Molding composition containing a black colorant

Abstract

The present invention relates to a molding composition comprising, based on the total weight of the molding composition: (A) 20 to 98% by weight of a crystalline polymer material selected from polyamide, polyester, polyamide-containing blend, polyester-containing blend, or any combination thereof; (B) 0.01 to 0.5% by weight of a black colorant; (C) 0 to 50% by weight of a reinforcing agent; (D) 0 to 50% by weight of an amorphous polymer material selected from polystyrene, styrene-acrylonitrile copolymer, polyester copolymer, polyamide, or any combination thereof; and (E) 0 to 10% by weight of one or more additives, wherein the molding composition has an initial laser transmittance of at least 20% at 1064 nm and the ratio of the initial laser transmittance at 780 nm to the initial laser transmittance at 1064 nm is in the range of less than 20% when measured in the form of a 2 mm thick test piece.

Description

Technical Field

[0001] The present invention relates to a molding composition containing a black colorant, a plastic article made therefrom, and the use of the molding composition in laser welding.

Background Art

[0002] Black plastic materials are very popular in many fields, especially in automotive parts, household appliances, electronic products, etc., because the manufactured products will have an appearance that is not influenced by fashion. In certain manufacturing processes for plastic articles, black plastic materials are required to have special optical properties, such as transparency in a laser welding process.

[0003] Laser welding is likely to become a commonly used method as a tool for joining plastic parts. The prerequisite for using laser welding is that the radiation emitted by the laser, usually in the wavelength range of 780 - 1200 nm, first passes through a part made of a plastic material (i.e., a laser-transmissive part) that has sufficient transparency to the laser light of the wavelength used, and then is absorbed in a thin layer by a second part made of a laser-absorbing plastic material (i.e., a laser-absorbing part) beneath the laser-transmissive part. In the thin layer that absorbs the laser light, the laser energy is converted into heat, which causes melting within the contact area and ultimately results in a weld that joins the laser-transmissive part to the laser-absorbing part. Carbon black is most commonly used in plastic materials to provide a laser-absorbing plastic material because significant economic benefits can be obtained. Therefore, black laser-transmissive materials are also commonly used to make the color between the laser-absorbing part and the laser-transmissive part uniform. To impart black color to the laser-transmissive material, various laser-transmissive colorants can be used, such as black colorants like nigrosine, naphthalocyanine, aniline black, phthalocyanine, porphyrin, perinone, quarterrylene, azo dyes, anthraquinone, pyrazolone, squaric acid derivatives, and indium dyes, or mixtures of colored colorants to simulate black colorants, such as a mixture of a red colorant and a green colorant.

[0004] Laser-transparent plastic materials based on common polymers such as polyamides and polyesters have been proposed. For example, International Publication No. 2019 / 216368 describes a resin composition with high light transmittance that can provide molded articles with extremely excellent laser weldability to an absorbent resin member. This resin composition contains a polyamide resin, a maleic anhydride-modified polyphenylene ether resin, a phosphazene flame retardant, a zinc metal oxide, and an optically transparent dye. International Publication No. 2011 / 154518 describes a laser-transparent PBT composition containing organic additives, to which inorganic and organic pigments and dyes such as nigrosine and anthraquinone can be added as colorants.

[0005] Parts or articles made of these black laser-transparent plastic materials can exhibit good laser transmittance, but it has been found that they are not sufficiently resistant to ultraviolet (UV) rays and cause strong discoloration during UV exposure. As the use of parts or articles made of laser-transparent plastic materials expands and they are exposed to sunlight, the demand for UV-resistant laser-transparent plastic materials is increasing.

[0006] The inventors have found that conventional UV absorbers and / or UV stabilizers cannot effectively improve the UV resistance of laser-transparent plastic materials. UV absorbers and / or UV stabilizers can protect polymers or resins from discoloration, but they cannot prevent UV-induced discoloration of the laser-transparent colorants contained in plastic materials.

[0007] The present inventors have also found that conventional laser-transparent plastic materials containing laser-transparent colorants generally exhibit insufficient printability when laser marking is applied. Laser marking, as a tool for labeling products, especially plastic articles, is an important process in various fields because it is a non-contact, fast, and highly flexible marking process that provides durable and wear-resistant markings. Lasers useful in the laser marking process can be within a wavelength range of 150 nm to 2000 nm, for example, 150 nm to 380 nm (i.e., UV laser marking). In such a process, the laser beam impinges on the article to be marked, and the laser energy is converted into heat, which causes a color change and a conversion of the molecular structure or destruction (cutting) of the material, thereby generating a visible mark in the form of a desired pattern or image. Laser marking can be used to create marks on or under the surface of an article.

[0008] Therefore, there is a need to provide a black laser-transparent plastic material that exhibits excellent laser transparency and at the same time has desirable UV resistance. It would be more desirable if the black laser-transparent plastic material could exhibit improved laser marking performance (i.e., printability).

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0010] Surprisingly, the inventors have found that by using a specific black colorant, a UV-resistant laser-transparent plastic material based on polyamide and polyester can be provided. It has also been found that the laser-transparent plastic material containing the specific black colorant can exhibit improved laser printing suitability. **Means for Solving the Problems**

[0011] Accordingly, in a first aspect, the present invention provides, based on the total weight of the molding composition, (A) 20 to 98% by weight of a crystalline polymer material selected from polyamide, polyester, polyamide-containing blends, polyester-containing blends, or any combination thereof, (B) 0.01 to 0.5% by weight of a black colorant, (C) 0 to 50% by weight of a reinforcing agent, (D) 0 to 50% by weight of an amorphous polymer material selected from polystyrene, styrene-acrylonitrile copolymer, polyester copolymer, polyamide, or any combination thereof, (E) 0 to 10% by weight of one or more additives and comprising a molding composition, wherein the molding composition has an initial laser transmittance of at least 20% at 1064 nm and the ratio of the initial laser transmittance at 780 nm to the initial laser transmittance at 1064 nm is in the range of less than 20% when measured in the form of a 2 mm thick test piece.

[0012] In a second aspect, the present invention provides the use of the molding composition described herein for producing a laser-transparent plastic part or a laser-transparent plastic article.

[0013] In a third aspect, the present invention provides an article produced using the molding composition described herein, such as a housing for an automotive radar or an automotive camera. **Brief Description of the Drawings**

[0014]

Figure 1

Embodiments for Carrying Out the Invention

[0015] The present invention will be described in detail below. It should be understood that the present invention can be embodied in many different ways and should not be construed as limited to the embodiments described herein.

[0016] The singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. The terms "comprise" (such as "comprise", "comprising", etc.) can be used interchangeably with "contain" (such as "contain", "containing", etc.) and should be construed in an open, non-limiting form. That is, for example, additional components or elements may exist. The expression "consists of" (such as "consists of" or "consisting of") or a related expression can be included within the expression "comprises" (such as "comprises" or "comprising") or a related expression.

[0017] The term "initial laser transmittance" as used herein is intended to refer to the laser transmittance measured for a freshly prepared, for example, within 72 hours, preferably within 24 hours under moisture protection after its preparation, molded test piece.

[0018] The term "crystalline polymer material" as used herein is intended to refer to a polymer material having crystalline domains between polymer chains, as evidenced by the presence of one or more distinct endothermic peaks in the melting point measurement by differential scanning calorimetry (DSC). The enthalpy of fusion is expressed relative to the weight of the polymer. As used herein, a "distinct" endothermic peak refers to a peak having a melting enthalpy of at least 5 J / g.

[0019] As used herein, the term "amorphous polymer material" is intended to mean a polymer material that has no crystalline domains between polymer chains or essentially no crystalline domains, as evidenced by the absence of an endothermic peak in melting point measurements by differential scanning calorimetry (DSC) or by a melting enthalpy of the existing endothermic peak of less than 5 J / g.

[0020] <Forming composition> As described above, the present invention is based on the total weight of the forming composition, respectively, (A) 20 to 98% by weight of a crystalline polymer material selected from polyamide, polyester, polyamide-containing blends, polyester-containing blends, or any combination thereof, (B) 0.01 to 0.5% by weight of a black colorant, (C) 0 to 50% by weight of a reinforcing agent, (D) 0 to 50% by weight of an amorphous polymer material selected from polystyrene, styrene-acrylonitrile copolymer, polyester copolymer, polyamide, or any combination thereof, (E) 0 to 10% by weight of one or more additives and a forming composition comprising: The forming composition has an initial laser transmittance of at least 20% at 1064 nm and a ratio of the initial laser transmittance at 780 nm to the initial laser transmittance at 1064 nm in the range of less than 20% when measured in the form of a 2 mm thick test piece. A forming composition is provided.

[0021] Component (A) The forming composition of the present invention includes, as component (A), a crystalline polymer material selected from at least one of polyamide, polyester, polyamide-containing blends, and polyester-containing blends.

[0022] Polyamide Useful polyamides can be derived from at least one monomer selected from the group consisting of lactams, amino acids, combinations of dicarboxylic acids and diamines, and combinations of dicarboxylic acid chlorides and diamines.

[0023] For example, useful polyamides can be derived from lactams having 4 to 30 carbon atoms or amino acids having 4 to 30 carbon atoms.

[0024] Suitable lactams preferably have 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms. Examples of lactams can include, but are not limited to, caprolactam, enanthlactam, caprylolactam, caprinolactam, undecalactam, laurolactam, or any combination thereof.

[0025] Suitable amino acids preferably have 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms. Examples of amino acids can include, but are not limited to, 2-aminoadipic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, or any combination thereof.

[0026] Examples of useful polyamides can also include those derived from combinations of dicarboxylic acids having 6 to 32 carbon atoms and diamines having 4 to 24 carbon atoms or combinations of dicarboxylic acid chlorides having 6 to 32 carbon atoms and diamines having 4 to 24 carbon atoms.

[0027] Suitable aliphatic diamines preferably have 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, such as 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms. The aliphatic diamine can be a straight-chain or branched-chain aliphatic diamine. Examples of aliphatic diamines include 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, 1,18-octadecanediamine, 1,20-eicosanediamine, 1,22-docosanediamine, 2-methylpentane-1,5-diamine, 3-methylpentane-1,5-diamine, 2,5-dimethylhexane-1,6-diamine, 2,4-dimethylhexane-1,6-diamine, 3,3-dimethylhexane-1,6-diamine, 2,2-dimethylhexane-1,6-diamine, 2,2,4-trimethylhexane-1,6-diamine, 2,4,4-trimethylhexane-1,6-diamine, 2,3-dimethylheptane-1,7-diamine, 2,4-dimethylheptane-1,7-diamine, 2,5-dimethylheptane-1,7-diamine, 2,2-dimethylheptane-1,7-diamine, 2-methyloctane-1,8-diamine, 1,3-dimethyloctane-1,8-diamine, 1,4-dimethyloctane-1,8-diamine, 2,4-dimethyloctane-1,8-diamine, 3,4-dimethyloctane-1,8-diamine, 4,5-dimethyloctane-1,8-diamine, 2,2-dimethyloctane-1,8-diamine, 3,3-dimethyloctane-1,8-diamine, 4,4-dimethyloctane-1,8-diamine, 2,4-diethylhexane-1,6-diamine, 5-methylnonane-1,9-diamine, and any combination thereof, but are not limited thereto.

[0028] Suitable dicarboxylic acids can be aliphatic or aromatic, preferably having 4 to 22 carbon atoms, such as 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Examples of dicarboxylic acids can include, but are not limited to, adipic acid, pimelic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, terephthalic acid, isophthalic acid, and any combination thereof.

[0029] Suitable dicarboxylic acid chlorides can be aliphatic or aromatic, preferably having 4 to 22 carbon atoms, such as 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Examples of dicarboxylic acid chlorides can include, but are not limited to, adipoyl chloride, heptanedioyl dichloride, azelaoyl dichloride, sebacoyl dichloride, undecanedioyl dichloride, and any combination thereof.

[0030] For example, the polyamide as component (A) can be at least one selected from the group consisting of PA6, PA7, PA8, PA9, PA11, PA12, PA410, PA510, PA513, PA515, PA66, PA69, PA610, PA612, PA613, PA614, PA618, PA636, PA88, PA810, PA812, PA1010, PA1012, PA1014, PA1018, PA1210, PA1212, PA1214, PA1218, PA1313, PA1410, PA1412, PA1414, PA1418, PA4T, PA9T, PA10T, PA11T, or any combination thereof, preferably PA6 or PA66.

[0031] Useful polyamides have a weight average molecular weight (Mw) of preferably at least 6,000, more preferably at least 10,000, even more preferably 15,000 or more, and even more preferably 20,000 or more, as measured by gel permeation chromatography (GPC). The weight average molecular weight (Mw) is preferably 35,000 or less, more preferably 30,000 or less, and even more preferably 26,000 or less. Alternatively or additionally, useful polyamides can have a relative viscosity in the range of 1.8 to 4.0 when measured in 96 wt% sulfuric acid at 25°C.

[0032] In some embodiments of the present invention, the molding composition of the present invention contains, as component (A), a polyamide selected from PA6, PA66 or any combination thereof, preferably PA66.

[0033] Polyamide-containing blend Suitable polyamide-containing blends can be any blend containing the above-described polyamides, which include not only blends of different polyamides but also blends of polyamides with polymers other than polyamides. Blends of different polyamides are particularly useful as polyamide-containing blends.

[0034] Polyester Useful polyesters can be derived from aromatic dicarboxylic acids and aliphatic or aromatic dihydroxy compounds. This type of polyester containing an aromatic ring derived from an aromatic dicarboxylic acid is known per se, and the aromatic ring may be substituted by a halogen such as chlorine or bromine, or by a C1-C4-alkyl group such as methyl, ethyl, iso- or n-propyl, or n-, iso- or tert-butyl group.

[0035] Suitable aromatic dicarboxylic acids are, for example, 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid or combinations thereof.

[0036] For example, useful polyesters can be derived from polyalkylene terephthalates, particularly those derived from aliphatic dihydroxy compounds having 2 to 10 carbon atoms. Preferred aliphatic dihydroxy compounds are diols having 2 to 6 carbon atoms, such as 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and neopentyl glycol, or any combination thereof.

[0037] Examples of preferred polyesters are polyalkylene terephthalates derived from alkanediols having 2 to 6 carbon atoms, particularly polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT) and any combination thereof, among which PBT is most preferred.

[0038] In some embodiments, the molding composition of the present invention comprises polybutylene terephthalate. Polybutylene terephthalate can be a homopolyester derived by esterification from 1,4-butanediol and terephthalic acid, or a homopolyester derived by transesterification from an ester of 1,4-butanediol and terephthalic acid.

[0039] Alternatively, polybutylene terephthalate may be a copolyester derived from 1,4-butanediol and terephthalic acid or its ester and at least one other monomer selected from diols, dicarboxylic acids or combinations thereof in an amount of 30 mol% or less. There is no limitation on the type of copolyester, and this includes, for example, block copolymers, random copolymers, graft copolymers and alternating copolymers.

[0040] Preferably, the polybutylene terephthalate contains units derived from the at least one other monomer in an amount of 20 mol% or less, preferably 10 mol% or less, more preferably 5 mol% or less, based on all the monomers constituting the polybutylene terephthalate.

[0041] Examples of the other monomers include aliphatic dicarboxylic acids having up to 20 carbon atoms, alicyclic dicarboxylic acids having 7 to 12 carbon atoms, aromatic dicarboxylic acids having 8 to 16 carbon atoms, or any combination thereof, preferably succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, dimer acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, himic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylketonedicarboxylic acid, and any combination thereof, more preferably selected from the group consisting of succinic acid, glutaric acid, adipic acid, pimelic acid, isophthalic acid, phthalic acid, or any combination thereof.

[0042] Examples of the other monomers include aliphatic glycols having 2 to 12 carbon atoms, alicyclic glycols having 6 to 12 carbon atoms, a plurality of C 2~4Examples include polyoxyalkylene glycols having oxyalkylene units, aromatic glycols having 6 to 14 carbon atoms, or any combination thereof, preferably 1,2 - ethanediol, 1,2 - propanediol, 1,3 - propanediol, 1,3 - butanediol, 1,6 - hexanediol, neopentanediol, 1,3 - octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, ditetramethylene glycol, decanediol, 1,4 - cyclohexanediol, 1,4 - cyclohexanedimethanol, bis - 1,4 - (hydroxymethyl)cyclohexane, diethylene glycol, polytetramethylene glycol, bisphenol, xylylene glycol, naphthalenediol and any combination thereof, more preferably selected from the group consisting of ethylene glycol, diethylene glycol or a combination thereof.

[0043] Useful polybutylene terephthalate preferably has a viscosity in the range of 90 - 170 ml / g, preferably 100 - 135 ml / g, more preferably 100 - 120 ml / g when measured in a 0.005 g / ml phenol / 1,2 - dichlorobenzene solution (mass ratio 1:1) according to ISO1628 - 5. Alternatively or additionally, useful polybutylene terephthalate can have a weight - average molecular weight (Mw) of 60,000 - 100,000 when measured by gel permeation chromatography (GPC).

[0044] Polyester - containing blend Suitable polyester - containing blends can be any blend containing the above - mentioned polyesters, which includes not only blends of different polyesters but also blends of polyesters with polymers other than polyesters. Blends of polyesters with polymers other than polyesters are particularly useful as polyester - containing blends.

[0045] This polymer material can be present in the molding composition of the present invention in an amount of 20 to 98% by weight, preferably 30 to 80% by weight, more preferably 35 to 75% by weight, such as 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70% or 75%, based on the total weight of the molding composition.

[0046] It should be understood that the amount of the polymer material as component (A) referred to herein is intended to refer to the corresponding polymer itself. Commercially available polymer materials often have certain additives intentionally added in advance to impart one or more desirable properties such as color, strength, stability, etc., but these additives are not included in the amount of the polymer material.

[0047] Component (B) The molding composition of the present invention contains, as component (B), a black colorant that is laser-transmissive and enables the molding composition of the present invention to have an initial laser transmittance of at least 20% at 1064 nm and a ratio of the initial laser transmittance at 780 nm to the initial laser transmittance at 1064 nm in the range of less than 20% when measured in the form of a 2 mm thick test piece.

[0048] Preferably, the molding composition of the present invention has an initial laser transmittance of at least 20% at 1064 nm and a ratio of the initial laser transmittance at 780 nm to the initial laser transmittance at 1064 nm in the range of less than 10%, or even less than 5%.

[0049] The laser transmittance of the molding composition specified herein is determined by the thermoelectric power measurement or UV-visible spectrophotometric measurement described in the following examples of this specification, preferably by UV-visible spectrophotometric measurement.

[0050] The ratio of the initial laser transmittance at 780 nm to the initial laser transmittance at 1064 nm is specifically determined by the UV-visible spectrophotometric measurement described in the following examples of this specification.

[0051] Useful black colorants can in particular be selected from perylene-derived pigments comprising isomers of formula Ia, isomers of formula Ib, or combinations thereof:

Chemical formula

[0052] In formula Ia and formula Ib, the phenylene, naphthylene and pyridylene groups as R 1 and R 2 may be mono- or polysubstituted by C1-C 12 -alkyl, especially C1-C4-alkyl, C1-C6-alkoxy, especially C1-C4-alkoxy, hydroxyl, nitro and / or halogen, especially chlorine or bromine.

[0053] Alternatively, the phenylene, naphthylene and pyridylene groups as R 1 and R 2 in formula Ia and formula Ib may be unsubstituted. Preferably, R 1 and R 2 are each independently an unsubstituted 1,2-phenylene or 1,8-naphthylene group. More preferably, R 1 and R 2 are the same and are selected from unsubstituted 1,2-phenylene or 1,8-naphthylene.

[0054] Useful perylene-derived pigments are in particular R 1 and R 2It includes isomers of formula Ia, isomers of formula Ib, or combinations thereof, wherein they are the same and are selected from unsubstituted 1,2-phenylene or 1,8-naphthylene, and n is 0.

[0055] The perylene derivative pigments can be prepared by known processes, as described, for example, in International Patent Publication No. WO 2005 / 078023 A3, which is incorporated herein by reference.

[0056] The black colorant can be present in the molding composition of the present invention in an amount of 0.01 to 0.5% by weight, preferably 0.03 to 0.3% by weight, more preferably 0.04 to 0.2% by weight, for example 0.05%, 0.1% or 0.2% based on the total weight of the molding composition.

[0057] Component (C) Optionally, the molding composition of the present invention may further contain a reinforcing agent as component (C). This can be of various types without particular limitation, such as fibers, whiskers, flakes and particles.

[0058] Useful reinforcing agents can be selected in particular from fibrous reinforcing agents and particulate fillers.

[0059] Examples of fibrous reinforcing agents can include, but are not limited to, glass fibers, carbon fibers, boron fibers, asbestos fibers, polyvinyl alcohol fibers, polyester fibers, acrylic fibers, wholly aromatic polyamide fibers, polybenzoxazole fibers, polytetrafluoroethylene fibers, kenaf fibers, bamboo fibers, hemp fibers, bagasse fibers, high-strength polyethylene fibers, alumina fibers, silicon carbide fibers, potassium titanate fibers, brass fibers, stainless steel fibers, steel fibers, ceramic fibers, wollastonite fibers, basalt fibers. Among these, glass fibers and carbon fibers are particularly preferred.

[0060] The fiber length and fiber diameter of the fibrous reinforcing agent are not particularly limited. For example, chopped fibers having a length in the range of 1 to 10 mm, preferably 2 to 6 mm, or continuous fibers can be used as the starting material for the reinforcing agent. The fibers will be broken down to a length of several hundred microns present in the resulting molded article during processing, for example, during kneading of the molding composition. The fiber diameter is generally in the range of 3 to 20 μm, preferably 7 to 13 μm.

[0061] Examples of the cross-sectional shape of the fibrous reinforcing agent include, for example, circular, rectangular, elliptical, and other non-circular shapes, among which the circular shape is particularly preferred. The fibrous reinforcing agent can have a cross-section with an aspect ratio in the range of 1:1 to 5:1.

[0062] Glass fibers are particularly useful as the fibrous reinforcing agent for the present invention. The glass fibers may be surface-treated with a silane coupling agent, for example, a vinyl silane-based coupling agent, an acrylic silane-based coupling agent, an epoxy silane-based coupling agent, and an amino silane-based coupling agent, preferably an amino silane-based coupling agent. The silane coupling agent can be dispersed in a sizing agent. Examples of the sizing agent are acrylic acid compounds, acrylic acid / maleic acid derivative-modified compounds, epoxy compounds, urethane compounds, urethane / maleic acid derivative-modified compounds, and urethane / amine-modified compounds.

[0063] The particulate filler can be an organic filler or an inorganic filler and can have various particle sizes from powdery particles to coarse particles. Examples of materials that can be used as the inorganic particulate filler include, but are not limited to, kaolin, chalk, wollastonite, talc, calcium carbonate, silicate, titanium dioxide, zinc oxide, graphite, mica, vermiculite, montmorillonite, and glass particles (e.g., glass beads).

[0064] In some embodiments, the reinforcing agent as component (C) is selected from glass fibers. The glass fibers can be, for example, E glass fibers, A glass fibers, D glass fibers, AR glass fibers, C glass fibers and S glass fibers, or any other high-elasticity or high-strength glass fibers such as M glass fibers and HMG glass fibers.

[0065] When the reinforcing agent is included, it can be present in the molding composition of the present invention in an amount of 0.5 to 50% by weight, preferably 10 to 40% by weight, more preferably 20 to 40% by weight, such as 20%, 25%, 30%, 35% or 40% based on the total weight of the molding composition.

[0066] Component (D) Optionally, the molding composition of the present invention can further contain, as component (D), an amorphous polymer material selected from polystyrene, styrene-acrylonitrile copolymer, polyester copolymer, polyamide, or any combination thereof.

[0067] Useful amorphous polymer materials can have a refractive index of at least 1.55, preferably in the range of 1.55 to 1.6, when determined according to ASTM D542 at 25 °C and a wavelength of 589 nm.

[0068] Useful amorphous polystyrene can be a polymer containing units derived from at least 50 mol%, preferably at least 60 mol%, most preferably at least 70 mol% of substituted or unsubstituted styrene monomers.

[0069] Examples of substituted or unsubstituted styrene monomers include styrene, alpha-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, para-alpha-dimethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-isopropylstyrene, 3-isopropylstyrene, 4-isopropylstyrene, ortho-divinylbenzene, meta-divinylbenzene, para-divinylbenzene, ethoxystyrene, chlorostyrene, bromostyrene, dibromostyrene, dichlorostyrene, tribromostyrene, trichlorostyrene, 2-vinylnaphthalene, 2-isopropenylnaphthalene or any combination thereof, preferably styrene, alpha-methylstyrene, 4-methylstyrene, chlorostyrene, para-divinylbenzene, bromostyrene, dibromostyrene, trichlorostyrene, 2-vinylnaphthalene, 2-isopropenylnaphthalene or any combination thereof, more preferably styrene, alpha-methylstyrene, 4-methylstyrene or any combination thereof, but are not limited thereto.

[0070] Generally, useful amorphous polystyrene may have a weight average molecular weight (Mw) in the range of 50,000 to 300,000, preferably 100,000 to 200,000, when measured by GPC.

[0071] It should be understood that the term "polystyrene" is not intended to encompass what is referred to herein as "styrene-acrylonitrile copolymer".

[0072] Useful amorphous styrene-acrylonitrile copolymers are copolymers derived from substituted or unsubstituted styrene monomers and substituted or unsubstituted vinyl cyanide monomers. The substituted or unsubstituted styrene monomer can be selected from the molecular species described above, preferably styrene, alpha-methylstyrene, 4-methylstyrene, 4-chloro-styrene or any combination thereof. The vinyl cyanide monomer can be acrylonitrile, methacrylonitrile or a combination thereof.

[0073] The styrene-acrylonitrile copolymer may contain 50 to 99% by weight of a substituted or unsubstituted styrene monomer and 1 to 50% by weight of a substituted or unsubstituted vinyl cyanide monomer.

[0074] The styrene-acrylonitrile copolymer may further contain a comonomer selected from C1-C8 alkyl (meth)acrylates, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, or other unsaturated carboxylic acid derivatives, such as their anhydrides or imides, particularly maleic anhydride or N-phenylmaleimide.

[0075] Examples of the styrene-acrylonitrile copolymer include, but are not limited to, styrene / acrylonitrile (SAN copolymer), α-methylstyrene / acrylonitrile (AMSAN copolymer), styrene / acrylonitrile / maleic anhydride, styrene / acrylonitrile / phenylmaleimide, α-methylstyrene / acrylonitrile / methyl methacrylate, α-methylstyrene / acrylonitrile / t-butyl methacrylate, styrene / acrylonitrile / t-butyl methacrylate copolymer, or any combination thereof.

[0076] The styrene-acrylonitrile copolymer may have a weight average molecular weight (Mw) of 150,000 to 350,000, preferably 150,000 to 300,000, more preferably 150,000 to 250,000, and most preferably 150,000 to 200,000 when measured by GPC.

[0077] Useful amorphous polyester copolymers can have at least two different repeating units (RP1 and RP2) in a total amount of at least 55 mol%, preferably at least 80 mol%, more preferably at least 90 mol% based on all the repeating units of the polyester copolymer. The repeating unit RP1 is derived from a glycol monomer and a dicarboxylic acid monomer, where the dicarboxylic acid monomer includes terephthalic acid and optionally another dicarboxylic acid. The repeating unit RP2 is derived from a glycol monomer and a dicarboxylic acid monomer. The molar ratio of the glycol moiety of RP1 to the glycol moiety of RP2 is preferably from 2:8 to 8:2.

[0078] The glycol monomers for deriving the RP1 unit and the RP2 unit can each independently be selected from aliphatic glycols having 2 to 12 carbon atoms, alicyclic glycols having 4 to 12 carbon atoms, or any combination thereof. Examples of aliphatic glycols having 2 to 12 carbon atoms include ethylene glycol, 1,2 - propylene glycol, 1,3 - propylene glycol, 1,3 - butylene glycol, 1,6 - hexanediol, neopentyl glycol, 1,3 - octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, ditetramethylene glycol and decanediol, more preferably ethylene glycol, diethylene glycol and neopentyl glycol. Examples of alicyclic glycols having 4 to 12 carbon atoms include 1,2 - cyclobutanediol, 1,3 - cyclobutanediol, 1,4 - cyclohexanediol, 1,4 - cyclohexanedimethanol and bis - 1,4 - (hydroxymethyl)cyclohexane, more preferably 1,4 - cyclohexanediol and 1,4 - cyclohexanedimethanol.

[0079] The other dicarboxylic acid for inducing the RP1 unit and the dicarboxylic acid for inducing the RP2 unit can each independently be selected from aliphatic dicarboxylic acids having 2 to 20 carbon atoms, alicyclic dicarboxylic acids having 7 to 12 carbon atoms, aromatic dicarboxylic acids, or any combination thereof. Examples of aliphatic dicarboxylic acids having 2 to 20 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanoic acid, and hexadecanedioic acid, more preferably succinic acid, glutaric acid, adipic acid, and pimelic acid. Examples of alicyclic dicarboxylic acids having 7 to 12 carbon atoms include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid. Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, and phthalic acid. It will be understood that the other dicarboxylic acid in RP1 is other than terephthalic acid.

[0080] The glycol monomer for inducing the RP1 unit is preferably selected from aliphatic glycols having 2 to 12 carbon atoms, more preferably selected from ethylene glycol, diethylene glycol, neopentyl glycol, or any combination thereof. The glycol monomer for inducing the RP2 unit is preferably selected from alicyclic glycols having 6 to 12 carbon atoms, preferably 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, or a combination thereof. Preferably, the dicarboxylic acid monomer for inducing the RP2 unit is terephthalic acid, and the other dicarboxylic acid monomer for inducing the RP1 unit does not exist.

[0081] In some embodiments, the RP1 unit is derived from ethylene glycol and terephthalic acid, and the RP2 unit is derived from 1,4-cyclohexanedimethanol and terephthalic acid. The molar ratio of ethylene glycol to 1,4-cyclohexanedimethanol is preferably in the range of 8:2 to 7:3. Such an amorphous polyester copolymer is also called PETG (cyclohexanedimethylene glycol-modified polyethylene terephthalate).

[0082] In some other embodiments, RP1 is derived from ethylene glycol and terephthalic acid, and RP2 is derived from 1,4-cyclohexanedimethanol and terephthalic acid. The molar ratio of ethylene glycol to 1,4-cyclohexanedimethanol is preferably 2:8 to 3:7. Such an amorphous polyester copolymer is also called PCTG (ethylene glycol-modified poly(1,4-cyclohexanedimethylene terephthalate)).

[0083] PETG and PCTG are commercially available, for example, from Eastman Chemical Co. and SK Chemicals Co., Ltd., such as Skygreen® S2008 of SK Chemicals Co., Ltd., Easter6763 and Easter5445 of Eastman Chemical Co.

[0084] Useful amorphous polyamides can be, for example, block copolymers, random copolymers, graft copolymers or alternating copolymers. Examples of amorphous polyamides include, but are not limited to, PA6I, PA6T, PA6 / PA66, PA66 / 6, PA6 / 510, PA56 / 66, PA56 / 6, PA5T / 66, PA5T / 6, PA6 / 610, PA6 / 612, PA6 / 636, PA6 / 1010, PA66 / 410, PA66 / 510, PA66 / 610, PA66 / 612, PA66 / 1010, PA6T / 66, PA6T / 6, PA6I / 6T, PA56 / 5T, PA5T / 56, PA6 / 6T, PA66 / 6T and PA6T / 6I. Among these, PA6I, PA6 / PA66, PA66 / 6, PA6T / 66, PA66 / 6T, PA6T / 6I and PA6I / 6T are preferred, and PA6I, PA6I / 6T or a combination thereof are more preferred.

[0085] In some specific embodiments, the molding composition of the present invention comprises an amorphous polymer material selected from the combination of polystyrene and PETG. Polystyrene and PETG can be present in a weight ratio in the range of 10:1 to 1:10, preferably 5:1 to 1:5, more preferably 3:1 to 1:3, for example 2:1, 1:1, or 1:2. In these embodiments, the molding composition of the present invention preferably comprises a crystalline polymer material selected from polyester or a polyester-containing blend as component (A).

[0086] In some other specific embodiments, the molding composition of the present invention comprises an amorphous polymer material selected from amorphous polyamides, particularly PA6I, PA6I / 6T or a combination thereof. In these embodiments, the molding composition of the present invention preferably comprises a crystalline polymer material selected from polyamide or a polyamide-containing blend as component (A).

[0087] When an amorphous polymer material is included, it is present in the molding composition of the present invention in a total amount of 1 to 50% by weight, preferably 10 to 40% by weight, more preferably 15 to 35% by weight, such as 15%, 20%, 25%, 30% or 35%, based on the total weight of the molding composition.

[0088] Component (E) Optionally, the molding composition of the present invention may further contain, as component (E), one or more additives such as a nucleating agent, a mold release agent, an impact modifier, a heat stabilizer, a light stabilizer, a compatibilizer, a lubricant, an antioxidant, an adhesion aid, a plasticizer, a colorant other than component (B), a surfactant, a flame retardant, a flame retardant synergist, a coupling agent, an antimicrobial agent, an antistatic agent, etc.

[0089] The molding composition of the present invention may contain, for example, a nucleating agent. Suitable nucleating agents may be selected from talc, boron nitride, mica, kaolin, carbonates, bicarbonates or sulfates of alkali metals or alkaline earth metals, such as alkali metal titanates, silicon nitride or molybdenum disulfide. The nucleating agent is preferably selected from alkali metal carbonates, alkali metal bicarbonates, or any combination thereof.

[0090] In some embodiments, the molding composition of the present invention contains, as one of the additives of component (E), an alkali metal carbonate or bicarbonate, preferably sodium carbonate (Na2CO3), potassium carbonate (K2CO3), sodium bicarbonate (NaHCO3) and potassium bicarbonate (KHCO3), and among these, sodium carbonate is most preferred.

[0091] When a nucleating agent is included, it may be present in an amount of 0.01 to 10% by weight, preferably 0.05 to 6% by weight, more preferably 0.1 to 2% by weight or 0.1 to 0.5% by weight, such as 0.1%, 0.15%, 0.2%, 0.3%, 0.4% or 0.5% by weight, based on the total weight of the molding composition.

[0092] The molding composition of the present invention may contain, for example, a lubricant. Suitable lubricants may be selected from esters or amides of saturated aliphatic carboxylic acids having 10 to 40 carbon atoms, saturated aliphatic alcohols or amines having 2 to 40 carbon atoms, or any combination thereof. The lubricant is preferably a pentaerythritol ester of a fatty acid having 10 to 20 carbon atoms, more preferably pentaerythritol tetrastearate. When a lubricant is included, it may be present in an amount of 0.01 to 3% by weight, such as 0.1 to 2%, or 0.2 to 1% based on the total weight of the molding composition.

[0093] The molding composition of the present invention may contain, for example, an antioxidant. Suitable antioxidants may be selected from aromatic amine-based antioxidants, hindered phenol-based antioxidants, phosphite-based antioxidants, or any combination thereof, preferably hindered phenol-based antioxidants. Examples of hindered phenol-based antioxidants include α-[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-ω-[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]poly(oxy-1,2-ethanediyl), 2,4-bis[(octylthio)methyl]-o-cresol, octyl 3,5-di-tert-butyl-4-hydroxy-hydrocinnamate, 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid C 7~9- branched alkyl esters, 2,4 - bis[(dodecylthio)methyl]-o - cresol, 4,4'-butylidenebis-(3 - methyl - 6 - tert - butylphenol), octadecyl 3,5 - bis(1,1 - dimethylethyl)-4 - hydroxybenzenepropanoate, pentaerythritol tetrakis(3-(3,5 - di - tert - butyl - 4 - hydroxyphenyl)propionate), triethylene glycol bis[3-(3 - tert - butyl - 5 - methyl - 4 - hydroxyphenyl)propionate], 2,4 - bis(n - octylthio)-6-(4 - hydroxy - 3,5 - di - tert - butylanilino)-1,3,5 - triazine, tris-(3,5 - di - tert - butyl - 4 - hydroxybenzyl)isocyanurate, and 2,2 - thiodiethylene bis[3-(3,5 - di - tert - butyl - 4 - hydroxyphenyl)propionate] are included. When an antioxidant is included, it may be present in an amount of 0 to 2% by weight, or 0.01 to 1% by weight, or 0.2 to 0.8% by weight, based on the total weight of the molding composition.

[0094] The molding composition of the present invention may contain, for example, an adhesion promoter. Suitable adhesion promoters may be selected from epoxides, such as epoxidized alkyl esters of fatty acids, such as epoxidized linseed oil, epoxidized soybean oil and epoxidized rapeseed oil, epoxy resins, such as bisphenol - A resins, or any combination thereof. When an adhesion promoter is included, it may be present in an amount of 0 to 2% by weight, for example 0.01 to 1% by weight or 0.2 to 0.8% by weight, based on the total weight of the molding composition.

[0095] Formulation Regarding components (A), (B), (C), (D) and (E), it will be understood that any of the options for the molecular species and / or amounts described herein, generally or as preferred examples, can be combined in any form without limitation. For example, combinations of the general range of the amount of one component with any preferred range of the amount of another component, or combinations of the preferred range of the amount of one component with the general range of the amount of another component, etc. are included in the present invention.

[0096] As an example of the formulation of the molding composition of the present invention, the following embodiments will be described.

[0097] In some embodiments, the molding composition of the present invention is, based on the total weight of the molding composition, respectively, (A) 30 to 80% by weight of a crystalline polymer material selected from polyamide, polyester, polyamide-containing blend, polyester-containing blend, or any combination thereof, and (B) 0.03 to 0.3% by weight of a black colorant, and (C) 0 to 50% by weight of a reinforcing agent, and (D) 0 to 50% by weight of an amorphous polymer material selected from polystyrene, styrene-acrylonitrile copolymer, polyester copolymer, polyamide, or any combination thereof, and (E) 0 to 10% by weight of one or more additives and wherein the present molding composition has an initial laser transmittance of at least 20% at 1064 nm and the ratio of the initial laser transmittance at 780 nm to the initial laser transmittance at 1064 nm is in the range of less than 20% when measured in the form of a 2 mm thick test piece.

[0098] Preferably, the molding composition of the present invention is, based on the total weight of the molding composition, respectively, (A) 35 to 75% by weight of a crystalline polymer material selected from polyamide, polyester, polyamide-containing blend, polyester-containing blend, or any combination thereof, and (B) 0.04 to 0.2% by weight of a black colorant, and (C) 0 to 50% by weight of a reinforcing agent, and (D) 0 to 50% by weight of an amorphous polymer material selected from polystyrene, styrene-acrylonitrile copolymer, polyester copolymer, polyamide, or any combination thereof, and (E) 0 to 10% by weight of one or more additives and Here, when the molding composition is measured in the form of a 2 mm thick test piece, it has an initial laser transmittance of at least 20% at 1064 nm, and the ratio of the initial laser transmittance at 780 nm to the initial laser transmittance at 1064 nm is in the range of less than 20%.

[0099] In some other embodiments, the molding composition of the present invention is, based on the total weight of the molding composition, respectively, (A) 30 to 80% by weight of a crystalline polymer material selected from polyamide, polyester, a polyamide-containing blend, a polyester-containing blend, or any combination thereof, (B) 0.03 to 0.3% by weight of a black colorant, (C) 0 to 50% by weight of a reinforcing agent, (D) 10 to 40% by weight of an amorphous polymer material selected from polystyrene, a styrene-acrylonitrile copolymer, a polyester copolymer, polyamide, or any combination thereof, (E) 0 to 10% by weight of one or more additives and contains, Here, when the molding composition is measured in the form of a 2 mm thick test piece, it has an initial laser transmittance of at least 20% at 1064 nm, and the ratio of the initial laser transmittance at 780 nm to the initial laser transmittance at 1064 nm is in the range of less than 20%.

[0100] Preferably, the molding composition of the present invention is, based on the total weight of the molding composition, respectively, (A) 30 to 80% by weight of a crystalline polymer material selected from polyamide, polyester, a polyamide-containing blend, a polyester-containing blend, or any combination thereof, (B) 0.03 to 0.3% by weight of a black colorant, (C) 10 to 40% by weight of a reinforcing agent, (D) 10 to 40% by weight of an amorphous polymer material selected from polystyrene, a styrene-acrylonitrile copolymer, a polyester copolymer, polyamide, or any combination thereof, (E) 0 to 10 wt% of one or more additives and comprising wherein the molding composition has an initial laser transmittance of at least 20% at 1064 nm and the ratio of the initial laser transmittance at 780 nm to the initial laser transmittance at 1064 nm is in the range of less than 20% when measured in the form of a 2 mm thick test piece.

[0101] More preferably, the molding composition of the present invention is, based on the total weight of the molding composition, respectively, (A) 35 to 75 wt% of a crystalline polymer material selected from polyamide, polyester, polyamide-containing blend, polyester-containing blend, or any combination thereof, (B) 0.04 to 0.2 wt% of a black colorant, (C) 10% to 40% by weight of a reinforcing agent, (D) 10% to 40% by weight of an amorphous polymer material selected from polystyrene, styrene-acrylonitrile copolymer, polyester copolymer, polyamide, or any combination thereof, (E) 0 to 10 wt% of one or more additives and comprising wherein the molding composition has an initial laser transmittance of at least 20% at 1064 nm and the ratio of the initial laser transmittance at 780 nm to the initial laser transmittance at 1064 nm is in the range of less than 20% when measured in the form of a 2 mm thick test piece.

[0102] In some specific embodiments, the molding composition of the present invention is, based on the total weight of the molding composition, respectively, ]>(A) 35 to 75 wt% of a crystalline polymer material selected from polyamide or polyamide-containing blend, (B) 0.04 to 0.2 wt% of a black colorant selected from perylene-derived pigments comprising isomers of formula Ia, isomers of formula Ib, or combinations thereof as described herein, (C) 10% to 40% by weight of a reinforcing agent, (D) An amorphous polymer material selected from polyamides, 10% to 40% by weight, and (E) One or more additives of 0 to 10% by weight and comprising wherein the molding composition has an initial laser transmittance of at least 20% at 1064 nm and the ratio of the initial laser transmittance at 780 nm to the initial laser transmittance at 1064 nm is in the range of less than 20% when measured in the form of a 2 mm thick test piece.

[0103] In some other specific embodiments, the molding composition of the present invention is, based on the total weight of the molding composition, respectively, (A) A crystalline polymer material selected from polyesters or polyester-containing blends, 35% to 75% by weight, (B) A black colorant of 0.04% to 0.2% by weight selected from perylene-derived pigments containing isomers of formula Ia, isomers of formula Ib, or combinations thereof described herein, (C) A reinforcing agent of 10% to 40% by weight, (D) An amorphous polystyrene and polyester copolymer of 10% to 40% by weight selected from PETG, PCTG, or combinations thereof, (E) One or more additives of >0 to 10% by weight, preferably 0.05% to 6% by weight, more preferably 0.1% to 2% by weight, or 0.1% to 0.5% by weight, containing a nucleating agent comprising wherein the molding composition has an initial laser transmittance of at least 20% at 1064 nm and the ratio of the initial laser transmittance at 780 nm to the initial laser transmittance at 1064 nm is in the range of less than 20% when measured in the form of a 2 mm thick test piece.

[0104] In the embodiments described above as examples of the formulation of the molding composition of the present invention, the ratio of the laser transmittance at 780 nm to the laser transmittance at 1064 nm is preferably in the range of less than 10%, or even less than 5%.

[0105] The molding composition of the present invention can be processed by any conventional method without particular limitation. For example, the molding composition can be processed by mixing and kneading the components in any conventional kneading device, such as a single-screw or twin-screw extruder, a Brabender mixer, or a Banbury mixer. The polymer material as component (A) can also add other components to the polyamide resin component as a premix or in sequence. Among these, when using a reinforcing agent such as glass fiber, it is preferably side-fed into the kneading device. Mixing and kneading can preferably be carried out at a temperature in the range of 220 to 290 °C. The obtained mixture can be cooled and pulverized.

[0106] For example, any conventional molding method such as injection molding, blow molding, extrusion molding, and press molding can be applied to the molding composition of the present invention to obtain plastic parts or plastic articles.

[0107] <Use of the molding composition> The molding composition described herein is particularly useful for manufacturing laser-transmissive plastic parts or laser-transmissive plastic articles that are processed by laser welding or laser marking.

[0108] In the case of laser welding applications, the molding composition can be processed into a molded part and then, without particular limitation, used in any conventional laser welding process as a laser-transmissive part to be joined to a laser-absorbing part.

[0109] Any laser-absorbing plastic material can be used for the laser-absorbing component without particular limitation. For example, a composite material or a thermosetting material can be used, but preferably a thermoplastic composition is used. A suitable thermoplastic composition is one that exhibits sufficient laser absorption within the wavelength range used. Examples of suitable thermoplastic compositions include thermoplastic polymers and laser-absorbing fillers, preferably those that exhibit maximum absorption in the wavelength range of 780 nm to 1100 nm, particularly 900 nm to 1100 nm, such as inorganic pigments like carbon black, and / or organic pigments, or other light-absorbing fillers such as glass fibers, carbon fibers, silica, alumina, talc, etc. Among these, carbon black is preferred.

[0110] Conventional thermoplastic polymers such as, for example, polyamide, olefin polymer, vinyl polymer, styrene polymer, acrylic polymer, polyphenylene ether, polyester, polycarbonate, polyacetal, or any combination thereof can be used without limitation.

[0111] <Article> Accordingly, the present invention provides an article produced using the molding composition described herein.

[0112] The articles of the present invention are useful in a variety of applications, such as storage containers, electrical / electronic devices, office automation (OA) devices, household appliances, automotive devices or parts, etc. Particularly preferred applications include automotive hollow parts such as tanks, intake manifolds, camera housings and radar housings, automotive electrical parts such as control units and ignition coils, sensor devices, connectors. The articles of the present invention are particularly suitable as housings for automotive radars or automotive cameras.

[0113] Embodiments Various embodiments are listed below. It will be understood that the embodiments listed below can be combined with all aspects and other embodiments falling within the scope of the present invention.

[0114] 1. Based on the total weight of the molding composition, (A) 20 to 98% by weight of a crystalline polymer material selected from polyamide, polyester, polyamide-containing blends, polyester-containing blends, or any combination thereof, (B) 0.01 to 0.5% by weight of a black colorant, (C) 0 to 50% by weight of a reinforcing agent, (D) 0 to 50% by weight of an amorphous polymer material selected from polystyrene, styrene-acrylonitrile copolymer, polyester copolymer, polyamide, or any combination thereof, (E) 0 to 10% by weight of one or more additives and a molding composition comprising: The molding composition has an initial laser transmittance of at least 20% at 1064 nm and a ratio of the initial laser transmittance at 780 nm to the initial laser transmittance at 1064 nm in the range of less than 20% when measured in the form of a 2 mm thick test piece.

[0115] 2. The molding composition according to Embodiment 1, wherein the ratio of the initial laser transmittance at 780 nm to the initial laser transmittance at 1064 nm is in the range of less than 10%.

[0116] 3. The molding composition according to Embodiment 2, wherein the ratio of the initial laser transmittance at 780 nm to the initial laser transmittance at 1064 nm is in the range of less than 5%.

[0117] 4. The molding composition according to any one of Embodiments 1 to 3, comprising a black colorant selected from perylene-derived pigments containing isomers of Formula Ia, isomers of Formula Ib, or a combination thereof:

Chemical formula

[0118] 5. The molding composition according to embodiment 4, wherein the phenylene, naphthylene and pyridylene groups are unsubstituted.

[0119] 6. R 1 and R 2 are each independently unsubstituted 1,2-phenylene or 1,8-naphthylene, the molding composition according to embodiment 5.

[0120] 7. R 1 and R 2 are the same, the molding composition according to embodiment 4 or embodiment 5.

[0121] 8. The molding composition according to any one of embodiments 4 to 7, wherein n is 0.

[0122] 9. The molding composition according to any one of embodiments 1 to 8, comprising a crystalline polymer material selected from polyamides or polyamide-containing blends as component (A).

[0123] 10. The molding composition according to embodiment 9, comprising an amorphous polymer material selected from polyamides as component (D).

[0124] 11. The molding composition according to any one of embodiments 1 to 10, comprising a crystalline polymer material selected from polyamides or polyamide-containing blends as component (A) and an amorphous polymer material selected from PA6I, PA6I / 6T or combinations thereof as component (D).

[0125] 12. The molding composition according to any one of Embodiments 1 to 8, comprising, as component (A), a crystalline polymer material selected from polyester or a polyester-containing blend.

[0126] 13. The molding composition according to Embodiment 12, comprising, as component (A), a polyalkylene terephthalate or a blend containing polyalkylene terephthalate.

[0127] 14. The molding composition according to any one of Embodiments 10 or 11, comprising, as component (D), a combination of a polyester copolymer selected from PETG, PCTG, or a combination thereof and polystyrene.

[0128] 15. The molding composition according to Embodiment 14, comprising, as component (D), a combination of polystyrene and PETG.

[0129] 16. The molding composition according to any one of Embodiments 12 to 15, comprising a polyalkylene terephthalate or a blend containing polyalkylene terephthalate as component (A) and a combination of polystyrene and PETG as component (D).

[0130] 17. The molding composition according to any one of Embodiments 1 to 16, wherein component (E) comprises a nucleating agent, preferably a nucleating agent selected from alkali metal carbonates, alkali metal bicarbonates, or any combination thereof, more preferably a nucleating agent selected from sodium carbonate, sodium bicarbonate, or any combination thereof.

[0131] 18. The molding composition according to any one of Embodiments 1 to 17, wherein component (B) comprises glass fibers.

[0132] 19. The molding composition according to any one of Embodiments 1 to 18, wherein component (A) is present in an amount of 30 to 80% by weight.

[0133] The molding composition according to embodiment 19, wherein component (A) is present in an amount of 35 to 75% by weight.

[0134] 21. The molding composition according to any one of embodiments 1 to 20, wherein component (B) is present in an amount of 0.03 to 0.3% by weight.

[0135] 22. The molding composition according to embodiment 21, wherein component (B) is present in an amount of 0.04 to 0.2% by weight.

[0136] 23. The molding composition according to any one of embodiments 1 to 22, wherein component (C) is present in an amount of 0.5 to 50% by weight.

[0137] 24. The molding composition according to embodiment 23, wherein component (C) is present in an amount of 10 to 40% by weight.

[0138] 25. The molding composition according to embodiment 24, wherein component (C) is present in an amount of 20 to 40% by weight.

[0139] 26. The molding composition according to any one of embodiments 1 to 25, wherein component (D) is present in an amount of 1 to 50% by weight.

[0140] 27. The molding composition according to embodiment 26, wherein component (D) is present in an amount of 10 to 40% by weight.

[0141] 28. The molding composition according to embodiment 27, wherein component (D) is present in an amount of 15 to 35% by weight.

[0142] 29. The molding composition according to any one of embodiments 1 to 28, wherein component (E) is present and contains a nucleating agent in an amount of 0.01 to 10% by weight based on the total weight of the molding composition.

[0143] 30. The molding composition according to embodiment 29, wherein component (E) contains a nucleating agent in an amount of 0.05 to 6% by weight based on the total weight of the molding composition.

[0144] 31. The molding composition according to embodiment 30, wherein component (E) contains a nucleating agent in an amount of 0.1 to 2% by weight based on the total weight of the molding composition.

[0145] 32. The molding composition according to embodiment 31, wherein component (E) contains a nucleating agent in an amount of 0.1 to 0.5% by weight based on the total weight of the molding composition.

[0146] 33. Use of the molding composition according to any one of embodiments 1 to 32 for producing a laser-transparent plastic part or a laser-transparent plastic article.

[0147] 34. An article produced using the molding composition according to any one of embodiments 1 to 31, for example, a housing for an automotive radar or an automotive camera.

Examples

[0148] The embodiments of the present invention will be described in more detail with reference to the following examples. These examples are described for the purpose of explaining certain aspects of the present invention and should not be construed as limiting them.

[0149] All the preparations and measurements described in this specification were carried out in an air atmosphere under ambient temperature and ambient humidity, unless otherwise specified.

[0150] Materials PA66: Torzen® U4800 NC01, crystalline polyamide 66, available from Invista; PA6I: TM01, amorphous polyamide 6I, available from Shandong Dongchen New Technology Co., Ltd; PA6I / 6T: TI1207, amorphous polyamide 6I / 6T, available from Shandong Guangyin New Materials Co., Ltd; PBT: Ultradur® B 4500, a crystalline polybutylene terephthalate, available from BASF SE, having 34 meq / kg of terminal carboxyl groups and an intrinsic viscosity of 130 ml / g as measured at 25 °C in a 0.5 wt% solution of phenol / o-dichlorobenzene (1:1 mixture); PS: POLYREX® PG-383M, an amorphous polystyrene, available from CHIMEI Corporation; PETG: SKYGREEN® S2008, available from SK chemicals Co., Ltd; Glass fiber: (1) ECS 301HP-3-H, E-glass fiber, available from Chongqing Polycomp International Corp; (2) PBT-NEG-T187H, E-glass fiber, available from Nippon Electric Glass; Heat stabilizer: Ultrabatch® 101, a masterbatch of KI and CuI, available from BASF; Lubricant: CRODAMIDE EBS™, ethylene-bis-stearamide, available from Croda; Nigrosine: COLORANT BLACK 500, available from Orient Chemical Industries Co., Ltd; Macrolex® Green 5B Gran: a solvent-soluble anthraquinone-type green dye, available from LANXESS; Macrolex® Red E2G Gran: a solvent-soluble perinone-type red dye, available from LANXESS; Perylene-derived pigment 1: R 1 =R 2 = 1,8-naphthylene and n is 0, an isomer mixture of black pigments of Formula 1a and Formula 1b, prepared according to the process described in Example 2 of International Publication No. WO 2005 / 078023 A3; Perylene-derived pigment 2: R 1 =R 2An isomer mixture of black pigments of formula 1a and formula 1b, where X is 1,2-phenylene and n is 0, prepared according to the process described in Example 1 of International Publication No. WO 2005 / 078023 A3.

[0151] Preparation of Specimens An injection-molded test sheet with an edge gate, having dimensions of 60 mm × 60 mm × 2 mm (length × width × thickness), was prepared by injection molding with parameters set to the values below, according to the formulation specified in the table below. [Table 1]

[0152] The injection-molded sheet was used as a test sheet for the following measurements.

[0153] Measurement of Laser Transmittance 1) Measurement of Thermoelectric Energy The laser transmittance shown in Table 1 below was determined at a wavelength of 1064 nm by measurement of thermoelectric energy. The measurement geometry was set as follows. Using a beam splitter (SQ2 non-polarizing beam splitter manufactured by Laseroptik GmbH), a reference beam with an output of 1 watt was split at an angle of 90° from a laser beam with a total output of 2 watts (diode-pumped Nd-YAG laser with a wavelength of 1064 nm, FOBA Vario S50; laser source model DP50). The reference beam impinged on a reference sensor. Of the original beam, the portion that passed through the beam splitter became a measurement beam with an output of 1 watt as well. This beam was focused to a spot diameter of 0.18 μm by a mode diaphragm (5.0) behind the beam splitter. A laser transmissivity (LT) measurement sensor was placed 80 mm below the focus. The test sheet was placed 2 mm above the LT measurement sensor. The total measurement time was 30 seconds, and the measurement result was determined within the last 5 seconds. Signals from the reference sensor and the measurement sensor were captured simultaneously. The measurement started simultaneously with the insertion of the sample. The measurement was performed at the center of the test sheet (the intersection of the two diagonals).

[0154] The laser transmittance (LT) was determined according to the following formula.

Number

[0155] The measurement results were reported as the average LT value calculated from 5 measurements per sheet. The average value for 10 sheets was calculated for each material.

[0156] 2) UV-Visible Spectrophotometry Also, the laser transmittance shown in the following table was determined by a UV-visible spectrophotometer (Mettler Evolution (trademark) 220). The measurement results were reported as the average LT value calculated from 5 measurements per sheet. The average value for 10 sheets was calculated for each material.

[0157] Laser Marking and Contrast Measurement Using an LS-U type LAISAI laser marking machine manufactured by Laser Technology Co., Ltd., a laser beam of less than 355 nm was used to mark the test piece sheet. The printability of the test piece sheet was characterized by the contrast obtained according to the following formula.

Number

[0158] The luminance intensity was measured by a Konica Minolta LS-160 luminance meter.

[0159] Measurement of UV Aging Resistance The test piece sheet was subjected to UV exposure for the specified period shown in the following table according to ISO4892-2:2013, and for UV aging resistance, ΔE abCharacterized by value and grayscale. The test specimen sheets were measured initially, after an intermediate specified period within 1 hour, and at the end of the exposure.

[0160] The ΔEab values were measured in accordance with ASTM D2244-16 by using an X-rite Ci6X sphere spectrophotometer under D65 standard light, with a 10° observer and an 8 mm aperture. The results were reported as ΔEab SCE (specular component excluded) and ΔEab SCI (specular component included).

[0161] The grayscale was measured in accordance with GB / T 250-2008 under D65 standard light. The results were reported as rating numbers with 5 being the best and 1 being the worst.

[0162] The formulations and test results of the molding compositions containing polyamide are summarized in Table 1 below.

Table 2

[0163] Samples E1 and E2 of the present invention had similar blackness levels compared to Sample C2 containing the commonly used black colorant nigrosine, but had much higher laser transmittance. Surprisingly, Samples E1 and E2 exhibited much better UV resistance than Samples C2 and C3, even though Sample C3 had a higher laser transmittance than Samples E1 and E2.

[0164] The laser transmittance of the samples of the present invention can be further significantly improved by incorporating an amorphous polymer material.

[0165] Surprisingly, it was also found that Samples E1 and E2 exhibited better laser printing suitability than Samples C2 and C3 in the laser marking process, as demonstrated by the mark contrast results in Table 1. The better printing suitability of Samples E1 and E2 can also be directly observed from the mark images, as shown in FIG. 1. The excellent laser printing suitability of Samples E1 and E2 may be attributed to their non-transparency to lasers in the UV region. However, this is unexpected because conventional laser-transparent plastic materials could not exhibit a desirable laser transmittance while presenting satisfactory laser printing suitability.

[0166] The formulations and test results of the molding compositions containing polyester are summarized in Tables 2 and 3 below. [Table 3]

[0167] It can be seen that Samples E5 and E6 of the present invention exhibited a laser transmittance comparable to that of Sample C4 containing a conventional combination of a red dye and a green dye, even at a much lower usage amount (comparing E5 and C4). Similar results can also be seen in the comparison between Samples E7 - E9 of the present invention and Sample C5.

[0168] Surprisingly, it was also found that the laser transmittance can be significantly improved by incorporating an amorphous polymer material. [Table 4]

[0169] The inventors have found that conventional UV absorbers or UV stabilizers for plastic materials (e.g., PBT), such as Tinuvin-234 (a benzotriazole UV absorber), Hostavin N30 P (an oligomeric hindered amine light stabilizer), and Tinuvin 770 DF (a solid basic hindered amine light stabilizer), cannot effectively protect colorant-containing laser-transparent plastic materials from color shift due to UV aging, as demonstrated by the high ΔEab values of Samples C6 - C9. Surprisingly, the UV aging resistance of the laser-transparent plastic materials was successfully improved by using perylene-derived pigments (compare C4 and E10).

[0170] It will be apparent to those skilled in the art that various changes and modifications can be made to the present invention without departing from the scope and spirit of the invention. The embodiments and examples are intended to be illustrative only. Therefore, the present invention is intended to cover changes and modifications that fall within the scope of the appended claims and their equivalents.

Claims

1. Based on the total weight of each molding composition, (A) 20 to 98% by weight of a crystalline polymer material selected from polyamide, polyester, polyamide-containing blend, polyester-containing blend, or any combination thereof, (B) 0.01 to 0.5% by weight of a black coloring agent, (C) 0-50% by weight of a reinforcing agent, (D) 0 to 50% by weight of an amorphous polymer material selected from polystyrene, styrene-acrylonitrile copolymer, polyester copolymer, polyamide, or any combination thereof, (E) One or more additives in an amount of 0 to 10% by weight A molding composition comprising, The molding composition, when measured in the form of a 2 mm thick test piece, has an initial laser transmittance of at least 20% at 1064 nm, and the ratio of the initial laser transmittance at 780 nm to the initial laser transmittance at 1064 nm is in the range of less than 20%.

2. The molding composition according to claim 1, wherein the ratio of the initial laser transmittance at 780 nm to the initial laser transmittance at 1064 nm is less than 10%, or even less than 5%.

3. The molding composition according to claim 1, wherein the constituent component (B) comprises a black coloring agent selected from perylene derivative pigments including an isomer of formula Ia, an isomer of formula Ib, or a combination thereof: 【Chemistry 1】 [In the formula, R １ , R ２ Each is independent, and each is C １ ~C １２ - Alkyl, C １ ~C ６ -1,2-phenylene, 1,8-,1,2- or 2,3-naphthylene, or 2,3- or 3,4-pyridylene, which may be monosubstituted or polysubstituted with alkoxy, hydroxyl, nitro and / or halogen, X is a halogen, particularly chlorine or bromine. n is between 0 and 4.

4. The molding composition according to claim 3, wherein the phenylene, naphthylene, and pyridylene groups are unsubstituted.

5. R １ and R ２ are each independently unsubstituted 1,2-phenylene or 1,8-naphthylene, preferably R １ and R ２ are the same, the molding composition according to claim 4.

6. The molding composition according to claim 3, wherein n is 0.

7. The molding composition according to claim 1, wherein the constituent component (A) comprises a crystalline polymer material selected from polyamide or a polyamide-containing blend.

8. The molding composition according to claim 1, wherein the constituent component (D) comprises an amorphous polymer material selected from polyamides.

9. The molding composition according to claim 1, comprising a crystalline polymer material selected from polyamide or a polyamide-containing blend as component (A), and an amorphous polymer material selected from PA6I, PA6I / 6T, or a combination thereof as component (D).

10. The molding composition according to claim 1, wherein the constituent component (A) comprises a crystalline polymer material selected from polyester or a polyester-containing blend.

11. The molding composition according to claim 10, wherein the constituent component (A) comprises polyalkylene terephthalate or a blend containing polyalkylene terephthalate.

12. The molding composition according to claim 10, wherein the constituent component (D) includes a combination of a polyester copolymer selected from PETG, PCTG, or a combination thereof and polystyrene.

13. The molding composition according to claim 12, wherein the constituent component (D) includes a combination of polystyrene and PETG.

14. The molding composition according to claim 10, comprising a polyalkylene terephthalate or a blend containing polyalkylene terephthalate as component (A), and a combination of polystyrene and PETG as component (D).

15. The molding composition according to claim 1, wherein the constituent component (E) comprises a nucleating agent, preferably selected from alkali metal carbonates, alkali metal bicarbonates, or any combination thereof, more preferably selected from sodium carbonate, sodium bicarbonate, or a combination thereof.

16. The molding composition according to claim 1, wherein the constituent component (B) contains glass fibers.

17. The molding composition according to claim 1, wherein the constituent component (A) is present in an amount of 30 to 80% by weight, preferably 35 to 75% by weight.

18. The molding composition according to claim 1, wherein the constituent component (B) is present in an amount of 0.03 to 0.3% by weight, preferably 0.04 to 0.2% by weight.

19. The molding composition according to claim 1, wherein the constituent component (C) is present in an amount of 0.5 to 50% by weight, preferably 10 to 40% by weight, and more preferably 20 to 40% by weight.

20. The molding composition according to claim 1, wherein the constituent component (D) is present in an amount of 1 to 50% by weight, preferably 10 to 40% by weight, and more preferably 15 to 35% by weight.

21. The molding composition according to claim 1, wherein the above-mentioned component (E) is present, and the molding composition contains a nucleating agent in an amount of 0.01 to 10% by weight, preferably 0.05 to 6% by weight, more preferably 0.1 to 2% by weight or 0.1 to 0.5% by weight, based on the total weight of the molding composition.

22. Use of the molding composition according to any one of claims 1 to 21 for producing laser-transparent plastic parts or laser-transparent plastic articles.

23. An article produced using the molding composition according to any one of claims 1 to 21, for example, a housing for an automotive radar or an automotive camera.

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