KR20190054514A - Resin composition and molded article comprising the same - Google Patents

Abstract

The present invention relates to a resin composition and a molded article comprising the same.
Specifically, in one embodiment of the present invention, there is provided a polyamide resin composition comprising a black colorant which exhibits black color by a combination of an organic dye and an inorganic pigment, and which comprises a flame retardant. Further, another embodiment of the present invention provides a molded article comprising the resin composition.

Description

Technical Field [0001] The present invention relates to a resin composition,

The present invention relates to a resin composition and a molded article containing the same.

In general, a resin composition used as a laser welding transmission material has been mainly used with a dye or a non-pigmented NP color (natural pigment color), and black (BK) As demands increase, various natural pigments have been used in combination to impart color.

Natural dyes imparting black color have been developed to develop dyes capable of laser transmission, for example, metallic dyes, phthalocyanine dyes, methine dyes and the like by expressing or combining black with itself to develop black color .

Organic dyes such as metallic azo composite dyes, phthalocyanine dyes, and methine dyes are known as the known black (BK) coloring agents or raw materials for producing the same. All of them are changed in structure at high temperature, There is a problem that is caused.

However, dyes including azo groups are easily broken due to attack of radicals due to their chemical structures, and there is a problem that discoloration of the resulting resins may be caused. In addition, phthalocyanine dyes have problems in that the laser transmittance is lowered And methine dyes are also vulnerable to discoloration.

In other words, when a black colorant known to date is imparted to the resin composition, there is a problem of discoloring.

In order to solve the above-mentioned problems, a black colorant of a new composition in which organic dyes and inorganic pigments are combined is designed in the present invention. In this connection, a polyamide resin composition comprising a black colorant in combination with the organic dye and the inorganic pigment is provided as one embodiment.

The black colorant combined with the organic dye and the inorganic pigment is excellent in compatibility with the flame retardant agent and can be maintained in its discoloration inhibiting effect even when it is blended with the flame retardant agent in the polyamide resin composition.

Specifically, in one embodiment, a polyamide-based resin; A black colorant in combination with organic dyes and inorganic pigments; And a flame retardant, wherein the color difference (DELTA E ^* _ab ) according to the CIE1976 L * a * b * coloring system is 0.01 to 2.0 before and after exposure to high temperature at 200 to 400 ° C.

In another embodiment, a molded article comprising the resin composition is provided.

The black colorant in combination with the organic dye and the inorganic pigment can be obtained by allowing the polyamide resin composition containing the organic dye and the inorganic pigment to exhibit a black color similar to that of the natural pigment and at the high temperature It is possible to minimize the discoloration caused by the light.

The discoloration inhibiting effect expressed by the black colorant in combination with the organic dye and the inorganic pigment appears in a state blended in the polyamide resin composition together with the flame retardant agent. Such a resin composition is subjected to a molding process and / or an aging process The produced product can be expressed in an environment where the product is exposed for a long time at a high temperature,

Therefore, the black colorant combined with the organic dye and the inorganic pigment is not only used in a field where a polyamide resin composition is conventionally applied, but also a field known to be difficult to apply to a conventional laser fusion black dye composition For example, automobile engine parts exposed for a long time at a high temperature, and the like, and can contribute to the expansion of applications.

In this specification, when a part is referred to as " including " an element, it is to be understood that it may include other elements as well, without departing from the other elements unless specifically stated otherwise. The terms " about ", " substantially ", etc. used to the extent that they are used throughout the specification are intended to be taken to mean the approximation of the manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure. The word " step (or step) " or " step " used to the extent that it is used throughout the specification does not mean " step for.

In the present specification, the term " combination thereof " included in the expression of the machine form means one or more combinations or combinations selected from the group consisting of the constituents described in the expression of the machine form, ≪ / RTI > and the like.

Based on the above definitions, embodiments of the present invention will be described in detail. It should be noted, however, that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Resin composition I

In one embodiment, a polyamide-based resin; A black colorant in combination with organic dyes and inorganic pigments; (I) wherein the color difference (DELTA E ^* _ab ) according to the CIE1976 L * a * b * coloring system is 0.01 to 2.0 before and after the high temperature exposure at 200 to 400 ° C.

In the resin composition (I), the black colorant combined with the organic dye and the inorganic pigment is excellent in the effect of suppressing discoloration due to high temperature particularly in a state blended with the flame retardant in the polyamide resin composition.

1) Specifically, the black coloring agent in which the organic dye and the inorganic pigment are combined can cause the polyamide-based resin composition containing the organic dye and the inorganic pigment to exhibit a black color similar to that of the natural coloring matter.

More specifically, the black colorant of the new composition in which the organic dye and the inorganic pigment are combined is a whole combined with an organic dye and an inorganic pigment each having an inherent color, and exhibits a level of black equivalent to that of a natural colorant.

Therefore, the black colorant in combination with the organic dye and the inorganic pigment can be applied to the resin composition in place of the natural coloring matter which expresses black.

2) Further, the black colorant in which the organic dye and the inorganic pigment are combined can exhibit excellent laser transmittance and laser weldability to the polyamide resin composition containing the same.

In general, inorganic pigments are known as materials with low permeability and weldability to laser, and are materials avoided in the field of laser transmissive materials.

Nevertheless, in one embodiment, an inorganic pigment is used as the material of the black colorant, and its application limit to the laser-transmissive material is overcome by a combination with an organic dye. Specifically, the organic dye combined with the black colorant is excellent in transmittance in a laser welding processing range (for example, 800 to 1080 nm), and even in combination with inorganic pigments having low permeability and weldability to a laser, It is possible to maintain the weldability.

Therefore, the black colorant combined with the organic dye and the inorganic pigment can be used to realize the polyamide resin composition as a laser penetrant. The laser transmissive material can be used as a component that requires a laser transmittance by itself, and can be used to control the laser absorbing ability of the absorber by being fused to a separate laser absorbing material including carbon black or the like. In the latter case, high fusion strength can be realized, and it can be applied to control the absorption ability of the laser absorbing material according to the design of the molded product, the thickness, and the specifications of the laser welding equipment.

3) On the other hand, the black coloring agent in which the organic dye and the inorganic pigment are combined minimizes discoloration of the black imparted to the polyamide resin composition containing the organic dye and the inorganic pigment by the high temperature applied in the molding step and / or the aging step can do.

As mentioned above, metallic azo complex dyes, phthalocyanine dyes, and methine dyes are known as the dyes capable of expressing black by expressing or combining black, and capable of laser transmission. However, these dyes are applied to a resin composition and their structure is easily changed during a high-temperature injection process, resulting in discoloration of the final product.

Nevertheless, in one embodiment, the organic dye is used as the material of the black colorant, and the high temperature discoloration problem is overcome by a combination with an inorganic pigment. Specifically, the inorganic pigment combined with the black coloring agent can be used for a product manufactured through a molding process and / or an aging process as well as a high temperature applied in a molding process and / or an aging process, Heat resistance can be exhibited. The structural stability and heat resistance of the inorganic pigment are also exhibited when the black colorant in combination with the organic dye and the inorganic pigment is exposed at a high temperature to suppress the structural change (particularly, the destruction of the chromophore) of the combined organic dye, It is possible to prevent the deterioration of the appearance quality caused by the heat radiation.

In this connection, the greatest advantage of the black colorant in combination with the organic dye and the inorganic pigment is that the black colorant can be designed based on the degree of discoloration before and after exposure at high temperature in suppressing high-temperature discoloration.

Specifically, when the color of the black colorant combined with the organic dye and the inorganic pigment is tested in accordance with the CIE 1976 L * a * b * colorimetry before and after exposure at high temperature of 200 to 400 ° C in a state of being applied to the polyamide resin composition , And the color difference (? E ^* _ab ) falls within the range of 0.01 to 2.0.

These criteria are derived from the reference example in which the organic colorant and the inorganic pigment are actually combined with the black colorant and a test example thereof.

More specifically, in a later-described test example, an organic dye and an inorganic pigment were combined and applied to a polyamide resin composition, and the resin composition was allowed to stand at 200 to 400 占 폚 for 10 to 60 minutes, and then an injection molded article was obtained. At this time, when the color difference (DELTA E ^* _ab ) of the molded article was within the range of 0.01 to 2.0 based on the initial resin composition, it was confirmed that the color change observed with the naked eye was insignificant and judged to meet the criteria of an embodiment Respectively.

4) In particular, the black colorant in combination with the organic dye and the inorganic pigment is excellent in compatibility with the flame retardant agent, and the discoloration inhibiting effect can be maintained even when it is blended with the flame retardant agent in the polyamide resin composition.

In this connection, the black colorant in combination with the organic dye and the inorganic pigment still exhibits black even when applied to the polyamide resin composition together with the flame retardant, and the color before and after exposure at high temperatures of 200 to 400 ° C. in the state is CIE1976 L * a * b * Colorimetric (ΔE ^* _ab ) can also be made to fall within the range of 0.01 to 2.0 when tested according to the colorimetric system.

Of course, the black colorant combined with the organic dye and the inorganic pigment may not lower the flame retardancy of the flame retardant. Therefore, it is preferable that the black colorant in combination with the organic dye and the inorganic pigment is contained in the polyamide resin When applied to a composition, the composition not only excellently exhibits a high temperature discoloration inhibiting effect, but also can exhibit considerable flame retardancy.

Specifically, the black colorant combined with the organic dye and the inorganic pigment is compatible with all the flame retardants generally applicable to the resin composition. Accordingly, in one embodiment, among commonly known flame retardants, flame retardants having characteristics compatible with the development purpose can be selected and applied.

5) Further, the black colorant in combination with the organic dye and the inorganic pigment is applied to the polyamide resin composition together with the flame retardant. The discoloration inhibiting effect can be exhibited not only in a product manufactured through a molding process and / or an aging process, but also in an environment in which the product is exposed for a long time at a high temperature.

Therefore, the black coloring agent in which the organic dye and the inorganic pigment are combined can be used not only in a field where a polyamide resin composition is conventionally applied, but also in a field known to be difficult to apply to a conventional laser fusion black dye composition (for example, And automobile engine parts which are exposed to high temperature for a long period of time), and contributes to expanding the use thereof.

For example, nylon-based polyamides, particularly PA46 / PA6T / 6I, PA66 / 6T / 6I, PA66 / 6T, PA66 / DT and PA66 / DT / (More specifically, a powertrain product such as AIM, CHC, and Engine Cover), and / or a molding process of an automobile engine component (more specifically, a powertrain product such as an AIM, a CHC, and an Engine Cover) is applied to the polyamide resin composition, 1) exhibits a black color comparable to that of natural pigments, and 2) has excellent laser transmittance and high transparency even under an aging process and even in an environment in which the component is exposed to high temperatures (for example, 160 to 220 degrees) for a long period of time. Laser weldability, and 3) discoloration is suppressed, whereby excellent appearance quality and physical properties can be maintained.

Furthermore, the above-mentioned black colorant combined with the organic dye and the inorganic pigment, together with the above-mentioned flame retardant, The present invention can also be applied to a case where a plastic product used in an automobile field is manufactured by laser welding such as a battery package such as a secondary battery which is an auxiliary power source and a battery which is a main driving force of an electric vehicle, The present invention can also be applied to a case where the laser welding method is changed and manufactured in all the industrial fields in which the welding was performed using welding, ultrasonic welding, bonding, and bolting.

Of course, in the resin composition (I), the characteristics 1) to 5) described in detail with respect to the black colorant combined with the organic dye and the inorganic pigment need not always be utilized at the same time, and laser permeability is not required Can be suitably used in various fields such as a field requiring high temperature discoloration inhibition, a field requiring mechanical property without need of high temperature discoloration inhibition, and the like.

Hereinafter, a polyamide resin composition to which a black colorant in combination with the organic dye and the inorganic pigment is applied together with a flame retardant will be described in detail.

Before and after high temperature exposure Color difference

In the resin composition (I), as described above, the black colorant in combination with the organic dye and the inorganic pigment is mixed with the flame retardant in the state of being applied to the polyamide resin composition and before the high temperature exposure at 200 to 400 ° C The color difference (? E ^* _ab ) according to the CIE 1976 L * a * b * coloring system can be set in the range of 0.01 to 2.0, specifically 0.01 to 1.5, more specifically 0.01 to 1.0.

That is, the resin composition (I) has a color difference (DELTA E ^* _ab ) according to the CIE1976 L * a * b * coloring system before and after exposure at high temperature of 200 to 400 DEG C in the range of 0.01 to 2.0, specifically 0.01 to 1.5, In the range of 0.01 to 1.0.

In general, it is known that the difference of the two colors having a color difference (DELTA E ^* _ab ) of less than 1.0 is not felt by the naked eye.

Transmittance

On the other hand, the laser transmittance that can be realized with the resin composition (I) can be excellent, based on the characteristics of the organic dyes in combination with the above-mentioned organic dyes and inorganic pigments, especially the combination thereof.

Specifically, the resin composition (I) has a similar or superior level to that of a black colorant (that is, a metallic azo compound dye, a phthalocyanine dye, a methine-based dye, etc.) It is possible to exhibit a laser transmittance similar or superior to that of a natural pigment. Therefore, the resin composition according to one embodiment of the present invention can be utilized in fields requiring laser permeability

Specifically, the resin composition (I) is preferably at least 10%, at least 40%, at least 60%, more preferably at least 10% A transmittance of 70% or more can be secured. However, as described later, the transmittance can be varied depending on the blending of the organic dyes and the thickness of the molded article, and the thickness can be further improved by further reducing the thickness of the molded article.

Flame retardant

In the resin composition (I), the black colorant in combination with the organic dye and the inorganic pigment is compatible with all the flame retardants generally applicable to the resin composition, as mentioned above. Accordingly, in one embodiment, one or more of commonly known phosphorus (P) based flame retardants, nitrogen (N) based flame retardants, and halogen based flame retardants may be selected and applied.

More specifically, phosphorus (P) type flame retardants, nitrogen (N) type flame retardants, and halogen type flame retardants are generally known as flame retardants applicable to resin compositions.

Among them, the material having the most excellent flame retarding effect is a halogen flame retardant, particularly a bromine flame retardant, and can be selected when a material having excellent flame retardancy is desired.

Examples of the halogen-based flame retardant include polybrominated diphenyl ethers (PBDEs), polybrominated biphenyl (PBB), brominated cyclohydrocarbons, decabromodiphenyl ether (Deca-BDE or DeBDE), hexabromocyclododecane HBCD or HBCDD), Tetrabromobisphenol A (TBBPA or TBBP-A), Brominated polystyrene, and Propylene dibromo styrene may be used. Compounds containing Halogen element such as Chlorine may be used instead of Brome.

However, in recent years, it has been decreasing its use in accordance with global environmental regulations. Particularly, in Europe, which is known to be strict in environmental regulations, halogen-free flame retardants that do not contain halogen elements are required, and phosphorus (P) flame retardants, nitrogen (N) flame retardants and inorganic flame retardants . In this regard, when an eco-friendly material is desired, a phosphorus (P) based flame retardant, a nitrogen (N) based flame retardant, an inorganic flame retardant or a flame retardant mixed with them may be used. Halogen flame retardant may also be implemented.

Here, in the case of the nitrogen (N) based flame retardant, it is generally used for a resin composition not reinforced with an inorganic reinforcing material, and may also be used for an inorganic reinforced resin composition. The phosphorus (P) -based flame retardant is mainly used in a resin composition reinforced with an inorganic reinforcing material, and a flame retardant function can be realized in a resin composition that is not reinforced. Accordingly, when an eco-friendly material having excellent mechanical properties is desired, a phosphorus (P) type flame retardant may be used alone, or a flame retardant mixed with a phosphorus (P) type flame retardant and a nitrogen (N) type flame retardant may be used. Therefore, a halogen halogen flame retardant can be realized together with a halogen flame retardant.

In the case of the above-mentioned nitrogen (N) type flame retardant, it is not particularly limited as long as it is a flame retardant containing nitrogen (N) in its molecular structure and has compatibility with a black colorant combined with the organic dye and inorganic pigment.

Examples of the nitrogen (N) flame retardant include melamine polyphosphate (MPP), melamine cyanurate, melamine, melamine isocyanurate, melamine cyanurate, Melamine-cyanuric acid, and triazine-based compounds.

In the case of the phosphorus (P) type flame retardant, there is no particular limitation as long as it is a flame retardant containing phosphorus (P) in its molecular structure and the organic dye and the inorganic pigment have compatibility with a black colorant combined therewith.

Examples of the phosphorus-based flame retardant include red phosphorus (RP) flame retardants, phosphate flame retardants, phosphine flame retardants such as phosphine oxide and phosphine oxide diol, phosphites Phosphite flame retardants, phosphonate flame retardants, phosphinate flame retardants, phosphoric acid ester flame retardants, phosphoric acid ester and salts flame retardants, etc. have. Phosphinate is a kind of phosphorus compounds and is represented by the formula of OP (OR) R ₂ .

More specifically, the phosphorus (P) flame retardant corresponding to the phosphinate-based flame retardant includes, for example, an organic phosphinate and an organic-inorganic complex phosphinate, and aluminum diethyl-phosphinate a mixture of two or more selected from the group consisting of ammonium phosphate, ammonium phosphate, ammonia phosphate, ammonium phosphate, ammonium phosphate, ammonium phosphate, ammonium phosphate, ammonium phosphate and ammonium phosphate. You may.

Phosphate flame retardants such as phosphorus (P) type flame retardants include Aromatic polyphosphate (RDX), Monomeric Trialkylphosphate, Alkyldiarylphosphate, Triarylphosphate, TCE (2-chloroethyl) Phosphate, TDCPP (RDP), Resorcinol Disphenyl Phosphate (RDP), etc., in the form of oligosaccharides such as 1,3-dichloro-2-propyl phosphate), TCPP Mixtures may be used.

As the inorganic flame retardant, boron (B) -based, antimony-based, metal hydrate-based or the like can be used.

On the other hand, as mentioned above, the phosphorus (P) type flame retardant, the nitrogen (N) type flame retardant, or the flame retardant mixed therewith has a lower flame retardancy than the case of using a halogen type flame retardant. A flame retardant synergist, a stabilizer, or a mixture thereof.

Herein, examples of melamine polyphosphate (MPP), melamine cyanurate, melamine, silicon based polymer, magnesium hydroxide (Mg (OH) ₂ ), aluminum trihydroxide (Al OH) ₃ ), Aluminum hydroxide oxide (AlO (OH)), MgCo ₃ , PTFE, and Aromatic polyphosphate (RDX) as a synergist, (P) type flame retardant, a nitrogen (N) type flame retardant, or a flame retardant mixed therewith.

It is also possible to use any one or a mixture of two or more selected from the group consisting of Zinc borate and Antimony Trioxide (Sb- ₂ O ₃ ) as a stabilizer, (N) based flame retardant, or a flame retardant mixed therewith.

However, the flame retardant synergist and the stabilizer are materials that can cause a decrease in laser transmittance, respectively, so that it is preferable to avoid addition thereof in order to realize a material having high laser transmittance.

Further, the flame-retardant component may be subjected to a reaction polymerization in the polymer polymerization step to form a flame retardant element (the flame retardant including Br, Cl, P, N, etc.) in the polymer chain.

In summary, the resin composition (I) comprises the phosphor (P) -based flame retardant; The nitrogen (N) type flame retardant; The halogen-based flame retardant; (I), wherein at least one member selected from the group consisting of the above-mentioned inorganic flame retardant and the above-mentioned flame retardant element is used as the flame retardant, 3 to 40 wt%, 3 to 37 wt%, 3 to 35 wt%, 3 to 33 wt%, or 3 to 33 wt% of the total amount of 100 wt%.

The flame retardant in the above range may be such that the flame retardancy of the resin composition (I) according to UL94 is 0.4 mm? V-0 or more. Further, the higher the content of the flame retardant in the above range, the better the flame retardancy can be. However, this is an example of the content of the flame retardant agent capable of exhibiting an improved effect, and thus the embodiment is not limited thereto.

Black colorant

In the black colorant in which the organic dye and the inorganic pigment are combined, the combination of the inorganic pigments may be selected from among generally known inorganic pigments having heat resistance capable of inhibiting the chromophore of the organic dye from breaking at high temperatures .

Since carbon black among inorganic pigments generally known is a laser absorbing material, if an inorganic pigment other than carbon black is combined with an organic dye to realize a black colorant, as described above, it can be used as a laser transmitting material itself.

Specifically, in the black colorant in which the organic dye and the inorganic pigment are combined, an inorganic pigment such as an ultramarine pigment, a titanium dioxide, a zinc sulfide, a zinc tetraoxide, and an iron oxide, Can be used in combination with the above organic dyes. For example, an ultramarine blue pigment can be used as the organic inorganic pigment.

On the other hand, in the black colorant in which the organic dye and the inorganic pigment are combined, as the organic pigment which can be combined, a material superior in the laser transmittance among the generally known organic dyes can be selected. However, in consideration of the comparative reference example to be described later, it may be preferable that the nigrosine dye is not combined with the inorganic pigment, or may be combined with the inorganic pigment in a small amount together with other organic dyes.

For example, a perinone type, an anthraquinone type, an azo type, a quinolone type, a quinacridone type, a perylene type, a phthalocyanine type, , And methane-based dyes may be used as the organic dyes.

Specific examples are selected from the group of organic dyes including perinone red dye, anthraquinone blue dye, anthraquinone violet dye, anthraquinone yellow dye, anthraquinone green dye, azo red dye, azo orange dye, and phthalocyanine blue dye May be used as the organic dye.

The perynone red dye is not particularly limited as far as it is selected from perionone dyes having a good transmittance at 1200 to 800 nm, and examples thereof include CI solvent orange 60, 78, C.I. Solvent Red (CI solvent Red) 135,162,178,179, Mr. C. I. solvent violet 29, C.I. At least one selected from the group consisting of C.I. pigment Orange 43 and C.I pigment Red can be used.

The anthraquinone dyes are not particularly limited as long as they are selected from anthraquinone dyes having a good transmittance at 1200 to 800 nm, and examples thereof include CI basic red dyes 1, 2, 9, 10, 11, 12, 13, 15, 16, 17, 19, 20, 26, 27, 35, 36, 37, 48, 49, 52, 53, 54, 66,68, Mr. Child. CI basic blue dye 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,18,20,21,22,23,24 , 25,26,35,36,37,45,46,47,49,50,55,56,60,62,67,75,77,79,80,81,83,87,88,89,90 , 94,95,96,97, Mr. Child. CI basic violet dye 1,2,3,4,5,6,7,8,10,11,12,13,14,15,16,17,20,21,23,24,25 , 27,40, and Mr. Child. At least one selected from the group consisting of CI basic green dyes 1, 3, 4, 6, 9, 10 can be used.

The anthraquinone dye may include an amine capable of forming a salt in the dye, and may be an amine having an aliphatic amine, an alicyclic amine, an alkoxyalkylamine, an alkanol, a diamine, an amine of a guanidine derivative, .

For example, as the organic dye, the ratio (a2 / a1) of the weight (a2) of the anthraquinone blue dye to the weight (a1) of the perinone red dye is 0.01 to 5, 0.01 to 4, 0.01 to 3 (A3 / a1) of the anthraquinone violet dye (a2) to the weight (a1) of the perinone red dye is 0.01 to 5, 0.01 to 4, 0.01 to 2.5, 0.01 to 3, 0.01 to 2.5, or 0.01 to 1.5.

The organic dyes thus compounded can have a color similar to that of natural pigments, and the resin composition containing the organic dyes can have an excellent transmittance in the above-mentioned range. However, this is an example of an organic dye capable of exhibiting an improved effect, and thus the embodiment is not limited thereto.

In the black colorant in which the organic dye and the inorganic pigment are combined, the inorganic pigment and the organic dye can be combined in a weight ratio (inorganic: organic) of from 0.01: 1 to 0.5: 1, which is independent of each kind or form .

The black colorant, which is combined to satisfy the above requirements, has a black color similar to that of natural pigments on the basis of the above-described organic dye characteristics, and allows the molded product of the resin composition containing the black colorant to exhibit the above- So as to obtain an excellent transmittance of < RTI ID = 0.0 > It is possible to obtain a minimized color difference (DELTA E ^* _ab ) value by suppressing the structural change at high temperature of the organic dye based on the inorganic pigment characteristics described above. However, this is merely an example of a combination of an organic dye and an inorganic pigment that can exhibit an improved effect, and thus the embodiment is not limited thereto.

The black colorant in combination with the organic dye and the inorganic pigment may be contained in an amount of 0.1 to 10.0% by weight, specifically 0.1 to 0.6% by weight, based on 100% by weight of the total amount of the resin composition (I).

The black colorant in this range is required to sufficiently exhibit the above-mentioned properties, namely, color (black), laser transmittance, laser weldability, heat resistance and discoloration inhibiting properties, So that the mechanical properties of the resin can be sufficiently manifested and the synergistic effect of the black colorant and the polyamide resin can be exhibited. However, this is merely an example of the content of the black coloring agent in the total resin composition which can exhibit the improved effect, and the embodiment is not limited thereto.

Meanwhile, in the black colorant in which the organic dye and the inorganic pigment are combined, each of the inorganic pigment and the organic dye may be in the form of a powder or a master batch (M / B). The latter form may be made in a manner generally known in the art based on organic materials such as CEBA, waxes such as PE, polymeric resins, and the like.

Polyamide resin

In the resin composition (I), the polyamide resin exhibits excellent mechanical properties by including a polyamide in its structure, and is not particularly limited as long as it is generally used in the art.

For example, a lactam-based polymer; Amino acid polymers; Diacid; Diamines; Homopolyamide; And copolyamide; a mixture of two or more of them, or a polymer containing two or more of them as monomers.

In the case of the lactam-based polymer, a polymer of one kind of the monomer or a condensate of two kinds of the monomers may be a lactam such as? -Caprolactam or? -Raurolactam as a monomer.

In the case of the above-mentioned amino acid polymer, it is preferable to use p-aminomethylbenzoic acid such as 6-aminocaproic acid, 11-aminoundecanoic acid or 12-aminododecanoic acid as a monomer and to polymerize one kind of the monomer or two kinds of monomers Polymer.

In the case of the above-mentioned diacid, the diacid may be selected from the group consisting of lonic acid, dimethyl malonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2- Terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylpentanedicarboxylic acid, Aliphatic, alicyclic or aromatic dicarboxylic acids such as isophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, diglycolic acid and the like.

Examples of the diamine include tetramethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4- (Aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-cyclohexanedimethanol, trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylenediamine, paraxylylenediamine, 3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2- ) Propane, bis (aminopropyl) piperazine, aminoethylpiperazine, and the like. The aliphatic, alicyclic or aromatic diamine may be used alone or in combination.

The homopolyamide may be at least one selected from the group consisting of nylon 6, nylon 66, nylon 610, nylon 1010, nylon 46, nylon 11, nylon 12, nylon MXD6 and polyphthalamide.

Specifically, as the polyamide-series resin, condensation products of dicarboxylic acid and diamine, condensation products of aminocarboxylic acid, and ring-opening polymerization products of cyclic lactam can be used. Examples of dicarboxylic acids include adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, isophthalic acid, and terephthalic acid. Examples of diamines include tetramethylenediamine, hexamethylenediamine, octamethylenediamine, nonamethylenediamine, dodecamethylenediamine, 2-methylpentamethylenediamine, 2-methyloctamethylenediamine, trimethylhexamethylenediamine, bis (p- aminocyclo Hexyl) methane, m-xylenediamine and p-xylenediamine. As an example of the aminocarboxylic acid, 11-aminododecanoic acid can be used. As examples of cyclic lactams, caprolactam and laurolactam can be used. Specific examples of the entangled product and ring-opening product include aliphatic polyamides such as nylon 6, nylon 66, nylon 46, nylon 610, nylon 612, nylon 11, nylon 12, nylon 1010, semi-aromatic polyamides such as polymethoxylene (Nylon 6T), polynonamethylene terephthalamide (nylon 9T), copolymers thereof, or a mixture thereof, may be used in combination with the polyamide resin . As examples of the copolymer, nylon 6/66, nylon 66 / 6I, nylon 6I / 6T, nylon 66 / 6I / 6T and nylon 66 / 6T may be used.

The polyamide-based resin may be semi-crystalline or amorphous depending on its crystal structure. Specifically, amorphous polyamide resin can be selected, and in this case, there is an effect of exhibiting a transmittance characteristic superior to crystallinity.

The resin composition (I) may further comprise, in addition to the polyamide-series resin, a polymer resin selected from the group including polyesters and polycarbonates within a range that does not change the essential characteristics thereof .

additive

The resin composition (I) contains, in addition to the phosphorus (P) type flame retardant, a fibrous reinforcement such as glass fiber and carbon fiber, glass flake, glass bead, talc, kaolin, wollastonite, silica, Or a reinforcing material.

For example, the resin composition according to one embodiment of the present invention comprises: Further comprises at least one glass-based reinforcement selected from the group comprising glass fibers, milled GF, glass bubbles and glass beads. can do. The resin composition in this case can be improved in mechanical properties, thermal properties and the like.

For example, the glass fiber (GF) and the processed glass fiber (Milled GF) have a diameter of 4 to 200 μm and a chopped length of 1 to 10 mm Can be used. Also, the glass fiber (GF) may be selected from a flat shape, a cocoon shape, and a circular shape. This range is advantageous for being evenly dispersed in the resin composition, but is not limited thereto.

The glass fiber may be selected from those surface treated with at least one selected from aminosilane, epoxy and urethane, or may be used after such treatment. The glass fiber in this case may be dispersed evenly in the resin composition And has the effect of improving the mechanical properties and thermal properties of the resin composition. It is also possible to use one that has not been surface-treated.

In the case of the glass beads, those having a diameter of 1 to 25 탆 can be selected or prepared and used. However, the present invention is not limited by these examples. This range is advantageous for being evenly dispersed in the resin composition, but is not limited thereto.

In the case of the glass bubble, a glass having a diameter of 1 to 25 탆 can be selected or prepared and used. However, the present invention is not limited by these examples. This range is advantageous for being evenly dispersed in the resin composition, but is not limited thereto.

In the resin composition further comprising the glass-based reinforcement, the content of the glass-based reinforcement in 100 wt% of the total composition may be 10 to 50 wt%. This is a sufficient amount to improve the mechanical properties, thermal properties and the like in addition to the basic physical properties of the polyamide resin.

In addition, as will be understood by those skilled in the art, depending on the application for which the resin composition according to one embodiment of the present invention is utilized, any additive may be further included, have.

Usually, additives added to the resin composition include a flame retardant, an impact modifier, a viscosity modifier, a heat resistance improver, a lubricant, an antioxidant, and a UV stabilizer.

Resin composition II

In another embodiment of the present invention, a polyamide-based resin; coloring agent; And a flame retardant; wherein the resin composition (II) has a transmittance of 10% or more when irradiated with light in a region of 800 to 1080 nm and a flame retardancy of 0.4 mm@V-0 or more according to UL94.

In general, phosphorus (P) based flame retardant products produced by flame retardant manufacturers are classified into two types.

One of them is a flame retardant product made of a phosphorus (P) based flame retardant component. This is because, as mentioned above, the flame retardancy is low as compared with the case of using a halogen-based flame retardant. In particular, when a flame retardant product composed of the flame retardant component of the phosphorus (P) system is used together with a polyamide resin that does not contain an aromatic ring in its molecular structure such as PA6 or PA66, .

Another developed product is a flame retardant (Synergist), a stabilizer, or a mixture thereof, in a proper blending ratio, for a flame retardant composed of the flame retardant component of the phosphorus (P) system . This is because, even when applied together with a polyamide resin containing no aromatic ring in its molecular structure such as PA6 or PA66, the flame retardancy of the flame retardant component of the phosphorus (P) Can be improved. However, the flame retardant synergist mixed with the above products may lower the laser weldability and permeability when used as an additive for a laser transmissive material.

On the other hand, the flame retardant to be applied to the resin composition (II) does not include the flame retardant synergist, the stabilizer, or a mixture thereof; Flame retardancy is ensured even when it is applied together with a polyamide-based resin containing an aromatic ring in its molecular structure, as well as a polyamide-based resin containing no aromatic ring in its molecular structure such as PA6 or PA66 (P) based flame retardant component; The above transmittance and flame retardancy can be ensured even if it is applied together with any coloring agent.

Accordingly, the resin composition (II), even when any of the polyamide based resin and the colorant are applied, can secure both a transmittance of 10% or more and a flame retardancy of 0.4 mm@V-0 or more according to UL94 at the time of light irradiation in the range of 800 to 1080 nm . The flame retardancy of the resin composition (II) can be further improved in accordance with the content of the flame retardant.

For example, the flame retardant applied to the resin composition (II) may be selected from the group consisting of a red-phosphorus (RP) flame retardant, a phosphate flame retardant, a phosphine flame retardant, a phosphite flame retardant, Phosphonate flame retardants, phosphinate flame retardants, phosphoric acid esters, and phosphoric acid ester and salts. In the present invention, Lt; / RTI >

In order to further improve the flame retardancy of the resin composition (II) to which such a flame retardant is applied, a flame retardant synergist, a stabilizer, or a mixture thereof may be used. However, the flame retardant synergist may be a material which does not lower the transmittance, for example, melamine polyphosphate (MPP), melamine cyanurate, melamine, silicone polymer (Silicon based polymer, magnesium hydroxide (Mg (OH) ₂ ), aluminum trihydroxide (Al (OH) ₃ ), aluminum hydroxide oxide (AlO (OH)), MgCo ₃ , PTFE, and Aromatic polyphosphate , Or a mixture of two or more of them may be used.

Examples of the colorant to be applied to the resin composition (II) include not only the above-mentioned black colorants but also nigrosine, metallazo, phthalocyanine, methine dyes, perinone, anthraquinone, Organic dyes including azo dyes, quinolone dyes, quinacridone dyes, perylene dyes, phthalocyanine dyes, and methane dyes; An inorganic pigment group including carbon black, ultramarine pigment, titanium dioxide, zinc sulfide, zinc oxide, and iron oxide; And a natural pigment (NP) group, or one or more coloring agents selected from all commonly known coloring agent groups may be used.

The coloring agent to be applied to the resin composition (II) is preferably applied to the resin composition (II) in combination with a suitable coloring agent in accordance with the desired characteristics, for example, the characteristics such as color, laser weldability, laser transmittance, can do.

Here, as a method for variously implementing color, laser weldability, laser transmittance, and high-temperature discoloration suppression, a description about the above-mentioned black colorant and a method generally known in the art can be used.

As described above, the polyamide resin to be applied to the resin composition (II) is not particularly limited whether it contains an aromatic ring in its molecular structure. For example, the lactam-based polymer described above with the polyamide-based resin; Amino acid polymers; Diacid; Diamines; Homopolyamide; And copolyamide; a mixture of two or more of them, or a polymer containing two or more of them as monomers may be used, and a detailed description thereof is as described above.

For example, nylon-based polyamides, especially PA46, PA6T / 6I, PA66 / 6T / 6I, PA66 / 6T, PA66 / DT and PA66 / DT / 6I are also applicable. The transmittance may not be lowered.

In addition, the constituents, additives, etc. of the resin composition (II) according to the above embodiment are the same as those of the resin composition (I) described above.

Molded product

In another embodiment of the present invention, there is provided a molded article comprising the resin composition (I) or the resin composition (II) described above.

Specifically, the molded article is obtained by molding the above-mentioned resin composition (I) or resin composition (II) by injection molding or extrusion, and can exhibit excellent transmittance.

Particularly, in the case of a molded article based on the resin composition (II), discoloration is suppressed even when a high temperature is applied in the production (molding) process or even when it is aged by a high temperature after molding, and excellent black appearance quality can be maintained have.

As mentioned above, the above molded article is produced by a generally known method of injection, extrusion and the like, regardless of the above-mentioned resin composition (I) or resin composition (II), and is produced by a generally known method such as thermal aging It can be post-processed. Therefore, the detailed description of the method of manufacturing the molded article and the post-manufacturing method will be omitted.

Hereinafter, preferred examples of the present invention, comparative examples thereof, and test examples for testing them are described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited to the following examples.

Test Example  One

(1) Exam contents

In Test Example 1, a combination of an organic dye and an inorganic pigment is tested in the absence of a flame retardant.

Specifically, through the combination of organic dyes and inorganic pigments, it is possible to overcome the limitations of various physical properties exhibited by conventional black coloring agents and to test whether they can substitute existing black coloring agents, while realizing a black color similar to that of existing black coloring agents do.

(2) Preparation of test composition

Manufacturing example  1: Black colorant

As raw materials, perinone red, anthraquinone blue, and anthraquinone violet, which are organic dyes, and ultramarine blue, an inorganic pigment, were prepared.

These raw materials were combined to prepare a coloring agent which exhibited black color, and this was referred to as Production Example 1. Specifically, the colorant of Production Example 1 contained 47 wt% of anthraquinone blue, 28 wt% of anthraquinone violet, 20 wt% of perinone red, and 5 wt% of ultramarine blue, based on 100 wt% It is a combination.

Reference example  1-1 to 1-5

The black colorant of Production Example 1 was mixed with polyamide 66 (relative viscosity: 2.4, specific gravity: 1.14, melting temperature: 260 ° C) in the composition shown in the following Table 1, A composition was prepared.

Comparative Reference Example  1-1

As shown in the following Table 1, only polyamide 66 (relative viscosity: 2.4, specific gravity: 1.14, melting temperature: 260 占 폚) was used alone.

Comparative Reference Example  1-2 to 1-6

(Relative viscosity: 2.4, specific gravity: 1.14, melting temperature: 260 占 폚) with a composition shown in the following Table 1, and comparing one or more of a nigrosine dye and a carbon black pigment with a polyamide 66 Resin compositions of Reference Examples 1-2 to 1-6 were prepared.

However, the Nigrosine dyes and carbon black pigments used in Comparative Reference Examples 1-2 to 1-6 were prepared as follows.

Nigrosine Dye: Master batch (M / B) based on Nylon 6, PA6 containing 30% by weight of Nigrosine dye was prepared.

Carbon Black Pigment: A master batch (M / B) based on Nylon 6, PA6 containing 20% by weight of carbon black was prepared.

Comparative Reference Example  1-7 to 1-8

Nigrosine dye or carbon black was used in addition to the black colorant of Production Example 1 and the polyamide 66 (relative viscosity: 2.4, specific gravity: 1.14, melting temperature: 260 ° C) One of the pigments was mixed to prepare each resin composition of Comparative Reference Examples 1-7 and 1-8.

However, in Comparative References 1-7 and 1-8, the Nigrosine dye and the Carbon Black pigment were prepared in the same manner as Comparative Reference Examples 1-2 to 1-6.

Polyamide 66
Suzy Preparation Example 1
Black colorant
Nigro New World
dyes Carbon black
Pigment Reference Example 1-1 99.9 0.1 0 0 Reference Example 1-2 99.5 0.5 0 0 Reference Example 1-3 99 1.0 0 0 Reference Example 1-4 95 5.0 0 0 Reference Example 1-5 90 10.0 0 0 Comparative Reference Example 1-1 100 0 0 0 Comparative Reference Example 1-2 99.9 0 0.1 0 Comparative Reference Example 1-3 99.5 0 0.5 0 Comparative Reference Example 1-4 99 0 1.0 0 Comparative Reference Example 1-5 99.9 0 0.5 0.1 Comparative Reference Example 1-6 99.4 0 0 0.1 Comparative Reference Example 1-7 99.4 0.5 0.1 0 Comparative Reference Example 1-8 99.4 0.5 0 0.1

(In Table 1, the content of each component is described based on the total amount of 100% by weight, and the unit (% by weight) is omitted for each reference example / comparative reference example item.)

(3) Test conditions

The respective resin compositions of Reference Examples 1-1 to 1-5 and Comparative Reference Examples 1-1 to 1-8 were tested under the following conditions.

Changes in physical properties before and after injection retention

Each composition of Reference Examples 1-1 to 1-5 and Comparative Reference Examples 1-1 to 1-8 was heated at 280 DEG C or 300 DEG C for 0 minute, 10 minutes and 20 minutes using an 80 ton injection machine manufactured by Engel Co. , 30 minutes, or 40 minutes and then injected to prepare specimens each having a thickness of 2.5 T, and then cooled to room temperature (natural standing). The tensile strength and elongation were measured according to ISO 527, and the appearance was observed.

Changes in physical properties before and after aging

Using the injection molding machine, the respective compositions of Reference Examples 1-1 to 1-5 and Comparative Reference Examples 1-1 to 1-8 were injection-molded at a high temperature of 2.5T, Before and after aging with heat, tensile strength and elongation were measured according to ISO 527, and appearance was observed.

Laser transmittance

Using the injection machine, each composition of Reference Examples 1-1 to 1-5 and Comparative Reference Examples 1-1 to 1-8 was injection-molded at a high temperature to prepare a specimen having a thickness of 2.5 T, and the transmittance of Euro Vision The transmittance at the laser wavelength band was measured using a measuring instrument. Specifically, the transmittance at 980 nm and 1080 nm, which are generally used laser wavelengths, was measured.

Laser weldability

Each of the compositions of Reference Examples 1-1 to 1-5 and Comparative Reference Examples 1-1 to 1-8 was injected into the specimen of 2.5T thick by using the injector without hot stagnation to prepare a specimen of 60mm X 60mm X 2.5 mm, and were arranged so as to overlap each other by 10 mm. The overlapped region was welded using a CW laser of 1070 nm wavelength with a 3 mm diameter (Beam size 3 mm).

The results of each test are reported in Tables 2 to 4 below.

(4) Test results

Reference Example 1-1 Reference Example 1-2 Reference Example 1-3 Reference Example 1-4 ejaculation
visit 280 degrees 0 minutes Tensile Strength (MPa) 82 82 83 80 Elongation (%) 50 52 55 55 Exterior color black black black black 10 minutes Tensile Strength (Mpa) 82 82 83 80 Elongation (%) 50 52 55 55 Exterior color black black black black 20 minutes Tensile Strength (Mpa) 81 81 79 77 Elongation (%) 49 53 52 53 Exterior color black black black black 30 minutes Tensile Strength (Mpa) 79 79 78 78 Elongation (%) 51 52 54 51 Exterior color black black black black 40 minutes Tensile Strength (Mpa) 73 72 73 68 Elongation (%) 49 50 54 52 Exterior color black black black black 300 degrees 0 minutes Tensile Strength (Mpa) 84 82 83 80 Elongation (%) 50 52 55 55 Exterior color black black black black 10 minutes Tensile Strength (Mpa) 84 82 83 80 Elongation (%) 50 52 55 55 Exterior color black black black black 20 minutes Tensile Strength (Mpa) 80 80.5 82 78 Elongation (%) 54 51 52 53 Exterior color black black black black 30 minutes Tensile Strength (Mpa) 74 73 75 73 Elongation (%) 52 49 55 52 Exterior color black black black black 40 minutes Tensile Strength (Mpa) 65 66 68 58 Elongation (%) 50 51 51 54 Exterior color black black black black ferment Before aging Tensile Strength (Mpa) 82 82 83 80 Elongation (%) 50 52 55 55 After aging Tensile Strength (Mpa) 72 71 70 69 Elongation (%) 38 34 38 37 Laser transmission 980 nm 77 80 82 77 1080 nm 79 82 84 79 Laser welding Good
welding Good
welding Good
welding Good
welding

Reference Example 1-5 compare
Reference example
1-7 compare
Reference example
1-8 compare
Reference example
1-1 ejaculation
visit 280 degrees 0 minutes Tensile Strength (MPa) 65 80 81 82 Elongation (%) 60 42 45 50 Exterior color black black black White 10 minutes Tensile Strength (MPa) 65 80 81 82 Elongation (%) 60 42 45 50 Exterior color black black black White 20 minutes Tensile Strength (MPa) 60 78 80 80 Elongation (%) 58 40 46 52 Exterior color black black black Light yellow 30 minutes Tensile Strength (MPa) 61 77 81 80 Elongation (%) 59 42 43 52 Exterior color black black black Light yellow 40 minutes Tensile Strength (MPa) 51 68 79 70.4 Elongation (%) 55 43 40 48 Exterior color black black black Light yellow 300 degrees 0 minutes Tensile Strength (MPa) 65 80 81 82 Elongation (%) 60 42 45 50 Exterior color black black black White 10 minutes Tensile Strength (MPa) 65 80 81 82 Elongation (%) 60 42 45 50 Exterior color black black black White 20 minutes Tensile Strength (MPa) 61 76 82 78 Elongation (%) 58 39 44 49 Exterior color black black black Light yellow 30 minutes Tensile Strength (MPa) 62 68 80 72 Elongation (%) 56 41 42 49 Exterior color black black black Light yellow 40 minutes Tensile Strength (MPa) 48 62 72 63 Elongation (%) 51 44 46 52 Exterior color black black black Light yellow ferment Before aging Tensile Strength (MPa) 65 80 81 82 Elongation (%) 60 42 45 50 After aging Tensile Strength (MPa) 56 68 72 70 Elongation (%) 32 30 32 35 Exterior color black black black Light yellow Laser transmission 980 nm 70 35 0 75 1080 nm 74 38 0 77 Laser welding Good
welding Insufficient
welding Not adhered
Not Good
welding

compare
Reference example
1-2 compare
Reference example
1-3 compare
Reference example
1-4 compare
Reference example
1-5 compare
Reference example
1-6 ejaculation
visit 280 degrees 0 minutes Tensile Strength (MPa) 83 82 84 83 85 Elongation (%) 52 51 54 53 40 Exterior color black black black black black 10 minutes Tensile Strength (MPa) 83 83 84 83 85 Elongation (%) 52 53 54 53 40 Exterior color black black black black black 20 minutes Tensile Strength (MPa) 81 82 81 83 84 Elongation (%) 53 51 53 49 42 Exterior color black black black black black 30 minutes Tensile Strength (MPa) 78 78 81 80 85 Elongation (%) 52 53 55 51 43 Exterior color black black black black black 40 minutes Tensile Strength (MPa) 71 70 72 72 78 Elongation (%) 53 52 49 48 45 Exterior color black black black black black 300 degrees 0 minutes Tensile Strength (MPa) 83 82 84 83 85 Elongation (%) 52 51 54 53 40 Exterior color black black black black black 10 minutes Tensile Strength (MPa) 83 83 84 83 85 Elongation (%) 52 53 54 53 40 Exterior color black black black black black 20 minutes Tensile Strength (MPa) 77 78 82 80 84 Elongation (%) 53 51 53 47 41 Exterior color black black black black black 30 minutes Tensile Strength (MPa) 73 73 75 73 78 Elongation (%) 55 51 48 49 45 Exterior color black black black black black 40 minutes Tensile Strength (MPa) 64 65 67 69 75 Elongation (%) 52 49 52 51 42 Exterior color black black black black black ferment Before aging Tensile Strength (MPa) 83 83 84 83 85 Elongation (%) 52 52 54 53 40 After aging Tensile Strength (MPa) 71 71 73 73 78 Elongation (%) 38 37 40 32 35 Exterior color bitumen bitumen bitumen black black Laser transmission 980 nm 34 32 29 0 0 1080 nm 36 34 30 0 0 Laser welding Good welding Insufficient
welding Poor
welding Not adhered
Not Not adhered
Not

In general, when nigrosine dyes (Comparative Reference Examples 1-2 to 1- (1) to (1-5)) are used in the case of containing the black colorant (Production Example 1) 4), carbon black (Comparative Reference Example 1-6), or a combination thereof (Reference Example 1-5).

Further, the black colorant (Production Example 1), when singly used as the nigrosine dye, is different from carbon black (Comparative Reference Example 1-2) in that the discoloration (Comparative Reference Example 1-2) occurs at the injection temperature and / It can be seen that the heat resistance similar to that in the case of using Example 1-6 alone is secured and the high temperature discoloration is suppressed.

The black colorant (Production Example 1) is superior in mechanical properties, laser transmittance and weldability to nigrosine dyes, carbon black, or a combination thereof.

In short, the above-mentioned black colorant has an improved physical property in combination with an organic dye and an inorganic pigment to realize a black color while exhibiting a high-temperature discoloration-suppressing property, a mechanical property, a laser transmittance and a weldability. Thus, a nigrosine dye, a carbon black, It is possible to replace the existing black coloring agent such as a combination.

On the other hand, in the case where only the black colorant (Production Example 1) was included in the black colorant (Production Example 1) (Comparative Reference Examples 1-7 and 1-8) in which nigrosine dye or carbon black was added (Reference Example 1 -1 to 1-5), the laser transmittance and the laser weldability are lowered.

In contrast to the case of containing only the black colorant (Production Example 1) (Reference Examples 1-1 to 1-5), when a nigrosine dye was added (Comparative Reference Example 1-7) It was confirmed that the transmittance was lowered at 980 nm and 1080 nm. Thus, it is not preferable to add a nigrosine dye to the black colorant (Production Example 1) in consideration of the problem of lowering the transmittance.

In addition, when carbon black was added to the black colorant (Production Example 1) (Comparative Reference Example 1-8), not only transmission at 980 nm and 1080 nm, which are generally used laser wavelengths, Transmittance of 0), it was confirmed that laser welding was not performed. Thus, it is difficult to achieve the purpose of the black colorant when a small amount of carbon black is added to the black colorant (Production Example 1).

Among them, in consideration of the problem of lowering the laser transmittance, it is preferable that the nigrosine dye is not combined with the above inorganic pigment or is used in combination with other organic dye in combination with the inorganic pigment.

Test Example  2

(1) Exam contents

In Test Example 2, various combinations of organic dyes and inorganic pigments, which can replace conventional black coloring agents, are presented. Test Example 2 Further, the test was conducted without using a flame retardant.

(2) Preparation of test composition

Manufacturing example  2-1 to 2-11: Black coloring agent and resin composition containing the same

(A1), anthraquinone blue (a2), anthraquinone violet (a3), anthraquinone yellow (a4), anthraquinone green (a5), azo red (a6) Azo orange (a7), phthalocyanine blue (a8) and ultramarine blue (b) which is an inorganic pigment (B).

These raw materials were variously combined to prepare a coloring agent which exhibits black color. Specifically, the raw material combinations of the respective black colorants of Production Examples 2-1 to 2-11 were listed in Table 5 below, and the units omitted in the following Table 5 are " parts by weight ".

Each of the black colorants of Production Examples 2-1 to 2-11 was mixed with a polyamide 66 (relative viscosity: 2.4, specific gravity: 1.14, melting temperature: 260 占 폚) to prepare a resin composition. In this case, when the total amount of each composition is 100% by weight, the content of each black colorant in Production Examples 2-1 to 2-11 is set to 0.1% by weight, and the remainder is made of polyamide 66. [

Organic dye (A) Inorganic pigment (B) a1 a2 a3 a4 a5 a6 a7 a8 a9 Production Example 2-1 0.5 0.5 0 0 0 0 0 0 0 Production example 2-2 0.2 0.5 0.3 0 0 0 0 0 0 Production Example 2-3 0.2 0.3 0.5 0 0 0 0 0 0 Production example 2-4 0.3 0 0 0.1 0.6 0 0 0 0 Production example 2-5 0.2 0.5 0.3 0 0 0 0 0 0.01 Production Example 2-6 0.2 0.5 0.3 .0 0 0 0 0 0.1 Production example 2-7 0.2 0.5 0.3 0 0 0 0 0 0.3 Production example 2-8 0.2 0.5 0.3 .0 0 0 0 0 0.5 Production Example 2-9 0 0 0 0 0 0.3 0.1 0.6 0 Production Example 2-10 0 0.6 0 0 0 0.3 0.1 0 0 Production Example 2-11 0 0.6 0 0 0 0.3 0.1 0 0.1

(3) Test conditions

Tests were conducted under the same conditions as in Test Example 1 for each of the resin compositions of Production Examples 2-1 to 2-11, and the results are shown in Tables 6 and 7 below.

(4) Test results

Manufacturing example
2-1 Manufacturing example
2-2 Manufacturing example
2-3 Manufacturing example
2-4 Manufacturing example
2-5 ejaculation
visit 280 degrees 40 minutes Exterior color black
(Red at the gate) black
(Red color of gate part) black
(Red color of gate part) black
(Light green light) black 300 degrees 40 minutes Exterior color Red color Red color Red color Dark green black Appearance color after aging Sword-red Dark green black black black laser
Permeation 980 nm 75 78 78 75 78 1080 nm 76 80 80 77 80 Laser welding Good
welding Good
welding Good
welding Good
welding Good
welding evaluation Comparative Reference Example Reference example

Manufacturing example
2-6 Manufacturing example
2-7 Manufacturing example
2-8 Manufacturing example
2-9 Manufacturing example
2-10 Manufacturing example
2-11 ejaculation
visit 280 degrees 40 minutes Exterior color black black black Red color Partial red color black 300 degrees 40 minutes Exterior color black black black Red color Red color black Appearance color after aging Sword-red Sword-red Sword-red Sword-red Sword-red Sword-red laser
Permeation 980 nm 77 76 72 58 70 70 1080 nm 80 78 73 60 73 72 Laser welding Good
welding Good
welding Good
welding Good
welding Good
welding Good
welding evaluation Reference example Comparative Reference Example Reference example

The black colorant is not limited to Production Example 1, but may be prepared in various combinations of organic dyes and inorganic pigments as in Production Examples 2-5 to 2-8 and Production Examples 2-11. And it can be understood that it is possible to overcome the limitations of various physical properties represented by the conventional black coloring agent. Particularly, it can be seen that the great advantage of the black colorant in combination with the organic dye and the inorganic pigment resides in suppressing the discoloration at high temperature.

Test Example  3

(1) Exam contents

In Test Example 3, the criteria for designing the black colorant in combination with the organic dye and the inorganic pigment in the absence of a flame retardant are specifically shown.

Specifically, criteria for designing a black coloring agent in combination with the organic dye and the inorganic pigment are set forth in detail, with parameterization before and after exposure to high temperature.

(2) Preparation of test composition

Reference example  3-1 to 3-5

The same black colorants as Production Examples 2-5, 2-6, 2-7, 2-8, and Production Example 1 were produced in Reference Examples 3-1 to 3-5, A resin composition containing a black colorant in an amount of 0.1 wt% and a polyamide 66 in an amount of 0.5 wt% was prepared.

Comparative Reference Example  3-1 to 3-3

In Comparative Reference Examples 3-1 to 3-3, the same resin compositions as Comparative Reference Examples 1-1 to 1-3 and Production Example 2-2 were prepared.

For reference, in Table 8 below, the content of each component is described with the total amount of each composition of Reference Examples 3-1 to 3-5 and Comparative Reference Examples 3-1 to 3-3 as 100% by weight, &Quot;% by weight " is omitted.

Comparative Reference Example 3-1 Comparative Reference Example 3-2 Comparative Reference Example 3-3 Comparative Reference Example 3-4 Reference Example 3-1 Reference Example 3-2 Reference Example 3-3 Reference Example 3-4 Reference Example 3-5 Polyamide
66 100 99.9 99.9 99.9 99.9 99.9 99.9 99.9 90 Perion
Red dye - - 0.02 0.018 0.01 0.005 0.003 2.0 Anthraquinone
Blue dye - - 0.05 0.045 0.025 0.0125 0.008 4.7 Anthraquinone
Violet dye - - 0.03 0.027 0.015 0.0075 0.005 2.8 Ultramarine
Blue dye - - - 0.01 0.05 0.075 0.084 0.5 Nigro New World
dyes - 0.1 - - - - - - - Carbon black
Pigment - - 0.1 - - - - - - Total amount 100 100 100 100 100 100 100 100 100 color
(Visual observation) White black black black black black black black black

(3) Test conditions

Each composition was held at 280 캜 or 300 캜 for 0, 10, 20, 30, or 40 minutes using an 80-ton injecting machine manufactured by Engel, and then injected to prepare specimens having a thickness of 2.5 T And then cooled to room temperature (natural standing).

For each injection specimen, the color difference (? E ^* _ab ) for the initial composition was measured using a spectrocolorimeter (X-rite CI7800, Engel) according to the CIE1976 L * a * b * Were observed.

The test results are reported in Table 9 below.

(4) Test results

Comparative Reference Example 3-1 Comparative Reference Example 3-2 Comparative Reference Example 3-3 Comparative Reference Example 3-4 Reference Example 3-1 Reference Example 3-2 Reference Example 3-3 Reference Example 3-4 Reference Example 3-5 280 ° C,
10 minutes The color difference
(? E * ab) 0.4 0.01 0.01 0.72-1.17 0.41 0.1 0.02 0.02 0.01 Exterior color White black black Partial deviation Black generated black black black black black 280 ° C,
20 minutes The color difference
(? E * ab) 1.0 0.02 0.01 1.5 to 1.9 0.72 0.27 0.19 0.09 0.03 Exterior color Light yellow black black Black with red color black black black black black 280 ° C,
40 minutes The color difference
(? E * ab) 1.3 0.04 0.02 2.2 ~ 2.8 0.85 0.38 0.37 0.32 0.05 Exterior color Light yellow black black Red black black black black black 300 ° C,
40 minutes The color difference
(? E * ab) 2.4 0.08 0.05 3.8 to 4.5 0.92 0.43 0.42 0.33 0.09 Exterior color Light yellow black black Red black black black black black

Taking comprehensive examination of Tables 8 and 9, it can be seen that the resin compositions of Reference Examples 3-1 to 3-5, regardless of the injection retention conditions (temperature and time), were evaluated visually It can be seen that the color change of each injection specimen to be confirmed is insignificant and falls within the range of 0.01 to 2.0 when the color change is parameterized to the color difference (? E ^* _ab ) according to the CIE1976 L * a * b * colorimetric system.

On the other hand, in each of the resin compositions of Comparative Reference Examples 3-1 to 3-3, the color change of each injection specimen was visually observed on the basis of the black color expressed by each initial composition, depending on the injection retention condition (temperature and time) And in such a case, when the color change is parameterized to the color difference (? E ^* _ab ) according to the colorimetric system of CIE1976 L * a * b *, it is found out that it is out of the range of 0.01 to 2.0.

In this connection, the black colorant exhibits black as a whole in combination with an organic dye and an inorganic pigment, and has a color before and after exposure at a high temperature of 200 to 400 ° C in a state of being applied to a polyamide resin composition to CIE 1976 L * a * b * Colorimetric (DELTA E ^* _ab ) when tested according to the colorimetric system is designed to fall within the range of 0.01 to 2.0.

Test Example  4

(1) Exam contents

In Test Example 4, it is confirmed whether the black coloring agent derived from Test Examples 1 to 3 exhibits black color even in the case where the black coloring agent is applied to the polyamide resin composition together with the P-type flame retardant, and that the effect of suppressing the discoloration at high temperature can be maintained .

(2) Preparation of test composition

Example  1 to 8

Each of the resin compositions of Examples 1 to 8 was prepared with the composition shown in Table 10 below.

However, in the following Table 10, in the same manner as in Production Example 1, the black colorant was changed to 47% by weight of anthraquinone blue, 28% by weight of anthraquinone violet, 20% by weight of perinone red, And 5% by weight of Marine Blue.

The flame retardants used in Table 10 are as follows.

N flame retardant: Melamine cyanurate.

Br flame retardant: The Brominated Polystyrene, its synergist is Sb ₂ O _3, the stabilizer was used as the Zinc borate.

P system Flame retardant 1: aluminum diethyl-phosphinate.

P System Flame Retardant 2: Aluminum diethyl-phosphinate (1), melamine polyphosphate (MPP) as a synergist, and Zinc borate as a stabilizer are mixed.

Synergist: Aromatic polyphosphate used separately from P flame retardant 2.

Example  9-13

Resin compositions of Examples 9 to 13 were prepared with the compositions shown in Table 11 below.

However, in the following Table 11, the black colorant is a combination of 50% by weight of anthraquinone blue, 30% by weight of anthraquinone violet and 20% by weight of perinone red, based on 100% by weight of the total amount of the colorant, No combination.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Polyamide 66 87.9 42.9 42.9 55.9 55.9 47.9 52.9 59.9 Glass fiber
(Glass fiber) 25 25 25 25 25 25 25 N flame retardant 12 - - - - - - - Br flame retardant - 25 25 - - - - - Rising agent of Br-based flame retardant - 7 4 - - - - - Stabilizer of Br-based flame retardant - - 3 - - - - - P type flame retardant 1 - - - - 19 24 19 12 P type flame retardant 2 - - - 19 - - - - P flame retardant agent - - - - - 3 3 3 The black colorant of Preparation Example 1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Total amount 100 100 100 100 100 100 100 100

Example 9 Example 10 Example 11 Example 12 Example 13 Polyamide 66 87.9 42.9 42.9 55.9 55.9 Glass fiber
(Glass fiber) 25 25 25 25 N flame retardant 12 - - - - Br flame retardant - 25 25 - - Rising agent of Br-based flame retardant - 7 4 - - Stabilizer of Br-based flame retardant - - 3 - - P type flame retardant 1 - - - - 19 P type flame retardant 2 - - - 19 - The black colorant of Comparative Example 1 0.1 0.1 0.1 0.1 0.1 Total amount 100 100 100 100 100

(3) Test conditions

The resin compositions of Examples 1 to 13 were tested under the same conditions as in Test Examples 1 to 3 except that the flame retardancy test was carried out in accordance with UL94 after injection molding at a temperature of 2.5T and a test piece of 2.5T, , And the results of the tests are recorded in Tables 12 to 14.

(4) Test results

Example 9 Example 10 Example 11 Example 12 Example 13 ejaculation
visit 280 degrees 0 minutes Tensile Strength (MPa) 80 150 150 125 125 Elongation (%) 30 3.0 3.0 3.0 3.1 Exterior color black black black black black 10 minutes Tensile Strength (MPa) 82 151 151 127 125 Elongation (%) 30 3 3 3 3 Exterior color black black black black black 20 minutes Tensile Strength (MPa) 78 145 146 123 121 Elongation (%) 28 3.1 2.9 3.1 3.0 Exterior color Partial deviation Black generated Partial deviation Black generated Partial deviation Black generated Partial deviation Black generated Partial deviation Black generated 30 minutes Tensile Strength (MPa) 72 135 133 118 115 Elongation (%) 35 3.4 3.5 3.4 3.6 Exterior color Black with red Black with red Black with red Black with red Black with red 40 minutes Tensile Strength (MPa) 71 134 133 113 110 Elongation (%) 36 3.6 3.4 3.6 3.8 Exterior color Strong red area Strong red area Strong red area Strong red area Strong red area 300 degrees 0 minutes Tensile Strength (MPa) 80 150 150 125 125 Elongation (%) 30 3.0 3.0 3.0 3.0 Exterior color black black black black black 10 minutes Tensile Strength (MPa) 81 150 152 126 126 Elongation (%) 30 3.2 3.1 3.2 3.1 Exterior color Partial deviation Black generated Partial deviation Black generated Partial deviation Black generated Partial deviation Black generated Partial deviation Black generated 20 minutes The tensile strength
(MPa) 75 146 143 116 109 Elongation (%) 34 3.5 3.3 3.8 3.6 Exterior color Black with red Black with red Black with red Black with red Black with red 30 minutes The tensile strength
(MPa) 68 127 125 104 102 Elongation (%) 36 3.6 3.5 3.6 3.8 Exterior color Red strong Red strong Red strong Red strong Red strong 40 minutes Tensile Strength (MPa) 62 118 116 99 96 Elongation (%) 35 3.4 3.5 3.7 3.9 Exterior color Red Red Red Red Red ferment Before aging Tensile Strength (MPa) 80 150 150 125 125 Elongation (%) 30 3.0 3.0 3.0 3.1 After aging Tensile Strength (MPa) 82 153 152 126 126 Elongation (%) 28 3.1 3.1 3.0 3.2 Exterior color Red powder Red powder Red powder Red powder Red powder Laser transmission 980 nm 78 12 10 15 38 1080 nm 80 15 13 17 40 Flammability UL94 0.8
mm @ V-2 0.8
mm @ V-0 0.8
mm @ V-0 0.8
mm @ V-0 1.6
mm @ V-0 Laser welding Good
welding Good
welding Good
welding Good
welding Good
welding

Example 1 Example 2 Example 3 Example 4 ejaculation
visit 280 degrees 0 minutes Tensile Strength (MPa) 82 153 152 127 Elongation (%) 33 3.0 3.1 3.2 Exterior color black black black black 10 minutes Tensile Strength (MPa) 83 154 152 128 Elongation (%) 32 3.1 3.2 3.1 Exterior color black black black black ΔE * ab 0.42 0.45 0.45 0.43 20 minutes Tensile Strength (MPa) 80 148 148 124 Elongation (%) 34 3.0 3.4 3.4 Exterior color black black black black ΔE * ab 0.70 0.83 0.83 0.74 30 minutes Tensile Strength (MPa) 75 142 140 119 Elongation (%) 35 3.5 3.6 3.3 Exterior color black black black black 40 minutes Tensile Strength (MPa) 73 136 135 113 Elongation (%) 34 3.6 3.7 3.8 Exterior color black black black black ΔE * ab 0.83 0.87 0.87 0.82 300 degrees 0 minutes Tensile Strength (MPa) 82 153 152 127 Elongation (%) 33 3.0 3.1 3.2 Exterior color black black black black 10 minutes Tensile Strength (MPa) 83 154 152 128 Elongation (%) 33 3.2 3.4 3.2 Exterior color black black black black 20 minutes Tensile Strength (MPa) 78 145 143 120 Elongation (%) 37 3.4 3.6 3.9 Exterior color black black black black 30 minutes Tensile Strength (MPa) 70 131 130 108 Elongation (%) 33 3.7 3.4 3.8 Exterior color black black black black 40 minutes Tensile Strength (MPa) 64 119 119 101 Elongation (%) 38 3.7 3.8 3.8 Exterior color black black black black ΔE * ab 0.94 0.98 0.99 0.89 ferment Before aging Tensile Strength (MPa) 82 153 152 127 Elongation (%) 33 3.0 3.1 3.2 After aging Tensile Strength (MPa) 85 157 158 130 Elongation (%) 30 3.4 3.3 3.2 Exterior color black black black black Laser transmission 980 nm 79 14 11 15 1080 nm 82 17 15 18 Flammability UL94 0.8mm@V-2 0.8mm@V-0 0.8mm@V-0 0.8mm@V-0 Laser welding Good
welding Good
welding Good
welding Good
welding

(In Table 13,? E * ab is a chrominance value for the initial composition)

Example 5 Example 6 Example 7 Example 8 ejaculation
visit 280 degrees 0 minutes Tensile Strength (MPa) 127 120 125 145 Elongation (%) 3.2 2.8 3.1 3.5 Exterior color black black black black 10 minutes Tensile Strength (MPa) 127 121 126 147 Elongation (%) 3.1 2.9 3.0 3.1 Exterior color black black black black ΔE * ab 0.43 0.45 0.43 0.46 20 minutes Tensile Strength (MPa) 123 118 125 149 Elongation (%) 3.3 3.1 3.4 3.6 Exterior color black black black black ΔE * ab 0.72 0.74 0.68 0.72 30 minutes Tensile Strength (MPa) 118 112 120 131 Elongation (%) 3.9 3.4 3.6 3.7 Exterior color black black black black 40 minutes Tensile Strength (MPa) 110 105 114 127 Elongation (%) 3.9 3.4 3.6 3.5 Exterior color black black black black ΔE * ab 0.83 0.84 0.77 0.78 300 degrees 0 minutes Tensile Strength (MPa) 127 120 125 145 Elongation (%) 3.2 2.8 3.1 3.5 Exterior color black black black black 10 minutes Tensile Strength (MPa) 127 122 123 141 Elongation (%) 3.3 2.7 3.2 3.6 Exterior color black black black black 20 minutes Tensile Strength (MPa) 118 110 121 135 Elongation (%) 3.5 3.4 3.6 3.7 Exterior color black black black black 30 minutes Tensile Strength (MPa) 108 101 110 123 Elongation (%) 3.7 3.4 3.7 3.8 Exterior color black black black black 40 minutes Tensile Strength (MPa) 99 92 106 111 Elongation (%) 3.9 3.5 3.7 3.9 Exterior color black black black black ΔE * ab 0.97 0.98 0.92 0.85 ferment Before aging Tensile Strength (MPa) 127 120 125 145 Elongation (%) 3.2 2.8 3.1 3.5 After aging Tensile Strength (MPa) 129 122 128 147 Elongation (%) 3.4 2.7 3.2 3.7 Exterior color black black black black Laser transmission 980 nm 40 40 40 42 1080 nm 42 41 42 45 Flammability UL94 1.6mm@V-0 0.8mm@V-0 1.2mm@V-0 1.6mm@V-0 Laser welding Good
welding Good
welding Good
welding Good
welding

(In Table 14, [Delta] E * ab is the chrominance value for the initial composition)

As mentioned above, the flame retardant, especially the phosphorus (P) based flame retardant, is problematic in that it is not used in the field of laser transmissive materials due to the problem of lowering the transmittance by a flame retardant synergist and / or a stabilizer Lt; / RTI >

However, from the comprehensive examination of Tables 10 to 14, it can be seen that, regardless of which coloring agent and flame retardant are applied, each of the polyamide resin compositions (Examples 1 to 13) can secure laser permeability, Time) injection molded specimen is excellent in flame retardancy. Of course, in order to improve the laser transmittance, it is preferable to lower the flame retardant content.

On the other hand, the polyamide resin composition (Examples 1 to 8) to which the flame retardant is applied together with the coloring agent combined with the organic dye and the inorganic pigment (Examples 1 to 8) It can be seen that the color change of each injection specimen, which is visually confirmed on the basis of the black color expressed by each initial composition, is insignificant, irrespective of the injection residence condition (temperature and time).

Specifically, in the polyamide resin compositions (Examples 1 to 8) to which the flame retardant was applied together with the coloring agent combined with the organic dye and the inorganic pigment (Examples 1 to 8), the color change before and after the high temperature stay injection was measured according to the CIE1976 L * a * b * It can be seen that when parameterized by the color difference (DELTA E ^* _ab ), it is still within the range of 0.01 to 2.0 as in Test Examples 1 to 3.

Further, in Tables 10 to 14, the polyamide resin compositions (Examples 1 to 8) to which the flame retardant was applied together with the colorant combined with the organic dye and the inorganic pigment (Examples 1 to 8) were found to have different flame retardancy and laser transmittance .

Specifically, when the P type flame retardant is applied in contrast to the case where the Br type flame retardant is applied together with the coloring agent combined with the organic dye and the inorganic pigment, the flame retardancy is low, but its flame retardancy is improved by the addition of a synergist and / It can be seen that However, it is understood that addition of a synergist and / or a stabilizer causes a decrease in laser transmittance, so that it is necessary to avoid addition of a synergist and / or a stabilizer for application to a laser-transmissive material.

Test Example  5

(1) Exam contents

In Experimental Example 5, a polyamide resin composition to which a flame retardant was applied together with a colorant combined with the organic dye and the inorganic pigment was realized as a laser penetrant, and a laser absorber containing carbon black was separately fused Make sure you see what effect you have.

(2) Preparation of test composition

Transparent Material Specimen: The composition of Example 8 was injection-molded into a specimen of 2.5 T (2.5 mm) thickness using an 80-ton extruder manufactured by Engel, without hot stagnation, and cooled to room temperature. Thereafter, the sample was cut into a width of 2.7 mm, a length of 12.7 cm, and a thickness of 2.5 mm, and was obtained by laser-transmissive test pieces.

Preparation of Absorbent Material Specimens: The compositions of Referential Examples 5-1 to 5-5 were prepared according to the following Table 15, and each of the compositions was injection-molded at a high temperature of 2.5 T (2.5 mm) . Thereafter, the substrate was cut into a width of 2.7 mm, a length of 12.7 cm, and a thickness of 2.5 mm, respectively, to obtain laser absorber specimens.

Part of the laser absorbing material specimens prepared from the respective compositions of Reference Examples 5-1 to 5-5 were brought into contact with a part of the permeable material specimen and fusion-bonded using a laser welding equipment. However, the length (fusion length) of the contact portions in each of the specimens was 1 cm.

In this fused state, a tensile force was applied to both ends of the fused specimen using a tensile tester (Zwick), and the maximum tensile strength until the fused portion was dropped was measured.

At this time, the measured maximum tensile strength (F) was divided by the fusing length to obtain a tensile strength value.

Tensile Strength (Mpa) = F / fusion length

Reference Example 5-1 Reference Example 5-2 Reference Example 5-3 Reference Example 5-4 Reference Example 5-5 Polyamide 66 59.9 59.85 59.7 59.5 59.0 Glass fiber
(Glass fiber) 25 25 25 25 25 P type flame retardant 1 12 12 12 12 12 P flame retardant agent 3 3 3 3 3 Carbon black pigment 0.05 0.15 0.3 0.5 1.0 Total amount 100 100 100 100 100

(Note that the units omitted in Table 15 are " wt% ").

Reference Example 5-1 Reference Example 5-2 Reference Example 5-3 Reference Example 5-4 Reference Example 5-5 Tensile Strength (Mpa) 47 52 55 57 58

According to Tables 15 and 16, when a polyamide based resin composition to which a flame retardant is applied together with a coloring agent combined with the organic dye and the inorganic pigment is used as a permeable material, it is fused to a separate laser absorbing material including carbon black, It can be seen that it may also be used to control the laser absorption capacity. Particularly, according to the carbon black content of the absorber, stronger fusion strength can be realized even under the same laser welding condition, and the absorption capacity of the laser absorber can be improved by the design of the molded product, thickness, It can be seen that it is applicable to control.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention.

It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be interpreted as being included in the scope of the present invention .

Claims (18)

Polyamide based resin;
A black colorant in combination with organic dyes and inorganic pigments; And
A flame retardant;
A color difference (DELTA E ^* _ab ) according to the CIE1976 L * a * b * coloring system is 0.01 to 2.0 before and after high temperature exposure at 200 to 400 DEG C,
Resin composition.
The method according to claim 1,
The flame-
Phosphorus (P) type flame retardant; Nitrogen (N) based flame retardants; Halogen-based flame retardants; Inorganic flame retardants; And a polymer polymer comprising a flame retardant element, wherein the polymer comprises at least one member selected from the group consisting of:
Resin composition.
3. The method of claim 2,
The phosphorus (P)
Based flame retardant, a red phosphorus (RP) flame retardant, a phosphate flame retardant, a phosphine flame retardant, a phosphite flame retardant, a phosphonate flame retardant, a phosphinate A flame retardant, a phosphoric acid ester, and a phosphoric acid ester and salts, or a mixture of two or more thereof.
Resin composition.
3. The method of claim 2,
The nitrogen (N)
Melamine polyphosphate (MPP), melamine cyanurate, melamine, melamine isocyanurate, melamine-cyanuric acid, triazine, and the like. Based compound, or a mixture of two or more selected from the group consisting of the above-
Resin composition.
3. The method of claim 2,
The halogen-
Brominated flame retardants (BFRs), polybrominated biphenyls (PBB), brominated cyclohydrocarbons, decabromodiphenyl ether (Deca-BDE or DeBDE), hexabromocyclododecane (HBCD or HBCDD), tetrabromobisphenol A (TBBPA or TBBP-A), brominated polystyrene, propylene dibromo styrene Or a mixture of two or more thereof,
Resin composition.
3. The method of claim 2,
The inorganic flame-
Wherein the flame retardant is selected from the group consisting of a boron (B) -based flame retardant, an antimony-based flame retardant, and a metal hydrate-based flame retardant,
Resin composition.
The method according to claim 1,
The flame-
A flame retardant synergist, a stabilizer, or a mixture thereof.
Resin composition.
8. The method of claim 7,
The flame-
Melamine polyphosphate (MPP), melamine cyanurate, melamine, silicon based polymer, magnesium hydroxide (Mg (OH) ₂ ), aluminum trihydroxide (Al (OH) ₃ ), aluminum hydroxide oxide ((AlO (OH) 2), MgCo ₃ , PTFE, and Aromatic polyphosphate (RDX)
Resin composition.
8. The method of claim 7,
The stabilizer may comprise,
Zirconium borate, zirconium borate, zinc borate, and antimony trioxide.
Resin composition.

The method according to claim 1,
Wherein the flame retardant is contained in an amount of 3 to 40% by weight, based on 100% by weight of the total amount of the resin composition,
Resin composition.
The method according to claim 1,
And has a transmittance of 10% or more when irradiated with light in the 800 to 1080 nm region.
The method according to claim 1,
Wherein the inorganic pigment is one or a mixture of two or more selected from the group including an ultramarine pigment, titanium dioxide, zinc sulfide, zinc oxide, and iron oxide,
Resin composition.
The method according to claim 1,
Wherein the organic dye is any one or a mixture of two or more selected from the group consisting of a perinone dye, an anthraquinone dye, an azo dye, a phthalocyanine dye, and a methine dye,
Resin composition.
The method according to claim 1,
Wherein the polyamide-based resin is a lactam-based polymer; Amino acid polymers; Diacid; Diamines; Homopolyamide; And copolyamide; a mixture of two or more thereof, or a polymer comprising two or more of them as monomers;
Resin composition.
The method according to claim 1,
Wherein the black colorant is contained in an amount of 0.1 to 10.0% by weight, based on 100% by weight of the total amount of the resin composition,
Resin composition.
Polyamide based resin;
coloring agent; And
A flame retardant;
A transmittance of 10% or more when irradiated with light in the 800 to 1080 nm region,
According to UL94, flame retardancy is 0.4mm@V-0 or more,
Resin composition.
17. The method of claim 16,
The colorant may be,
Organic dyes, inorganic pigments, and natural pigments (NP).
Resin composition.
A molded article comprising the resin composition according to any one of claims 1 to 17.