KR100825538B1 - Polyester resin composition with excellent coating property - Google Patents

Abstract

The present invention relates to a mineral-reinforced aromatic polyester resin composition, the composition is 0.1 to 2.0 parts by weight of talc 5 to 30 parts by weight of talc having a particle size of 3 to 30 μm and a polar group per 100 parts by weight of an aromatic polyester resin, which is a base resin. The resin of this composition is excellent in the flatness and glossiness of the surface of the molded article, and in particular, the adhesion of the coating of the molded article is excellent, such as automobile headlamp bezel or decorative material, which is a product requiring metal deposition. Very useful as a material.

Description

Polyester resin composition with excellent coating property

The present invention relates to an aromatic polyester resin composition, and more particularly, the surface of the molded article is excellent, glossiness, excellent smoothness and adhesion characteristics, so that the coating property of the molded article, for example, in the vacuum coating of aluminum It relates to a mineral-reinforced polyester resin composition having excellent adhesion.

 In addition to the regeneration problem, the thermoplastic materials show an increase of 10% or more per year with the development of related industries such as the electric, electronic, and automotive industries, and metals and thermosetting resins are being replaced by thermoplastics.

  Such polyester resins have been widely used in various industrial fields such as automobile parts and electrical and electronic parts because of their excellent mechanical properties such as strength, rigidity, heat resistance, dimensional stability, and moldability.

 Representative examples of thermoplastic aromatic polyesters used as engineering plastics include polyethylene terephthalate (hereinafter referred to as PET) and polybutylene terephthalate (hereinafter referred to as PBT).

However, in the case of PET, the long-term heat resistance is excellent, but the crystallization rate of the resin is low and the crystallinity is low, so that difficulties in productivity, mold release, etc. occur in injection molding and extrusion processing.

In the case of PBT, the long-term heat resistance is inferior to that of PET, but due to the fast crystallization rate, the molding productivity is good, and thus the market is rapidly expanding.

However, since PBT has a high crystallization rate, surface addition of the reinforcing agent occurs when a large amount of reinforcing agent is added. This phenomenon causes a poor surface state of the coating film in the post-coating process, that is, aluminum deposition, after molding.

Conventionally, as a method for improving the paintability of PBT, by melting and mixing PBT and PET having a large number of amorphous regions at an appropriate ratio according to the product, the heat resistance of PBT is improved and the surface coating property is increased by controlling the degree of crystallization and crystallization rate. This has been proposed. However, when a filler is contained, such a modification effect by PET is reduced. For example, in the case of glass fiber, the surface of the molded article is expressed and the surface whitening occurs in the coated article. Significantly reduce Therefore, in the case of paint products requiring rigidity, the rigidity and paintability as minerals are controlled. In general, even resin-added resins have considerably higher paintability than products formed by resin alone due to the surface expression of minerals. Will fall.

Korean Patent 2001-0058981 describes a UV-curable coating composition of the fluorine-modified rosin ester type in relation to such adhesion. It has excellent adhesion in all resins used as general molded products, namely PBT, PET, and nylon, but does not satisfy excellent heat resistance and adhesion.

Korean Patent No. 149695 proposes a modified polyester resin having excellent weatherability and a coating composition containing the same by reacting an acrylic and urethane-modified polyester resin with a dihydric alcohol mixture and a branched acid mixture in the presence of an ester catalyst. This is because the acrylic resin and urethane-based polymers are introduced into the polyester resin, which also has a disadvantage in that heat resistance is bad.

Korean Patent 2001-0028819 relates to a high-transparent polyester film with excellent adhesiveness, there is a method of applying the water-dispersible acrylic resin as an active layer on the polyester film as an easily adhesive layer, but unlike the film, when the same method is applied in injection molded articles Excellent adhesion properties could not be obtained. Therefore, the polar bond with the water-dispersible acrylic resin whose active group is an active layer in a resin composition is required.

And the talc composition added to the PBT and PET copolymer is very excellent in terms of dimensional stability and heat resistance when forming a general product, but has a disadvantage in that the adhesion properties are not satisfactory. In particular, when forming a thin film, the smoothness and adhesion are further insufficient.

Therefore, the present invention, in view of the above-mentioned problems of the prior art, the surface of the molded article is beautiful, excellent gloss, excellent smoothness and adhesion characteristics in the coating properties of the molded article, for example, in the aluminum vacuum deposition coating It is an object to provide a polyester resin composition having excellent adhesion.

In the study of the present inventors for achieving the above object, excellent properties that are the basic characteristics of a resin composition in which PBT and PET are mixed or talc is introduced into a copolymer thereof in order to improve adhesion of the polyester resin with the coating material. Adhesiveness between the coated material and the resin is introduced by introducing a lubricant containing a polar group into a product molded from a polyester resin having heat resistance and low dimensional stability, which has a chemical bond with the base coating materials coated before aluminum deposition. The fact that it will be able to improve the will be to complete the present invention.

According to the present invention, there is provided an aromatic polyester resin composition comprising 5 to 30 parts by weight of talc having a particle size of 3 to 30 µm and 0.1 to 2.0 parts by weight of a lubricant having a polar group per 100 parts by weight of the aromatic polyester resin. .

Hereinafter, the present invention will be described in more detail.

In this composition, the mixed resin of polybutylene terephthalate and a polyethylene terephthalate is preferable as aromatic polyester-type resin which is a base resin. The mixing ratio between the two resins is suitably 10 to 100 parts by weight of polyethylene terephthalate, more preferably 30 to 70 parts by weight, per 100 parts by weight of polybutylene terephthalate.

When aromatic polyester resin which is a base resin consists only of polybutylene terephthalate, the heat distortion temperature which is heat resistance characteristic becomes unsuitable. In addition, if 100 parts by weight of polyethylene terephthalate per 100 parts by weight of polybutylene terephthalate is too low since the crystallization rate is too low during injection molding, there is no product value because of a long molding cycle.

It is preferable that the talc contained in this composition is 3-30 micrometers in particle size. If the particle size of talc is smaller than 3 μm, it is difficult to put it into the extruder in the resin manufacturing process, which reduces the productivity. On the other hand, if the particle size is larger than 30 μm, the surface of the minerals may be severely exposed after molding. Due to this, even if the base coating on the resin, the smoothness is inappropriate.

The content of talc in this composition is suitably 5-30 weight part per 100 weight part of aromatic polyester-type resin which is a base resin. If the content of talc is less than 5 parts by weight, the thermal properties and mechanical strength are insufficient, and if it exceeds 30 parts by weight, the dimensional stability is excellent, but there is a problem that the smoothness is poor due to the surface expression of minerals.

In order to improve adhesiveness, the present composition is formulated with a lubricant having a polar group. According to the present invention, when a lubricant having excellent thermal stability and a low volatility polar group is applied to the resin, the coating material applied to the molded article has excellent adhesiveness with the resin. The content of the lubricant having a polar group in the present composition is preferably 0.1 to 2.0 parts by weight per 100 parts by weight of the base resin. If the amount of the lubricant having a polar group is less than 0.1 part by weight, the chemical bonding is weak, so that excellent adhesion cannot be obtained. If the amount of the lubricant is greater than 2.0 parts by weight, there is a problem of lowering the physical properties due to excessive content in the resin.

The lubricant used in the present composition is required to have high thermal stability, low volatility, and a polar group. Even if the lubricant used is low volatility, if the thermal stability is low, it is severely decomposed in the course of passing through the twin screw extruder, so that it does not function as a lubricant or a large amount of lubricant added to the vacuum system to remove the low molecular material from the discharge part of the extruder. Even if it is not present in the resin or a small amount of lubricant is mixed in the resin, the lubricant is migrated to the surface of the product after molding, thereby interfering with the interfacial adhesion between the coating material and the molded article.

In addition, even when using a low volatile lubricant having excellent thermal stability, there is no compatibility with the coating material when the polar group does not have a good physical bonding strength but the chemical bonding strength is not excellent excellent adhesion is not obtained. In other words, the physical bond increases proportionally by the surface area and the shape of the surface area, but due to the nature of the plastic, the polyester-based resin is exposed to the glass transition temperature or higher during the process of base coating and deposition at high temperature, so that the flow of molecules in the amorphous region is reduced. As a starting point, the resin shrinks and expands before and after the process. Therefore, although initially having excellent adhesion on the surface, through this process, a small space between the interfaces is generated, the adhesion strength that was physically bonded is reduced. In other words, when evaluated by the adhesion test method, the weak adhesive strength parts fall.

Therefore, the present invention was able to obtain excellent adhesion by increasing the chemical bonding force by introducing a polar group in the resin to maintain the adhesion does not fall even if the shrinkage and expansion of the resin during the process such as base coating aluminum deposition in the present invention.

There are various methods of introducing the polar group, but in the present invention, the polar group is introduced through the lubricant.                     

Lubricant with polar group is better than the bonding force that is applied evenly on the surface of the molded part after injection molding or partly bonds with the resin and chemically bonds with the base coating agent such as acrylic UV paint in the state that is over the surface. It has adhesion.

Particularly suitable lubricants having polar groups for the present compositions are montan waxes having the structure of Formula 1.

Where n is an integer from 25 to 35 and x + y is 1.0.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the following Examples.

<Examples 1-5 and Comparative Examples 1-11>

Intrinsic viscosity 0.975 (orsometaphenol) in the twin-screw extruder of AUTOMATIK, whose cylinder temperature is controlled at 230-255-255-260 ° C in the all-mid-rear-nozzle (die) direction. A heat-resistant agent (Ciba-Geigy Co., IRGANOX-1010) and an intrinsic viscosity of 0.645 (25 ° C with orthomethaphenol solution) in PBT resin (KOLON, KP-210) Mixing with PET resin, measured by Ubelrod viscometer at, through the main raw material inlet, talc (particle size 11㎛) and lubricant was added through the secondary raw material inlet, uniformly melt kneading extrusion was prepared as pellets. At this time, the lubricant is Montan wax in Examples 1 to 5 and Comparative Examples 10 to 11, ethylene-bis-steamid (hereinafter referred to as EBS) in Comparative Examples 1 to 3, and calcium in Comparative Examples 4 to 6. Stearate was used in Comparative Examples 7 to 9 in an amount as shown in Table 1 of silicon (203F from Dow Corning).

The pellet chips were dried in a dehumidifying dryer at a temperature of 130 ° C. for 5 hours. The dried pellet-like material was prepared in an adhesive force test piece under the conditions of an injection pressure of 80 Kg / cm 2, an injection temperature of 265 ° C., and a mold temperature of 80 ° C. in a Nissei 150-ton injection molding machine. With this test piece, adhesion as a measure of paintability was evaluated in the following manner.

* Adhesion evaluation method: Adhesion is formed by applying a base coating of acrylic UV curing paint (Korea Chemical) on a square specimen of width × length × thickness of 10cm × 10cm × 0.3cm, and depositing it on an aluminum vacuum evaporator on the base-coded coating film. After the cross-cut method, 100 squares of 1mm × 1mm in width and length were made and bonded to the whole compartment using a commercially available OPP tape. The number of compartments separated by tape (mean value after 5 evaluations) was measured, and the smaller the number of compartments separated from the tape, the better the adhesion between the resin and the coating agent. A value of 30 is relatively good, and a value of 30 or less indicates a bad level.

The results of the adhesion evaluation are shown in Table 1.

division Furtherance result Polyester resin Heat-resistant Talc Lubricant Adhesion PBT PET Montan wax EBS Calcium Sterate silicon Example 1 100 30 0.5 30 0.1 5 Example 2 100 30 0.5 30 0.5 3 Example 3 100 30 0.5 30 1.0 0 Example 4 100 30 0.5 30 1.5 6 Example 5 100 30 0.5 30 2.0 4 Comparative Example 1 100 30 0.5 30 0.1 70 Comparative Example 2 100 30 0.5 30 0.5 80 Comparative Example 3 100 30 0.5 30 1.0 70 Comparative Example 4 100 30 0.5 30 0.1 50 Comparative Example 5 100 30 0.5 30 0.5 40 Comparative Example 6 100 30 0.5 30 1.0 60 Comparative Example 7 100 30 0.5 30 0.1 40 Comparative Example 8 100 30 0.5 30 0.5 50 Comparative Example 9 100 30 0.5 30 1.0 55 Comparative Example 10 100 30 0.5 30 0.05 15 Comparative Example 11 100 30 0.5 30 3.0 5

As described in detail above, according to the present invention to obtain a mineral-reinforced aromatic polyester resin composition that can significantly improve the disadvantages of the detachment due to the lack of adhesion between the resin and the base coating after coating the injection molded product and aluminum deposition. Such a resin composition can be usefully used for various applications such as products requiring paintability, that is, headlamp bezels of automobiles, or aluminum deposited products as decorative materials.

Claims (3)

In the mineral-reinforced aromatic polyester resin composition, it contains 5 to 30 parts by weight of talc having a particle size of 3 to 30 µm and 0.1 to 2.0 parts by weight of a lubricant having a polar group per 100 parts by weight of the aromatic polyester resin, which is a base resin. An aromatic polyester resin composition. The aromatic polyester resin composition according to claim 1, wherein the lubricant having a polar group is montan wax having the structure of Formula 1. Formula 1

Where n is an integer from 25 to 35 and x + y is 1.0. The aromatic polyester resin composition according to claim 1, wherein the base resin is a mixed resin consisting of 10 to 100 parts by weight of polyethylene terephthalate per 100 parts by weight of polybutylene terephthalate.