Molded products

Abstract

To provide a molded article which has a first member containing a polyamide resin and a dye and a different member (resin member) brought into contact with the first member, and in which the dye contained in the first member is less likely to be migrated to the different member, and an on-vehicle camera module.SOLUTION: A molded article has: a first member which is formed of a composition containing 10-60 pts.mass of a reinforcement filler and 0.1-0.5 pts.mass of a dye with respect to 100 pts.mass of a polyamide resin having a glass transition temperature measured according to differential scan calorimetry of 80°C or higher; and a second member which is brought into contact with the first member, wherein a difference (absolute value) of the glass transition temperature of the polyamide resin contained in the first member and the glass transition temperature of the resin contained in the second member is 11°C or more, and the glass transition temperature of the resin contained in the second member is -30 to 200°C.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a molded product. In particular, it relates to a molded product suitable for an in-vehicle camera module.

Background Art

[0002] Polyamide resin, which is a typical engineering plastic, is easy to process and furthermore has excellent mechanical properties, electrical properties, heat resistance, and other physical and chemical properties. For this reason, it is widely used in vehicle parts, electrical and electronic equipment parts, and other precision equipment parts. Recently, parts with complex shapes have also come to be manufactured from polyamide resin. For example, for joining parts having a hollow portion such as an intake manifold, various welding techniques such as adhesive welding, vibration welding, ultrasonic welding, hot plate welding, injection welding, laser welding techniques, etc. are used. For example, laser welding using polyamide resin is described in Patent Document 1.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Here, when joining a member molded from polyamide resin and another resin member, it has been found that when the member molded from polyamide resin contains a dye, the dye may migrate to the other resin member. In particular, when the dye contains sulfur, it may also have an adverse effect on the electrical and electronic functions of the member. In recent years, there have also been many cases where dissimilar members with a large difference in glass transition temperature (Tg) between the first member and the second member are joined. The present invention aims to solve the above problems and to provide a molded article having a first member containing a polyamide resin and a dye, and a dissimilar member (resin member) in contact with the first member, wherein the dye contained in the first member is less likely to transfer to the dissimilar member, and an in-vehicle camera module. [Means for solving the problem]

[0005] Based on the above-mentioned problems, the inventors conducted research and found that by increasing the glass transition temperature of the first component containing polyamide resin and dye, the transfer of dye to dissimilar components can be effectively suppressed. Specifically, the above problem was solved by the following means. <1> A first member formed from a composition comprising 100 parts by mass of polyamide resin having a glass transition temperature of 80°C or higher as measured by differential scanning calorimetry, 10 to 60 parts by mass of reinforcing filler, and 0.1 to 0.5 parts by mass of dye, It has a second member that is in contact with the first member, The difference (absolute value) between the glass transition temperature of the polyamide resin contained in the first member and the glass transition temperature of the resin contained in the second member is 11°C or more. A molded product in which the glass transition temperature of the resin contained in the second component is -30 to 200°C. <2> The aforementioned dye contains sulfur. <1> Molded product as described above. <3> The first member comprises copper iodide and / or potassium iodide. <1> or <2> Molded product as described above. <4> The second member includes at least one of polycarbonate resin, polyester resin, and silicone resin. <1> ~ <3> A molded product as described in any one of the following. <5> <1> ~ <4> An in-vehicle camera module containing a molded product as described in any one of the following. <6> The dye contains perinone with a molecular weight of 300 or more and / or anthraquinone with a molecular weight of 600 or more. <1> ~ <5> A molded product as described in any one of the following. <7> The dye comprises at least one of Solvent Red 179, Acid Blue 80, and Solvent Yellow 163. <1> ~ <6> A molded product as described in any one of the following. [Effects of the Invention]

[0006] The present invention makes it possible to provide a molded article having a first member containing a polyamide resin and a dye, and a dissimilar member (resin member) in contact with the first member, wherein the dye contained in the first member is less likely to transfer to the dissimilar member, and also provides an in-vehicle camera module. [Brief explanation of the drawing]

[0007] [Figure 1] Figure 1 is a schematic cross-sectional view showing a molded product according to this embodiment. [Modes for carrying out the invention]

[0008] The following describes in detail embodiments for carrying out the present invention (hereinafter simply referred to as "this embodiment"). Note that the following embodiment is illustrative for explaining the present invention, and the present invention is not limited to this embodiment. In this specification, "~" is used to mean that the numbers before and after it are included as the lower and upper limits, respectively. In this specification, all physical properties and characteristic values ​​shall be those at 23°C unless otherwise specified. If the measurement methods, etc., described in the standards shown herein differ from year to year, unless otherwise specified, the standards as of January 1, 2021 shall apply.

[0009] The molded article of this embodiment comprises a first member formed from a composition containing 100 parts by mass of polyamide resin having a glass transition temperature of 80°C or higher as measured by differential scanning calorimetry, 10 to 60 parts by mass of reinforcing filler, and 0.1 to 0.5 parts by mass of dye, and a second member in contact with the first member, wherein the difference between the glass transition temperature of the polyamide resin contained in the first member and the glass transition temperature of the resin contained in the second member is 11°C or higher, and the glass transition temperature of the resin contained in the second member is -30 to 200°C. Even when the first and second components are different materials, and there is a large difference in the glass transition temperatures of the resins contained in both components, color transfer can be effectively suppressed by increasing the glass transition temperature of the polyamide resin contained in the first component. In particular, the fact that the glass transition temperature of the polyamide resin can effectively suppress dye migration is quite remarkable.

[0010] <First component> The first component is formed from a composition containing 100 parts by mass of polyamide resin, which has a glass transition temperature of 80°C or higher as measured by differential scanning calorimetry, 10 to 60 parts by mass of reinforcing filler, and 0.1 to 0.5 parts by mass of dye.

[0011] The composition used in this embodiment includes a polyamide resin having a glass transition temperature of 80°C or higher, as measured by differential scanning calorimetry. By including such a polyamide resin, it is possible to make it difficult for the dye contained in the first component to move from the first component to the second component. The glass transition temperature of the polyamide resin is preferably 90°C or higher, more preferably 95°C or higher, and may be 105°C or higher. There is no particular upper limit to the glass transition temperature, but for example, it may be 150°C or lower, or 130°C or lower. If the composition used in this embodiment contains two or more polyamide resins, the glass transition temperature is calculated by multiplying the mass fraction of each polyamide resin by its respective glass transition temperature. For example, if the composition contains 10 parts by mass of a polyamide resin with a glass transition temperature of 80°C and 90 parts by mass of a polyamide resin with a glass transition temperature of 100°C, the glass transition temperature of the polyamide resin in this embodiment is calculated as 80 × 0.1 + 100 × 0.9 (°C). The glass transition temperature of the polyamide resin in this embodiment is measured according to the description in the examples below.

[0012] The type of polyamide resin used in this embodiment is not particularly specified; it may be an aliphatic polyamide resin, an aromatic polyamide resin, or a blend of both. Examples of polyamide resins include polyamide 6I, 6 / 66, 6T / 6I, 6 / 6T, 66 / 6T, 66 / 6T / 6I, polyamide MXD6I, polytrimethylhexamethylene terephthalamide, and polyundecamethylene hexahydroterephthalamide. In addition, "I" indicates the isophthalic acid component, "T" indicates the terephthalic acid component, and "XD" indicates the xylylenediamine component. An example of the polyamide resin used in this embodiment is a resin containing hexamethylenediamine-derived structural units and / or adipic acid-derived structural units in a proportion of 30 mol% to 50 mol% of the total structural units.

[0013] The composition used in this embodiment preferably contains polyamide resin in an amount of 30% by mass or more, more preferably 40% by mass or more, even more preferably 45% by mass or more, even more preferably 50% by mass or more, even more preferably 55% by mass or more, and even more preferably 60% by mass or more. Furthermore, the upper limit of the polyamide resin content is preferably 80% by mass or less, and more preferably 75% by mass or less. In addition, in the present embodiment, preferably 95% by mass or more, more preferably 98% by mass or more, and still more preferably 99% by mass or more of the resin contained in the first member (composition) is a polyamide resin. When the composition used in the present embodiment contains two or more polyamide resins, the total amount is preferably within the above range.

[0014] The composition used in the present embodiment contains a reinforcing filler. By including a reinforcing filler, high mechanical strength can be achieved for the molded product. The reinforcing filler used in the composition used in the present embodiment has an effect of improving the mechanical properties of the composition or molded product obtained by blending it with the resin, and commonly used reinforcing materials for plastics can be used. The reinforcing filler may be an organic substance or an inorganic substance, but an inorganic substance is preferred. The reinforcing filler is preferably a fibrous reinforcing filler such as glass fiber, carbon fiber, basalt fiber, wollastonite, potassium titanate fiber, etc. Also, fillers such as granular or amorphous fillers such as calcium carbonate, titanium oxide, feldspar minerals, clay, organic clay, glass beads; and flaky reinforcing materials such as glass flakes, mica, graphite, etc. can be used. Among them, from the viewpoints of mechanical strength, rigidity, and heat resistance, it is preferable to use a fibrous filler, particularly glass fiber. As the glass fiber, either a round cross-sectional shape or a special cross-sectional shape can be used. It is more preferable to use a reinforcing filler that has been surface-treated with a surface treatment agent such as a coupling agent. Glass fiber with a surface treatment agent attached is preferable because it is excellent in durability, heat and humidity resistance, hydrolysis resistance, and heat shock resistance.

[0015] The glass fiber is composed of a glass composition such as A glass, C glass, E glass, S glass, R glass, M glass, D glass, etc., and particularly, E glass (non-alkali glass) is preferable. The glass fiber refers to a fiber-like appearance with a cross-sectional shape that is circular, elliptical, or polygonal when cut perpendicular to the length direction.

[0016] The glass fibers used in the composition used in this embodiment may be single fibers or multiple single fibers twisted together. The glass fibers can take any form, including single fibers, "glass roving" made by continuously winding multiple single fibers twisted together, "chopped strands" cut to a length of 1 to 10 mm, or "milled fibers" crushed to a length of 10 to 500 μm. Such glass fibers are readily available commercially from Asahi Fiber Glass Co., Ltd. under the product names "Glasslon Chopped Strands" and "Glasslon Milled Fiber." Different forms of glass fibers can also be used in combination.

[0017] Furthermore, the glass fibers used in this embodiment may have a circular or non-circular cross-section. By using glass fibers with a non-circular cross-section, warping of the resulting molded product can be suppressed more effectively. In addition, in this embodiment, warping can be effectively suppressed even when using glass fibers with a circular cross-section.

[0018] The reinforcing filler content in the composition used in this embodiment is 10 parts by mass or more, more preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 40 parts by mass or more, per 100 parts by mass of polyamide resin. The upper limit is 60 parts by mass or less, more preferably 55 parts by mass or less, and even more preferably 50 parts by mass or less, per 100 parts by mass of polyamide resin. The reinforcing filler content in the composition used in this embodiment is preferably 20% by mass or more, and more preferably 25% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, and even more preferably 40% by mass or less. The composition used in this embodiment may contain only one type of reinforcing filler, or it may contain two or more types. If it contains two or more types, the total amount will be within the above range. Note that the amount of reinforcing filler in this embodiment includes the amount of sizing agent and surface treatment agent.

[0019] The composition used in this embodiment includes a dye. The dye is, for example, a dye that is incorporated into the component that is irradiated with light during laser welding. The dye used in this embodiment is preferably a black dye, a blackish-purple dye, etc. The black dye may be a single black dye, but it is preferable that it be a black dye composition which is a mixture of multiple dyes. In particular, since red dyes tend to bleed, this embodiment is especially effective when the dye contains a red dye. In particular, the dye used in this embodiment is preferably a pigment that appears black to the human eye. Furthermore, the dye incorporated into the member that is irradiated with light in laser welding refers to a dye that, for example, is obtained by blending a polyamide resin with 30% by mass of a reinforcing filler and 0.2% by mass of a dye to a total of 100% by mass, and when the light transmittance at a wavelength of 1070 nm is measured, the transmittance is 20% or more. The light transmittance can be determined by referring to the description in paragraph 0070 of Japanese Patent Application Publication No. 2020-012093, and this content is incorporated herein. Examples of dyes that may be involved include those containing sulfur. This is because, in the case of sulfur-containing dyes, color transfer can cause serious damage, especially if the second component is an electronic device component. In this embodiment, examples of dyes include pyrazolone, perinone, and anthraquinone, and it is preferable to include at least anthraquinone, more preferably perinone and / or anthraquinone, and even more preferably perinone with a molecular weight of 300 or more (preferably 600 or less) and / or anthraquinone with a molecular weight of 600 or more (preferably 1000 or less). The dye used in this embodiment preferably includes at least one of Solvent Red 179, Acid Blue 80, and Solvent Yellow 163.

[0020] The composition used in this embodiment preferably contains 0.1 parts by mass or more, more preferably 0.5 parts by mass or less, more preferably 0.4 parts by mass or less, and even more preferably 0.3 parts by mass or less, per 100 parts by mass of polyamide resin. The composition used in this embodiment may contain only one type of dye, or it may contain two or more types. If it contains two or more types, it is preferable that the total amount is within the above range.

[0021] The composition used in this embodiment preferably contains copper iodide and / or potassium iodide. Including copper iodide tends to further improve the heat resistance of the resulting molded article. In addition, including potassium iodide tends to facilitate the formation of complexes in the polyamide resin, thereby more effectively suppressing the decomposition of the resin.

[0022] The proportion of copper iodide in the composition used in this embodiment is preferably 0.01 to 1% by mass, more preferably 0.02% by mass or more, more preferably 0.5% by mass or less, and even more preferably 0.3% by mass or less. The proportion of potassium iodide in the composition used in this embodiment is preferably 0.01 to 2% by mass, more preferably 0.02% by mass or more, and even more preferably 1% by mass or less.

[0023] The composition used in this embodiment may contain a mold release agent. Examples of release agents include aliphatic carboxylic acids, salts of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds with a number average molecular weight of 200 to 15,000, polysiloxane-based silicone oils, ketone waxes, and light amides. Aliphatic carboxylic acids, salts of aliphatic carboxylic acids, and esters of aliphatic carboxylic acids and alcohols are preferred, and salts of aliphatic carboxylic acids are more preferred. Details of the release agent can be found in paragraphs 0055 to 0061 of Japanese Patent Publication No. 2018-095706, and these contents are incorporated herein by reference. If the composition used in this embodiment contains a release agent, its content is preferably 0.05 to 3% by mass, more preferably 0.1 to 2% by mass, and even more preferably 0.2 to 1.5% by mass. The composition used in this embodiment may contain only one type of release agent, or it may contain two or more types. When two or more types are included, it is preferable that the total amount is within the above range.

[0024] The composition used in this embodiment may contain a nucleating agent. The nucleating agent is not particularly limited as long as it remains unmelted during the melting process and can act as a nucleus for crystals during the cooling process, but talc and calcium carbonate are preferred, with talc being more preferred. The number-average particle diameter of the nucleating agent is preferably 0.1 μm or more at the lower limit, more preferably 1 μm or more, and even more preferably 3 μm or more. The number-average particle diameter of the nucleating agent is preferably 40 μm or less at the upper limit, more preferably 30 μm or less, even more preferably 28 μm or less, even more preferably 15 μm or less, and still even more preferably 10 μm or less.

[0025] The proportion of the nucleating agent in the composition used in this embodiment is preferably 0.01 to 1% by mass, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or less. The composition used in this embodiment may contain only one nucleating agent or two or more. When two or more are included, it is preferable that the total amount is within the above range.

[0026] The composition used in this embodiment may contain other components without departing from the spirit of the present invention. Examples of such additives include light stabilizers, antioxidants, ultraviolet absorbers, fluorescent whitening agents, anti-dripping agents, antistatic agents, anti-fogging agents, anti-blocking agents, flow improvers, plasticizers, dispersants, antibacterial agents, and flame retardants. In this embodiment, the composition is prepared such that the total amount of each component is 100% by mass, with adjustments made to the content of polyamide resin, reinforcing filler, dye, and other additives. In this embodiment, an example is given in which the total amount of polyamide resin, reinforcing filler, dye, copper iodide, potassium iodide, nucleating agent, and release agent accounts for 99% by mass or more of the composition.

[0027] The first component can be manufactured by known methods for manufacturing resin molded articles. For example, refer to paragraphs 0052 and 0053 of Japanese Patent Application Publication No. 2020-012093, which are incorporated herein by reference.

[0028] <Second component> Next, I will explain the second component. In this embodiment, the second member contains a resin in which the difference (absolute value) between the glass transition temperature of the polyamide resin contained in the first member and the glass transition temperature of the resin contained in the second member is 11°C or more, and the glass transition temperature of the resin contained in the second member is -30 to 200°C. In recent years, there has been an increase in the joining of dissimilar components, where there is a large difference between the glass transition temperature of the polyamide resin contained in the first component and the glass transition temperature of the resin contained in the second component. The molded product of this embodiment is preferably used for joining such dissimilar components.

[0029] In this embodiment, the difference between the glass transition temperature of the polyamide resin contained in the first member and the glass transition temperature of the resin contained in the second member is 11°C or more, preferably 13°C or more, more preferably 15°C or more, even more preferably 16°C or more, even more preferably 17°C or more, and even more preferably 20°C or more. Furthermore, the upper limit of the difference in glass transition temperatures is preferably 200°C or less, more preferably 150°C or less, even more preferably 130°C or less, even more preferably 100°C or less, and even more preferably 90°C or less. By setting the difference below the upper limit, when the first member and the second member are joined by welding or melting, the melting temperatures of the first member and the second member can be brought closer together, thereby improving the joint strength.

[0030] In this embodiment, the glass transition temperature of the resin contained in the second member is -30°C or higher, preferably 0°C or higher, more preferably 10°C or higher, even more preferably 20°C or higher, and even more preferably 30°C or higher. Setting it above the lower limit tends to reduce the amount of color transfer to the mating material after a heat resistance test at 100°C or a moist heat test at 85°C and 85% relative humidity. Furthermore, the glass transition temperature of the resin contained in the second member is 200°C or lower, preferably 180°C or lower, more preferably 160°C or lower, and may also be 140°C or lower. Setting it below the upper limit tends to reduce the amount of color transfer to the mating material after a heat resistance test at 100°C or a moist heat test at 85°C and 85% relative humidity. If the second component contains two or more types of resin, the value is calculated by multiplying the mass fraction of each resin by its glass transition temperature. The glass transition temperature of the resin in this embodiment is measured according to the description in the examples below.

[0031] The resin used for the second component is not particularly specified in terms of type, and a wide range of known thermoplastic resins can be used. Examples of resins include polyamide resins, olefin resins, vinyl resins, styrene resins, acrylic resins, polyphenylene ether resins, polycarbonate resins, polyester resins, polyacetal resins, and silicone resins, and it is preferable that it contains at least one of polycarbonate resin, polyester resin, and silicone resin. Polybutylene terephthalate resin is preferred for the polyester resin.

[0032] Furthermore, in this embodiment, preferably 30 to 100% by mass, more preferably 40 to 100% by mass, and even more preferably 50 to 100% by mass of the components contained in the second member is a thermoplastic resin. If the second component used in this embodiment contains two or more types of resin, it is preferable that the total amount be within the above range.

[0033] The second component may contain, in addition to the resin, reinforcing fillers, dyes and / or pigments, copper iodide and / or potassium iodide, mold release agents, nucleating agents, light stabilizers, antioxidants, ultraviolet absorbers, fluorescent whitening agents, anti-dripping agents, antistatic agents, anti-fogging agents, anti-blocking agents, flow improvers, plasticizers, dispersants, antimicrobial agents, or flame retardants.

[0034] The second component can be manufactured by known methods for manufacturing resin molded articles. For example, refer to paragraphs 0052 and 0053 of Japanese Patent Application Publication No. 2020-012093, which are incorporated herein by reference.

[0035] <Molded products> In this embodiment, the first member and the second member are in contact. "In contact" includes, for example, a part of the first member and a part of the second member being in contact without any gaps. In this embodiment, the first member and the second member may be welded together by welding technology, or they may simply be in contact. In this embodiment, it is preferable that the first member and the second member are welded together by welding technology.

[0036] In this embodiment, it is particularly preferable that the glass transition temperature of the polyamide resin contained in the first member is 90 to 130°C, and the glass transition temperature of the resin contained in the second member is 30 to 190°C (preferably 30 to 95°C, or 120 to 190°C). In this embodiment, the glass transition temperature of the polyamide resin contained in the first member and the glass transition temperature of the resin contained in the second member may be higher. The first embodiment is one in which the glass transition temperature of the resin contained in the second component is 11°C or more higher than the glass transition temperature of the polyamide resin contained in the first component. In this case, color transfer can be suppressed more effectively. The second embodiment is one in which the glass transition temperature of the polyamide resin contained in the first component is 11°C or more higher than the glass transition temperature of the resin contained in the second component. In this case, color transfer can be suppressed, and the thermal fusion of the first component and the second component can be promoted more effectively. As a result, the welding strength of the first component and the second component in the resulting molded product can be increased.

[0037] As an example of this embodiment, the molded product of this embodiment is a laser-welded product. In this case, it is preferable that the first member functions as a resin member that is transparent to (also called non-absorbent or weakly absorbent) to laser light (transmissive resin member), and the second member functions as a resin member that is absorbent to laser light (absorbent resin member). Details of the case where the molded product of this embodiment is a laser-welded product can be found in Japanese Patent Application Publication No. 2020-012093, in particular in paragraphs 0057 to 0060, and this content is incorporated herein by reference.

[0038] The molded product of this embodiment can be applied to various uses, for example, various storage containers, electrical and electronic equipment parts, office automation (OA) equipment parts, home appliance parts, mechanical mechanism parts, vehicle mechanism parts, etc. In particular, it can be suitably used for food containers, medicine containers, oil and fat product containers, hollow parts for vehicles (various tanks, intake manifold parts, camera housings, etc.), vehicle electrical parts (various control units, ignition coil parts, etc.), motor parts, various sensor parts, connector parts, switch parts, breaker parts, relay parts, coil parts, transformer parts, lamp parts, etc. In particular, the molded product of this embodiment is suitable for in-vehicle camera modules.

Example

[0039] The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. When measuring instruments used in the examples are difficult to obtain due to obsolescence or the like, measurements can be made using other instruments having equivalent performance.

[0040] 1. First member <Raw material> PA6IT: Polyamide resin synthesized from hexamethylenediamine, isophthalic acid and terephthalic acid, manufactured by EMS, G21, Tg: 125 °C MXD6I: Polyamide resin synthesized from metaxylylenediamine, adipic acid and isophthalic acid synthesized in the following synthesis example, Tg: 125 °C

[0041] <<Synthesis example of MXD6I>> In a jacketed 50L reaction vessel equipped with a stirrer, partial condenser, condenser, thermometer, dropping tank, and nitrogen gas inlet tube, 7.5 kg of adipic acid, 8.5 kg of isophthalic acid, 9.3 g of sodium hypophosphite monohydrate, and 4.8 g of sodium acetate were charged. The vessel was thoroughly purged with nitrogen, and the temperature was raised to 180°C under a small stream of nitrogen gas to uniformly dissolve the adipic acid and isophthalic acid. Then, while stirring the system, 13.9 kg of metaxylylenediamine was added dropwise over 170 minutes. During this time, the internal temperature was continuously raised to 265°C. The water produced by polycondensation was removed from the system through the partial condenser and condenser. After the addition of metaxylylenediamine was complete, the internal temperature was further raised to 270°C, and the reaction was continued for 10 minutes. The polymer was then removed as strands from a nozzle at the bottom of the reaction vessel, cooled with water, and pelletized to obtain the polymer. Next, the polymer obtained in the above procedure was placed in a 250L rotary tumbler equipped with a heating jacket, nitrogen gas introduction tube, and vacuum line. The system was rotated while the pressure was reduced, and then the pressure was restored to atmospheric pressure with nitrogen of 99% or higher purity. This process was repeated three times. After that, the system was heated to 115°C under nitrogen flow. The system was then reduced in pressure and maintained at 115°C for 24 hours. After that, nitrogen was introduced to return the system to atmospheric pressure, and then it was cooled to obtain polyamide resin (MXD6I).

[0042] MXD6: Polyamide resin synthesized from metaxylylenediamine and adipic acid, manufactured by Mitsubishi Gas Chemical Company, part number: #6000, Tg 85℃ PA66: Polyamide 66, manufactured by Shima Trading Co., Ltd., U4800, Tg: 50℃ MXD6 / PA66: A resin composed of 100 parts by mass of MXD6 and 11 parts by mass of PA66. Tg=(85×100 / 111)+(55×11 / 111)=82℃ GF: Glass fiber, manufactured by Nippon Electric Glass Co., Ltd., ECS03T-756H Talc: #5000S, manufactured by Hayashi Chemical Co., Ltd., Micron White Cuprous iodide: Manufactured by Nippon Chemical Industries, Ltd. Potassium iodide: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Zinc(II) stearate: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Release agent: WH255, manufactured by Kyoeisha Chemical Co., Ltd., fatty acid amide wax Dye: LTW-8701H, manufactured by Orient Chemical Industry Co., Ltd., dye concentration 0.14% by mass Contains the following dyes. [ka] [ka] [ka]

[0043] <Glass transition temperature> The glass transition temperature of the resin (including the resin contained in the second component described later) was measured according to the following method. Based on differential scanning calorimetry, the molten polyamide resin was heated from 25°C to a temperature above its expected melting point at a heating rate of 10°C / min. The molten polyamide resin was then rapidly cooled with dry ice, and the temperature was raised again to 300°C at a rate of 10°C / min to determine the glass transition temperature. The measurement device used was the DSC7200 manufactured by SII Nanotechnology Co., Ltd.

[0044] <Compounding (Preparation of Composition)> To obtain the composition shown in Table 1 below (each component in Table 1 is expressed in parts by mass), all components except glass fiber (GF) were weighed, dry-blended, and then fed into a twin-screw extruder (Shibaura Machinery Co., Ltd., TEM26SS) from the screw root using a twin-screw cassette weighing feeder (Kubota Corporation, CE-W-1-MP). The glass fiber was fed into the twin-screw extruder from the side using a vibrating cassette weighing feeder (Kubota Corporation, CE-V-1B-MP), where it was melt-mixed with the resin components to obtain composition pellets. The extruder temperature was set to 280°C.

[0045] After drying the composition pellets obtained above at 120°C for 4 hours, test pieces (60 mm × 60 mm × 2.0 mm thick) were produced using an injection molding machine (NEX140III-12EG manufactured by Nissei Plastic Industrial Co., Ltd.). At the time of molding, for Composition 1 and Composition 3, the cylinder temperature was 280°C and the mold temperature was 80°C. Also, at the time of molding, for Composition 2, after molding at a cylinder temperature of 280°C and a mold temperature of 80°C, in order to sufficiently promote crystallization while suppressing the warping of the molded product, it was sandwiched between stainless metal plates (SUS304) and heat-treated in a drying oven at 130°C for 3 hours.

[0046]

Table 1

[0047] 2. The second member <Manufacture of PBT member> Using polybutylene terephthalate resin (Tg: 40°C, Novadurant, 5010G30 / P / NA (natural color), manufactured by Mitsubishi Engineering Plastics Corporation), test pieces (60 mm × 60 mm × 2.0 mm thick) were produced using an injection molding machine (NEX140III-12EG manufactured by Nissei Plastic Industrial Co., Ltd.). At the time of molding, the cylinder temperature was 260°C and the mold surface temperature was 80°C.

[0048] <Manufacture of polyamide member (MXD6 / PA66)> Using polyamide resin (Tg: 85°C, Reny, 1002H / N, manufactured by Mitsubishi Engineering Plastics Corporation), test pieces (60 mm × 60 mm × 2.0 mm thick) were produced using an injection molding machine (NEX140III-12EG manufactured by Nissei Plastic Industrial Co., Ltd.). At the time of molding, the cylinder temperature was 280°C and the mold surface temperature was 80°C.

[0049] <Manufacture of PC member> Test specimens (60mm x 60mm x 2.0mm thick) were fabricated using polycarbonate resin (Tg: 150℃, Yupiron, S-3000RC / 7333 (white), manufactured by Mitsubishi Engineering Plastics Co., Ltd.) and an injection molding machine (NEX140III-12EG, manufactured by Nissei Plastic Industrial Co., Ltd.). During molding, the cylinder temperature was set to 280°C and the mold temperature to 80°C.

[0050] <Manufacturing of silicone rubber components> A test specimen (60mm x 60mm x 2.0mm thick) was prepared using silicone rubber (Tg: -30℃, manufactured by Togawa Rubber Co., Ltd., product number: K-124).

[0051] Examples 1-7, Comparative Examples 1-3 The obtained first and second members were joined together, and ΔE after 50 hours was measured. * And ΔYI was measured.

[0052] <ΔE * > A spectrophotometer was used to calculate the values ​​using the reflection method with a whiteboard, in accordance with the color difference measurement method specified in JIS-Z8730. A spectrophotometer, model SE6000, manufactured by Nippon Denshoku Industries Co., Ltd., was used.

[0053] <ΔYI> Using a spectrophotometer, the yellowness measurement method according to the ASTM-D1925 standard was performed using the reflection method with a whiteboard, and ΔYI, which is the difference between the reference value and the comparison value of YI, was calculated. A spectrophotometer, model SE6000, manufactured by Nippon Denshoku Industries Co., Ltd., was used.

[0054] [Table 2]

[0055] As is clear from the above results, the present invention relates to ΔE * Furthermore, ΔYI was low, indicating that translocation was effectively suppressed. [Explanation of symbols]

[0056] 1 Molded product 2. First component 3. Second component

Claims

1. A first member formed from a composition comprising 100 parts by mass of polyamide resin having a glass transition temperature of 80°C or higher as measured by differential scanning calorimetry, 10 to 60 parts by mass of reinforcing filler, and a dye, It has a second member that is in contact with the first member, The difference (absolute value) between the glass transition temperature of the polyamide resin contained in the first member and the glass transition temperature of the resin contained in the second member is 11°C or more and 200°C or less. The glass transition temperature of the resin contained in the second member is -30 to 200°C. The reinforcing filler included in the first component is at least one selected from glass fiber, carbon fiber, basalt fiber, wollastonite, potassium titanate, calcium carbonate, titanium oxide, feldspar-based minerals, clay, organic clay, glass beads, glass flakes, and graphite. The composition used for the first component consists of polyamide resin, reinforcing filler, dye, copper iodide, potassium iodide, nucleating agent, and release agent, with the total of these components accounting for 99% or more by mass of the composition. The aforementioned dye is at least one selected from pyrazolone, perinone, and anthraquinone. The composition used for the first member is a molded article comprising 55 to 75% by mass of polyamide resin, 20 to 40% by mass of reinforcing filler, 0.01 to 1% by mass of copper iodide, 0.01 to 2% by mass of potassium iodide, 0.01 to 1% by mass of a nucleating agent, and 0.05 to 3% by mass of a release agent.

2. The molded article according to claim 1, wherein the dye contains sulfur.

3. The molded article according to claim 1 or 2, wherein the second member comprises at least one of polycarbonate resin, polyester resin, and silicone resin.

4. An in-vehicle camera module comprising a molded article according to any one of claims 1 to 3.

5. The molded article according to any one of claims 1 to 4, wherein the dye comprises perinone having a molecular weight of 300 or more and / or anthraquinone having a molecular weight of 600 or more.

6. The molded article according to any one of claims 1 to 5, wherein the dye comprises at least one of Solvent Red 179, Acid Blue 80, and Solvent Yellow 163.

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