 1 to 15% by weight based on the weight of polypropylene. (1 0) It is used for marking as described in (9) above. The composition wherein the content of aluminum hydroxide is 1 to 10% by weight. (11) As described above The composition for marking as described in (9), wherein the content of aluminum hydroxide is 2 to 5% by weight. (1 2) After the composition for marking as described in (1) above is subjected to molding (1 3) Resin obtained after molding the composition for marking as described in (4) or (9) above at a temperature not higher than 240 ° C (1 4) A method for forming a mark on a resin molded article, which includes applying a laser beam to the resin molded article described in (1 2) or (1 3) above. (1 5) The marking method as mentioned in (1 4) above, in which the laser beam is a far-infrared laser beam. This paper size applies the Chinese National Standard (CNS) m specification (win gift) — 6 _ (Please Read the notes on the back before filling in this page) Order A7 B7 V. Description of the invention (4) Detailed description of the present invention The thermoplastic resin used in the present invention can be any one known in the art 'as long as it is It only needs to show plasticity when heated. Typical examples of such thermoplastic resins are: polyethylene, polypropylene, polystyrene, poly Ethylene, polyvinylidene chloride, polyvinyl acetate, polymethacrylate, polypropylene, polycarbonate, their copolymers, polyethylene terephthalate, polybutylene terephthalate, poly Esters (such as: completely aromatic polyesters), polyurethane elastomers, polyamides, fluororesins, polyacetals, polyethers, polyethylene, polyphenylene sulfide, polyphenylene ether, and Its analogs. Among these resins, polypropylene and polyethylene are preferred. The thermoplastic resin used in the present invention does not have fluidity at 50 ° C, and does not have fluidity at 80 ° C. Preferably, its melt index (MI) is preferably about 0.01 to 60, and most preferably about 0.02 to 55. As for the inorganic material used in the present invention, talc, calcium carbonate, aluminum oxide, clay, magnesium oxide, aluminum hydroxide, silica, magnesium carbonate, and magnesium hydroxide can be used. Among these materials, talc, calcium carbonate, and molybdenum hydroxide are preferred in terms of the sharpness of the mark. These inorganic materials may be used alone, or a mixture of two or more of them in an appropriate ratio may be used. Examples of preferred mixtures are: calcium carbonate / talc, alumina / talc, silica / talc, calcium carbonate / silica, calcium carbonate / alumina, aluminum hydroxide / talc, magnesium hydroxide / talc, calcium carbonate / Aluminum hydroxide and calcium carbonate / magnesium hydroxide. The average particle size of the inorganic material used in the present invention is 0.1-. This paper size is applicable to Chinese National Standard (CNS) A4 specifications (210X 297 mm) -7-(Please read the precautions on the back before filling this page) Order ------ 々I *-

VD.V Printed by the Consumers 'Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. A7 B7 5. Invention Description (5) 100 microns, preferably 0.2 to 50 microns, most preferably 0 5-10 microns, their content in the composition is from 1 to 300% by weight, preferably from 2 to 250% by weight, based on the weight of the thermal resin. When its content is less than 1% by weight, no obvious contrast ratio can be obtained; when its content exceeds 300% by weight, the molding properties of the composition are severely impaired and cannot be effectively applied. Further explanation of the inorganic materials used in the present invention is as follows. When the thermoplastic resin is polyethylene (for example), the inorganic material used is preferably aluminum hydroxide. The higher the content, the sharper the mark, but when the content is too high, it will negatively affect the properties of the composition (such as brittleness). Therefore, in order to take into account the properties of the composition, the amount of the inorganic material is 1 to 20% by weight based on the total amount of polyethylene, preferably 1 to 15% by weight, and most preferably 1 to 10% by weight. %. Even if the amount is less than 5% by weight, a sufficiently clear mark can be obtained. The content of the inorganic material may even exceed 20% by weight when the properties of the parent mixture are not specifically considered. Β If the thermoplastic resin used is polypropylene or other resins, it is recommended to use aluminum hydroxide, talc or calcium carbonate. "Inorganic Materials" In order to make the mark clear, the content of inorganic materials must be high, but in the case of aluminum hydroxide and polyethylene, too high a content will negatively affect the properties of the composition, so 'in the nature In consideration, it is recommended that the amount of the inorganic material is 1 to 20% by weight based on the total weight of the polypropylene, preferably 1 to 15% by weight, and most preferably 1 to 10% by weight. When the content is less than 5% by weight, a mark with satisfactory sharpness is formed. If it is not necessary to list the nature of the parent mixture as an important consideration, of course, the amount of inorganic materials can be exceeded 20 This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) '„(Please read the back Note for this page, please fill out this page) I Order ------ tl- Ί. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A 7 ____-_ ^ _ B7 _ V. Description of the Invention (6) Weight% »In the use of hydrogen For alumina, because of its poor heat resistance, depending on the kneading temperature or molding temperature with the resin, it will form a silver wire-like mark on the surface of the molded object. Avoid this. Although the set upper temperature of the kneading temperature or the molding equipment depends on the content of aluminum hydroxide, it is usually about 240 ° C. This temperature will vary with the composition of the kneading equipment, the molding process The residence time in the equipment, the pressure or friction applied to the composition, and other factors change. "The above phenomenon does not occur when using talc or calcium carbonate. When using talc or calcium carbonate, its content has a significant effect on the properties of the composition. Little impact, but In order to obtain a clear mark, it is recommended that the amount of the material used is 5% by weight or more based on the total weight of the resin, preferably 8% by weight or more, and most preferably 10% by weight or more. The composition optionally contains additives. The additives that can be used in the present invention include colorants, fillers, lubricants, plasticizers, and the like. The coloring agent used can be a variety of organic pigments (such as carbon black, cyanine) , Azo, diazo, quinac.ridone, M Wing, flavan Shilin, per.inone, perillene, dioxanzine, condensed azo, methylimine and metaline) and inorganic pigments (eg: Titanium oxide, lead sulfate, zinc oxide, black iron oxide, chrome yellow, zinc yellow, red iron oxide, cobalt violet, chrome red, ultramarine blue, Prussian blue, chrome green, chromium oxide, and cobalt green. Organic pigments are preferred. Such organic or inorganic pigments can be added as required in a proportion of 0.1 to 5.0% by weight based on the weight of the thermoplastic resin. The filler used can be mica, calcium silicate, glass fiber, carbon fiber, etc. Applicable paper size National Standard (CNS) A4 specification (210 '乂 297 mm) --- -9-{Please read the notes on the back before filling out this page} Order A), r. Staff Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs Print A7 B7 5. Description of the invention (7), etc. The amount of these fillers can usually be 1-100% by weight based on the weight of the thermoplastic resin »In the present invention, the lubricant used as an additive Includes stearic acid, behenic acid and esters or salts, waxes (such as: Carunauba wax and polyethylene fluorene) and various types of lubricants. These lubricants can be 0. 1-5. A proportion of 0% by weight is added to the thermoplastic resin. Plasticizers used include terephthalates, phosphates, and sebacates. Other additives commonly used in plastics, such as antioxidants, heat stabilizers, light stabilizers, flame retardants, etc. can also be used as required. When these components are used in the invention, The additives can be added in the form of a powder or in the form of a matrix mixture. Use an extruder, double-strand kneader, rolling mill or other appropriate equipment to 'make the thermoplastic resin, talc, calcium carbonate, alumina, clay, magnesium oxide, hydrogen, with an average particle size generally less than 100 microns More than one of alumina, silica, magnesium carbonate, and magnesium hydroxide and one or more additives (such as colorants, fillers, lubricants, plasticizers, and thermal stabilizers) added as needed Blended, the labeled composition of the present invention can be obtained. By the presently known methods, the composition of the present invention obtained in such a manner is in its original form, or is processed into a pellet-like or bead-like precursor mixture, or a thermoplastic resin and other materials are added as necessary. After the additives are 'molded into the desired resin molding form', the resin moldings that can be made from the composition of the present invention include two-dimensional moldings (such as films) or three-dimensional moldings (such as: Containers, lids, parts) ... # · · 〇 This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling out this page) Order 5! -10-Ministry of Economy Printed by the Standards Bureau Consumers Cooperative A7 B7 V. Description of the Invention (8) This method can be used to form this two-dimensional molded object * such as a film. The methods used include: an expansion method for forming a film from a thermoplastic resin, an expansion method for forming a multilayer film, a T-mold film forming method, including a flat film forming method that performs biaxial stretching simultaneously or successively, and a tubular film forming Law ... wait. The film made in the way described above can be used in the same application range as general thermoplastic resin film, such as: food packaging, fiber packaging, grocery packaging, pharmaceutical packaging, tape, insulators, agricultural films, various Types of boards, various types of tapes or envelopes, labels ... etc. The film of the present invention can also be firmly laminated to various types of substrates (such as: paper (such as kraft paper or smooth paper), plastic film, metal foil (such as aluminum foil), etc.) to form a laminate. " Such a base layer can be used for a variety of applications, such as: containers (such as: milk and snow grams) containers, pharmaceutical packaging, food packaging, various types of boards, various types of encapsulants, labels, etc. Use known molding methods according to the desired target product, such as: injection molding, extrusion molding, hollow molding, rotary molding, expansion molding, powder molding, vacuum Molding method ... etc., a three-dimensional molded article made of the composition for marking according to the present invention can be obtained. Examples of these moldings are containers for food, detergents, medicines, cosmetics, fakes, etc., the lids of these containers, food trays, tubes, medicine bottles, clothing containers, appliances switches, appliances, automotive parts (such as: Fenders), joysticks for automobiles, audiovisual equipment (such as cassettes), items for information processing equipment (such as floppy disks), water pipes, building materials, various types of containers, clothing containers), multilayer film containers , Miscellaneous goods, various types of commercial machinery, office supplies, and other commercially available molded articles mainly composed of thermoplastic resins. -This paper size applies to Chinese National Standard (CNS) A4 (210 ×: 297 mm) (Please read the precautions on the back before filling this page)

-11 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 ____ B7 __ ^ _ V. Description of the Invention (9) When a laser beam is used on the surface of the aforementioned molded object, a white mark that effectively contrasts in the illuminated area. The lasers used are: far-infrared lasers (such as carbon dioxide lasers with a wavelength of about 10,600 nm), near-infrared lasers (such as: yAG lasers with a wavelength of about 1.00 nm), and ultraviolet light Laser (such as excimer laser with a wavelength of about 190-350n m). In the present invention, far-infrared laser is preferred. The energy of the laser beam used for the D EA carbon dioxide laser is 3-6 Joules per square centimeter. The present invention will be further illustrated by the following examples, which are for illustrative purposes only and are not intended to limit the present invention in any way. In the following examples and comparative examples, unless otherwise stated, all parts are "by weight" Example 1. 1,000 parts of polyethylene (UP POLYETHYLENE J110K, MI: 10, manufactured by C. hisso Corp. ), 50 parts of Hydroxide (B · —703, average. Particle size: 2 microns, manufactured by Nihon Keikinzoku KK), and 3 parts of pigmented Muya Ya red (Pigment Violet 19) in a double-stranded spiral The kneader was kneaded at 160 ° C and granulated to obtain the composition for marking according to the present invention. An injection mold (SAV-40 manufactured by San joh Seiki KK) was used. This model is used in the following examples and comparisons. In the injection molding method, this composition was molded into a board at 150 ° C, and a carbon dioxide laser (XYmark 7000 manufactured by Coherent Hull, Ltd.) was used to mark the surface of the board. This paper Standards apply to Chinese national standards (CNS > A4 specifications (210X297 mm) ----, ------ IX ------ 1T ----- 1 products (please read the note on the back first) Please fill in this page again for details) -12-A7 _B7 Five 'Invention Description (10) Example 2 1 0 0 0 copies ° Polyethylene J110K, 100 parts of aluminum hydroxide (B — 7 0 3) and 2 parts of pigmented phthalocyanine (Pigment Blue 16) in a double-stranded screw kneader at 160 ° C Kneaded and granulated to obtain the marked composition of the present invention. This composition was injection-molded into a plate at 150 ° C, and a carbon dioxide laser (XYmark 70 0 0) was used to mark the surface of the plate. A very clear white mark was formed. Example 3 1 0 0 parts of polyethylene (UP POLYETHYLENE J110K) and 100 parts of aluminum hydroxide (B-7 沱 3) in a double-stranded screw kneader at 160 ° C is kneaded and granulated to obtain the composition for marking according to the present invention. This composition is injection molded at 150 ° C into a board, and a carbon dioxide laser (XYmark 7 0 0 0) is used to make the board. Marking, forming a very clear white.color mark. Example 4 1 0 0 0 parts of polypropylene (TONEN POLYPROPYLENE J-215, MI: 15, manufactured by Tonen Corp.), 50 parts of hydroxide name (B -7 0 3) and 2 parts of colored phthalocyanine (Pigment Blue 16) were kneaded at 200 ° C with a double-stranded screw kneader, and granulated to obtain the labeled group of the present invention. Thereof. This composition is injection molded at 220 ° C using TEA carbon dioxide laser (the paper size manufactured by Laser Technics, Ltd. applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please first (Read the notes on the back and fill out this page)

-13-Printed A7 B7 by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention (11) BLAZAR 6000) at 26,700 volts (4 Joules / cm2) and a reduction ratio of 1: 2 , Mark on this board, forming a very clear white mark. Example 5 1 0 0 parts of polyethylene terephthalate (SUNPELLET 32 0 0G manufactured by Asahi Kasei Kogyo KK), 30 parts of aluminum hydroxide (B — 7 0 3) and 2 parts of colored phthalate The cyanine (Pigment Blue 16) was kneaded with a double-stranded screw kneader at 230 ° C and granulated to obtain the labeled composition of the present invention. This composition was injection-molded at 230 ° C into a plate, and a carbon dioxide laser (XYmark 7 0 0 0) was used to mark the surface of the plate to form a very clear white mark. Example 6. 100 parts of polypropylene (CHISSO POLYPROPYLENE K8140T, MI: 40, manufactured by Chisso Corp.), 300 parts of carbonic acid age (Super 1700, average particle size 2 micron, manufactured by Maruo Calciuii KK) Two parts of colored phthalocyanine (CI Pigment Blue 16) were kneaded with a double-stranded screw kneader at 200 ° C, and granulated to obtain the composition for marking according to the present invention. This composition was injection-molded into a plate at 2300 ° C, and a carbon dioxide laser (BLAZAR 6000) was used at 26 '700 volts (4 joules / cm2) with a reduction ratio of 1: 3. Marks are made on this board to form very clear white marks. This paper size applies to China National Standard (CNS) A4 (210X 297 mm) (Please read the precautions on the back before filling this page)

-14-Printed A7 by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs ______B7 __ V. Description of the Invention (12) Example 7 1 0 0 0 parts of polypropylene i Kase i Kogyo KK), 4.0 parts of talc (P 3, average particle size: 3 μm, manufactured by Nippon. Talc KK) and 3 parts of red pigment (KST RED E-3B , Manufactured by Nippon Kayaku KK) kneaded at 200 ° C with a double-stranded screw kneader, and granulated to obtain the composition for marking according to the present invention. This composition was injection molded at 230 ° C into a board, using a carbon dioxide laser (BLAZAR 6000) at 26,700 volts (4 Joules / cm2) and a reduction ratio of 1: 3. Marking on the surface forms a very clear white mark. Example 8 100 parts of polypropylene used in Example 7, 100 parts of calcium carbonate (Super 1700, average particle size: 2 microns), 100 parts of talc (P-3, average particle size: 3 microns) ) And 3 parts of colored phthalocyanine green (CIPigment Green 7) were kneaded at 200 ° C with a double-stranded screw kneader, and granulated to obtain the labeled composition of the present invention. This composition is injection-molded at 2 30 ° C into a board, using a carbon dioxide laser (BLAZAR 6000) at 26,700 volts (4 Joules / cm2) and a reduction ratio of 1: 3. Marked on it, forming a very clear white mark. Example 9 This paper size applies to Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) (Please read the precautions on the back before filling this page)

15 Printed by A7 B7, Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs 5. Description of the Invention (13) 1,000 parts polyethylene (SUNTEC M6545, MI: 45 'manufactured by Asahi Kasei Kogyo KK), 300 parts alumina (A — 3 3 F, average particle size: 0. 7 microns, manufactured by Nihon Keikinzoku KK) and 2 parts of colored quinacridine red (CI Pigment Violet 1 9) were kneaded with a double-stranded screw kneader at 200 ° C, passed. The composition for granulation was obtained by granulating. This composition was injection-molded at 170 ° C, and a carbon dioxide laser (BLAZAR 6000) was used at 26,700 volts (4 joules per square centimeter) with a reduction ratio of 1: 3. Make a mark to form a clear white mark. Example 1 100 100 parts of the polyethylene used in Example 9, 300 parts of silica (RD-8, average particle size: 15 microns, manufactured by Tatsumori KK), and 2 parts of colored Phthalocyanine (CI Pigment Blue 16) was kneaded in a double-stranded screw kneader at 200 ° C, and granulated to obtain the labeled composition of the present invention. This composition was injection molded at 180 ° C into a board using carbon dioxide laser (BLAZAR 6000) at 26,700 volts (4 Joules / cm2) and a reduction ratio of 1: 3. Mark on the surface of the lens to form a clear white mark. Example 1 1 100 parts of polyethylene terephthalate (SUNPET 3200G, manufactured by Asahi Kasei Kogyo KK), 15.0 parts of clay and 5 parts of colored phthalocyanine (CIPigment Blue 16) Double-stranded spiral pinch, this paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm ^ ~~~ 1 ^^:-" .Order. Color / 、 (Please read the precautions on the back before filling in this (Page) A7 _ B7 V. Description of the invention (14) The machine is kneaded at 200 ° C and granulated to obtain the labeled composition of the present invention. This composition is made by injection molding at 250 ° C Using a carbon dioxide laser (BLAZAR 6000) at 26,700 volts (4 joules per square centimeter) and a reduction ratio of 1: 3, mark the surface of the plate to form a clear white mark. Example 1 2 1000 parts of polyethylene terephthalate used in Example 11, 100 parts of magnesium oxide (manufactured by Ube Kagaku Ko.gy.o) and 5 parts of red pigment (KST RED Ε-3Β, by Nippon Kayaku (Manufactured by KK) Kneaded with a double-stranded screw kneader at 200 ° C and granulated to obtain the labeled composition of the present invention This composition is injection molded at 250 ° C into a board, using a carbon dioxide laser (BLAZAR 6000) at 26.7 volts (4 joules / cm2) and a reduction ratio of 1: 3. Mark on the surface to form a clear white mark. Example 1 3 Printed by the consumer cooperation department of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling in the form page) 1 0 0 0 Propylene, .80 parts of magnesium carbonate (manufactured by Tokuyama Soda KK) and 5 parts of colored phthalocyanine green (C.I. Pigment Green 7) were kneaded at 200 ° C with a double-stranded screw kneader, Granulation to obtain the labeled composition of the present invention "This composition was injection molded into a plate at 250 ° C, using carbon dioxide laser (blaZAR 6 000) at 26,700 volts (4 joules per square) In the case of a reduction ratio of 1: 3, make a note on the surface of the board to form a clear paper size. This paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) '~ -17-Central Ministry of Economic Affairs A7 B7 printed by Standards Bureau Consumer Cooperative __ V. White mark of invention description (15). Example 1 4 1 000 parts of polycarbonate (TAFLON SC-250, manufactured by Idemit-su Petrochemical C + orp.), 400 parts of hydrogen, magnesium oxide, and 3 parts of colored phthalocyanine (CIPigment Blue 16) Knead with a double-stranded screw kneader at 200 ° C and granulate to obtain the labeled composition of the present invention. This composition was injection-molded at 250 ° C into a plate, using a carbon dioxide laser (BLAZAR 6000) at 26,00. Volts (4 Joules / cm2), and a reduction ratio of 1: 3. Here, Mark on the surface of the board to form a white mark. Example 15 100 parts of polypropylene used in Example 7, 150 parts of calcium carbonate (Super l700, average particle size: 2 microns), 50 parts of talc (P-3, average particle size: 3 microns) , 50 parts of aluminum hydroxide (B-703) and 3 parts of red pigment (KST RED E-3B) were kneaded at 200 ° C with a double-stranded screw kneader, and granulated to obtain the labeled product of the present invention.组合 物。 Composition. This composition was injection molded at 230 ° C into a plate, using a carbon dioxide laser (BLAZAR 6 0 0 0) at 26,700 volts (4 Joules / cm2), with a reduction ratio of 1: 3 Next, make a mark on the surface of this board to form a very clear white mark. Example 16 6. This paper is again applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ~: -18-(Please read the back first Please note this page before filling in this page). Order A7 B7 V. Description of the invention (16) (Please read the notes on the back before filling this page) 1 0 0 0 parts of polypropylene used in Example 7, 50 parts of oxidation Aluminum (into -3 ?, average particle size: 0.7 micron, manufactured by 〇111 ^ 丨 1 ^ 112-oku KK) and 3 parts of pigmented phthalocyanine (CI Pigment Blue 16) with a double-stranded spiral The kneader was kneaded at 200 ° C and granulated to obtain the labeled shake composition of the present invention. This composition was injection molded at 230 ° C into a plate, using a carbon dioxide laser (SAV—40) at 26,700 volts (4 joules per square centimeter) and a reduction ratio of 1: 3. , Mark on this board, forming a very clear white mark. Example 1 7 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, 100 parts of polypropylene used in Example 7, 200 parts of talc (P-3, average particle size: 3 microns), 200 parts of silica (RD -8, average particle size: 15 microns) and 3 parts of colored phthalocyanine (CI Pigment Blue 16) were kneaded with a double-stranded spiral kneader at 200 ° C, and granulated to obtain the subject of the present invention. Composition for marking. This composition was injection-molded at 250 ° C into a plate, using a carbon dioxide laser (BLAZAR 60 0 0) at 26,700 volts (4 Joules / cm2) and a reduction ratio of 1: 3. Here, Marking on the surface of the board forms a very clear white mark. Example 1 8 1 0 0 0 parts of polypropylene (CHISSO POLYPROPYLENE K8140T, MI: 40), 300 parts of calcium carbonate (Super 1 700, average particle size: 2- This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -19-A7 __ ^^ _ B7 _ V. Description of the invention (17 microns) and 3 parts of colored phthalocyanine (CIPigment Blue 16) with a double-stranded screw kneader at 20 ° C Kneading and granulation yield the labeled composition of the present invention. This composition is injection-molded into a board at 230 ° C, using a carbon dioxide laser (BLAZAR 6000) at 26,700 volts (4 joules / cm2) and a reduction ratio of 1: 3. Marks on the surface of the surface to form very clear white marks. Example 1 Θ 1 0 0 0 0 parts of the polypropylene used in Example 18 and 250 parts of aluminum hydroxide (B — 703, average particle size: 0.4 μm) with a double-stranded screw kneader at 2000 ° C is kneaded and granulated to obtain the labeled composition of the present invention. This composition is injection molded at 230 ° C into a board, using a carbon dioxide laser (BLAZAR 6000) at 26.7 volts (4 joules square centimeters) and a reduction ratio of 1: 2. Here, The surface of the board is marked to form a very clear white mark. Example 2 0 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) 1 0 0 0 Used in Example 7 Polypropylene and 1,000 parts of aluminum hydroxide (B-7003) were kneaded at 200 ° C with a double-stranded screw kneader, and granulated to obtain the labeled composition of the present invention. This composition is injection molded at 230 ° C, using a carbon dioxide laser (BLAZAR 6000) at 26,700 volts (4 Joules / cm2) and a reduction ratio of 1: 2. Marked on it to form a very clear white mark. "This paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm). 20 Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. A7 B7. 5. Description of the invention (18) Examples 2 1 1 0 0 0 parts of polyethylene (SUNTEC M6545), 2 500 parts of aluminum hydroxide (B-303, manufactured by Nihon Keikinzoku KK, particle size: 30 microns), and 5 parts of colored quinacridine red ( c. I .. Pigment V-iolet 19) Kneaded with a double-stranded screw kneader at 200 ° C and granulated to obtain the composition for labeling of the present invention. This composition was injection molded at 180 ° C into a board using carbon dioxide laser (BLAZAR 60 00) at 26,700 volts (4 Joules / cm2) and a reduction ratio of 1: 2. Marks on the surface, forming very clear white marks. Example 2 2 1 0 0 0 parts of polystyrene (IDEMITSU SYTROL GP HF10, MI: 30, manufactured by Idemitsu Petrochemical Cor p. ·), 1 0 0 parts of gas oxidation name (B — 153, by Nihon Keikinzoku KK Manufacturing, particle size: 15 microns) and 3 parts of colored phthalocyanine (C. 丨. Pigment Blue 16) were kneaded with a double-stranded spiral kneader at 200 ° C to obtain the present invention. Marked composition. This composition was injection molded at 200 ° C into a board, using a carbon dioxide laser (BLAZAR 6000) at 26,700 volts (4 Joules / cm2) and a reduction ratio of 1: 2. Mark on it to form a fairly clear white mark. This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 1 21 (Please read the precautions on the back before filling in this page)

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (19) Example 2 3 1 0 0 0 parts of polyethylene terephthalate (SUNPET 3200G), 400 parts of aluminum hydroxide (3- 1〇3, manufactured by ^ 11〇111 ^ 11 ^ 112-oku KK, particle size: 8 microns) and 5 parts of colored oddness 丨 Irrazine Yellow 3RL (made by Ciba Geigy Corp.) in double strands The screw kneader was kneaded at 200 ° C to obtain the labeled composition of the present invention after granulation. This composition is injection molded at 240 ° C using a carbon dioxide laser (BLA2AR 6000) at 2 6 '70 0 volts (4 Joules / cm2) with a reduction ratio of 1: 2 'here The surface of the board is marked to form a very clear white mark. Example 2 4 1 0 0 0 parts of polybutylene terephthalate (TEIJIN PBT C 7000, manufactured by Teijin Co., Ltd.), 400 parts of aluminum hydroxide (B-3 03, by Nihon Keikinzoku KK manufactured, particle size: 30 microns) and 3 parts of pigmented phthalocyanine (CI Pigment Blue 7) were kneaded with a double-stranded spiral kneader at 200 ° C to obtain granules of the present invention. Remember the composition. This composition was injection-molded at 240 ° C into a plate, using a carbon dioxide laser (BLAZAR 6000) at 26'700 volts (4 Joules / cm2) and a reduction ratio of 1: 2. The surface of this board is marked to form a very clear white mark. Example 2 5 1 00 parts AB S resin (SAik〇LAC EX102, Saikon This paper size applies Chinese National Standard (CNS) A4 specifications (210X297) (Please read the precautions on the back before filling this page)

-22 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (20) KK) and 100 parts of aluminum hydroxide (B-153, particle size: 15 microns) with a double-stranded spiral The kneader was kneaded at 200 ° C, and was granulated to obtain the labeled composition of the present invention. This composition was injection molded at 20 ° C into a board, using a carbon dioxide laser (BLAZAR 6000) at 26,700 volts (4 joules / cm2) and a reduction ratio of 1: 2. Here, Marking on the surface of the board forms a very clear white mark. Example 2 6 1 0 0 0 parts of polyvinyl chloride (KANE-VINYL COMPOUND KVC I-2 2 9C, manufactured by Kanegaf uchi Kogyo KK), 500 parts of aluminum hydroxide (BW — 53, manufactured by Nihon Keikinzoku KK, Particle size: 50 microns) and 2 parts of carbon black (ΜΑ—100, manufactured by Mitsubishi • Chemical Industries, 'Ltd.) were kneaded at 140 ° C with a double-stranded screw kneader, and granulated to The labeling composition of the present invention is obtained. This composition was injection molded at 150 ° C into a plate, using a carbon dioxide laser (BLAZAR 6000) at 26,700 volts (4 joules / cm2) and a reduction ratio of 1: 2 at Marks are made on this board to form very clear white marks. Example 2 7 1 0 0 0 parts of polyethylene (UP POLYETHYLENE J110K, manufactured by Chisso Corp.), 100 parts of aluminum hydroxide (B — 7 0 3, manufactured by Nihon Keikinzoku KK), and 2 parts of colored phthalate Cyan (-This paper size applies Chinese National Standard (CNS) A4 specification (210X29? Mm) ~ '' ~ ---------- ^ ------ 1τ _------ ην. (Please read the notes on the back before filling this page) Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Invention Description (21) CI Pigment Blue 16) Double-stranded screw kneader at 1 6 0 Kneaded at ° C and granulated to obtain the labeled composition of the present invention. This composition was injected at 150 ° C to make a lid with a diameter of 22 mm and a height of 5 mm, and a carbon dioxide laser (XYmark 70 00) was used to mark the cover to form a very clear white mark. Example 2 8 1000 parts of polyethylene used in Example 27, 100 parts of aluminum hydroxide (B-7 0 3), and 2 parts of pigmented phthalocyanine (Pigment Blu-e 16) in a double-stranded screw kneader at 160 Kneaded at ° C and passed through a roller to form the marking-receiving composition of the present invention, which is a thick film having a thickness of 500 microns. A carbon dioxide laser (XYmark 70 00) was used to mark the surface of the film to form a very clear white mark. Example 2 9 100 parts of polyethylene (UP POLYETHYLENE J110K), 30 parts of aluminum hydroxide (B-7 0 3), and 1 part of pigmented phthalocyanine (Pigment Blue 16) were blended. The blend was kneaded with a double-stranded screw kneader at 160 ° C, and granulated to obtain the labeled composition of the present invention. These granules were molded into a board at an injection mold (SAV — 40) at 160 ° C and marked with carbon dioxide laser (XYmark 7 0 0 0) to form a very clear white mark. . Comparative Example 1 This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X297 mm) (Please read the notes on the back before filling in this I ·). Order-24-Consumption Cooperation by the Central Bureau of Standards, Ministry of Economic Affairs A7 ______B7 V. Description of the invention (22) 1 0 0 0 parts of polyethylene (UP 'POLYETHYLENE J110K) is injection molded into a board at 150 ° C, and a carbon dioxide laser (XYmark 7000) is used on the board surface Mark, but cannot form a mark. Comparative Example 2 A mixture of 100 parts of polyethylene used in Comparative Example 1 and 2 parts of pigmented phthalocyanine (Pigment Blue 16) was injection-molded into a plate at 150 ° C, and a carbon dioxide laser was used. (XYmark 7 0 0 0) Mark on the surface of the board, but cannot form a mark. ., Comparative Example 3 1 0 0 0 parts of polypropylene (CHISSO POLYPROPYLENE K8140T) and 2 parts of pigmented phthalocyanine (CI Pigment Blue 16) were kneaded at 200 ° C with a double-stranded screw kneader and granulated. A comparative labeling composition was obtained. This composition is injection molded at 230 ° C into a board, using a carbon dioxide laser (BLAZAR 6000) at 26,00 volts (4 Joules / cm2) and a reduction ratio of 1: 3. Here, Mark on the board. But the mark could not be formed. Comparative Example 4 1 0 0 0 parts of polyethylene (SUNTEC M6545) and 5 parts of colored quinacridine red (CIPigment Violet 19) were kneaded with a double-stranded screw kneader at 2000 ° C. A comparative labeled composition was obtained by granulation. This composition is injection-molded at 170 ° C using carbon dioxide laser. The paper size is applicable to China National Standard (CNS) A4 (210X 297 mm) (Please read the precautions on the back before filling this page)

-25-Consumption cooperation by employees of the Central Bureau of Standards, Ministry of Economic Affairs, printed mmn at B7 V. Description of the invention (23) (BLAZAR 6000) at 2 6 '7000 volts (4 Joules / cm2), reduction rate 1: In the case of 3, make a mark on this board. However, a mark cannot be formed. The molded articles obtained from the above-mentioned examples and comparative examples were marked ′ to evaluate their color development with the naked eye. The results obtained are shown in Table 1. Table 1 Vividness of color development of resin inorganic materials Example 1 PE aluminum hydroxide ◎ Example 2 PE aluminum hydroxide. ◎ Example 3 PE aluminum hydroxide ◎ Example 4 PE aluminum hydroxide ◎ Example 5 PET aluminum hydroxide ◎ Example 6 PP carbonic acid Calcium ◎ Example 7 PP Talc ◎ Example 8 PP Calcium Carbonate / Talc ◎ Example 9 PP Oxidation Error 〇 Example 10 PE Silica 〇 Example 11 PET Clay 〇 Example 12 PET Magnesium Oxide 〇 Example 13 PP Carbonate Table 〇 Example 14 PC S. Hydrogen Magnesium oxide △ This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) r J line "; (Please read the precautions on the back before filling this page) -26-B86999 V. Description of the invention (24 ) A7 B7 Table 1 Vividness of color development of resin and inorganic materials

Example 1 5 PP calcium carbonate / talc / hydroxide. Ming ◎ Example 1 6 PP talc / alumina ◎ Example 1 7 PP talc / silica ◎ Example 18 PP calcium carbonate ◎ Example 1 9 PP hydroxide ◎ ◎ Example 2 0 PP Aluminum hydroxide ◎ Example 2 1 PE aluminum hydroxide ◎ Example 2 2 PS aluminum hydroxide ◎ Example 23 PET aluminum hydroxide ◎ Example 2 4. PBT hydroxide name ◎ Example 25 ABS aluminum hydroxide ◎ Example 26 PVC hydroxide name ◎ Example 27 PE silver hydroxide ◎ Example 28 PE aluminum hydroxide ◎ Example 29 PE aluminum hydroxide ◎ Comparative Example 1 PE — X Comparative Example 2 PE — X Comparative Example 3 PP — X Comparative Example 4 PE — X (Please read first Note on the back, please fill in this page again.) Threading r This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -27-V. Description of invention (25) The criteria for evaluation are as follows: The appearance of white is very clear. 0: The appearance of white is sharp. △: The appearance of white is discernible. X: Failure to develop color. It can be seen from the table that the laser beam is applied to the group of the present invention. Was prepared on the molding composition, it can achieve the purpose of forming a mark on a thermoplastic resin molded Gamma]. Thereof. It was also found that when using aluminum hydroxide, calcium carbonate or clear stone as a developer, very clear marks can be obtained. 、 二 ；: '-.ν..Ί -㈤ ^ (Please read the notes on the back before filling out this page) Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, India 褽, «τ --------- 5 ---- This paper size applies to China National Standard (CNS) A4 (2 丨 0X297mm)

Claims (1)

8888 ABCD% Printed by the Consumer Cooperative of the China National Standards Bureau of the Ministry of Economic Affairs. 6. Application for patents 1 ~ 1. A method for forming a mark on a resin mold, including applying a laser beam to the resin mold. The product is obtained by molding a composition for marking. The composition contains a polyolefin resin that does not have fluidity at 50 ° C and at least one inorganic material. It is selected from the group consisting of talc, calcium carbonate, and clay. , Aluminum hydroxide, and magnesium hydroxide, the mixing ratio of the inorganic material to the polyolefin resin is 1 to 300w / w% · 2 · As in the method of claim 1 in the patent application range, wherein the laser beam is a carbon dioxide laser Light beam < · 3. The method according to item 1 of the patent application range, wherein the polyolefin resin is polypropylene or polyethylene. 4. The method of claim 1 in which the inorganic material is talc, calcium carbonate or aluminum hydroxide. 5. The method according to item 1 of the patent application range, wherein the polyolefin resin is polyethylene 'and the inorganic material is aluminum hydroxide, and the ratio of the aluminum hydroxide to polyethylene is 1 to 15 w / w%. 6. The method according to item 5 of the scope of patent application, wherein the ratio of the content of aluminum hydroxide to polyethylene is 1 to 10 w / w%. 7. The method according to item 5 of the patent application, wherein the proportion of aluminum hydroxide is 2 to 5 w / w%. 8. The method according to item 1 of the scope of patent application, wherein the polyolefin resin is polypropylene, and the inorganic material is talc or calcium carbonate, and the ratio of the talc or calcium carbonate to polypropylene is 5 to 25 〇w / w% »9. The method according to item 8 of the scope of patent application, wherein the ratio of talc or carbonate is 10 to 100w / .w%. This paper is suitable for China. National Standard (CNS) A4 specification (210X297mm) (Please read the precautions on the back before filling this page) 8888 ABCD% Printed by the Consumer Cooperative of the China National Standards Bureau of the Ministry of Economic Affairs. 6. Application for patents 1 ~ 1. A method for forming a mark on a resin mold, including applying a laser beam to the resin mold. The product is obtained by molding a composition for marking. The composition contains a polyolefin resin that does not have fluidity at 50 ° C and at least one inorganic material. It is selected from talc, calcium carbonate, and clay , Aluminum hydroxide, and magnesium hydroxide, the mixing ratio of the inorganic material to the polyolefin resin is 1 to 300w / w% · 2 · As in the method of claim 1 in the patent application range, wherein the laser beam is a carbon dioxide laser Light beam < · 3. The method according to item 1 of the patent application range, wherein the polyolefin resin is polypropylene or polyethylene. 4. The method of claim 1 in which the inorganic material is talc, calcium carbonate or aluminum hydroxide. 5. The method according to item 1 of the patent application range, wherein the polyolefin resin is polyethylene 'and the inorganic material is aluminum hydroxide, and the ratio of the aluminum hydroxide to polyethylene is 1 to 15 w / w%. 6. The method according to item 5 of the scope of patent application, wherein the ratio of the content of aluminum hydroxide to polyethylene is 1 to 10 w / w%. 7. The method according to item 5 of the patent application, wherein the proportion of aluminum hydroxide is 2 to 5 w / w%. 8. The method according to item 1 of the scope of patent application, wherein the polyolefin resin is polypropylene, and the inorganic material is talc or calcium carbonate, and the ratio of the talc or calcium carbonate to polypropylene is 5 to 25 〇w / w% »9. The method according to item 8 of the scope of patent application, wherein the ratio of talc or carbonate is 10 to 100w / .w%. This paper is suitable for China. National Standard (CNS) A4 specification (210X297mm) (Please read the precautions on the back before filling this page) A8 B8 C8 D8 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs ^ 86999 VI. Application for patent scope 1 10. The method of applying for patent scope item 1 wherein the polyolefin resin is polypropylene 'the inorganic material is aluminum hydroxide, The ratio of aluminum hydroxide to polypropylene is 1 to 15 w / w% v 1 1. As in the method of the scope of application for patent; item M), the ratio of aluminum hydroxide is 1 to 10 w / w%. 12. The method according to item 10 of the scope of patent application, wherein the ratio of aluminum hydroxide is 2 to 5 w / w%. This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X297 mm) Art (Please read the precautions on the back before filling this page), τ-衮! -30-