TWI731011B - 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 metals, thermal stability, chemical resistance, dimensional stability, and discoloration resistance, and a metal-resin composite and a product using the same.

Description

Polymer resin composition for metal adhesion, and metal resin using it Compounds and electronic products

This application claims the priority of the South Korean application No. 10-2016-0002851 filed at the South Korea Wisdom Bureau on January 8, 2016, the entire content of which is incorporated herein by reference.

The present invention relates to a polymer resin composition for metal adhesion, a metal resin composite and a product using it, and particularly refers to a polymer resin composition with excellent adhesion to metal, thermal stability, and chemical Polymer resin compositions for metal adhesion with chemical resistance, dimensional stability and discoloration resistance, and metal resin composites and products using them.

Miniaturization of portable electrical and electronic products such as smart phones, mobile phones and tablet PCs has been a trend in recent years. Therefore, it is included in portable electrical and electronic products The components need to be reduced.

In particular, while electrical and electronic products tend to shrink, in order to avoid external shocks that may occur in daily life and improve safety, the outermost surface is mainly made of metal.

However, electrical and electronic products are devices that perform wireless communication. When the appearance is only configured with metal, the quality of wireless communication may be degraded due to the electromagnetic wave shielding effect. In order to solve this problem, researches have been actively conducted to combine polymer resins whose electromagnetic wave shielding effect around wireless communication elements is relatively low.

For example, when a resin composition including polyphenylene sulfide (PPS) is used as the main component, it has high chemical resistance to the acidic substance used to anodize the metal after being bonded to the metal, and has With high mechanical strength and dimensional stability, it can be used as the internal material of mobile phones. However, it has a disadvantage that it is easy to cause discoloration before and after processing according to the environment of the user. Therefore, its use in components exposed to the outside of the product is limited, and it has relatively low adhesion to metal.

In addition, compared with polyphenylene sulfide, a resin composition including polybutylene terephthalate (PBT) as the main component can have excellent adhesion to metals and relatively high discoloration resistance, so , Has been used as the internal/external material of mobile phones. However, due to the large size variation caused by its self-shrinkage rate, there are limitations in its use in high-precision products, and its discoloration resistance cannot be fully preserved, so the use of materials as external components has limitations.

Therefore, for the application of products such as electrical and electronic products, there is an urgent need to develop new materials with excellent metal adhesion, chemical resistance, dimensional stability, and heat resistance.

An object of the present invention is to provide a polymer resin composition for metal adhesion, which has excellent metal adhesion, chemical resistance, dimensional stability and discoloration resistance.

Another object of the present invention is to provide a metal resin composite and a product using the above-mentioned polymer resin composition.

One aspect of the present invention provides a polymer resin composition for metal adhesion, which includes: polycyclohexylenedimethylene terephthalate resin; polyethylene terephthalate resin terephthalate resin); and fillers. Among them, relative to 100 parts by weight of polyethylene terephthalate resin, the content of polyethylene terephthalate resin is less than 200 parts by weight, and it is used for metal adhesion according to the ASTM D648 measurement method. The polymer resin composition has a heat resistance of 225°C or higher under a pressure of 1.82 megapascals (MPa).

Another aspect of the present invention provides a metal resin composite, which includes: a metal substrate; and the above-mentioned polymer resin composition for metal adhesion, which is adhered to the surface of the metal substrate.

Another aspect of the present invention provides a product including the above-mentioned metal resin composite.

Specific examples of the polymer resin composition for metal adhesion, metal resin composites and products using the same will be described in detail below.

The term "residue" as used herein refers to a predetermined part or unit in a chemical reaction product that includes when a specific compound participates in a chemical reaction, and is derived from a specific compound, for example, The "residue" derived from dicarboxylic acid or the "residue" derived from diol means the part derived from the dicarboxylic acid component or the diol component in the polyester formed by the esterification reaction or the polycondensation reaction, respectively.

According to a specific example of the present invention, a polymer resin composition for metal adhesion can be provided, which includes: polyethylene terephthalate resin; polyethylene terephthalate resin; and filler . Among them, relative to 100 parts by weight of polyethylene terephthalate resin, the content of polyethylene terephthalate resin is less than 200 parts by weight, and it is used for metal adhesion according to the ASTM D648 measurement method. The heat resistance of the polymer resin composition under a pressure of 1.82MPa is 225°C or higher.

The inventors have found through experiments that when the above-mentioned specific polymer resin composition is used, its heat resistance can vary with the relative content of polyethylene terephthalate resin to polyethylene terephthalate resin. Increase and remarkably improve, thereby completing the present invention.

In particular, relative to 100 parts by weight of polyethylene terephthalate resin, by adjusting the content of polyethylene terephthalate resin to be less than 200 parts by weight, it is used as a polymer for metal adhesion. The resin composition not only has a heat resistance of 225°C or higher under a pressure of 1.82 MPa in accordance with the ASTM D648 measurement method, but also makes it possible to achieve high heat resistance. It can also be used in the metal resin composite described later, Highly adheres to metal.

In addition, relative to 100 parts by weight of polyethylene terephthalate resin, by adjusting the content of polyethylene terephthalate resin to be less than 200 parts by weight, the discoloration resistance and size of the resin composition The stability is improved, which can be easily applied to the manufacturing process of products such as electrical and electronic products through the adhesion of metal.

In addition, the polymer resin composition may include a filler, thereby achieving not only heat resistance but also excellent mechanical properties.

Specifically, according to the above-mentioned specific example, the polymer resin composition for metal adhesion may include polydimethylcyclohexyl terephthalate resin, polydimethylcyclohexyl terephthalate (hereinafter referred to as PCT (indicated by PCT) resin can be obtained by the esterification of a dicarboxylic acid and a diol compound, or can be obtained by the transesterification of a dicarboxylic acid ester compound and a diol compound.

30 to 1,000 parts per million (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 can remain in the PCT resin, provided that the germanium atoms remain in the PCT resin When the content of PCT resin is reduced below the above range, the rate of the polymerization reaction of the PCT resin may be delayed, and the polymerization 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 rate of thermal decomposition of the resin will increase. As a result, it may not be possible to obtain a resin with the expected degree of polymerization, or the haze value ( The haze value) may increase due to the catalyst components remaining in the resin, adversely affecting the transparency of the resin.

Specifically, the PCT resin with trace amounts of germanium atoms remaining can be obtained by esterification reaction or transesterification reaction with germanium compound as a catalyst. The specific type of germanium compound is not particularly limited. Examples include germanium dioxide (germanium dioxide). dioxide) etc.

On the other hand, a trace amount of titanium atoms (Ti) may remain in the PCT resin, and specifically, 20 ppm or less, 0.1 to 20 ppm, or 5 to 15 ppm of titanium atoms may remain in the PCT resin. Within the above range, PCT resin can be polymerized without worrying about side reactions including titanium atoms, such as the problem of molecular weight reduction during extrusion molding or injection molding. It can also be avoided, and the product can have excellent yellowing resistance.

The PCT resin with trace amounts of germanium atoms and titanium atoms remaining as described above can be obtained by using a germanium compound and a titanium compound as a catalyst for an esterification reaction or a transesterification reaction. The specific type of the titanium compound used as the catalyst is not particularly limited. Examples thereof include titanium oxide, tetra-n-propyl titanate, and tetra-isopropyl titanate. , Tetra-n-butyl titanate, tetra-isobutyl titanate or butyl-isopropyl titanate, etc.

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

Dicarboxylic acids may include terephthalic acid (TPA), isophthalic acid (IPA), 2,6-naphthalenedicarboxylic acid (2,6-naphthalenedicarboxylic acid, 2,6-NDA) or The combination thereof, for example, 90 or more parts by weight of the total dicarboxylic acid may be terephthalic acid, and 10 or less parts by weight of the total dicarboxylic acid may include 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.

Dicarboxylic acid ester compounds may include dimethyl terephthalate, dimethyl isophthalate (DMI), dimethyl 2,6-naphthalate (dimethyl 2,6- naphthalenedicarboxylate (2,6-NDC)) or a combination thereof, for example, 90 or more parts by weight of the total dicarboxylic acid ester compound may be dimethyl terephthalate, and 10 or less parts by weight of the total two The carboxylic acid ester compound may include other dicarboxylic acid ester compounds. In particular, when the dicarboxylic acid ester compound is terephthalic acid In the case of dimethyl acid, a resin composition having excellent weather resistance and yellowing resistance can be provided.

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

On the other hand, the PCT resin can be prepared by adding a phosphorus stabilizer in the early stage of the esterification reaction or transesterification reaction. Therefore, the side reaction that occurs during the esterification reaction or transesterification reaction at high temperature Can be effectively avoided.

Examples of phosphorus-based stabilizers that can be used include phosphorus-containing compounds such as phosphoric acid, phosphorous acid, etc., and phosphate compounds such as triethyl phosphate, trimethyl phosphate, etc. phosphate), triphenyl phosphate, triethyl phosphonoacetate, etc.

The PCT resin can be polymerized by additionally using other additives in addition to the above-mentioned compounds and commonly used in the technical field involved in the present invention. In addition, PCT resins can also be polymerized using these components by methods generally used in the technical field involved in the present invention. For example, the PCT resin can be obtained by the following steps: in the presence of the above catalyst, esterification of dicarboxylic acid and diol compound or transesterification of dicarboxylic acid ester compound and diol compound; and polycondensation of the above The product obtained by the reaction. In addition, such as If necessary, the PCT resin can be prepared by additionally using the following steps: molding and processing the product of the polycondensation reaction to form particles; and/or crystallizing the product or particles of the polycondensation reaction and polymerizing it in a solid state.

The PCT resin of crystalline polyester has a high melting point (Tm) and a high crystallization speed, and therefore, has been used as a connector and a heat-resistant component in the electrical and electronic fields and automotive fields that require high heat resistance.

The content of the polydimethylcyclohexyl terephthalate resin may be 10% by weight to 70% by weight, 15% by weight to 60% by weight, or 30% by weight to 70% by weight relative to the polymer resin composition used for metal adhesion. %weight.

If the content of the polydimethylcyclohexyl terephthalate resin is excessively increased to more than 70% by weight relative to the polymer resin composition used for metal adhesion, it will be difficult for the polymer resin composition used for metal adhesion to achieve Adequate adhesion of the metal substrate.

In addition, if the content of polydimethylcyclohexyl terephthalate resin is excessively reduced to less than 10% by weight relative to the polymer resin composition used for metal adhesion, according to the ASTM D648 measurement method, at a pressure of 1.82MPa The heat resistance below will be reduced to less than 225°C, so it will be difficult to achieve sufficient heat resistance. In addition, the increase in mold shrinkage ratio makes it extremely difficult to control the value of precision products, and in the subsequent manufacturing process, the dimensional stability may decrease as the mold shrinkage ratio increases.

In addition, according to the above specific example, the polymer resin composition for metal adhesion may include polyethylene terephthalate resin. As known in the art, polyethylene terephthalate (hereinafter (Expressed as PET) resin is usually polymerized by dicarboxylic acid and diol.

Examples of dicarboxylic acids and their derivatives used to polymerize PET resins include terephthalic acid (TPA), isophthalic acid (IPA), 2,6-naphthalenedicarboxylic acid (2,6-NDA), dimethyl Dimethyl terephthalic acid (DMT), dimethyl isophthalic acid (DMI), dimethyl 2,6-naphthalene dicarboxylate, dimethyl 1,4-cyclohexane dicarboxylate (dimethyl terephthalic acid) 1,4-cyclohexanedicarboxylate, DMCD) etc., but not limited to this.

Examples of glycols used to polymerize PET resins include ethylene glycol (EG), diethylene glycol (DEG), propylene glycol (PG), neopentyl glycol (NPG), cyclohexanedimethanol, CHDM) etc., but not limited thereto, any diol known in the art can be used in the preparation of PET resin, but preferably it can be ethylene glycol (EG).

The polymerization of PET resin is by introducing dicarboxylic acid and diol as raw materials into a high-temperature and high-pressure reactor. If necessary, reaction catalyst, stabilizer, coloring agent, etc. can be added to the preparation. The oligomer is then reacted under high-temperature vacuum, but it is not particularly limited. In addition to this, the PET resin can be polymerized as known in the art.

The intrinsic viscosity of the PET resin can 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 lower than 0.50 dL/g, the mechanical properties are expected to decrease due to the low molecular weight. , And when the intrinsic viscosity of the PET resin exceeds 1.2dL/g, the mixing and molding process needs to be under high temperature and high pressure, which may reduce efficiency.

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

If the content of the polyethylene terephthalate resin is excessively reduced to less than 5% by weight relative to the polymer resin composition used for metal adhesion, it may be difficult for the polymer resin composition used for metal adhesion to achieve Adequate adhesion of the metal substrate.

In addition, if the content of the polyethylene terephthalate resin is excessively increased to more than 60% by weight relative to the polymer resin composition used for metal adhesion, according to the ASTM D648 measurement method, under the pressure of 1.82MPa The heat resistance will be reduced to less than 225°C, so it will be difficult to achieve sufficient heat resistance. In addition, the increase in molding shrinkage makes it extremely difficult to control the value of high-precision products, and in the subsequent manufacturing process, the dimensional stability may decrease with the increase in molding shrinkage.

Specifically, in the polymer resin composition for metal adhesion, the content of the polyethylene terephthalate resin can be less than 100 parts by weight of the polyethylene terephthalate resin. In 200 parts by weight, 0.1 parts by weight to 150 parts by weight, or 10 parts by weight to 140 parts by weight. The polymer resin composition used for metal adhesion is a mixture of PCT resin and PET resin, and the heat resistance and metal adhesion suitable for products such as electrical and electronic products can be achieved by adjusting the mixing ratio.

Relative to 100 parts by weight of polyethylene terephthalate resin, if the content of polyethylene terephthalate resin is excessively increased to more than 200 parts by weight, according to the ASTM D648 measurement method, it is 1.82MPa The heat resistance will be reduced to less than 225°C under the pressure of, so when applied to electrical and electronic products and other products, its heat resistance may be reduced.

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

In addition, according to the above-mentioned specific example, the polymer resin composition for metal adhesion may include fillers. Therefore, the polymer resin composition for metal adhesion may have significantly improved mechanical properties, heat resistance, and discoloration resistance.

Regarding fillers, any organic fillers or inorganic fillers commonly used in the technical field involved in the present invention can be used. Examples of fillers are not particularly limited, but include those selected from glass fiber and carbon fiber. (carbon fiber), boron fiber, glass bead, glass flake, talc, wollastonite, calcium titanate whisker, aluminum borate At least one of the group consisting of aluminum boric acid whisker, zinc oxide whisker, and calcium whisker.

For example, needle-shaped fillings can be used as fillings to provide molded products with excellent surface smoothness. In particular, in order to provide a white molded product with excellent surface smoothness, the filler can be glass fiber, wollastonite, titanium calcium whisker, aluminum borate whisker or a mixture thereof, among which the plasticity of the composition can be determined by It is improved by using glass fiber, and the mechanical properties of the molded product such as tensile strength, bending strength, modulus of elasticity, and heat resistance such as heat distortion temperature Can be improved.

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

The content of the filler can be 10% by weight to 60% by weight, 20% by weight to 50% by weight, or 25% by weight to 45% by weight relative to the polymer resin composition used for metal adhesion. Therefore, it can provide excellent A resin composition with mechanical strength and heat resistance.

If the content of the filler is excessively reduced to less than 10% by weight relative to the polymer resin composition for metal adhesion, the heat resistance of the polymer resin composition for metal adhesion decreases, and if the content of the filler is relative to the polymer resin composition used The polymer resin composition for metal adhesion is excessively increased to more than 60%, and the polymer resin composition for metal adhesion may have a problem of reduced adhesion to metal.

In addition, according to the above specific example, according to the ASTM D648 measurement method, the polymer resin composition used for metal adhesion has a heat resistance of 225° C. or higher, or 225° C. to 300° C., under a pressure of 1.82 MPa. According to the ASTM D648 measurement method, if the heat resistance of the polymer resin composition used for metal adhesion is reduced to less than 225°C under a pressure of 1.82MPa, when the polymer resin composition is used in electrical and electronic products and other products , Its heat resistance may be reduced.

The polymer resin composition used for metal adhesion may exist in a state of being attached, adhered or joined to the surface of the metal substrate, more specifically, used for attaching, adhering or joining the polymer resin composition for metal adhesion and The example of the method of the surface of the metal substrate is not particularly limited, but for example, a method of injecting or extruding the polymer resin composition onto the metal surface can be used.

In order to additionally strengthen the adhesion between the metal and the resin composition, a pretreatment process of the metal surface can be additionally performed. Specifically, for example, the process can include an etching process (nano molding technology (nano molding technology, NMT) treatment method) to form micron or nano-sized pores on the metal surface, or to form an anodic oxide layer on the metal surface, and then form triazine derivatives through anodic electrolysis (TRI treatment method) [1 ,3,5-triazine 2,4-dithiol-6-sodium thiolate (1,3,5-triazine 2,4-dithiol-6-sodium thiolate, TTN)] in the anodic oxide layer, etc. .

According to the following equation, the polymer resin composition used for metal adhesion can have an adhesive force of 20 MPa or higher, or 20 MPa to 50 MPa, and the adhesive force is between the metal and the polymer for metal adhesion that adhere to the metal surface Between resin compositions.

[Equation] Adhesion (MPa)=(Measure the tensile strength at a crosshead speed of 5mm/min according to ASTM D638 measurement method)/(The contact area between the metal and the polymer resin composition for metal adhesion ).

More specifically, in the case where the metal resin composite is prepared by the above-mentioned NMT processing method, the adhesion force of the polymer resin composition for metal adhesion to the metal can be 20 MPa to 30 MPa. In the case where the above-mentioned TRI treatment method is prepared, the adhesion force of the polymer resin composition for metal adhesion to the metal may be 25 MPa to 40 MPa.

Therefore, in the case of the NMT treatment method, the adhesion force of the polymer resin composition for metal adhesion to the metal substrate can be 20 MPa to 30 MPa, and in the case of the TRI treatment method, the polymer resin composition for metal adhesion The adhesion force to the metal substrate can be 25 MPa to 40 MPa.

In addition, according to the above-mentioned specific example, the polymer resin composition for metal adhesion may further include a highly crystalline polyethylene terephthalate having a melt crystallization temperature of 285°C or higher, or 285°C to 500°C. Methylcyclohexyl resin, highly crystalline polydimethylcyclohexyl terephthalate resin can be esterified by esterifying 1,4-cyclohexanedimethanol and terephthalic acid with a high trans-isomer ratio It is prepared, or is prepared by transesterification of 1,4-cyclohexanedimethanol and terephthalic acid ester compounds with a high trans-isomer ratio.

The commonly used 1,4-cyclohexanedimethanol includes 70 mole percent (mol%) of the trans isomer and the remaining amount of the cis isomer. When 1,4-cyclohexanedimethanol is present in the When it is isomerized under the catalyst, the content of the cis and trans isomers of 1,4-cyclohexanedimethanol, which is the cis and trans isomers, can be changed.

Specifically, highly crystalline polydimethylcyclohexyl terephthalate resin can be used to have a trans isomer ratio of 70 mol% or higher, 73 mol% or higher, or 75 mol% or higher It is formed by polymerization of 1,4-cyclohexanedimethanol. Therefore, the resin can have a high melting point and high heat resistance and can exhibit high crystallinity.

In addition, according to the above specific example, the polymer resin composition used for metal adhesion may further include epoxy resin or phenol-based resin, epoxy resin or phenol-based resin. The specific example is not particularly limited, and various epoxy resins or phenol resins widely used in the field of resin compositions can be used without limitation.

In addition, according to the above-mentioned specific example, the polymer resin composition for metal adhesion may further include at least one selected from impact modifier, nucleating agent, Antioxidant, lubricant, releasing agent, coloring agent, compatibilizing agent, heat stabilizer, UV stabilizer, hydrolysis stabilizer ( hydrolysis stabilizer, viscosity enhancer, fluorescent whitening agent, physical property modifier, main chain extender, pigment, Additives in the group consisting of dyes and antistatic agents. The specific types of additives are not particularly limited, and various additives widely used in the field of resin compositions can be used without limitation.

Specifically, examples of impact modifiers include ethylene-based copolymers, which include (meth)acrylate repeating units substituted with at least one crosslinking functional group ((meth)acrylate). repeating unit). Vinyl copolymers containing (meth)acrylate repeating units substituted with at least one cross-linking functional group can be copolymerized as monomers of ethylene (ethylene) and (former) substituted with at least one cross-linking functional group. (Meth)acrylate (meth)acrylate.

The (meth)acrylate repeating unit substituted by at least one crosslinking functional group means the basic repeating unit included in the homopolymer of the (meth)acrylate compound substituted with at least one crosslinking functional group , (Meth)acrylate is used in the sense of including acrylate or methacrylate.

The (meth)acrylate repeating unit substituted by at least one cross-linking functional group can increase the compatibility by cross-linking the compound, polymer or resin in the composition through the cross-linking functional group. Specific examples of the bifunctional group are not particularly limited. For example, glycidyl or maleic anhydride can be used.

On the other hand, the vinyl copolymer may further include (meth)acrylate or vinyl acetate repeating units to increase polarity. That is, the vinyl copolymer may include a terpolymer, and the terpolymer is obtained by copolymerizing ethylene as a monomer, (meth)acrylate substituted with at least one crosslinking functional group, and (meth) Acrylate or vinyl acetate repeating units are prepared.

The (meth)acrylate repeating unit or vinyl acetate repeating unit means the basic repeating unit included in the (meth)acrylate compound or vinyl acetate compound, respectively.

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

The impact modifier can be used to improve the mechanical strength and adhesion of the polymer resin composition, and the content of the impact modifier can be 0.1% to 10% by weight relative to the polymer resin composition used for metal adhesion . If the content of the impact modifier is increased excessively, the viscosity may become too high during the process, which may reduce the plasticity, and the viscosity between the polymer resin composition and the metal surface may be insufficient, which may Will reduce viscosity.

Examples of pigments include titanium oxide, zinc oxide (zinc oxide), zinc sulfide (zinc sulfide), zinc sulfate (zinc sulfate), barium sulfate (barium sulfate), lithopone (BaSO4. ZnS), white lead (white) lead, 2PbCO3. Pb(OH)2), calcium carbonate, alumina, boron nitride or mixtures thereof, etc. Examples of antioxidants include AO-60 manufactured by ADEKA, etc., as hindered phenol-based antioxidants.

The lubricant can be used to stably disperse fillers or pigments in the resin composition and to facilitate the release of the resin composition. Regarding lubricants, stearate (stearate) can be used including at least acid amide, acid ester, fatty acid, hydrocarbon wax, and metallic soap. One, amides include erucamide, oleamide or stearamide, and acid esters include montan wax, stearyl stearate ) And distearyl phthalate, fatty acids include lauric, myristic, palmitic, and stearic; hydrocarbon waxes include polyethylene ), polypropylene and paraffin, metal soaps include calcium, zinc, magnesium, lead, aluminum, sodium, tin, barium and cobalt, and more specific examples thereof include N,N'-vinyl bis( Stearamide) (N,N'-ethylenebis(stearamide)) and so on.

The nucleating agent acts as a crystallization nucleus for crystallization in the molding process of the resin composition, thereby improving the crystallization rate of the resin composition. Regarding the nucleating agent, sodium salt of montanic acid (Licomont NaV101 manufactured by Clariant) or calcium salt (Licomont CaV102 manufactured by Clariant) or the like can be used.

The content of the additives is not particularly limited, but for example, the content may be 0.1% by weight to 10% by weight relative to the polymer resin composition used for metal adhesion. If the content of the additives is excessively increased to more than 10% by weight relative to the polymer resin composition used for metal adhesion, the heat resistance of the polymer resin composition and its adhesion to metals may be reduced.

In addition, according to the above-mentioned specific example, the polymer resin composition used for metal adhesion may additionally include at least one selected from nylon, polypropylene terephthalate (PTT), and polyethylene terephthalate. Polybutylene terephthalate (PBT), modified Polyethylene terephthalate glycol modified (PETG), modified polycyclohexylenedimethylene terephthalate glycol modified, polyethylene naphthalate (polyethylene naphthalate, PEN), polyethylene isosorbide terephthalate (PEIT), polyethylene isosorbide cyclohexylene dimethylene terephthalate (PEICT), polyethylene terephthalate Butane 2,2,4,4, tetramethylcyclobutylene (poly(2,2,4,4,tetramethylcyclobutylene terephthalate)) and polyphenylene sulfide (polyphenylene sulfide, PPS) resin in the group.

The content of the resin is not particularly limited, but for example, the content may be 0.1% by weight to 10% by weight relative to the polymer resin composition used for metal adhesion. If the content of the resin is excessively increased above 10% by weight relative to the polymer resin composition used for metal adhesion, the heat resistance of the polymer resin composition and its adhesion to metals may be reduced.

On the other hand, the polymer resin composition used for metal adhesion can have a reflectivity-discoloration resistance of 50% or more, or 50% to 90%, at a wavelength of 450 nanometers (nm). , The anti-tarnish reflectance is expressed by the following equation.

[Equation] Discoloration resistance reflectance (%) at a wavelength of 450nm = (measured at a wavelength of 450nm the reflectance of a polymer resin composition for metal adhesion after 24 hours of heat treatment at 200°C)/( The initial reflectance of the polymer resin composition for metal adhesion was measured at a wavelength of 450 nm)×100.

The wavelength of 450nm is the blue wavelength, and the decrease in reflectance indicates the opposite color of yellow The color value increases, that is, it means that the color-b value (color-b value, according to Hunter Lab color system, Hunter Lab color space) increases. Therefore, the reflectance at a wavelength of 450 nm decreases and the color b value Increase means that yellowing occurs frequently. Therefore, if the anti-tarnish reflectance at a wavelength of 450nm is reduced to less than 50% as expressed by the equation of the polymer resin composition for metal adhesion, yellowing will occur in the resin composition for metal adhesion. Phenomenon, this may reduce the discoloration resistance.

On the other hand, according to another specific example of the present invention, a metal resin composite can be provided. The metal resin composite includes a metal substrate and a polymer resin composition for metal adhesion adhered to the surface of the metal substrate.

The inventors have found through experiments that when the above-mentioned specific metal resin composite is used, the metal resin composite can be formed simply by adhesion of the polymer resin composition without using an additional adhesive, thereby completing the present invention .

The details of the polymer resin composition for metal adhesion include the description in the above-mentioned specific example.

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

The metal resin composite may include a polymer resin composition for metal adhesion formed on a metal substrate. Specifically, in the metal resin composite, the polymer resin composition for metal adhesion may be attached, The state of being adhered or bonded to the surface of the metal substrate.

More specifically, in the metal resin composite, there are no particular limitations on the method for attaching, adhering or joining the polymer resin composition for metal adhesion and the surface of the metal substrate, but for example, it can be used A method of injecting or extruding a polymer resin composition onto a metal surface.

In order to additionally strengthen the adhesion between the metal and the resin composition, a pretreatment process of the metal surface may be additionally performed. Specifically, for example, the process may include an etching process (NMT processing method) to form micron or Nano-sized pores on the metal surface, or used to form an anodic oxide layer on the metal surface, and then through anodic electrolysis (TRI treatment method) to form triazine derivatives [1,3,5-triazine2,4 -Dithiol-6-sodium thiolate (TTN)] in the anodic oxide layer, etc.

According to the following equation, the metal resin composite can have an adhesive force of 20 MPa or higher between the metal and the polymer resin composition for metal adhesion adhered to the metal surface.

[Equation] Adhesion (MPa)=(Measure the tensile strength at a crosshead speed of 5mm/min according to ASTM D638 measurement method)/(The contact area between the metal and the polymer resin composition for metal adhesion ).

More specifically, in the case where the metal resin composite is prepared by the above-mentioned NMT processing method, the adhesion force of the polymer resin composition for metal adhesion to the metal can be 20 MPa to 30 MPa. In the case where the above-mentioned TRI treatment method is prepared, the adhesion force of the polymer resin composition for metal adhesion to the metal may be 25 MPa to 40 MPa.

On the other hand, according to another specific example of the present invention, it is possible to provide The product of the metal resin composite of the example, and the details of the metal resin composite include all the descriptions in the above-mentioned specific examples.

The function of the product is not particularly limited, and it can be used in various product groups in materials, accessories and components made of metal without limitation. For example, the product can include various information processing devices (specific examples include computers, mobile phones, Smartphones, etc.), electrical and electronic products (specific examples include video reproduction devices, sound generating devices, etc.), and household electrical equipment (specific examples include refrigerators, washing machines, cars, etc.). More preferably, products may include portable electrical and Electronic products such as smart phones, mobile phones, tablet computers, etc., and components included therein or components of wireless communication devices.

The appearance of the product, such as specific shape, weight, size, color, etc., and examples of the internal structure are not particularly limited, and can be applied without limitation to the appearance and internal structure of various products known in the art, as well as accessories and components included therein. .

According to the present invention, it is possible to provide a polymer resin composition for metal adhesion with excellent metal adhesion, heat resistance, chemical resistance, dimensional stability and discoloration resistance, and its metal resin composite and its products.

Hereinafter, the present invention will be described in more detail through the following examples. However, these examples are provided for illustrative purposes only, and the details of the present invention are not limited thereto.

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

The polymer resin composition having the composition listed in Table 1 below was melted and kneaded using a twin-screw extruder (twin-screw extruder, Φ: 40mm, L/D=40) heated to about 300°C To prepare particles.

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

* PCT resin: resin obtained by polymerizing cyclohexanedimethanol (CHDM) and terephthalic acid (TPA) through esterification and polycondensation, and has an intrinsic viscosity (IV) of about 0.65dL/g.

* PET resin: A resin obtained by polymerizing ethylene glycol (EG) and terephthalic acid (TPA) through esterification and polycondensation, and has an intrinsic viscosity (IV) of about 0.80dL/g.

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

* Highly crystalline PCT resin: PCT resin with an intrinsic viscosity of 0.65dL/g is obtained by polycondensing cyclohexane dimethanol (CHDM) and terephthalic acid (TPA) containing 75 mol% of trans isomer use.

* Impact modifier: ethylene-methyl acrylate-glycidyl methacrylate (Ethylene-methyl acrylate-glycidyl methacrylate(GMA)) terpolymer (Lotader AX8900, manufactured by Arkema) has a melt flow index at 190℃/2.16 kg (kg) The lower is 6g/10min, and its melting point is 65°C.

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

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

Except for using the polymer resin composition having the composition listed in Table 2 below, the particles can be prepared in the same manner as in the above-mentioned Examples.

<Experimental Example: Measurement of physical properties of polymer resin compositions obtained in Examples and Comparative Examples>

The physical properties of the polymer resin compositions obtained in the above examples and comparative examples were measured by the following methods, and the results are shown in Table 1 and Table 2.

Experimental Example 1: Adhesion

(1) NMT processing

Micron or nanometer-sized pores are formed on the metal surface through an etching process. Then, the polymer resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 4 are subjected to insert injection molding. ) And injected into the pores to prepare a resin-to-metal adhesive to make the metal adhere to the polymer resin composition.

Regarding the resin-metal adhesive, according to the ASTM D638 measurement method, using a universal testing machine (UTM) at a crosshead speed of 5mm/min under normal temperature and pressure conditions A tensile test is performed, where the breaking pressure is measured, and the adhesive force is determined by dividing the measured pressure by the area where the metal and plastic adhere.

(2) TRI processing

After forming an anodic oxide layer on the metal surface through the anodic oxidation reaction of the pretreated metal, a triazine thiol derivative [1,3,5-triazine2,4-dithiol is used -6-Sodium thiolate (TTN)] electrolyte is used to anodic this layer to form triazine thiol derivatives on or in the anodic oxide layer.

After that, the polymer resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 4 were inserted and injected through the anodic oxide layer with the triazine thiol derivative formed on the metal surface. To form a resin-metal adhesive for adhering metal and polymer resin composition.

Regarding the resin-metal adhesive, according to the ASTM D638 measurement method, a universal testing machine (UTM) is used to conduct a tensile test at a crosshead speed of 5mm/min under normal temperature and pressure conditions, and the breaking pressure is measured here, and the adhesion The force is determined by dividing the measured pressure by the area where the metal and plastic adhere.

Experimental Example 2: Heat resistance

For the polymer resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 4, samples for measurement were prepared according to the ASTM D638 measurement method, and a heat resistance tester (HDT Tester, Toyoseiki) measured the heat resistance under a pressure of 1.82MPa.

Experimental Example 3: Discoloration resistance

For samples obtained by injection molding the polymer resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 4 into flat plates at about 290°C, ultraviolet light-visible light-near infrared light was used. Spectrometer (UV-vis-NIR spectrometer, Spectrophotometer "CM-3600d" manufactured by Konica Minolta Co., Ltd.) makes D65 light source incident, whiteness (whiteness) The index "L" value (Color-L value of the initial color) and reflectance (initial stage) at a wavelength of 450nm are measured according to the Hunter Lab color system.

The sample was heated at 200°C for 24 hours, and then the whiteness index "L" value (the L value of the color after 24 hours of heating at 200°C) and the reflectance at a wavelength of 450nm (after 24 hours The reflectance after heating at 200°C) can be measured in the same way.

Then, the whiteness and discoloration resistance can be calculated by the following equation 1, and the discoloration resistance reflectance can be calculated by the following equation 2.

[Equation 1] Whiteness and discoloration resistance (%)=(L value of color after heat treatment at 200°C for 24 hours)/(L value of initial color)×100.

[Equation 2] Discoloration resistance reflectance (%)=(reflectance at a wavelength of 450 nm after 24 hours of heating at 200° C.)/(initial reflectance at a wavelength of 450 nm)×100.

Experimental Example 4: Molding shrinkage

Regarding the polymer resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 4, According to ISO 294-4, a 100×100mm sample test piece for evaluating molding shrinkage was prepared by injection. A three-dimensional measuring instrument (Flash300 manufactured by Optical Gaging Products Co., Ltd.) capable of accurately measuring 0.001 mm was used to measure the thus prepared sample The exact size of the mold shrinkage rate is determined by the following equation 3.

[Equation 3] Molding shrinkage rate (%)=(length of mold-length of prepared sample)/length of mold×100.

Experimental Example 5: Dimensional stability

For the polymer resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 4, according to ISO 294-4, a 100×100mm sample test piece for evaluating molding shrinkage was prepared by injection method. A three-dimensional space measuring instrument (Flash300 manufactured by Aozhipin Optical Instruments Co., Ltd.) capable of accurately measuring 0.001 mm was used to measure the precise size of the sample prepared in this way. The first molding shrinkage rate is determined by the following equation 3.

[Equation 3] Molding shrinkage rate (%)=(length of mold-length of prepared sample)/length of mold×100.

Next, the sample was placed in a convection oven at 150° C. for 12 hours, and then the second molding shrinkage rate was measured by the above formula 3, and then the dimensional stability can be measured by the following equation 4.

[Equation 4] Dimensional stability (%) = second molding shrinkage rate-first molding shrinkage rate.

As shown in Table 1, in the case of Comparative Examples 1 to 3 using PBT resin, PET resin or a mixture thereof and excluding any PCT resin, the heat resistance can be reduced to less than 225° C., thereby reducing the heat resistance. In addition, compared to the initial stage, the whiteness after the heat treatment is reduced to the range of 65% to 70%, and the reflectivity at the wavelength of 450nm is reduced to less than 50%, which will lead to the occurrence of yellowing. Therefore, it can be confirmed that the discoloration resistance is poor. In addition, compared with the initial stage, after the heat treatment, the dimensional change rate in the TD direction is higher, which exceeds 0.01%, which can prove that the dimensional stability is also poor.

On the other hand, in the case of Comparative Example 4 where the content of the PCT resin is less than 30% by weight and the content of the PET resin is increased to more than 50% by weight, even if the PCT resin and the PET resin are mixed as in the examples, the heat resistance is lower than 225°C. In addition, compared with the initial stage, the whiteness after the heat treatment is reduced to less than 80%, and the reflectance at a wavelength of 450 nm is reduced to less than 50%, so it can be confirmed that the discoloration resistance is poor. In addition, the dimensional change rate in the TD direction after the heat treatment is 0.013%, which is higher than the initial stage, and it can be confirmed that the dimensional stability is also poor.

Therefore, it has been confirmed through experiments that the polymer resin composition for metal adhesion of the examples or the products using the same can achieve excellent heat resistance, color discoloration resistance, and dimensional stability with an appropriate degree of metal adhesion. . The foregoing descriptions are only preferred embodiments of the present invention, and all equivalent changes and modifications made in accordance with the scope of the patent application of the present invention shall fall within the scope of the present invention.

Claims (12)

A polymer resin composition for metal adhesion, comprising: a polycyclohexylenedimethylene terephthalate resin; a polyethylene terephthalate resin; and A filling, wherein, relative to 100 parts by weight of the polyethylene terephthalate resin, the content of the polyethylene terephthalate resin is less than 200 parts by weight, wherein the polyethylene terephthalate resin The content of the dimethylcyclohexyl dicarboxylate resin is 30% to 70% by weight relative to the polymer resin composition for metal adhesion, wherein the content of the polyethylene terephthalate resin is relative to the The polymer resin composition for metal adhesion is 5% to 45% by weight, wherein the content of the filler is 25% to 45% by weight relative to the polymer resin composition for metal adhesion, and according to ASTM D648 measurement method, a heat resistance of 225°C or higher under a pressure of 1.82 megapascals (MPa), and according to the following equation, between the polymer resin composition for metal adhesion and a metal substrate The adhesion force is 20MPa or higher: [Equation] Adhesion force (MPa)=(Measure the tensile strength at a crosshead speed of 5mm/min according to ASTM D638 measurement method)/(The polymer resin for metal adhesion The contact area between the composition and the metal). The polymer resin composition for metal adhesion as described in claim 1, wherein the reflectivity-discoloration resistance (%) expressed by the following equation is 450 nm 50% or higher at the wavelength of (nm): [Equation] Discoloration resistance reflectance (%) at a wavelength of 450nm = (measured at a wavelength of 450nm after 24 hours of heat treatment at 200°C. The reflectance of the polymer resin composition for metal adhesion)/(The initial reflectance of the polymer resin composition for metal adhesion is measured at a wavelength of 450 nm)×100. The polymer resin composition for metal adhesion according to claim 1, wherein the intrinsic viscosity of the polyethylene terephthalate resin and the intrinsic viscosity of the polyethylene terephthalate resin are The ratio is 10:1 to 1:10. The polymer resin composition for metal adhesion according to claim 1, wherein the filler includes glass fiber (glass fiber), carbon fiber (carbon fiber), boron fiber (boron fiber), glass beads (glass fiber), bead, glass flake, talc, wollastonite, calcium titanate whisker, aluminum boric acid whisker, zinc oxide At least one of the group consisting of whisker and calcium whisker. The polymer resin composition for metal adhesion according to claim 1, wherein the filler includes a glass fiber, and the glass fiber has a cross-sectional aspect ratio of 10 to 2000. The polymer resin composition for metal adhesion as described in claim 1, further comprising a crystalline polydimethylcyclohexyl terephthalate resin having a melting crystallization temperature of 285°C or higher. The polymer resin composition for metal adhesion as described in claim 1 further includes an epoxy resin or a phenol-based resin. The polymer resin composition for metal adhesion as described in claim 1, further comprising at least one selected from impact modifier, nucleating agent, antioxidant, lubricant Lubricant, releasing agent, coloring agent, compatibilizing agent, heat stabilizer, UV stabilizer, hydrolysis stabilizer, Viscosity enhancer, fluorescent whitening agent, physical property modifier, main chain extender, pigment, dye And additives in the group consisting of antistatic agents. The polymer resin composition for metal adhesion according to claim 8, wherein the impact modifier includes an ethylene-based copolymer, and the vinyl copolymer includes an ethylene-based copolymer that is crosslinked by at least one (Meth)acrylate repeating unit substituted by a group. A metal resin composite includes a metal substrate and a polymer resin composition for metal adhesion. The polymer resin composition for metal adhesion is formed on the metal substrate. The molecular resin composition includes a polyethylene terephthalate resin, a polyethylene terephthalate resin and a filler, wherein relative to 100 parts by weight of the polyethylene terephthalate resin The content of the polyethylene terephthalate resin is less than 200 parts by weight. According to the ASTM D648 measurement method, the polymer resin composition for metal adhesion is 1.82 trillion A heat resistance under a pressure of Pa (MPa) is 225°C or higher, and according to the following equation, an adhesive force between the polymer resin composition for metal adhesion and the metal substrate is 20 MPa or higher : [Equation] Adhesion (MPa) = (Measure the tensile strength at a crosshead speed of 5mm/min according to the ASTM D638 measurement method)/(The contact between the polymer resin composition for metal adhesion and metal area). An electrical and electronic product, comprising the metal resin composite as described in claim 10. A product for a wireless communication device, comprising the metal resin composite as described in claim 10.