WO2006085643A1 - アントラキノン系酸性染料のアルカリ土類金属塩を含有するレーザー光透過性部材のレーザー溶着体 - Google Patents
アントラキノン系酸性染料のアルカリ土類金属塩を含有するレーザー光透過性部材のレーザー溶着体 Download PDFInfo
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- WO2006085643A1 WO2006085643A1 PCT/JP2006/302429 JP2006302429W WO2006085643A1 WO 2006085643 A1 WO2006085643 A1 WO 2006085643A1 JP 2006302429 W JP2006302429 W JP 2006302429W WO 2006085643 A1 WO2006085643 A1 WO 2006085643A1
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- laser light
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- earth metal
- alkaline earth
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- 0 Cc1cc(C)c(*c(cc(C)c(O)c2C(c3ccccc33)=*=**)c2C3=O)cc1 Chemical compound Cc1cc(C)c(*c(cc(C)c(O)c2C(c3ccccc33)=*=**)c2C3=O)cc1 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
- C09B1/20—Preparation from starting materials already containing the anthracene nucleus
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- C09B1/34—Dyes with amino groups substituted by hydrocarbon radicals substituted by aryl groups sulfonated
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- B29C66/737—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined
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- B29C66/73771—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined amorphous, semi-crystalline or crystalline the to-be-joined area of at least one of the parts to be joined being amorphous
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- B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
- B29C66/737—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined
- B29C66/7377—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined amorphous, semi-crystalline or crystalline
- B29C66/73775—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined amorphous, semi-crystalline or crystalline the to-be-joined area of at least one of the parts to be joined being crystalline
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- B29C66/80—General aspects of machine operations or constructions and parts thereof
- B29C66/83—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools
- B29C66/836—Moving relative to and tangentially to the parts to be joined, e.g. transversely to the displacement of the parts to be joined, e.g. using a X-Y table
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- B29K2995/0026—Transparent
- B29K2995/0027—Transparent for light outside the visible spectrum
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Definitions
- the present invention comprises an alkaline earth metal salt of an anthraquinone acid dye.
- a method using laser welding is known for joining members made of thermoplastic synthetic resin.
- Such laser welding is performed, for example, as follows. As shown in FIG. 1, a member exhibiting laser beam permeability is used as one member, and a member exhibiting laser beam absorbency is used as the other member, and both members are brought into contact with each other.
- the laser light transmitted through the laser light-transmitting member is absorbed by the laser light-absorbing member and causes heat generation. With this heat, the laser light absorbing member is melted around the portion that has absorbed the laser light, and further the laser light transmitting member is melted to fuse both. When this is cooled, the laser light transmitting member and the laser light absorbing member are firmly bonded with sufficient welding strength.
- the features of laser welding are that it can be welded without bringing the laser beam generator into contact with the part to be welded, and local heating. Therefore, the influence of heat on the peripheral part is negligible, there is no possibility of being subjected to mechanical vibration, and it is possible to weld parts having minute parts and three-dimensional complicated structures, and reproducibility. It is high, can maintain high airtightness, has high welding strength, has difficulty in visually observing the boundary of the welded part, and does not generate dust.
- laser welding can be surely performed with simple operations, and fastening with fastening parts (bolts, screws, clips, etc.), which is a conventional method for joining grease parts, is possible with an adhesive.
- a welding strength equal to or better than that of bonding, vibration welding, ultrasonic welding, etc. can be obtained.
- vibration welding since there is little influence of vibration and heat, it is possible to achieve labor savings, improved productivity, and reduced production costs. For this reason, laser welding is suitable for joining functional parts and electronic parts that should avoid the effects of vibration and heat, for example, in the automobile industry and the electrical / electronics industry, as well as for joining resin parts with complex shapes. It is.
- Japanese Patent Application Laid-Open No. 11-117 0 3 7 1 discloses an opaque member made of a thermoplastic synthetic resin that absorbs laser light and a colorless transparent made of a thermoplastic synthetic resin that transmits laser light.
- a laser welding method is described which includes a step of irradiating a laser beam so that the focal point coincides with a portion in contact with a member.
- the welded portion is different in color and smoothness from the non-welded portion, so that it does not look good.
- Japanese Patent Application Laid-Open No. 2000-300-094 describes an anthraquinone dye used as a colorant for a laser light-transmitting colored thermoplastic resin composition.
- This colorant will sublime during long-term storage. For this reason, the member formed of this composition has a color tone fading, resulting in poor appearance of the welded portion.
- the laser light-transmitting colored thermoplastic resin composition is required to have high laser light transmittance without causing sublimation of the colorant in the heat treatment process before laser welding and causing no color fading. It is done.
- the colorant contained in the laser light transmitting colored thermoplastic resin composition It is important to have high heat resistance and fastness.
- the present invention has been made in order to solve the above-mentioned problems.
- the sublimation of the colorant is performed in the heat treatment step of the previous step of forming a laser beam transmitting member made of colored thermoplastic synthetic resin and laser welding the same. Virtually does not occur, does not cause color fading of the member, has good long-term storage stability, has high permeability that allows laser welding, and has the strength of anthraquinone acid dyes It is an object of the present invention to provide a laser light-transmitting colored resin composition having a re-earth metal salt.
- the laser welded body of the present invention made to achieve the above object is formed of a laser light transmissive member containing an alkaline earth metal salt of an anthraquinone acid dye.
- the laser welded body of the present invention is a laser light-transmitting colored resin composition containing an anthraquinone acid dye alkaline metal salt and a thermoplastic resin.
- a laser light transmissive member formed by the step (b) and a laser light absorptive member that is in contact with the laser light transmissive member are irradiated to the laser light transmissive member, transmitted therethrough, and absorbed by the laser light absorptive member It is characterized by being laser-welded at the abutting portion by light.
- the alkaline earth metal salt of the anthraquinone acid dye is preferably represented by the following chemical formula (1) and Z or (2).
- one R 1 represents a hydrogen atom, a hydroxyl group, an amino group, an alkylamino group or an acylamino group
- one R 2 represents a hydrogen atom, an alkyl group, a halogen group, an alkoxy group or one SO 3 M 1 / 2 (M is an alkaline earth metal)
- 1 R 3 may be the same as or different from 1 R 2 , hydrogen atom, alkyl group, halogen group, alkoxy group, 1 S ⁇ 3 M 1/2 (where M is an alkaline earth metal) or an alkyl group, halogen group, amino group, nitro group, or an anilino group that may have SO 3 M 1/2 as a substituent
- — R 4 , 1 R 5 , 1 R 6 , 1 R 7 and 1 R 8 may be the same or different, a hydrogen atom, an alkyl group, an amino group, a nitrogen group, an acyl group, An acylamino group, an acyl-1-
- one R 14 and one R 15 may be the same or different, and may be a hydrogen atom, an alkyl group, a halogen group, an alkoxy group, an amino group, a nitro group, or a single S 0 3 M 1/2 (M is an alkaline earth metal) indicates, - R 9 R 13 ⁇ Pi one R 16 ⁇ one R 2.
- the laser welding method of the present invention comprises an alkaline earth metal salt of an anthraquinone acid dye, preferably an alkaline earth metal of an anthraquinone acid dye represented by the chemical formula (1) and / or (2).
- a laser light transmitting member formed of a laser light transmitting colored resin composition containing salt and a laser light absorbing member are brought into contact with each other, and then laser light is applied to the laser light transmitting member.
- the laser light passes through the laser light transmissive member and is absorbed by the laser light absorptive member. It is made to weld in the site
- the energy amount X (J / mm) given by the laser beam irradiated while scanning is expressed by the following formula.
- T preferably represents the transmittance of the laser light transmissive member at the wavelength of the laser light). This makes it possible to satisfactorily adjust the practically sufficient strength and the clean surface and appearance of the welded body.
- the laser light transmitting colored resin composition of the present invention contains at least an alkaline earth metal salt of an anthraquinone acid dye represented by the following chemical formula (1) and / or (2) and a thermoplastic resin.
- the transmittance T of laser light having a wavelength of 9400 nm with respect to this laser light transmitting colored resin composition is preferably at least 15%.
- thermoplastic resin used in the laser light-transmitting colored resin composition containing the alkaline earth metal salt of an anthraquinone acid dye should be a polyethylensulfide resin. preferable.
- the product has high heat resistance during the molding process of the laser light transmissive member near the high melting point of the polyphenylene sulfide resin, the heat treatment process before the laser welding process, and the laser welding process. Expresses sexuality and robustness.
- a laser welded body of a laser light transmitting member formed from a laser light transmitting colored resin composition containing an alkaline earth metal salt of an anthraquinone acid dye of the present invention is a laser light transmitting colored resin composition. This is because it can be obtained by laser welding under a wide range of conditions, because of its good laser light transmittance, laser weldability and stability. Furthermore, it is possible to perform laser welding of complicated members having convexities. Furthermore, the laser welded body is excellent in terms of its clean appearance and weldability with high tensile strength.
- the laser light transmitting colored resin composition of the present invention is highly transmissive to light having a wavelength from about 80 nm by a semiconductor laser to about 120 nm by a YAG laser, that is, laser light. It has high fastness such as heat resistance and light resistance, and also has good migration resistance and chemical resistance, and shows a clear hue. For this reason, it is a resin composition suitable for the laser welding method.
- a laser light transmitting member formed of a laser light transmitting colored resin composition containing an alkaline earth metal salt of an anthraquinone acid dye, a laser light absorbing member,
- the laser beam is irradiated while scanning so that the laser beam is transmitted through the laser beam transmitting member and absorbed by the laser beam absorbing member.
- both members are heat-melted, and as a result, the abutting portion can be firmly welded.
- FIG. 1 shows a laser welding of a laser beam transmitting member molded with a laser beam transmitting colored resin composition to which the present invention is applied and a laser beam absorbing member.
- FIG. 2 ′ is a diagram showing another configuration of a laser light-transmitting member and a laser light-absorbing member for carrying out the laser welding method to which the present invention is applied.
- FIG. 3 is a diagram showing another configuration of the laser light-transmitting member and the laser light-absorbing member for carrying out the laser welding method to which the present invention is applied.
- a laser light transmitting member containing at least an alkaline earth metal salt of an anthraquinone acid dye and a laser light absorbing member containing a laser light absorbing agent are welded.
- the laser welded body of the present invention is welded between a plurality of laser light transmitting members with a laser light absorber-containing film layer or a laser light absorber-containing coating layer interposed as a laser light absorbing member. It is configured.
- the laser light transmitting member is molded with a resin composition in which at least a thermoplastic resin and an alkaline metal salt of an anthraquinone acid dye are mixed, and various additives are additionally mixed as desired. Can be obtained.
- the laser light absorbing member is configured to have at least a layer capable of absorbing laser light on the surface in contact with the laser light transmitting member.
- the laser light absorbing member include a single layer member formed into a thick plate shape with a laser light absorbing agent-containing laser light absorbing colored resin composition.
- a laser light absorbing member-containing film layer or a laser light absorbing agent-containing coating is used as a laser light absorbing member between a plurality of laser light transmitting members.
- a multilayer member that is combined and integrated through layers is exemplified.
- the laser welded body of the present invention includes those obtained by a single laser welding and those obtained by a plurality of laser weldings.
- a laser light-transmitting member that is stacked several times and a laser light-absorbing member that is sandwiched between them are welded.
- the laser light-absorbing member is thin, it can be surely welded from the outermost laser / light-transmitting member side by one laser welding at the same time.
- the laser light-absorbing member is thick, multiple laser weldings are required simultaneously or sequentially from both outer laser-light-transmitting member sides and repeated as necessary.
- the manufacturing process includes the following (A) to (E).
- a laser light transmitting member 1 comprising a laser light transmitting colored resin composition containing at least an alkaline earth metal salt of an anthraquinone acid dye is formed.
- the laser beam 3 is irradiated with appropriate adjustment so that the laser beam 3 passes through the laser beam transmitting member 1 and is absorbed by the laser beam absorbing member 2.
- the contact portion between the laser light transmitting member 1 and the laser light absorbing member 2 is welded at the welding site 6.
- the laser-welded body in which the laser light transmitting member and the laser light absorbing portion are welded needs to exhibit a practically sufficient strength at the welded portion.
- the tensile weld strength in the tensile test according to JISK 7 1 1 3-1 995 is 15 Mpa or more, and more preferably 20 to 60 Mpa.
- the manufacturing process includes the following (F) to (J).
- a laser light absorbent containing layer 8 (or 9) constituting a laser light absorbing member is interposed between the plurality of laser light transmitting members 1 and 7.
- the resin film layer 8 containing the laser one light absorber and the molded laser light transmitting member 7 are preliminarily attached to the laser light absorbing member 2 before laser welding. It may be formed or formed simultaneously with laser welding. Also, as shown in FIG. 3, a molded laser light transmitting member 7 and an ink containing a laser light absorbing agent on the molded laser light transmitting member 7 may be used.
- the laser light-absorbing member 2 may be formed with the coating layer 9 to which Z or a paint is applied.
- the laser beam 3 is irradiated while adjusting the laser beam 3 from a plurality of directions so that the laser beam 3 is transmitted through the laser beam transmitting member and absorbed by the laser beam absorbing member.
- the resin film layer 8 containing the laser light absorber and the ink and / or paint containing the laser light absorber are applied.
- the coated layer 9 is a thin layer
- the laser light transmissive member 1, the laser one light absorption layer, and the molded laser light transmissive member 7 are thermally melted simultaneously by irradiating the laser light once from one direction. Can be welded.
- the molded laser light transmissive member 7 can be selected without considering the laser transmittance.
- the laser-welded body in which the laser light transmitting member and the laser light absorbing member are welded has a tensile weld strength in a tensile test according to JISK 7 1 1 3-1 995 as described above. 1 is preferably 5 Mpa or more,
- 3 may be irradiated from above or below, and may be irradiated simultaneously, sequentially or repeatedly.
- Examples of the laser light absorber contained in this laser light absorbing member include carbon black, niggin cin, aniline black, phthalocian cyanine, naphthalocyanine, porphyrin, cyanine compound, perylene, quaterily.
- Examples include len, metal complexes, azo dyes, anthraquinones, squaric acid derivatives, and immonium dyes. Of these, inexpensive and highly stable carbon black and Z or Niguchishin are preferred.
- the laser light transmitting colored resin composition used in the present invention contains an alkaline earth metal salt of an anthraquinone acid dye and a resin.
- the salt of the anthraquinone acid dye contained in this composition has the chemical formula (1) Or (2). This will be specifically described below.
- the alkaline earth metal salt of an azitraquinone acid dye is an ionic group of an alkaline earth metal ion to a sulfone group in the structure of an anthraquinone dye.
- the anthraquinone acid dye alkaline earth metal salt can exhibit the effects of the present invention.
- the anthraquinone dye is represented by the chemical formula (1) or (2).
- the bonded state of the sulfone group and the alkaline earth metal (combination of monovalent anion and divalent cation) )
- 1 SO 3 M 1/2 (M represents an alkaline earth metal). Therefore, the cation of M 1/2 can bind to acidic groups such as sulfone groups and other anions in dyes and other dyes.
- R 1 is a hydrogen atom; a hydroxyl group; an amino group; an alkylamino group [eg, methylamino, ethylamino, propylamino, iso-propylamino, n-butylamino, tert-butylamino, n-pentylamino, isopentylamino.
- Alkylamine groups having 1 to 12 carbon atoms such as hexylamino, heptylamino, octylamino, etc .; or acylamino groups [for example, formylamino, acetylamino, propionylamino, butyrrylamino, norylamino, bivaleroylamino, etc.
- An acylamino group for example, formylamino, acetylamino, propionylamino, butyrrylamino, norylamino, bivaleroylamino, etc.
- R 2 is a hydrogen atom; an alkyl group [for example, carbon atoms such as methyl, ethyl, propyl, iso-propinole, n-butinole, tert-butinole, n-pentinole, iso-pentinole, hexyl, heptyl, octinole, etc.
- halogen group [e.g., F, C1, Br, etc.]
- alkoxy group e.g., alkoxy group having 1 to 8 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, etc.]
- SO 3 M 1/2 M is an alkaline earth metal [eg, Be, Mg, Ca, Sr, Ba, etc.]) —R 3 may be the same as or different from R 2 ; a hydrogen atom; an alkyl 'group, a halogen group [eg, F, C l, Br, etc.]; an alkoxy group [eg, 1- to 8-carbon alkoxy group such as toxi, ethoxy, propoxy, butoxy]; 1 SO 3 M 1/2 (M is an alkaline earth metal [eg, Be, Mg, Ca, Sr, B a)]; or an alkyl group [for example, methinole, ethinole, propyl, iso
- R 4 , 1 R 5 , 1 R 6 , 1 R. 7 and 1 R 8 may be the same or different, a hydrogen atom; an alkyl group [for example, methyl, ethyl, propyl , Iso-propinole, n-butinole, tert-butylene, n-pentyl, iso-pentyl, hexyl, heptyl, octyl / le, etc.
- an alkyl group for example, methyl, ethyl, propyl , Iso-propinole, n-butinole, tert-butylene, n-pentyl, iso-pentyl, hexyl, heptyl, octyl / le, etc.
- alkyl group having 1 to 12 carbon atoms amino group having 1 to 12 carbon atoms
- amino group nitrogen Group
- asil group e.g., formyl, acetinole, propioninore, butinorelinore, parellinole, bivaleroyl, etc., a C1-C1 2 acyl group
- an acylamino group e.g.
- Cylamino groups such as bis, bivaleroylamino and the like]; acyl N-alkylamino groups [eg, acetyl N-methylamino, acetyl -N-ethylamino, acetyl N-ethylamino, propionyl — N-methylamino, petitro N-methylrylamino, etc.
- the salt of the dye of the chemical formula (1) is one in which at least one of 1 R 2 to 1 R 8 is a sulfone group—S 0 3 M 1/2 . In other words, it has at least one SO 3 M 1/2 in its chemical structure.
- one R 14 and R 15 may be the same or different, a hydrogen atom; an alkyl group [for example, methyl, ethyl, propyl, iso-propinole, n— Alkyl groups having 1 to 12 carbon atoms, such as butynole, tert-pentinole, n-pentyl, iso-pentyl, hexyl, heptyl, octyl, etc.; haguchigen group [eg, F, C 1, Br, etc.
- an alkyl group for example, methyl, ethyl, propyl, iso-propinole, n— Alkyl groups having 1 to 12 carbon atoms, such as butynole, tert-pentinole, n-pentyl, iso-pentyl, hexyl, heptyl, octyl, etc.
- haguchigen group eg, F, C 1, Br, etc
- Alkoxy group [e.g., alkoxy group having 1 to 12 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, etc.]; Amino group; Nitro group; One S 0 3 M 1/2 (M represents an alkaline earth metal [eg, B e, Mg, C a, S r, B a, etc.)]
- R 9 R 13 and one R 16 to one R 2 May be the same or different and are a hydrogen atom; an alkyl group [eg, methyl, ethyl, propyl, iso-propyl, n-butyl, tert-butyl, n-pentinole, iso-pentinole, hexyl, An alkyl group having 1 to 12 carbon atoms such as heptyl, octinole, etc.]; an acyl group [for example, an acyl group having 1 to 12 carbon atoms, such as formyl, acetyl, propionyl, butylyl, pareryl, bivaleroyl, etc.]; an acylamino group [for example, Formylamino, acetylamino, propionylamino, ptyllylamino, valerylamino, bivaleroylamino, etc., an acylamine group having 1 to 12 carbon
- the salt of the dye represented by the chemical formula (2) is one in which at least one of 1 R 9 to 1 R 2 ° is a sulfone group S 0 3 M 1/2 .
- the chemical structure has at least one S 0 3 M 1/2 .
- M is Ca among the alkaline earth metals since the above effect is further improved.
- An alkaline earth metal salt of an anthraquinone acid dye can be obtained by substituting an alkaline earth metal with H or an alkali metal of a sulfonic acid group in the acid dye. Specifically, it can be obtained by reacting a known or commercially available anthraquinone acid dye with an alkaline earth metal compound (for example, an alkaline earth metal hydroxide, sulfate or chloride). As this method, a known ion reaction method can be used. This substitution reaction dramatically improves the heat resistance of the dye.
- the measurement method of thermal analysis is as follows: [TGZDTA measuring instrument (trade name: SII EX S TAR 600 00 manufactured by Seiko Instruments Ltd.) It is heated from 30 ° C to 55 ° C and measured at the same temperature for 2 8 minutes after reaching 55 ° C. The decomposition temperature of this Na salt by thermal analysis was 2 35 ° C. In contrast, the Ca salt did not decompose. Therefore, thermal decomposition is unlikely to occur, thermal stability is good, and the influence of heat is reduced during resin molding and laser welding. Therefore, it is excellent in application suitability for laser welding. Thus, by having a sulfone group derivative in the dye structure, the anchor effect, which is a phenomenon of staying in the resin, is exhibited.
- the alkaline earth metal salt of an anthraquinone acid dye used in the present invention has one SO 3 M 1/2 (M in the chemical structure as represented by the chemical formula (1) or (2). Indicates an earth-strength earth metal).
- the anchor effect is strongly expressed in the resin composition by making this M part an Al-strength earth metal. For this reason, it has stronger sublimation resistance, heat resistance, and chemical resistance than conventional neutral anthraquinone dyes and organic amine salts of anthraquinone dyes. This shows that the laser welded body of the present invention shows high practicality even in the use of high-melting engineering plastics. ⁇
- an alkaline earth metal salt of the anthraquinone acid dye of the above chemical formula (2) it is preferable to use an alkaline earth metal salt of the anthraquinone acid dye of the above chemical formula (2).
- the alkaline earth metal salt of the anthraquinone acid dye has a stronger suppression of the sublimation phenomenon as its purity increases.
- the purity thereof is preferably 80% or more, more preferably 90% or more.
- a by-product having a lower molecular weight than the anthraquinone acid dye represented by the chemical formulas (1) and (2) is an impurity. It becomes easy to obtain by mixing. For this reason, impurities with high solubility in rosin are increased, so that the sublimation phenomenon at high temperature becomes remarkable and the heat resistance of the resin composition tends to be impaired.
- alkaline earth metal salt of the anthraquinone acid dye represented by the chemical formula (1) or (2) include the following compound examples. Of course, the present invention is not limited to these.
- the alkaline earth metal salts of the anthraquinone acid dyes represented by the chemical formulas (1) and (2) mainly exhibit a blue or green hue.
- these anthraquinone acid dyes may be used singly or in combination of two or more, and may be used in combination with various dyes.
- a compounding colorant used in a laser light-transmitting colored resin composition together with the alkaline earth metal salt of the anthraquinone acid dye, it absorbs only outside or within the visible light absorption range it has.
- the colorant can be used as a colorant of various hues by mixing dyes exhibiting hues such as red, yellow, or orange with good laser light transmission.
- a colorant exhibiting a black hue obtained by combining a blue dye, which is an alkaline earth metal salt of the anthraquinone acid dye, with another red colorant or a yellow colorant. It is.
- the black resin composition is important for industrial use of the laser light transmitting colored resin composition. It is preferable that the black compounding colorant has a black color by mixing the alkaline earth metal salt of the anthraquinone acid dye and a yellow and / or red dye.
- a specific example of the colorant mixture is expressed by combining an alkaline earth metal salt of each blue or purple anthraquinone acid dye with a yellow and / or red colorant to produce green (for example, blue + Colorants exhibiting various hues such as yellow combination), purple (for example, blue + red combination), and black (for example, blue + yellow + red combination, or purple + yellow combination) may be mentioned.
- an anthrapyridone dye is preferably used as a red colorant.
- Examples of the colorant that can be used in the present invention include organic dyes and pigments having laser light transmittance. There are no particular restrictions on their structures, and more specifically, azomethine, quinatalidone, dioxazine, diketopyrrolopyrrole, anthrapyridone, isoindolinone, indanthrone, perinone Organic dyes such as various dyes such as perylene, indigo, thioindigo, quinophthalone, quinoline, and triphenylmethane.
- yellow colorants that can be used in combination with the above-mentioned anthraquinone-based acid dye alkaline metal salts include C.I.Solvent Y e 1 1 ow 1 6 3 and C.I.S olvent.
- Yellow oil-soluble dyes such as Y ellow 1 1 4 etc. Yellow like C.I.A cid Y ellow 3, C.I.A cid Y ellow 4 2, C.I.A cid Y ellow 4 9 etc.
- acid dyes Y ellow 1 1 4 etc.
- an orange colorant that can be used in combination with the above-mentioned anthraquinone acid dye alkaline metal salt, specifically, an orange acid dye such as C.I.A cid O range 56, C Orange oil-soluble dyes such as I. S o 1 vent O range 6 0 etc. are mentioned.
- the content of the colorant in the laser light transmitting colored resin composition is preferably from 0.01 to 10% by weight based on the thermoplastic resin. More preferably, it is 0.1 to 5% by weight, and still more preferably 0.1 to 1% by weight.
- a transmittance T of laser light having a wavelength of 9400 nm with respect to the laser light transmitting colored resin composition is 15% or more.
- the ratio ⁇ 2 to the transmittance ⁇ 2 of the laser light with a wavelength of 94 nm to the same non-colored resin composition except that the colorant is not contained is 0.5 or more. Is preferably 0.7 to 1.1, more preferably 0.8 to 1.1.
- the resin used in the laser light transmissive member and the laser light transmissive colored resin composition melts when heated, and returns to its original hardness when cooled. It is composed of a thermoplastic resin that is reversible in melting and solidification by cooling and insoluble in solvents, and is, for example, a resin that has laser light transparency and is used as a facial dispersant, master patch or Examples include known resins used as carrier resins for colored pellets.
- thermoplastic resins include polyphenylene sulfide resin (PPS), polyamide resin (PA), polyethylene resin (PE), polypropylene resin (PP), and polystyrene resin.
- PPS polyphenylene sulfide resin
- PA polyamide resin
- PE polyethylene resin
- PP polypropylene resin
- the thermoplastic resin may be a copolymer resin composed of two or more of the thermoplastic resins.
- AS acrylonitrile-styrene
- ABS acrylonitrile-butadiene-styrene
- AES acrylonitrile-styrene EP DM-styrene
- thermoplastic elastomers such as polystyrene-based thermoplastic elastomers, polyolefin-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers; Synthetic wax or natural wax or the like can be mentioned.
- thermoplastic resins are not particularly limited. Les. Moreover, you may use two or more said different resin.
- thermoplastic resin is made of polyphenylene sulfide resin (PPs), polyester resin (including PET and PBT), polyolefin resin, polyamide resin (nylon), polyacetal resin, or polysulfone resin ( PES, PA SF, and PSF are preferable.
- PPs polyphenylene sulfide resin
- polyester resin including PET and PBT
- polyolefin resin polyamide resin (nylon)
- polyacetal resin polysulfone resin
- PES polysulfone resin
- PA SF polysulfone resin
- PPS polyphenylene sulfide resin
- PPS polyphenylene sulfide resin
- PPS polyphenylene sulfide resin
- This resin is a polymer mainly composed of This resin is obtained by polymerizing monomers synthesized by reacting paradichlorobenzene and alkali sulfide at high temperature and pressure.
- This resin consists of a straight-chain type that achieves the desired degree of polymerization only by a polymerization process using a polymerization aid, and a cross-linked type that is obtained by thermally crosslinking a low-molecular polymer in the presence of oxygen. Roughly classified into two types. In particular, a straight-chain type is preferable in terms of excellent transmittance. '
- melt viscosity of the polyphenylene sulfide resin is not particularly limited as long as it can be melt-kneaded, but usually one having a range of 5 to 200 Pa.s is used. A range of 6 0 0 Pa ′ s is more preferable.
- Polyphenylene sulfide resin has properties suitable for applications such as electronic parts and automobile parts.
- Polyphenylene sulfide resin can also be a polymer alloy.
- PPS / polyolefin alloy PPS / polyamide alloy, PPS / polyester alloy, PPS / poly-polyone alloy, PPS / polyphenylene ether alloy, PPS / liquid crystal polymer alloy, PPS / polyimid CPS alloy and PPS / polysulfone alloy.
- the polyester resin include polyethylene terephthalate resin obtained by a polycondensation reaction between terephthalic acid and ethylene glycol, and polybutylene terephthalate resin obtained by a polycondensation reaction between terephthalic acid and butylene glycol.
- polyester resins include a part of the terephthalic acid component in the polyester resin (for example, 15 mol% or less [for example, 0, 5 to 15 mol%], preferably 5 mol% or less [for example, 0 . 5-5 mole 0/0]) ⁇ Pi Z or ethylene glycidyl copolymers Lumpur or Puchirenguri call some of the components (e.g., 1 to 5 mol. /. the following [for example from 0.5 to 1 5 mole 0/0, Preferably, a copolymer in which 5 mol% or less [for example, 0.5 to 5 mol%:]) is substituted may be mentioned. It may also be a mixture of two or more polyester resins.
- Examples of those that replace a part of the terephthalic acid component include aromatic dicarboxylic acids such as isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenyl / laeterdicarboxylic acid, diphenylsulfonic dicarboxylic acid; Cycloaliphatic dicarboxylic acids such as hexahydrodrothephthalic acid and hexahydroisophthalic acid; aliphatic dicarboxylic acids such as adipic acid, sebacic acid and azelaic acid; p--bifunctional carboxylic acids such as hydroxyxoxybenzoic acid Or a combination of two or more of these.
- aromatic dicarboxylic acids such as isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, di
- Examples of those that replace part of the ethylene glycol or butylene glycol component include trimethylene glycol, tetramethylene glycol, hexamethylene glycol / le, decamethylene glycol, neopentino glycol, and diethylene glycol. 1,1-cyclohexanedimethylolone, 1,4-cyclohexanedimethylolone, 2,2-bis (4,1-hydroxyhydroxy) pronone, bis (4,1) 3-hydroxyxylphenyl ) Dalicol such as sulfonic acid, and functional derivatives of these And a combination of one or more polyfunctional compounds. '
- the polyolefin resin is not particularly limited. Examples include ethylene, propylene, butene-1, 3-methenolevbutene-1, 4-methinopentene-1, and otene1-1 homopolymers or copolymers of these, And other copolymerizable unsaturated monomers (Examples of the copolymer include a block copolymer, a random copolymer, and a graft copolymer). .
- polyethylene-based resins such as high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, ethylene monoacetate butyl copolymer, ethylene monoethyl acrylate copolymer, and the like; Polypropylene resins such as propylene homopolymer, propylene-ethylene block copolymer, or random copolymer, propylene-ethylene-butene-1 copolymer; polybutene-1, poly-4-methylpentene-1, etc. .
- These polyolefin resins may be used alone or in combination of two or more. Among these, it is preferable to use polypropylene resin and z or polyethylene resin. More preferred is a polypropylene-based resin. There are no particular restrictions on this polypropylene resin, and a wide range of molecular weights can be used.
- an acid-modified polyolefin modified with unsaturated ruponic acid or its derivative may be a resin containing a foaming agent such as foamed polypropylene.
- a foaming agent such as foamed polypropylene.
- rubbers such as these hydrogenated products may be contained in the polyolefin resin.
- the polyamide resin may be a mixed polymer of the polyamide resin and another synthetic resin.
- Examples of such mixed polymers are: Polyamide z Polyester mixed polymer, Polyamide / Polyphenylene oxide mixed polymer, Polyamide polycarbonate mixed polymer, Polyamide / Polyolefin mixed polymer, Polyamide Z styrene. / Acrylonitrile mixed polymer, polyamido acrylate mixed polymer, polyamide / silicone mixed polymer, and the like. These polyamide resins may be used alone or in admixture of two or more.
- Polyacetal resin is a polymer compound mainly composed of oxymethylene group (one CH 2 0—). Polyoxymethylene homopolymer, copolymer containing small amount of other structural units in addition to oxymethylene group, terpolymer, block Any copolymer may be used, and the molecule may have a branched or crosslinked structure as well as a linear shape. There is no particular restriction on the degree of polymerization.
- Polysulfone-based resin is an amorphous thermoplastic resin that has a (one so 2- ) bond in the molecule, is amber transparent, and has a glossy appearance. . It is synthesized by polycondensation reaction of dichlorodiphenylsulfone and bisphenol A Na salt.
- Other resins in this series include, for example, polyethersulfone rosin (PES, poly Ether sulfone resin), polyallyl sulfone resin (PASF, polyaryl sulfone resin), polyphenyl sulfone resin (PSF polyphenyl sulfone resin), and the like.
- the polysulfone-based resin can contain other resins within a range not impairing the effects of the present invention.
- a polysulfone-based resin a copolymer of polysulfone and polycarbonate, a copolymer of polysulfone and polyamid, a copolymer of polysulfone, polycarbonate and liquid crystal polymer, or a polysulfone, polyamido and liquid crystal polymer Copolymers can be used, blends of polysulfone and polycarbonate, blends of polysulfone and polyamid, blends of polysulfone and polyforce-bonate and liquid crystal polymer, polysulfone and polyamide and liquid crystal high Blends with molecules, polysulfone / polyamide copolymers and liquid crystal polymer blends can also be used.
- These polysulfone resins may be used alone or in admixture of two or more.
- the laser light transmitting colored resin composition may contain various additives as required.
- additives include auxiliary colorants, dispersants, reinforcing materials or fillers, stabilizers, plasticizers, modifiers, UV absorbers or light stabilizers, antioxidants, antistatic agents, Examples include lubricants, mold release agents, crystal accelerators, crystal nucleating agents, flame retardants, and elastomers for improving impact resistance.
- the laser light-transmitting colored rosin composition may contain appropriate amounts of various reinforcing materials or fillers depending on the application and purpose.
- the reinforcing material is not particularly limited as long as it can be used for reinforcing a normal synthetic resin.
- glass fibers, carbon fibers, other inorganic fibers, and organic fibers alamide, polyphenylene sulfide, nylon, polyester, liquid crystal polymer, etc.
- reinforcement of resins that require transparency For this, glass fiber is preferred.
- Glass fiber that can be suitably used The fiber has a fiber length of 2 to 15 mm and a fiber diameter of 1 to 20 ⁇ ⁇ .
- the 'form of the glass fiber there is no particular limitation on the 'form of the glass fiber, and any of, for example, roving and milled fiber may be used. These glass fibers can be used alone or in combination of two or more.
- the content is preferably 5 to 120 parts by weight with respect to 100 parts by weight of the thermoplastic resin. When the amount is less than 5 parts by weight, it is difficult to obtain a sufficient glass fiber reinforcing effect, and when it exceeds 120 parts by weight, the formability tends to decrease.
- the amount is preferably 10 to 60 parts by weight, particularly preferably 20 to 50 parts by weight.
- fillers include plate-like fillers such as My strength, sericite, and glass flakes, silicates such as talc, kaolin, clay, wollastonite, bentonite, asbestos, and alumina silicate, alumina , Metal oxides such as silicon oxide, transported magnesium, zirconium oxide and titanium oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, glass beads, ceramic beads, nitriding Particulate fillers such as boron and silicon carbide can be added.
- silicates such as talc, kaolin, clay, wollastonite, bentonite, asbestos, and alumina silicate, alumina
- Metal oxides such as silicon oxide, transported magnesium, zirconium oxide and titanium oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, glass beads,
- the colored resin composition used in the present invention can be obtained by combining raw materials by an arbitrary blending method. These blending components are usually preferably as uniform as possible. Specifically, for example, all raw materials can be obtained by mixing and homogenizing using a blender such as a blender, kneader, Banbury mixer, roll, or extruder. Alternatively, the resin composition can be obtained by mixing a part of raw materials with a mixer, adding the remaining components, and further mixing and homogenizing. Alternatively, the resin composition may be prepared by melting and kneading the raw material that has been dry-dried in advance with a heated extruder, then extruding it into a wire, and then cutting it into a desired length to form a colored granule.
- a blender such as a blender, kneader, Banbury mixer, roll, or extruder.
- the resin composition can be obtained by mixing a part of raw materials with a mixer, adding the remaining components, and further mixing and homogenizing.
- the masterbatch of the colored resin composition used in the present invention can be obtained by any method. For example, after mixing the resin powder or pellets and colorant used as the base of the masterbatch with a mixer such as a tumbler or a super mixer, use an extruder, a batch kneader, or a roll kneader. It can be obtained by heating and melting to pelletize or coarse particles. Further, for example, after the resin synthesis, after adding a colorant to the resin for master patch in a solution state, the master batch can be obtained by removing the solvent.
- a mixer such as a tumbler or a super mixer
- Molding of the colored resin composition used in the present invention can be performed by various commonly performed procedures.
- a colored pellet can be used for molding by a processing machine such as an extruder, an injection molding machine, or a roll mill.
- a transparent resin pellet or powder, a pulverized colorant, If necessary, various additives can be mixed in a suitable mixer, and the mixture can be formed by using a processing machine.
- a colorant can be added to a monomer containing an appropriate polymerization catalyst, and this mixture can be polymerized to obtain a desired resin, which can be molded by an appropriate method.
- molding methods include injection molding, extrusion molding, compression molding, foam molding, professional molding, vacuum molding, injection blow molding, rotational molding, calendar molding, solution casting, and any commonly used molding method. Can be adopted. 'By such molding, various shapes of laser light transmissive members can be obtained.
- a laser light transmissive member 1 made of the laser one light transmissive colored thermoplastic resin composition and a laser light absorptive member 2 are each step 4.
- the laser light 3 passes through the laser-light-transmitting member 1 and passes through the laser-light-absorbing member 2 in at least a part of the abutting portion while being in a state of being in contact with each other in the five portions.
- a contact portion between the transmissive member 1 and the laser light absorbing member 2 is welded.
- the advantages of laser welding methods are that three-dimensional welding is possible, increasing the degree of freedom of the mold shape, and improving the design by eliminating the Paris on the welding surface unlike vibration welding, vibration and wear powder This means that it does not occur and can be applied to electronic components.
- the disadvantages are the upfront investment in laser welding machines, and the generation of gaps between welded members due to sink marks after molding of the resin material. In particular, this gap problem is the biggest problem for those who actually operate laser welding machines, and the holding jigs such as clamps are made independently according to the shape of the welding member.
- Currently is known that if a gap of 0.02 mm is generated, it is halved compared to the welding strength when there is no gap, and if a gap of 0.05 mm or more is generated, it is known that no welding occurs.
- Laser operating methods include a scanning type in which the laser moves, a masking type in which the welding material moves, and a type in which the welding member is irradiated simultaneously from many directions. Is a scanning type, and the value of 5 m / min is used as the basis for production tact time.
- a wavelength from about 800 nm by a semiconductor laser to about 110 nm by a YAG laser, that is, laser light used for laser welding is used.
- a material that transmits at least 15% of the wavelength is used.
- the infrared transmittance of one or more wavelengths at 8 08 nm, 840 nm, 940 nm, and 1064 nm is at least 20%. If it is too low, a sufficient amount of laser light of these wavelengths cannot be transmitted, so even if laser welding is performed, the intensity is insufficient, or excessive laser light energy that is not suitable for practical use is required. It becomes.
- the amount of energy X (J / mm) given by the laser beam irradiated while scanning is expressed by the following formula (II).
- p (W) is the laser beam output
- q (mmZ seconds) is the laser beam scanning speed
- ⁇ is the transmittance of the laser beam transmitting member at the wavelength of the laser beam. It is industrial that it is adjusted to meet This is a preferable condition for use as a structural member.
- X in the welding of the amorphous thermoplastic resin having excellent permeability such as the polysulfone resin (PSU, polysulfone resin) of the present invention is preferably 0.3 to 2.0, and more preferably 0.4 to A range of 1.5 is preferred. On the other hand, welding strength that can be used practically is not shown under welding conditions where X is less than 0.3.
- x in the welding of a crystalline thermoplastic resin with poor permeability such as the polyphenylene sulfide resin of the present invention is preferably 1.0 to 5.0, and more preferably in the range of 2.0 to 5.0. preferable.
- X is greater than 5.0, the energy is too strong and rapid melting occurs, so the accuracy of the welded portion decreases, and burrs and other defects occur, resulting in a decrease in welding strength.
- the laser welding method of the present invention comprises a laser light absorbing member 2 having an ink and / or paint coating layer 9 containing a laser light absorber as a laser light absorber containing coating layer. And a laser welding method with the laser light transmissive member 1. More specifically, first, an ink and / or paint containing, for example, a laser light absorber and, if necessary, a resin is prepared. The ink and / or paint is applied to the laser light transmitting member 7 by any method such as spraying or painting with a marking pen, brush, brush, etc., preferably 0.1 mm or less. Pre-apply with lower thickness.
- a laser light absorber-containing coating layer 9 is formed, and the laser light-absorbing member 2 in which the laser light transmitting member 7 and the coating layer 9 are integrated is obtained. After this laser light absorbent-containing coating layer 9 and the laser light transmitting member 1 to be welded are brought into contact with each other, the laser light transmitting member 1 is irradiated with laser light from the side of the member 1. Is obtained.
- the laser light absorbing member is a laser light absorbing colored resin composition using at least carbon black as a laser light absorber and black colorant.
- it may be formed of a laser light absorbing colored thermoplastic resin composition.
- the primary particle diameter of Tatsumi Bon Black is 18 to 30 nm.
- Niguchi syn dye may be used together with carbon black.
- the Niguchi syn dye is preferably a Niguchi syn dye belonging to CI Solvent Black 7, which adjusts the laser absorption rate well.
- the laser light absorbing member is formed of a laser light absorbing colored resin composition containing a colorant other than carbon black and a laser light absorbing agent exemplified by phthalocyanine-based, cyanine-based, and metal complexes. It may be done. It may be formed of a laser light-absorbing colored resin composition containing a laser light absorber and colorant other than carbon black.
- the laser light absorbing member can be produced in the same manner as described for the laser light transmitting member except that it contains a laser light absorbing agent. It may contain an appropriate amount of additives.
- the above blending and molding methods can be used. It is also possible to use an alkaline earth metal salt of an anthraquinone acid dye used in the production of the aforementioned laser light transmitting member, and an organic dye such as various colorants and various dyes.
- the materials used to manufacture the laser light absorbing member can be selected from a wide range because there is no restriction of laser light transmission compared to the material used for the laser light transmitting member.
- the amount of the colorant used in the laser light absorbing colored resin composition can be, for example, 0.1 to 10% by weight with respect to the resin (preferably a thermoplastic resin), and preferably 0.0. 5 to 5% by weight.
- the laser welded body of the present invention can be obtained by the laser welding method described above. You can.
- This laser welded body has high fastness such as heat resistance and light resistance, and also has good migration resistance, chemical resistance, etc. and exhibits a clear hue.
- examples of main applications of the laser welded body of the present invention include automobile parts. More specifically, an instrument panel in the interior and a resonator (muffler) in the engine room can be mentioned.
- an adhesive When joining parts made of thermoplastic resin, it was difficult to use an adhesive if the surface was not treated before, so it was necessary to devise methods such as pre-treating the surface.
- this laser welding does not require a complicated process such as pre-treatment of alloying of the resin, and is superior in strength and recycling compared to the case of using an adhesive.
- Production Examples 1 to 11 shown in Table 1 are colorants used in each Example, and Comparative Production Examples 1 to 7 are colorants used in each Comparative Example.
- the dyes shown in the above compound examples correspond to the dyes for each production example.
- Production Examples 3, 7, 10 and 11 and Comparative Production Example 5 are black colorants obtained by blending a plurality of dyes with a simple mixer according to the weight blending ratio indicated in the blending ratio column.
- the anthraquinone acid dye used in the present invention is an alkaline earth metal salt, an anthraquinone acid dye, and an anthraquinone acid dye as an alkaline earth metal salt.
- M salt for example, Ca salt
- I. Solvet Y ellow 1 6 3 (C.I .5 8 8 4 0) and C.I.Pigment Y ellow 1 4 7 (C.I .6 0 6 4 5) is an anthraquinone yellow dye
- C.I.Solvent Green 3 (C.I.6 1 5 6 5) is an anthraquinone green dye
- C.I.Solvent V iolet 1 3 (C.I.6 0 7 2 5) is an anthraquinone purple dye
- C.I.Solvent B 1 ue 9 7 (C.I .6 1 5 2 9 0) is an anthraquinone blue dye
- C.I.Solvent R ed 2 2 (C I. 2 1 2 5 0) indicates a disazo red dye.
- Examples 1 to 8 and Comparative Examples 1 to 5 are examples in which a polyethylene welded resin is used to manufacture a laser welded body to which the present invention is applied with the same size and shape. (Example 1)
- Polyphenylene sulfide resin ⁇ 4 0 0 g (Product name: 0 2 2 0 A 9 Melt viscosity: 3 5 0 Pa ⁇ s)
- the above blend was placed in a stainless steel tumbler and mixed with stirring for 1 hour.
- the injection mixture product name: S i — 50
- the mixture obtained was obtained in a normal manner at a cylinder temperature of 3 20 ° C and a mold temperature of 1400 ° C.
- the plate is 60 mm long, 18 mm wide, 3 mm thick, 20 mm long at one end of its long edge, and a step 4 with a thickness of 1.5 mm.
- a uniform blue laser light transmitting member 1 with good appearance and surface gloss and no color unevenness was obtained.
- polyphenylene sulfide resin (trade name: 0 220 A 9) manufactured by Polyplastics Co., Ltd. 1 O O O g and 5 g of carbon black were placed in a stainless steel tumbler and mixed with stirring for 1 hour.
- the injection molding machine (trade name: S i — 50) manufactured by Toyo Kikai Kogyo Co., Ltd.
- the mixture obtained was obtained in a normal manner at a cylinder temperature of 320 ° C and a mold temperature of 140 ° C.
- 60 mm long x 18 mm wide x 3 mm thick, 20 mm long at one end of the long side is missing on the top surface, and has a step 5 with a thickness of 1.5 mm.
- a uniform black laser light-absorbing member 2 with good appearance and surface gloss and no color unevenness was obtained.
- the laser light transmitting member and laser welded body obtained in Example 1 were evaluated for physical properties by the following methods.
- a laser light transmissive member on a spectrophotometer (trade name: V-5570, manufactured by JASCO Corporation), and the thickness of the laser light transmissive member 1 shown in Fig. 1 is 1.5 mm.
- Table 3 shows the transmittance of the semiconductor laser light used at a wavelength of 940 nm for the laser light transmissive member.
- Example 1 In the injection molding of Example 1 above, after performing a normal shot 1 with the mixture of the blend, the remaining mixture was retained for 15 minutes at a cylinder temperature of 320 ° C at that time, and then injection molding was performed. A laser light transmitting member was obtained.
- the color difference ( ⁇ E) between the laser light transmissive member obtained by staying in a cylinder for 15 minutes and the laser light transmissive member obtained in a normal shot is a color difference meter (J UK I product name) : JP 7 0 0 0) Measured, and if the color difference ( ⁇ E) is 1.0 or less, it was judged to be heat resistant.
- the laser light transmitting member obtained by the injection molding of Example 1 was left for 1 month in an open set at 190 ° C.
- Laser after one month Measure the difference ( ⁇ ⁇ ) between the light transmissive member and the laser light transmissive member newly obtained in the normal shot, and if the color difference ( ⁇ ⁇ ) is 1.0 or less, the thermal stability is Judged that there was.
- PET film A white polyethylene terephthalate (PET) film is affixed to the laser light transmissive member, placed in an oven and left at 160 ° C for 3 hours, and then the PET film is peeled off from the laser light transmissive member. It was pasted on a colorless and transparent overhead projector (OHP) sheet for easy observation. If the PET film had little coloration, it was judged to be sublimation resistant.
- OHP overhead projector
- a tensile tester (trade name: AG—50 k NE manufactured by Shimadzu Corporation) A tensile test was conducted in the longitudinal direction (direction in which the welded part was pulled away) at a test speed of 10 mm / min, and the tensile weld strength was measured.
- Example 1 the same procedure as in Example 1 was used except that the product of Production Example 2 was used instead of Production Example 1. Uniform blue laser light transmission with good appearance and surface gloss and no color unevenness Member 1 was obtained.
- Example 1 a black laser light absorbing member 2 and a laser welded body as shown in FIG. 1 were obtained in the same manner as in Example 1. In addition, physical properties of the obtained product were evaluated in the same manner as in Example 1.
- the above blend was placed in a stainless steel tumbler and stirred and mixed for 1 hour.
- the obtained mixture was converted into a single screw extruder (manufactured by Engineering Plastics Co., Ltd. SV) was used and melt mixed at a cylinder temperature of 320 ° C. Thereafter, it was cooled in a water tank, then cut with a pelletizer, and after a drying process, a black master patch with a colorant concentration of 10% by weight was obtained.
- Polyphenylene sulfide resin ⁇ ⁇ ⁇ 4 7 5 g (Polyplastics product name: 0 2 2 0 A 9)
- polyphenylene sulfide resin (trade name: 0 2 20 A 9) manufactured by Polyplastics Co., Ltd. was placed in a stainless steel tumbler and stirred and mixed for 1 hour.
- the injection molding machine (trade name: S i — 50) manufactured by Toyo Kikai Kogyo Co., Ltd.
- the resulting mixture was molded according to the molding conditions of a cylinder temperature of 260 ° C and a mold temperature of 80 ° C.
- the length is 6 O mm x width 18 mm x thickness 3 mm, and the length of one end of the long 20 mm is cut off on the top surface and injected into a plate with a step 5 of thickness 1.5 mm. Molding was performed to obtain a laser light absorbing member 2.
- a laser welded body was obtained in the same manner as in Example 1 (11 c).
- physical properties of the obtained product were evaluated in the same manner as in Example 1.
- Example 4 Fabrication of laser light transmissive member
- Production Example 4 was used instead of Production Example 1, it was carried out in the same manner as Example 1 ', and a uniform blue laser light transmitting member having good appearance and surface gloss and no color unevenness 1 was obtained.
- Example 1 a black laser light absorbing member 2 and a laser welded body as shown in FIG. 1 were obtained in the same manner as in Example 1. In addition, physical properties of the obtained product were evaluated in the same manner as in Example 1.
- Polyphenylene sulfide resin ⁇ 4 0 0 g (Product name: 0 2 2 0 A 9 Melt viscosity: 3 5 0 Pa ⁇ s)
- the above blend was placed in a stainless steel tumbler and mixed with stirring for 1 hour.
- the injection mixture product name: S i — 50
- the mixture obtained was obtained in a normal manner at a cylinder temperature of 3 20 ° C and a mold temperature of 1400 ° C.
- the length is 60 mm x width 18 mm x thickness 3 mm
- the length of one end of 20 mm is missing on the bottom surface, and has a step 4 with a thickness of 1.5 mm.
- a laser light absorbing film layer was prepared as follows. Polypropylene 'pyrene resin 4 0 0 g (Nippon Polychem brand name: BC 0 5 B) and carbon black 0.8 g (Mitsubishi Chemical brand name: S i — 50) make cylinder temperature 2 A laser light-absorbing resin film layer 8 containing carbon black was obtained by an ordinary method of 20 ° C. and a mold temperature of 40 ° C.
- a laser light-absorbing film layer 8 is sandwiched between the obtained two laser light-transmissive members 1 and 7, and the laser light 3 is irradiated by the same irradiation method as in Example 1. Then, a laser welded body of the laser light transmissive member 1 and the laser light transmissive member 2 composed of the laser light transmissive member 7 and the laser light absorbent film layer 8 was obtained. In addition, physical properties of the obtained product were evaluated in the same manner as in Example 1.
- Polyphenylene sulfide resin ⁇ 4 0 0 g (Product name: 0 2 2 0 A 9 Melt viscosity: 3 5 0 Pa ⁇ s)
- the above blend was placed in a stainless steel tumbler and stirred and mixed for 1 hour.
- the injection mixture (trade name: S i — 50) manufactured by Toyo Kikai Co., Ltd.
- the resulting mixture was drawn in the usual manner at a cylinder temperature of 3 20 and a mold temperature of 1400 ° C.
- the plate has a height of 6 O mm x width of 18 mm x thickness of 3 mm, a length of 20 mm at one end of the length is cut off at the bottom, and a step of 1.5 mm in thickness.
- a uniform blue laser light transmitting member 1 having good appearance and surface gloss and no color unevenness was obtained.
- an ink marking pen ink having a laser light absorbent as a laser light absorbing ink was prepared as follows.
- Nigguchi Shin Base E X (Product name C. Solvent Black 7 manufactured by Orient Kogyo Co., Ltd.)
- Ink was prepared by uniformly mixing and dissolving the above formulation at 40 ° C. This ink was packed in a commercially available marking pen.
- a laser light absorbing ink is applied on the step of the laser light transmitting member 7 with this pen, and an ink coating layer 9 is attached on the laser light transmitting member 7.
- a laser light absorbing member 2 comprising a laser light transmitting member 7 and an ink coating layer 9 was obtained.
- the other laser one light-transmitting member 1 is overlaid on the ink-coated layer 9, and laser light is irradiated from both sides of these parts 1 and 7 by the same irradiation method as in Example 1.
- a laser welded body of member 1 and laser light absorbing member 2 was obtained.
- physical properties of the obtained product were evaluated in the same manner as in Example 1.
- Example 3 the same procedure as in Example 3 was used except that Production Example 7 was used instead of Production Example 3. Uniform black with good appearance and surface gloss and no color unevenness. A colored laser light transmissive member 1 was obtained.
- Example 1 a black laser light absorbing member 2 and a laser welded body as shown in FIG. 1 were obtained in the same manner as in Example 1. In addition, physical properties of the obtained product were evaluated in the same manner as in Example 1.
- Example 3 the same procedure as in Example 3 was used except that Production Example 10 was used in place of Production Example 3. Uniform black laser light transmitting member with good appearance and surface gloss and no color unevenness 1 was gotten.
- Example 1 a black laser light absorbing member 2 and a laser welded body as shown in FIG. 1 were obtained in the same manner as in Example 1. In addition, physical properties of the obtained product were evaluated in the same manner as in Example 1.
- a black laser light absorbing member 2 and a laser welded body as shown in FIG. 1 were obtained in the same manner as in Example 1.
- physical properties of the obtained product were evaluated in the same manner as in Example 1.
- a blue laser light transmitting member 1 was obtained in the same manner as in Comparative Example 1 except that Comparative Production Example 2 was used instead of Comparative Production Example 1 in Comparative Example 1.
- a black laser light absorbing member 2 and a laser welded body as shown in FIG. 1 were obtained in the same manner as in Example 1.
- physical properties of the obtained product were evaluated in the same manner as in Example 1.
- amber laser light absorbing member 2 and the laser welded body as shown in FIG. 1 were obtained in the same manner as in Example 1.
- physical properties of the obtained product were evaluated in the same manner as in Example 1.
- Comparative Example 1 was carried out in the same manner as in Comparative Example 1 except that Comparative Production Example 4 was used instead of Comparative Production Example 1, and a blue laser light transmitting member 1 was obtained.
- Example 1 a black laser light absorbing member 2 and a laser welded body as shown in FIG. 1 were obtained in the same manner as in Example 1. In addition, physical properties of the obtained product were evaluated in the same manner as in Example 1.
- a black laser light transmitting member 1 was obtained in the same manner as in Example 3 except that Comparative Production Example 5 was used instead of Production Example 3 in Example 3.
- Example 1 a black laser light absorbing member 2 and a laser welded body as shown in FIG. 1 were obtained in the same manner as in Example 1. In addition, the physical properties of these were evaluated in the same manner as in Example 1.
- Examples 9 to 10 are examples in which a laser welded body to which the present invention is applied is manufactured with the same size and shape using a polybutylene terephthalate resin.
- the above blend was placed in a stainless steel tumbler and mixed with stirring for 1 hour.
- the resulting mixture is shown in Fig. 1 by an ordinary method using an injection molding machine (trade name: S i — 50) manufactured by Toyo Machine Metal Co., Ltd. at a cylinder temperature of 26 Ot and a mold temperature of 80 ° C.
- S i — 50 injection molding machine manufactured by Toyo Machine Metal Co., Ltd.
- a cylinder temperature of 26 Ot and a mold temperature of 80 ° C.
- it is injection molded into a plate with a height difference of 1.5 mm, with a length of 6 O mm x width of 18 mm x thickness of 3 mm, and a length of 20 mm at one end of the length is cut off at the bottom.
- a uniform green laser light transmitting member 1 with good appearance and surface gloss and no color unevenness was obtained.
- the polyphenylene sulfide resin used in Example 1 (trade name: 5 0 0 8 AS manufactured by Mitsubishi Engineering Plastics) ) Instead of poly (butylene terephthalate) resin, depending on the molding conditions of a cylinder temperature of 2600 ° C and a mold temperature of 80 ° C, as shown in Fig. 1, length 60 mm x width 1 8 mmX thickness 3 mm, 2 O mm at one end of the long part is chipped on the top surface and injection molded into a plate with a step 5 with a thickness of 1.5 mm to obtain a laser light-absorbing member 2 It was. Further, a laser welded body was obtained in the same manner as in Example 1 (11 c). In addition, physical properties of the obtained product were evaluated in the same manner as in Example 1.
- Example 9 the same procedure as in Example 9 was used except that Production Example 7 was used instead of Production Example 6, and a uniform black laser light transmitting member with good appearance and surface gloss and no color unevenness 1 was gotten.
- a laser light-absorbing member and a laser welded body were prepared in the same manner as in Example 9. Obtained. In addition, physical properties of the obtained product were evaluated in the same manner as in Example 1. '
- Examples 11 and 12 are examples in which a polyamide 6 resin was used and a laser-welded body to which the present invention was applied was manufactured with the same size and shape.
- the above blend was placed in a stainless steel tumbler and stirred and mixed for 1 hour.
- the injection mixture (trade name: S i — 50) manufactured by Toyo Kikai Kogyo Co., Ltd.
- the mixture obtained was obtained in the usual manner at a cylinder temperature of 2700 ° C and a mold temperature of 80 ° C.
- the length is 60 mm x width l 8 mm x thickness 3 mm, and 20 mm length at one end of the long part is cut off at the bottom, and it is injected into a plate with a step 4 of thickness 1.5 mm.
- a uniform green laser light transmitting member 1 having good appearance and surface gloss and no color unevenness was obtained.
- Example 1 For the black laser light absorbing member 2 and the laser welded body as shown in FIG. 1, instead of the polyphenylene sulfide resin used in Example 1, a polyamide 6 resin (trade name, manufactured by Ube Industries, Ltd.) : 1 0 1 5 GU 9), using the usual method at a cylinder temperature of 2700 ° C and a mold temperature of 80 ° C as in Example 1, as shown in Fig. 1. 18 mm wide x 3 mm thick, 20 mm long at its long end is cut off on the top surface and injection molded into a plate with a step of 5 mm with a thickness of 1.5 mm. Obtained. Furthermore, the laser welding conditions have been partially changed to a scanning speed of 10 mmZ sec. A laser welded body was obtained in the same manner as (1 c) in Example 1 except for the above. In addition, physical properties of the obtained product were evaluated in the same manner as in Example 1.
- a polyamide 6 resin (trade name, manufactured by Ube Industries, Ltd.) : 1 0 1 5
- Example 1 In Example 1, except that Production Example 7 was used instead of Production Example 6, the same procedure as in Example 1 1 was performed. Uniform black laser light transmitting member with good appearance and surface gloss and no color unevenness 1 was gotten. "
- a laser light absorbing member and a laser welded body were obtained in the same manner as in Example 11.
- physical properties of the obtained product were evaluated in the same manner as in Example 1. '.
- Examples 13 to 14 are examples in which a polyacetal resin is used and a laser welded body to which the present invention is applied is manufactured in the same size and shape.
- Polyacetal resin ⁇ 4 0 0 g (Product name: Diyuracon M9 0—44, manufactured by Polyplastics)
- the length is 60 mm x 18 mm x width. Thickness of 3 mm, 20 mm length of one long end was cut off on the top surface and injection molded into a plate shape with a step 5 of 1.5 mm thickness to obtain a laser single light absorbing member 2 . Further, a laser weld was obtained in the same manner as in (1 c) of Example 1 except that the laser welding conditions were partially changed to 8 mm / sec. In addition, physical properties of the obtained product were evaluated in the same manner as in Example 1.
- Polyacetal fat and oil g o O g (trade name: Diyuracon M 90-44, manufactured by Polyplastics Co., Ltd.)
- the above blend was placed in a stainless steel tumbler and mixed with stirring for 1 hour.
- the obtained mixture was melt-mixed at a cylinder temperature of 230 ° C. using a single screw extruder (product number: E 30 S V, manufactured by Engineering Plastics Industries). Thereafter, the mixture was cooled in a water tank, then cut with a pelletizer, and after a drying process, a black masterbatch with a colorant concentration of 10% by weight was obtained.
- Polyacetal resin ⁇ 4 7 5 g (Product name: Diyuracon M 9 0—44, manufactured by Polyplastics Co., Ltd.)
- Black master patch ... 2 5 g The above blend was placed in a stainless steel tumbler and mixed with stirring for 1 hour.
- the obtained mixture was obtained by a conventional method using an injection molding machine (trade name: S i — 50) manufactured by Toyo Machine Metal Co., Ltd. at a cylinder temperature of 230 ° C and a mold temperature of 70 ° C. Similar to Example 13, when injection-molded into a shape as shown in FIG. 1, uniform black laser light transmitting member 1 having good appearance and surface gloss and no color unevenness was obtained.
- a laser light absorbing member and a laser welded body were obtained in the same manner as in Example 1 3.
- physical properties of the obtained product were evaluated in the same manner as in Example 1. ' ⁇ .
- Examples 15 to 16 are examples in which a polysulfone resin was used and a laser-one welded body to which the present invention was applied was manufactured with the same size and shape.
- Polysulfone resin ⁇ 4 0 0 g (Product name: Udel P— 1700 0 NT 1 1)
- the above blend was placed in a stainless steel tumbler and mixed with stirring for 1 hour.
- the injection mixture (trade name: S i — 50) manufactured by Toyo Machine Metal Co., Ltd.
- the resulting mixture was processed at a cylinder temperature of 3400 ° C and a mold temperature of 1550 in the usual manner. As shown in Fig. 1, it is 60 mm long x 18 mm wide x 3 mm thick, with a length of 20 mm cut off at the bottom and with a step of 4 mm with a thickness of 1.5 mm.
- a uniform blue laser light transmitting member 1 having good appearance and surface gloss and no color unevenness was obtained.
- Polysulfone resin ⁇ 9 00 g (Product name: Udel P— 1 700 NT 1 1)
- the above blend was placed in a stainless steel tumbler and mixed with stirring for 1 hour.
- the obtained mixture was melt-mixed at a cylinder temperature of 340 ° C. using a single screw extruder (Product Number: E 30 S V, manufactured by Engineering Plastics Industries). Thereafter, the mixture was cooled in a water tank, then cut with a pelletizer, and after a drying process, a black masterbatch with a colorant concentration of 10% by weight was obtained.
- Polysulfone resin ⁇ 4 90 g (Product name: Udel P— 1 700 NT 1 1)
- a laser light absorbing member and a laser welded body were obtained in the same manner as in Example 15. In addition, physical properties of the obtained product were evaluated in the same manner as in Example 1.
- Examples 1 to 20 and Comparative Examples 6 to 7 are examples in which a polyether welded resin is used and a laser welded body to which the present invention is applied is manufactured in the same size and shape.
- Polyethersulfone resin ⁇ ⁇ 4 0 0 g (Product name: Radel A— 3 0 0 AN T)
- the above blend was placed in a stainless steel tumbler and mixed with stirring for 1 hour.
- the injection mixture (trade name: S i — 50) manufactured by Toyo Machine Metal Co., Ltd.
- the resulting mixture was subjected to the usual method at a cylinder temperature of 3 60 3 ⁇ 4 and a mold temperature of 1550 ° C.
- the plate has a height difference of 60 mm x width 18 mm x thickness 3 mm, with a height of 1.5 mm and a length of 20 mm.
- a uniform blue laser light transmitting member 1 with good appearance and surface gloss and no color unevenness was obtained.
- polyestersulfone resin Solvey Advanced Polymer
- the product name: Radel A—300 ANt was used in the same manner as in Example 1, but at a cylinder temperature of 3600 ° C and a mold temperature of 1550.
- laser A light absorbing member 2 was obtained.
- a laser welded body was obtained in the same manner as (1-c) of Example 1 except that the laser welding conditions were partially changed to 50 mm / sec.
- physical properties of the obtained product were evaluated in the same manner as in Example 1.
- Example 17 the same procedure as in Example 17 except that Production Example 1 1 was used instead of Production Example 9 was achieved. Uniform black laser light transmission with good appearance and surface gloss and no color unevenness Member 1 was obtained.
- Example 17 In the same manner as in Example 17, a laser light absorbing member and a laser welded body were obtained. In addition, physical properties of the obtained product were evaluated in the same manner as in Example 1.
- Example 1 7 was carried out in the same manner as Example 1 7 except that Production Example 8 was used instead of Production Example 9, and the appearance and surface gloss were uniform and there was no uneven color. A blue laser light transmissive member 1 was obtained.
- Example 17 In the same manner as in Example 17, a laser light absorbing member and a laser welded body were obtained. Also, for those obtained was lines evaluation of physical properties in the same manner as in Example 1 0
- Example 17 In Example 7 except that Example 10 was used in place of Preparation Example 9, the same procedure as in Example 1 7 was performed, and a uniform black laser light transmitting member having good appearance and surface gloss and no color unevenness 1 'was obtained.
- Example 17 In the same manner as in Example 17, a laser light absorbing member and a laser welded body were obtained. Also, for those obtained, line evaluation of physical properties in the same manner as in Example 1 ivy 0
- Polyethersulfone oil ⁇ ⁇ ⁇ ⁇ 400 g (Product name: Radel A—300 ANT)
- Example 17 For the black laser light absorbing member 2 and the laser welded body as shown in FIG. 1, a laser light absorbing member and a laser welded body were obtained in the same manner as in Example 17. In addition, physical properties of the obtained product were evaluated in the same manner as in Example 1.
- Comparative Example 6 a blue laser light transmitting member 1 was obtained in the same manner as Comparative Example 6 except that Comparative Production Example 7 was used instead of Comparative Production Example 6.
- Example 17 a laser light absorbing member and a laser welded body were obtained in the same manner as in Example 17. In addition, physical properties of the obtained product were evaluated in the same manner as in Example 1.
- Tables 3 and 4 show the results of the physical property evaluation of the laser light transmitting members and laser welds obtained in Examples 1 to 20 and Comparative Examples 1 to 7, respectively.
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Abstract
Description
Claims
Priority Applications (3)
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KR1020077017374A KR101156586B1 (ko) | 2005-02-09 | 2006-02-07 | 안트라퀴논계 산성 염료의 알칼리 토금속염을 함유하는레이저광 투과성 부재의 레이저 용착체 |
EP06713571A EP1847375B1 (en) | 2005-02-09 | 2006-02-07 | Laser welded material of laser beam permeable member containing alkaline earth metal salt of anthraquinone acid dye |
JP2006519679A JP3928734B2 (ja) | 2005-02-09 | 2006-02-07 | アントラキノン系酸性染料のアルカリ土類金属塩を含有するレーザー光透過性部材のレーザー溶着体 |
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JP2005-033648 | 2005-02-09 | ||
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US (1) | US7713607B2 (ja) |
EP (1) | EP1847375B1 (ja) |
JP (1) | JP3928734B2 (ja) |
KR (1) | KR101156586B1 (ja) |
CN (1) | CN100551677C (ja) |
WO (1) | WO2006085643A1 (ja) |
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JP4176986B2 (ja) | 2000-11-13 | 2008-11-05 | オリヱント化学工業株式会社 | レーザー光透過性黒色樹脂組成物及びレーザー光透過材形成用黒色樹脂組成物 |
EP1399506A1 (en) * | 2001-05-14 | 2004-03-24 | Ciba SC Holding AG | New pigmentary compositions |
JP2004155888A (ja) * | 2002-11-06 | 2004-06-03 | Orient Chem Ind Ltd | レーザー光透過性着色熱可塑性樹脂組成物及びレーザー溶着方法 |
JP4446706B2 (ja) * | 2002-11-06 | 2010-04-07 | オリヱント化学工業株式会社 | レーザー光透過性着色熱可塑性樹脂組成物及びレーザー溶着方法 |
US20050003301A1 (en) * | 2003-01-29 | 2005-01-06 | Orient Chemical Industries, Ltd. | Laser ray transmitting colored thermoplastic resin composition and method of laser welding |
JP2006152007A (ja) | 2003-01-29 | 2006-06-15 | Orient Chem Ind Ltd | レーザー光透過性着色熱可塑性樹脂組成物及びレーザー溶着方法 |
EP1533105A1 (en) * | 2003-10-15 | 2005-05-25 | Orient Chemical Industries, Ltd. | Laser-transmissible colored resin composition and method for laser welding |
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2006
- 2006-02-07 WO PCT/JP2006/302429 patent/WO2006085643A1/ja active Application Filing
- 2006-02-07 EP EP06713571A patent/EP1847375B1/en active Active
- 2006-02-07 JP JP2006519679A patent/JP3928734B2/ja active Active
- 2006-02-07 US US11/794,122 patent/US7713607B2/en active Active
- 2006-02-07 KR KR1020077017374A patent/KR101156586B1/ko active IP Right Grant
- 2006-02-07 CN CNB200680004091XA patent/CN100551677C/zh not_active Expired - Fee Related
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JP2002228830A (ja) * | 2000-11-13 | 2002-08-14 | Orient Chem Ind Ltd | レーザー光透過性着色樹脂組成物用着色剤及びその関連技術 |
WO2004072175A1 (ja) * | 2003-02-13 | 2004-08-26 | Orient Chemical Industries, Ltd. | レーザー光透過性着色ポリオレフィン系樹脂組成物及びレーザー溶着方法 |
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Cited By (10)
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JP2008155519A (ja) * | 2006-12-25 | 2008-07-10 | Hamamatsu Photonics Kk | レーザ溶着方法、レーザ溶着装置、レーザ包装方法、レーザ包装装置及び樹脂フィルム包装製品の製造方法 |
EP2047970A2 (fr) * | 2007-10-10 | 2009-04-15 | Alstom Transport S.A. | Procédé de soudage de deux éléments en matériau polymère opaques et résistants à haute température |
FR2922149A1 (fr) * | 2007-10-10 | 2009-04-17 | Alstom Transport Sa | Procede de soudage de deux elements en materiau polymere opaques et resistant a haute temperature |
EP2047970A3 (fr) * | 2007-10-10 | 2014-05-28 | ALSTOM Transport SA | Procédé de soudage de deux éléments en matériau polymère opaques et résistants à haute température |
JP2014507539A (ja) * | 2011-03-07 | 2014-03-27 | ビーエーエスエフ ソシエタス・ヨーロピア | レーザー透過性のポリエステル |
JP2013052683A (ja) * | 2012-10-22 | 2013-03-21 | Hamamatsu Photonics Kk | レーザ包装方法及び樹脂フィルム包装製品の製造方法 |
JP2021507962A (ja) * | 2017-12-18 | 2021-02-25 | ビーエイエスエフ・ソシエタス・エウロパエアBasf Se | 光学特性が改善されたポリアミド成形用組成物及びその中に着色剤を使用する方法 |
JP7317829B2 (ja) | 2017-12-18 | 2023-07-31 | ビーエーエスエフ ソシエタス・ヨーロピア | 光学特性が改善されたポリアミド成形用組成物及びその中に着色剤を使用する方法 |
US20210370614A1 (en) * | 2018-10-22 | 2021-12-02 | Solvay Specialty Polymers Usa, Llc | Polyphenylene sulfide polymer compositions and corresponding laser welding applications |
US11794417B2 (en) * | 2018-10-22 | 2023-10-24 | Solvay Specialty Polymers Usa, Llc | Polyphenylene sulfide polymer compositions and corresponding laser welding applications |
Also Published As
Publication number | Publication date |
---|---|
US7713607B2 (en) | 2010-05-11 |
KR101156586B1 (ko) | 2012-06-20 |
US20070292651A1 (en) | 2007-12-20 |
CN101119838A (zh) | 2008-02-06 |
JP3928734B2 (ja) | 2007-06-13 |
EP1847375B1 (en) | 2012-06-27 |
EP1847375A4 (en) | 2011-07-06 |
JPWO2006085643A1 (ja) | 2008-06-26 |
EP1847375A1 (en) | 2007-10-24 |
CN100551677C (zh) | 2009-10-21 |
KR20070108164A (ko) | 2007-11-08 |
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