Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
  • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
  • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
  • B29C65/16—Laser beams
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/5399—Phosphorus bound to nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
  • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
  • C08L71/12—Polyphenylene oxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/02—Flame or fire retardant/resistant

Definitions

• the present invention relates to a resin composition, a molded product, a kit, and a method for manufacturing a molded product.
• the present invention relates to a resin composition suitable for laser welding, a kit using the resin composition, a method for producing a molded product, and a molded product.
• the resin composition of the present invention is mainly used as a resin composition (light-transmitting resin composition) on the side that transmits light for laser welding.
• Polyamide resin which is a typical engineering plastic, is easy to process and has excellent mechanical properties, electrical properties, heat resistance, and other physical and chemical properties. Therefore, it is widely used for vehicle parts, electrical / electronic equipment parts, other precision equipment parts, and the like. Recently, parts having complicated shapes are also manufactured from polyamide resin. For example, various welding techniques such as adhesive welding are used for bonding parts having a hollow portion such as an intake manifold. Vibration welding, ultrasonic welding, hot plate welding, injection welding, laser welding technology, etc. are used.
• laser welding includes a resin member having transparency (also referred to as non-absorbent or weakly absorbent) to laser light (hereinafter, may be referred to as “transmissive resin member”) and absorbability to laser light.
• transparent resin member also referred to as non-absorbent or weakly absorbent
• absorbability to laser light.
• This is a method of joining the two resin members by contacting and welding the resin member having the above (hereinafter, may be referred to as “absorbent resin member”). Specifically, it is a method of irradiating a joint surface with laser light from the transmission resin member side to melt and join the absorbent resin member forming the joint surface with the energy of the laser light.
• Laser welding does not generate abrasion powder or burrs, causes less damage to the product, and since the polyamide resin itself is a material with relatively high laser transmittance, processing of polyamide resin products by laser welding technology is possible. It has been attracting attention recently.
• the transmissive resin member is usually obtained by molding a light transmissive resin composition.
• Patent Document 1 states that (A) a reinforced filler having a refractive index of (B) 23 ° C. of 1.560 to 1.600 with respect to 100 parts by mass of a polyamide resin.
• a laser comprising 1 to 150 parts by mass of a polyamide resin composition, wherein at least one monomer constituting at least one of the above-mentioned (A) polyamide resins contains an aromatic ring.
• Welded polyamide resin compositions are described.
• a resin composition in which a glass fiber and a colorant are blended in a blend of polyamide MXD6 and polyamide 66 or a blend of polyamide 6I / 6T and polyamide 6 is disclosed. ..
• the Charpy impact strength may be required for the resin composition for laser welding. Further, the resin composition for laser welding may also be required to have flame retardancy.
• the resin composition for laser welding may also be required to have flame retardancy.
• a resin composition having a notch-free Charpy impact strength of 50 kJ / m 2 or more according to ISO 179 when molded to a thickness of 4 mm flame retardancy is achieved while achieving such a value. It turned out that it is difficult to provide excellent molded products.
• the present invention aims to solve such a problem, and is a resin composition that can be used for laser welding, achieves high light transmittance and high flame retardancy, and has Charpy.
• An object of the present invention is to provide a resin composition capable of providing a molded product having a high impact strength, and a molded product, a kit, and a method for producing the molded product.
• the impact strength without notch according to ISO179 is 50 kJ / m 2 or more and the impact strength with notch according to ISO179 when the resin composition is molded to a thickness of 4 mm, which is 30% or more.
• the polyamide resin is composed of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and 70 mol% or more of the diamine-derived structural unit is derived from xylylenediamine, and the dicarboxylic acid-derived structural unit.
• the resin composition according to ⁇ 1> wherein 70 mol% or more of the resin composition contains a xylylenediamine-based polyamide resin derived from an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms.
• ⁇ 3> The above-described 2>, wherein the xylylenediamine contains m-xylylenediamine and paraxylylenediamine, and the ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms contains an adipic acid. Resin composition.
• ⁇ 4> The resin composition according to any one of ⁇ 1> to ⁇ 3>, which comprises a styrene block polymer as the elastomer.
• ⁇ 5> The resin composition according to ⁇ 4>, wherein the amount of polystyrene in the styrene block polymer is 0.3 to 1.0% by mass in the resin composition.
• ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, further containing a polyphenylene ether-based resin.
• ⁇ 7> Any of ⁇ 1> to ⁇ 6>, which contains a styrene block polymer and a polyphenylene ether resin, and the mass ratio of the styrene block polymer to the polyphenylene ether resin is 1: 1 to 1:35.
• the resin composition according to one. ⁇ 8> The resin composition according to any one of ⁇ 1> to ⁇ 7>, further containing a flame retardant aid.
• ⁇ 9> The resin composition according to ⁇ 8>, which contains zinc oxide as the flame retardant aid.
• ⁇ 10> The resin composition according to ⁇ 8> or ⁇ 9>, wherein the content of the flame retardant aid is 1.1 to 6.0% by mass of the resin composition.
• ⁇ 11> The resin according to any one of ⁇ 1> to ⁇ 10>, wherein the content of the polyamide resin other than the xylylenediamine-based polyamide resin in the resin composition is 4% by mass or less of the resin composition.
• Composition. ⁇ 12> The resin composition according to any one of ⁇ 1> to ⁇ 11>, wherein the flame retardant contains a phosphazene-based flame retardant.
• the content of polystyrene in the styrene block polymer is 0.3 to 1.0% by mass of the resin composition
• the xylylenediamine is m-xylylenediamine and para. 6.
• the ⁇ , ⁇ -linear aliphatic dicarboxylic acid containing xylylenediamine and having 4 to 20 carbon atoms contains adipic acid, and the content of the flame retardant aid is 1.1 to 6 of the resin composition.
• a resin composition which is 0% by mass and the content of the polyamide resin other than the xylylenediamine-based polyamide resin in the resin composition is 4% by mass or less of the resin composition.
• a kit comprising the resin composition according to any one of ⁇ 1> to ⁇ 13> and a light-absorbing resin composition containing a thermoplastic resin and a light-absorbing dye.
• ⁇ 16> A molded product obtained by molding the resin composition according to any one of ⁇ 1> to ⁇ 13> and a light-absorbing resin composition containing a thermoplastic resin and a light-absorbing dye are molded.
• a method for producing a molded product which comprises laser welding the molded product.
• ⁇ 17> A molded product obtained by molding the resin composition according to any one of ⁇ 1> to ⁇ 13> or the kit according to ⁇ 15>.
• a resin composition that can be used for laser welding and can provide a molded product that achieves high light transmittance and high flame retardancy and has high Charpy impact strength.
• molded articles, kits, and methods for manufacturing articles are provided.
• the resin composition of the present invention is a resin composition containing a polyamide resin, a flame retardant, an elastomer, and a light-transmitting dye, and has a wavelength of 940 nm when the resin composition is molded to a thickness of 1 mm.
• the light transmittance in the above is 30% or more
• the notch-free impact strength according to ISO179 when the resin composition is molded to a thickness of 4 mm is 50 kJ / m 2 or more
• there is a notch according to ISO179 It is characterized by having a Sharpy impact strength of 10 kJ / m 2 or more and conforming to V-0 in a UL94 flammability test when the resin composition is molded to a thickness of 0.75 mm.
• the above-mentioned Charpy impact strength and flame retardancy are generally adjusted as follows. In order to impart flame retardancy, it is necessary to add a flame retardant and further a flame retardant aid, but if the content of these components is large, the Charpy impact strength tends to be low. Further, when an elastomer is blended, the Charpy impact strength tends to increase, but if the content of the elastomer is large, the light transmittance becomes low.
• the Charpy impact strength tends to be further increased. On the contrary, when the amount of other resin components increases, the Charpy impact strength may decrease.
• a resin composition capable of providing a molded product having high light transmittance and high flame retardancy and high Charpy impact strength by adjusting the components and contents constituting the resin composition. was successfully provided.
• the resin composition of the present invention contains a polyamide resin.
• the polyamide resin known ones can be used, and it is preferable to include a semi-aromatic polyamide resin and / or an aliphatic polyamide resin, and more preferably to include a semi-aromatic polyamide resin.
• the semi-aromatic polyamide resin is composed of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and 20 to 80 mol% of the total structural unit of the diamine-derived structural unit and the dicarboxylic acid-derived structural unit forms an aromatic ring. It means that it is a constituent unit including.
• the semi-aromatic polyamide resin examples include terephthalic acid-based polyamide resins (polyamide 6T, polyamide 9T, polyamide 10T) and xylylene diamine-based polyamide resins, and xylylene diamine-based polyamide resins are preferable.
• the aliphatic polyamide resin is a polymer having an amide bond linked by an amide bond such as an acid amide obtained by ring-opening polymerization of lactam, polycondensation of aminocarboxylic acid, or polycondensation of diamine and dibasic acid.
• a non-aromatic compound in which more than 80 mol% (preferably 90 mol% or more) of the raw material monomer is used.
• the aliphatic polyamide resin examples include polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 610, polyamide 612, polyamide 6/66, and polyamide 1010, and polyamide 66 is preferable.
• the polyamide resin used in the present invention preferably contains a xylylenediamine-based polyamide resin.
• the xylylenediamine-based polyamide resin used in the present invention is composed of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and 70 mol% or more of the diamine-derived structural unit is derived from xylylenediamine and the dicarboxylic acid. 70 mol% or more of the derived constituent unit is a polyamide resin derived from ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms.
• the diamine-derived constituent unit of the xylylenediamine-based polyamide resin is more preferably 80 mol% or more, further preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more.
• the xylylenediamine preferably contains at least one of metaxylylenediamine and paraxylylenediamine, and preferably contains 10 to 100 mol% of metaxylylenediamine and 90 to 0 mol% of paraxylylenediamine.
• the dicarboxylic acid-derived constituent unit of the xylylenediamine-based polyamide resin preferably has 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and has a carbon number of 95 mol% or more.
• Is derived from 4 to 20 ⁇ , ⁇ -linear aliphatic dicarboxylic acids As the ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms, adipic acid, sebacic acid, suberic acid, dodecanedioic acid, ecodionic acid and the like can be preferably used, and adipic acid and sebacic acid are more preferable. Adipic acid is more preferred.
• Diamines other than xylylenediamine that can be used as the raw material diamine component of the xylylenediamine-based polyamide resin include tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, and octamethylenediamine.
• Alibo diamines such as nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane , 1,4-bis (aminomethyl) cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis ( Examples thereof include alicyclic diamines such as aminomethyl) decalin and bis (aminomethyl) tricyclodecane, diamines having an aromatic ring such as bis (4-aminophenyl) ether, paraphenylenediamine, and bis (aminomethyl) naphthalene. It is possible to use one kind or a mixture of two
• dicarboxylic acid component other than the ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms examples include phthalic acid compounds such as isophthalic acid, terephthalic acid and orthophthalic acid, 1,2-naphthalenedicarboxylic acid and 1,3.
• naphthalenedicarboxylic acids such as dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid can be exemplified, and one kind or a mixture of two or more kinds can be used.
• the xylylene diamine-based polyamide resin used in the present invention is composed mainly of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, but the other structural units are not completely excluded, and ⁇ - Needless to say, it may contain a constituent unit derived from lactams such as caprolactam and laurolactam, and aliphatic aminocarboxylic acids such as aminocaproic acid and aminoundecanoic acid.
• the main component means that among the constituent units constituting the xylylenediamine-based polyamide resin, the total number of the constituent units derived from diamine and the constituent units derived from dicarboxylic acid is the largest among all the constituent units.
• the total of the diamine-derived structural unit and the dicarboxylic acid-derived structural unit in the xylylenediamine-based polyamide resin preferably occupies 90% by mass or more of all the structural units, and preferably 95% by mass or more. More preferred.
• the resin composition of the present invention preferably contains a polyamide resin (preferably a xylylenediamine-based polyamide resin) in a proportion of 20 to 70% by mass of the resin composition.
• the polyamide resin preferably, a xylylenediamine-based polyamide resin
• the polyamide resin is more preferably contained in a proportion of 22% by mass or more, and further preferably in a proportion of 25% by mass or more. Further, it is more preferably contained in a proportion of 65% by mass or less, further preferably contained in a proportion of 60% by mass or less, further preferably contained in a proportion of 50% by mass or less, and contained in a proportion of 40% by mass or less.
• the xylylenediamine-based polyamide resin may contain only one type, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.
• the resin composition of the present invention may or may not contain a resin component other than the above-mentioned polyamide resin, the elastomer described later, and the polyphenylene ether-based resin.
• resins include olefin resins other than elastomers, vinyl resins, styrene resins, acrylic resins, polyester resins, polycarbonate resins, polyacetal resins, and the like.
• the resin composition of the present invention is substantially free of resin components other than the polyamide resin (preferably xylylenediamine-based polyamide resin), the elastomer and the polyphenylene ether-based resin.
• substantially free means that the content of the other resin component is 4% by mass or less of the resin composition, preferably 1% by mass or less, and 0.5% by mass or less. Is more preferable, and it may be 0.1% by mass or less, and further may be 0% by mass.
• the resin composition of the present invention contains a flame retardant.
• a flame retardant various flame retardants such as halogen-based flame retardants and phosphorus-based flame retardants can be used, but phosphorus-based flame retardants are preferable, and phosphazen-based flame retardants are more preferable.
• a phosphazene-based flame retardant By blending a phosphazene-based flame retardant, the flame retardancy of the resin composition tends to be higher.
• the flame retardant the descriptions in paragraphs 0049 to 0059 of JP2012-001580A can be referred to, and these contents are incorporated in the present specification.
• the lower limit of the content of the flame retardant (preferably phosphazene-based flame retardant) in the resin composition of the present invention is preferably 1% by mass or more, more preferably 2% by mass or more of the resin composition. More preferably, it is 3% by mass or more.
• the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 8% by mass or less, and 6% by mass. It is even more preferably less than or equal to, and even more preferably 5% by mass or less.
• the resin composition of the present invention may contain only one kind of flame retardant, or may contain two or more kinds of flame retardants. When two or more types are included, the total amount is preferably in the above range.
• the resin composition of the present invention does not substantially contain a flame retardant other than the phosphazen flame retardant.
• substantially free means that the content of the flame retardant other than the phosphazen-based flame retardant is 10% by mass or less of the blended amount of the phosphazen-based flame retardant, preferably 5% by mass or less. It is more preferably mass% or less.
• the resin composition of the present invention may contain a flame retardant aid.
• the flame retardant aid is preferably a metal-containing oxide selected from the group consisting of zinc, antimony, copper, magnesium, molybdenum, zirconium, tin, iron, titanium and aluminum.
• the flame retardant aid is preferably zinc oxide.
• the zinc oxide is preferably zinc borate.
• Zinc borate can be obtained from zinc oxide and boric acid, for example, ZnO ⁇ B 2 O 3 ⁇ 2H 2 O and 2ZnO ⁇ 3B 2 O 3 ⁇ 3.5H 2 dihydrate and anhydrides such O Can be mentioned.
• the lower limit of the content of the flame retardant aid in the resin composition of the present invention is preferably 1.1% by mass or more, more preferably 1.5% by mass or more of the resin composition. It is more preferably 0.0% by mass or more. By setting the amount of the flame retardant aid to 1.1% by mass or more, the flame retardancy can be exhibited more effectively.
• the upper limit of the amount of the flame retardant aid is preferably 6.0% by mass or less, more preferably 5.5% by mass or less, and further preferably 3.0% by mass or less. By setting the content to 6.0% by mass or less, the Charpy impact strength, particularly the notch-free Charpy impact strength can be effectively improved.
• the resin composition of the present invention may contain only one kind of flame retardant aid, or may contain two or more kinds. When two or more types are included, the total amount is preferably in the above range.
• the resin composition of the present invention contains an elastomer.
• the elastomer By including the elastomer, it becomes possible to improve the impact resistance.
• the elastomer include the elastomer described in paragraph 0033 of JP2017-210591A, the elastomer described in paragraphs 0075 to 0088 of JP2012-251061A, and paragraphs 0101 to 0107 of JP2012-177047A. Elastomers and the like can be used, and these contents are incorporated in the present specification.
• the elastomer used in the present invention is preferably a block polymer.
• the block polymer is preferably a styrene block polymer. By blending the styrene block polymer, the transmittance can be further increased.
• styrene block polymer examples include polystyrene-poly (ethylene / butylene) -polystyrene block polymer (SEBS), polystyrene-poly (ethylene / propylene) -polystyrene block polymer (SEPS), and polystyrene-poly (ethylene / butylene).
• SEBS polystyrene-poly (ethylene / butylene) -polystyrene block polymer
• SEPS polystyrene-poly (ethylene / propylene) -polystyrene block polymer
• SEB Block polymer
• SEP polystyrene-poly (ethylene / propylene) block polymer
• SEBC polystyrene-poly (ethylene / butylene) -polystyrene crystal block polymer
• the styrene block polymer may have a cyclic acid anhydride group in the side chain, and examples of the cyclic acid anhydride group include a maleic anhydride group, a succinic anhydride group, a phthalic anhydride group, and a glutaric anhydride group. Maleic anhydride groups are preferred.
• examples of commercially available thermoplastic elastomers having a cyclic acid anhydride group in the side chain include tough tech (maleic anhydride-modified SEBS, M1913 (manufactured by Asahi Kasei Chemicals)) and tough tech (maleic anhydride-modified SEBS, M1943 (Asahi Kasei Chemicals)).
• the amount of polystyrene in the styrene block polymer in the resin composition of the present invention is preferably 0.3% by mass or more, more preferably 0.5% by mass or more in the resin composition.
• the upper limit of the content of the elastomer is preferably 3% by mass or less, more preferably 1.0% by mass or less, and further preferably 0.8% by mass or less. Within such a range, it is possible to achieve high light transmittance while maintaining excellent flame retardancy.
• the content of the elastomer in the resin composition of the present invention can be 1.0 to 3.0% by mass in the resin composition.
• the resin composition of the present invention may contain only one type of elastomer, or may contain two or more types of elastomer. When two or more types are included, the total amount is preferably in the above range.
• the resin composition of the present invention substantially does not contain an elastomer other than the styrene block polymer.
• substantially free means that the content of the elastomer other than the styrene block polymer is 10% by mass or less of the blending amount of the styrene block polymer, preferably 5% by mass or less, and 1% by mass. More preferably, it is less than%.
• the resin composition of the present invention contains a light-transmitting dye.
• the light-transmitting dye used in the present invention is usually a black dye, and specifically, naphthalocyanine, aniline black, phthalocyanine, porphyrin, perinone, perylene, quaterylene, azo dye, anthraquinone, pyrazolone, square acid derivative, and Examples include immonium dyes.
• Commercially available products include e-BIND (trade name) LTW-8731H (model number), e-BIND (trade name) LTD-8701H (model number), which are colorants manufactured by Orient Chemical Industries, Ltd., and coloring manufactured by Arimoto Chemical Co., Ltd.
• the content of the light-transmitting dye in the resin composition of the present invention is preferably 0.001 part by mass or more, more preferably 0.006 part by mass or more, based on 100 parts by mass of the resin composition. Further, it may be 0.018 parts by mass or more, 0.024 parts by mass or more, 0.030 parts by mass or more, and 0.050 parts by mass or more.
• the upper limit of the content of the light-transmitting dye is preferably 5.0 parts by mass or less, more preferably 3.0 parts by mass or less, and 1.0 part by mass or less of the resin composition. It is more preferable to have 0.20 parts by mass or less, 0.10 parts by mass or less, and 0.060 parts by mass or less.
• the content of the light-transmitting dye in the resin composition of the present invention is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more.
• the upper limit of the content of the light-transmitting dye is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and 1.0% by mass of the resin composition. Is even more preferable. Only one type of light-transmitting dye may be contained, or two or more types may be contained. When two or more types are contained, the total amount is preferably in the above range. Further, it is preferable that the resin composition of the present invention does not substantially contain carbon black.
• substantially free means, for example, 0.0001% by mass or less of the resin composition.
• the resin composition of the present invention preferably contains a polyphenylene ether-based resin.
• the polyphenylene ether-based resin is preferably a polyphenylene ether-based resin modified with maleic anhydride.
• the amount of maleic anhydride in the maleic anhydride-modified polyphenylene ether-based resin is 0.01 to 1.0% by mass, preferably 0.1 to 0.7% by mass, in terms of the amount of maleic acid. .. By setting it in such a range, high mechanical strength can be achieved.
• the amount of maleic anhydride in the maleic anhydride-modified polyphenylene ether-based resin is the amount of maleic anhydride used for modifying the polyphenylene ether-based resin that reacts with the polyphenylene ether-based resin, and is converted into the amount of maleic acid. It says the mass when it is done.
• polyphenylene ether-based resin examples include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, and poly (2,6).
• -Dipropyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) d -Tel and the like can be mentioned, and poly (2,6-dimethyl-1,4-phenylene) ether is particularly preferable.
• the polyphenylene ether-based resin has an intrinsic viscosity of 0.2 to 0.6 dL / g, more preferably 0.3 to 0.5 dL / g, measured in chloroform at a temperature of 30 ° C.
• the intrinsic viscosity within the above range may be adjusted by using two or more kinds of polyphenylene ether-based resins having different intrinsic viscosities in combination.
• the lower limit of the content of the polyphenylene ether-based resin is preferably 1.0% by mass or more, more preferably 2.5% by mass or more, and preferably 5% by mass or more of the resin composition. It is even more preferably 7% by mass or more, even more preferably 8.5% by mass or more, and even more preferably 9.0% by mass or more.
• the upper limit is preferably 20.0% by mass or less, more preferably 15.0% by mass or less, further preferably 12.0% by mass or less, and 11.0% by mass or less. It is more preferable to have. By setting it to 20.0% by mass or less, the laser welding property can be further improved even if the total energy input amount at the time of laser welding is reduced.
• the resin composition of the present invention may contain only one type of polyphenylene ether-based resin, or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.
• the resin composition of the present invention contains both a block polymer and a polyphenylene ether-based resin.
• the polystyrene block polymer and the polyphenylene ether-based resin are contained, and the mass ratio of the styrene block polymer and the polyphenylene ether-based resin is 1: 1 to 1:35, preferably 1:10 to 1:35. It is more preferably 20 and even more preferably 1:12 to 1:18. By setting such a mass ratio, the effect of the present invention is more effectively exhibited.
• the resin composition of the present invention may contain a mold release agent.
• the release agent include an aliphatic carboxylic acid, a salt of an aliphatic carboxylic acid, an ester of an aliphatic carboxylic acid and an alcohol, an aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15,000, and a polysiloxane-based silicone oil.
• Ketone wax, light amide and the like preferably an aliphatic carboxylic acid, a salt of an aliphatic carboxylic acid, an ester of an aliphatic carboxylic acid and an alcohol, and more preferably a salt of an aliphatic carboxylic acid.
• the description in paragraphs 0055 to 0061 of JP-A-2018-0950706 can be referred to, and these contents are incorporated in the present specification.
• the content thereof is preferably 0.05 to 3% by mass, preferably 0.1 to 0.8% by mass in the resin composition. More preferably, it is 0.2 to 0.6% by mass.
• the resin composition of the present invention may contain only one type of release agent, or may contain two or more types of mold release agent. When two or more types are included, the total amount is preferably in the above range.
• the resin composition of the present invention preferably contains glass fibers.
• the glass fiber has a glass composition such as A glass, C glass, E glass, R glass, and S glass, and E glass (non-alkali glass) is particularly preferable.
• the glass fiber used in the resin composition of the present invention may be a single fiber or a plurality of single fibers twisted together.
• the morphology of glass fibers is "glass roving", which is a continuous winding of single fiber or multiple twisted fibers, "chopped strand", which has a cut length (number average fiber length) of 1 to 10 mm, and crushed length (crushed length). It may be any of "milled fibers” having a number average fiber length of 10 to 500 ⁇ m.
• Such glass fibers are commercially available from Asahi Fiber Glass Co., Ltd. under the trade names of "Glaslon chopped strand” and “Glaslon milled fiber” and are easily available.
• As the glass fiber those having different morphologies can be used in combination.
• glass fibers having an irregular cross-sectional shape are also preferable.
• the irregular cross-sectional shape means that the flatness represented by the major axis / minor axis ratio (D2 / D1) when the major axis of the cross section perpendicular to the length direction of the fiber is D2 and the minor axis is D1 is, for example, 1. It is 5 to 10, and more preferably 2.5 to 10, more preferably 2.5 to 8, and particularly preferably 2.5 to 5.
• the description in paragraphs 0065 to 0072 of JP-A-2011-195820 can be referred to, and the contents thereof are incorporated in the present specification.
• the glass fiber in the present invention may be glass beads.
• the glass beads are spherical beads having an outer diameter of 10 to 100 ⁇ m, and are commercially available, for example, from Potters Barotini under the trade name “EGB731” and are easily available.
• glass flakes are scaly flakes having a thickness of 1 to 20 ⁇ m and a side length of 0.05 to 1 mm. For example, they are commercially available from Nippon Sheet Glass Co., Ltd. under the trade name of “Fleka”. , Easily available.
• the glass fiber used in the present invention is particularly preferably a glass fiber having a weight average fiber diameter of 1 to 20 ⁇ m and a cut length (number average fiber length) of 1 to 10 mm.
• the weight average fiber diameter is calculated as the weight average fiber diameter in a circle having the same area.
• the glass fiber used in the present invention may be focused with a sizing agent.
• a sizing agent an acid-based sizing agent containing maleic anhydride or the like, a urethane-based sizing agent, an epoxy-based sizing agent, or the like is preferable.
• the content of the glass fiber in the resin composition of the present invention is preferably 20% by mass or more, more preferably 25% by mass or more, and further preferably 30% by mass or more in the resin composition. , 35% by mass or more, and even more preferably 40% by mass or more. Further, the content of the glass fiber in the resin composition of the present invention is preferably 60% by mass or less, more preferably 55% by mass or less, and even if it is less than 50% by mass in the resin composition. Good. By blending the glass fiber in the above range, it becomes possible to maintain a higher light transmittance.
• the resin composition of the present invention may contain only one type of glass fiber, or may contain two or more types of glass fibers. When two or more types are contained, the total amount is preferably in the above range.
• the resin composition of the present invention may contain other components as long as the gist of the present invention is not deviated.
• additives include nucleating agents, fillers other than glass fiber, light stabilizers, antioxidants, UV absorbers, optical brighteners, anti-dripping agents, antistatic agents, anti-fog agents, anti-blocking agents, etc. Examples include fluidity improvers, plasticizers, dispersants, antibacterial agents and the like. Only one of these components may be used, or two or more of these components may be used in combination.
• the resin composition of the present invention contains a polyamide resin (preferably a xylylenediamine-based polyamide resin), a flame retardant, an elastomer, a light-transmitting dye, and glass so that the total of each component is 100% by mass. The content of fiber and other additives is adjusted.
• the resin composition of the present invention contains a xylylene diamine-based polyamide resin, a phosphazene-based flame retardant, a styrene block polymer, a polyphenylene ether-based resin, and a zinc oxide, and the content of the styrene block polymer is high.
• the xylylene diamine which is 1 to 2% by mass of the resin composition and constitutes the xylylene diamine-based polyamide resin contains metaxylylene diamine and paraxylylene diamine and has 4 carbon atoms constituting the xylylene diamine-based polyamide resin.
• the ⁇ , ⁇ -linear aliphatic dicarboxylic acid of ⁇ 20 contains adipic acid, and the content of the flame retardant aid is 1.1 to 6.0% by mass of the resin composition.
• the content of the polyamide resin other than the rangeamine-based polyamide resin is preferably 4% by mass or less of the resin composition.
• the resin composition of the present invention has a notched Charpy impact strength of 50 kJ / m 2 or more according to ISO179 and a notched Charpy impact strength of 10 kJ according to ISO179 when molded to a thickness of 4 mm. / M 2 or more.
• the impact strength of Charpy with a notch is preferably 11 kJ / m 2 or more. Since the molded product obtained from the resin composition of the present invention has a high Charpy impact strength, it can be preferably used in applications requiring impact resistance. In particular, the present invention is highly valuable in that the above-mentioned Charpy impact strength can be achieved while blending a flame retardant.
• the upper limit of the notch-free Charpy impact strength is not particularly defined, but even if it is 70 kJ / m 2 or less, and further 60 kJ / m 2 or less, it is a sufficiently practical level. Further, notched Charpy impact strength is not specifically limited, 20 kJ / m 2 or less, more, even 15 kJ / m 2 or less, a sufficiently practical level.
• the resin composition of the present invention has a light transmittance of 30% or more, preferably 35% or more, at a wavelength of 940 nm when molded to a thickness of 1 mm. The upper limit may be 100%, but in reality, 50% or less sufficiently satisfies the required performance.
• the resin composition of the present invention conforms to V-0 in a UL94 flammability test (combustibility and heat aging property) when molded to a thickness of 0.75 mm. Further, the resin composition of the present invention is preferably molded to a thickness of 0.75 mm and placed in an environment of 70 ° C. for 168 hours, and then conforms to V-0 in a UL94 flammability test. The details of the UL94 flammability test follow the methods described in Examples below.
• the method for producing the resin composition of the present invention is not particularly limited, but a method using a single-screw or twin-screw extruder having equipment capable of devolatile from the vent port is preferable as a kneader.
• the above-mentioned polyamide resin component, glass fiber and other additives to be blended as needed may be collectively supplied to the kneader, or the other blending components may be sequentially supplied to the polyamide resin component.
• the glass fiber is preferably supplied from the middle of the extruder in order to suppress crushing during kneading. Further, two or more kinds of components selected from each component may be mixed and kneaded in advance.
• the light-transmitting dye is prepared in advance as a masterbatch of a polyamide resin or the like, and then kneaded with another component (polyamide resin (preferably xylylenediamine-based polyamide resin) or the like) to obtain the present invention.
• polyamide resin preferably xylylenediamine-based polyamide resin
• the resin composition in the invention may be adjusted.
• the method for producing a molded product using the resin composition of the present invention is not particularly limited, and is a molding method generally used for thermoplastic resins, that is, a molding method such as injection molding, hollow molding, extrusion molding, or press molding. Can be applied.
• a particularly preferable molding method is injection molding because of its good fluidity.
• the present invention also discloses a kit having the above resin composition and a light absorbing resin composition containing a thermoplastic resin and a light absorbing dye.
• the kit of the present invention is preferably used for producing a molded product by laser welding. That is, the resin composition contained in the kit serves as a light-transmitting resin composition, and the molded product obtained by molding the light-transmitting resin composition is a transparent resin member for laser light during laser welding. Become. On the other hand, a molded product obtained by molding a light-absorbing resin composition serves as an absorbing resin member for laser light during laser welding.
• the light-absorbing resin composition used in the present invention contains a thermoplastic resin and a light-absorbing dye.
• the thermoplastic resin include polyamide resin, olefin resin, vinyl resin, styrene resin, acrylic resin, polyphenylene ether resin, polyester resin, polycarbonate resin, and polyacetal resin, and the compatibility with the resin composition is high. From a good point of view, a polyamide resin, a polyester resin, and a polycarbonate resin are particularly preferable, and a polyamide resin is more preferable. Further, the thermoplastic resin may be one kind or two or more kinds.
• the type of the polyamide resin used in the light-absorbing resin composition is not specified, but the xylylenediamine-based polyamide resin is preferable. It may also contain an inorganic filler.
• the inorganic filler include fillers capable of absorbing laser light, such as glass fiber, carbon fiber, silica, alumina, talc, carbon black, and inorganic powder coated with a material that absorbs laser, and glass fiber is preferable.
• the glass fiber has the same meaning as the glass fiber that may be blended in the resin composition of the present invention, and the preferable range is also the same.
• the light-absorbing dye has a maximum absorption wavelength in the range of the laser light wavelength to be irradiated, that is, in the present invention, in the range of 800 nm to 1100 nm, and is an inorganic pigment (carbon black (for example, acetylene black, lamp black)). , Thermal black, furnace black, channel black, Ketjen black, etc.), red pigments such as iron oxide red, orange pigments such as molybdate orange, white pigments such as titanium oxide), organic pigments (yellow pigments, Orange pigments, red pigments, blue pigments, green pigments, etc.) and the like.
• the inorganic pigment generally has a strong hiding power and is preferable, and the black pigment is more preferable. Two or more of these light-absorbing dyes may be used in combination.
• the content of the light-absorbing dye is preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of the resin component.
• the kit of the present invention preferably has 80% by mass or more in common of the component excluding the light-transmitting dye in the resin composition and the component excluding the light-absorbing dye in the light-absorbing resin composition, preferably 90% by mass. It is more preferable that the above is common, and it is more preferable that 95 to 100% by mass is common.
• a molded product (transmissive resin member) obtained by molding the resin composition of the present invention and a molded product (absorbent resin member) obtained by molding the light-absorbing resin composition are molded by laser welding. Goods can be manufactured.
• the transmissive resin member and the absorbent resin member can be firmly welded without using an adhesive.
• the shape of the members is not particularly limited, but since the members are used by joining them by laser welding, they usually have at least surface contact points (plane, curved surface). In laser welding, the laser beam transmitted through the transmitting resin member is absorbed by the absorbing resin member and melted, and both members are welded.
• the molded product of the resin composition of the present invention has high transparency to laser light, it can be preferably used as a transmissive resin member.
• the thickness of the member through which the laser light is transmitted (the thickness in the laser transmission direction in the portion through which the laser light is transmitted) can be appropriately determined in consideration of the application, the composition of the resin composition, and the like, and is, for example, 5 mm. It is less than or equal to, preferably 4 mm or less.
• the laser light source used for laser welding can be determined according to the light absorption wavelength of the light-absorbing dye, and a laser having a wavelength in the range of 800 to 1100 nm is preferable, and for example, a semiconductor laser or a fiber laser can be used.
• the welded portions of both are brought into contact with each other.
• the welding points of both are in surface contact, and may be a combination of planes, curved surfaces, or a flat surface and a curved surface.
• the laser beam is irradiated from the transmission resin member side.
• a lens may be used to focus the laser beam on the interface between the two. The focused beam transmits through the transmitting resin member, is absorbed near the surface of the absorbing resin member, generates heat, and melts.
• the molded product in which the transparent resin member and the absorbent resin member are welded in this way has high welding strength.
• the molded product in the present invention is intended to include not only finished products and parts but also members forming a part thereof.
• the molded product obtained by laser welding in the present invention has good mechanical strength, high welding strength, and less damage to the resin due to laser light irradiation. Therefore, it is used for various purposes such as various storage containers and electricity.
• It can be suitably used for various sensor parts, connector parts, switch parts, breaker parts, relay parts, coil parts, transformer parts, lamp parts and the like.
• the resin compositions and kits of the present invention are suitable for in-vehicle camera modules.
• Clayton FG1901X Manufactured by Clayton Japan, contains 30% by mass of maleic anhydride-modified polystyrene-poly (ethylene / butylene) -polystyrene block copolymer, 1.7% by mass of maleic anhydride, and 30% by mass of polystyrene.
• CS8CP Calcium montanate, light transmissive dye (LTW-8701H) manufactured by Nitto Kasei Kogyo Co., Ltd .: Masterbatch glass of e-BIND LTD LTW-8701H, polyamide 66 and light transmissive dye manufactured by Orient Chemical Industry Co., Ltd.
• Flame Retardant (Ravitor FP-110) Phosphazen compound, Fushimi Pharmaceutical Co., Ltd.
• the glass fiber is put into the above-mentioned twin-screw extruder from the side of the extruder using a vibrating cassette waving feeder (CE-V-1B-MP manufactured by Kubota), and melt-kneaded with the resin component and the like. , Pellets for forming a transparent resin member were obtained.
• the temperature setting of the extruder was 280 ° C.
• the resin composition of the present invention was able to achieve high Charpy impact strength while achieving high light transmittance and excellent flame retardancy (Examples 1 to 3).
• the resin compositions of Comparative Examples could not achieve high notch-free Charpy impact strength (Comparative Examples 1 to 8).
• the absorption resin member was formed in the same manner except that 6 parts by mass of carbon black masterbatch (manufactured by Nikko Bics Co., Ltd., PA-0895) was blended without blending the light-transmitting dye. Pellets were obtained. Using the permeation resin member forming pellet obtained in Example 1 and the absorbing resin member forming pellet, laser welding was performed according to paragraphs 0072, 0073, and FIG. 1 of JP-A-2018-168346. It was. It was confirmed that laser welding was performed properly.

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