JP5042459B2 - Laser light transmitting composition and laser welding method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a laser-transmissible composition for forming a laser-transmissible molded workpiece that contains a dynamic crosslinking polyolefin thermoplastic elastomer colored distinctly and does not discolor and does not bleed through a heat treatment process such as injection-molding, and also to provide a method for laser welding of the molded workpiece with sufficient tensible strength and prettiness by efficient energy. <P>SOLUTION: The laser-transmissible composition comprises the dynamic crosslinking polyolefin thermoplastic elastomer that has a melting point ranging from 160-210&deg;C in case of non-coloring, and a dye salt exhibiting transmission of a laser having a wavelength of 800-1,200 nm. The method for laser welding comprises putting the laser-transmissible molded workpiece 1 made from the laser-transmissible composition onto a laser-absorptive molded workpiece 2 having a laser-absorbent 7, irradiating laser 3 towards the laser-transmissible molded workpiece 1 to weld the laser-transmissible molded workpiece 1 and the laser-absorptive molded workpiece 2. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention is used to mold a laser light-transmitting molded article, and contains a laser light-transmitting composition containing a dynamically cross-linked polyolefin-based thermoplastic elastomer, and a molded article molded therewith by laser welding. It is about the method.

  A thermoplastic elastomer is a synthetic polymer material having the properties of a plastic such as a thermoplastic resin that softens at high temperatures and the properties of rubber that exhibits elasticity at room temperature. Thermoplastic elastomers are injection-molded in the same way as thermoplastic resins to form molded products of various shapes, and because of their excellent productivity and recyclability, they can be used in a wide range of fields such as the automobile industry and electrical / electronic industry. Therefore, it is widely used as a material of a molded body that plays an intermediate role between plastic and rubber of a thermoplastic resin.

  Thermoplastic elastomer mainly contains rubber components such as styrene-butadiene copolymer rubber (SBR), ethylene-propylene-diene-methylene copolymer (EPDM), and acrylonitrile-butadiene copolymer rubber (NBR) as a soft segment. Furthermore, a thermoplastic plastic component such as polyolefin, polystyrene, polyvinyl chloride, polyester, polyamide or polyurethane is included as a hard segment.

  Among them, polyolefin-based thermoplastic elastomers (TPO) are most frequently used as molding materials because of their low cost and excellent physical properties such as tensile strength, elongation at break and permanent elongation. Polyolefin thermoplastic elastomer consists of a plastic component such as a thermoplastic resin such as polypropylene or polyethylene and a rubber component such as a polyolefin, and is prepared by simply blending, polymerizing, or crosslinking. Is.

  One method of joining molded articles made of thermoplastic resin such as polypropylene is laser welding. For example, as described in Patent Document 1, laser welding is performed by bringing a laser-light-transmitting molded body made of a thermoplastic resin into contact with a laser-light-absorbing formed body made of a thermoplastic resin, and applying laser light to the laser beam. By irradiating and transmitting from the side of the permeable molded body, reaching the absorbent molded body and absorbing it, heat is generated, and the contact portions of both molded bodies are thermally melted and welded. In order to perform laser welding with sufficient strength, the laser beam transmittance of the transmissive molded body must be high so that a sufficient amount of laser beam can be transmitted to generate heat.

JP-A-11-170371

  However, since polyolefin-based thermoplastic elastomers are modified by blending, polymerization, or crosslinking, the laser light transmittance tends to be lower than thermoplastic resins with good laser light transmittance, such as polypropylene and polyamide. It is. Furthermore, since the polyolefin-based thermoplastic elastomer gradually yellows due to oxidation or deterioration, it needs to be colored in advance with a pigment as a colorant in order to make it inconspicuous or cleanly color-coded. For this reason, because of this pigment that significantly impairs the laser beam transmission, such a composition has a lower laser beam transmission. As a result, there is a problem in that even if such a polyolefin-based thermoplastic elastomer permeable molded body is laser-welded, it cannot be welded with sufficient strength as when a thermoplastic resin-made laser light transmissive molded body is used. there were. In addition, if a laser beam with a considerably strong output is applied to compensate for the low laser beam transmittance, and a sufficient amount of laser beam is transmitted to attempt laser welding, the surface of the molded body is overheated and deteriorated. May occur or the smoothness may be impaired. On the other hand, in place of a pigment as a colorant, a laser light-transmitting molded product made of a polyolefin-based thermoplastic elastomer colored with a known oil-soluble dye that does not significantly impair laser light transmission tends to fade during molding and welding. Furthermore, if the welded material is left under high temperature and high humidity, the bleed (migration) of the dye from the laser light-transmitting molded product to the laser light-absorbing molded product made of thermoplastic resin or polyolefin-based thermoplastic elastomer becomes remarkable. It will end up ruining the beauty.

  The present invention has been made in order to solve the above-mentioned problems, and the dynamically crosslinked polyolefin-based thermoplastic elastomer is vividly colored and does not fade even after a heat treatment step such as injection molding or bleed. It is a first object of the present invention to provide a laser light transmitting composition for forming a molded article having no laser light high transmittance. Another object of the present invention is to provide a method for neatly laser-welding a molded article molded with this composition with energy efficiency and sufficient tensile strength.

Was made in order to achieve the above object, a laser welding method according to claim 1 of the claims is dynamically crosslinked polyolefin to the melting temperature during uncolored 16 5.2 ° C. to 210 ° C. An anionic component comprising a thermoplastic elastomer, an acid dye selected from a monoazo acid dye, a disazo acid dye, an anthraquinone acid dye, an anthrapyridone acid dye and a triphenylmethane acid dye, and 1,3-diphenylguanidine, 1-o-tolylguanidine and a guanidine derivative selected from di-o-tolylguanidine and salted with a cation component comprising an organic amine, monoazo salt-forming dye, disazo salt-forming dye, anthraquinone-based dye Selected from salt dyes, anthrapyridone salt-forming dyes, and triphenylmethane acid dyes Is a 0.05 to 2 wt% of the salt forming member colorant which transmits laser light 800~1200nm consists of at least one salt-forming dye, a light transmissive molded with the laser-transmissible composition are contained Molded article, and
0.05 to 5% by weight of the laser light absorber, which is carbon black as a colorant, and a melting temperature of 165.2 ° C. to 210 ° C. when not colored, and an optical density at least 0.1% by weight. A black light-absorbing molded article molded from a laser-light-absorbing composition containing a dynamically crosslinked polyolefin-based thermoplastic elastomer having a molecular weight of 5 or more,
The light-transmitting molded body and the light-absorbing molded body are welded by contacting the light-transmitting molded body with laser light .

The laser light-transmitting composition is prepared by mixing an uncolored dynamic cross-linked polyolefin thermoplastic elastomer having a melting temperature of 160 ° C. to 210 ° C. , preferably 165.2 ° C. to 210 ° C. , and a salt-forming colorant. Prepared. When the laser light transmissive composition is molded, for example, a light transmissive molded body 1 as shown in FIG. 1 is obtained. When the melting temperature is 160 ° C. to 210 ° C. , preferably 165.2 ° C. to 210 ° C. , the colorant is not deteriorated and the dispersibility is good. Therefore, a laser light transmitting composition excellent in appearance and surface gloss is obtained. It has been found that the above problems can be solved.

  Melting temperature is measured in accordance with ISO 1133 test method. Dynamic crosslinkable polyolefin thermoplastic elastomer is set in a flow tester (trade name: CFT-500D, manufactured by Shimadzu Corporation), the load is 5 kgf, the length of the die hole The temperature at which the dynamically cross-linked polyolefin-based thermoplastic elastomer melts is measured at a heating rate of 5 ° C./min in the range from 150 ° C. to 250 ° C. with a diameter of 1 mm and a die hole diameter of 1 mm. Is.

  The melting temperature is calculated by finding one-half of the difference between the end point of the outflow and the lowest point in the flow curve and setting the temperature at that point as the melting temperature (1/2 method).

The laser beam welding method according to claim 2 is such that the carbon black has a primary particle diameter of 18 to 30 nm.
The laser beam welding method according to claim 3 is characterized in that the value of the compressive strain based on JIS K-6262-1997 at 100 ° C. of the dynamically cross-linked polyolefin-based thermoplastic elastomer contained in the light-transmitting molded article. It is 20 to 70%.

The laser welding method according to claim 4 , wherein the wavelength of the laser beam is 840 nm, and the transmittance of the dynamically cross-linked polyolefin-based thermoplastic elastomer contained in the light-transmitting molded article is at least at the wavelength. It is 35%.

Laser-transmissible composition of this, the Zoshiotai colorant, the monoazo salt forming dye, an anionic component comprising disazo acid dye and a cation component composed of an anion component and an organic amine composed of monoazo acid dye The disazo salt-forming dye comprising a cation component comprising an organic amine and an anion component comprising an anion component comprising an anthraquinone acid dye and a cation component comprising an organic amine, and an anion component comprising an anthrapyridone acid dye At least one selected from the anthrapyridone salt-forming dye with a cationic component composed of an organic amine , and the triphenylmethane salt-forming dye composed of an anionic component composed of a triphenylmethane acid dye and a cationic component composed of an organic amine That is the salt-forming dye.

In the laser welding method according to claim 5, the dynamically cross-linked polyolefin-based thermoplastic elastomer contained in the light-transmitting molded body is produced in the presence of a metallocene-based catalyst.

Laser-transmissible composition This Shore hardness of the dynamic crosslinking type polyolefin-based thermoplastic elastomer is that it is 60 to 90 (A).

In the laser welding method according to claim 6 , the dynamically cross-linked polyolefin-based thermoplastic elastomer contained in the light-transmitting molded body is mainly composed of an ethylene / α-olefin copolymer elastomer. is there.

Laser welding method according to claim 7, copolymerization ratio of the ethylene · alpha-olefin copolymer of the body in an elastomer of ethylene and alpha-olefin, the weight ratio 55: 45 to 80: those that are 20 is there.

Moreover, the laser-absorptive composition of this includes a dynamically crosslinked type thermoplastic polyolefin elastomers 16 5.2 ° C. to 210 ° C. The melt temperature during uncolored, that contains a laser absorbent Is.

Laser-absorptive composition of this, the laser-light-absorbing agent, is that it is carbon black.

Laser-absorptive composition of this, the dynamic cross-linked polyolefin thermoplastic elastomer of, is that the main component of ethylene · alpha-olefin copolymer elastomer.

Laser-absorptive composition of this are for example those that talc is contained.

The laser welding method of the present invention will be described with reference to FIG. 1 corresponding to the embodiment. The light transmissive molded body 1 of the laser light transmissive composition according to claim 1 and a laser light absorbent 7. The light-absorbing molded body 2 is brought into contact, and the light-transmitting molded body 1 is irradiated with the laser beam 3 to weld the light-transmitting molded body 1 and the light-absorbing molded body 2. Is. As shown in FIG. 2, the light-transmitting molded body 1 may be laser-welded on both surfaces of the light-absorbing molded body 2.

In the laser welding method according to claim 8 , as shown in FIG. 3, the light-absorbing molded body 2 is formed through the layer 8 containing the laser light-absorbing agent 7 attached thereto. It may be in contact with the body 1.

Laser welding method of this, the light-absorptive molded body 2, Ru der which the dynamic crosslinking type polyolefin-based thermoplastic elastomer and the laser absorbent 7 were molded composition contained.

Les Za welding method, for example the absorptive molded body 2, Ru der which the thermoplastic resin and the laser absorbent were molded composition contained.

Les Za welding method, for example the thermoplastic resin, Ru polypropylene resin der.

Laser welding method of this are talc in the thermoplastic resin is characterized in that it is contained.

In the laser welding method according to claim 9 , the amount of heat K (J / mm ² ) supplied to the surface of the light-absorbing molded body 2 by irradiating the laser beam 3 while scanning is expressed by the following formula ( I)
K = (p × T) / (100 × q × d) ≧ 0.5 (I)
(In the formula (I), p is the output (W) of the laser beam 3, T is the transmittance (%) of the laser beam 3 in the light-transmitting molded body 1, and q is the scanning speed (mm / Sec), d represents the diameter (mm) of the irradiation range of the laser beam 3 on the surface)
It is to satisfy.

The laser welded body according to claim 10 is a dynamically cross-linked polyolefin thermoplastic elastomer having a melting temperature of 165.2 ° C. to 210 ° C. when uncolored, a monoazo acid dye, a disazo acid dye, and an anthraquinone acid dye. An anionic component comprising an acid dye selected from a dye, an anthrapyridone acid dye and a triphenylmethane acid dye, and a guanidine derivative selected from 1,3-diphenylguanidine, 1-o-tolylguanidine and di-o-tolylguanidine It is salted with a cationic component composed of an organic amine, and from monoazo salt forming dyes, disazo salt forming dyes, anthraquinone salt forming dyes, anthrapyridone salt forming dyes, and triphenylmethane acid forming dyes Consisting of at least one salt-forming dye selected from 800 to 1200 nm And 0.05 to 2 wt% of the salt forming member colorant which transmits Za light, and a light transmissive molded body formed by laser-transmissible composition are contained,
When it is in contact with it , 0.05 to 5% by weight of the laser light absorber which is carbon black as a colorant, and when the melting temperature is 165.2 ° C. to 210 ° C. and 0.1% by weight when uncolored And a black light-absorbing molded article molded from a laser-light-absorbing composition containing a dynamically crosslinked polyolefin-based thermoplastic elastomer having an optical density of at least 1.5 or more ,
Laser welding is performed at a site in contact with the laser beam irradiated to the light transmission molded body , transmitted therethrough, and absorbed by the light absorption molded body .

  The laser light transmitting composition of the present invention is obtained by coloring a dynamically crosslinked polyolefin thermoplastic elastomer with a clear hue with a salt-forming colorant. Laser-light-transmitting and laser-welded molded articles molded by heat treatment processes such as injection molding using this composition do not cause hue fading and have high transmittance of laser light in the near-infrared wavelength region. In addition, the non-bleeding property of the salt-forming body colorant to the light-absorbing molded body to be laser welded is excellent. Further, according to the laser welding method of the present invention, it is possible to obtain a beautiful welded product excellent in design without causing discoloration with sufficient tensile strength by laser welding both molded bodies with energy efficiency.

BEST MODE FOR CARRYING OUT THE INVENTION

  Hereinafter, the laser light transmitting composition, the laser light absorbing composition, the laser welding method, and the laser welded body of the present invention will be described in detail.

  Dynamically cross-linked polyolefin-based thermoplastic elastomers are most suitable as molding materials because they are low in cost and have a good balance of performance such as tensile strength, elongation at break and permanent elongation compared to other thermoplastic elastomers. It is an important material.

  The dynamically cross-linked polyolefin-based thermoplastic elastomer preferably contains a hard segment and a soft segment in a weight composition ratio of 20:80 to 50:50, and is prepared, for example, by mixing.

  The dynamically crosslinked polyolefin-based thermoplastic elastomer generally has improved transparency as it becomes in the infrared region. The dynamically crosslinked polyolefin-based thermoplastic elastomer preferably has a laser beam transmittance of at least 35% at a wavelength of 840 nm. When a molded body of a composition containing an elastomer having such a high transmittance is laser welded, it can be firmly welded by irradiation of a relatively weak laser beam, so that energy conversion efficiency is good, laser beam control is easy, and molding is performed. The conditions for industrialization can be set smoothly regardless of the shape of the body. Furthermore, the cost is low, and it is difficult to cause scorching and unevenness on the surface of the molded body, and a practical and sufficient tensile strength is obtained, and a beautiful welded product with a conspicuous welded portion is obtained.

  Examples of the hard segment of the dynamically cross-linked polyolefin-based thermoplastic elastomer include plastic components that are thermoplastic resins such as polypropylene and polyethylene (low density polyethylene, linear polyethylene, high density polyethylene).

  As a soft segment of dynamically cross-linked polyolefin thermoplastic elastomer, ethylene-propylene-diene-methylene copolymer (EPDM), ethylene-propylene copolymer (EPM), ethylene-butene rubber (EBM), acrylonitrile-butadiene copolymer Combined rubber (NBR), acrylic rubber (ACM), ethylene-vinyl acetate copolymer (EVA), chlorinated polyethylene elastomer (CPE), epichlorohydrin rubber (ECO), natural rubber (NR), butyl rubber, metallocene catalyst, etc. Examples thereof include rubber components such as an ethylene / α-olefin copolymer elastomer (rubber) synthesized using a single site catalyst or the like, and other copolymer elastomers (rubber).

  Among the above examples, the soft segment is preferably an ethylene / α-olefin copolymer elastomer. The ethylene / α-olefin copolymer elastomer is, for example, a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. Examples of the α-olefin having 3 to 20 carbon atoms include propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, heptene-1, octene-1, nonene-1, decene-1, Examples include undecene-1 and dodecene-1. Of these, hexene-1, 4-methylpentene-1, and octene-1 are preferable. Octene-1 is more preferable because it is excellent in the effect of softening even in a small amount, and the copolymer obtained therefrom is excellent in mechanical strength.

  Dynamically cross-linked polyolefin-based thermoplastic elastomers are classified into three types: polymerized, partially cross-linked, and high-density cross-linked. Since the physical properties such as elasticity are different for each type, they can be used according to the application.

  Preferable examples include “TPV A6110”, “TPV A9110”, “TPV A8120”, and “TPV B8130” manufactured by Asahi Kasei Chemicals, which are metallocene catalyst-based dynamically crosslinked polyolefin thermoplastic elastomers, and polyethylene and ethylene-propylene-diene-methylene. “Milastomer soft” and “Miralastomer hard” manufactured by Mitsui Chemicals, Inc., which are dynamically cross-linked polyolefin-based thermoplastic elastomers with a copolymer (EPDM).

  Among these, the cross-linked polyolefin-based thermoplastic elastomer is preferably an ethylene / α-olefin copolymer elastomer produced in the presence of a single site catalyst such as a metallocene catalyst.

  The metallocene catalyst is a highly active single site catalyst with uniform active species. This catalyst can be appropriately activated by precisely designing the structure of the catalyst. When this catalyst is used, copolymerization with cyclic olefins such as α-olefins and higher olefins can proceed more easily than Ziegler-Natta catalysts, the molecular weight distribution of the copolymer is narrow, and it is a comonomer in the copolymer. An ethylene / α-olefin copolymer elastomer having a uniform distribution of C 3-20 α-olefin and a low content of low molecular weight components can be obtained. A cross-linked polyolefin-based thermoplastic elastomer prepared using the same has uniform cross-linking and exhibits excellent rubber elasticity.

  An ethylene / α-olefin copolymer produced as a highly random copolymer using a metallocene catalyst in a cross-linked polyolefin-based thermoplastic elastomer and having high permeability in the near infrared region necessary for laser welding More preferably, the elastomer is a main component and contains at least 50% by weight.

  The dynamically cross-linked polyolefin-based thermoplastic elastomer is formed by performing a vulcanization (cross-linking) reaction simultaneously with physical mixing in a kneading machine such as a Banbury mixer or a biaxial kneader in a short time. The cross-linking reaction includes a case where the cross-linking reaction is performed only on the soft segment and a case where the soft segment and the hard segment are cross-linked. Examples of the crosslinking agent used therefor include organic peroxides, phenol resin compounds, quinoid compounds, sulfur compounds, bismaleimide compounds, and the like. By such a method, a dynamically cross-linked polyolefin-based thermoplastic elastomer is prepared. The dynamically cross-linked polyolefin-based thermoplastic elastomer is preferably produced with a cross-linking time (Tc90), which is an index of cross-linking speed, of 400 seconds or shorter, and more preferably 300 seconds or shorter.

  The dynamically crosslinked polyolefin-based thermoplastic elastomer is an elastomer alloy having a stable microphase separation state in which a crosslinking agent is present at the interface between them. This dynamically cross-linked polyolefin thermoplastic elastomer is a multi-component system that is simply a mixture of a rubber component and a plastic component, and has a higher compression set and heat resistance than a simple blend type polyolefin-based thermoplastic elastomer that is not dynamically cross-linked. Since various properties such as properties are improved, it is more suitable for laser welding. Furthermore, the dynamically cross-linked polyolefin-based thermoplastic elastomer has a further improved dispersibility and color development of the dye / pigment in the elastomer phase than when a dye / pigment is added to a polyolefin-based thermoplastic elastomer that has not been dynamically cross-linked. ing.

  The dynamically cross-linked polyolefin-based thermoplastic elastomer is preferably a cross-linked polyolefin-based thermoplastic elastomer obtained from polypropylene or polyethylene and an ethylene / α-olefin copolymer elastomer. In this case, the composition ratio of ethylene and α-olefin in the ethylene / α-olefin copolymer elastomer is 55:45 to 80:20 by weight, and thus more favorable characteristics are exhibited.

  The dynamically cross-linked polyolefin-based thermoplastic elastomer is molded so that the compression set value according to the JIS K-6262-1997 test method at 100 ° C. is 10 to 90%, preferably 20 to 70%. A weld with high accuracy and good adhesion can be obtained.

  The dynamically crosslinked polyolefin-based thermoplastic elastomer preferably has a shore hardness of 30 to 90 (A), more preferably 60 to 90 (A), according to a hardness test method based on JIS K-6253-1997. .

  The laser light transmissive composition may contain only the dynamically crosslinked polyolefin thermoplastic elastomer as the thermoplastic elastomer, but may further contain another kind of thermoplastic elastomer. As another thermoplastic elastomer, for example, a thermoplastic plastic component such as polystyrene, polyvinyl chloride, polyester, polyamide, polyurethane, which is a hard segment, and a styrene-butadiene copolymer rubber (SBR, which is a soft segment). ), Ethylene-propylene-diene-methylene copolymer (EPDM), rubber component such as acrylonitrile-butadiene copolymer rubber (NBR), and may be simply blended and contained. It may be contained after being cross-linked.

  The laser light transmitting composition containing the dynamically cross-linked polyolefin-based thermoplastic elastomer exhibits elasticity like vulcanized rubber at room temperature and can be freely plastically deformed by an injection molding machine at high temperature. Shows the properties of plastics such as thermoplastics. Therefore, this composition is useful as a molding material that plays an intermediate role between thermoplastic plastics and rubber, and is used to mold members and parts in a wide range of industrial fields, especially in the fields of automobiles, electrical / electronics, etc. Used to do.

  The salt-forming colorant used in the present invention has good compatibility with the dynamically crosslinked polyolefin-based thermoplastic elastomer, and the color tone fades in a heat treatment process such as injection molding or laser welding before laser welding. The non-bleeding property of the colored molded product is not generated, and high transparency is exhibited at one or two or more wavelengths corresponding to a laser beam of 800 to 1200 nm. Since this colorant is a salt-forming body, the bleed phenomenon is considered to be suppressed as a result of the ionic group exhibiting an anchor effect in the laser light transmitting composition.

  The salt-forming colorant is composed of an anion component obtained from an acid dye and a cation component obtained from an organic amine. The salt-forming colorant comprises (a) a monoazo salt-forming dye, (b) a disazo salt-forming dye, (c) an anthraquinone salt-forming dye, (d) an anthrapyridone salt-forming dye, and (e) a tri-salt dye. One or more salt-forming dyes selected from the group consisting of phenylmethane-based salt-forming dyes are preferred. In order to develop good dispersibility of the salt-forming dye in the dynamically cross-linked polyolefin-based thermoplastic elastomer, a sulfone group that can be an anionic group of the anion component is included in the molecule of the chemical structure of the salt-forming dye. It is preferable to have two.

  The salt-forming colorant includes an anionic component obtained from an acid dye, and a cationic component obtained from an organic amine (eg, primary amine, secondary amine, tertiary amine, guanidine, or rosin amine). It can be obtained by the salt formation reaction. An ion reaction can be used for this salt formation reaction. For example, an acidic dye having two sulfonic acid groups in the molecule is dispersed in water to make a dispersion, while a solution in which 1.5 to 2.5 times moles of an organic amine of the dye is dissolved in aqueous hydrochloric acid is used. The solution is dropped into the dispersion and stirred for several hours to react. The salt mixture colorant can be obtained by filtering the reaction mixture, washing the filtered material with water and drying.

  Examples of the organic amine include aliphatic amines and aromatic amines. Specific examples of organic amines include butylamine, hexylamine, pentylamine, octylamine, laurylamine, myristylamine, palmitylamine, cetylamine, oleylamine, stearylamine, dibutylamine, 2-ethylhexylamine, di- (2-ethylhexyl). ) Aliphatic amines such as amine and dodecylamine; Alicyclic amines such as cyclohexylamine, di-cyclohexylamine and rosinamine; 3-propoxypropylamine, 2-ethoxyhexylamine, di- (3-ethoxypropyl) amine, 3 -Alkoxyalkylamines such as butoxypropylamine, octyloxypropylamine, 3- (2-ethylhexyloxy) propylamine; N-cyclohexylethanolamine, N-dodecylimino-di-ethylene Amines containing alkanol groups such as diols; diamines such as dimethylaminopropylamine and dibutylaminopropylamine; amines of guanidine derivatives such as 1,3-diphenylguanidine, 1-o-tolylguanidine and di-o-tolylguanidine; aniline , Aromatic amines such as benzylamine, naphthylamine, phenylamine, phenylenediamine, methylphenylenediamine, xylenediamine, and N-monoalkyl-substituted products thereof. Particularly preferred examples of organic amines are alicyclic amines and guanidine derivatives.

(a) Description of monoazo salt-forming dye The monoazo salt-forming dye is a salt-forming dye composed of, for example, an anion component obtained from a monoazo acid dye and a cation component obtained from an organic amine. The monoazo acid dye is preferably represented by the following chemical formula (1).

[In the chemical formula (1),
R ¹ -has no substituent or a substituent on the ring (eg, an alkyl group [eg, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, An alkyl group having 1 to 8 carbon atoms such as an isopentyl group, a hexyl group, a heptyl group, and an octyl group], a substituent [for example, an alkyl group having 1 to 4 carbon atoms, a halogen group such as a chlorine group or a bromine group], or the like. Carbon number such as aryl group [eg phenyl group, naphthyl group etc.], hydroxyl group, sulfone group, carboxyl group, halogen group [eg chlorine group, bromine group etc.], alkoxy group [eg methoxy group, ethoxy group, propoxy group etc.] 1-8 alkoxy group], an amino group, or a substituent [for example, a halogen group such as an alkyl group having 1 to 4 carbon atoms, a chlorine group, a bromine group, or the like] or An aryl group having anilide group) that do not;
-R ² has no substituent or a substituent on the ring (eg, an alkyl group [eg, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, An alkyl group having 1 to 8 carbon atoms such as an isopentyl group, hexyl group, heptyl group and octyl group], a substituent [for example, a halogen group such as an alkyl group having 1 to 4 carbon atoms, a chlorine group and a bromine group] Carbon number such as aryl group [eg phenyl group, naphthyl group etc.], hydroxyl group, sulfone group, carboxyl group, halogen group [eg chlorine group, bromine group etc.], alkoxy group [eg methoxy group, ethoxy group, propoxy group etc.] 1 to 8 alkoxy groups], amino groups, or substituents [for example, halogen groups such as alkyl groups having 1 to 4 carbon atoms, chlorine groups, bromine groups, etc.] Non-anilide group), or
A substituent (for example, an alkyl group [for example, carbon such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, etc. An alkyl group having a number of 1 to 8], an aryl group [for example, a phenyl group or a naphthyl group having no substituent or a substituent [for example, a halogen group such as an alkyl group having 1 to 4 carbon atoms, a chlorine group, or a bromine group]] Etc.], a hydroxyl group, a carboxyl group, a sulfone group, a halogen group [eg, a chlorine group, a bromine group, etc.], or an alkoxy group [eg, an alkoxy group having 1 to 8 carbon atoms such as a methoxy group, an ethoxy group, or a propoxy group]) Represents a pyrazolone group;
At least ^{one of} R ¹ — and —R ² has a sulfone group (—SO ₃ M, where M is hydrogen, an alkali metal, or ammonium) as a substituent. ]
That is, the monoazo acid dye represented by the chemical formula (1) has at least one sulfone group in its chemical structure.

  Specific examples of the monoazo acid dye represented by the chemical formula (1) include the following compound examples. However, of course, the present invention is not limited to these.

(b) Description of Disazo Salt-Forming Dye The disazo salt-forming dye is a salt-forming dye composed of, for example, an anion component obtained from a disazo acid dye and a cation component obtained from an organic amine. The disazo acid dye is preferably represented by the following chemical formula (2).

[In the chemical formula (2),
R ³ — and —R ⁴ may be the same or different and have no substituent or have a substituent on the ring (for example, an alkyl group [for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, isopentyl group, hexyl group, heptyl group, octyl group and other alkyl groups having 1 to 8 carbon atoms], substituents [for example, alkyl groups having 1 to 4 carbon atoms] An aryl group having or not having a halogen group such as a chlorine group or a bromine group] [eg, a phenyl group, a naphthyl group, etc.], a hydroxyl group, a sulfone group, a carboxyl group, a halogen group [eg, a chlorine group, a bromine group, etc., an alkoxy group [For example, an alkoxy group having 1 to 8 carbon atoms such as a methoxy group, an ethoxy group, or a propoxy group], an amino group, or a substituent [for example, an alkyl group having 1 to 4 carbon atoms, a chlorine group An aryl group having or not having anilide group) having a halogen group such as bromine radical, or,
No substituent or substituent (eg, alkyl group [eg, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, isopentyl group, hexyl group, heptyl group An alkyl group having 1 to 8 carbon atoms such as an octyl group], an aryl group having no substituent or having a substituent [for example, a halogen group such as an alkyl group having 1 to 4 carbon atoms, a chlorine group, or a bromine group] For example, phenyl group, naphthyl group etc.], hydroxyl group, carboxyl group, sulfone group, halogen group [eg chlorine group, bromine group etc.], or alkoxy group [eg methoxy group, ethoxy group, propoxy group etc. A pyrazolone group having an alkoxy group]);
-E- is the following formula (3) to formula (5)

(In the formula (3), -R ⁵ and -R ⁶ may be the same or different, and are a hydrogen atom, an alkyl group having or not having a substituent [for example, a methyl group, an ethyl group, a propyl group, An isopropyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, a hexyl group, a heptyl group, an octyl group or other alkyl group having 1 to 8 carbon atoms], a halogen group [eg, a chlorine group, a bromine group, etc.], An alkoxy group [for example, an alkoxy group having 1 to 8 carbon atoms such as a methoxy group, an ethoxy group, or a propoxy group], or a sulfone group [-SO ₃ M, where M is the same as above].

(In the formula (4), -R ⁷ and -R ⁸ are each independently, [a -SO ₃ M, M is as defined above] hydrogen atom or a sulfonic group showing a.),

(In the formula (5), -R ⁹ represents a sulfone group [-SO ₃ M, M is the same as described above]);
Any one or more of —E—, R ³ —, and —R ⁴ have a sulfone group (—SO ₃ M, where M is the same as described above) as a substituent. ]
That is, the disazo acid dye represented by the chemical formula (2) has at least one sulfone group in its chemical structure.

  Specific examples of the disazo acid dye represented by the chemical formula (2) include the compound examples shown in Table 1. However, of course, the present invention is not limited to these.

(c) Description of anthraquinone salt-forming dye The anthraquinone salt-forming dye is a salt-forming dye composed of, for example, an anion component obtained from an anthraquinone acid dye and a cation component obtained from an organic amine. The anthraquinone acid dye is preferably one represented by the following chemical formula (6) or (7).

[In the chemical formula (6),
-R ¹⁰ represents hydrogen, hydroxyl or a unsubstituted or substituted group substituents (e.g., alkyl group, halogen group, an aryl group, a cycloalkyl group) to an amino group that has;
-R ¹¹ and -R ¹² may be the same or different, and may be hydrogen, an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, n- C1-C12 alkyl group such as pentyl group, isopentyl group, hexyl group, heptyl group, octyl group), halogen group (eg chlorine group, bromine group etc.), alkoxy group (eg methoxy group, ethoxy group, propoxy group) alkoxy group having 1 to 12 carbon atoms etc.), or a sulfone group _(-SO 3 M, M represents the same) and the;
-R ^{13 ~-R 17} may be different even in the same, hydrogen, an alkyl group (e.g. methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group, tert- butyl group, n- A pentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group or other alkyl group having 1 to 12 carbon atoms), an acyl group, an acylamide group, an acyl-N-alkylamide group (alkyl includes, for example, a methyl group, an ethyl group) , Propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, isopentyl group, hexyl group, heptyl group, octyl group and other alkyl groups having 1 to 8 carbon atoms), halogen group (for example, chlorine) Group, bromine group, etc.), alkoxy group (for example, alkoxy group having 1 to 8 carbon atoms such as methoxy group, ethoxy group, propoxy group), or sulfone _(-SO 3 M, M is as defined above) indicates;
Any one of -R ^{10 ~-R 17} is a sulfonic group. ]
That is, the anthraquinone acid dye represented by the chemical formula (6) has one sulfone group in its chemical structure.

[In the chemical formula (7),
-R ²³ and -R ²⁴ may be the same or different, and may be hydrogen, an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, n- C1-C12 alkyl group such as pentyl group, isopentyl group, hexyl group, heptyl group, octyl group), halogen group (eg chlorine group, bromine group etc.), alkoxy group (eg methoxy group, ethoxy group, propoxy group) alkoxy group having 1 to 12 carbon atoms etc.), an amino group, a nitro group or a sulfonic group, _(-SO 3 M, M is as defined above);
-R ^{18 ~-R 22} and ^-R 25 ^{~-R 29} may be different even in the same, hydrogen, an alkyl group (e.g. methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group Tert-butyl group, n-pentyl group, isopentyl group, hexyl group, heptyl group, octyl group and other alkyl groups having 1 to 12 carbon atoms), acyl group, acylamide group, acyl-N-alkylamide group (as alkyl) Is, for example, alkyl having 1 to 8 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, isopentyl group, hexyl group, heptyl group and octyl group. Group), halogen groups (for example, chlorine group, bromine group, etc.), alkoxy groups (for example, methoxy group, ethoxy group, propoxy, etc.) Group), or a sulfone group _(-SO 3 M, M represents the same) and the;
Any one of -R ^{18 ~-R 29} is a sulfonic group. ]
That is, the anthraquinone acid dye represented by the chemical formula (7) has one sulfone group in its chemical structure.

  Specific examples of the anthraquinone acid dye represented by the chemical formula (6) or (7) include the following compound examples. However, of course, the present invention is not limited to these.

(d) Description of the anthrapyridone salt-forming dye The anthrapyridone salt-forming dye is a salt-forming dye composed of, for example, an anion component obtained from an anthrapyridone acid dye and a cation component obtained from an organic amine. . Anthrapyridone-based acid dyes can be vividly colored on elastomers, have excellent laser light transmission properties, and have essential heat resistance during molding and laser welding with laser light-transmitting compositions. Among red dyes, it has practically sufficient characteristics as a colorant for laser welding. The anthrapyridone acid dye is preferably one represented by the following chemical formula (8).

[In the chemical formula (8),
-R ³⁰ is hydrogen or a substituent on not having or benzene ring substituents (e.g., substituent [for example, a methyl group, an ethyl group, an alkyl group having 1 to 3 carbon atoms such as propyl, methoxy group, An alkoxy group having 1 to 3 carbon atoms such as an ethoxy group and a propoxy group, a hydroxyl group, or a halogen group such as a chlorine group, a bromine group, an iodine group, and a fluorine group], a phenyl group, a methoxy group, an ethoxy group, A benzoyl group having 1 to 3 carbon atoms such as propoxy, a hydroxyl group, or a halogen group such as a chlorine group, a bromine group, an iodine group or a fluorine group);
-R ³¹ does not have hydrogen, an alkyl group (for example, an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and a tert-butyl group) and a substituent. Or an aryl group having a substituent on the ring (for example, a phenyl group, a naphthyl group, a lower alkyl-substituted phenyl group, a lower alkyl-substituted naphthyl group, a halogenated phenyl group, a halogenated naphthyl group, etc.) Aryl group optionally substituted by a lower alkyl group or a halogen group such as chlorine group, bromine group, iodine group, fluorine group, etc.), alkoxy group (for example, methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy) Group, hexyloxy group and the like, preferably an alkoxy group having 1 to 18 carbon atoms), amino group, hydroxyl group, or halogen group ( For example, chlorine group, bromine group, iodine group, fluorine group, etc.);
-R ³² and -R ³³ are hydrogen, an alkyl group (for example, preferably an alkyl group having 1 to 5 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group), substituted An aryl group having no group or having a substituent on the ring (for example, phenyl group, naphthyl group, lower alkyl-substituted phenyl group, lower alkyl-substituted naphthyl group, halogenated phenyl group, halogenated naphthyl group, etc.) 1 to 3 lower alkyl groups or aryl groups optionally substituted by a halogen group such as a chlorine group, bromine group, iodine group or fluorine group), an alkenyl group (for example, vinyl group, allyl group, propenyl group, butenyl) Preferably an alkenyl group having 2 to 18 carbon atoms), an alkoxy group (for example, methoxy group, ethoxy group, propoxy group, butto Si group, pentyloxy group, hexyloxy group and the like, preferably an alkoxy group having 1 to 18 carbon atoms), amino group, hydroxyl group, halogen group (for example, chlorine group, bromine group, iodine group, fluorine group etc.), acyl group ( For example, formyl group, acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, toluoyl group, etc.), acyloxy group (for example, -O-acetyl group, -O-propionyl group, -O-benzoyl group, -O- Toluoyl group), acylamide group (for example, formylamide group, acetylamide group), sulfone group, acyl-N-alkylamide group, carboxyl group, alkoxylcarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxy group) Carbonyl group), cyclohexylamide group, or the following formula (9)

(In the formula (9), -X- represents -O- or -NH-; -R ³⁶ and -R ³⁷ may be the same or different, and may be hydrogen, an alkyl group [for example, a methyl group; , An ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl etc., preferably an alkyl group having 1 to 5 carbon atoms], an aryl group having no substituent or having a substituent on the ring [for example, phenyl Group, naphthyl group, lower alkyl substituted phenyl group, lower alkyl substituted naphthyl group, halogenated phenyl group, halogenated naphthyl group and the like, lower alkyl group having 1 to 3 carbon atoms or chlorine group, bromine group, iodine group, Aryl group optionally substituted by a halogen group such as a fluorine group], an alkenyl group [for example, a vinyl group, an allyl group, a propenyl group, a butenyl group, etc., preferably having 2 to 1 carbon atoms An alkenyl group], an alkoxy group [for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group or the like, preferably an alkoxy group having 1 to 18 carbon atoms], an amino group, a hydroxyl group, a halogen group [ For example, chlorine group, bromine group, iodine group, fluorine group, etc.], acyl group [for example, formyl group, acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, toluoyl group, etc.], acyloxy group [for example, —O— Acetyl group, -O-propionyl group, -O-benzoyl group, -O-toluoyl group], acylamide group [eg, formylamide group, acetylamide group], acyl-N-alkylamide group, carboxyl group, alkoxylcarbonyl group [For example, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl A group, a butoxycarbonyl group] or a cyclohexylamide group; M represents a hydrogen, an alkali metal, or an ammonium);
-R ³⁴ is hydrogen, an alkyl group (e.g. methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group, tert- preferably an alkyl group having 1 to 5 carbon atoms of butyl), an alkoxy group (e.g. methoxy Group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group and the like, preferably an alkoxy group having 1 to 18 carbon atoms), or a hydroxyl group;
-R ³⁵ is hydrogen, an alkyl group (e.g. methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group, preferably an alkyl group having 1 to 5 carbon atoms, such as tert- butyl), alkoxy groups (e.g. methoxy Group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group and the like, preferably an alkoxy group having 1 to 18 carbon atoms), or a hydroxyl group;
M represents hydrogen, alkali metal, ammonium;
m represents 1, 2 or 3;
n represents 1, 2 or 3.
If having a plurality of -R ^34, -R ³⁴ each other definitive them may be different may be the same. When having a plurality of sulfone groups (—SO ₃ M, M is the same as described above) including those in formula (9), Ms in them may be the same or different. ]

  Specific examples of the anthrapyridone acid dye represented by the chemical formula (8) include the following compound examples. However, of course, the present invention is not limited to these.

(e) Description of triphenylmethane salt-forming dye The triphenylmethane salt-forming dye is composed of, for example, an anion component obtained from a triphenylmethane acid dye and a cation component obtained from an organic amine. It is a dye. The triphenylmethane acid dye is preferably represented by the following chemical formula (10).

〔化学式（１０）中、
−Ｒ^３８は、水素原子、またはアルキル基（例えばメチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ヘキシル基、ヘプチル基、オクチル基等の炭素数１〜８のアルキル基）を示し；
−Ｒ^３９は、水素原子、アルキル基（例えばメチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ヘキシル基、ヘプチル基、オクチル基等の炭素数１〜８のアルキル基）、水酸基、カルボキシル基、またはスルホン酸基を示し；
−Ｒ^４０は、水素原子、スルホン酸基、置換基を有しない若しくは環上に置換基（例えば、スルホン酸基、水酸基、ニトロ基、アミノ基、ハロゲン基［例えば塩素基、臭素基等］、カルボキシル基、アルコキシ基［例えばメトキシ基、エトキシ基、プロポキシ基等の炭素数１〜８のアルコキシ基］、アルキル基［例えばメチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ヘキシル基、ヘプチル基、オクチル基等の炭素数１〜８のアルキル基］等）を有するアリール基（例えばフェニル基、トリル基、ナフチル基）、または下記式（１１）

[In the chemical formula (10),
-R ³⁸ is a hydrogen atom or an alkyl group (e.g. methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group, tert- butyl group, n- pentyl group, an isopentyl group, a hexyl group, heptyl group, octyl An alkyl group having 1 to 8 carbon atoms such as a group);
-R ³⁹ is a hydrogen atom, an alkyl group (e.g. methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group, tert- butyl group, n- pentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group An alkyl group having 1 to 8 carbon atoms, etc.), a hydroxyl group, a carboxyl group, or a sulfonic acid group;
-R ⁴⁰ is a hydrogen atom, a sulfonic acid group, no substituent, or a substituent on the ring (eg, a sulfonic acid group, a hydroxyl group, a nitro group, an amino group, a halogen group [eg, a chlorine group, a bromine group, etc.), A carboxyl group, an alkoxy group [for example, an alkoxy group having 1 to 8 carbon atoms such as a methoxy group, an ethoxy group, or a propoxy group], an alkyl group [for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert- A butyl group, an n-pentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group or other alkyl group having 1 to 8 carbon atoms]) or the like, or the following Formula (11)

(In the formula (11), -R ⁴¹ and -R ⁴² may be the same or different, and may be a hydrogen atom, a substituent that does not have a substituent, or a substituent [for example, a sulfonic acid group, a hydroxyl group, a nitro group, Alkyl groups having an amino group, a halogen group exemplified by a chlorine group or a bromine group, a carboxyl group, an alkoxy group exemplified by an alkoxy group having 1 to 8 carbon atoms such as a methoxy group, an ethoxy group, or a propoxy group. For example, an alkyl group having 1 to 8 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, isopentyl group, hexyl group, heptyl group, octyl group] , Having no substituent or a substituent [for example, a halogen group, a carboxyl group, such as a sulfonic acid group, a hydroxyl group, a nitro group, an amino group, a chlorine group or a bromine group, Alkoxy groups exemplified by alkoxy groups having 1 to 8 carbon atoms such as methoxy group, ethoxy group and propoxy group, and 1 carbon atom such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and tert-butyl. An aryl group having an alkyl group exemplified by 8 to 8] [for example, a phenyl group, a tolyl group, a naphthyl group], or an unsubstituted or substituted group [for example, a sulfonic acid group, a hydroxyl group, a nitro group, Halogen group exemplified by amino group, chlorine group or bromine group, carboxyl group, alkoxy group exemplified by C1-C8 alkoxy group such as methoxy group, ethoxy group or propoxy group, or methyl group or ethyl Group, propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, isopentyl group, hexyl group and heptyl group Or an aralkyl group having an alkyl group having 1 to 8 carbon atoms such as octyl group] [for example, benzyl group, α-methylbenzyl group, α, α-dimethylbenzyl group, α-butylbenzyl group, A phenethyl group, and a naphthylalkyl group exemplified by a naphthylmethyl group, a naphthylethyl group, and the like]);
A ¹ -and -A ² may be the same or different, and each represents a hydrogen atom, no substituent, or a substituent (for example, a hydroxyl group, a halogen group [for example, a chlorine group, a bromine group, etc.], etc.). Alkyl group having (for example, 1 to 8 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, isopentyl group, hexyl group, heptyl group, octyl group) An alkyl group);
B ¹ -and -B ² may be the same or different and have no substituent or a substituent (for example, sulfonic acid group, hydroxyl group, nitro group, amino group, halogen group [for example, chlorine group, bromine group) Group, etc.], carboxyl group, alkoxy group [e.g., alkoxy group having 1 to 8 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group], alkyl group [e.g., methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, isopentyl group, hexyl group, heptyl group, alkyl group having 1 to 8 carbon atoms such as octyl group] etc.)) Group, naphthyl group or the like, or no substituent or a substituent (for example, sulfonic acid group, hydroxyl group, nitro group, amino group, halogen group [for example, chlorine , A bromine group, etc.], a carboxyl group, an alkoxy group [for example, an alkoxy group having 1 to 8 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group], an alkyl group [for example, a methyl group, an ethyl group, a propyl group, isopropyl Group, n-butyl group, tert-butyl group, n-pentyl group, isopentyl group, hexyl group, heptyl group, alkyl group having 1 to 8 carbon atoms such as octyl group], etc.)) , Α-methylbenzyl group, α, α-dimethylbenzyl group, α-butylbenzyl group, phenethyl group, naphthylalkyl group [for example, naphthylmethyl group, naphthylethyl etc.]);
Any one or more of —R ³⁸ , —R ⁴⁰ , B ¹ —, and —B ² have a sulfone group (—SO ₃ M, M is the same as described above). ]

  Specific examples of the triphenylmethane acid dye represented by the chemical formula (10) include the following compound examples. However, of course, the present invention is not limited to these.

  These dyes exhibit hues such as yellow, orange, red, brown, green, blue, purple, or gray to black, and exhibit hues in the range of 400 to 700 nm in terms of the maximum absorption wavelength. The salt-formant colorant contained in the laser light-transmitting composition has an absorption range only in or in the visible light absorption region of the dye, and the wavelength region of the laser light (wavelength of 800 to 1200 nm). 1) or a mixture of two or more dyes having transparency. As the colorant, another dye colorant that is similarly good in laser light transmittance and has a hue such as yellow, orange, red, brown, green, blue, or purple may be appropriately mixed. For example, a mixed colorant exhibiting a black hue obtained by combining and mixing a blue or green dye and another red and yellow dye colorant. In the industrial use of the laser light transmitting composition, a gray to black composition is important.

  Examples of colorant mixtures include blue or green or purple dyes (eg, anthraquinone dyes, triphenylmethane dyes) and yellow (eg, monoazo dyes) and / or red colorants (eg, disazo dyes, By combining an anthrapyridone dye), green (for example, a combination of blue and yellow), purple (for example, a combination of blue and red), black (for example, a combination of blue, yellow and red, purple and yellow) And those exhibiting various hues (combination or a combination of green and red).

  Furthermore, it can be set as the coloring agent containing the 1 type (s) or 2 or more types of well-known dye / pigment within the range which has the desired effect of this invention. Examples of such dyes include azo dyes, azo metal-containing dyes, naphthol azo dyes, azo lake dyes, azomethine dyes, anthraquinone dyes, quinacridone dyes, dioxazine dyes. Pigments, diketopyrrolopyrrole dyes, anthopyridone dyes, isoindolinone dyes, indanthrone dyes, perinone dyes, perylene dyes, indigo dyes, thioindigo dyes, Examples thereof include organic dyes such as quinophthalone dyes, quinoline dyes, benzimidazolone dyes, and triphenylmethane dyes.

  The content of the colorant in the laser light transmissive composition is preferably 0.01 to 10% by weight with respect to the dynamically crosslinked polyolefin-based thermoplastic elastomer. More preferably, it is 0.05-5 weight%, More preferably, it is 0.05-2 weight%.

T ₁ which is the transmittance of laser light having a wavelength of 840 nm in this colored laser light transmissive composition containing a colorant, and the same non-colored laser light transmittance except that it does not contain a colorant the ratio of _{T 2} the transmittance of laser light having a wavelength of 840nm in the composition _(T 1 / _{T 2)} is 0.5 or more, preferably 0.7 to 1.0, more preferably 0.8 to 1 .0.

  Next, the light absorbing molded body 2 will be described. The light-absorbing molded article is a laser light-absorbing composition containing a thermoplastic elastomer or a thermoplastic resin colored with, for example, carbon black as a laser light absorber that also serves as a black colorant. It is preferable that In this case, it is preferable to use carbon black having a primary particle diameter of 18 to 30 nm. By using such carbon black, carbon black is very sufficiently dispersed, and as a result, a light-absorbing molded body capable of absorbing laser light at a high absorption rate is obtained. Moreover, a nigrosine dye can be used together with carbon black, and the laser light absorption rate can be adjusted well.

  Examples of the thermoplastic resin include polyamide resin, polyethylene resin, polypropylene resin, polystyrene resin, polymethacrylic resin, acrylic polyamide resin, ethylene vinyl alcohol (EVOH) resin, polycarbonate resin, polyethylene terephthalate (PET), and polybutylene terephthalate (PBT). Polyester resins, etc. are mentioned and may be used alone or in combination.

  For example, a thermoplastic resin containing talc as a filler in a polypropylene resin may be used. It is more preferable to use a thermoplastic resin containing talc in terms of mechanical strength and dimensional stability.

  Even if carbon black is not used, other colorants and other laser light absorbers (eg, nigrosine, aniline black, phthalocyanine, naphthalocyanine, perylene, quaterylene, metal complexes, squaric acid derivatives, immonium dyes, polymethine, etc. ) Or a colorant that also serves as another laser light absorber can be used to obtain a laser light absorbing composition containing a thermoplastic elastomer (rubber) or a thermoplastic resin. By this, the light-absorbing molded object of chromatic colors, such as yellow, orange, red, brown, green, blue, purple, can also be obtained.

Moreover, used in laser-absorptive composition, the melting temperature of the dynamic cross-linked polyolefin thermoplastic elastomer uncolored is 160 ° C. to 210 ° C., Ri preferably 165.2 ° C. to 210 ° C. der, at its melting temperature When it exists, since the dispersibility is good without deterioration of the colorant, a laser light-absorbing composition excellent in appearance and surface gloss can be obtained.

  The melting temperature is measured in the same manner as the measuring method described in the explanation of the laser light transmitting composition.

  The amount of the colorant used in such a laser light absorbing composition is, for example, 0.01 to 10% by weight, preferably 0.05 to 5% with respect to the dynamically crosslinked polyolefin thermoplastic elastomer or thermoplastic resin. % By weight. The light-absorbing molded body can be produced in the same manner as the light-transmitting molded body except that it contains a laser light absorber.

  Industrially, black members occupy a particularly important position. In order to achieve clear coloring, it is important to select a thermoplastic elastomer material having high transparency, a colorant having good dispersibility in the thermoplastic elastomer material, and selection of kneading conditions. By selecting a thermoplastic elastomer having an optical density (OD value) of 1.5 or more when the addition concentration to the thermoplastic elastomer is 0.1% by weight, an excellent black material is obtained.

  By using a dynamically crosslinked polyolefin-based thermoplastic elastomer, good dispersibility can be obtained with respect to pigments, particularly carbon black. As a result, the energy absorption rate with respect to the laser beam is made uniform, and laser welding without unevenness can be achieved. Furthermore, since the elastomer is highly transparent, it is difficult to turn gray when black pigments are blended, and even when the addition amount is small, the color is vividly black, so that it is optimal as a light absorbing material. As the dynamically crosslinked polyolefin thermoplastic elastomer, an ethylene / α-olefin copolymer elastomer is preferably used.

  The composition for molding into a light-transmitting molded article or a light-absorbing molded article used in the present invention may contain appropriate amounts of various reinforcing materials or fillers depending on the purpose and purpose. The reinforcing material or filler may be any material that can be used for reinforcing a normal synthetic resin, and is not particularly limited to a fibrous shape, a plate shape, a powder shape, a granular shape, and the like. Fillers can be used as needed.

  As filler, plate-like filler such as mica, sericite, glass flake, silicate such as talc, kaolin, clay, wollastonite, bentonite, asbestos, alumina silicate, alumina, silicon oxide, magnesium oxide, zirconium oxide, Metal oxides such as titanium oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, particulate fillers such as glass beads, ceramic beads, boron nitride and silicon carbide Can be added. The addition amount of the filler is preferably in the range of 5 to 50% by mass. These fiber reinforcing agents and fillers can be used in combination of two or more. Furthermore, when these fiber reinforcements and fillers are used after being treated with a surface treatment agent such as a coupling agent such as a silane, epoxy or titanate, it is possible to obtain better mechanical strength. preferable. In particular, use of talc is more preferable in terms of mechanical strength and dimensional stability.

  Other fibrous reinforcing agents include, for example, glass fibers, carbon fibers, other inorganic fibers, and organic fibers (such as aramid, polyphenylene sulfide, nylon, polyester, and liquid crystal polymer), fibrous potassium titanate whiskers, and barium titanate. Whisker, aluminum borate whisker, silicon nitride whisker, or the like can be used. The content is preferably 5 to 120% by weight with respect to 100% by weight of the dynamically crosslinked thermoplastic elastomer or thermoplastic resin. If it is less than 5% by weight, it is difficult to obtain a sufficient glass fiber reinforcing effect, and if it exceeds 120% by weight, the moldability tends to deteriorate. The amount is preferably 10 to 60% by weight, particularly preferably 20 to 50% by weight.

  The composition for molding into a light-transmitting molded article or a light-absorbing molded article used in the present invention can be blended with various additives as necessary. Examples of such additives include auxiliary colorants such as titanium oxide and zinc oxide, dispersants, stabilizers, plasticizers, modifiers, ultraviolet absorbers or light stabilizers, phenol-based, phosphorus-based, and the like. Inhibitors, antistatic agents, lubricants, mold release agents, crystal accelerators, crystal nucleating agents such as metal phosphates, metal carboxylates, benzylidene sorbitols, flame retardants, and the like.

  The master batch of the composition for molding into this light-transmitting molded body or light-absorbing molded body can be obtained by any method. For example, after the pellets of the dynamically crosslinked polyolefin-based thermoplastic elastomer as the base of the masterbatch and the colorant are mixed with a mixer such as a tumbler or a super mixer, an extruder, a batch-type kneader or a roll-type kneader is used. It can be obtained by heating and melting to form pellets or coarse particles.

  Molding of the composition for forming the light-transmitting molded body or the light-absorbing molded body can be performed by various procedures that are usually performed. For example, using colored pellets, it can also be performed by molding with a processing machine such as an extruder, injection molding machine, roll mill, etc. Also, a pellet of a thermoplastic elastomer having translucency, a pulverized colorant, and If necessary, various additives can be mixed in a suitable mixer, and the resulting mixture can be molded by using a processing machine. As the molding method, for example, any generally used molding method such as injection molding, extrusion molding, compression molding, foam molding, blow molding, vacuum molding, injection blow molding, rotational molding, calendar molding, solution casting, etc. should be adopted. You can also. By such molding, molded articles made of thermoplastic elastomer and molded articles made of a thermoplastic resin having various shapes can be obtained.

  Next, a laser welding method using the laser light transmitting composition of the present invention will be described. An example of the laser welding method will be described with reference to FIG. As shown in FIG. 1, a step 4 provided at the end of the light-transmitting molded body 1 of the laser light-transmitting composition and a step 5 provided at the end of the light-absorbing molded body 2 are provided. Make contact. When the laser beam 3 is irradiated from the light-transmitting molded body 1 toward the light-absorbing molded body 2, the laser light 3 transmitted through the light-transmitting molded body 1 is absorbed by the light-absorbing molded body 2, Causes fever. With this heat, the light-absorbing molded body 2 is melted around the portion that has absorbed the laser light, and the light-transmitting molded body 1 is further melted so that both are fused at the welded portion 6. When this is cooled, the light-transmitting molded body 1 and the light-absorbing molded body 2 are joined with sufficient welding strength.

  A more preferable specific embodiment of the laser welding method of the present invention is as follows, for example.

As shown in FIG. 1, the first embodiment includes a light-transmitting molded body 1 of a laser light-transmitting composition containing a dynamically crosslinked polyolefin-based thermoplastic elastomer A and a salt-forming body colorant, and a laser. The light absorbing molded body 2 of the laser light absorbing composition containing the light absorbent 7 and the dynamically cross-linked polyolefin-based thermoplastic elastomer B is brought into contact with the laser light from the light transmitting molded body 1 side. It is a method of irradiating and laser welding. In this case, the dynamically crosslinked olefin-based thermoplastic elastomer A preferably has a permeability of 35% or more.
A laser in which the light-transmitting molded body 1 and a laser light-absorbing thermoplastic resin molded body 2 molded with a composition containing a laser light absorber and a polypropylene resin are laser-welded. It may be a welding method.

In the second embodiment, as shown in FIG. 2, a light-absorbing molded body 2 of the same type as that of the first embodiment is sandwiched between two light-transmitting molded bodies 1 of the same type as the first embodiment. In this method, the laser light 3 is irradiated from each side of the two light-transmitting molded bodies 1 and laser welding is performed.
One of the two light transmissive molded bodies 1 may be replaced with a laser light transmissive thermoplastic resin molded body which may be colored. The light-absorbing molded body 2 may be a thermoplastic-absorbing thermoplastic resin molded body as described above.

A third embodiment will be described with reference to FIG. Between the two light-transmitting molded bodies 1 of the same type as the first embodiment, a very thin light-absorbing molded body 2 of the same type as that of the first embodiment is sandwiched and brought into contact, and either one of the light-transmitting molded bodies 1 is transmitted. The laser beam 3 is irradiated only from the side of the moldable molded body 1 (for example, the upper side in FIG. 2), and the laser beam 3 is absorbed by the thin light-absorbent molded body 2 to generate heat. This is a method of laser welding the absorbent molded body 2.
One of the two light-transmitting molded bodies 1 may be colored, and a laser-light-transmitting thermoplastic resin molded body, a laser-light-absorbing thermoplastic elastomer molded body, Alternatively, it may be replaced with a laser light-absorbing thermoplastic resin molding. In addition, the light-absorbing molded body 2 may be a thermoplastic resin-molded body that absorbs laser light as described above.

In the fourth embodiment, as shown in FIG. 3, an ink and / or paint containing a laser light absorbent 7 is applied to one of the two types of light-transmitting molded bodies of the same type as the first embodiment. Then, the light-absorbing molded body 2 having the laser light absorber-containing layer 8 is placed, the other light-transmitting molded body 1 is brought into contact therewith, and laser light 3 is irradiated from each side to perform laser welding. It is a method of doing.
The light-absorbing molded body 2 having the laser light absorbent-containing layer 8 may be replaced with a laser light-transmitting thermoplastic resin molded body having the laser light absorbent-containing layer 8 and may be colored. Good. The laser light absorber-containing layer 8 is obtained, for example, by applying an ink or / and a paint containing a laser light absorber and, if necessary, a resin. This application is performed by an arbitrary application method such as spraying or painting with a marking pen, a brush, a brush, or the like. The coating layer 8 is preferably applied so as to have a thickness of 0.1 mm or less.

A fifth embodiment will be described with reference to FIG. Light absorption having a laser light absorber-containing layer 8 by applying ink and / or paint containing the laser light absorber 7 to one of the two light-transmitting molded bodies 1 of the same type as the first embodiment. A light-transmitting molded body 2, the other light-transmitting molded body 1 is brought into contact therewith, and the laser beam 3 is irradiated only from the side of the light-transmitting molded body 1. In this method, the compacts 1 and 2 are heated by being absorbed at 8 and laser-welded the molded bodies 1 and 2 through the laser-absorbing-containing layer 8.
The light-absorbing molded body 2 having the laser light absorber-containing layer 8 may have a laser light absorber-containing layer 8 and may be colored, and is a laser-light-transmitting thermoplastic resin molded body, laser A light-absorbing thermoplastic elastomer molded body or a laser light-absorbing thermoplastic resin molded body may be used instead.

  These laser welding methods may join molded articles formed from laser light transmitting and laser light absorbing compositions each containing a polyolefin-based thermoplastic elastomer having the same or different hardness.

As an advantage of laser welding,
(1) Welding is possible without bringing the laser beam generator into contact with the part to be welded.
(2) Because it is local heating, there should be very little thermal effect on the periphery of the weld location,
(3) There is no risk of mechanical vibration,
(4) It is possible to weld minute parts and three-dimensional structures.
(5) Able to maintain high airtightness,
(6) Because there are no burrs on the weld surface, the boundary between the welds is difficult to see visually.
(7) Do not generate dust, etc.
There is. In addition, these methods can be applied to automobile members and electric / electronic product members.

  In this laser welding method, as a light-transmitting molded article, a wavelength from around 800 nm by a semiconductor laser to around 1200 nm by a YAG laser, that is, at least 20% transmission with respect to the wavelength of laser light used for laser welding. What is to be used is used. For example, the infrared transmittance of one or more wavelengths at 808 nm, 840 nm, 940 nm, and 1064 nm, which are practical laser oscillation wavelengths, is at least 20%. If it is lower than this, a sufficient amount of laser light of these wavelengths cannot be transmitted, so that the strength of the laser welded material is insufficient, or the energy of the laser light is so strong that it is not practically suitable.

  At the time of laser welding, a method of fixing the light-transmitting molded body and the light-absorbing molded body in close contact with no gap is important. About the said clearance gap, it is preferable to adjust so that a clearance gap may be less than 0.02 mm, adjusting to the shape of molded objects with pressing jigs, such as a clamp. It is known that if the gap is 0.02 mm, it is halved compared to the welding strength when there is no gap, and if it is 0.05 mm or more, it is not welded.

  Examples of the laser operation method include a scanning type in which the laser beam irradiation device is moved to move the laser beam, a masking type in which the welding member is moved, and a type in which the molded body is simultaneously irradiated from various directions. A method desired by the automobile manufacturing industry is a scanning type, and a scanning speed of 5 m / min is suitable for production efficiency.

  Laser welding uses the principle of converting the light energy of laser light into thermal energy, so the welding performance is significantly affected by the laser welding conditions. In general, the amount of heat K received by the irradiated laser beam on the surface of the absorbent molded body can be calculated by the following equation.

Amount of heat (J / mm ² ) = laser power (W) / (scanning speed (mm / sec) x laser spot diameter (mm))

  In order to increase the scanning speed in order to increase the production efficiency, it can be seen from this formula that a high-power type laser welding machine is necessary. On the other hand, in order to increase the welding strength, a sufficient amount of heat on the surface of the absorbent molded body is required. Therefore, the output of the laser beam is increased, the scanning speed is somewhat reduced, or the laser beam is illuminated. It is necessary to set optimum conditions by changing various conditions such as reducing the spot diameter of the irradiation range on the surface of the heat-resistant molded body. When the amount of surface heat applied by the laser beam is too large, extreme distortion due to heat is generated at the welding site, and the appearance is impaired. If it is larger, smoke will blow from the absorbent molded body. Therefore, the laser welding condition setting is very important.

The amount of heat K (J / mm ² ) supplied to the surface of the light-absorbing molded article by irradiating while scanning with laser light is expressed by the following formula (I)
K = (p × T) / (100 × q × d) ≧ 0.5 (I)
(In the formula (I), p is the output (W) of the laser beam, T is the transmittance (%) of the laser beam in the light-transmitting molded article, q is the scanning speed (mm / sec), d shows the diameter (mm) of the irradiation range of the laser beam on the surface.)
It is preferable to satisfy.

  Next, a laser welded body using the laser light transmitting composition and the laser light absorbing composition of the present invention will be described.

  The laser welded body of the present invention is constituted by welding a laser light transmitting member made of a laser light transmitting composition and a laser light absorbing member made of a laser light absorbing composition as described above. The The laser light transmitting member contains at least an uncolored dynamically cross-linked polyolefin elastomer having a melting temperature of 160 to 210 ° C. and a salt-forming colorant that transmits a laser beam of 800 to 1200 nm. It is obtained by molding a resin composition in which additives are additionally mixed.

  The laser light absorbing member is configured to have at least a laser absorbing layer on a surface in contact with the laser light transmitting member. Such an example is a member obtained by a resin composition to which a laser absorber is added, and a member combined with a resin layer having a laser absorber.

  The laser welded body of the present invention includes those obtained by one laser welding and those obtained by a plurality of laser weldings. As an example of what is laser-welded a plurality of times, an example in which a laser light transmitting member, a laser light absorbing member, and a laser light transmitting member are welded can be given. In this case, when the laser light absorbing member is thin, it can be surely welded by one laser welding. When the laser light absorbing member is thick, multiple laser weldings are required.

  A specific manufacturing process of the laser welded body will be described with reference to the drawings.

  The laser welded body of the present invention comprises the following (A) to (E) or (F) to (J), but is not necessarily limited thereto.

  When manufacturing as shown in FIG. 1, the manufacturing process consists of the following (A)-(E).

(A) It consists of a laser-light-transmitting colored resin composition containing a dynamically crosslinked polyolefin-based elastomer having a melting temperature of 160 ° C. to 210 ° C. and a salt-forming colorant that transmits laser light of 800 to 1200 nm when uncolored. The laser light transmitting member 1 is formed.
(B) A laser light absorbing member 2 containing a dynamically cross-linked polyolefin elastomer having a melting temperature of 160 ° C. to 210 ° C. and a laser light absorbent 7 in an uncolored state is brought into contact with the laser light transmitting member 1.
(C) Next, the laser beam 3 is irradiated so that the laser beam 3 passes through the laser beam transmitting member 1 and is absorbed by the laser beam absorbing member 2.
(D) The irradiated laser beam 3 reaches the laser beam absorbing member 2 and is absorbed to generate heat, and both the resin members 1 and 2 are melted by heat.
(E) The contact portion between the laser beam transmitting member 1 and the laser beam absorbing member 2 is securely welded.

  Moreover, when manufacturing as shown in FIG. 2, the manufacturing process consists of following (F)-(J).

(F) From a laser light transmitting colored resin composition containing a dynamically crosslinked polyolefin elastomer having a melting temperature of 160 ° C. to 210 ° C. or less and a salt-forming colorant that transmits laser light of 800 to 1200 nm when uncolored. A plurality of laser light transmitting members 1 are formed.
(G) A laser light absorbing member 2 containing a dynamically crosslinked polyolefin elastomer having a melting temperature of 160 ° C. to 210 ° C. or less and a laser light absorbing agent 7 in an uncolored state between the plurality of laser light transmitting members 1. Intervene.
(H) Next, the laser beam 3 is irradiated from a plurality of directions so that the laser beam 3 passes through the laser beam transmitting member 1 and is absorbed by the laser beam absorbing member 2.
(I) The laser beam 3 irradiated from a plurality of directions reaches the laser beam absorbing member 2 and is absorbed to generate heat, and both the resin members 1 and 2 are thermally melted.
(J) The contact portions of the plurality of laser light transmitting members 1 and the laser light absorbing member 2 are securely welded.

  The same applies when manufacturing as shown in FIG.

  EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

  Production Examples 1 to 7 shown in Table 3 are colorants used in each Example, and Comparative Production Examples 1 to 4 are colorants used in each Comparative Example. The compounds shown in the above compound examples correspond to the acid dyes for the respective production examples. However, Production Examples 4 to 6 shown in Table 3 are black colorants obtained by blending a plurality of compounds with a simple mixer according to the weight blending ratio shown in the blending ratio column.

  Next, Examples 1 to 3 in which the present invention is applied to a laser-light-transmitting composition using a dynamically cross-linked polyolefin-based thermoplastic elastomer and a homogenous test piece that is a light-transmitting molded body using the composition. 19 and a non-application example of the present invention will be described in Comparative Examples 1-7.

  Note that TPV is an abbreviation for a dynamically cross-linked polyolefin-based thermoplastic elastomer, and TPO is an abbreviation for a polyolefin-based thermoplastic elastomer.

For the melting temperature, a sample sample is set in a flow tester (trade name: CFT-500D manufactured by Shimadzu Corporation), a load is 5 kgf, a die hole length is 1 mm, and a die hole diameter is 1 mm. The temperature at which the sample sample melts at a temperature rising rate of 5 ° C./min in the range from 150 ° C. to 250 ° C. was measured.
The melting temperature was calculated by calculating one half of the difference between the outflow end point and the lowest point in the flow curve and setting the temperature at that point as the melting temperature (1/2 method).

Example 1
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Product number: Asahi Kasei TPV A6110; Melting temperature: 178.6 ° C)
Colorant of Production Example 1 ... 0.40 g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The mixture obtained as a laser light-transmitting composition was subjected to an ordinary method using an injection molding machine (trade name: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. 1 is injection molded into a shape having a step 4 with a thickness of 2 mm with a long side of 70 mm × short side of 18 mm × thickness of 4 mm, and the lower surface side from one end to 20 mm is cut off in the vicinity of one short side. In addition, a uniform yellow-colored test piece with good surface gloss and no color unevenness was obtained.

(Example 2)
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Product number: Asahi Kasei TPV A6110, manufactured by Asahi Kasei Chemicals Corporation; melting temperature: 178.6 ° C.)
Colorant of Production Example 2 ... 0.40 g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (trade name: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A uniform red-colored test piece with good and no color unevenness was obtained.

(Example 3)
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Product number: Asahi Kasei TPV A6110; Melting temperature: 178.6 ° C)
Colorant of Production Example 3 ... 0.40g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (trade name: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A uniform green-colored test piece having good and no color unevenness was obtained.

Example 4
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Product number: Asahi Kasei TPV A6110; Melting temperature: 178.6 ° C)
Colorant of Production Example 4 ... 0.40g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (trade name: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A uniform purple-colored test piece having good and no color unevenness was obtained.

(Example 5)
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Product number: Asahi Kasei TPV A6110; Melting temperature: 178.6 ° C)
Colorant of Production Example 4 ... 4.00 g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (trade name: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A uniform black test piece with good and no color unevenness was obtained.

(Example 6)
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Product number: Asahi Kasei TPV A6110; Melting temperature: 178.6 ° C)
Colorant of Production Example 5 ... 4.00 g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (trade name: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A uniform black test piece with good and no color unevenness was obtained.

(Example 7)
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Product number: Asahi Kasei TPV A6110; Melting temperature: 178.6 ° C)
Colorant of Production Example 6 ... 4.00 g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (trade name: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A uniform black test piece with good and no color unevenness was obtained.

(Example 8)
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Product number: Asahi Kasei TPV A6110; Melting temperature: 178.6 ° C)
Colorant of Production Example 7 ... 4.00 g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (trade name: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A uniform blue-colored test piece having good and no color unevenness was obtained.

Example 9
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Product number manufactured by Asahi Kasei Chemicals Corporation: Asahi Kasei TPV A9110; Melting temperature: 172.0 ° C.)
Colorant of Production Example 1 ... 0.40 g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (trade name: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A uniform yellow-colored test piece having good and no color unevenness was obtained.

(Example 10)
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Product number manufactured by Asahi Kasei Chemicals Corporation: Asahi Kasei TPV A9110; Melting temperature: 172.0 ° C.)
Colorant of Production Example 2 ... 0.40 g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (trade name: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A uniform red-colored test piece with good and no color unevenness was obtained.

(Example 11)
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Product number manufactured by Asahi Kasei Chemicals Corporation: Asahi Kasei TPV A9110 Melting temperature: 172.0 ° C)
Colorant of Production Example 3 ... 0.40g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (trade name: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A uniform green-colored test piece having good and no color unevenness was obtained.

(Example 12)
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Product number manufactured by Asahi Kasei Chemicals Corporation: Asahi Kasei TPV A9110; Melting temperature: 172.0 ° C.)
Colorant of Production Example 4 ... 0.40g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (trade name: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A uniform purple-colored test piece having good and no color unevenness was obtained.

(Example 13)
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Product number manufactured by Asahi Kasei Chemicals Corporation: Asahi Kasei TPV A9110; Melting temperature: 172.0 ° C.)
Colorant of Production Example 4 ... 4.00 g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (trade name: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A uniform black test piece with good and no color unevenness was obtained.

(Example 14)
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Product number manufactured by Asahi Kasei Chemicals Corporation: Asahi Kasei TPV A9110; Melting temperature: 172.0 ° C.)
Colorant of Production Example 5 ... 4.00 g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (trade name: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A uniform black test piece with good and no color unevenness was obtained.

(Example 15)
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Product number manufactured by Asahi Kasei Chemicals Corporation: Asahi Kasei TPV A9110; Melting temperature: 172.0 ° C.)
Colorant of Production Example 6 ... 4.00 g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (trade name: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A uniform black test piece with good and no color unevenness was obtained.

(Example 16)
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Product number: Asahi Kasei TPV A8120 manufactured by Asahi Kasei Chemicals Corporation; Melting temperature: 165.2 ° C.)
Colorant of Production Example 4 ... 4.00 g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (trade name: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A uniform blue-black test piece with good and no color unevenness was obtained.

(Example 17)
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Product number manufactured by Asahi Kasei Chemicals Corporation: Asahi Kasei TPV B8130; Melting temperature: 171.0 ° C.)
Colorant of Production Example 4 ... 4.00 g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (trade name: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A uniform black test piece with good and no color unevenness was obtained.

(Example 18)
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Mitsui Chemicals product name: Milastomer soft; Melting temperature: 202.4 ° C.)
Colorant of Production Example 4 ... 4.00 g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (trade name: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A uniform black test piece with good and no color unevenness was obtained.

(Example 19)
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Mitsui Chemicals, trade name: Miralastomer hard; melting temperature: 175.5 ° C.)
Colorant of Production Example 4 ... 4.00 g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (trade name: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A uniform black test piece with good and no color unevenness was obtained.

(Comparative Example 1)
Dynamic cross-linked polyolefin-based cross-linked thermoplastic elastomer ... 400g
(Asahi Kasei Chemicals Corporation product number: Asahi Kasei TPV A6110; Melting temperature: 178.6 ° C.) Colorant of Comparative Example 1... 0.40 g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (trade name: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A green specimen with poor dispersion was obtained.

(Comparative Examples 2 to 4)
Comparative Examples 2 to 4 produced test pieces in the same manner as Comparative Example 1 according to Table 4.

(Comparative Example 5)
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Product number manufactured by AES Japan Co., Ltd .: Santoprene 8211-65; Melting temperature: 235.1 ° C.)
Colorant of Production Example 4 ... 4.00 g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (trade name: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A slightly inferior black specimen was obtained.

(Comparative Example 6)
An uncolored product of a dynamically crosslinked polyolefin-based thermoplastic elastomer (trade name: Santoprene “8211-65” manufactured by AES Japan; melting temperature: 235.1 ° C.).

  Using an injection molding machine (trade name: Si-50, manufactured by Toyo Kikai Kogyo Co., Ltd.), a white test piece was obtained when injection molding was performed by a normal method at a cylinder temperature of 200 ° C. and a mold temperature of 40 ° C.

(Comparative Example 7)
A non-colored product of a polyolefin-based thermoplastic elastomer (trade name: Byram “9201-65” manufactured by AES Japan, which cannot be measured because the sample sample did not melt).

  Using an injection molding machine (trade name: Si-50, manufactured by Toyo Kikai Kogyo Co., Ltd.), injection molding was carried out in a usual manner at a cylinder temperature of 200 ° C. and a mold temperature of 40 ° C., and a pale yellow test piece was obtained.

(Evaluation of the physical properties)
Uncolored polyolefin cross-linked thermoplastic elastomer test similarly molded as a test piece of a light-transmitting molded article using the laser light-transmitting composition obtained in Examples 1 to 19 and Comparative Examples 1 to 7, and a blank About the piece, physical property evaluation was performed by the following method. The results are shown in Table 5 below.

(1) Dispersibility evaluation test If the test piece obtained by the injection molding was uniformly colored visually, it was judged that the dispersibility was good.

(2) Transmittance measurement test Each test piece was set on a spectrophotometer (manufactured by JASCO Corporation, product number: V-570 type), and the test piece (the portion of the step 4 having a thickness of 2 mm in the test piece 1 in FIG. 1). The transmittance was measured in a wavelength range of λ = 400 to 1200 nm. Table 5 shows the transmittance of semiconductor laser light having a wavelength of 840 nm for each test piece.

(3) Heat resistance evaluation test In each of the injection moldings of Examples 1 to 19 and Comparative Examples 1 to 5, after performing a normal shot with the mixture of the blends, the remaining mixture was retained at the cylinder temperature at that time for 15 minutes. After that, another test piece was obtained by injection molding.
If the hue change of the test piece obtained by staying in the cylinder for 15 minutes did not progress compared to the hue of the test piece obtained by normal shot, it was judged that the test piece had good heat resistance.

(4) Bleed resistance evaluation test In each of the injection moldings of Examples 1 to 19 and Comparative Examples 1 to 5, after performing a normal shot with each colorant, the obtained test piece should be laser welded. A predetermined test piece was superposed, a pressure of about 200 g (1.96 N) / cm ² was applied in the superposition direction, and the sample was left at 80 ° C. for 48 hours, and the degree of coloring on the predetermined test piece was observed.
When there was no migration of the colorant in the predetermined test piece, it was judged that there was bleeding resistance and good.

  Next, in Examples 20 to 27 and Comparative Examples 8 and 9, a laser light absorbing composition using a dynamically crosslinked polyolefin thermoplastic elastomer and a polypropylene resin, and a light absorbing molded body using the same. An isomorphic test piece will be described.

(Example 20)
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Product name: Asahi Kasei TPV “A-6110” manufactured by Asahi Kasei Chemicals; melting temperature: 178.6 ° C.)
Carbon black ... 0.40g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was subjected to an ordinary method using an injection molding machine (product number: Si-50 manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C. and a mold temperature of 40 ° C., as shown in FIG. × Short side 18mm × Thickness 4mm and the top side of 20mm width along one end of the short side is chipped and injection molded into a shape having a step 5 of 2mm thickness. Good appearance and surface gloss and no color unevenness A uniform black laser beam absorptive test piece was obtained.

(Example 21)
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Asahi Kasei Chemicals product name: Asahi Kasei TPV "A-9110")
Carbon black ... 0.40g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (product number: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A uniform black laser light-absorbing test piece with good and no color unevenness was obtained.

(Example 22)
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Product name: Asahi Kasei TPV “A-8120” manufactured by Asahi Kasei Chemicals; melting temperature: 165.2 ° C.)
Carbon black ... 0.40g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (product number: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A uniform black laser light-absorbing test piece with good and no color unevenness was obtained.

(Example 23)
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Product name: Asahi Kasei TPV “B-8130” manufactured by Asahi Kasei Chemicals; melting temperature: 171.0 ° C.)
Carbon black ... 0.40g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (product number: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A uniform black laser light-absorbing test piece with good and no color unevenness was obtained.

(Example 24)
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Mitsui Chemicals product name: Milastomer soft; Melting temperature: 202.4 ° C.)
Carbon black ... 0.40g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (product number: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A uniform black laser light-absorbing test piece with good and no color unevenness was obtained.

(Example 25)
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Mitsui Chemicals, trade name: Miralastomer hard; melting temperature: 175.5 ° C.)
Carbon black ... 0.40g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (product number: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A uniform black laser light-absorbing test piece with good and no color unevenness was obtained.

(Comparative Example 8)
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(AES Japan product name: Santoprene “8211-65”; melting temperature: 235.1 ° C.)
Carbon black ... 0.40g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (product number: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A slightly inferior gray laser light absorption specimen was obtained.

(Comparative Example 9)
Polyolefin thermoplastic elastomer (TPO) ... 400g
(Product name: Viram “9201-65” manufactured by AES Japan; the melting temperature was not measurable because the sample sample was insufficiently melted.)
Carbon black ... 0.40g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. When the obtained mixture was injection-molded by an ordinary method at an injection molding machine (product number: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C. and a mold temperature of 40 ° C., a poor dispersion was observed. A gray laser light absorbing specimen was obtained.

(Example 26)
Talc filled polypropylene resin (PP-T) ... 400g
Carbon black ... 2.0g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (product number: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A uniform black laser light-absorbing test piece with good and no color unevenness was obtained.

(Example 27)
Dynamic cross-linked polyolefin thermoplastic elastomer ... 400g
(Product name: Asahi Kasei TPV “A-6110” manufactured by Asahi Kasei Chemicals; melting temperature: 178.6 ° C.)
Phthalocyanine dye "CI Solvent Blue 70" ... 4.00g

  The blend was placed in a stainless steel tumbler and stirred for 1 hour. The obtained mixture was injection-molded by an ordinary method using an injection molding machine (product number: Si-50, manufactured by Toyo Machine Metal Co., Ltd.) at a cylinder temperature of 200 ° C and a mold temperature of 40 ° C. A uniform blue laser light-absorbing test piece having good and no color unevenness was obtained.

(Evaluation of the physical properties)
Examples 20-27 performed the same physical property evaluation as Examples 1-19. The results are shown in Tables 6 and 7 below.

(5) Appearance and surface gloss (OD value measurement test)
The appearance of the test piece was evaluated by measuring the reflection density (OD) of the test piece with a reflection density meter TR-927 manufactured by Macbeth. A test plate having a higher OD value exhibits better surface smoothness and gloss and is judged to have a high blackness.

(Evaluation of the physical properties)
Next, using the light-transmitting molded bodies (test pieces) obtained in Examples 1 to 19 and the light-absorbing molded bodies (test pieces) obtained in Examples 20 to 27, lasers were used as follows. Welding was performed, and physical properties of the obtained welded material were evaluated.

(6) Weldability Evaluation Test As shown in FIG. 1, each of the test pieces 1 of Examples 1 to 19 and Comparative Examples 1 to 7 and the Examples 20 to 27 and Comparative Examples 8 and 9 were used. Each test piece 2 of the light-absorbing molded body [all long side 70 mm × short side 18 mm × thickness 4 mm (20 mm from the end of the long side is 2 mm thick)] is 20 mm long × 18 mm wide × thickness, respectively. The steps 4 and 5 between the 2 mm portions were brought into contact with each other and overlapped.

  Various laser beams 3 (spot diameter of 0.6 mm) from a diode laser [wavelength: 840 nm continuous] (manufactured by Fine Devices) from above the test piece 1 in FIG. Irradiation was performed while scanning in the horizontal direction (the direction of the arrow in FIG. 1) at a scanning speed of.

When the laser light passes through the test piece 1 and is absorbed by the laser light-absorbing test piece 2, the laser light-absorbing test piece 2 generates heat, and this heat absorbs the laser light around the portion that absorbed the laser light. The test piece 2 is melted, the test piece 1 is also melted, both resins are fused, and both are joined by cooling. 1 in FIG. 1 indicates a welded portion.
If the weld of the test piece obtained by laser welding was sufficient, the weldability was judged to be good. The results are shown in Tables 8-10.

(7) Tensile strength test With respect to the welded material obtained above, in accordance with JIS K-6251-1993, the tensile tester (A & D Tensilon RTC1300) was used. A tensile test was performed at a test speed of 500 mm / min in the longitudinal direction of the light-absorbing molded body with respect to the test piece 2 side (the direction in which the test pieces 1 and 2 in FIG. 1 are separated), and the tensile weld strength was measured. The results are shown in Tables 8-10.

  As apparent from Tables 5 to 10, the test pieces of the examples were excellent in transmittance, heat resistance, bleed resistance, laser weldability, and tensile strength.

  A simple blend type polyolefin-based thermoplastic elastomer is compared with a dynamically crosslinked polyolefin-type thermoplastic elastomer. As is apparent from Table 5, the simple blend type polyolefin-based thermoplastic elastomer (TPE “Byram 9201-65” manufactured by AES Japan Co., Ltd.) has a low laser light transmittance when used as a light-transmitting molded product, Since the dispersive color developability is low, it is not suitable as a material for a light-transmitting molded article. On the other hand, dynamically cross-linked polyolefin-based thermoplastic elastomers (TPV “A6110”, “A9110”, “A8120”, “B8130” manufactured by Asahi Kasei Chemicals, Inc., “Milastomer soft”, “Milastomer hard” manufactured by Mitsui Chemicals, Inc.) In this case, the laser light transmittance is high, and the dispersibility and coloring property of the colorant are good. Further, as is apparent from Table 6, it can be seen that when a light-absorbing molded article is obtained, the color development of the colorant is good, so that it is also suitable as a material for the light-absorbing molded article.

  Next, a dynamically crosslinked polyolefin thermoplastic elastomer produced with a metallocene catalyst, a dynamically crosslinked polyolefin thermoplastic elastomer produced with a Ziegler catalyst, and a simple blended polyolefin thermoplastic elastomer will be compared. As is clear from Table 6, when the same amount (0.1%) of carbon black was added, the blackness (OD value) of the polyolefin-based thermoplastic elastomer was compared. Catalyst-based dynamically cross-linked polyolefin-based thermoplastic elastomers (TPV “A6110”, “A9110”, “B8130”, “A8120” manufactured by Asahi Kasei Chemicals) 2): Zigler catalyst-based dynamically cross-linked polyolefin-based thermoplastic elastomer (AES) TPV “Santoprene 8211-65” manufactured by Japan), 3: simple blend type polyolefin-based thermoplastic elastomer (“Bairam 9201-65” manufactured by AES Japan). Accordingly, the metallocene catalyst-based dynamically cross-linked polyolefin-based thermoplastic elastomer is suitable for the material of the light-absorbing molded article because it has good dispersibility and color development of the colorant.

  Further, when the hue of the uncolored elastomer is visually determined, the hue of the simple blend type polyolefin-based thermoplastic elastomer is light yellow, and the hue of the Ziegler catalyst-based dynamically crosslinked polyolefin-based thermoplastic elastomer is opaque white. Metallocene catalyst-based dynamically cross-linked polyolefin thermoplastic elastomer is translucent and has good dispersibility and color development even when a small amount of colorant used in the light-transmitting molded article is added. Suitable for material.

  In addition, a dynamically cross-linked polyolefin thermoplastic elastomer (AES Japan TPV "Santoprene 8211-65") mainly composed of ethylene propylene diene rubber is a simple blend type polyolefin thermoplastic elastomer (AES Japan "Byram" 9201-65 "), which is more suitable as a material for a light-transmitting molded article, but is a dynamically cross-linked polyolefin-based thermoplastic elastomer mainly composed of an ethylene-α-olefin copolymer elastomer (TPV" Asahi Kasei Chemicals Corporation "). A6110 "etc.) is insufficient in terms of transparency as a material for a light transmissive molded article.

  Further, as is apparent from Table 8, dynamically crosslinked polyolefin thermoplastic elastomers having different hardness (made by Asahi Kasei Chemicals Corporation, TPV “A6110” having a hardness of 60 (A) and TPV “TPV“ having a hardness of 90 (A) ” A9110 ") can be laser-welded, and can also be laser-welded between polyolefin-based thermoplastic elastomers (TPV" A6110 "manufactured by Asahi Kasei Chemicals Corporation) and polyolefin-based thermoplastic resins such as talc-filled polypropylene. is there.

  Further, as is apparent from Table 9, the laser welding composition using the comparative laser light transmitting composition or the comparative laser light absorbing composition is inferior in the weldability evaluation test. Moreover, the transmittance, heat resistance, bleed resistance, laser weldability, and tensile strength were excellent by using a dynamically crosslinked polyolefin thermoplastic elastomer having a melting temperature of 160 ° C to 210 ° C.

  The laser light transmitting composition containing the dynamically cross-linked polyolefin-based thermoplastic elastomer of the present invention has a light having an oscillation wavelength from about 800 nm by a semiconductor laser used for laser welding to about 1200 nm by a YAG laser, that is, laser light. It has high transparency, high fastness such as heat resistance and light resistance, good bleed resistance (migration resistance), chemical resistance, etc., and exhibits a clear hue.

  According to the laser welding method of the present invention using the molded article of the laser light-transmitting composition, laser welding can be surely performed by a simple operation, and fastening is a conventional joining method of thermoplastic elastomer members. It is possible to obtain a welded material having a strength equal to or higher than that of a method such as fastening with a component (bolt, screw, clip, etc.), adhesion with an adhesive, vibration welding, ultrasonic welding or the like. Moreover, since there is little influence of vibration and heat, it is possible to realize labor saving, improvement of productivity, reduction of production cost, and the like. Further, laser welding of a molded article having a complicated shape of the same or different composition containing this thermoplastic elastomer, or laser welding of a molded article of the composition containing this thermoplastic elastomer and a molded article made of a thermoplastic resin. It is also applicable to.

  Therefore, it is particularly suitable for laser welding of precision instrument parts, functional parts, electrical / electronic parts, etc. that should avoid the effects of vibration and heat, for example, in the automobile industry and the electrical / electronic industry.

It is a figure of an example which shows the middle of the laser welding of the light-transmitting molded object of the laser-light-transmitting composition to which this invention is applied, and a light absorptive molded object. It is a figure of another example which shows the middle of the laser welding of the light-transmitting molded object of the laser-light-transmitting composition to which this invention is applied, and a light absorptive molded object. It is a figure of another example which shows the middle of the laser welding of the light-transmitting molded object of the laser-light-transmitting composition to which this invention is applied, and a light absorptive molded object.

Explanation of symbols

  1 is a light-transmitting molded body, 2 is a light-absorbing molded body, 3 is a laser beam, 4 and 5 are steps, 6 is a welding site, 7 is a laser light absorber, and 8 is a laser light absorber-containing layer.

Claims (10)

And dynamic crosslinked polyolefin-based thermoplastic elastomers 16 5.2 ° C. to 210 ° C. The melt temperature during uncolored, monoazo acid dyes, disazo acid dye, anthraquinone acid dyes, anthrapyridone acid dye and triphenyl An anionic component comprising an acidic dye selected from methane-based acidic dyes, and a cationic component comprising an organic amine which is a guanidine derivative selected from 1,3-diphenylguanidine, 1-o-tolylguanidine and di-o-tolylguanidine. Made of salt, consisting of at least one salt-forming dye selected from monoazo salt-forming dyes, disazo salt-forming dyes, anthraquinone salt-forming dyes, anthrapyridone salt-forming dyes, and triphenylmethane-based acid dyes It transmits laser light 800~1200nm salt formation member colorant .05～2 wt% and is light transmissive molded body formed by Relais Za optically transparent composition is contained, and
0.05 to 5% by weight of the laser light absorber, which is carbon black as a colorant, and a melting temperature of 165.2 ° C. to 210 ° C. when not colored, and an optical density at least 0.1% by weight. A black light-absorbing molded article molded from a laser-light-absorbing composition containing a dynamically crosslinked polyolefin-based thermoplastic elastomer having a molecular weight of 5 or more,
A laser welding method, wherein the light-transmitting molded body and the light-absorbing molded body are welded by contacting the light-transmitting molded body with laser light . The laser welding method according to claim 1, wherein the carbon black has a primary particle diameter of 18 to 30 nm. The value of the compressive strain according to JIS K-6262-1997 at 100 ° C. of the dynamically cross-linked polyolefin-based thermoplastic elastomer contained in the light-transmitting molded article is 20 to 70%. The laser welding method according to claim 1. The wavelength of the laser beam is 840 nm, and the transmittance of the dynamically cross-linked polyolefin-based thermoplastic elastomer contained in the light-transmitting molded body at the wavelength is at least 35%. The laser welding method according to 1. The laser welding method according to claim 1, wherein the dynamically cross-linked polyolefin-based thermoplastic elastomer contained in the light-transmitting molded body is produced in the presence of a metallocene-based catalyst. 2. The laser welding method according to claim 1, wherein the dynamically cross-linked polyolefin-based thermoplastic elastomer contained in the light-transmitting molded body contains an ethylene / α-olefin copolymer elastomer as a main component. . The laser welding method according to claim 6 , wherein a copolymerization ratio of ethylene and α-olefin in the ethylene / α-olefin copolymer elastomer is 55:45 to 80:20 by weight. . The laser welding method according to claim 1 , wherein the light-absorbing molded body is in contact with the light-transmitting molded body through a layer containing the laser light absorber attached thereto. The amount of heat K (J / mm ² ) supplied to the surface of the light-absorbing molded body by irradiating the laser beam while scanning is represented by the following formula (I)
K = (p × T) / (100 × q × d) ≧ 0.5 (I)
(In the formula (I), p is the output (W) of the laser beam, T is the transmittance (%) of the laser beam in the light-transmitting molded article, q is the scanning speed (mm / sec), d represents the diameter (mm) of the irradiation range of the laser beam on the surface)
The laser welding method according to claim 1 , wherein: Dynamic cross-linked polyolefin thermoplastic elastomer having a melting temperature of 165.2 ° C. to 210 ° C. when uncolored, monoazo acid dye, disazo acid dye, anthraquinone acid dye, anthrapyridone acid dye, and triphenylmethane An anionic component composed of an acidic dye selected from a series of acidic dyes, and a cationic component composed of an organic amine which is a guanidine derivative selected from 1,3-diphenylguanidine, 1-o-tolylguanidine and di-o-tolylguanidine. 800 salt consisting of a monoazo salt forming dye, a disazo salt forming dye, an anthraquinone salt forming dye, an anthrapyridone salt forming dye, and a triphenylmethane acid dye 0 of a salt-forming colorant that transmits laser light of ˜1200 nm 05-2% by weight and comprises a light transmissive molded body formed by laser-transmissible composition are contained,
When it is in contact with it , 0.05 to 5% by weight of the laser light absorber which is carbon black as a colorant, and when the melting temperature is 165.2 ° C. to 210 ° C. and 0.1% by weight when uncolored And a black light-absorbing molded article molded from a laser-light-absorbing composition containing a dynamically crosslinked polyolefin-based thermoplastic elastomer having an optical density of at least 1.5 or more ,
A laser welded body characterized in that the laser welded body is laser-welded at a portion in contact with the laser beam irradiated to the light- transmitting molded body and transmitted therethrough and absorbed into the light- absorbing molded body.

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