KR20170041930A - Molded article having analysis power of thermal history - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition comprising 100 parts by weight of a thermoplastic resin; And 1 to 30 parts by weight of a polyamic resin containing a repeating unit represented by the following formula (1):
[Chemical Formula 1]

(Wherein R is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, and n is an integer of 2 to 1,000).

Description

[0001] MOLDED ARTICLE HAVING ANALYSIS POWER OF THERMAL HISTORY [0002]

The present invention relates to a molded article having a thermal history analyzing ability. More specifically, the present invention relates to a molded article having a thermal history analyzing ability, which is excellent in heat resistance improving effect, realizes quality control easiness and reliability improvement effect.

Recently, there is a growing demand for materials having various functions in the fields of automobiles, electric / electronic and industrial parts. A laser welding camera, which is a mounting part of an automobile, is designed in consideration of the improvement of the transmittance in manufacturing.

However, there is a problem that the laser transmittance and the bonding force are lowered depending on the injection mold temperature during the manufacturing process. In order to solve this problem and to improve the quality, a black color was used in contrast to the case of using a natural or transparent material as a conventional laser-transmissive material.

These black color pigments consist of a combination of special pigments other than carbon black in order not to absorb the laser. In particular, a polyester-based resin into which a laser-transmissible black pigment has been introduced has been developed and used for mass production of products.

On the other hand, the laser transmissivity of the laser fused permeable material for laser welding is drastically decreased according to the injection condition and the annealing condition, so it is important to track the thermal history of the material when a quality problem occurs.

However, such black color pigments have different laser transmission characteristics depending on the injection conditions, but no change related to the characteristic change has been observed in the analysis apparatus such as DSC, TGA, FTIR.

Therefore, there is an urgent need to develop a material that improves these problems, has excellent heat resistance, easily tracks quality variations due to manufacturing process differences, and realizes quality control and reliability improvement effects.

An object of the present invention is to provide a molded article having thermal history analyzing ability which is excellent in heat resistance improving effect by including a thermoplastic resin and a polyamic resin containing a repeating unit represented by the formula (1).

Another object of the present invention is to provide a molded article having a thermal history analyzing ability which can easily follow the quality deviation due to the difference in manufacturing process by analyzing the difference of imidization reaction according to thermal history through FTIR, DSD, TGA and the like .

It is still another object of the present invention to provide a molded article having thermal history analysis capability that realizes ease of quality management and reliability improvement through analysis evaluation.

Another object of the present invention is to provide a molded article which is used in laser-transmissive materials for injection molding, which is an injection molding material for automobile parts, and which realizes excellent thermal history analysis capability.

The above and other objects of the present invention can be achieved by the present invention described below.

One aspect of the present invention is a thermoplastic resin composition comprising 100 parts by weight of a thermoplastic resin; And 1 to 30 parts by weight of a polyamic resin containing a repeating unit represented by the following formula (1):

[Chemical Formula 1]

(Wherein R is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, and n is an integer of 2 to 1,000).

In one embodiment, the thermoplastic resin may have a melting point of from 150 to 400 캜.

In one embodiment, the thermoplastic resin may be a polyester-based resin.

In one embodiment, the polyester-based resin may have an intrinsic viscosity (?) Of 0.5 to 1.5 dl / g.

In one embodiment, the thermoplastic resin is selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexanedimethylene terephthalate, polytrimethylene terephthalate, polyamide-6, polyamide- Acetal, polyphenylene sulfide, m-polyphenylene oxide, and the like, or a mixture of two or more thereof.

In one embodiment, the molded article is one or more additives selected from antioxidants, lubricants, UV stabilizers, compatibilizers, pigments, dyes, inorganic additives, coupling agents, impact modifiers, antistatic agents, antiwear agents and antimicrobial agents As shown in FIG.

In one embodiment, the molded article may be an injection molded material for an automotive part.

In one embodiment, the injection-molding material may be a laser-transmissive material.

In one embodiment, the laser fusible permeable material may be injection molded at 260-300 < 0 > C.

The molded article having the thermal history analyzing ability according to the present invention is excellent in heat resistance, can easily track the quality deviation due to the manufacturing process difference, realizes the ease of quality control and reliability improvement, There is an effect that can be used for the laser-transmissive material.

The present invention relates to a molded article having a thermal history analyzing ability which comprises a thermoplastic resin and a polyamic resin containing a repeating unit represented by the formula (1) in a specific content ratio.

Hereinafter, each component and content thereof will be described in detail.

(A) a thermoplastic resin

The thermoplastic resin is included as a basic base resin for the purpose of improving physical properties of a molded article according to one embodiment of the present invention and realizing excellent physical properties such as heat resistance.

The thermoplastic resin is at least one selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexanedimethylene terephthalate, polytrimethylene terephthalate, polyamide-6, polyamide-66, polyacetal, Phenylene oxide, m-phenylene oxide, and the like, or a mixture of two or more thereof. For example, polyethylene terephthalate or polybutylene terephthalate which is excellent in heat resistance, chemical resistance, electrical properties, mechanical strength and molding processability, and is economically advantageous.

The thermoplastic resin may have a melting point of 150 to 400 占 폚, for example, 200 to 350 占 폚, for example, 250 to 300 占 폚. When the melting point is less than 150 ° C, the imide reaction by mixing with a polyamic acid or a polyamic acid ester to be described later proceeds very slowly and the production efficiency is decreased. On the contrary, when the melting point is higher than 400 ° C, There is a problem that it is difficult to obtain a significant difference rapidly. That is, within the range of the melting point, the thermoplastic resin exhibits excellent heat resistance properties and exhibits sufficient thermal history analysis capability, thereby facilitating tracking of thermal history, thereby enhancing the quality control effect and reliability in forming a laser- .

In another embodiment, the thermoplastic resin may be a polyester-based resin. The polyester resin may be formed, for example, by intensifying at least one aromatic, aliphatic or alicyclic dicarboxylic acid with at least one aliphatic or alicyclic glycol. For example, the aromatic dicarboxylic acid is composed of 6 to 20 carbon atoms, the aliphatic or alicyclic dicarboxylic acid is composed of 3 to 20 carbon atoms, and the aliphatic or alicyclic glycol is composed of 2 to 20 carbon atoms have. The polyester resin may be synthesized using a dicarboxylic acid compound and a glycol compound. The production of the polyester resin using the dicarboxylic acid compound and the glycol compound can be generally carried out in two steps of an esterification reaction and a polycondensation reaction, and the production process thereof is well known in the art. Examples of the dicarboxylic acid compound include terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, dipric acid, -, 2,3-, 2,6- or 2,7-) naphthalene dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-dibenzyldicarboxylic acid and the like can be used have. However, the type is not necessarily limited thereto as long as the technical idea of the present invention can be realized. Preferably, for example, terephthalic acid, isophthalic acid or a mixture thereof can be used. Examples of the glycol compound include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- -Cyclohexanediol, (1,2-, 1,3- or 1,4-) cyclohexanedimethanol, neopentyl glycol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol and the like . However, the present invention is not limited thereto as long as the technical idea of the present invention can be realized. Preferably, for example, ethylene glycol, cyclohexanedimethanol or a mixture thereof can be used. The polyester resin preferably has an intrinsic viscosity (IV) at 25 of from 0.5 to 1.5 dl / g, for example, from 0.7 to 1.3 dl / g, for example, 0.9 to 1.0 dl / g in terms of heat resistance, workability, 1.1 dl / g. It is possible to prevent the reduction of the mechanical properties of the molded article having the thermal history analyzing ability according to one embodiment of the present invention within the range of the intrinsic viscosity and to solve the problem that the flow property is deteriorated and the molding processability is deteriorated. The polyester-based resin may have a viscosity-average molecular weight (Mv) of, for example, 10,000 to 200,000, for example, 50,000 to 100,000 as measured in a methylene chloride solution. If the viscosity average molecular weight of the polyester-based resin is less than 10,000, heat resistance and mechanical properties may be significantly deteriorated. On the contrary, when the viscosity average molecular weight of the polyester-based resin exceeds 200,000, There may be problems.

If the content of the thermoplastic resin in the molded product is too small, sufficient thermal history analysis ability can not be exhibited and heat resistance and the like may be lowered. On the other hand, if the content is too large, thermal history tracking is difficult, There is a problem that the quality control effect and the reliability are deteriorated in forming the transparent material.

(B) Polyamic resin

The polyamic resin is used in combination with the thermoplastic resin for the purpose of realizing improvement in reliability of automotive interior parts by facilitating quality control and high-quality analysis of materials whose material characteristics vary according to thermal history.

In one embodiment of the present invention, it is more preferable to use a polyamic acid or a polyamic acid ester as the polyamic resin for the object of the present invention.

The molded article according to one embodiment of the present invention may be a copolymer containing a polyimide precursor, such as an amic acid or an amic ester, in a molded article structure. In addition, the molded article according to one embodiment of the present invention may be a mixture of a conventional molded article and a polyamic acid or a polyamic ester.

In one embodiment of the present invention, the polyamic acid resin, more specifically, the polyamic acid or polyamic acid ester, comprises a repeating unit of the following formula:

[Chemical Formula 1]

(Wherein R is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, and n is an integer of 2 to 1,000).

In the formation of the polyamic acid or polyamic acid ester, the imidization reaction in which the polyimide precursor is dehydrocondensed is generally thermal imidization or chemical imidization. Preferably, the chemical imidization in which the imidization reaction progresses at a relatively low temperature is more preferable because the molecular weight of the obtained polyimide is not lowered.

The chemical imidization can be carried out by stirring the polyimide precursor in an organic solvent in the presence of a basic catalyst and an acid anhydride. The melting point in the reaction may be 150 to 400 占 폚, for example, 200 to 350 占 폚, for example, 250 to 300 占 폚. When the melting point is less than 150 ° C, the imide reaction by mixing with polyamic acid or polyamic acid ester proceeds very slowly and the production efficiency is decreased. On the other hand, when the melting point is higher than 400 ° C, There is a problem that it is difficult to obtain a significant difference. In the above range of melting point, it has excellent heat resistance and exhibits a sufficient thermal history analyzing ability and is easy to track thermal history, thereby improving the quality control effect and reliability in forming laser penetration material for laser welding.

The reaction time of the chemical imidization is preferably from 1 to 100 hours, for example, from 5 to 95 hours, for example, from 10 to 90 hours. It is possible to form a thermoplastic resin composition which is suitable for imide reaction and exhibits excellent heat resistance and sufficient thermal history analysis capability in the above reaction time range.

Examples of the basic catalyst used for imidization include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine is preferred since it has a suitable basicity for promoting the reaction.

The amount of the basic catalyst may be 1 to 30 molar times, for example, preferably 3 to 25 molar times, for example, more preferably 5 to 20 molar times of the polyimide precursor. When the amount of the basic catalyst is less than 1 molar times, the reaction does not proceed sufficiently. On the other hand, when the amount of the basic catalyst is more than 30 molar times, there is a problem that complete removal is difficult after completion of the reaction.

Examples of the acid anhydride used in the imidization include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, the use of acetic anhydride is preferable since the purification after completion of the reaction becomes easy.

The amount of the acid anhydride may be 1.5 to 50 moles, preferably 3 to 40 moles, and more preferably 5 to 35 moles, of the polyimide precursor, for example. When the amount of the acid anhydride is less than 1.5 molar times, the reaction does not proceed sufficiently. On the contrary, when the amount of the acid anhydride is more than 50 molar times, there is a problem that complete removal is difficult after completion of the reaction.

Examples of the organic solvent include benzene; Toluene, o-xylene, p-xylene, m-xylene, mesitylene, 1,2,4-trimethylbenzene, tetramethylbenzene, ethylbenzene, n-propylbenzene, Butylbenzene, n-pentylbenzene, n-hexylbenzene, n-heptylbenzene, n-octylbenzene, n-nonylbenzene, n-decylbenzene, o-diethylbenzene, m Diethylbenzene, p-diethylbenzene, 1,2,4-triethylbenzene, 1,3,5-triethylbenzene, tetraethylbenzene, o-ethylmethylbenzene, p- Propylbenzene, ethyl-n-propylbenzene, ethyl-n-propylbenzene, methyl-i-propylbenzene, di- At least one alkylbenzene selected from benzene, methyl-n-propylbenzene, cyclohexylbenzene, tetralin, methyltetralin, styrene, biphenyl, indene and fluorene; naphthalene; at least one alkyl naphthalene selected from? -methyl naphthalene,? -methyl naphthalene,? -ethyl naphthalene,? -ethyl naphthalene, n-propyl naphthalene and 1,4-dimethyl naphthalene; At least one aromatic hydrocarbon organic solvent selected from anthracene, phenanthrene, xylene, and the like can be used.

In the polyimide solution thus obtained, since the added catalyst remains in the solution, it is preferable that the polyimide solution is put into a poor solvent which has been stirred to recover the polyimide. Examples of the poor solvent used for the precipitation and recovery of the polyimide include, but are not limited to, methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, . The precipitated polyimide may be recovered by filtration and washing by pouring into a poor solvent, and then recovered as a powder at room temperature or under reduced pressure or by heating and drying. The polyimide may be purified by repeating the operation of dissolving the powder in a good solvent and reprecipitating it 2 to 10 times. When the impurities can not be completely removed by one settling recovery operation, it is preferable to repeat this purifying step. It is preferable to mix or sequentially use three or more poor solvents such as alcohols, ketones and hydrocarbons as the poor solvent in the repeated purification process because the purification efficiency is further improved.

The imidization rate by the chemical imidization can be controlled by the optimum efficiency ratio by controlling the amount of catalyst used in the reaction, the reaction temperature, and the reaction time. The imidization rate of the polyimide according to the present invention is not particularly limited and may be set to any value in consideration of the solubility of the polyimide. The molecular weight of the polyimide according to one embodiment of the present invention is not particularly limited, but preferably the weight average molecular weight may be 4,000 to 600,000, for example 8,000 to 400,000, for example, 10,000 to 300,000. When the weight average molecular weight is less than 4,000, there is a problem that the imidization reaction for realizing thermal history analysis ability is weakened and the physical properties of the obtained molded article become insufficient. On the contrary, when the weight average molecular weight exceeds 600,000, There is a problem that the workability at the time of resin formation is lowered and the uniformity in the resin is reduced.

In the molded article having the thermal history analyzing ability according to one embodiment of the present invention, the polyamic resin may be used in an amount of 1 to 30 parts by weight, for example, 5 to 25 parts by weight per 100 parts by weight of the thermoplastic resin, 10 to 20 parts by weight may be included. When the content of the polyamic resin in the molded article of the present invention is less than 1 part by weight based on 100 parts by weight of the thermoplastic resin, it is difficult to easily change by heat and it is difficult to satisfy the chemical resistance or heat resistance of the molded article. On the other hand, when the amount is more than 30 parts by weight, the properties of the thermoplastic resin may be lost, the imidization reaction may be weakened, and thermal tracing may be difficult, and laser fusion bonding for laser welding may deteriorate quality control effect and reliability. There is a problem that the thermal stability of the molded article is deteriorated due to dimensional instability due to deformation.

Polycarbonate resin

The molded article according to one embodiment of the present invention may further include a polycarbonate resin for improving physical properties such as fluidity, heat resistance and impact strength at room temperature.

The polycarbonate resin that can be contained in the molded article of the present invention may be, for example, an aromatic polycarbonate resin. However, as long as the technical idea of the present invention can be realized, the type thereof is not particularly limited thereto, and for example, a thermoplastic aromatic polycarbonate resin commonly used in the art can be used.

The aromatic polycarbonate resin may be prepared from a divalent phenol, a carbonate precursor, a molecular weight modifier, and the like. The dihydric phenols are one of the monomers constituting the aromatic polycarbonate resin. The dihydric phenols include, for example, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis Ethyl-1,1-bis (4-hydroxyphenyl) propane, 1-phenyl-1,1-bis (4-hydroxyphenyl) Bis (4-hydroxyphenyl) ethane, 1-naphthyl-1,1-bis (4-hydroxyphenyl) ethane, (4-hydroxyphenyl) decane, 2-methyl-1,1-bis (4-hydroxyphenyl) propane and 2,2- Bisphenol A can be used.

The carbonate precursor is another monomer constituting the aromatic polycarbonate resin, and examples thereof include carbonyl chloride (phosgene), carbonyl bromide, bishaloformate, diphenyl carbonate, dimethyl carbonate and the like . Preferably, carbonyl chloride (phosgene) can be used.

As the molecular weight modifier, a monofunctional compound similar to the monomer used in the production of the thermoplastic aromatic polycarbonate resin may be used. Non-limiting examples of such molecular weight regulators include phenol-based derivatives (e.g., para-isopropylphenol, para-tert-butylphenol (PTBP), para- cumyl phenol, para- Para-isononylphenol and the like), aliphatic alcohols and the like. Preferably, para-tert-butylphenol (PTBP) can be used.

Examples of the aromatic polycarbonate resin produced from such a dihydric phenol, a carbonate precursor and a molecular weight modifier include linear polycarbonate resin, branched polycarbonate resin, copolycarbonate resin and polyester carbonate resin , And these may be used alone or in combination of two or more.

The preferred viscosity average molecular weight (Mv) of the aromatic polycarbonate resin may be from 15,000 to 40,000, for example from 17,000 to 30,000, for example from 20,000 to 30,000, as measured in a methylene chloride solution. If the viscosity average molecular weight of the aromatic polycarbonate resin is less than 15,000, mechanical properties such as impact strength and tensile strength may be significantly deteriorated. If the aromatic polycarbonate resin is more than 40,000, there may be a problem in resin processing due to an increase in melt viscosity.

When the molded article of the present invention further comprises a polycarbonate resin, the content thereof is 5 to 50 parts by weight, for example, 10 to 40 parts by weight, for example, 15 to 35 parts by weight, per 100 parts by weight of the thermoplastic resin can do. It is possible to improve the physical properties such as fluidity, heat resistance and impact strength at room temperature in the above content range, and to realize excellent thermal history analysis capability of the laser welding permeable material.

additive

As long as the object of the present invention is not impaired, the molded article having the thermal history analyzing ability of the present invention can be used in addition to the above-mentioned components in addition to other additives.

Examples of the additives include antioxidants, lubricants, UV stabilizers, compatibilizers, pigments, dyes, inorganic additives, coupling agents, impact modifiers, antistatic agents, antiwear agents and antimicrobial agents. In addition, the type of the present invention is not limited thereto as long as it can implement the technical idea of the present invention. These may be used alone or in combination of two or more.

Examples of the antioxidant include phenol type, phosphite type, thioether type, and amine type antioxidants. Examples of the releasing agent include polyethylene wax, silicone oil, and metal salts of stearic acid. Can be preferably used as an endurance agent such as benzophenone type, benzotriazole type or benzotriazine type.

As the filler, glass fiber, carbon fiber, silica, mica, or the like can be used. When such a filler is added, physical properties such as mechanical strength and heat resistance can be improved.

Such an additive may be contained in an amount of 0.1 to 20 parts by weight, for example, 1.0 to 15 parts by weight, for example, 5 to 10 parts by weight, based on 100 parts by weight of the whole molded article of the present invention.

The method of kneading the component resins forming the molded article is not limited to those used in the related art, but it is possible to apply the method of dry blending the components and additives of the present invention, followed by heating and melt kneading. At this time, the kneading can be performed so that each component can physically and chemically maintain sufficient affinity within the range of 200 to 300 ° C, for example, 220 to 280 ° C, for example, 240 to 260 ° C.

The molded article having the thermal history analyzing ability of the present invention formed by mixing the respective component resins has excellent heat resistance and can easily track the quality deviation due to the manufacturing process difference and realizes the quality control easiness and reliability improvement effect Particularly, there is an effect that can be used for a laser-transmissive material which is an injection molding material for an automobile part.

The method for producing the molded article is not particularly limited, and a molded article can be manufactured by a method generally used in various molding fields such as injection molding and plastic molding.

The molded article having the thermal history analyzing ability of the present invention can be utilized in various fields such as automobile, electric / electronic and industrial material parts.

The molded article may be an injection molding material for automobile parts. The injection-molding material for automobile parts is installed in various interior and exterior parts of a car to enhance the performance of a car on the basis of various functions such as sound absorption, sound absorption and appearance.

The injection-molding material may be a laser-melt-permeable material. When the laser welding material is used as the permeable material, it is possible to easily analyze the change of the material according to the thermal history such as the injection condition or the re-melting through general material analysis methods such as FTIR, DSC and TGA, Reliability can be secured.

Wherein the molded article is formed by mixing a thermoplastic resin and a polyamic resin; And can be manufactured through conventional well-known molding processes such as an injection process and a mold transfer process.

In the mixing step, the amic acid or the amic ester described above or a separate polyamic acid or polyamic ester may be mixed in the polymerization step of the thermoplastic resin, for example, PBT or PET resin.

In the injection step, the laser-transmissible material having a molded article according to one embodiment of the present invention is melted at a temperature of 250 to 300 ° C, for example, 260 to 290 ° C, for example, 270 to 280 ° C, . In the above range of melting point, a laser fusing permeable material for a vehicle having excellent heat resistance and excellent thermal history analysis capability can be formed.

In the mold transferring step, the molded article is retained in an injection machine and transferred to a mold. In this process step, the imidization reaction proceeds with the amic acid or the like in the material.

Can be easily measured by analyzing ^{- (1} 1390 cm) the imidation reaction proceeds in proportion to the melting point and the total standing time of the laser ridge transmitting material wear, where imidation reaction degree CNC Peak via FTIR.

The laser-transmissive material for vehicles including the molded article having the thermal history analysis capability according to the present invention has excellent heat resistance, can easily track the quality deviation due to the manufacturing process difference, .

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.

Example

Specific specifications of each component used in the following examples and comparative examples are as follows.

(A) a thermoplastic resin

PBT-GF30 (SDU A1 GF30 LW), a transparent material for laser welding with a thermoplastic resin and having a black color visually, was used.

(B) Polyamic resin

Polyamic acid or polyamic acid ester was used as the polyamic resin, and polyamic acid obtained by polymerizing PMDA and ODA in a 1: 1 equivalent as an example of the polyamic acid or polyamic acid ester resin was used.

Example 1

The ingredients shown in Table 1 were mixed and dispersed uniformly in a Henschel mixer and then extruded at a temperature of 270 DEG C in a biaxial melt mixing extruder having L / D = 40 and? = 25 mm to prepare pellets. The resulting pellets were dried in a hot air drier at 100 ° C. for 5 hours and then injection molded at 280 ° C. to prepare plate-like specimens having a thickness of 1 mm.

Examples 2 to 5

The pellets were prepared and dried in the same manner as in Example 1, and the injection-molded specimens were heat-treated at 200 ° C for different times to apply different heat histories. The above procedure and results are shown in Table 1 below.

Comparative Examples 1 to 2

The pellets were produced and dried in the same manner as in Example 1 except that the polyamic acid resin was not included in the production of the molded article, and the injection-molded specimens were heat-treated at 200 ° C to apply heat history differently. The above procedure and results are shown in Table 2 below.

Comparative Examples 3 to 4

Pellets were produced and dried in the same manner as in Example 1 except that the polyamic acid resin was excessively contained in the production of the molded article, and the injection-molded specimens were thermally treated at 200 ° C to apply heat history differently. The above procedure and results are shown in Table 2 below.

Example 1 Example 2 Example 3 Example 4 Example 5 (A) a polyester resin 100 parts by weight 100 parts by weight 100 parts by weight 100 parts by weight 100 parts by weight (B) Polyamic acid resin 5 parts by weight 5 parts by weight 5 parts by weight 25 parts by weight 25 parts by weight Heat treatment time 0 minutes 30 minutes 60 minutes 30 minutes 60 minutes Melt Index (MI)
(g / 10 min, 260 DEG C, 2.16 kg) 28 29 35 29 35 Before and after heat treatment
FT-IR change standard In change In change In change In change Laser transmittance
(980 nm, thickness 1 mm) 75% 42% 13% 42% 13%

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 (A) a polyester resin 100 parts by weight 100 parts by weight 100 parts by weight 100 parts by weight (B) Polyamic acid resin none none 50 parts by weight 50 parts by weight Heat treatment time 0 minutes 60 minutes 0 minutes 60 minutes Melt Index (MI)
(g / 10 min, 260 DEG C, 2.16 kg) 29 35 29 35 FT-IR change before and after heat treatment standard No change standard No change Laser transmittance
(980 nm, thickness 1 mm) 76% 13% 25% 3%

Thermal history analysis ability test result

As described above, in order to confirm the change of the laser transmittance according to the thermal history of the molded article according to one embodiment of the present invention, the change of the laser transmittance through the FT-IR test was confirmed before using the material of the laser welding part.

As a result of the test, the polyamic acid resin (B) was not included (Comparative Examples 1 and 2) or the polyamic acid resin (B) was used as the thermoplastic resin (polyester resin) When the excess amount of the mixed acid resin is included (Comparative Examples 3 to 4), it can be seen that the FT-IR change before and after the heat treatment can not be confirmed, and the thermal history analysis of the material for automobile parts is impossible. Therefore, according to the prior art, it is difficult to implement the thermal history analyzing capability, so that it is difficult to track the quality deviation due to the manufacturing process difference, and it is difficult to expect quality control and reliability improvement effects.

On the other hand, as shown in Table 1, as the component resin of the molded article according to one embodiment of the present invention, a thermoplastic resin and a polyamic acid resin having a specific content range including the above-mentioned formula 1 as a repeating unit relative to the thermoplastic resin (Examples 1 to 5), it is easy to confirm the FT-IR change before and after the heat treatment, so that it is possible to analyze the thermal history of the material for automobile parts. Therefore, according to the present invention, it is possible to improve the quality control and the reliability improvement by easily observing the quality deviation due to the manufacturing process difference through the heat resistance analysis capability and realizing the heat resistance analysis capability .

As described above, the molded article having the thermal history analyzing ability according to the present invention can be manufactured by mixing a thermoplastic resin and a polyamic acid or a polyamic acid ester in an optimum composition ratio. Thus, the thermoplastic resin is excellent in heat resistance, It is possible to easily track the quality deviation, to improve the quality control easiness and reliability, and in particular, to have an effect that can be used for an optimal injection molding material for automobile parts, that is, laser penetration material.

While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. This is possible.

Therefore, the scope of the present invention should not be limited by the described embodiments, but should be determined by the scope of the appended claims as well as the appended claims.

Claims (9)

100 parts by weight of a thermoplastic resin; And
1 to 30 parts by weight of a polyamic resin containing a repeating unit represented by the following formula (1):
[Chemical Formula 1]

(Wherein R is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, and n is an integer of 2 to 1,000).
The method according to claim 1,
Wherein the thermoplastic resin has a melting point of 150 to 400 占 폚.
The method according to claim 1,
Wherein the thermoplastic resin is a polyester-based resin.
The method of claim 3,
Wherein the polyester-based resin has an intrinsic viscosity (?) Of 0.5 to 1.5 dl / g.
The method according to claim 1,
The thermoplastic resin may be at least one selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexanedimethylene terephthalate, polytrimethylene terephthalate, polyamide-6, polyamide-66, polyacetal, Polyphenylene oxide, polyphenylene oxide, polyphenylene oxide, polyphenylene oxide, polyphenylene oxide, polyphenylene oxide, and polyphenylene oxide.
The method according to claim 1,
The molded article may further include at least one additive selected from the group consisting of an antioxidant, a lubricant, a UV stabilizer, a compatibilizer, a pigment, a dye, an inorganic additive, a coupling agent, an impact modifier, an antistatic agent, A molded article having thermal history analysis capability.
The method according to claim 1,
Wherein the molded article is an injection molding material for automobile parts.
8. The method of claim 7,
Wherein the injection-molding material is a laser-fusion wear-permeable material.
9. The method of claim 8,
Wherein the laser-transmissible material is injection-molded at a temperature of 250 to 300 占 폚.