WO2005068557A1 - 多色発色レーザーマーキング用有彩色着色剤、多色発色レーザーマーキング用組成物及びそれを含む成形品、多色マーキング付き成形品並びにレーザーマーキング方法 - Google Patents

多色発色レーザーマーキング用有彩色着色剤、多色発色レーザーマーキング用組成物及びそれを含む成形品、多色マーキング付き成形品並びにレーザーマーキング方法 Download PDF

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Publication number
WO2005068557A1
WO2005068557A1 PCT/JP2005/000312 JP2005000312W WO2005068557A1 WO 2005068557 A1 WO2005068557 A1 WO 2005068557A1 JP 2005000312 W JP2005000312 W JP 2005000312W WO 2005068557 A1 WO2005068557 A1 WO 2005068557A1
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WIPO (PCT)
Prior art keywords
laser
marking
color
polymer
mass
Prior art date
Application number
PCT/JP2005/000312
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English (en)
French (fr)
Japanese (ja)
Inventor
Kazuyoshi Kawakami
Hideyuki Kurimoto
Akira Shimizu
Toshiyuki Kosakai
Mio Ishida
Original Assignee
Techno Polymer Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
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Application filed by Techno Polymer Co., Ltd. filed Critical Techno Polymer Co., Ltd.
Priority to EP05703551.1A priority Critical patent/EP1705226B1/en
Priority to US10/586,358 priority patent/US20080139707A1/en
Priority to KR1020067016349A priority patent/KR101155815B1/ko
Publication of WO2005068557A1 publication Critical patent/WO2005068557A1/ja

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/267—Marking of plastic artifacts, e.g. with laser
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/34—Multicolour thermography
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0017—Influencing the physical properties by treatment with an acid, H2SO4
    • C09B67/0019—Influencing the physical properties by treatment with an acid, H2SO4 of phthalocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass

Definitions

  • Chromatic colorant for multicolor laser marking composition for multicolor laser marking and molded articles containing the same, molded articles with multicolor marking, and laser marking method
  • the present invention relates to a chromatic colorant for multicolor laser marking, a thread for multicolor laser marking, a molded article containing the same, a molded article with multicolor marking, and a laser marking method. More specifically, when a molded article containing the present chromatic colorant is irradiated with two or more laser beams having different energies, markings of two or more different colors including a chromatic color derived from the colorant are clearly formed.
  • Multicolorable chromatic colorants for laser marking that can be formed, and compositions for multicolor laser marking that are marked in two or more different colors by irradiating two or more laser beams having different energies
  • the present invention relates to an article, a molded article containing the same, a molded article with multicolor marking, and a laser marking method.
  • a laser marking method has attracted attention as a technique for easily and quickly marking a character, a symbol, a pattern, or the like of a desired color on the surface of a molded article having a composition such as resin or the like (patented).
  • Reference 1 A composition for diversifying the colors of markings have also been developed, for example, for molded articles containing a substance that changes color or decolorizes due to the absorption of laser light and a dye substance that is not easily affected by laser light.
  • Patent Documents 2 and 3 A method of irradiating laser light (see Patent Documents 2 and 3), a method of irradiating laser light to a synthetic resin molding material composed of a thermoplastic organic polymer, a mineral black pigment and a coloring agent (see Patent Document 4), and the like.
  • a method of irradiating laser light to a synthetic resin molding material composed of a thermoplastic organic polymer, a mineral black pigment and a coloring agent
  • Patent Document 1 Japanese Patent Application Laid-Open No. 5-92657
  • Patent Document 2 JP-A-6-297828
  • Patent Document 3 JP-A-8-127175
  • Patent Document 4 JP-A-7-165979
  • the present invention has been made in view of the above circumstances. That is, the present invention provides markings of two or more different colors including a chromatic color derived from a colorant on the surface of a molded article exhibiting a black or dark ground color, and further comprises a colorant derived from a colorant.
  • a chromatic coloring agent for multicolor laser marking to be included in a molded article in order to form clear markings of colored and white colors, and a multicolor laser marking thread capable of forming the above markings
  • An object of the present invention is to provide a molded article, a molded article containing the same, a molded article with multicolor marking, and a laser marking method. Means for solving the problem
  • the present inventors have studied the thermal properties of black colorants and the relationship between the energy of the irradiating laser beam and the color developing properties, etc., to achieve the above object.
  • By irradiating two or more laser beams having different energies to the polymer composition for coloring laser marking it was found that the two or more different color tones were clearly marked, and the present invention was completed. Reached.
  • the gist of the present invention is as follows.
  • a molded article containing a chromatic colorant, a black substance that disappears or changes color by receiving laser light, and a polymer is irradiated with one or more lasers having different energies.
  • a chromatic colorant for marking in two or more different colors the chromatic colorant having a heat generation peak in the range of 360 ° C to 590 ° C by differential thermal analysis. Characteristic chromatic colorant for multicolor laser marking.
  • the chromatic colorant includes at least one skeleton selected from a phthalocyanine skeleton, a diketopyrrolopyrrole skeleton, a dioxazine skeleton, a quinacridone skeleton, a quinophthalone skeleton, a perylene skeleton, and a metal complex skeleton.
  • a chromatic colorant for laser coloring is selected from a phthalocyanine skeleton, a diketopyrrolopyrrole skeleton, a dioxazine skeleton, a quinacridone skeleton, a quinophthalone skeleton, a perylene skeleton, and a metal complex skeleton.
  • a multicolored laser marking material which is marked in a color tone, comprising: a chromatic colorant; and a black substance which disappears or discolors itself by receiving laser light.
  • the composition for multicolor laser marking is 0.01 to 2 parts by mass based on 100 parts by mass.
  • the chromatic colorant comprises at least one skeleton selected from a phthalocyanine skeleton, a diketopyrrolopyrrole skeleton, a dioxazine skeleton, a quinacridone skeleton, a quinophthalone skeleton, a perylene skeleton, and a metal complex skeleton.
  • a composition for color developing laser marking wherein the chromatic colorant comprises at least one skeleton selected from a phthalocyanine skeleton, a diketopyrrolopyrrole skeleton, a dioxazine skeleton, a quinacridone skeleton, a quinophthalone skeleton, a perylene skeleton, and a metal complex skeleton.
  • the above-mentioned polymer includes a thermoplastic polymer and a thermosetting polymer, and the content of the thermosetting polymer is 0.01% when the content of the thermoplastic polymer is 100 parts by mass. 4.
  • composition for multicolor laser marking according to the above item 3, wherein the black substance is at least one selected from carbon black, titanium black, and black iron oxide.
  • the antimicrobial agent content is 0.01 to 10 parts by mass
  • the filler content is 110 to 30 parts by mass
  • the metallic pigment content power is 0.1 to 10 parts by mass.
  • the multicolor coloring described above is a thread for laser marking.
  • a composition comprising the composition for multicolor laser marking according to (3) above.
  • Shape TOo
  • Molded TOo characterized by including the composition for multicolor laser marking according to 6 above.
  • a molded TOo comprising the composition for multicolor laser marking according to 7 above.
  • a molded TOo comprising the composition for multicolor laser marking according to 9 above.
  • a laser marking method which comprises irradiating the molded article according to the above item 10 with two or more laser beams having different energies to mark in two or more different colors.
  • a molded TOo with multicolor marking characterized by irradiating the molded article according to 10 above with two or more laser beams having different energies and marking two or more different colors.
  • a molded article (composition) containing a chromatic colorant, a specific black substance, and a polymer is irradiated with two or more laser beams having different energies in a simple and convenient manner. It is possible to form markings of various colors clearly at high speed. Therefore, it is possible to mark desired characters, symbols, patterns, etc. on keyboards such as computer consoles, game consoles, calculators, etc., and on plastic products such as buttons and cases for cars, home appliances, telephones, etc. Is expected to expand.
  • the laser marking method of the present invention It is also possible to form white or near-white markings on the surface of a molded article that exhibits a black or dark ground color, so it is necessary to form a display that is very easy to identify and decode. Can be.
  • the display obtained by laser marking is much more durable than the display obtained by other methods such as printing, as it is less likely to deform or wear the marking part and can maintain high visibility for a long time. ing.
  • FIG. 1 is an explanatory view showing a laser marking method of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing one example of a molded product with multicolor markings of the present invention.
  • FIG. 3 is a schematic cross-sectional view showing another example of a molded product with multicolor markings of the present invention.
  • FIG. 4 is a diagram showing a color solid of the Lab color system.
  • FIG. 5 is a graph showing a differential thermal analysis result of (1) ⁇ -type copper phthalocyanine pigment in [I 1] of Example.
  • FIG. 6 is a graph showing the result of differential thermal analysis of (2) aluminum phthalocyanine pigment in [I 1] of Example.
  • FIG. 7 is a graph showing the results of differential thermal analysis of (3) a solvent-soluble copper phthalocyanine dye in 1) of Example.
  • FIG. 8 is a graph showing the results of a differential thermal analysis of (4) a diketopyrrolopyrrole-based pigment in [I1] of Examples.
  • FIG. 9 is a graph showing the results of differential thermal analysis of (5) a dioxazine-based pigment in [I1] of Examples.
  • FIG. 10 is a graph showing the results of differential thermal analysis of the (6) quinacridone pigment in Example [1].
  • FIG. 11 is a graph showing the results of differential thermal analysis of (7) quinophthalone-based pigment in Example [1].
  • FIG. 12 is a graph showing the results of differential thermal analysis of (8) perylene-based pigment in [G1] of Examples.
  • FIG. 13 is a graph showing the results of differential thermal analysis of (9) a metal complex-based pigment in Example [1].
  • FIG. 14 is a graph showing the results of a differential thermal analysis of (10) anthraquinone-based dye in [I1] of Example.
  • FIG. 15 is a graph showing a result of a differential thermal analysis of (11) perinone-based dye in [G1] of Example.
  • FIG. 16 is a graph showing a result of a differential thermal analysis of (13) perylene black in [I1] of the example.
  • FIG. 17 is an image showing a cross section of a white marking portion in Example B-1.
  • FIG. 18 is an image showing a cross section of a chromatic marking portion in Example B-1.
  • the chromatic colorant used for the multicolor laser marking according to the present invention (hereinafter, also simply referred to as “the chromatic colorant of the present invention”) is a multicolor containing a chromatic colorant, a specific black substance, and a polymer.
  • the composition of the present invention By irradiating two or more laser beams having different energies to a molded article containing a composition for color-developing laser marking (hereinafter, also simply referred to as “the composition of the present invention”), the surface of the molded article is irradiated with two or more laser beams. The marking is performed in the above different colors.
  • the coloring mechanism of the multicolor laser marking according to the present invention has not been elucidated, but is presumed to be generally based on the following phenomena.
  • the coloring mechanism of the multicolor coloring laser marking according to the present invention is not limited to the following mechanism.
  • the chromatic colorant When a molded article containing the composition of the present invention is irradiated with laser light, the chromatic colorant is decomposed, scattered, etc., such as disappearance and discoloration of the black substance, depending on the energy of the laser light.
  • the parts where black matter disappears (evaporation etc.), discoloration, etc. have a stronger appearance of the color of the substance other than the black matter, as compared with the parts where these do not occur.
  • the portion where the chromatic colorant is decomposed or scattered becomes a color in which the density of the color derived from the chromatic colorant is relatively reduced or white, as compared with the portion where these are not generated.
  • the degree to which such a color change occurs is different depending on the difference in the energy of the irradiated laser light.Therefore, it is considered that by irradiating two or more laser lights having different energies, two or more different color tones are marked.
  • the chromatic colorant of the present invention usually causes decomposition, scattering, and the like with energy higher than the energy for vaporizing, discoloring, and the like of a black substance.For example, for a molded article exhibiting a black or dark ground color, When irradiated with low-energy laser light, the irradiated area develops a color that is strongly influenced by the chromatic colorant (hereinafter, also simply referred to as “color derived from the chromatic colorant”), and When the laser beam of the energy is irradiated, it is possible to obtain each marking in which the irradiated part has a reduced color density of the color derived from the chromatic colorant or a white color. . As described above,
  • the chromatic colorant of the present invention is not particularly limited as long as it does not interfere with the excellent performance of the multicolor laser marking of the present invention. It has an exothermic peak in the range of C or less.
  • the lower limit temperature of the exothermic peak range is more preferably 380 ° C, particularly preferably 400 ° C, and the upper limit temperature is more preferably 585 ° C. If the temperature of the exothermic peak is too low, the marking of the color derived from the chromatic colorant tends to be unclear when irradiated with a low-energy laser beam.
  • the chromatic colorant of the present invention may be used in combination of two or more chromatic colorants as long as the temperature of the exothermic peak is within the above range.
  • the color of the chromatic colorant of the present invention is not particularly limited as long as it is other than black and white, such as red, yellow, blue, purple, and green. Yes. Further, it may be a pigment or a dye.
  • chromatic colorants having an exothermic peak temperature in the above range by differential thermal analysis are shown below.
  • An example of the color of each colorant is shown in parentheses.
  • the composition (molded product) has at least one skeleton selected from the group consisting of a phthalocyanine skeleton, a diketopyrrolopyrrole skeleton, a dioxazine skeleton, a quinacridone skeleton, a quinophthalone skeleton, an anthraquinone skeleton, a perylene skeleton, and a metal complex skeleton.
  • a chromatic colorant When a chromatic colorant is included, two or more different color markings including the color derived from the chromatic colorant are clearly formed on the surface of the composition (article) that exhibits a black or dark ground color. Is preferred.
  • a chromatic colorant having at least one skeleton selected from a phthalocyanine skeleton, a diketovirolopyrrole skeleton, a dioxazine skeleton, a quinacridone skeleton, a quinophthalone skeleton, a perylene skeleton, and a metal complex skeleton is more preferable.
  • Pyrrole skeleton and dioxazine skeleton A chromatic colorant having at least one skeleton whose strength is also selected is particularly preferred.
  • Examples of the chromatic colorant having a phthalocyanine skeleton include a compound represented by the following general formula), and this compound is a pigment or a dye.
  • M is a coordinating metal atom or two hydrogen atoms, and R 1 to R 16 are each independently an arbitrary functional group.
  • M is copper (Cu), aluminum (A1), zinc (Zn), tin (Sn), or copper (Cu), which is preferably two hydrogen atoms. Copper (Cu) or aluminum (A1) is particularly preferred, with aluminum (A1) or zinc (Zn) being more preferred.
  • M When M is a metal, it may have a ligand such as a halogen atom or OH.
  • R 1 to R 16 are an unsubstituted hydrogen atom; a halogen atom such as fluorine, chlorine, bromine, or iodine; a sulfonamide group (one SO NHR), one SO— ⁇ R + etc.
  • R is an alkyl group having 1 one 20 carbon atoms.
  • R 1 one R 16 are preferred.
  • Particularly preferred is an unsubstituted hydrogen atom or a sulfonamide group.
  • chromatic colorants having a phthalocyanine skeleton are listed in (1)-(6) below. Of these, (1), (3) and (4) are particularly preferred.
  • the crystals of the copper phthalocyanine pigment may be ⁇ -type or ⁇ -type.
  • the average secondary particle diameter of the ⁇ -type copper phthalocyanine pigment is generally more than 20 m and 30 m or less, but in the present invention, the upper limit is preferably 20 m, more preferably 10 / zm, The lower limit is 1 m.
  • the average secondary particle diameter can be measured by a laser scattering particle size distribution measuring device or the like.
  • the halogen atom is preferably a chlorine atom or a bromine atom.
  • M in the above general formula (I) is Cu, and 418, preferably 4 of R 1 —R 16 are the above-mentioned sulfonic acid amide groups or —SO— ⁇ R +, preferably sulfone Is an acid amide
  • Solvent soluble copper phthalocyanine dye Particularly preferably, the structure of the solvent-soluble copper phthalocyanine dye is represented by the following general formula (II).
  • each R is independently an alkyl group having 120 carbon atoms.
  • each R is independently an alkyl group having 418 carbon atoms.
  • An aluminum phthalocyanine pigment wherein M in the general formula (I) is A1, and R 1 to R 16 are unsubstituted hydrogen atoms.
  • A1 preferably has 1 OH or —C1 as a ligand, and more preferably has 1 OH.
  • a particularly preferred structure of the aluminum phthalocyanine pigment is represented by the following formula (IV).
  • a tin phthalocyanine pigment wherein M in the above general formula (I) is Sn, and R 1 to R 16 are each independently a hydrogen atom or a halogen atom.
  • the structure of the zinc phthalocyanine pigment is represented by the following general formula (V).
  • R 1 -R i6 are each independently an unsubstituted hydrogen atom or a halogen atom.
  • a zinc phthalocyanine pigment in which R 1 to R 16 in the above general formula (V) are all hydrogen atoms is particularly preferable.
  • Examples of the chromatic colorant having a diketopyrrolopyrrole skeleton include a compound represented by the following general formula (VI), and this compound is usually a pigment.
  • Ar and Ar are each independently an aromatic ring which may have a substituent.
  • the aromatic ring constituting Ar and Ar ′ is not particularly limited as long as it has aromaticity, and is usually a 5- or 6-membered monocyclic or 2- to 6-condensed aromatic ring.
  • a ring, 0, S , N, etc. may be included.
  • a 6-membered ring is more preferable, and a 6-membered single ring is more preferable. Particularly preferred.
  • the aromatic ring preferably has a substituent, and examples of the preferred substituent include a halogen atom, an alkyl group having 11 to 12 carbon atoms, an alkoxyl group having 11 to 12 carbon atoms, an amino group, NHCOR ', and one COR. , And COOR '(where R is an alkyl group having 11 to 12 carbon atoms or a (hetero) aryl group having 12 or less carbon atoms), of which a halogen atom, particularly a chlorine atom, is preferable. .
  • Examples of the chromatic colorant having a dioxazine skeleton include a compound having a skeleton represented by the following general formula (VII), and this compound is usually a pigment.
  • the coloring agent having the skeleton may be a compound having a substituent or a compound having no substituent, but is preferably a compound having a substituent.
  • the structure of the compound having a substituent is represented, for example, by the following general formula (VIII).
  • each of R 17 — is independently a halogen atom, NHCOR ′ (provided that R ′ is an alkyl group having 11 to 12 carbon atoms or a (hetero) aryl group having 12 or less carbon atoms.) A C11-C12 alkyl group or a C11-C12 alkoxyl group. ]
  • the chromatic colorant having a dioxazine skeleton has the substituents R 17 and R 18 in the general formula (VIII).
  • R 17 and R 18 are preferably a halogen atom or NHCOR ′, more preferably —NHCOR ′.
  • R 19 to R 22 are preferably a halogen atom, NHCOR, an alkyl group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms or NHCOR '. More preferred.
  • Examples of the chromatic colorant having a quinacridone skeleton include a compound having a skeleton represented by the following general formula (IX), and this compound is usually a pigment.
  • the coloring agent having the skeleton may be a compound having a substituent or a compound having no substituent.
  • the structure of the compound having a substituent is represented by, for example, the following general formula (X) [ 10
  • the substituent is preferably bonded at the position of R 23 to R 26 .
  • Preferred substituents include a halogen atom and an alkyl group having 11 to 12 carbon atoms. It is.
  • Examples of the chromatic colorant having a quinophthalone skeleton include a compound having a skeleton represented by the following general formula (XI), and this compound is a pigment or a dye.
  • the coloring agent having the skeleton may be a compound having a substituent or a compound having no substituent.
  • the structure of the compound having a substituent is represented by, for example, the following general formula ( ⁇ ).
  • each of R 27 -R d is independently an unsubstituted hydrogen atom, a halogen atom, an alkyl group having 1-12 carbon atoms, an alkoxyl group having 1-12 carbon atoms, or a group containing a ring structure.
  • R 31 is an unsubstituted hydrogen atom, a halogen atom, an alkoxyl group having 1 to 12 carbon atoms, an aryloxy group having 5 to 12 carbon atoms, a heteroaryloxy group having 1 to 12 carbon atoms, An alkylthio group having 12 carbon atoms, an arylthio group having 5 to 12 carbon atoms or a heteroarylthio group having 1 to 12 carbon atoms, R 32 is an unsubstituted hydrogen atom or a hydroxyl group, and R 33 — R 36 is Each independently represents an unsubstituted hydrogen atom, halogen atom, carboxyl group, An alkyl group, an alkoxyl group having 1 to 12 carbon atoms, COOR, or CONR '(provided that R
  • R 28 and R 29 , R 31 and R 32 , R 33 and R 34 , R 34 and R 35 , and R 35 and R 36 may be connected to each other to form a ring.
  • X 1 -X 4 are each independently an unsubstituted hydrogen atom or a halogen atom.
  • the structure of the colorant in the case where R 27 in the above general formula (XII) is a substituent represented by the above general formula ( ⁇ ) is shown below as a general formula (XIV).
  • R 28 to R 36 are the same as those described above, and X 5 to X. Are each independently an unsubstituted hydrogen atom or a halogen atom. ]
  • R 28 to R 3 may be an unsubstituted hydrogen atom, a halogen atom, an alkyl group having 11 to 12 carbon atoms or a carbon atom.
  • An alkoxyl group having 1 one 12, R and R is an unsubstituted hydrogen atom, and, R 33 - compounds R 36 is a halogen atom.
  • R 28 and R 29 are unsubstituted hydrogen atoms or halogen atoms
  • R 3G —R 32 are unsubstituted hydrogen atoms
  • R 33 —R 36 are halogen atoms
  • This colorant is usually a pigment.
  • Particularly preferred colorants are those in which R 28 and R 29 are unsubstituted hydrogen atoms, R 3 ° — R 32 is an unsubstituted hydrogen atom, and R 33 — R 36 are halogen atoms (X 9 — X 12 ) And X 5 —X 8 are halogen atoms (see the following general formula (XV)).
  • X 5 to X 12 are each independently a halogen atom.
  • R 27 and R 3 ° are unsubstituted hydrogen atoms
  • R 28 and R 29 are a halogen atom, an alkyl group having 11 to 12 carbon atoms or an alkyl group having 11 to 11 carbon atoms.
  • the compound having 12 alkoxyl groups (see the following general formula (XVI)) is usually a dye.
  • R and R 29 are each independently a halogen atom, an alkyl group having 11 to 12 carbon atoms or an alkoxyl group having 11 to 12 carbon atoms, and R 31 is an unsubstituted hydrogen atom or a halogen atom.
  • R 32 is an unsubstituted hydrogen atom or a hydroxyl group
  • R 33 to R 36 are each independently an unsubstituted hydrogen atom or a halo group.
  • R 28 and R 29, R 31 and R 32, R 33 and R 34, R 34 and R 35, and, R 35 and R 36 are each, Chiyoi to form a ring. ]
  • Examples of the chromatic colorant having an anthraquinone skeleton include compounds having a skeleton represented by the following general formula (XVII). This colorant may be a compound containing only one of the following skeletons, or a compound containing two or more of the following skeletons.
  • a compound represented by the following general formula (XVIII), a compound having a plurality of the above skeletons, and a compound having an amino group are preferable.
  • R d7 -R 44 each independently represent an unsubstituted hydrogen atom, a halogen atom, an amino group, a hydroxyl group, an alkyl group having 1-12 carbon atoms, an alkoxyl group having 1-12 carbon atoms, 5-12 carbon atoms aryl group, 1-12 carbon heteroaryl group, 1 NHR, 1 NR, 2, OR
  • R is an alkyl group having 1 to 12 carbon atoms or a (hetero) aryl group having 12 or less carbon atoms.
  • the compound represented by the general formula (XVIII) is usually a yellow-blue dye.
  • Examples of the compound having two anthraquinone skeletons and two amino groups include compounds represented by the following general formula (XIX) and structural formula (XX). These compounds are usually blue pigments.
  • R 45 and R 4 ° each independently represent an unsubstituted hydrogen atom, an alkyl group having 11 to 12 carbon atoms, an aryl group having 5 to 12 carbon atoms, or a heteroaryl having 11 to 12 carbon atoms.
  • a hydrogen atom bonded to an aromatic ring may be substituted by a halogen atom or the like.
  • Examples of the chromatic colorant having a perylene skeleton include a compound represented by the following general formula (XXI), and this compound is usually a pigment.
  • R 47 and R 48 are each independently a hydrogen atom, an alkyl group having 11 to 12 carbon atoms, an aryl group having 5 to 12 carbon atoms, a heteroaryl group having 11 to 12 carbon atoms, COR, or — COOR '(where R' is an alkyl group having 11 to 12 carbon atoms and a (hetero) aryl group having 12 or less carbon atoms).
  • chromatic colorant having a perylene skeleton represented by the general formula (XXI) a colorant in which R 47 and R 48 are an alkyl group having a carbon number of 11 to 12 is preferred. Alkyl-based colorants are more preferred.
  • Examples of the chromatic colorant having a metal complex skeleton include a conjugated product in which a metal ion is coordinated to an organic dye skeleton.
  • Examples of the organic dye skeleton include those having an azo group and those having an azomethine group. It may have a hydroxyl group, an amino group, an imino group and the like at the peri position.
  • Examples of metal ions include ions of copper, nickel, cobalt, zinc, and the like.
  • the black substance according to the present invention is not particularly limited as long as it disappears or changes its color upon receiving laser light. That is, the color of the component receiving the laser beam in the composition of the present invention and the molded article containing the same is changed to the color of the component other than the black substance by disappearing or discoloring itself by the energy of the laser beam. Any color that has a strong influence can be used.
  • the term “disappearance” of the black substance means that the black substance does not exist due to vaporization, volatilization or decomposition, and the term “discoloration” means that at least a part or all of the substance has a different color (e.g. (Preferably white) (for example, black ⁇ light blue or white).
  • Black of a black substance is a dark color including black, for example, red-black (brown-black), green-black, blue-black, purple-black, gray- Includes black-based colors such as black.
  • a laser having an output of 31 A, a frequency of 5.5 kHz and a wavelength of 1,064 nm is used for a black test piece composed of only 100 parts by mass of polymethyl methacrylate and 0.1 part by mass of the black substance. It is preferable that the irradiated part change color to a color other than white or black when irradiated with light.
  • the black substance may be an inorganic substance or an organic substance, and may be a pigment or a dye. Further, the black substance may contain a compound, a mineral, or the like that is not included in these unless the excellent effects of the present invention are impaired. Good.
  • the above black substances can be used alone or in combination of two or more.
  • the black substance include inorganic pigments such as carbon black, titanium black, and black iron oxide, graphite, and activated carbon.
  • carbon black, titanium black and black iron oxide which are liable to be foamed by laser beam irradiation as described below, are preferably composed mainly of a substance, and especially those mainly composed of carbon black. preferable.
  • Examples of the carbon black include acetylene black, channel black, and furnace black. These can be used alone or in combination of two or more.
  • the lower limit of the average particle size of the carbon black is preferably 0.1 nm, more preferably 1 nm, particularly preferably 5 nm, and most preferably lOnm, and the upper limit is preferably 1, OOO nm, More preferably, it is 500 nm, particularly preferably 100 nm, most preferably 80 nm.
  • the lower limit of the nitrogen adsorption specific surface area of the carbon black is preferably lm 2 Zg, more preferably 5 mg, particularly preferably 10 m 2 Zg, and most preferably 20 m 2 Zg, and the upper limit is preferably 10,000 m 2 / g, more preferably 5,000 m 2 / g, particularly preferably 2,000 m 2 / g, and most preferably 1,500 m 2 Zg.
  • the composition (molded article) of the present invention contains carbon black
  • carbon black it is known that when irradiated with laser light, the composition absorbs the laser light and vaporizes.
  • the carbon black is vaporized and disappears, the color of the laser beam irradiated portion becomes less or less affected by the color (black or dark color) derived from the carbon black, and the color other than the carbon black contained in the composition (molded product) of the present invention is reduced.
  • the effect of the color derived from the component (mixture) becomes stronger, that is, the color derived from the chromatic colorant develops.
  • Titanium black is generally obtained by reducing titanium dioxide.
  • the lower limit of the average particle size of the titanium black is preferably 0.01 ⁇ m, more preferably 0.05 ⁇ m, particularly preferably 0.1 ⁇ m, and the upper limit is preferably 2 ⁇ m. ⁇ m, preferably 1.5 m, particularly preferably 1. m, most preferably 0.8 ⁇ m.
  • the titanium black changes to white titanium dioxide when irradiated with laser light. Therefore, when the composition (molded article) of the present invention contains titanium black, the color of the laser light-irradiated portion is black as in the case where the composition (molded article) containing carbon black is irradiated with laser light. The density of the chromatic color decreases or disappears, and a color derived from the chromatic colorant develops.
  • black iron oxide is generally an oxidized iron product represented by FeO or FeO'FeO.
  • the lower limit of the average particle size of the black iron oxide is preferably 0.01 ⁇ m, more preferably 0.05 m, particularly preferably 0.1 m, and most preferably 0.3 ⁇ m.
  • the upper limit is preferably 2 ⁇ m, more preferably 1.5 m, particularly preferably 1.0 m, and most preferably 0.8 ⁇ m.
  • the above-mentioned black iron oxide changes to white with a strong red tint when irradiated with laser light. Therefore, when the composition (molded article) of the present invention contains black iron oxide, a laser beam is applied to the yarn (molded article) containing carbon black or titanium black. In the same manner as in the case where the laser light is irradiated, the density of the black color is reduced or lost, and the color is derived from the chromatic colorant.
  • the polymer according to the present invention (hereinafter, also referred to as “polymer for laser marking”) is not particularly limited as long as it does not prevent multicolor coloring by irradiation with one laser beam. Therefore, it is preferable to include a polymer such as thermoplasticity, thermosetting, light (including visible light-ultraviolet light, electron beam, etc.) curability, and room temperature curability. These may be any of resin, elastomer, polymer alloy, rubber and the like. Also, one of the above may be used, or two or more of them may be used in combination, including the combined use of other polymers not belonging to these.
  • the “curable” polymer includes an oligomer or the like that becomes a polymer after curing.
  • the curing time of the curable polymer or the like is not particularly limited, and may be, for example, when a molded article is manufactured using the composition of the present invention, or when the molded article is irradiated with laser light.
  • Can be The curable polymer and the like are not cured at the time of kneading with the chromatic colorant of the present invention, the black substance, etc., at the time of forming the composition of the present invention, and at the time of manufacturing a molded article. Is also good.
  • the uncured polymer or oligomer is included in the laser marking polymer.
  • thermoplastic resin examples include styrene resins such as polystyrene, styrene'acrylonitrile copolymer, styrene • maleic anhydride copolymer, (meth) acrylate ester'styrene copolymer, and ABS resin; Rubber-reinforced thermoplastic resin; polyethylene, polypropylene, ionomer, ethylene-butyl acetate copolymer, ethylene-butyl alcohol copolymer, cyclic olefin copolymer, olefin resin such as chlorinated polyethylene; One or more types of butyl-based resins such as butyl, ethylene 'chloroidyl butyl polymer, polychloridized biylidene, and the like, and (meth) acrylates such as polymethyl methacrylate (PMMA) were used.
  • styrene resins such as polystyrene, styrene
  • Acrylic resin such as (co) polymer; Polyamide resin (PA) such as polyamide 6, polyamide 6, 6, polyamide 6, 12; polyethylene terephthalate Polyester resins such as (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate; polyacetal resin (POM); polycarbonate resin (PC); polyarylate resin; polyphenylene ether; polyphenylene sulfa Fluorinated resins such as polytetrafluoroethylene and polyvinylidene fluoride; liquid crystal polymers; Polyimide, Polyamide imide, Polyether imide and other imide resins; Polyether ketone, Polyether ether ketone and other ketone resins; Polysulfone, polyether sulfone and other sulfone resins; Urethane resins; Polyethylene oxide; Polybutyl alcohol; Polybutyl ether; Polybutyl butyral; Phenoxy resin; Photosensitive resin
  • a biodegradable plastic or the like can be used alone or in combination of two or more.
  • rubber-reinforced thermoplastic resin acrylic resin, polyamide resin (PA), polyacetal resin (POM), and urethane resin are preferred.
  • the “rubber-reinforced thermoplastic resin” refers to a rubber-reinforced copolymer resin obtained by polymerizing a vinyl monomer in the presence of a rubbery polymer, or this rubber-reinforced copolymer resin and a vinyl resin. Such a compound also has a mixed power with a (co) polymer of a system monomer.
  • thermoplastic elastomer examples include an olefin-based elastomer; a gen-based elastomer; a styrene-based elastomer such as styrene-butadiene-styrene block copolymer; a polyester-based elastomer; a urethane-based elastomer; Elastomers; polyamide elastomers; fluoroelastomer elastomers and the like. These can be used alone or in combination of two or more.
  • polymer alloy examples include PAZ rubber-reinforced thermoplastic resin, PCZ rubber-reinforced thermoplastic resin, PBTZ rubber-reinforced thermoplastic resin, PCZPMMA, and the like. These can be used alone or in combination of two or more.
  • Rubbers include natural rubber, isoprene rubber, butadiene rubber, styrene'butadiene rubber, acrylonitrile, butadiene rubber, chloroprene rubber, butynole rubber, ethylene propylene rubber, acrylic rubber, urethane rubber, chlorinated polyethylene, silicone rubber, epichlorohydrin rubber, and fluorine. Rubber and polysulfur rubber. These can be used alone or in combination of two or more.
  • Curable polymers such as thermosetting, photocurable, and room temperature curable include acrylic resins (including acrylic polymers having an epoxy group), epoxy resins, phenolic resins, and the like. Unsaturated polyester resin, alkyd resin, melamine resin, urethane resin, urea resin, silicone resin, polyimide resin, bismaleimide 'triazine resin, furan resin, xylene resin, guanamine' And dicyclopentadiene resin. These can be used alone or Two or more kinds can be used in combination. These resins may contain a curing agent or the like, or may consist of only a self-crosslinkable polymer. Of these, acrylic polymers having an epoxy group are preferred.
  • the polymer for laser marking according to the present invention contains a polymer that is foamed by receiving laser light, multicolor coloring by laser light irradiation becomes clearer. Therefore, the laser marking polymer according to the present invention, when irradiated with a laser beam having an output of 31 A, a frequency of 5.5 kHz, and a wavelength of 1,064 nm, to a test piece that is also strong only in this polymer, has a cross section of an irradiated portion.
  • the polymer is a foam whose foaming state is observed by an electron microscope.
  • the irradiated portion becomes a foamed portion, depending on the behavior of the chromatic colorant at the time of laser beam irradiation, the laser beam irradiated portion (foamed portion) ) And the surrounding unirradiated portion have a large difference in refractive index, and the marking becomes clearer.
  • the laser light irradiation unit Because of the large difference in the refractive index between the foamed part and the surrounding unirradiated part, a clearer marking is formed.
  • the polymer for laser marking according to the present invention includes: (1) a rubber-reinforced thermoplastic resin using methyl methacrylate as a monomer component; (2) polymethyl methacrylate (PMMA), methacryl An acrylic resin such as a copolymer containing 30% by mass or more of methyl acid monomer units; (3) a polyacetal resin; and (4) a thermoplastic resin such as a polyamide resin is easily foamed and is preferred.
  • the rubber-reinforced thermoplastic resin preferred in the present invention is a rubber-reinforced copolymer obtained by polymerizing a butyl monomer (bl) in the presence of a rubbery polymer (a). Resin (A1) or a mixture of this rubber-reinforced copolymer resin (A1) and a (co) polymer (A2) of a vinyl monomer (b2), etc.
  • the amount of the (meth) acrylate monomer unit in (A1) or the mixture is preferably 30% by mass based on the total amount of the monomer units constituting the polymer component other than the rubbery polymer ( a ).
  • the content is more preferably 40% by mass or more, and still more preferably 50% by mass or more. Beyond this range force, you can easily get clear markings May not be possible.
  • a (meth) acrylate for the formation of the (co) polymer (A2) of the rubber-reinforced copolymer resin (A1) and the vinyl monomer (b2).
  • a rubber-reinforced copolymer resin (A1) obtained by polymerizing a vinyl monomer (bl) containing a (meth) acrylate ester in the presence of a rubbery polymer (a)
  • a rubber-reinforced copolymer resin which has a mixture power of the rubber-reinforced copolymer resin (A1) and the (co) polymer (A2) of the vinyl monomer (b2).
  • the graft monomer in which the butyl monomer (bl) is graft-polymerized to the rubber polymer is obtained.
  • a mixture of the polymer component and the (co) polymer component of the vinyl monomer (bl) can be obtained by grafting.
  • acrylic acid esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, and acrylic acid Isobutyl, amyl acrylate, hexyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, fluor acrylate, benzyl acrylate Acrylic esters such as methyl methacrylate, methyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, isobutyl methacrylate,
  • Examples of the rubbery polymer ( a ) include polybutadiene, butadiene 'styrene copolymer, butadiene' acrylonitrile copolymer, styrene 'butadiene' styrene block copolymer, and styrene 'isoprene' styrene block copolymer.
  • Polymers such as copolymers, isobutylene 'isoprene copolymers, etc .; hydrides of these polymers; butyl rubber; ethylene' a one-year-old olefin copolymer; ethylene, a-olefin, non-conjugated gen copolymer; silicone rubber; System rubber, etc. Is mentioned. These polymers can be used alone or in combination of two or more.
  • the vinyl-based monomer (bl) used for forming the rubber-reinforced copolymer resin (A1) may be an aromatic vinyl compound, a vinyl cyanide compound, or a maleimide-based compound in addition to the (meth) acrylate. It may contain a compound or the like. If necessary, a vinyl compound having a functional group such as an epoxy group, a hydroxyl group, a hydroxyl group, an amino group, or an oxazoline group may be used. These compounds can be used alone or in combination of two or more.
  • Examples of the vinyl monomer (b2) used for forming the (co) polymer (A2) include the above-mentioned (meth) acrylic acid ester; an aromatic vinyl compound; a cyanuric vinyl compound; a maleimide compound; Examples include vinyl compounds having a functional group such as an epoxy group, a hydroxyl group, a carboxyl group, an amino group, and an oxazoline group. These compounds can be used alone or in combination of two or more. As the vinyl monomer (bl) and the vinyl monomer (b2), the same monomer may be used in the same amount or in different amounts, or different types of monomers may be used. May be used.
  • aromatic vinyl compound styrene, ⁇ -methylstyrene, o-methylstyrene, p-methylstyrene, ethylstyrene, vinyltoluene, vinylxylene, methyl- ⁇ -methylstyrene, tert-butylstyrene, divinylbenzene, 1, 1 -Chlorinated styrenes such as diphenylstyrene, vinylnaphthalene, butylpyridine, monochlorostyrene and dichlorostyrene; brominated styrenes such as monobromostyrene and dibutomostyrene; monofluorostyrene.
  • these compounds can be used alone or in combination of two or more. Of these compounds, styrene, ⁇ -methylstyrene and ⁇ -methylstyrene are preferred.
  • Cyanidani Viridui conjugation product examples include acrylonitrile, methacrylonitrile, and ethacrylotrile. These compounds can be used alone or in combination of two or more. Of these compounds, acrylonitrile and metatali-tolyl are preferred.
  • the maleimide-based compound includes maleimide, ⁇ -methylmaleimide, ⁇ -butylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N-cyclohexylmaleimide, imide compounds of ⁇ , ⁇ unsaturated dicarboxylic acids, etc. . These compounds can be used alone or in combination of two or more.
  • the introduction of the maleimide-based compound unit into the polymer may be carried out by copolymerizing maleic anhydride and subjecting the polymer to imidation.
  • Examples of the vinyl compound having a functional group include glycidyl methacrylate, glycidyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, acrylic acid, methacrylic acid, and ⁇ , ⁇ -dimethyl.
  • the vinyl monomer (bl) used to form the rubber-reinforced copolymer resin (A1) or the vinyl monomer (b2) used to form the (co) polymer (A2) ) Is used as shown below.
  • the lower limit of the amount used relative to the total amount of the vinyl monomer is preferably 5% by mass, more preferably 10% by mass, and particularly preferably 20% by mass. Is preferably 100% by mass, more preferably 80% by mass.
  • the lower limit of the amount of the butyl monomer used is preferably 1% by mass, more preferably 3% by mass, and particularly preferably 5% by mass.
  • the upper limit is preferably 50% by mass, more preferably 40% by mass, and particularly preferably 35% by mass.
  • the lower limit of the amount of the vinyl monomer used is preferably 1% by mass, more preferably 5% by mass, and the upper limit is preferably 100% by mass. %, More preferably 95% by weight, particularly preferably 90% by weight.
  • the lower limit of the amount of the vinyl-based monomer used is preferably 1% by mass, more preferably 5% by mass, and the upper limit is preferably 70% by mass. The content is more preferably 60% by mass, and particularly preferably 55% by mass.
  • the lower limit of the amount used relative to the total amount of the vinyl monomer is preferably 0.1% by mass, more preferably 0.5% by mass, and particularly preferably 1% by mass. %, And the upper limit is preferably 30% by mass, more preferably 25% by mass. When the amount of the vinyl monomer used is within the above range, the effect of the monomer used is sufficiently exerted. This is preferred.
  • the rubber-reinforced copolymer resin (A1) is obtained by producing a vinyl monomer (bl) in the presence of the rubbery polymer ( a ) by a method such as emulsion polymerization, solution polymerization, or bulk polymerization. can do. Of these, emulsion polymerization is preferred.
  • a polymerization initiator In the case of production by emulsion polymerization, a polymerization initiator, a chain transfer agent (molecular weight regulator), a milking agent, water and the like are used.
  • a chain transfer agent molecular weight regulator
  • Examples of the polymerization initiator include organic compounds represented by cumenehydride peroxide, diisopropylbenzenehydroxide peroxide, paramenthanehydroxide peroxide, and the like, formulations of sugar containing pyrophosphoric acid, sulfoxylate, and the like.
  • Redox system in combination with a reducing agent represented by, for example, or a persulfate such as potassium persulfate, benzoyl peroxide (BPO), lauroyl peroxide, tert-butylperoxylaurate, tert-butylperoxide Peroxides such as xymonocarbonate can be used, and these can be used alone or in combination of two or more.
  • the addition to the reaction system may be performed all at once or continuously.
  • the amount of the polymerization initiator used is usually 0.1 to 1.5% by mass, preferably 0.2 to 0.7% by mass, based on the total amount of the vinyl monomer (bl). .
  • Examples of the chain transfer agent include octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecyl mercaptan and the like.
  • Mercaptans; terpinolene, ⁇ -methylstyrene dimer, etc. and these can be used alone or in combination of two or more.
  • the amount of the chain transfer agent to be used is usually 0.05 to 2.0% by mass based on the total amount of the above-mentioned bullet-based monomer (bl).
  • Examples of the emulsifier include sulfates of higher alcohols and sodium dodecylbenzenesulfonate.
  • Alkyl benzene sulfonates such as lium; aliphatic sulfonates such as sodium lauryl sulfate; higher aliphatic carboxylate; aionic surfactants such as rosinate; alkyl ester type of polyethylene glycol; alkyl ether Noon-based surfactants such as molds.
  • the amount of the dairy sardine to be used is usually 0.3 to 5.0% by mass based on the total amount of the vinyl monomer (bl).
  • the vinyl monomer (bl) may be charged all at once in the presence of the total amount of the rubbery polymer (a), or may be divided or continuously added. Good. Further, the whole or a part of the rubbery polymer (a) may be added during the polymerization.
  • the latex obtained by emulsion polymerization is usually coagulated with a coagulant to make a polymer component into a powdery form, and then purified by washing with water and drying.
  • a coagulant include inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride and sodium chloride; inorganic acids such as sulfuric acid and hydrochloric acid; and organic acids such as acetic acid and lactic acid.
  • the graft ratio of the graft polymer (mass ratio of the vinyl monomer (bl) grafted to the rubbery polymer (a)) contained in the rubber-reinforced copolymer resin (A1) is preferably 10%. — 200%, more preferably 15-150%, particularly preferably 20-100%. If the graft ratio of the graft polymer is too low, a molded article obtained by using the composition of the present invention may have poor appearance and reduced impact strength. On the other hand, if it is too high, workability is poor.
  • the graft ratio is defined as xg of the rubbery polymer (a) in the rubber-reinforced copolymer resin (Al) lg, and acetone of the rubber-reinforced copolymer resin (Al) lg in the rubber polymer (Al).
  • acrylic rubber is used as a
  • use acetonitrile when acrylic rubber is used as a), use acetonitrile).
  • the value is obtained by the following equation.
  • the graft ratio (%) is determined based on the type and amount of the polymerization initiator, chain transfer agent, emulsifier, solvent, etc., and the polymerization time, polymerization temperature, etc., when producing the rubber-reinforced copolymer resin (A1). By changing it, it can be easily controlled.
  • the (co) polymer (A2) can be obtained by, for example, barta polymerization, solution polymerization, emulsion polymerization, suspension polymerization, or the like.
  • the intrinsic viscosity [7?] (Measured in methyl ethyl ketone at 30 ° C) of the acetone-soluble component (A2) of the above (co) polymer (A2) is the balance between the physical properties of molding and impact resistance. From the viewpoint, it is preferably 0.1-1. Odl / g, more preferably 0.15-0.7 dlZg.
  • the intrinsic viscosity [7?] Can be controlled by adjusting the production method, similarly to the rubber-reinforced copolymer resin (A1).
  • the intrinsic viscosity [7?] (Measured at 30 ° C.
  • thermoplastic resin in methyl ethyl ketone, the acetone-soluble portion of the above-mentioned rubber-reinforced thermoplastic resin is determined based on the balance between physical properties of molding and impact resistance. Therefore, it is preferably 0.1-0.8 dlZg, more preferably 0.15-0.7 dl / g.
  • thermoplastic resins can be used alone or in combination of two or more.
  • a rubber-reinforced copolymer resin obtained by polymerizing a monomer containing methyl methacrylate in the presence of a rubbery polymer.
  • thermoplastic resin obtained by combining the above (1) with a (co) polymer obtained by polymerizing a monomer containing methyl methacrylate.
  • thermoplastic resin obtained by combining the above (1) with a (co) polymer obtained by polymerizing a monomer containing an aromatic vinyl compound and a vinyl cyanide compound.
  • a rubber-reinforced copolymer resin obtained by polymerizing a monomer containing an aromatic vinyl compound and a cyanide butyl compound without using methyl methacrylate in the presence of a rubbery polymer A rubber-reinforced thermoplastic resin obtained by combining a (co) polymer obtained by polymerizing a monomer containing methyl acrylate.
  • the polymer for laser marking according to the present invention mainly contains the above-mentioned rubber-reinforced thermoplastic resin, a composition that gives a molded article having excellent impact resistance can be obtained.
  • the lower limit of the content of the rubbery polymer (a) in the polymer is preferably 0.5% by mass, It is more preferably 1% by weight, particularly preferably 3% by weight, most preferably 5% by weight.
  • the upper limit is preferably 60% by mass, more preferably 40% by mass, and particularly preferably 35% by mass. It is. If the content of the rubbery polymer (a) is too small, the impact resistance of the molded article tends to be inferior, and if it is too large, the hardness and rigidity tend to be inferior.
  • the rubber-reinforced thermoplastic resin may be used alone as the polymer for laser marking, or may be used in combination with another polymer.
  • Other polymers include thermoplastic resins such as polycarbonate resins, polyester resins, and polyamide resins; acrylic resins (including acrylic polymers having an epoxy group), epoxy resins, and phenolic resins.
  • Thermosetting resins such as cellulose resins, unsaturated polyester resins, alkyd resins, melamine resins, urethane resins, and urea resins. These other polymers can be used alone or in combination of two or more.
  • acrylic resin is a polymer for laser marking according to the present invention.
  • a (co) polymer formed from a monomer containing a (meth) acrylic acid ester includes the (meth) acrylic acid used for forming the rubber-reinforced thermoplastic resin. It is preferable to include an acid ester.
  • the other monomer include an aromatic vinyl compound; a vinyl cyanide compound; a maleimide compound; and a vinyl compound having a functional group such as an epoxy group, a hydroxyl group, a carboxyl group, an amino group, and an oxazoline group. Is received.
  • the acrylic resin a (co) polymer containing 30% by mass or more of a methyl methacrylate monomer unit, which is particularly preferable for a resin obtained using a monomer containing methyl methacrylate, Polymethyl methacrylate (PMMA) is preferred.
  • the weight average molecular weight of the above acrylic resin in terms of polystyrene by gel permeation chromatography is not particularly limited, but is preferably 50,000 to 500,000, more preferably ⁇ . Also, 70,000-400,000, specially preferred ⁇ 80,000-300,000.
  • the polyacetal resin which is preferably used as the polymer for laser marking according to the present invention, is a polymer compound having an oxymethylene group (one CH group) as a main constituent unit.
  • the polyacetal resin can be any of polyoxymethylene homopolymer, copolymer (including block copolymer) and terpolymer containing other structural units in addition to oxymethylene groups. Has a branched or cross-linked structure It may be.
  • the polyacetal resin may have a functional group such as a carboxyl group and a hydroxyl group. Furthermore, this polyacetal resin can be used alone or in combination of two or more.
  • polyamide resin which is preferable as the polymer for laser marking according to the present invention, is a polymer compound having an acid amide bond (one CO-NH-) in the main chain.
  • the polyamide resin is usually produced by polymerization of a ring structure of ratatam or amino acid, or polycondensation of dicarboxylic acid and diamine. Therefore, this polyamide resin can be used as a homopolyamide, a copolyamide and the like.
  • Monomers that can be polymerized singly include ⁇ -proprotamam, aminocaproic acid, enantholactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, and piperidone.
  • dicarboxylic acid for the condensation polymerization of dicarboxylic acid and diamine
  • diamines include tetramethylene diamine, hexamethylene diamine, nonamethylene diamine, decamethylene diamine, pendecamethylene diamine, dodecamethylene diamine, norfenerylene diamine, metaphenylene diamine, and the like. No.
  • polyamides described above are nylon 4, 6, 7, 8, 11, 12, 6.6, 6.9, 6.10, 6.
  • the terminal of the polyamide resin may be sealed with a carboxylic acid, an amine or the like.
  • carboxylic acid include aliphatic monocarboxylic acids such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid.
  • amine include aliphatic primary amines such as hexylamine, octylamine, decylamine, laurylamine, myristylamine, palmitylamine, stearylamine, and behylamine.
  • the above polyamide resins can be used alone or in combination of two or more.
  • polyurethane resin which is preferable as the polymer for laser marking according to the present invention, is a polymer compound having a urethane bond (mono-COO-) in the main chain.
  • This polyurethane resin is usually obtained by reacting a diol and a diisocyanate.
  • the diol include a polyester polyol, a polyether polyol, a polycarbonate polyol, and a polyester polycarbonate polyol. These can be used alone or in combination of two or more.
  • diisocyanate examples include 4,4'-dimethanemethanediisocyanate, tolylene diisocyanate, phenylenediisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3, dichloro-4,4, diphenyl.
  • Aromatic diisocyanates such as dinolemethane diisocyanate and tolylene diisocyanate; hexamethylene diisocyanate, isophorone diisocyanate, 4,4, dicyclohexylmethane diisocyanate, hydrogenated oxy Aliphatic or alicyclic diisocyanates such as lilylene diisocyanate. These can be used alone or in combination of two or more.
  • a chain extender may be used.
  • thermoplastic polymer and a thermosetting polymer can be used in combination.
  • the content of the thermoplastic polymer is 100%.
  • the lower limit of the content of the thermosetting polymer with respect to parts by mass is preferably 0.01 part by mass, more preferably 0.05 part by mass, particularly preferably 0.1 part by mass, and the upper limit is preferably.
  • the amount is preferably 20 parts by mass, more preferably 10 parts by mass, and particularly preferably 5 parts by mass.
  • thermosetting polymer when a thermoplastic polymer and a thermosetting polymer are used in combination, in the composition of the present invention, the thermosetting polymer may be in a connected state or may be in the form of small pieces such as particles. And may be included in a dispersed state. The same applies to molded articles obtained using the composition of the present invention.
  • the composition of the present invention contains a chromatic colorant, a black substance that disappears or discolors itself by receiving laser light, and a polymer, and the content of the chromatic colorant is as described above.
  • the amount is 0.001 to 3 parts by mass when the polymer is 100 parts by mass, and the content of the black substance is 0.01 to 2 parts by mass when the polymer is 100 parts by mass.
  • a molded article of the present invention is characterized by containing the above-mentioned composition of the present invention.
  • composition of the present invention contains the above-mentioned chromatic colorant, black substance, and polymer in a predetermined amount, respectively, and applies two or more laser beams having different energies to a molded article containing the yarn. Irradiation causes marking in two or more different colors.
  • the composition of the present invention has the following composition of each component. That is, when the polymer for laser marking is 100 parts by mass, the content of the chromatic coloring agent is 0.001 to 3 parts by mass, and the content of the black substance is 0.01 to 2 parts by mass. is there.
  • the lower limit of the content of the chromatic colorant is preferably 0.002 parts by mass, particularly preferably 0.005 parts by mass, and the upper limit is preferably 1 part by mass, particularly preferably 0.8 parts by mass. is there.
  • the content of the chromatic colorant is too large, it becomes difficult to obtain white marking, and it is difficult to distinguish high-energy laser light-irradiated parts from low-energy laser light-irradiated parts by high-energy laser light irradiation. Easy to be.
  • the amount is too small, it becomes difficult to obtain a marking of a color derived from a chromatic colorant, and it becomes difficult to distinguish between low-energy laser single-light irradiation and unirradiated portions.
  • the lower limit of the content of the black substance is preferably 0.03 parts by mass, particularly preferably 0.05 parts by mass, and the upper limit is preferably 1 part by mass, particularly preferably 0.8 parts by mass. is there . If the content of the black substance is too large, the laser light irradiated part is too black, and it becomes easy to identify the marking by laser light irradiation.
  • the ground color of the composition of the present invention and the molded article obtained by using the same are black or dark because the chromatic colorant, black substance, and the like are dispersed in the polymer for laser marking. It takes on a color.
  • a white substance such as a white substance
  • the brightness of the ground color can be adjusted, and the whiteness of the color developed at the time of laser marking can be improved.
  • identification of the multicolor laser marking according to the present invention is not required. It is not particularly limited as long as it does not significantly impair the excellent performance of the present invention, such as making it always difficult, and examples thereof include titanium dioxide, zinc oxide, zinc sulfide, and barium sulfate. These can be used alone or in combination of two or more.
  • the average particle size of the white substance is not particularly limited, but is usually 0.1 to 0.3 O / zm, preferably 0.1 to 0.2 O / zm, and more preferably 0.1 to 0.1 O / zm. O / zm.
  • the content is preferably 0.001 to 1 part by mass, more preferably 0.001 to 0.1 part by mass, when the polymer for laser marking is 100 parts by mass. It is 5 parts by mass, more preferably 0.001 to 0.1 part by mass. If the content is too large, good marking of the contrast may not be obtained, while if too small, the degree of freedom of the ground color after molding may be limited.
  • the composition of the present invention may further comprise a flame retardant, an antistatic agent, an antibacterial agent, a filler, a decorating agent, an ultraviolet absorber, an antioxidant, an antioxidant, a weathering agent, depending on the purpose and application.
  • a lubricant, a plasticizer, a hydrophilicity-imparting agent, and a light-colored colorant are each contained in a predetermined amount, vivid color was formed.
  • an organic flame retardant an inorganic flame retardant, a reactive flame retardant, or the like can be used.
  • Organic flame retardants include brominated bisphenol-based epoxy resins, brominated bisphenol-based phenolic resins, brominated bisphenol-based polycarbonate resins, brominated polystyrene resins, brominated cross-linked polystyrene resins, and brominated bisphenols.
  • Halogenic flame retardants such as phenol cyanurate resin, brominated polyphenylene ether, decab-modified dimethyl oxide, tetrabromobisphenol A and its oligomers, and brominated alkyltriazine compounds; trimethyl phosphate, triethyl Phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, toxic hexinole phosphate, tricyclohexinole phosphate, trifluoro-nore phosphate, tricresinole phosphate, trixylene phenol Sufeto, Kurejinorejifue - Norehosufeto, Jikurejinorefue - Norehosufue over door, dimethicone Norre ethyl Norre phosphate, methylate Norre Djibouti Norre phosphate, E Chino register professional Pinot Reho Phosphat
  • inorganic flame retardants include aluminum hydroxide, antimony oxide, magnesium hydroxide, zinc borate, zinc stannate, guanidine salts, zirconium compounds, molybdenum compounds, and silicone compounds. And phosphazene compounds. These can be used alone or in combination of two or more.
  • the reactive flame retardants include tetrabromobisphenol A, dibromophenol glycidyl ether, brominated aromatic triazine, tribromophenol, tetrabromophthalate, tetrachlorophthalic anhydride, dibromoneopentyl glycol, poly (pentabromobenzyl) Polyaltalate), chlorendic acid (hetic acid), chlorendic acid anhydride (hetic acid anhydride), brominated phenol glycidyl ether, dibu-mouthed mocresyl glycidyl ether, and the like. These can be used alone or in combination of two or more.
  • the content of the flame retardant is preferably 110 to 30 parts by mass, more preferably 3 to 20 parts by mass, when the polymer for laser marking is 100 parts by mass.
  • a flame retardant auxiliary in combination.
  • the flame retardant include antimony trioxide, diantimony tetroxide, diantimony pentoxide, sodium antimonate, antimony tartrate and the like, zinc borate, barium metaborate, and hydrated alumina. , Zirconium oxide, ammonium polyphosphate, tin oxide and the like. These can be used alone or in combination of two or more.
  • antistatic agent examples include a low molecular type antistatic agent and a high molecular type antistatic agent, and these can be used alone or in combination of two or more. Further, these may be of an ion conduction type or an electron conduction type.
  • low molecular weight antistatic agent examples include anionic antistatic agents; cationic antistatic agents; nonionic antistatic agents; amphoteric antistatic agents; complex conjugates; and alkoxysilanes, alkoxy titanium, alkoxy zirconium and the like.
  • polymer type antistatic agent examples include a vinyl copolymer having a metal sulfonic acid salt in the molecule, a metal alkyl sulfonic acid salt, a metal alkyl benzene sulfonic acid salt, and betaine. Further, polyamide elastomer, polyester elastomer, and the like can be used. These can be used alone or in combination of two or more.
  • the content of the antistatic agent is preferably 0.5 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, when the polymer for laser marking is 100 parts by mass.
  • antibacterial agents include inorganic antibacterial agents, organic antibacterial agents, inorganic / organic hybrid antibacterial agents, natural antibacterial agents and the like. These can be used alone or in combination of two or more.
  • inorganic antibacterial agents examples include zeolite antibacterial agents such as silver zeolite and silver-zinc zeolite; silica gel antibacterial agents such as Complexi Dangin 'silica gel; glass antibacterial agents; calcium phosphate antibacterial agents; Antibacterial agents; silicate antibacterial agents such as silver / magnesium aluminate; titanium-containing antibacterial agents; ceramic antibacterial agents; and whisker-based antibacterial agents.
  • organic antibacterial agents examples include formaldehyde releasing agents, halogenated aromatic compounds, rhodopronorgyl derivatives, thiocyanato compounds, isothiazolinone derivatives, trihalomethylthio compounds, quaternary ammonium salts, biguanide compounds, aldehydes, phenols. , Benzimidazole derivatives, pyridine oxides, fulvalides, diphenyl ethers, carboxylic acids, organometallic compounds and the like.
  • the content of the antibacterial agent is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, when the polymer for laser marking is 100 parts by mass.
  • Examples of the filler include fibers such as glass fiber, carbon fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, and potassium titanate whisker; Organic fibrous fillers of metals such as stainless steel, aluminum, titanium, copper, and brass; organic fibrous fillers; silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, Clays, silicates such as diatomaceous earth, metal oxides such as alumina, carbonates such as calcium carbonate and magnesium carbonate, calcium sulfate , Such as sulfate, silicon carbide, silicon nitride, and boron nitride; and plate-like fillers such as talc, mica, glass flake, and metal foil. These can be used alone or in combination of two or more. Note that these fillers are better used as reinforcing materials.
  • the content of the filler is 100 parts by mass of the polymer for laser marking, preferably 110 to 30 parts by mass, more preferably 121 to 25 parts by mass, and still more preferably 112 to 20 parts by mass. is there.
  • decorating agent those which can form a metallic pattern such as a metallic tone and a metallic luster on the surface of a molded product can be used.
  • a metallic pigment or the like can be used.
  • the metallic pigment it is preferable to use particles having an average particle diameter within a predetermined range and having a metallic luster.
  • the shape of the particles is not particularly limited, and may be spherical, substantially spherical, square (cube, rectangular parallelepiped, polyhedron, etc.), scale, star, rod, and the like. Of these, polyhedron is excellent because of its excellent metallic luster. Is preferred,.
  • the above-mentioned metallic pigment has an average particle size of 1 to 500 ⁇ m, more preferably 2 to 300 ⁇ m. By setting the content in this range, the pattern on the surface of the molded product is likely to be clear.
  • the “average particle size” means the maximum length.
  • Particles having metallic luster include nickel, aluminum, silver, copper, tin, chromium, zinc, conoret, iron, molybdenum, manganese, tungsten, gold, titanium, antimony, silicon, platinum, magnesium.
  • metals such as the above, including alloys of the above metals, further including metal compounds having a metallic-like luster (oxides, nitrides, sulfides, etc.), including calcium carbonate glass, and minerals such as mica And the like.
  • a film containing the above-mentioned metal, alloy, metal compound or the like, or a film of glass or the like may be formed on the surface of a particulate material having no metallic luster by plating, vapor deposition, or the like, and used as a metallic pigment.
  • a particulate material having no metallic luster by plating, vapor deposition, or the like, and used as a metallic pigment.
  • Each of these particles can be used alone or in combination of two or more.
  • the content of the above-mentioned decorating agent is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, when the polymer for laser marking is 100 parts by mass, depending on the purpose and application. And more preferably 0.5-5 parts by mass.
  • the ultraviolet absorber include benzophenones, benzotriazoles, salicylate esters, metal complex salts and the like. These can be used alone or in combination of two or more.
  • the content of the ultraviolet absorber is preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the polymer for laser marking.
  • antioxidants examples include hindered amines, hydroquinones, hindered phenols, and sulfur-containing compounds. These can be used alone or in combination of two or more.
  • the content of the antioxidant is preferably 0.1 to 5 parts by mass, when the polymer for laser marking is 100 parts by mass.
  • antiaging agents examples include naphthylamine compounds, diphenylamine compounds, p-phenylenediamine compounds, quinoline compounds, hydroquinone derivatives, monophenol compounds, bisphenol compounds, and trisphenol compounds. And phenol-based compounds, thiobisphenol-based compounds, hindered phenol-based compounds, and phosphite-based compounds. These can be used alone or in combination of two or more.
  • the content of the antioxidant is preferably 0.1 to 5 parts by mass, when the polymer for laser marking is 100 parts by mass.
  • Examples of the weathering agent include organic phosphorus compounds, organic sulfur compounds, and organic compounds having a hydroxyl group. These can be used alone or in combination of two or more.
  • the content of the weathering agent is preferably 0.1 to 5 parts by mass when the polymer for laser marking is 100 parts by mass.
  • Examples of the lubricant include fatty acid esters, hydrocarbon resins, paraffins, higher fatty acids, oxyfatty acids, fatty acid amides, alkylenebisfatty acid amides, aliphatic ketones, fatty acid lower alcohol esters, fatty acid polyhydric alcohol esters, and fatty acid polyhydric esters.
  • the content of the lubricant is preferably 0.1 to 5 parts by mass, when the polymer for laser marking is 100 parts by mass.
  • the light colorant a colorant having a color such as light red, light yellow, light blue, or light green can be used. Further, a fluorescent whitening agent or the like can be used.
  • a light-colored colorant having a color similar to the color derived from the chromatic colorant of the present invention is used, for example, when a low-energy laser beam is irradiated, the irradiated part of the chromatic colorant of the present invention The marking of the color derived from the colorant becomes clearer.
  • the composition of the present invention mainly uses a thermoplastic polymer as the polymer for laser marking
  • the above-mentioned raw material components may be mixed with various extruders, Banbury mixers, kneaders, and rolls. And kneading the mixture.
  • each component may be added at once, or may be kneaded by a multi-stage addition method.
  • the composition obtained in this way, or after further mixing with another polymer is subjected to injection molding, extrusion molding, hollow molding, compression molding, sheet extrusion, vacuum molding, foam molding, blow molding.
  • a molded article having a predetermined shape (a molded article of the present invention) can be obtained by a molding method such as molding.
  • the composition (molded article) of the present invention is obtained by combining the above-mentioned raw material components with a curing agent and the like, if necessary, into a predetermined shape. It can be obtained by injecting it into a mold and subjecting it to a known method, for example, heat treatment or light irradiation.
  • the molded article of the present invention contains at least a polymer, a chromatic colorant and a black substance, and its base color is usually a black or dark color.
  • the composition of the polymer include (1) when it contains only a thermoplastic polymer, (2) when it contains both a thermoplastic polymer and a (thermo) curable polymer, and (3) when it contains a thermoplastic polymer and The case where both of the polymers are included, (4) the case where only the cured polymer is included, and the like are included. In any of the above cases, it can be formed by the "polymer for laser marking" contained in the composition of the present invention.
  • the shape of the molded article of the present invention can be selected from various shapes depending on the purpose, application, and the like. If laser light can be irradiated, the marked portion has a flat surface, a curved surface, and a corner portion. The surface may have an uneven surface.
  • the laser marking method of the present invention forms a marking of two or more different colors by irradiating a molded article containing the composition of the present invention with two or more laser lights having different energies. is there.
  • the “energy” of laser light depends on the irradiation conditions of the laser light. Therefore, by changing the type, wavelength, pulse width, frequency, and output of the laser beam to be irradiated, irradiation time, irradiation area, distance and angle from the light source to the molded product, irradiation method, etc., two or more laser beams can be used. Laser light having “different energies” at the time of irradiation. Specifically, different energies can be obtained not only when using laser beams having different wavelengths but also when using laser beams having the same wavelength and other irradiation conditions such as irradiation time are different.
  • the energy applied to the object to be irradiated is different in the case of one irradiation and in the case of two or more irradiations.
  • the irradiation time is longer, and the latter is “higher, energy”. It becomes.
  • the "two or more laser beams having different energies" refer to two or more laser beams having different degrees of damage to an irradiation target.
  • a force that causes damage to an object to be irradiated is different between a case where the irradiation is performed once and a case where the irradiation is performed in a plurality of times.
  • the conditions for irradiating the yarn and the molded article with laser light are not particularly limited as long as the excellent performance of the multicolor coloring laser marking of the present invention is not impaired.
  • the irradiation method may be a scan method, a mask method, or the like, and two or more laser beams having different energies may be irradiated simultaneously or one by one.
  • a laser beam irradiation device a general laser masking device or the like can be used as a laser beam irradiation device. This device usually includes a laser oscillator, a laser modulator, a handling unit, a controller, etc.
  • the laser light oscillated from the laser is pulse-modulated by a laser modulator and illuminated on the surface of the molded product to form a marking.
  • a laser modulator At the time of laser marking, one device may irradiate two or more laser beams having different energies, or a plurality of devices may be used.
  • a laser marking system “RSM50D”, “RSM30D” manufactured by Roffin Basel or the like can be used as an apparatus capable of performing two-wavelength laser marking.
  • the laser beam used in the multicolor laser marking according to the present invention may be a deviation of a gas laser, a solid laser, a semiconductor laser, a dye laser, an excimer laser, or a free electron laser.
  • Examples of the gas laser include a helium-neon laser, a rare gas ion laser, a helium-cadmium laser, a metal vapor laser, and a carbon dioxide laser.
  • Examples of the solid-state laser include a ruby laser, a neodymium laser, a tunable solid-state laser, and the like.
  • the semiconductor laser may be an inorganic or organic semiconductor laser, and examples thereof include a GaAsZGaAlAs laser, an InGaAs laser, and an InP laser.
  • Nd YAG
  • Nd YVO
  • a solid-state laser pumped by a semiconductor laser such as Nd: YLF can also be used.
  • the laser light exemplified above can be used alone or in combination of two or more.
  • laser light having a wavelength in the range of 100-2, OOOnm.
  • numbers indicating the “wavelength” of the laser beam such as 1, 064 nm and 532 nm, mean the center wavelength, and usually include an error of ⁇ 3%.
  • the laser marking method of the present invention when the molded article of the present invention is irradiated with a laser beam, the color of a substance other than the black substance appears strongly in a portion where a change (extinction, discoloration, etc.) of the black substance has occurred.
  • the portion where the change of the chromatic colorant (decomposition, scattering, etc.) occurs becomes a color in which the density of the color derived from the chromatic colorant is reduced or white.
  • the black substance When the energy of the laser beam is low, the black substance is vaporized, volatilized, disappears due to complete decomposition, etc., or at least a part or all of the black substance remains there, and the color changes to a color different from the original black due to decomposition, etc. Occurs, and the laser light irradiation part develops a color derived from the chromatic colorant. Les If the energy of the light increases further, the chromatic colorant contained in the molded article of the present invention changes usually at an energy higher than the energy at which the black substance changes as described above. The light-irradiated portion develops a white color or a color having a reduced density of a color derived from the chromatic colorant.
  • the molded article 1 of the present invention is irradiated with laser light having two different energies at different positions ([1] in FIG. 1). At this time, the irradiation with the laser beam may be performed simultaneously or separately.
  • the low-energy laser light illuminated area is marked with a color derived from the chromatic colorant (3a in Fig. 1), while the high-energy laser light illuminated area is colored with white or chromatic colorant. It is marked (3b in Fig. 1) on the color of which the density of the derived color has decreased ([II] in Fig. 1). In the above manner, it is possible to obtain a molded article 2 (a molded article with multicolor markings) marked with two different colors.
  • a marking area of a large area and a color derived from a chromatic colorant is formed, and then the marking area is formed.
  • the irradiated part can be marked with a white color or a color with a reduced density of the color derived from the chromatic colorant (see Fig. 2). That is, FIG.
  • the marking portion 3a of the color derived from the chromatic colorant formed by the irradiation of the low-energy laser light is further irradiated with the laser light to form white or 2A shows a molded article (molded article with multicolor marking) 2a having a marking portion 3b of a color having a reduced density of a color derived from a chromatic colorant and having two different colors.
  • the marking portion 3a of the color derived from the chromatic colorant and the marking portion 3b of the color having a reduced density of the white color or the color derived from the chromatic colorant are adjacent to each other.
  • Laser marking can be realized.
  • the energy of the laser light to be irradiated the second time may be the same as that of the first time or may be different, and is not particularly limited.
  • clear marking of three or more colors is obtained by the laser marking method of the present invention, it may be performed on a molded article containing only one chromatic colorant, or two types of chromatic colorants may be used. Although it may be performed on a molded article including the above, the latter is preferable because clearer marking is easily formed.
  • a method of irradiating a total of three types of laser light two types of energy having different degrees of change in the black substance and one type of energy reducing the density of the color derived from the chromatic colorant;
  • a method of irradiating a total of three types of laser light such as changing energy and two types of energy having different degrees of change of the chromatic colorant, may be used.
  • An example of using a red colorant is as follows. By irradiating a low-energy laser beam, a part of the black substance is extinguished or discolored, and the color derived from the black substance becomes lighter. It is possible to change the color to “red” by light irradiation, and to “white” or “light red” by irradiating laser light with high energy. That is, shading can be formed for red.
  • a simple method for obtaining laser beams having different energies is to use one laser beam having different wavelengths.
  • laser irradiation that differs only in wavelength
  • the difference between the wavelengths of the laser beams is preferably 100 nm or more, more preferably 200 nm or more, and particularly preferably 500 nm or more.
  • the upper limit is usually 1,500 nm.
  • two laser beams having different wavelengths are used.
  • the "color derived from the chromatic colorant” obtained by the laser marking method of the present invention mainly refers to a color obtained as a result of extinguishing or discoloring a black substance by laser light irradiation. Specifically, the effect of the color of the black substance is reduced due to the disappearance or discoloration of the black substance, which indicates that (a) the color of the chromatic colorant itself of the present invention (hereinafter simply referred to as “colored coloring”).
  • the color of the chromatic colorant is blackish (the color of the chromatic colorant + the color of the black substance, or the color of the chromatic colorant + the color of the black substance has changed) Color), (c) chromatic color, a color in which the colorant has changed color to change the color tone, (d) the above-mentioned color (c), a blackish color, and the like.
  • the “color having a reduced color density derived from the chromatic colorant” obtained by the laser marking method of the present invention is a color having a reduced density of the aforementioned “color derived from the chromatic colorant”.
  • This color is a color obtained mainly as a result of a change in the chromatic colorant caused by laser light irradiation.
  • the effect of the color of the chromatic colorant due to decomposition and scattering of the chromatic colorant is considered.
  • the color of the chromatic colorant of the present invention is discolored to change the color tone.
  • “a color having a reduced concentration of a color derived from a chromatic colorant” is preferably a color closer to white, because it is easier to distinguish it from the “color derived from a chromatic colorant”. ,.
  • the "white” obtained by the laser marking method of the present invention is generally the same as that of the present invention.
  • the color of the polymer itself contained in the molded article is not limited to pure white, but also includes white color mixed with other colors.
  • the color of the polymer In the case where the molded article of the present invention contains a polymer which is easily foamed by receiving laser light, the color developed in the high-energy laser-irradiated portion has a higher whiteness.
  • the whiteness of the above “white” can be evaluated by JIS K7105 or the like.
  • the degree of whiteness means the degree of whiteness of a color, and is evaluated by the reflectance when a certain amount of light is applied to an object. This reflectance can be measured by a Hunter whiteness meter or the like. Here, the reflectivity differs depending on the type of light (wavelength, etc.) to be irradiated. In the case of a hunter whiteness meter, measurement is performed using blue light, which is the three primary colors of light.
  • the whiteness (%) of the white markings obtained in the composition of the present invention and the molded article containing the composition can be represented by the ratio of the intensity of the magnesium oxide to the reflected light.
  • the whiteness of human vision and the whiteness of a whiteness meter may not always coincide with each other, the white markings obtained on the composition of the present invention and on molded articles containing the same have low civilization even if the whiteness is low. It just needs to look white in your eyes.
  • the measure of whiteness preferably 55- 100%, more preferably from 6 0-100%, further [this preferred ⁇ I or 70 one 100 0/0, JP [this preferred ⁇ I or 80 one 100 0/0.
  • La b value (L; lightness, a; Red value, b: yellow value) and Lab value (L: lightness, a: red) of the same molded article irradiated with low-energy laser light for example, a laser light having a wavelength of 1,064 nm
  • the lower limit is preferably 3, more preferably 3.5, particularly preferably 4, and the upper limit is usually 50, since a multicolor marking with a clear difference can be obtained.
  • ⁇ 2 can be obtained by the method described in Examples. Note that ⁇ 2 indicates that the larger the value, the clearer the color tone difference.
  • ⁇ ⁇ 2 ⁇ (L-L) 2 + (a— a) 2 + (bb) 2 ⁇
  • the Lab value is a value of a color system called "L. a. B Richard” by Richard S. Hunter, which is known as a numerical expression of color.
  • a target color tone is measured by a color difference meter.
  • the color of the laser-irradiated part is quantified as lightness (L) and hue (a, b) and plotted on a graph as shown in Fig. 4 to eliminate differences due to visual perception.
  • the color difference meter is an instrument that measures various quantities that indicate color, and measures the spectral distribution of light or the spectral reflectance (transmittance) of an object.
  • the lightness (L) is defined by a numerical value in the range of 0 to 100 on the vertical axis shown on the left, and the larger the value of L, the brighter.
  • the degree of red is strong
  • the degree of green is strong.
  • the lower scale shows that the degree of yellow is strong on the (+) side and the degree of blue is strong on the (1) side.
  • L value measured when each molded article is irradiated with laser light of each wavelength A value and b value are plotted in Fig. 4 and further quantified as Lab values. To set.
  • the molded article with the multicolor marking of the present invention is a molded article marked with two or more different colors, and irradiates the molded article containing the yarn and the composite of the present invention with two or more laser beams having different energies. It was obtained by the above.
  • the unmarked portion (laser single light non-light receiving portion) is composed of a polymer, a chromatic colorant, a black substance and the like.
  • the black substance has disappeared or changed color (whitened, etc.), and the chromatic colorant has been left as it is.
  • the light receiving portion of a higher energy laser beam (for example, a laser beam having a wavelength of 532 nm) exhibits white or a color in which the density of the color derived from the chromatic colorant has decreased, and in this portion,
  • the black substance is vaporized or whitened, and the chromatic colorant partially remains or may have little power. This is because the chromatic colorant was decomposed or scattered by the laser beam.
  • the molded article with multicolor markings of the present invention is preferably laser-marked in multiple colors including white and chromatic colors.
  • the multicolored markings are, as described above, formed by irradiating laser light to different positions on the molded article surface (see [II] in FIG. 1). Mode), and the part where the color derived from the chromatic colorant and the color whose density of white or the color derived from the chromatic colorant has decreased side by side are formed (as shown in Fig. 2). May have
  • the marking part by laser light may have a foamed marking part depending on the type of polymer.
  • the marking part by laser light may have a foamed marking part depending on the type of polymer.
  • polyacetal resin e.g., polyacetal resin, styrene resin using methyl methacrylate as a monomer component, rubber-reinforced thermoplastic resin using methyl methacrylate as a monomer component, etc.
  • the refractive index difference between the foamed marking portion (laser light receiving portion) and the surrounding non-light receiving portion increases, and the marking becomes clearer, and at least one portion of the marking portion is formed. Is preferably foamed.
  • the marking part (laser-light receiving part) by laser light may be deformed depending on the type of the polymer, the type of the black substance, and the like. . That is, foaming, swelling, etc. occur in the light-receiving part due to irradiation of the laser beam In some cases, a convex portion may be formed, or a concave portion may be formed due to shrinkage or the like. If the molded article before laser light irradiation contains a polymer that easily foams by receiving laser light, the light-receiving part tends to become a convex part due to foaming.
  • the marking part may be used. It may be convex.
  • the height is usually 1 to 200 m, preferably 1 to 100 ⁇ m, and more preferably 1 to 80 ⁇ m.
  • the depth is usually 1 to 200 m, preferably 1 to 100 m. If the height of the projections is too high, the visibility of the markings will be improved. On the other hand, in applications where the markings are in contact (keyboard, Braille, etc.), if the contact pressure is high or the contact pressure is low, the contact Is repeated, character collapse is likely to occur. In addition, the degree of these irregularities can be adjusted by the laser light irradiation conditions and the like.
  • thermosetting polymer when the molded article before laser light irradiation contains a thermoplastic polymer and a (thermosetting) thermosetting polymer, the thermosetting polymer is instantaneously cured by laser light irradiation. Therefore, regardless of whether the marking portion is deformed or not, the strength of the marking portion is improved by the thermosetting polymer (thermosetting polymer). In particular, when the marking portion is a convex portion, high visibility of the marking, which is less likely to be deformed or worn, can be maintained for a long time. That is, the durability of the marking is improved.
  • thermosetting polymer existing on the wall, etc. acts as a reinforcing material, and the marking area as a whole maintains sufficient strength (impact resistance) and durability. Further, depending on the type, content ratio, and the like of the thermosetting polymer, the thermosetting polymer may be present in voids formed by foaming.
  • the molded article with the multicolor marking of the present invention can be obtained as follows. It has vivid coloration, strength and durability. These effects are particularly remarkable when the voids are filled with the thermosetting polymer. In addition, it shows such an effect As described above, the thermosetting polymer may be in a connected state in the marking portion, may be in the form of particles, or may be present in other shapes.
  • the molded product with multicolor marking of the present invention may be provided with a protective layer on the surface having the marking portion.
  • the material forming the protective layer is not particularly limited as long as it is selected according to the purpose and application, but it should be transparent to protect the marking portion and maintain the visibility of the marking. Is preferred.
  • the above-mentioned protective layer may be provided on at least the entire surface of the molded article, which is preferably provided on the entire surface of the marking portion.
  • the above-mentioned protective layer it is also possible to improve the smoothness of the surface of the molded product that only protects the marking portion.
  • the method for forming the above-mentioned protective layer is not particularly limited.
  • FIG. 3 is a schematic cross-sectional view of a molded product 2b with a multicolor marking provided with a protective layer 4 on the surface having the multicolor marking portions 3a and 3b.
  • the exothermic peak temperatures of the coloring agents shown below were measured by differential thermal analysis.
  • the measuring device is “TG-DTA320 (horizontal furnace)” manufactured by Seiko Denshi.
  • a 3 mg sample was uniformly and densely packed in an aluminum dish 5 mm in diameter x 2.5 mm in height, and measured in air at a flow rate of 200 mlZ with a heating rate of 10 ° CZ.
  • the calibration of the temperature in the measuring device was performed using indium and tin.
  • the calibration of the weight was performed at room temperature using a weight, and further using calcium oxalate.
  • the exothermic peak temperature was determined by the peak top in the heating curve.
  • Figures 5 to 16 show the temperature rise curves for each colorant.
  • Table 1 shows the results of the exothermic peak temperatures.
  • Copper phthalocyanine pigment A ⁇ -type copper phthalocyanine pigment (the following formula ( ⁇ )) having an average secondary particle diameter of 7.1 ⁇ m measured by a laser scattering particle size distribution analyzer was used.
  • Laser marking is performed using the mouth fins, Basel's mouth fin power line “E / SHG type” and the company's laser marker “RSM30D”, and the laser beam wavelength is 532 nm and 1,064 nm, respectively.
  • the wavelength of the laser beam is 532 nm
  • the output is 23 A
  • the frequency is 8 kHz
  • the scanning speed is 400 mmZ second
  • the beam diameter is 30 m.
  • the laser beam wavelength is 1,064 nm
  • the output is 34 A
  • the frequency is 3 kHz
  • the scanning speed is Is 400mmZ seconds
  • a ⁇ is 2. Omm.
  • a separable flask equipped with a reflux condenser, a thermometer and a stirrer was charged with 100 parts of ion-exchanged water, 1.5 parts of sodium dodecylbenzenesulfonate, 0.1 part of tert-dodecylmercaptan, and a weight average particle size of 2,400 A. 15 parts of polybutadiene particles (in terms of solid content), 4 parts of styrene, 2 parts of acrylonitrile and 12 parts of methyl methacrylate were added, and the temperature was raised with stirring.
  • the polymer component was coagulated by charging 2 parts of the mixture, and the coagulated product was sufficiently washed with water. Then, it was dried at 75 ° C. for 24 hours to obtain a rubber-reinforced copolymer resin as a white powder.
  • the polymerization conversion was 98.5%
  • the grafting ratio was 60%
  • the intrinsic viscosity was 0.3 dlZg.
  • a test piece was prepared and evaluated in the same manner as in Example A-1, except that the chromatic colorant (2) was used in place of the chromatic colorant (1) and the amount was 0.1 part. did. The results are shown in Table 2.
  • Test pieces were prepared and evaluated in the same manner as in Example A-1, except that the chromatic colorant (3) was used instead of the chromatic colorant (1). The results are shown in Table 2.
  • test piece was prepared and evaluated in the same manner as in Example A-1 except that the chromatic colorant (4) was used instead of the chromatic colorant (1).
  • the results are shown in Table 2.
  • Test pieces were prepared and evaluated in the same manner as in Example A-1 except that the chromatic colorant (5) was used instead of the chromatic colorant (1). The results are shown in Table 2.
  • Example A-5 Specimens were prepared and evaluated in the same manner as in Example A-5 except that polyacetal resin (trade name “Upital F20-03N”, manufactured by Mitsubishi Engineering-Plastics Corporation) was used as the molding polymer. did. The results are shown in Table 2.
  • polyacetal resin trade name “Upital F20-03N”, manufactured by Mitsubishi Engineering-Plastics Corporation
  • Test pieces were prepared and evaluated in the same manner as in Example A-5 except that polymethyl methacrylate resin (trade name “VH001”, manufactured by Mitsubishi Rayon Co., Ltd.) was used as the molding polymer. Table 2 shows the results.
  • Example A—9 Specimens were prepared and evaluated in the same manner as in Example A-5 except that polyamide resin (trade name “NOVAMID1010”, manufactured by Mitsubishi Engineering-Plastics Corporation) was used as the molding polymer. The results are shown in Table 2.
  • polyamide resin trade name “NOVAMID1010”, manufactured by Mitsubishi Engineering-Plastics Corporation
  • test piece was prepared and evaluated in the same manner as in Example A-1 except that the chromatic colorant (6) was used instead of the chromatic colorant (1).
  • the results are shown in Table 2.
  • Example A-1 A test piece was prepared and evaluated in the same manner as in Example A-1 except that the chromatic colorant (7) was used instead of the chromatic colorant (1). The results are shown in Table 2.
  • Example A-1 A test piece was prepared and evaluated in the same manner as in Example A-1 except that the chromatic colorant (8) was used instead of the chromatic colorant (1). The results are shown in Table 2.
  • a test piece was prepared and evaluated in the same manner as in Example A-1 except that the chromatic colorant (9) was used instead of the chromatic colorant (1). The results are shown in Table 2.
  • test piece was prepared and evaluated in the same manner as in Example A-1 except that the chromatic colorant (10) was used instead of the chromatic colorant (1).
  • the results are shown in Table 2.
  • Example A-1 A test piece was prepared and evaluated in the same manner as in Example A-1 except that the chromatic colorant (11) was used instead of the chromatic colorant (1). The results are shown in Table 2.
  • test piece was prepared and evaluated in the same manner as in Example A-1 except that the chromatic colorant (12) was used instead of the chromatic colorant (1).
  • the results are shown in Table 2.
  • Example A-1 A test piece was prepared and evaluated in the same manner as in Example A-1 except that the chromatic colorant (13) was used instead of the chromatic colorant (1). The results are shown in Table 2.
  • Rubber reinforced thermoplastic resin (rubber reinforced resin)
  • a separable flask equipped with a reflux condenser, thermometer and stirrer 40 parts of polybutadiene rubber latex as an initial polymerization component in terms of solids, 65 parts of ion-exchanged water, 0.35 parts of rosin acid stone, and 15 parts of styrene And 5 parts of acrylonitrile, and then add a solution of 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate and 0.4 parts of glucose dissolved in 20 parts of ion-exchanged water.
  • a mixture of 40% of the above rubber-reinforced copolymer resin (P1) and 60% of the above copolymer (P2) is melt-kneaded and extruded at a cylinder setting temperature of 180 to 220 ° C using a 50 mm ⁇ extruder to obtain a rubber.
  • a reinforced thermoplastic resin (rubber reinforced resin) was obtained as pellets.
  • the dioxazine pigment (purple) (5) in the above [I1] was used.
  • the exothermic peak temperature is 402 ° C.
  • the (4) diketopyrrolopyrrole pigment (red) in the above [I1] was used.
  • the exothermic peak temperature is 550 ° C.
  • the (2) aluminum phthalocyanine pigment (green) in the above [I 1] was used.
  • the exothermic peak temperature is 581 ° C.
  • Carbon black "Mitsubishi Carbon # 45" (trade name) manufactured by Mitsubishi Idakugakusha was used.
  • FP500 (trade name) manufactured by Asahi Den-Daisha was used.
  • Metal pigment (trade name) manufactured by Nippon Sheet Glass Co., Ltd. was used as the metallic pigment.
  • This metallic pigment is obtained by forming an electroless silver plating film having a thickness of about 100 nm on the surface of glass particles having an average particle size of 80 / ⁇ and an average aspect ratio of 1.3.
  • thermoplastic polymer compositions were prepared using the above-mentioned raw material components and according to the blending recipes shown in Tables 3 to 9. That is, each raw material component was mixed by a mixer for 5 minutes, and then melt-kneaded and extruded with a 50 mm extruder at a cylinder set temperature of 180 to 220 ° C to obtain pellets. The obtained pellets were sufficiently dried, and test pieces (80 mm long, 55 mm wide, 2.5 mm thick) for evaluation were obtained with an injection molding machine (model name “EC-60”, manufactured by Toshiba Machine Co., Ltd.). Was.
  • the laser marking was performed using the mouth fins, Basel's mouth fin power line “E / SHG type” and the company's laser marker “RSM30D”, and the laser light wavelengths were 532 nm and 1,064 nm, respectively. According to each irradiation condition shown in Table 9, each laser beam was applied to different positions on the surface of the test piece.
  • each La b value (L; lightness, a; redness, b; yellowness) was measured between the white marking portion formed when the laser light was irradiated, and ⁇ ⁇ 1 Was calculated.
  • “Color-Eye 7000A” manufactured by Gretag Macbeth was used as a measuring device for Lab.
  • ⁇ ⁇ 1 ⁇ (L-L) 2 + (a— a) 2 + (bb) 2 ⁇
  • L, a and b are values of a white marking portion formed when a laser beam having a wavelength of 532 nm is irradiated, and L, a and b are a formula not containing the coloring agent.
  • a laser beam having a wavelength of 532 nm and a laser beam having a wavelength of 1,064 nm for different positions of the same test piece.
  • Each Lab value of the chromatic marking portion formed when the one light was irradiated was measured (the latter is referred to as La and b), and ⁇ 2 was calculated according to the following equation. The larger this ⁇ 2 is,
  • the color difference is clear.
  • ⁇ 2 ⁇ (L -L) 2 + (a— a) 2 + (bb) 2 ⁇
  • Example B-1 Further, the cross sections of the chromatic and white markings obtained in Example B-1 were photographed with a transmission electron microscope, and are shown in FIGS. 17 and 18, respectively.
  • Composition 5 Colorant (e) 0.2 min _ Black substance Carbon black 0.1 0.1 0.1 Color of test piece before laser irradiation Black Black Black Rating Laser marking part 532nm White Red Blue color 1064nm White Red Blue value ⁇ ⁇ 1 1.0 10.0 15.0
  • Comparative Example B-1 and Comparative Example B-4 do not contain a chromatic colorant and are examples using the composition. Only white marking was obtained and no power was obtained. .
  • Comparative Examples B-2, B3, B-5, and B-6 are examples using colorants that do not have an exothermic peak by differential thermal analysis, and are derived from each colorant even when irradiated with laser light. Color was obtained, and ⁇ ⁇ 1 force was larger than S 3, and ⁇ 2 was less than 3.
  • Example B-112 ⁇ ⁇ 1 was 3 or less and ⁇ ⁇ 2 was 3 or more, and in each case, the marking by irradiation with the laser single beam was clear.
  • Examples B-8 and B-19 using the composition containing the thermosetting polymer clear markings were obtained, which were inferior to Examples B-1 and B-13, respectively.
  • Example B-11 using a flame retardant as a function imparting agent, the flame resistance of UL94 was V-2, and a clear marking was obtained. Further, in Example B-12 using a metallic pigment, the molded article had a metallic appearance with excellent glitter, King was also clear.
  • the polymer composition for multicolored laser marking of the present invention can be easily formed into a molded article exhibiting a black or dark ground color, and by irradiating the molded article with laser light having different energy, It is suitable for clearly forming the markings of the different colors described above. Therefore, thin products such as films and sheets (for building materials, packaging, and office automation), housings for personal computers, keyboards, printers, facsimiles, telephones, mobile phones, etc., home appliances such as refrigerators, washing machines, various containers and Caps, covering materials such as electric wires, printed wiring boards or precision parts such as electronic components mounted on them, interior parts of automobiles, various pipes, cards such as credit cards and IC cards, and exterior materials such as signs and signs. It is useful for molded products such as.

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PCT/JP2005/000312 2004-01-16 2005-01-13 多色発色レーザーマーキング用有彩色着色剤、多色発色レーザーマーキング用組成物及びそれを含む成形品、多色マーキング付き成形品並びにレーザーマーキング方法 WO2005068557A1 (ja)

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EP05703551.1A EP1705226B1 (en) 2004-01-16 2005-01-13 Multi-color coloring laser marking-use chromatic color colorant, multi-color coloring laser marking-use composition and molding containing it, multi-color marking-carrying molding and laser marking method
US10/586,358 US20080139707A1 (en) 2004-01-16 2005-01-13 Multi-Color Coloring Laser Marking-Use Chromatic Color Colorant, Multi-Color Coloring Laser Marking-Use Composition And Molding Containing It, Multi-Color Making-Carrying Molding And Laser Marking Method
KR1020067016349A KR101155815B1 (ko) 2004-01-16 2005-01-13 다색 발색 레이저 마킹용 유채색 착색제, 다색 발색 레이저마킹용 조성물 및 그것을 포함하는 성형품, 다색 마킹부착 성형품 및 레이저 마킹 방법

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CN108948515A (zh) * 2018-05-31 2018-12-07 天津瑞杰塑料制品有限公司 一种用于激光标识的阻燃pp材料及其制备方法

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JP4505293B2 (ja) 2010-07-21
KR20070004624A (ko) 2007-01-09
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