JP2021123643A - Resin composition, kit, method for manufacturing molding, and molding - Google Patents

Abstract

To provide a resin composition that prevents movement of a light permeable dye for laser deposition, which does not hardly make differences in light transmittances depending on a surface temperature of a mold in injection molding, a kit, a method for manufacturing a molding, and a molding.SOLUTION: A resin composition contains a polyamide resin that is composed of a diamine-derived constitutional unit and a dicarboxylic acid-derived constitutional unit, in which 70 mol% or more of the diamine-derived constitutional unit is derived from xylylenediamine, and 70 mol% or more of the dicarboxylic acid-derived constitutional unit is derived from an α,ω-linear-chain aliphatic dicarboxylic acid having 4 to 20 carbon atoms, 0.1 to 2.0 mass% of boron nitride, 0.01 to 0.5 mass% of a chromium complex dye, and a release agent.SELECTED DRAWING: None

Description

The present invention relates to a resin composition, a kit, a method for producing a molded product, and a molded product. In particular, 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 is excellent in 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 with complicated shapes have come to be manufactured from polyamide resin. For example, various welding techniques, specifically, bonding, are used for bonding parts having a hollow portion such as an intake manifold. Agent welding, vibration welding, ultrasonic welding, hot plate welding, injection welding, laser welding technology, etc. are used.

However, welding with an adhesive has problems of environmental load such as pollution of the surroundings in addition to the time loss until curing. It has been pointed out that ultrasonic welding and hot plate welding have problems such as damage to products due to vibration and heat, and post-treatment due to the generation of abrasion powder and burrs. Further, injection welding often requires a special mold or molding machine, and further, there is a problem that it cannot be used unless the material has good fluidity.

On the other hand, 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. 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. As such a light-transmitting 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 composition comprising 1 to 150 parts by mass of a polyamide resin, 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. In the examples of Patent Document 1, 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. ..

Japanese Unexamined Patent Publication No. 2008-308526

Here, when a transmission resin member is formed by blending a laser welding light transmitting dye with a polyamide resin and the absorbing resin member is laser welded, the laser welding light transmitting dye is absorbed from another member (for example, absorption) from the transmitting resin member. It was found that it may move to the resin member). In particular, it was found that the tendency may be remarkable under high temperature and high humidity.
Therefore, the present inventor investigated a dye in which the movement of the light-transmitting dye transmitted by laser welding does not easily occur, and found a chromium complex dye.
However, when a chromium complex dye is blended with the polyamide resin and a mold release agent is further blended, in a molding method using a mold such as injection molding, the light transmittance of the laser of the molded product obtained depends on the surface temperature of the mold. It turned out that there may be a difference.
An object of the present invention is to solve such a problem, which is a resin composition in which laser welding light-transmitting dye is less likely to move to other members, and a mold for injection molding or the like is used. In the molding method, it is an object of the present invention to provide a resin composition in which the light transmittance of the obtained molded product does not easily differ depending on the surface temperature of the mold. Another object of the present invention is to provide a kit using the resin composition, a method for producing a molded product, and a molded product.

As a result of studies by the present inventor based on the above problems, it has been found that the above problems can be solved by blending a polyamide resin with a chromium complex dye, a mold release agent, and boron nitride. Specifically, the above problems have been solved by the following means.
<1> Consists of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, 70 mol% or more of the diamine-derived structural unit is derived from xylylene diamine, and 70 mol% or more of the dicarboxylic acid-derived structural unit is carbon. The polyamide resin derived from α, ω-linear aliphatic dicarboxylic acid of several 4 to 20, boron nitride 0.1 to 2.0% by mass, and chromium complex dye 0.01 to 0.5% by mass are separated from each other. A resin composition comprising a mold.
<2> The resin composition according to <1>, wherein the release agent contains a fatty acid metal salt.
<3> The resin composition according to <1>, wherein the release agent contains a metal salt of montanic acid.
<4> Any one of <1> to <3>, wherein the xylylenediamine contains paraxylylenediamine and the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms contains sebacic acid. The resin composition according to.
<5> The resin composition according to any one of <1> to <4>, further containing 20 to 60% by mass of glass fiber.
<6> A kit comprising the resin composition according to any one of <1> to <5>, and a light-absorbing resin composition containing a thermoplastic resin and a light-absorbing dye.
<7> Formed from a molded product formed from the resin composition according to any one of <1> to <5>, and a light-absorbing resin composition containing a thermoplastic resin and a light-absorbing dye. A method for producing a molded product, which comprises laser welding the molded product.
<8> A molded product obtained by molding the resin composition according to any one of <1> to <5> or the kit according to <6>.

<A> A resin composition according to any one of the above, which comprises a nucleating agent (preferably talc).
<B> A resin composition according to any one of the above, which comprises a copper compound (preferably copper halide).
<C> A resin composition according to any one of the above, which comprises an alkali metal halide.
<D> A resin composition according to any one of the above, wherein the content of the release agent is 0.05 to 3% by mass.
<E> A resin composition according to any one of the above, which is used for an in-vehicle camera module.
<F> A resin composition according to any one of the above, wherein the polyamide resin, boron nitride, chromium complex dye, mold release agent, glass fiber, nucleating agent, and copper compound are selectively contained. , A resin composition in which the total amount of alkali metals halide accounts for 99% by mass or more of the resin composition.
<F> An injection-molded product formed from any of the above resin compositions.

According to the present invention, a resin composition that does not easily move a laser-welded light-transmitting dye to other members, and is a molded product obtained by the surface temperature of the mold in a molding method using a mold such as injection molding. It has become possible to provide a resin composition in which there is little difference in light transmittance. Further, it has become possible to provide a kit using the resin composition, a method for producing a molded product, and a molded product.

Hereinafter, the contents of the present invention will be described in detail. In addition, in this specification, "~" is used in the meaning that the numerical values described before and after it are included as the lower limit value and the upper limit value.
In the present specification, various physical property values and characteristic values shall be at 23 ° C. unless otherwise specified.
In the present specification, the number average molecular weight is a polystyrene-equivalent value measured by a GPC (gel permeation chromatography) method.

The resin composition of 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 xylylene diamine, and 70 of the dicarboxylic acid-derived structural unit. A polyamide resin having a molar% or more of 4 to 20 carbon atoms derived from an α, ω-linear aliphatic dicarboxylic acid, 0.1 to 2.0% by mass of boron nitride, and a chromium complex dye 0.01 to 0.5. It is characterized by containing mass% and a mold release agent.
With such a configuration, the resin composition is a resin composition in which the movement of the light-transmitting dye for laser welding does not easily occur, and the light transmittance does not easily differ depending on the surface temperature of the mold during injection molding. The composition is obtained.
The reason for this is presumed to be as follows. In laser welding, a transmissive resin member and an absorbing resin member are laser welded to weld both of them. Here, after the transmissive resin member and the absorbent resin member are laser-welded, the light-transmitting dye in the transmissive resin member may move to the absorbent resin member. Therefore, the present inventor has extensively studied light-transmitting dyes and found that chromium complex dyes can suppress the movement of dyes to other members as compared with other dyes. On the other hand, it was found that as the amount of the chromium complex dye blended increased, the transmittance of the obtained molded product tended to differ remarkably depending on the temperature of the surface of the mold during injection molding. In particular, it was found that the transmittance of the molded product after the high-temperature and high-humidity treatment tended to be different. If the transmittance differs depending on the mold temperature, there is a problem in that a molded product with low transmittance during laser welding may be insufficiently welded and may not be compatible in the airtightness test of the in-vehicle camera module. .. As a result of further studies by the present inventor, it was presumed that the addition of the mold release agent together with the chromium complex dye had an effect on the difference in transmittance depending on the mold temperature. That is, it was presumed that when the chromium complex dye was blended, the curing rate of the polyamide resin changed, and the amount of the release agent that moved to the surface of the molded product also changed accordingly, and the transmittance of the obtained molded product was different. ..
Under such circumstances, in the present invention, by blending boron nitride, the transfer of the dye to other members is suppressed, and the difference in the transmittance of the obtained molded product is small even if the mold temperature is different. It was presumed that it became possible to provide molded products.

Hereinafter, the details of the resin composition of the present invention will be described.
<Xylylenediamine-based polyamide resin>
The resin composition of 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 70 of the dicarboxylic acid-derived structural unit. It contains a polyamide resin (hereinafter, may be referred to as “xylylenediamine-based polyamide resin”) in which mol% or more is derived from α, ω-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. Derived from amine.
The xylylenediamine preferably contains at least one of metaxylylenediamine and paraxylylenediamine, and more preferably contains at least paraxylylenediamine.
A preferred embodiment of the xylylenediamine in the present invention is a form containing 10 to 90 mol% of metaxylylenediamine and 90 to 10 mol% of paraxylylenediamine (however, metaxylylenediamine and paraxylylenediamine). The total does not exceed 100 mol%, preferably the total is 100 mol%, the same applies hereinafter), and contains 20 to 80 mol% of metaxylylenediamine and 80 to 20 mol% of paraxylylenediamine. The form is more preferable, and the form containing 40 to 20 mol% of paraxylylenediamine and 60 to 80 mol% of metaxylylenediamine is further preferable.

The dicarboxylic acid-derived constituent unit of the xylylene diamine-based polyamide resin is preferably 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 carbon. It is derived from α, ω-linear aliphatic dicarboxylic acid having a number of 4 to 20. As the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms, adipic acid, sebacic acid, suberic acid, dodecanedioic acid, ecodioic acid and the like can be preferably used, and adipic acid and sebacic acid are more preferable. Sebacic acid is more preferred.

Examples of 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 or more kinds.

Examples of the dicarboxylic acid component other than the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms include phthalic acid compounds such as isophthalic acid, terephthalic acid and orthophthalic acid, 1,2-naphthalenedicarboxylic acid and 1,3. -Naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalene Examples of isomers of 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 ε- 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. Here, 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. In the present invention, the total of the diamine-derived constituent units and the dicarboxylic acid-derived constituent units in the xylylenediamine-based polyamide resin preferably occupies 90% by mass or more, and preferably 95% by mass or more of all the constituent units. More preferably, it occupies 99% by mass or more.

The resin composition of the present invention preferably contains a xylylenediamine-based polyamide resin in a proportion of 20 to 75% by mass of the resin composition. The xylylene diamine-based polyamide resin is more preferably contained in a proportion of 40% by mass or more, further preferably 45% by mass or more, and further preferably contained in a proportion of 50% by mass or more. , 55% by mass or more, and even more preferably 60% by mass or more. Further, it is more preferably contained in a proportion of 75% by mass or less, further preferably contained in a proportion of 73% by mass or less, and further preferably contained in a proportion of 70% 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 kinds are included, the total amount is preferably in the above range.

<Other resin components>
The resin composition of the present invention may or may not contain a resin component other than the above-mentioned xylylenediamine-based polyamide resin.
Examples of other resins include polyamide resins other than xylylene diamine-based polyamide resins, olefin-based resins, vinyl-based resins, styrene-based resins, acrylic-based resins, and polyester resins, polycarbonate resins, and polyacetal resins.
The polyamide resin is a polymer containing at least one constituent unit of an acid amide obtained by ring-open polymerization of lactam, polycondensation of aminocarboxylic acid, and polycondensation of diamine and dicarboxylic acid. Specifically, polyamide. 6, 11, 12, 46, 66, 610, 612, 6I, 6/66, 6T / 6I, 6 / 6T, 66 / 6T, 66 / 6T / 6I, 9T, Polyamide XD6, Polyamide XD10, Polyamide XD12, Poly Examples thereof include trimethylhexamethylene terephthalamide, polybis (4-aminocyclohexyl) methadodecamide, polybis (3-methyl-4-aminocyclohexyl) methadodecamide, polyundecamethylene hexahydroterephthalamide and the like. The above-mentioned "I" indicates an isophthalic acid component, "T" indicates a terephthalic acid component, and "XD" indicates a xylylenediamine component.
Further, it is preferable that the resin composition of the present invention has a structure that does not substantially contain a polyamide resin other than the xylylenediamine-based polyamide resin. The term "substantially free" means that the content of the polyamide resin other than the xylylene diamine-based polyamide resin is 4% by mass or less of the resin composition, preferably 1% by mass or less, and is preferably 0.5. It is more preferably 0.1% by mass or less, and may be 0.1% by mass or less, and even 0% by mass.
Further, it is also preferable that the resin composition of the present invention does not substantially contain a resin component other than the xylylenediamine-based polyamide resin. The term "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.

<Boron Nitride>
The resin composition of the present invention contains boron nitride in the resin composition in a proportion of 0.1 to 2.0% by mass.
With such a configuration, it is possible to make it difficult for the chromium complex dye to move, and to make it difficult for the value of the light transmittance to differ depending on the surface temperature of the mold in the case of injection molding.
The form of boron nitride may be hexagonal or cubic, but hexagonal is preferable. In addition, the form of boron nitride is generally in the form of powder.
The content of boron nitride in the resin composition is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, still more preferably 0.7% by mass or more. It is more preferably 0.9% by mass or more. By setting the value to the lower limit or more, the mold temperature dependence of the transmittance tends to be smaller. Further, the content of boron nitride is preferably 1.8% by mass or less, more preferably 1.5% by mass or less, and further preferably 1.3% by mass or less in the resin composition. Preferably, it is 1.1% by mass or less, more preferably. By setting the value to the upper limit or less, the laser weldability tends to be more excellent.

Boron nitride may contain only one type, or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.

<Chromium complex dye>
The resin composition of the present invention contains a chromium complex dye in the resin composition in a proportion of 0.01 to 0.5% by mass.
By using the chromium complex dye, it is possible to effectively prevent the chromium complex dye contained in the transmissive resin member from moving to the absorbing resin member even when placed in a high temperature and high humidity. When the chromium complex dye in the present invention is a chromium complex dye, its effect is remarkable.
The chromium complex is a compound having a chromium atom as a nucleus and having a ligand, and preferably a compound having a trivalent chromium atom as a nucleus and having six ligands.
Further, the chromium complex dye is a chromium complex, which is colored when viewed by the human eye and is a dye that transmits a laser for laser welding at a certain ratio or more. As an example of the chromium complex dye preferably used in the present invention, 0.07 parts by mass of the chromium complex dye is blended with 100 parts by mass of the xylylene diamine-based polyamide resin (MP10) described in Examples described later, and the extruder is used. Examples thereof include a chromium complex having a light transmittance of 10% or more at a wavelength of 1070 mm measured by the method described in Examples described later using pellets melt-kneaded at a set temperature of 280 ° C. The mold temperature at this time is 110 ° C.
More specifically, the chromium complexes described in JP-A-2019-508554 are exemplified, and their contents are incorporated in the present specification.
The content of the chromium complex dye is preferably 0.02% by mass or more, and more preferably 0.04% by mass or more in the resin composition. By setting it to the above lower limit value or more, it tends to be more likely to appear black visually. The content of the chromium complex dye is preferably 0.4% by mass or less, more preferably 0.3% by mass or less, and more preferably 0.25% by mass or less in the resin composition. It is more preferably 0.2% by mass or less. By setting the value to the upper limit or less, dye transfer during high temperature test and wet heat test treatment tends to be suppressed more effectively.

The chromium complex dye may contain only one type, or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.
Further, it is preferable that the resin composition of the present invention substantially does not contain a light-absorbing dye, for example, carbon black. The term "substantially free" means, for example, 0.0001% by mass or less of the resin composition.

<Release agent>
The resin composition of the present invention contains a mold release agent.
By including a mold release agent, it is possible to improve the mold releasability from the mold when molding is performed using a mold such as injection molding.
The release agent preferably contains at least one selected from an amide wax and a fatty acid metal salt, and more preferably contains a fatty acid metal salt.

Examples of the amide wax include carboxylic acid amide wax and bisamide wax, and carboxylic acid amide wax is preferable.
The carboxylic acid amide wax is obtained, for example, by a dehydration reaction of a mixture of a higher aliphatic monocarboxylic acid and a polybasic acid and a diamine compound. As the higher aliphatic monocarboxylic acid, a saturated aliphatic monocarboxylic acid having 16 or more carbon atoms and a hydroxycarboxylic acid are preferable, and examples thereof include palmitic acid, stearic acid, behenic acid, montanic acid, and 12-hydroxystearic acid. Be done. The polybasic acid is a carboxylic acid of dibasic acid or more, for example, an aliphatic dicarboxylic acid such as malonic acid, succinic acid, adipic acid, sebacic acid, pimelli acid, azelaic acid, and aromatics such as phthalic acid and terephthalic acid. Examples thereof include dicarboxylic acids and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and cyclohexylsuccinic acid.
Examples of the diamine compound include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, m-xylylenediamine, tolylenediamine, paraxylylenediamine, phenylenediamine, isophoronediamine and the like. ..

The carboxylic acid amide-based wax in the present invention can arbitrarily adjust the softening point by changing the mixing ratio of the polybasic acid with respect to the higher aliphatic monocarboxylic acid used for its production. The mixing ratio of the polybasic acid is preferably in the range of 0.18 to 1 mol with respect to 2 mol of the higher aliphatic monocarboxylic acid. The amount of the diamine compound used is preferably in the range of 1.5 to 2 mol with respect to 2 mol of the higher aliphatic monocarboxylic acid, and varies depending on the amount of the polybasic acid used.

Examples of the bisamide wax include diamine compounds and fatty acid compounds such as N, N'-methylene bisstearic acid amide and N, N'-ethylene bisstearic acid amide, or N, N'-dioctadecyl terephthalic acid. Examples thereof include dioctadecyl dibasic acid amides such as amides.

As the fatty acid metal salt, a metal salt of a long-chain fatty acid having 16 to 36 carbon atoms is preferable, and for example, a metal stearate salt such as calcium stearate, zinc stearate, aluminum stearate, sodium stearate, lithium stearate, and the like. , Montanic acid metal salts such as calcium montanate and sodium montanate, and montanoic acid metal salts are preferable.

Examples of the release agent include esters of an aliphatic carboxylic acid and an alcohol, an aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15,000, a polysiloxane-based silicone oil, and a ketone wax.
For details of the release agent, the description of paragraphs 0055 to 0061 of JP-A-2018-0950706 and the description of paragraphs 0022 to 0027 of JP-A-2019-108526 can be referred to, and these contents are incorporated in the present specification. ..

The content of the release agent in the resin composition of the present invention is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and 0.2% by mass in the resin composition. The above is more preferable. By setting the value to the lower limit or more, the releasability tends to be further improved. The content of the release agent is preferably 3% by mass or less, more preferably 2% by mass or less, further preferably 1% by mass or less, and 0.8% by mass or less. It is more preferable that there is, and it is even more preferable that it is 0.6% by mass or less. By setting the value to the upper limit or less, the difference in transmittance depending on the mold temperature tends to be smaller.
The resin composition of the present invention may contain only one type of release agent, or may contain two or more types of release agents. When two or more kinds are included, the total amount is preferably in the above range.

<Glass fiber>
The resin composition of the present invention preferably contains glass fibers.
By containing the glass fiber, a resin composition having excellent mechanical strength can be obtained.
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 form of glass fiber 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 μm. 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.

Further, in the present invention, glass fibers having an irregular cross-sectional shape are also preferable. The irregular cross-sectional shape is defined as, 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. Regarding such flat glass, the description in paragraphs 0065 to 0072 of JP2011-195820A 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 or glass flakes. The glass beads are spherical beads having an outer diameter of 10 to 100 μm, and are commercially available, for example, from Potters Barotini under the trade name “EGB731” and are easily available. Further, the glass flakes are scaly flakes having a thickness of 1 to 20 μm 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 “Freka”. , 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 μm and a cut length (number average fiber length) of 1 to 10 mm. Here, when the cross section of the glass fiber is flat, 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. As the sizing agent in this case, 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 28% by mass or more in the resin composition. , 30% by mass or more is more preferable. 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. It may be 45% by mass or less and 40% by mass or less. 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 kinds are included, the total amount is preferably in the above range.

<Nuclear agent>
The resin composition of the present invention may contain a nucleating agent.
The nucleating agent is not particularly limited as long as it is unmelted at the time of melt processing and can become a crystal nucleus in the cooling process, but talc and calcium carbonate are preferable, and talc is more preferable.
The lower limit of the number average particle size of the nucleating agent is preferably 0.1 μm or more, more preferably 1 μm or more, and more preferably 3 μm or more. The upper limit of the number average particle size of the nucleating agent is preferably 40 μm or less, more preferably 30 μm or less, further preferably 28 μm or less, further preferably 15 μm or less, and even more preferably 10 μm. The following is even more preferable.

The proportion of the nucleating agent in the resin composition of the present invention is preferably 0.01 to 1% by mass, more preferably 0.1% by mass or more, and 0.5% by mass or less. Is more preferable.
The resin composition of the present invention may contain only one kind of nucleating agent or two or more kinds of nucleating agents. When two or more kinds are included, the total amount is preferably in the above range.

<Copper compound>
The resin composition of the present invention may contain a copper compound. By using a copper compound, it is possible to achieve remarkably excellent heat aging resistance.
Examples of the copper compound used in the present invention include copper halide (for example, copper iodide, copper bromide, copper chloride) and copper acetate, such as cuprous iodide, cupric iodide, and first bromide. Preferred from copper, cupric bromide, cuprous acetate and cupric acetate, cuprous chloride, cupric chloride, and from copper iodide, copper acetate and cuprous chloride. Is more preferable.
Further, the copper compound is preferably used in combination with an alkali metal halide described later. When a copper compound and an alkali metal halide are combined, it is preferably a mixture of a copper compound: an alkali metal halide in a ratio of 1: 3 to 1:15 (mass ratio), and a mixture of 1: 4 to 1: 8. It is even more preferable to have.
Regarding the case where the copper compound and the alkali metal halide are combined, the description in paragraphs 0046 to 0048 of Japanese Patent Application Laid-Open No. 2013-513681 can also be taken into consideration, and these contents are incorporated in the present specification.

The proportion of the copper compound in the resin composition of the present invention is preferably 0.01 to 1% by mass, more preferably 0.05% by mass or more, and 0.5% by mass or less. Is more preferable.
The resin composition of the present invention may contain only one type of copper compound or may contain two or more types of copper compounds. When two or more kinds are included, the total amount is preferably in the above range.

<Alkali metal halide>
The alkali metal halide used in the present invention refers to a halide of an alkali metal. As the alkali metal, potassium and sodium are preferable, and potassium is more preferable. Further, as the halogen atom, iodine, bromine and chlorine are preferable, and iodine is more preferable. Specific examples of the alkali metal halide used in the present invention include potassium iodide, potassium bromide, potassium chloride and sodium chloride, with potassium iodide being preferred.

The proportion of the alkali metal halide in the resin composition of the present invention is preferably 0.01 to 1% by mass, more preferably 0.1% by mass or more, and 0.5% by mass or less. More preferably.
The resin composition of the present invention may contain only one type of alkali metal halide, or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.

<Other ingredients>
The resin composition of the present invention may contain other components as long as the gist of the present invention is not deviated. Such additives include fillers other than glass fiber, light stabilizers, antioxidants other than the above, UV absorbers, optical brighteners, anti-dripping agents, antistatic agents, antifogging agents, anti-blocking agents, etc. Examples include fluidity improvers, plasticizers, dispersants, antibacterial agents, flame retardants and the like. Only one of these components may be used, or two or more of these components may be used in combination.
In the resin composition of the present invention, a xylylenediamine-based polyamide resin, boron nitride, a chromium complex dye, a mold release agent, glass fiber and other additions are added so that the total of each component is 100% by mass. The content of the agent and the like are adjusted. In the present invention, a xylylenediamine-based polyamide resin, boron nitride, a chromium complex dye, a mold release agent, and selectively added glass fibers, a nucleating agent, a copper compound, and an alkali metal halide are added. An embodiment in which the total accounts for 99% by mass or more of the resin composition is exemplified.

<Characteristics of resin composition>
The resin composition of the present invention can have a light transmittance of 25% or more at a wavelength of 1070 nm. The upper limit is not particularly defined, but for example, 70% or less is a sufficiently practical level. The light transmittance is measured by the method described in Examples described later. The mold temperature at this time can be set to any temperature, and is, for example, 110 ° C.
Further, in the resin composition of the present invention, the difference in light transmittance at a wavelength of 1070 nm can be 3% or less when the mold temperature is 110 ° C. and 140 ° C. The light transmittance is measured by the method described in Examples described later.

<Manufacturing method of resin composition>
The method for producing the resin composition of the present invention is not particularly limited, but a method of using a single-screw or twin-screw extruder having equipment capable of devolatile from the vent port as a kneader is preferable. The above-mentioned polyamide resin component, boron nitride, chromium complex dye, mold release agent and other additives to be blended as necessary may be collectively supplied to the kneader, or may be supplied to the xylylenediamine-based polyamide resin. Ingredients may be sequentially supplied. The glass fiber is preferably supplied from the middle of the extruder in order to prevent crushing during kneading. Further, two or more kinds of components selected from each component may be mixed and kneaded in advance.
In the present invention, the chromium complex dye is a thermoplastic resin such as polyamide 6 and polyamide 66, and a masterbatch is prepared in advance and then kneaded with other components (xylylenediamine-based polyamide resin, etc.) to obtain the present invention. The resin composition in the invention may be adjusted.

<Manufacturing method of molded products>
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. The resin composition of the present invention is particularly suitable for a method of molding using a mold. Further, it is suitable for a molding method of cooling by a mold. In the present invention, the difference between the temperature at which the resin composition is applied to the mold and the mold temperature is preferably 100 to 300 ° C.

The kit of the present invention has a light-absorbing resin composition containing the resin composition of the present invention, 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.

<< Light Absorbent Resin Composition >>
The light-absorbing resin composition used in the present invention contains a thermoplastic resin and a light-absorbing dye.
Examples of the thermoplastic resin include polyamide resin, olefin resin, vinyl resin, styrene resin, acrylic resin, polyphenylene ether resin, polyester resin, polycarbonate resin, polyacetal resin, etc., 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 of 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 above-mentioned xylylenediamine-based polyamide resin is preferable.
The light-absorbing resin composition may also contain an inorganic filler. Examples of 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 is a dye that is less likely to transmit a laser beam during laser welding than a chromium complex dye. Examples of the light-absorbing dye include those having a maximum absorption wavelength in the range of the laser light wavelength to be irradiated, for example, the wavelength range of 800 nm to 1100 nm. As one embodiment of the light-absorbing dye in the present invention, 0.07 parts by mass of the dye is blended with 100 parts by mass of the polyamide resin (MP10), and pellets melt-kneaded at a set temperature of an extruder of 280 ° C. are used. Examples thereof include dyes having a light transmittance of less than 10% at a wavelength of 1070 mm measured by the method described in Examples described later. The mold temperature at this time is 110 ° C.
Specific examples of the light-absorbing pigment include black pigments such as carbon blacks (for example, acetylene black, lamp black, thermal black, furnace black, channel black, Ketjen black, etc.), iron oxide red, and the like. Examples thereof include red pigments, orange pigments such as molybdate orange, and white pigments such as titanium oxide) and organic pigments (yellow pigments, orange pigments, red pigments, blue pigments, green pigments, etc.). Among them, 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 chromium complex dye in the resin composition and the component excluding the light-absorbing dye in the light-absorbing resin composition, preferably 90% by mass or more. Is more preferable, and 95 to 100% by mass is more preferable.

<< Laser welding method >>
Next, the laser welding method will be described. In the present invention, a molded product (transmissive resin member) formed from the resin composition of the present invention and a molded product (absorbent resin member) formed from the light-absorbing resin composition are laser-welded to obtain a molded product. Can be manufactured. By laser welding, the transmissive resin member and the absorbent resin member can be firmly welded without using an adhesive.
The shape of the member is not particularly limited, but since the members are joined by laser welding and used, the shape usually has at least a surface contact point (flat surface, curved surface). In laser welding, the laser light transmitted through the transmitting resin member is absorbed by the absorbing resin member and melted, and both members are welded. Since 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. Here, 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 lower limit of the thickness of the member through which the laser is transmitted is, for example, 0.01 mm or more.

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.

More specifically, for example, when welding a transparent resin member and an absorbing resin member, first, the welded portions of both are brought into contact with each other. At this time, it is desirable that the welding points of both are in surface contact, and may be a combination of flat surfaces, curved surfaces, or a flat surface and a curved surface. Next, the laser beam is irradiated from the transmission resin member side. At this time, if necessary, a lens may be used to condense the laser light on the interface between the two. The focused beam passes through the transmitting resin member, is absorbed near the surface of the absorbing resin member, generates heat, and melts. Next, the heat is transferred to the transmissive resin member by heat conduction and melted, a molten pool is formed at the interface between the two, and after cooling, the two are joined.
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. -Applicable to electronic equipment parts, office automation (OA) equipment parts, home appliance equipment parts, machine mechanism parts, vehicle mechanism parts, etc. In particular, food containers, chemical containers, oil and fat product containers, hollow parts for vehicles (various tanks, intake manifold parts, camera housings, etc.), electrical parts for vehicles (various control units, ignition coil parts, etc.), motor parts, 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. In particular, the resin compositions and kits of the present invention are suitable for hollow parts for vehicles such as in-vehicle camera housings.

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Example of MP10 synthesis>
10 kg (49.4 mol) of sebacic acid (TA grade manufactured by Ito Oil Chemicals Co., Ltd.) and sodium acetate in a reaction vessel equipped with a stirrer, a splitter, a total crimp, a thermometer, a dropping funnel and a nitrogen introduction tube, and a strand die. / 11.66 g of sodium hypophosphate monohydrate (molar ratio = 1 / 1.5) was charged, and after sufficient nitrogen substitution, 170 ° C while stirring the inside of the system under a small amount of nitrogen stream. Heated and melted until.
M-xylylenediamine (manufactured by Mitsubishi Gas Chemical Company, Inc.) and paraxylylenediamine (manufactured by Mitsubishi Gas Chemical Company, Inc.) have a molar ratio of 70/30. Paraxylylenediamine (14.64 mol) was added dropwise to molten sebacic acid under stirring, and the internal temperature was continuously raised to 240 ° C. over 2.5 hours while discharging the generated condensed water to the outside of the system. ..
After completion of the dropping, the internal temperature was raised, and when the temperature reached 250 ° C., the pressure inside the reaction vessel was reduced, and the internal temperature was further raised to continue the melt polycondensation reaction at 255 ° C. for 20 minutes. Then, the inside of the system was pressurized with nitrogen, the obtained polymer was taken out from the strand die, and this was pelletized to obtain a polyamide resin MP10.
The melting point of the obtained polyamide resin was 213 ° C., and the number average molecular weight was 15400.

尚、ポリアミド樹脂（ＭＰ１０）１００質量部に対し、クロム錯体染料０．０７質量部を配合し、後述の実施例と同様に成形したとき（金型温度は１１０℃）波長１０７０ｍｍにおける光線透過率が１０％以上であった。
また、ポリアミド樹脂（ＭＰ１０）１００質量部に対し、非クロム錯体染料を、色素が０．０７質量部となるように配合し、後述の実施例と同様に成形したとき（金型温度は１１０℃）波長１０７０ｍｍにおける光線透過率が１０％以上であった。

When 0.07 parts by mass of the chromium complex dye was mixed with 100 parts by mass of the polyamide resin (MP10) and molded in the same manner as in Examples described later (mold temperature is 110 ° C.), the light transmittance at a wavelength of 1070 mm was obtained. It was 10% or more.
Further, when a non-chromium complex dye is blended with 100 parts by mass of the polyamide resin (MP10) so that the dye is 0.07 parts by mass and molded in the same manner as in Examples described later (mold temperature is 110 ° C.). ) The light transmittance at a wavelength of 1070 mm was 10% or more.

[Examples 1 to 6, Comparative Examples 1 to 5]
<Compound>
The resin composition (pellet for forming a transparent resin member) shown in Table 2 or Table 3 described later was produced.
Specifically, each component shown in Table 2 or Table 3 to be described later is dry-blended with components other than glass fiber at the ratio shown in Table 2 or Table 3 (the unit is mass%), and then two. It was charged from the screw root of a shaft extruder (manufactured by Toshiba Machinery Co., Ltd., TEM26SS) using a 2-screw screw type cassette waving feeder (manufactured by Kubota Co., Ltd., CE-W-1-MP). Further, 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.

<Light transmittance>
The pellets obtained by the above-mentioned production method were dried at 120 ° C. for 4 hours, and then a test piece having a thickness of 1 mm was injection-molded using NEX140III manufactured by Nissei Resin Industry Co., Ltd. At the time of molding, the cylinder temperature was 280 ° C., and the surface temperature of the mold was the temperature shown in Table 2 or Table 3.
The light transmittance (unit:%) at a wavelength of 1070 nm was measured for the 1 mm-thick test piece obtained above using an ultraviolet-visible near-infrared spectrophotometer.
A UV-3100PC manufactured by Shimadzu Corporation was used as the ultraviolet-visible near-infrared spectrophotometer.

<Appearance after high temperature and high humidity treatment>
The pellets obtained by the above-mentioned production method were dried at 120 ° C. for 4 hours, and then a 60 × 60 × 2 mm test piece was injection-molded using NEX140III manufactured by Nissei Resin Industry Co., Ltd. At the time of molding, the cylinder temperature was 280 ° C. and the mold surface temperature was 130 ° C.
Further, Lenny 1002H / N (manufactured by Mitsubishi Engineering Plastics Co., Ltd.) was molded into 60 × 60 × 2 mm in the same manner as described above. Both were clipped at four corners using a binder clip (TANOSEE double clip edge width 19 mm, model number TWB-3). The clipped test piece molded product was allowed to stand in an atmosphere of 85 ° C. and a relative humidity (RH) of 85% for 400 hours, and the appearance thereafter was visually confirmed. The confirmation was carried out by five experts and a majority vote was adopted.

The results are shown in Table 2 or Table 3.

As is clear from the above results, in the resin composition of the present invention, the dye did not move to other members even after the high humidity heat test, and the difference in light transmittance due to the difference in mold temperature was small (Examples 1 to 1). 6).
On the other hand, when boron nitride was not blended and the chromium complex dye was blended (Comparative Examples 2 to 4), no movement of the light-transmitting dye was observed, but compared to the case where the light-transmitting dye was not blended (Comparative Examples 2 to 4). In Comparative Example 1), the difference in transmittance became large due to the difference in the surface temperature of the mold.
On the other hand, when the non-chromium complex dye was blended (Comparative Example 5), the difference in light transmittance due to the difference in mold temperature was suppressed to some extent, but the difference was still large, and the movement of the red dye was observed. Was done.

With respect to the resin composition according to Example 1, 6 parts by mass of carbon black masterbatch (manufactured by Nikko Bics Co., Ltd., PA-0895) was blended without blending the chromium complex dye, and the same procedure was carried out. Forming pellets were obtained. Using the pellets obtained in Example 1 and the pellets for forming an absorbent resin member, laser welding was performed according to paragraphs 0072, 0073, and FIG. 1 of JP-A-2018-168346. It was confirmed that laser welding was performed properly.

Claims (8)

It is composed of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit.
More than 70 mol% of the diamine-derived constituent units are derived from xylylenediamine,
Polyamide resin derived from α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms in which 70 mol% or more of the constituent unit derived from dicarboxylic acid is derived.
Boron nitride 0.1-2.0% by mass,
Chromium complex dye 0.01-0.5% by mass,
A resin composition containing a release agent. The resin composition according to claim 1, wherein the release agent contains a fatty acid metal salt. The resin composition according to claim 1, wherein the release agent contains a metal salt of montanic acid. The resin composition according to any one of claims 1 to 3, wherein the xylylenediamine contains paraxylylenediamine, and the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms contains sebacic acid. thing. The resin composition according to any one of claims 1 to 4, further comprising 20 to 60% by mass of glass fiber. The resin composition according to any one of claims 1 to 5 and
A kit having a light-absorbing resin composition containing a thermoplastic resin and a light-absorbing dye. A molded product formed from the resin composition according to any one of claims 1 to 5, and a molded product formed from a light-absorbing resin composition containing a thermoplastic resin and a light-absorbing dye. A method for producing an article, which comprises laser welding. The resin composition according to any one of claims 1 to 5, or a molded product obtained by molding the kit according to claim 6.