KR102478071B1 - Polymeric resin composition for metal adhesive, metal-resin composites and electrical and product using the same - Google Patents

Abstract

The present invention relates to a polymer resin composition for metal adhesion having excellent adhesion to metal, heat stability, chemical resistance, dimensional stability and discoloration resistance, and a metal-resin composite and an article using the same.
The polymer resin composition for metal bonding is a polycyclohexylenedimethylene terephthalate resin; polyethylene terephthalate resin; and a filler, wherein the content of the polyethylene terephthalate resin is less than 200 parts by weight based on 100 parts by weight of the polycyclohexylenedimethylene terephthalate resin, and the heat resistance at a load of 1.82 MPa according to ASTM D648 is 225° C. or more. to be.

Description

Polymer resin composition for metal adhesion, metal-resin composites and articles using the same

The present invention relates to a polymer resin composition for metal bonding, a metal-resin composite and an article using the same. More specifically, it relates to a polymer resin composition for metal adhesion having excellent adhesion to metal, heat stability, chemical resistance, dimensional stability and discoloration resistance, and a metal-resin composite and articles using the same.

Recently, portable electrical and electronic products such as smart phones, mobile phones, and tablet PCs have been miniaturized, and accordingly, components included in portable electrical and electronic products are also required to be miniaturized.

In particular, electrical and electronic products tend to be made of metal for their outermost surfaces in order to increase safety from external shocks that may occur in daily life while miniaturizing.

However, electrical and electronic products are devices that include wireless communication, and when the exterior is made of only metal, the quality of wireless communication may be deteriorated due to the electromagnetic wave shielding effect. In order to overcome this, research on constructing a polymer resin having a relatively low electric wave shielding effect around wireless communication components is being actively conducted.

For example, in the case of a resin composition made of polyphenylene sulfide (PPS) as a main raw material, after bonding with metal, it has high chemical resistance to acidic substances used in an anodizing process of metal, mechanical strength and dimensional stability. Although it is used as an internal material for mobile phones due to its excellent quality, it has the disadvantage of easily discoloring depending on the user's environment and before and after the process, so there are restrictions on the use of parts exposed on the exterior of the product, and the adhesive strength with metal is relatively low. there was

In addition, a resin composition based on polybutylene terephthalate (PBT) has excellent adhesion to metal and relatively excellent discoloration resistance compared to polyphenylene sulfide (PPS), so it is used as an interior/exterior material for mobile phones. However, there is a limit to use in precision products due to large dimensional deformation due to self-shrinkage, and there is a limit in not securing sufficient discoloration resistance to be used as an external part material.

Therefore, for application to articles such as electrical and electronic products, development of new materials having excellent metal adhesion, chemical resistance, dimensional stability, and heat resistance is required.

The present invention is to provide a polymer resin composition for metal adhesion having excellent adhesion to metal, thermal stability, chemical resistance, dimensional stability and discoloration resistance.

In addition, the present invention is to provide a metal-resin composite and an article using the polymer resin composition.

In the present specification, polycyclohexylenedimethylene terephthalate resin; polyethylene terephthalate resin; and a filler, wherein the content of the polyethylene terephthalate resin is less than 200 parts by weight based on 100 parts by weight of the polycyclohexylenedimethylene terephthalate resin, and the metal has a heat resistance of 225° C. or higher at a load of 1.82 MPa according to ASTM D648. A polymer resin composition for adhesion is provided.

In the present specification, also, a metal substrate; and a metal-resin composite comprising the polymer resin composition for metal adhesion adhered to the surface of the metal substrate.

In the present specification, an article including the metal-resin composite is also provided.

Hereinafter, a polymer resin composition for metal adhesion according to a specific embodiment of the present invention, a metal-resin composite using the same, and an article will be described in more detail.

In the present specification, 'residue' refers to a specific part or unit derived from a specific compound that is included in the product of a chemical reaction when a specific compound participates in a chemical reaction. For example, each of the 'residue' derived from the dicarboxylic acid or the 'residue' derived from the diol is derived from a dicarboxylic acid component or a diol component in a polyester formed by an esterification reaction or a polycondensation reaction. means part.

According to one embodiment of the invention, polycyclohexylenedimethylene terephthalate resin; polyethylene terephthalate resin; and a filler, wherein the content of the polyethylene terephthalate resin is less than 200 parts by weight based on 100 parts by weight of the polycyclohexylenedimethylene terephthalate resin, and the heat resistance at a load of 1.82 MPa according to ASTM D648 is 225° C. or more. A polymer resin composition for metal bonding may be provided.

The inventors of the present invention confirmed through experiments that the use of the above-described specific polymer resin composition, as the content of the polycyclohexylenedimethylene terephthalate resin is increased compared to the polyethylene terephthalate resin, the heat resistance can be greatly improved, and the present invention completed.

In particular, by adjusting the content of the polyethylene terephthalate resin to less than 200 parts by weight based on 100 parts by weight of the polycyclohexylenedimethylene terephthalate resin, the heat resistance at a load of 1.82 MPa according to ASTM D648 is as high as 225 ° C. or higher In addition, as will be described later, it is possible to have high adhesion to metal within the metal-resin composite.

In addition, by adjusting the content of the polyethylene terephthalate resin to less than 200 parts by weight with respect to 100 parts by weight of the polycyclohexylenedimethylene terephthalate resin, the discoloration resistance and dimensional stability of the resin composition are improved, and adhesion to metal is improved. Through this, it is easy to apply to the process of manufacturing items such as electrical and electronic products.

In addition, as the polymer resin composition further includes a filler, excellent mechanical properties as well as heat resistance can be implemented.

Specifically, the polymer resin composition for metal adhesion of one embodiment may include a polycyclohexylenedimethylene terephthalate resin. The polycyclohexylenedimethylene terephthalate (hereinafter referred to as 'PCT') resin is obtained by esterification of a dicarboxylic acid and a diol compound, or transesterification of a dicarboxylic acid ester compound and a diol compound can be obtained by reaction.

30 to 1,000 ppm, 30 to 800 ppm, 30 to 600 ppm, 30 to 500 ppm, 30 to 400 ppm, or 50 to 350 ppm of germanium atoms may remain in the PCT resin. If the content of the germanium atoms remaining in the PCT resin is reduced below the above range, the polymerization reaction rate of the PCT resin is delayed, and as a result, the obtained polymer product may be easily yellowed. On the other hand, if the content of germanium atoms remaining in the PCT resin increases beyond the above range, the thermal decomposition rate of the resin increases, and as a result, a resin having a desired degree of polymerization cannot be obtained or a catalyst component remaining in the resin. As a result, the haze value may increase, which may adversely affect the transparency of the resin.

Specifically, the PCT resin in which a small amount of germanium atoms remain can be obtained by using a germanium compound as a catalyst for an esterification reaction or a transesterification reaction. A specific type of the germanium compound is not particularly limited, and as an example, germanium dioxide and the like may be mentioned.

Meanwhile, a small amount of titanium atoms (Ti) may remain in the PCT resin. Specifically, 20 ppm or less, or 0.1 to 20 ppm, or 5 to 15 ppm of titanium atoms may remain in the PCT resin. The PCT resin contains titanium atoms within the above range so that it can be polymerized without fear of side reactions, can prevent problems such as a decrease in molecular weight in an extrusion or injection molding process, and can have excellent yellowing resistance.

As described above, the PCT resin in which trace amounts of germanium and titanium atoms remain can be obtained by using a germanium compound and a titanium compound as catalysts for esterification or transesterification. Specific types of titanium compounds that can be used as the catalyst are not particularly limited, and examples include titanium oxide, tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, and tetra-isobutyl. titanate and butyl-isopropyl titanate; and the like.

The PCT resin may be obtained by an esterification reaction of a dicarboxylic acid and a diol compound or a transesterification reaction of a dicarboxylic acid ester compound and a diol compound in the presence of the above-described catalyst.

The dicarboxylic acid may include terephthalic acid (TPA), isophthalic acid (IPA), naphthalene 2,6-dicarboxylic acid (2,6-NDA), or a mixture thereof. have. For example, 90 parts by weight or more of the total dicarboxylic acid may be terephthalic acid, and 10 parts by weight or less of the total dicarboxylic acid may include other dicarboxylic acids other than terephthalic acid. In particular, when terephthalic acid is used as the dicarboxylic acid, a resin composition having excellent weather resistance and yellowing resistance can be provided.

The dicarboxylic acid ester compound is dimethyl terephthalate, dimethyl isophthalate (DMI), dimethyl naphthalene 2,6-dicarboxylate (dimethyl 2,6-naphthalenedicarboxylate; 2,6-NDC) or a mixture thereof. can include For example, 90 parts by weight or more of the total dicarboxylic acid ester compounds may be dimethyl terephthalate, and 10 parts by weight or less of the total dicarboxylic acid ester compounds may include other dicarboxylic acid ester compounds. In particular, when the dicarboxylic acid ester compound is dimethyl terephthalate, a resin composition having excellent weather resistance and yellowing resistance may be provided.

The diol compound may include at least one selected from the group consisting of 1.4-cyclohexanedimethanol, ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propanediol, and neopentyl glycol. For example, 90 parts by weight or more of the total diol compounds may be 1,4-cyclohexanedimethanol, and 10 parts by weight or less of the total diol compounds may include other diol compounds other than 1,4-cyclohexanedimethanol. have. In particular, when the diol compound is 1,4-cyclohexanedimethanol, a resin composition having excellent weather resistance and yellowing resistance can be provided.

Meanwhile, a PCT resin may be prepared by further adding a phosphorus-based stabilizer at the beginning of the esterification or transesterification reaction. As a result, side reactions that may occur during esterification or transesterification at high temperatures can be effectively suppressed.

Phosphorus-based stabilizers that can be used in the above include phosphoric acid such as phosphoric acid or phosphorous acid and triethyl phosphate, trimethyl phosphate, triphenyl phosphate or triethyl phosphate Phosphoric acid ester-based compounds such as triethyl phosphonoacetate may be used.

In addition to the above compounds, the PCT resin may be polymerized using other additives commonly used in the art to which the present invention pertains. In addition, the PCT resin may be polymerized using these components by a method commonly employed in the art to which the present invention pertains. For example, the PCT resin may be prepared by an esterification reaction of a dicarboxylic acid and a diol compound or a transesterification reaction of a dicarboxylic acid ester compound and a diol compound in the presence of the above-described catalyst; And it can be prepared through the step of polycondensation of the reaction product obtained by the above reaction. In addition, forming the PCT resin into pellets by shaping the polycondensation reaction product, if necessary; and/or crystallizing the polycondensation reaction product or pellets to perform solid phase polymerization.

The PCT resin is a crystalline polyester, and as it has a high melting point (Tm) and a fast crystallization rate, it is a connector in the electrical and electronic fields and automobile fields where high heat-resistance is required. It was used for fire and heat-resistant parts.

The content of the polycyclohexylenedimethylene terephthalate resin may be 10 wt% to 70 wt%, or 15 wt% to 60 wt%, or 30 wt% to 70 wt% based on the polymer resin composition for metal bonding. .

When the content of the polycyclohexylenedimethylene terephthalate resin is excessively increased to more than 70% by weight with respect to the polymer resin composition for metal adhesion, it is difficult for the polymer resin composition for metal adhesion to realize sufficient adhesive strength to a metal substrate. can

In addition, when the content of the polycyclohexylenedimethylene terephthalate resin is excessively reduced to less than 10% by weight with respect to the polymer resin composition for metal adhesion, at a load of 1.82 MPa according to ASTM D648 of the polymer resin composition for metal adhesion It may be difficult to realize sufficient heat resistance, such as the heat resistance of the product decreases to less than 225℃, and the mold shrinkage rate increases, making it difficult to control numerical values, especially for precision products. can fall

In addition, the polymer resin composition for metal adhesion of one embodiment may include a polyethylene terephthalate resin. As known in the art, the polyethylene terephthalate (hereinafter referred to as 'PET') resin is usually polymerized from dicarboxylic acid and diol.

Examples of dicarboxylic acids and their derivatives used during polymerization of the PET resin include terephthalic acid (TPA), isophthalic acid (IPA), and naphthalene 2,6-dicarboxylic acid (2,6-naphthalenedicarboxylic acid; 2,6 -NDA), dimethyl terephthalic acid (DMT), dimethylisophthalate (DMI), dimethyl 2,6-naphthalenedicarboxylate (2,6-NDC), DMCD (1,4- Dimethyl cyclohexanedicarboxylate) and the like, but are not limited thereto.

In addition, diols used in the polymerization of the PET resin include ethylene glycol (EG), diethylene glycol (DEG), propylene glycol (PG), neopentyl glycol (NPG), and cyclohexane. Dimethanol (cyclohexanedimethanol; CHDM), but is not particularly limited thereto, and all diols known in the art may be used when preparing a PET resin, but ethylene glycol (EG) may be preferable.

In the PET resin, dicarboxylic acid and diol, which are raw materials, are introduced into a high-temperature and high-pressure reactor, and a reaction catalyst, a stabilizer, and a colorant are added to the oligomer produced thereto, as necessary, and reacted in a high-temperature vacuum state for polymerization. And, it is possible to polymerize the PET resin as known in the art without being particularly limited.

The intrinsic viscosity of the PET resin may be 0.50 to 1.2 dl/g, or 0.70 to 1.0 dl/g. When the intrinsic viscosity of the PET resin is less than 0.50 dl / g, mechanical properties are expected to deteriorate due to the low molecular weight, and when the intrinsic viscosity of the PET resin exceeds 1.2 dl / g, high pressure and temperature are required during blending and molding. This may result in a decrease in efficiency.

The content of the polyethylene terephthalate resin may be 5 to 60% by weight, or 10 to 50% by weight, or 5 to 45% by weight based on the polymer resin composition for metal adhesion.

If the content of the polyethylene terephthalate resin is excessively reduced to less than 5% by weight with respect to the polymer resin composition for metal adhesion, it may be difficult for the polymer resin composition for metal adhesion to realize sufficient adhesive strength to a metal substrate.

In addition, when the content of the polyethylene terephthalate resin is excessively increased to more than 60% by weight with respect to the polymer resin composition for metal adhesion, the heat resistance at a load of 1.82 MPa according to ASTM D648 of the polymer resin composition for metal adhesion is 225 It may be difficult to implement sufficient heat resistance, such as decreasing below ° C, and the mold shrinkage rate increases, making it difficult to control numerical values, especially for precision products, and as the mold shrinkage rate increases, numerical stability in the subsequent process may deteriorate.

Specifically, in the polymer resin composition for metal bonding, the content of the polyethylene terephthalate resin relative to 100 parts by weight of the polycyclohexylenedimethylene terephthalate resin is less than 200 parts by weight, or 0.1 parts by weight to 150 parts by weight, or 10 parts by weight. It may be 140 parts by weight to 140 parts by weight. That is, the polymer resin composition for metal bonding is a blend of PCT resin and PET resin, and by adjusting the mixing ratio, it is possible to implement heat resistance and metal adhesion applicable to articles such as electrical and electronic products.

When the content of the polyethylene terephthalate resin with respect to 100 parts by weight of the polycyclohexylenedimethylene terephthalate resin is excessively increased to more than 200 parts by weight, the heat resistance of the polymer resin composition is reduced at a load of 1.82 MPa according to ASTM D648. As the temperature decreases below 225 ° C, thermal stability may decrease when applied to articles such as electrical and electronic products.

The ratio of the intrinsic viscosity of the polycyclohexylenedimethylene terephthalate resin and the intrinsic viscosity of the polyethylene terephthalate resin may be 10:1 to 1:10, or 5:1 to 1:5. More specifically, the intrinsic viscosity of the polycyclohexylenedimethylene terephthalate resin may be 0.4 to 1.0 dl/g, or 0.5 to 0.9 dl/g, and the intrinsic viscosity of the polyethylene terephthalate resin may be 0.4 to 1.5 dl/g. g, or 0.5 to 1.3 dl/g.

In addition, the polymer resin composition for metal adhesion of one embodiment may include a filler. Accordingly, mechanical properties, heat resistance and discoloration resistance of the polymer resin composition for metal bonding may be further improved.

As the filler, organic fillers or inorganic fillers commonly used in the art to which the present invention pertains may be used. Examples of the filler are not particularly limited, but, for example, glass fiber, carbon fiber, boron fiber, glass beads, glass flakes, talc, wollastonite, calcium titanate whisker, aluminum borate whisker (aluminum boric acid whisker), zinc oxide whisker, and calcium whisker.

For example, a needle-shaped filler may be used as a filler in order to provide a molded product having excellent surface smoothness. In particular, in order to provide a white molded article with excellent surface smoothness, the filler is glass fiber, wollastonite, calcium titanate whisker, aluminum boric acid whisker, or a mixture thereof can be used. Among these, it is possible to improve moldability of the composition by using glass fibers, improve mechanical properties such as tensile strength, flexural strength, and flexural modulus, and heat resistance such as heat deflection temperature of molded products.

When glass fibers are used as the filler, glass fibers having an average length of 0.1 to 20 mm or 0.3 to 10 mm may be used. In addition, by using glass fibers having an aspect ratio (L (average length of fiber) / D (average outer diameter of fiber)]) of 10 to 2000 or 30 to 1000, the appearance quality such as surface characteristics and color characteristics is excellent And, it is possible to provide a resin composition with improved mechanical strength.

The content of the filler may be 10 wt% to 60 wt%, or 20 wt% to 50 wt%, or 25 wt% to 45 wt%, based on the polymer resin composition for metal adhesion. Accordingly, a resin composition having excellent mechanical strength and heat resistance can be provided.

If the content of the filler is excessively reduced to less than 10% by weight with respect to the polymer resin composition for metal adhesion, the heat resistance of the polymer resin composition for metal adhesion is reduced, and the content of the filler in the polymer resin composition for metal adhesion If the amount is excessively increased to more than 60% by weight, there is a problem in that the adhesive strength of the polymer resin composition for metal adhesion to metal is reduced.

In addition, the polymer resin composition for metal adhesion of one embodiment may have a heat resistance of 225° C. or more, or 225° C. to 300° C. under a load of 1.82 MPa according to ASTM D648. When the heat resistance of the polymer resin composition for metal bonding at a load of 1.82 MPa according to ASTM D648 is reduced to less than 225° C., thermal stability may be reduced when the polymer resin composition is applied to articles such as electrical and electronic products.

The polymer resin composition for metal adhesion may exist in an adhesive, adhered, or bonded state to the surface of the metal substrate. More specifically, an example of a method of attaching, adhering, or bonding the polymer resin composition for metal adhesion to the surface of the metal substrate is not greatly limited, but, for example, a method of injecting or extruding the polymer resin composition onto the metal surface can be used.

At this time, in order to further strengthen the adhesion between the metal and the resin composition, a pretreatment process of the metal surface may be additionally performed. Specifically, for example, micro to nano size pores are formed on the metal surface through an etching process (NMT treatment method), or an anodized film is formed on the metal surface, followed by anodic electrolysis. A method of forming a triazinethiol derivative [1,3,5-triazine 2,4-dithiol-6-sodium thiolate (TTN)] on the surface of the anodized film (TRI treatment method), etc. have.

The polymer resin composition for metal adhesion may have an adhesive force of 20 MPa or more, which is bonded to the metal and the metal surface according to the following equation.

[mathematical expression]

Adhesion (MPa) = (Tensile strength measured at Cross Head speed of 5 mm/min according to ASTM D638) / (Contact area of metal and polymer resin composition for metal adhesion)

More specifically, in the case of the metal-resin composite prepared by the NMT treatment method as described above, the adhesive strength between the metal and the polymer resin composition for metal adhesion is 20 MPa to 30 MPa, and prepared by the TRI treatment method as described above In the case of the metal-resin composite, the adhesive force between the metal and the polymer resin composition for metal adhesion may be 25 MPa to 40 MPa.

As such, in the case of the NMT treatment method, the adhesive force of the polymer resin composition for metal adhesion to the metal substrate is 20 MPa to 30 MPa, and in the case of the TRI treatment method, the polymer resin composition for metal adhesion to the metal substrate Adhesion may be 25 MPa to 40 MPa.

In addition, the polymer resin composition for metal adhesion of one embodiment may further include a highly crystalline polycyclohexylenedimethylene terephthalate resin having a crystal melting point of 285° C. or higher. The highly crystalline polycyclohexylenedimethylene terephthalate resin is obtained by esterification of 1,4-cyclohexanedimethanol having a high ratio of trans isomer with terephthalic acid, or 1,4-cyclohexanedi having a high ratio of trans isomer. It can be produced by transesterifying methanol with an ester compound of terephthalic acid.

Commonly used 1,4-cyclohexanedimethanol contains 70 mol% of the trans isomer and the remainder of the cis isomer. When 1,4-cyclohexanedimethanol is isomerized in the presence of a catalyst, the content of cis and trans isomers of 1,4-cyclohexanedimethanol can be changed.

Specifically, the highly crystalline polycyclohexylenedimethylene terephthalate resin may be polymerized using 1,4-cyclohexanedimethanol having a trans isomer ratio of 70 mol% or more, 73 mol% or more, or 75 mol% or more. It has a high melting point and heat resistance and can exhibit high crystallinity.

In addition, the polymer resin composition for metal adhesion of one embodiment may further include an epoxy resin or a phenolic resin. Specific examples of the epoxy resin or phenol-based resin are not particularly limited, and various epoxy resins or phenol-based resins widely used in the resin composition field may be used without limitation.

In addition, the polymer resin composition for metal adhesion of one embodiment is an impact modifier, a nucleating agent, an antioxidant, a lubricant, a release agent, a colorant, a compatibilizer, a heat stabilizer, a UV stabilizer, a hydrolysis stabilizer, a viscosity enhancer, a fluorescent whitening agent, a physical property reinforcing agent, It may further include one or more additives selected from the group consisting of a main chain extender, a pigment, a dye, and an antistatic agent. The specific type of the additive is not particularly limited, and various additives widely used in the conventional resin composition field can be applied without limitation.

In particular, an example of the impact modifier may be an ethylene-based copolymer containing a (meth)acrylate repeating unit in which one or more crosslinking functional groups are substituted. The ethylenic copolymer containing the (meth)acrylate repeating unit substituted with one or more crosslinking functional groups may be prepared by copolymerizing ethylene and (meth)acrylate with one or more crosslinking functional groups as monomers.

The (meth)acrylate repeating unit in which one or more crosslinking functional groups are substituted refers to a basic repeating unit included in a homopolymer of a (meth)acrylate compound in which one or more crosslinking functional groups are substituted, and the (meth)acrylate is acrylic It was used in the meaning including rate or methacrylate.

The (meth)acrylate repeating unit in which the at least one crosslinking functional group is substituted may increase compatibility by undergoing a crosslinking reaction with a compound, polymer or resin in the composition through the crosslinking functional group. Specific examples of the one or more crosslinking functional groups are not particularly limited, and for example, glycidyl or maleic anhydride may be used.

Meanwhile, the ethylene-based copolymer may further include (meth)acrylate or vinyl acetate repeating units to increase polarity. That is, the ethylene-based copolymer may include a (meth)acrylate in which ethylene and one or more crosslinking functional groups are substituted, and a terpolymer prepared by copolymerizing (meth)acrylate or vinyl acetate repeating units as monomers. can

The (meth)acrylate repeating unit or vinyl acetate repeating unit refers to a basic repeating unit included in a homopolymer of a (meth)acrylate compound or a vinyl acetate compound, respectively.

The content of the (meth)acrylate repeating unit or vinyl acetate repeating unit may be 2% to 50% by weight based on the weight of the ethylene-based copolymer.

The impact modifier is used to improve the mechanical strength and adhesive strength of the polymer resin composition, and may be included in an amount of 0.1% to 10% by weight relative to the polymer resin composition for metal bonding. When the content of the impact modifier is excessively increased, processability may be lowered due to excessively high viscosity during processing, and adhesion between the polymeric resin composition and the metal surface may be reduced due to insufficient contact.

The pigments include titanium oxide, zinc oxide, zinc sulfide, zinc sulfate, barium sulfate, lithopone (BaSO ₄ ZnS), white lead ( _{2PbCO 3} Pb(OH) ₂ ), calcium carbonate, alumina, boron nitride or a mixture thereof, and the like can be exemplified. Examples of the oxidation stabilizer include ADEKA's AO-60 as a hindered phenolic oxidation stabilizer.

The lubricant may be used for stably dispersing fillers or pigments in the resin composition and for easy release of the resin composition. Such lubricants include acid amides such as erucamide, oleamide, and stearamide; Acid Ester-type Montan Wax, Stearyl Stearate, Distearyl Pthalate; fatty acids (Lauric), Myristic (Myristic), Palmitic (Palmitic), Stearic (Stearic); Polyethylene, polypropylene, and paraffin of hydrocarbon waxes; Calcium, Zinc, Magnesium, Lead, Aluminum, Sodium, Tin, Barium, Cobalt (Metallic Soaps) Cobalt) may be used, and more specific examples include N,N'-ethylene bis (stearamide) and the like.

The nucleating agent may act as a crystallization nucleus during molding of the resin composition to improve the crystallization rate of the resin composition. As such a nucleating agent, a sodium salt of montanic acid (Licomont NaV101 from Clariant) or a calcium salt (Licomont CaV102 from Clariant) may be used.

The content of the additive is not particularly limited, but may be included, for example, in an amount of 0.1% to 10% by weight relative to the polymer resin composition for metal adhesion. If the content of the additive is excessively increased to more than 10% by weight in the polymer resin composition for metal adhesion, heat resistance and adhesion to metal of the polymer resin composition may decrease.

In addition, the polymer resin composition for metal adhesion of the embodiment is nylon, polypropylene terephthalate (PTT), polybutylene terephthalate (PBT), glycol modified polyethylene terephthalate (Polyethylene terephthalate glycol modified, PETG ), glycol modified polycyclohexylenedimethylene terephthalate glycol modified, polyethylene naphthalate (PEN), polyethylene isosorbide terephthalate (PEIT), polyethylene isosorbide cyclohexylene Polyethylene Isosorbide Cyclohexylenedimethylene Terephthalate (PEICT), Poly 2,2,4,4-tetramethylcyclobutylene terephthalate (Poly 2,2,4,4,tetramethylcyclobutylene terephthalate) and Poly Phenylene Sulfide sulfide, PPS) may further include one or more resins selected from the group consisting of.

The content of the resin is not particularly limited, but may be included in, for example, 0.1% by weight to 10% by weight with respect to the polymer resin composition for metal bonding. If the content of the resin is excessively increased to more than 10% by weight in the polymer resin composition for metal adhesion, heat resistance and adhesion to metal of the polymer resin composition may decrease.

Meanwhile, the polymer resin composition for metal adhesion may have a reflectance and discoloration resistance of 50% or more, or 50% to 90% at a wavelength of 450 nm represented by the following equation.

[mathematical expression]

Reflectance at a wavelength of 450 nm Discoloration resistance (%) = (Reflectance of the polymer resin composition for metal adhesion measured at a wavelength of 450 nm after heat treatment at 200 ° C for 24 hours) / (Polymer resin composition for metal adhesion measured at an initial wavelength of 450 nm reflectance) X 100

A wavelength of 450 nm is a blue-based wavelength, and a decrease in reflectance at a wavelength of 450 nm means that a yellow value, which is the opposite color, increases, that is, a color-b value increases. (Hunter lab color system, based on Hunter lab color space) Therefore, the decrease in the reflectance of the 450 nm wavelength and the increase in the Color-b value means that a lot of yellowing has occurred. Therefore, when the reflectance and discoloration resistance of the polymer resin composition for metal bonding is reduced to less than 50% at a wavelength of 450 nm, represented by the following equation, the yellowing phenomenon proceeds in the resin composition and the discoloration resistance is reduced. can

On the other hand, according to another embodiment of the invention, a metal substrate; And a metal-resin composite including the polymer resin composition for metal adhesion adhered to the surface of the metal substrate may be provided.

The inventors of the present invention confirmed through experiments that the metal-resin composite can be easily formed through the adhesive strength of the polymer resin composition without using a separate adhesive, by using the specific metal-resin composite described above, and discovered the present invention. completed.

Information regarding the polymer resin composition for metal bonding includes the above-described information in the embodiment.

The metal-resin composite may include a metal substrate. Examples of the metal are not particularly limited, and various metal materials widely used in articles such as electrical and electronic products may be used without limitation.

The metal-resin composite may include the polymer resin composition for metal adhesion formed on the surface of the metal substrate. Specifically, in the metal-resin composite, the polymer resin composition for metal adhesion may exist in an adhesive, adhered, or bonded state to the surface of the metal substrate.

More specifically, in the metal-resin composite, an example of a method of attaching, adhering, or bonding the polymer resin composition for metal adhesion to the surface of the metal substrate is not particularly limited, but, for example, the polymer resin composition is attached to the metal surface. A method of injecting or extruding the composition may be used.

At this time, in order to further strengthen the adhesive force between the metal and the resin, a pretreatment process of the metal surface may be additionally performed. Specifically, for example, micro to nano size pores are formed on the metal surface through an etching process (NMT treatment method), or an anodized film is formed on the metal surface, followed by anodic electrolysis. A method of forming a triazinethiol derivative [1,3,5-triazine 2,4-dithiol-6-sodium thiolate (TTN)] on the surface of the anodized film (TRI treatment method), etc. have.

The metal-resin composite may have an adhesive strength of 20 MPa or more of the polymer resin composition for metal adhesion bonded to the metal and the metal surface according to the following equation.

[mathematical expression]

Adhesion (MPa) = (Tensile strength measured at Cross Head speed of 5 mm/min according to ASTM D638) / (Contact area of metal and polymer resin composition for metal adhesion)

More specifically, in the case of the metal-resin composite prepared by the NMT treatment method as described above, the adhesive strength between the metal and the polymer resin composition for metal adhesion is 20 MPa to 30 MPa, and prepared by the TRI treatment method as described above In the case of the metal-resin composite, the adhesive force between the metal and the polymer resin composition for metal adhesion may be 25 MPa to 40 MPa.

Meanwhile, according to another embodiment of the present invention, an article including the metal-resin composite of the other embodiment may be provided. Information regarding the metal-resin composite includes all of the above-described information in the other embodiments.

The use of the above article is not significantly limited, and it can be applied without limitation to various product groups in which metal materials, parts, and parts are used. For example, various information processing devices (specific examples are computers, mobile phones, smart phones, etc.), electrical and electronic products (specific examples include video playback devices, sound generators, etc.), household appliances (specific examples include refrigerators, washing machines, automobiles, etc.), and more preferably smart phones and mobile phones. , portable electrical and electronic products such as tablet PCs and the parts included therein, or parts for wireless communication devices.

Examples of the specific shape, weight, size, color, etc. of the product and its internal structure are not particularly limited, and the external and internal structures of various previously known products and parts and parts included therein can be applied without limitation. have.

According to the present invention, a polymer resin composition for metal adhesion having excellent adhesion to metal, heat stability, chemical resistance, dimensional stability, and discoloration resistance, and a metal-resin composite and an article using the same can be provided.

The invention is explained in more detail in the following examples. However, the following examples are merely illustrative of the present invention, and the contents of the present invention are not limited by the following examples.

<Examples 1 to 7: Preparation of polymer resin composition>

Pellets were prepared by melting and kneading a polymer resin composition having the composition shown in Table 1 below using a twin screw kneading extruder (Φ: 40 mm, L/D = 40) heated to about 300 ° C.

Specifically, the characteristics of the components listed in Tables 1 and 2 below are as follows.

* PCT resin: It is a resin polymerized through esterification and polycondensation of cyclohexane dimethanol (CHDM) and terephthalic acid (TPA), and has an intrinsic viscosity (IV) of about 0.65 dl/ is g.

* PET resin: It is a resin polymerized through esterification and polycondensation of ethylene glycol (EG, Ethylene Glycol) and terephthalic acid (TPA), and has an intrinsic viscosity (IV). It is about 0.80 dl/g.

* Glass fiber: OCV910 (manufactured by OCV), diameter 10 ㎛, average length 3 mm, aspect ratio (L/D) 300

* Highly crystalline PCT resin: A PCT resin with an intrinsic viscosity of 0.65 dL/g was used by polycondensation of 1,4-cyclohexane dimethanol (CHDM) and terephthalic acid (TPA) containing 75 mol% of the trans isomer.

* Impact modifier: Ethylene-methylacrylate-glycidylmethacrylate (GMA) terpolymer (Lotader AX8900, manufactured by Arkema) Melt Flow Index is 6 (g/10min) at 190 ℃ / 2.16kg condition , and the melting point is 65 ° C.

* Epoxy resin: YP-50 (manufactured by Kukdo Chemical)

<Comparative Examples 1 to 4: Preparation of Polymer Resin Composition>

Pellets were prepared in the same manner as in the above example, except that the polymer resin composition having the composition shown in Table 2 was used.

<Experimental Example: Measurement of Physical Properties of Polymer Resin Compositions Obtained in Examples and Comparative Examples>

Physical properties of the polymer resin compositions obtained in Examples and Comparative Examples were measured by the following methods, and the results are shown in Tables 1 and 2.

Experimental Example 1: Adhesion

(1) When NMT (Nano molding Technology) treatment

After creating micro to nano size pores on the metal surface through an etching process, insert injection of the polymer resin composition prepared in Examples 1 to 7 and Comparative Examples 1 to 4 was performed. After molding, a polymer resin composition was impregnated into the pores to prepare a resin-metal bonded body in which the metal and the polymer resin composition were bonded.

With respect to the resin-metal bonded body, a tensile test was performed at a cross head speed of 5 mm/min using a universal testing machine (UTM) under normal temperature and pressure conditions in accordance with ASTM D638. At this time, the breaking load was measured, and the adhesive force was measured by dividing the measured load by the area where the metal and plastic were bonded.

(2) When treating TRI

After forming an anodic oxide film on the metal surface through anodic oxidation of the pretreated metal, it contains a triazinethiol derivative [1,3,5-triazine 2,4-dithiol-6-sodium thiolate (TTN)]. Anode electrolysis was performed with one electrolyte solution to form the triazinethiol derivative inside and on the anodized film.

Thereafter, the polymer resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 4 were subjected to insert injection molding to obtain metal and polymer resin through an anodized film having a triazinethiol derivative formed on the metal surface. A resin-metal bonded body to which the composition was bonded was prepared.

With respect to the resin-metal bonded body, a tensile test was performed at a cross head speed of 5 mm/min using a universal testing machine (UTM) under normal temperature and normal pressure conditions in accordance with ASTM D638. At this time, the breaking load was measured, and the adhesive force was measured by dividing the measured load by the area where the metal and plastic were bonded.

Experimental Example 2: Heat resistance

With respect to the polymer resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 4, in accordance with ASTM D648, specimens for measurement were made and tested at a high load of 1.82 MPa using a heat resistance tester (HDT Tester, Toyoseiki). Heat resistance was measured.

Experimental Example 3: Discoloration resistance

For specimens obtained by injection molding in the form of a flat plate at about 290 ° C. for the polymer resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 4, a UV-vis-NIR spectrometer (Konica Minolta Spectrophotometer "CM-3600d ") using a D65 light source to measure the whiteness level "L" value (initial Color-L value) and the reflectance at a wavelength of 450 nm (initial reflectance) based on the Hunter Lab Color System.

After heat-treating the specimen at a temperature of 200 ° C. for 24 hours, the whiteness level “L” value (Color-L value after heat treatment at 200 ° C. for 24 hours) and reflectance at a wavelength of 450 nm (24 hours Reflectance after heat treatment at 200° C.) was measured.

In addition, whiteness and discoloration resistance were obtained through Equation 1 below, and reflectance and discoloration resistance were obtained through Equation 2 below.

[Equation 1]

Whiteness and discoloration resistance (%) = (Color-L value after heat treatment at 200℃ for 24 hours) / (Initial Color-L value) X 100

[Equation 2]

Reflectance discoloration resistance (%) = (Reflectance at 450nm wavelength after heat treatment at 200°C for 24 hours) / (Reflectance at initial 450nm wavelength) X 100

Experimental Example 4: Mold Shrinkage Rate

With respect to the polymer resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 4, 100 X 100 mm flat test pieces for mold shrinkage evaluation were injection-manufactured in accordance with ISO 294-4. The fabricated test piece was measured using a three-dimensional measuring device (Flash300 from Optical Gaging Products) capable of precise measurement up to 0.001 mm, and the precise dimensions of the test piece were measured, and the mold shrinkage rate was measured through Equation 3 below.

[Equation 3]

Mold shrinkage rate (%) = (length of mold - length of fabricated specimen) / length of mold * 100

Experimental Example 5: Dimensional stability

With respect to the polymer resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 4, 100 X 100 mm flat test pieces for mold shrinkage evaluation were injection-manufactured in accordance with ISO 294-4. The manufactured test piece was measured using a three-dimensional measuring device (Flash300 from Optical Gaging Products) capable of precise measurement up to 0.001 mm, and the precise dimensions of the test piece were measured, and the first mold shrinkage was measured through Equation 3 below.

[Equation 3]

Mold shrinkage rate (%) = (length of mold - length of fabricated specimen) / length of mold * 100

Thereafter, the test piece was left for 12 hours at a temperature of 150 ° C. in a convection oven, and then the second mold shrinkage was measured through Equation 3, and dimensional stability was measured through Equation 4 below.

[Equation 4]

Dimensional stability (%) = 2nd mold shrinkage - 1st mold shrinkage

Composition of the polymer resin composition of Examples and results of experimental examples division Example 1 Example 2 Example 3 Example 4 Example
5 Example 6 Example 7 PCT resin
(Unit: % by weight) 60 50 40 30 35 35 37 Highly crystalline PCT resin
(Unit: % by weight) - - - - - 5 - PBT resin
(Unit: % by weight) - - - - - - - PET resin
(Unit: % by weight) 10 20 30 40 30 30 30 impact modifier
(Unit: % by weight) - - - - 5 - - epoxy resin
(Unit: % by weight) - - - - - - 3 fiberglass
(Unit: % by weight) 30 30 30 30 30 30 30 adhesion
(Unit: MPa) NMT treatment 21 27 28 30 31 28 30 TRI treatment 28 30 31 32 35 30 32 heat resistance
(Unit: ℃) @1.82MPa 247 237 232 235 232 229 232 discoloration resistance Whiteness (%) 93 92 94 90 81 91 88 reflectivity(%) 71 71 78 70 52 72 62 Mold shrinkage rate MD(%) 0.22 0.21 0.20 0.19 0.19 0.20 0.20 TD (%) 0.86 0.85 0.83 0.80 0.70 0.83 0.83 Dimensional stability MD(%) 0.001 0.002 0.002 0.002 0.002 0.002 0.002 TD (%) 0.005 0.006 0.008 0.009 0.006 0.008 0.008

Composition of the polymer resin composition of the comparative example and results of the experimental example division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 PCT resin
(Unit: % by weight) - - - 5 Highly crystalline PCT resin
(Unit: % by weight) - - - - PBT resin
(Unit: % by weight) 70 - 35 - PET resin
(Unit: % by weight) - 70 35 65 impact modifier
(Unit: % by weight) - - - - epoxy resin
(Unit: % by weight) - - - - fiberglass
(Unit: % by weight) 30 30 30 30 adhesion
(Unit: MPa) NMT treatment 13 34 30 33 TRI treatment 21 40 36 38 heat resistance
(Unit: ℃) @1.82MPa 208 224 195 223 discoloration resistance Whiteness (%) 65 75 70 76 reflectivity(%) 40 42 41 43 Mold shrinkage rate MD(%) 0.2 0.2 0.4 0.2 TD (%) 1.2 0.8 0.8 0.8 Dimensional stability MD(%) 0.002 0.003 0.005 0.003 TD (%) 0.013 0.013 0.011 0.013

As shown in Table 1, in the case of Comparative Examples 1 to 3 using a PBT resin, a PET resin, or a mixture thereof and not including a PCT resin at all, the heat resistance was lower than 225 ° C., and the heat resistance was reduced. In addition, it was confirmed that the whiteness decreased to 65% to 70% after heat treatment compared to the initial stage, and the reflectance with respect to a wavelength of 450 nm also decreased to less than 50%, resulting in a yellowing phenomenon and poor discoloration resistance. In addition, the dimensional change width in the TD direction after heat treatment was higher than 0.01% compared to the initial stage, and it was confirmed that the dimensional stability was also poor.

On the other hand, even if PCT resin and PET resin are mixed as in Example, even in the case of Comparative Example 4 in which the content of PCT resin is as low as less than 30% by weight and the content of PET resin is increased to more than 50% by weight, the heat resistance is 225 ° C. It was confirmed that the color resistance was poor, such that the whiteness decreased to less than 80% after heat treatment compared to the initial stage, and the reflectance with respect to a wavelength of 450 nm also decreased to less than 50%. In addition, the dimensional change width in the TD direction after heat treatment was as high as 0.013% compared to the initial stage, indicating poor dimensional stability.

Therefore, it was confirmed through experiments that the polymer resin composition for metal adhesion or a product using the same of Example can implement excellent heat resistance, discoloration resistance, and dimensional stability while having an appropriate level of metal adhesion.

Claims (18)

polycyclohexylenedimethylene terephthalate resin;
polyethylene terephthalate resin; and
contains a filler;
The content of the polyethylene terephthalate resin relative to 100 parts by weight of the polycyclohexylenedimethylene terephthalate resin is less than 200 parts by weight,
The heat resistance at a load of 1.82 MPa according to ASTM D648 is 225 ° C or higher,
The content of the polycyclohexylenedimethylene terephthalate resin is 30% to 60% by weight based on the polymer resin composition for metal bonding,
The content of the polyethylene terephthalate resin is 10% to 40% by weight based on the polymer resin composition for metal bonding,
The content of the filler is 25% to 45% by weight based on the polymer resin composition for metal adhesion,
The fillers are glass fibers, carbon fibers, boron fibers, glass beads, glass flakes, talc, wollastonite, calcium titanate whiskers, aluminum boric acid whiskers, zinc oxide whiskers ( zinc oxide whisker) and at least one selected from the group consisting of calcium whisker,
A polymer resin composition for metal adhesion having an adhesive force of 20 MPa or more of the polymer resin composition for metal adhesion bonded to the metal and the metal surface according to the following equation:
[mathematical expression]
Adhesion (MPa) = (tensile strength measured at a Cross Head speed of 5 mm/min according to ASTM D638) / (contact area between metal and polymer resin composition for metal adhesion).
According to claim 1,
A polymer resin composition for metal adhesion having a reflectance and discoloration resistance of 50% or more at a wavelength of 450 nm, represented by the following formula:
[mathematical expression]
Reflectance at a wavelength of 450 nm Discoloration resistance (%) = (Reflectance of the polymer resin composition for metal adhesion measured at a wavelength of 450 nm after heat treatment at 200 ° C for 24 hours) / (Polymer resin composition for metal adhesion measured at an initial wavelength of 450 nm reflectance) X 100.
According to claim 1,
The content of the polyethylene terephthalate resin relative to 100 parts by weight of the polycyclohexylenedimethylene terephthalate resin is 0.1 parts by weight to 150 parts by weight, a polymer resin composition for metal bonding.
According to claim 1,
The ratio of the intrinsic viscosity of the polycyclohexylenedimethylene terephthalate resin and the intrinsic viscosity of the polyethylene terephthalate resin is 10: 1 to 1: 10, the polymer resin composition for metal bonding.
delete delete delete delete According to claim 1,
The filler comprises a glass fiber having an aspect ratio of 10 to 2000 of the cross section, a polymer resin composition for metal bonding.
According to claim 1,
A polymer resin composition for metal bonding, further comprising a highly crystalline polycyclohexylenedimethylene terephthalate resin having a melt crystallization temperature of 285° C. or higher.
According to claim 1,
A polymer resin composition for metal adhesion, further comprising an epoxy resin or a phenolic resin.
According to claim 1,
Group consisting of impact modifier, nucleating agent, antioxidant, lubricant, release agent, colorant, compatibilizer, heat stabilizer, UV stabilizer, hydrolysis stabilizer, viscosity enhancer, optical whitening agent, physical property enhancer, main chain extender, pigment, dye and antistatic agent Further comprising at least one additive selected from, a polymeric resin composition for metal adhesion.
According to claim 12,
The impact modifier comprises an ethylene-based copolymer containing a (meth)acrylate repeating unit in which at least one crosslinking functional group is substituted, a polymer resin composition for metal adhesion.
According to claim 1,
Nylon, Polypropylene terephthalate (PTT), Polybutylene terephthalate (PBT), Polyethylene terephthalate glycol modified (PETG), Glycol modified polycyclohexylenedimethylene terephthalate ( Polycyclohexylenedimethylene terephthalate glycol modified), Polyethylene naphthalate (PEN), Polyethylene Isosorbide Terephthalate (PEIT), Polyethylene Isosorbide Cyclohexylenedimethylene Terephthalate (PEICT), At least one resin selected from the group consisting of poly 2,2,4,4-tetramethylcyclobutylene terephthalate (Poly 2,2,4,4,tetramethylcyclobutylene terephthalate) and polyphenylene sulfide (PPS) Further comprising a polymeric resin composition for metal adhesion.
metal base; and the polymer resin composition for metal adhesion of claim 1 formed on the surface of the metal substrate.
According to claim 15,
A metal-resin composite having an adhesive force of 20 MPa or more of the metal substrate and the polymer resin composition for metal adhesion according to the following equation:
[mathematical expression]
Adhesion (MPa) = (tensile strength measured at a Cross Head speed of 5 mm/min according to ASTM D638) / (contact area between metal and polymer resin composition for metal adhesion).
An electrical and electronic product comprising the metal-resin composite of claim 15.
A product for a wireless communication device comprising the metal-resin composite of claim 15.