KR20170043720A

KR20170043720A - Thermoplastic resin composite composition with light weight

Info

Publication number: KR20170043720A
Application number: KR1020150142970A
Authority: KR
Inventors: 김범호; 이혁; 권오민; 곽성복; 윤성현; 이재용
Original assignee: 현대이피 주식회사; 덕양산업 주식회사
Priority date: 2015-10-13
Filing date: 2015-10-13
Publication date: 2017-04-24

Abstract

The present invention relates to a thermoplastic resin composite composition having excellent light weight characteristics. More particularly, the present invention relates to a thermoplastic resin composite composition which comprises a matrix resin containing a polyamide resin and polypropylene resin, a compatibilizer of maleic anhydride graft polyporpylene, a rigidity-reinforcing agent of glass fibers surface treated with a silane polymer, and a filler of glass bubbles surface treated with a silane polymer, in a predetermined content ratio, wherein the glass fibers and glass bubbles used as materials for imparting a light weight are incorporated after they are surface treated with a silane polymer having a specific molecular weight considering the surface properties of each thereof to maximize the miscibility with the matrix resin and to reinforce the physical properties and light weight characteristics at the same time. The thermoplastic resin composite composition according to the present invention and thermoplastic long fiber-reinforced plastic (LFT) using the same have excellent adhesive properties and reinforced light weight characteristics, while maintaining impact properties and rigidity similar to those of the conventional products.

Description

TECHNICAL FIELD [0001] The present invention relates to a thermoplastic resin composite composition,

The present invention relates to a thermoplastic resin composite composition having excellent lightweight properties, and more particularly, to a thermoplastic resin composite composition excellent in light weight, which comprises a compatibilizing agent of a maleic anhydride graft polypropylene, a surface- And a filler of a glass bubble surface-treated with a silane-based polymer is contained at a predetermined ratio. Glass fibers and glass bubbles used as a lightweight material include silane having a specific molecular weight The present invention relates to a thermoplastic resin composite composition which is capable of maximizing compatibility with a matrix resin and simultaneously reinforcing physical properties and lightweight properties.

The depletion energy source is fossil fuel, which means it can not be regenerated from a short-term perspective because it takes a long time to regenerate. Globally, we are wary of the depletion of fossil fuels, and environmental laws are also strengthening due to increased interest in the environment. Therefore, in the automobile industry, where the business area is closely related to the above two, researches on depletion of energy resources and environmental problems are being actively carried out.

In order to prepare for the depletion of the energy source as one solution, we are trying to solve the problem through various studies on hybrid cars and electric cars. However, since there is not much practicality yet, it is necessary to solve the problems scattered in various fields through additional studies.

On the other hand, maximizing the fuel efficiency through weight reduction can be accomplished in a shorter period of time than a new one such as a hybrid car or an electric car, and exhibits higher efficiency. As a practical example, when the weight of a material is reduced by 10%, the fuel consumption is known to increase by about 6 to 8%.

Polymer materials have been widely used in various fields. In recent years, there have been widespread demands for high strength, high impact and high functional polymer materials, and thus it is necessary to apply long fiber reinforced plastic (LFT) materials, which are high strength and high impact composite materials.

Polypropylene (PP) as a thermoplastic resin has been used industrially for many years, and research on this has been carried out. However, the research on PP-LFT has been relatively underdeveloped, and there have been few studies on the weight reduction using PP-LFT.

The conventional PP-LFT is unsuitable for practical use in the automotive industry due to its large weight. Therefore, there is a need to fabricate a LFT that realizes weight reduction so that it can be practically used in the automobile industry.

The present applicant has disclosed a thermoplastic resin composite composition in which a polyamide resin and a polypropylene resin are used as a matrix resin and a specific compatibilizer and a rigid reinforcing agent are contained in Korean Patent No. 1,362,069.

The present invention has been accomplished by developing a new thermoplastic resin composite composition that improves adhesion strength and impact strength as well as lightness required as an LFT material as an improved invention of Korean Patent No. 1,362,069.

Korean Patent No. 1,362,069 entitled "Thermoplastic Resin Composite Composition for Thermoplastic Long Fiber Reinforced Plastics

An object of the present invention is to provide a thermoplastic resin composite composition which is improved in weight, adhesion strength and impact strength at the same time.

Another object of the present invention is to provide a long fiber reinforced plastic (LFT) produced by using the thermoplastic resin composite composition as a raw material.

As another means for solving the above problems, the present invention provides a polyamide resin composition comprising 20 to 50% by weight of a polyamide resin having a relative viscosity to a sulfuric acid solvent of 2.5 to 3; 5 to 25% by weight of a polypropylene resin; 0.1 to 20% by weight of maleic anhydride grafted polypropylene as a compatibilizing agent; 0.1 to 20% by weight of a glass fiber surface-treated with a silane-based polymer having a weight average molecular weight of 180 to 450 as a rigid reinforcing agent; And 10 to 40% by weight of a glass bubble surface-treated with a silane-based polymer having a weight average molecular weight of 2,650 to 15,600 as a filler; Which is excellent in lightweight property.

As another means for solving the above problems, the present invention provides a long fiber reinforced plastic (LFT) produced by using the above thermoplastic resin composite composition as a raw material.

The thermoplastic resin composite composition or the long fiber reinforced plastic (LFT) using the thermoplastic resin composite composition of the present invention is excellent in adhesion to metals or amorphous materials, and excellent in impact and rigidity.

Accordingly, the thermoplastic resin composite composition of the present invention or the long fiber reinforced plastic (LFT) using the same may be useful as a polymer composite material of a core part of a crash pad or a cow cross member.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing an internal bonding structure of an LFT including glass bubbles and glass fibers surface-treated with a silane-based polymer.
Fig. 2 is a schematic view showing the adhesion of the specimen for measuring the A type adhesive strength.
Description of the Drawings:
2,
1 is a specimen of a thermoplastic resin composite composition,
2 is a polyurethane adhesive.

The present invention provides a polyamide resin composition comprising: a) 20 to 50% by weight of a polyamide resin having a relative viscosity to a sulfuric acid solvent of 2.5 to 3; b) 5 to 25% by weight of a polypropylene resin; c) from 0.1 to 20% by weight of maleic anhydride grafted polypropylene as a compatibilizing agent; d) 0.1 to 20% by weight of a glass fiber surface-treated with a silane-based polymer having a weight average molecular weight of 180 to 450 as a rigid reinforcing agent; And 0.1 to 20% by weight of a glass fiber surface-treated with a silane-based polymer as a rigid reinforcing agent; And e) 10 to 40% by weight of a glass bubble surface-treated with a silane-based polymer having a weight average molecular weight of 2,650 to 15,600 as a filler; And a long fiber reinforced plastic (LFT) using the thermoplastic resin composite composition.

Each component constituting the thermoplastic resin composite composition according to the present invention will be described in more detail as follows.

a) a polyamide resin

The polyamide resin used in the present invention is excellent in adhesion properties with other materials and is therefore suitable as a thermoplastic resin composite material composition for LFT requiring adhesion with other materials. The polyamide resin is a crystalline linear polymer constituting the main chain through an amide bond of - [CONH] -, preferably a crystalline aliphatic polyamide. Wherein the crystalline aliphatic polyamide resin is selected from the group consisting of polyamide 3, polyamide 4, polyamide 6, polyamide 8, polyamide 9, polyamide 11, polyamide 12, polyamide 6,6 and polyamide 6,10 and polyamide 6,12. &Lt; / RTI >

Preferably, the polyamide resin has a relative viscosity to a sulfuric acid solvent of 2.5 to 3, preferably 2.7 to 3. When the relative viscosity of the polyamide resin is less than 2.5, the impregnation with other inorganic raw materials as well as the glass bubble which is an inorganic filler may be lowered. When the relative viscosity of the polyamide resin exceeds 3.0, The strength may be lowered.

The thermoplastic resin composite composition of the present invention contains 20 to 50% by weight, preferably 35 to 50% by weight, of the polyamide resin. By limiting the content range of the polyamide resin, the present invention can be made advantageous in weight reduction of the material and in improvement of the adhesion property.

b) Polypropylene resin

The polypropylene resin used in the present invention is not only excellent in chemical stability and corrosion resistance, but also useful for weight reduction of a material, and is suitable for use as a thermoplastic resin composite composition for LFT. The polypropylene resin may be a polypropylene homopolymer or a polypropylene copolymer having a weight average molecular weight of 100,000 to 150,000. The polypropylene homopolymer is preferably an isotactic polymer containing 99 wt% or more of a propylene monomer because the isotactic polymer has high crystallinity, a high melting point and a high mechanical strength. The polypropylene copolymer is a copolymer of a propylene monomer and an ethylene monomer, and the content of the ethylene monomer is 0.5 to 10% by weight, preferably 1 to 5% by weight, Can be increased.

Preferably, the polypropylene resin has a melt flow index of 30 to 100 g / 10 min, preferably 60 to 100 g / 10 min, at 230 ° C and a load of 2.16 kg. If the melt index of the polypropylene resin is less than 30 g / 10 min, the impregnation property with respect to the rigid stiffener may be deteriorated. If the melt index exceeds 100 g / 10 min, the flow may become too large and the impact strength may be decreased.

The thermoplastic resin composite composition of the present invention contains 5 to 25% by weight, preferably 10 to 20% by weight, of the polypropylene resin. By limiting the content range of the polypropylene resin, the present invention can improve adhesion properties with other materials and make it advantageous in weight reduction while maintaining rigidity and impact properties.

In the present invention, the polyamide resin and the polypropylene resin are mixedly used as the matrix resin. Preferably, the weight ratio of the polyamide resin to the polypropylene resin is 7: 3 to 9: 1 . When the weight ratio of the polyamide resin is less than 7, the adhesion property with other materials may be weakened due to the lowering of the adhesive property. When the weight ratio of the polyamide resin exceeds 9, the elastic modulus and dimensional stability may be lowered.

c) compatibilizer

The compatibilizer used in the present invention is used to improve the interfacial bonding force between the matrix resin and the inorganic additive. As the compatibilizing agent, a mixture of one or more selected from the group consisting of a polymer or a copolymer containing a furan-based polymer or derivative, a monomer containing a vinyl acetal or a derivative, or a copolymer thereof may be used. Specifically, the compatibilizing agent may be maleic anhydride grafted polypropylene, maleic anhydride grafted EPDM rubber, or a mixture thereof, preferably maleic anhydride grafted polypropylene.

The thermoplastic resin composite composition of the present invention contains 0.1 to 20% by weight, preferably 0.1 to 10% by weight, and more preferably 1 to 8% by weight of a compatibilizing agent. The present invention can improve the impregnating property of the matrix resin and the inorganic additive by improving the interfacial bonding strength between the matrix resin and the inorganic additive by limiting the content range of the compatibilizing agent.

d) Rigid reinforcing agent

The rigid reinforcing agent used in the present invention is used for improving the rigidity of the thermoplastic resin composite composition and for improving the molding processability. The rigid reinforcing agent may be glass fiber or carbon fiber. When the glass fiber is used as the rigid reinforcing agent, the glass fiber may have a diameter of 10 to 24 탆 and an elastic modulus of 70 GPa or more. When the carbon fiber is used as the rigid reinforcing agent, the carbon fiber is produced by using polyacrylonitrile or silicon carbide as a pitch-type carbon fiber as a precursor, the diameter of the carbon fiber is 5 to 20 탆, the modulus of elasticity is 230 GPa Or more.

Preferably, in the present invention, the glass fiber surface-treated with the silane-based polymer is used as the stiffener. The silane-based polymer used for the surface treatment of the glass fiber may be selected from the group consisting of polysiloxane, oligosiloxane, polysiloxane substituted with an amino group, and oligosiloxane substituted with an amino group.

The glass fiber surface-treated with the silane-based polymer used as the rigid reinforcing agent can increase the miscibility between the organic-inorganic composite material because the hydroxyl group or amine group contained in the silane-based polymer forms a covalent bond with the matrix resin. In this case, the silane-based polymer is preferably surface-treated in the range of 0.5 to 1% by weight, preferably 0.7 to 1% by weight based on the weight of the glass fiber, because if the surface treatment rate of the silane- If the above range is exceeded, the diameter of the fiber increases and the mechanical properties are deteriorated. The silane-based polymer used for the surface treatment of the glass fiber preferably has a weight average molecular weight in the range of 180 to 450, preferably 180 to 250, because when the molecular weight is less than 180, the carbonyl group in the polyamide resin Hydrogen bonds can not be induced. When the molecular weight exceeds 450, entry into the fiber bundles is difficult, which hinders induction of hydrogen bonding with carbonyl groups in the polyamide resin. The silane-based polymer may be more preferably a polysiloxane or oligosiloxane substituted with an amino group to induce hydrogen bonding, wherein the substitution ratio of the amino group is preferably 10 to 30% by weight based on the molecular weight of the silane-based polymer.

The thermoplastic resin composite composition of the present invention contains 0.1 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.1 to 1% by weight of the stiffness enhancer. The present invention can improve the rigidity of the thermoplastic resin composite composition and improve the molding processability by limiting the content range of the rigid reinforcing agent.

e) Filler

The filler used in the present invention is a glass bubble having a low surface area in the form of a sphere. (TALC) or glass fiber (GLASS FIBER) as a conventional filler which is used in the prior art, and thus an excellent weight reduction effect can be obtained.

The glass bubbles used in the present invention have an average diameter of 10 to 1,000 mu m, preferably 20 to 50 mu m. The glass bubble used in the present invention may have a specific gravity of 0.1 to 0.7 g / cc. Glass bubbles can affect filling rate, reduction of shrinkage, and prevention of twisting due to difference in average diameter and specific gravity.

In the present invention, a glass bubble is used as a filler, and a glass bubble surface-treated with a silane-based polymer is used. The silane-based polymer used for the surface treatment of the glass bubble may be selected from the group consisting of polysiloxane, oligosiloxane, polysiloxane substituted with an amino group, and oligosiloxane substituted with an amino group. Although general glass bubbles may be preferable as a filler capable of imparting a lightweight feeling, miscibility with an organic resin is low due to the inherent heterogeneous nature of the inorganic material added to the matrix resin, which ultimately causes degradation of physical properties . Therefore, in the present invention, the above-described problems can be solved by surface-treating the surface of the glass bubble with the silane-based polymer. That is, since the hydroxyl group or amine group contained in the silane-based polymer used as the surface treatment agent forms a covalent bond with the matrix resin, the miscibility between the organic-inorganic composite material can be increased. The silane-based polymer may be surface-treated in the range of 0.1 to 0.5% by weight, preferably 0.1 to 0.3% by weight based on the weight of the glass bubble. If the surface treatment rate of the silane- If the above range is exceeded, the effect of increasing the miscibility with the increase of the particle size is insignificant. The silane-based polymer used for the surface treatment of the glass bubble preferably has a weight-average molecular weight in the range of 2,650 to 15,600, preferably 3,000 to 7,000, because when the molecular weight is less than 2,650, the carbonyl group in the polyamide resin And when the molecular weight exceeds 15,600, processing becomes difficult due to a lump phenomenon between the surface-treated glass bubbles. The silane-based polymer may be more preferably a polysiloxane or an oligosiloxane substituted with an amino group to induce hydrogen bonding, wherein the substitution ratio of the amino group is preferably 10 to 20% by weight based on the molecular weight of the silane-based polymer.

The thermoplastic resin composite composition of the present invention contains 10 to 40% by weight, preferably 5 to 20% by weight, of the glass bubble. In the present invention, by limiting the content range of the glass bubble, the adhesive strength and the mechanical strength can be efficiently controlled, and weight reduction can be effectively achieved.

f) Other additives

The thermoplastic resin composite composition of the present invention may be added with an additive for further performance improvement. The additive may include at least one selected from the group consisting of a light stabilizer, a nucleating agent, an antioxidant, an antifogging agent, a dispersant, a lubricant, an antistatic agent, a slip agent, a metal deactivator, a coupling agent, a flame retardant agent, a mold release agent and a pigment. The additive is not particularly limited as a specific component, and those generally used in the art can be used.

The thermoplastic resin composite composition of the present invention contains 0.1 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight of the additive.

Further, the present invention is characterized by a long fiber reinforced plastic (LFT) produced by using the thermoplastic resin composite composition as a raw material.

The LFT of the present invention encompasses all kinds of resins prepared by using the above-described thermoplastic resin composite composition as raw materials. Further, the LFT of the present invention can be produced by a usual molding method. The ordinary molding method includes conditions and processes commonly used in the art, and the conditions and the process are not particularly limited.

The LFT of the present invention is excellent in adhesion to other materials, particularly metals or amorphous transparent materials while being advantageous in weight reduction of the material, can maintain high impact and high rigidity, It can be used as a material.

Further, the LFT of the present invention can be used as a polymer composite material for an automobile interior part, particularly a core part of a crash pad or a cow cross member, which requires high strength properties.

1 is a schematic view showing an internal coupling structure of an LFT including a glass bubble according to the present invention. 1, the LFT according to the present invention includes a polyamide resin together with a polypropylene resin in a matrix resin to improve the interfacial bonding force between the matrix resin and the rigid reinforcing agent (glass fiber) and the filler (glass bubble) . Specifically, it is possible to induce the covalent bond between the oxygen of maleic anhydride present in the compatibilizing agent molecule and the amine group present in the polyamide molecule in the matrix resin, and also to cause the covalent bond between the carbonyl group, the glass fiber and the glass bubble It can be confirmed that the interface bonding ability is improved by inducing additional covalent bonds between hydroxyl groups or amine groups of the polysiloxane treated on the surface.

The present invention will now be described in more detail with reference to the following examples, but the present invention is not limited thereto.

[Example]

Example 1

As a matrix resin, a polyamide resin and a polypropylene resin were used at a weight ratio of 7: 3. At this time, 45.5% by weight of polyamide 6 (PA6; EN200, manufactured by KP Chemtech) having a relative viscosity to a sulfuric acid solvent of 3 as a polyamide resin was prepared. 19.5 wt% of a polypropylene homopolymer having a melt index of 60 g / 10 min (measured under the load conditions of 230 DEG C and 2.16 kg) and a weight average molecular weight of 100,000 as a polypropylene resin (HA5029, manufactured by POLYMER) was prepared Respectively.

4.5% by weight of maleic anhydride graft polypropylene (GP090C, manufactured by Hyundai EP) was prepared as a compatibilizer. Treated with 0.75 wt% of a surface-treated polysiloxane (weight average molecular weight: 191, amino group bonding ratio: 12.7 wt%) whose surface was treated with untreated glass fiber (diameter 17 microns, 4000 strands) as a rigid reinforcing agent 20% by weight. (Weight average molecular weight: 3,250, amino group bonding ratio: 13.5 wt%) having an untreated surface as a filler (average diameter: 30 μm, specific gravity: 0.60 g / cc, isostatic crush strength: 18,000 psi or more) ) To prepare a glass bubble 10% by weight. 0.5% by weight of an antioxidant (ADK-A21B, Adeka Korea) was prepared as an additive.

Each of the components prepared above was mixed, and a thermoplastic resin composite composition for a long fiber reinforced plastic was prepared by a draw-molding method, and then the resulting mixture was formed into a pellet form using an extruder.

Example 2

LFT pellets were produced in the same manner as in Example 1 except that the content of the polyamide resin was changed from 45.5 wt% to 42 wt%, the content of the polypropylene resin was changed from 19.5 wt% to 18 wt%, and the surface was treated with an amino group-substituted polysiloxane The content of the glass bubbles was changed from 10 wt% to 15 wt%. At this time, the weight ratio of the polyamide resin to the polypropylene resin is 7: 3.

Example 3

LFT pellets were prepared in the same manner as in Example 1, except that the polyamide resin content was changed from 45.5 wt% to 38.5 wt%, the polypropylene resin content was changed from 19.5 wt% to 16.5 wt%, with an amino group-substituted polysiloxane The content of the glass bubbles was changed from 10 wt% to 20 wt%. At this time, the weight ratio of the polyamide resin to the polypropylene resin is 7: 3.

Example 4

LFT pellets were prepared in the same manner as in Example 1, except that the polyamide resin content was changed from 45.5 wt% to 35 wt%, the polypropylene resin content was changed from 19.5 wt% to 15 wt%, with an amino group-substituted polysiloxane The content of the glass bubbles was changed from 10 wt% to 25 wt%. At this time, the weight ratio of the polyamide resin to the polypropylene resin is 7: 3.

Example 5

LFT pellets were prepared in the same manner as in Example 1 except that the content of the polyamide resin was changed from 45.5% by weight to 31.5% by weight, the content of the polypropylene resin was changed from 19.5% by weight to 13.5% by weight with an amino group-substituted polysiloxane The content of the glass bubbles was changed from 10 wt% to 30 wt%. At this time, the weight ratio of the polyamide resin to the polypropylene resin is 7: 3.

Example 6

LFT pellets were prepared in the same manner as in Example 1, except that the content of the polyamide resin was changed from 45.5 wt% to 28 wt%, the content of the polypropylene resin was changed from 19.5 wt% to 12 wt%, and the surface was treated with an amino group-substituted polysiloxane The content of the glass bubbles was changed from 10 wt% to 35 wt%. At this time, the weight ratio of the polyamide resin to the polypropylene resin is 7: 3.

Example 7

LFT pellets were prepared in the same manner as in Example 1, except that the content of the polyamide resin was changed from 45.5 wt% to 24.5 wt%, the content of the polypropylene resin was changed from 19.5 wt% to 10.5 wt%, with an amino group-substituted polysiloxane The content of the glass bubbles was changed from 10 wt% to 40 wt%. At this time, the weight ratio of the polyamide resin to the polypropylene resin is 7: 3.

Comparative Example 1

LFT pellets were prepared in the same manner as in Example 1 except that the content of the polyamide resin was changed from 45.5 wt% to 49 wt%, the content of the polypropylene resin was changed from 19.5 wt% to 21 wt%, and the surface was treated with an amino group-substituted polysiloxane The content of the glass bubbles was changed from 10 wt% to 5 wt%. At this time, the weight ratio of the polyamide resin to the polypropylene resin is 7: 3.

Comparative Example 2

LFT pellets were prepared in the same manner as in Example 1, except that the content of the polyamide resin was changed from 45.5 wt% to 21 wt%, the content of the polypropylene resin was changed from 19.5 wt% to 9 wt%, with the amino group-substituted polysiloxane The content of the glass bubbles was changed from 10 wt% to 45 wt%. At this time, the weight ratio of the polyamide resin to the polypropylene resin is 7: 3.

Comparative Example 3

LFT pellets were prepared in the same manner as in Example 1, except that the content of the polyamide resin was changed from 45.5 wt% to 52.5 wt%, the content of the polypropylene resin was changed from 19.5 wt% to 22.5 wt%, with the amino group-substituted polysiloxane The glass bubble was changed from 10 wt% to 0 wt%. At this time, the weight ratio of the polyamide resin to the polypropylene resin is 7: 3.

Comparative Example 4

LFT pellets were prepared in the same manner as in Example 1 except that polypropylene was not used and the content of the polyamide resin was changed from 45.5 wt% to 65 wt%.

Comparative Example 5

LFT pellets were prepared in the same manner as in Example 1 except that the polypropylene resin content was changed from 19.5 wt% to 65 wt% without using polyamide.

Comparative Examples 6 to 10

LFT pellets were prepared in the same manner as in Example 1, except that the rigid reinforcing agent or filler was selected from the following.

(1) Rigid reinforcing agent

① GF_Untreat: Untreated glass fiber

(2) GF_Tr_A: Glass fiber produced by surface-treating 0.75 wt% with an amino group-substituted polysiloxane (weight average molecular weight 191, amino group bonding ratio 12.7 wt%)

(3) GF_Tr_B: Glass fiber produced by surface-treating 0.75 wt% with an amino group-substituted polysiloxane (weight average molecular weight: 1,000, amino group bonding ratio: 12.7 wt%

(2) Fillers

① GB_Untreat: Unprocessed glass bubble

GB_Tr_I: glass bubbles prepared by surface-treating 0.1% by weight of an amino group-substituted polysiloxane (weight average molecular weight: 3,250, amino group bonding ratio: 13.5% by weight)

3) GB_Tr_II: Glass bubbles prepared by surface-treating 0.1% by weight of an amino group-substituted polysiloxane (weight average molecular weight: 200, amino group bonding ratio: 13.5% by weight)

(4) GB_Tr Ⅲ: Glass bubbles prepared by surface treatment with 0.8% by weight of polysiloxane substituted with amino group (weight average molecular weight: 3,250, amino group bonding ratio: 13.5% by weight)

[Experimental Example]

The LFT pellets prepared in Examples 1 to 7 and Comparative Examples 1 to 10 were dried at 90 DEG C for 2 hours by using a dehumidifying dryer and then extruded at a cylinder temperature of 180 to 230 DEG C and a mold temperature of 70 DEG C using an extruder, . For each of the prepared LFT specimens, the bonding strength was measured by the following test methods, and the results are shown in Tables 1, 2 and 3, respectively.

[Measurement of physical properties]

(1) A type adhesive strength: Two LFT specimens were prepared as shown in Fig. 2, each having a width × height × height of 20 mm × 13 mm × 2.5 mm, and two specimens were stacked one on another (10 mm) of the specimen was superimposed on the specimen, and the specimen was bonded using a polyurethane adhesive (thickness of 2.5 +/- 0.5 mm). Thereafter, the sample was left for 72 hours at a temperature of 40 DEG C and a relative humidity of 50%, and then a force was applied to the adhesive portion to measure the force required to peel the adhesive portion, that is, the adhesive strength.

(2) Tensile strength: Measured according to ASTM D638 (TYPE I, speed: 50 mm / min).

(3) Flexural strength: Measured according to ASTM D790 (speed: 30 mm / min).

(4) Flexural modulus: Measured according to ASTM D790 (speed: 30 mm / min).

(5) Izod impact strength: Measured according to ASTM D256 (23 ℃).

division Example Comparative Example One 2 3 One 2 3 Furtherance
(weight%) Polyamide (PA6) 45.5 42 38.5 49 21 52.5 Polypropylene (HA5029) 19.5 18 16.5 21 9 22.5 Commercializer (GP090C) 4.5 4.5 4.5 4.5 4.5 4.5 Rigidity reinforcement (GF_Tr_A) 20 20 20 20 20 20 Filler (GB_Tr_I) 10 15 20 5 45 0 Antioxidant (ADK-A21B) 0.5 0.5 0.5 0.5 0.5 0.5 Properties A-type adhesive strength (MPa) 125 113 102 134 41 132 Impact strength (kgf · cm / cm) 17 16 15.3 17.3 9 18 Tensile strength (kgf / cm2) 1090 1063 1021 1100 905 1100 Flexural Strength (kgf / cm2) 1350 1320 1280 1360 1130 1360 Flexural modulus (㎏f / ㎠) 41900 43530 45090 41100 50400 41000 Specific gravity (g / cm3) 1.17 1.16 1.15 1.175 1.08 1.21

division Example Comparative Example 4 5 6 7 4 5 Furtherance
(weight%) Polyamide (PA6) 35 31.5 28 24.5 65 0 Polypropylene (HA5029) 15 13.5 12 10.5 0 65 Commercializer (GP090C) 4.5 4.5 4.5 4.5 4.5 4.5 Rigidity reinforcement (GF_Tr_A) 20 20 20 20 20 20 Filler (GB_Tr_I) 25 30 35 40 10 10 Antioxidant (ADK-A21B) 0.5 0.5 0.5 0.5 0.5 0.5 Properties A-type adhesive strength (MPa) 92 85 72 63 128 23 Impact strength (kgf · cm / cm) 14.2 13.5 12.9 12 17 12.2 Tensile strength (kgf / cm2) 998 983 971 965 1300 890 Flexural Strength (kgf / cm2) 1260 1240 1230 1220 1560 910 Flexural modulus (㎏f / ㎠) 46870 48600 49360 50010 57000 40010 Specific gravity (g / cm3) 1.13 1.12 1.10 1.09 1.31 1.01

division Comparative Example 6 7 8 9 10 Furtherance
(weight%) Polyamide (PA6) 45.5 45.5 45.5 45.5 45.5 Polypropylene (HA5029) 19.5 19.5 19.5 19.5 19.5 Commercializer (GP090C) 4.5 4.5 4.5 4.5 4.5 Rigid reinforcement GF_Untreat - - - 20 - GF_Tr_A 20 20 20 - - GF_Tr_B - - - - 20 Filler GB_Untreat 10 - - - - GB_Tr_I - - - 10 10 GB_Tr_II - 10 - - - GB_Tr Ⅲ - - 10 - - Antioxidant (ADK-A21B) 0.5 0.5 0.5 0.5 0.5 Properties A-type adhesive strength (MPa) 31 120 127 25 100 Impact strength (kgf · cm / cm) 7 13 16 5 12 Tensile strength (kgf / cm2) 920 1020 1170 810 990 Flexural Strength (kgf / cm2) 1100 1340 1290 980 1190 Flexural modulus (㎏f / ㎠) 38730 41500 40500 32720 39900 Specific gravity (g / cm3) 1.15 1.16 1.16 1.15 1.14

According to Tables 1 and 2, in Examples 1 to 7, the use of glass fibers and glass bubbles each surface-treated with a silane-based polymer having different molecular weights can realize a lightening effect while maintaining mechanical properties . On the other hand, in the case of Comparative Example 1, the content of the surface-treated glass bubble as a filler was lowered to 4% by weight and the effect of weight reduction was reduced. In Comparative Example 2, the content of the filler was over 45% It can be confirmed that the degradation is prominent. Further, in the case of Comparative Example 3, it was confirmed that the effect of weight reduction was remarkably lowered by not containing the filler, and in the case of Comparative Example 4, the effect of reducing the specific gravity could not be expected at all by using the whole amount of the polyamide resin as the matrix resin , And in Comparative Example 5, the polyamide resin was excluded as the matrix resin, and the mechanical properties such as the adhesive strength, the tensile strength, the flexural strength and the flexural modulus were deteriorated.

From the results of Table 3, it is also possible to directly confirm the effect of containing the reinforcing agent and the filler. In the case of Comparative Example 6, the glass bubble which is not surface-treated as a filler is included, which shows that the deterioration of the mechanical properties including the adhesive strength is remarkable. In the case of Comparative Example 7, the glass bubble surface-treated with a siloxane polymer having a low molecular weight as a filler was included, and the impact strength tended to be somewhat weaker among the mechanical properties. In Comparative Example 8, the siloxane polymer as the filler was excessively surface- It was confirmed that the effect of improving the mechanical properties was insignificant as compared with Example 1.

In addition, in the case of Comparative Example 9, it was confirmed that the tensile and flexural characteristics of the mechanical properties including the bonding strength were somewhat weak due to the glass fiber which was not surface-treated as the rigidity reinforcing agent. In the case of Comparative Example 10, glass fiber surface-treated with a siloxane polymer having a high molecular weight was included as a stiffness enhancer, which made it difficult to control the mechanical properties and control the specific gravity. In detail, due to the viscosity of the polymer siloxane polymer, there is a restriction on entry into the fiber bundle, which is not easy to process, and it is difficult to control the content of the rigid reinforcing agent of the final raw material by generating fuzz and single yarn during processing.

As described above, the thermoplastic resin composite composition of the present invention contains a polypropylene resin in a matrix resin together with a polyamide resin having a relative viscosity of 2.5 to 3, and a compatibilizer of maleic anhydride graft polypropylene and a silane-based polymer The surface treated glass fiber is included as a rigid reinforcing agent and the glass bubble surface-treated with the silane-based polymer is included as a filler, thereby improving the lightweight of the material and improving the impregnation property of the glass bubble of the matrix resin and the inorganic additive The adhesion between the back surface is improved, and the impact and rigidity can be maintained.

Claims

20 to 50% by weight of a polyamide resin having a relative viscosity to a sulfuric acid solvent of 2.5 to 3;
5 to 25% by weight of a polypropylene resin;
0.1 to 20% by weight of maleic anhydride grafted polypropylene as a compatibilizing agent;
0.1 to 20% by weight of a glass fiber surface-treated with a silane-based polymer having a weight average molecular weight of 180 to 450 as a rigid reinforcing agent; And
10 to 40% by weight of a glass bubble surface-treated with a silane-based polymer having a weight average molecular weight of 2,650 to 15,600 as a filler;
Wherein the thermoplastic resin composition is a thermoplastic resin.

The method according to claim 1,
Wherein the weight ratio of the polyamide resin to the polypropylene resin is maintained at 7: 3 to 9: 1.

The method according to claim 1,
The polyamide resin is selected from the group consisting of polyamide 3, polyamide 4, polyamide 6, polyamide 8, polyamide 9, polyamide 11, polyamide 12, polyamide 6,6, polyamide 6,10 and polyamide 6,12 Wherein the thermoplastic resin composition is one or a mixture of two or more selected from the group consisting of a thermoplastic resin and a thermoplastic resin.

The method according to claim 1,
Wherein the polypropylene resin has a melt flow index of 30 to 100 g / 10 min at a temperature of 230 DEG C and a load of 2.16 kg.

The method according to claim 1,
Wherein the polypropylene resin is a polypropylene homopolymer or a polypropylene copolymer having a weight average molecular weight of 100,000 to 150,000.

The method according to claim 1,
Wherein the glass bubble has an average diameter of 10 to 1,000 占 퐉.

The method according to claim 1,
Wherein the glass bubble has a specific gravity of 0.1 to 0.7 g / cc.

The method according to claim 1,
Wherein the silane-based polymer used for the surface treatment of the glass fiber or glass bubble is selected from the group consisting of polysiloxane, oligosiloxane, polysiloxane substituted with an amino group, and oligosiloxane substituted with an amino group. .

9. The method of claim 8,
Wherein the rigid reinforcing agent is a glass fiber surface-treated with 0.5 to 1 wt% of a silane-based polymer, and the filler is a glass bubble having a surface-treated 0.1 to 0.5 wt% of a silane-based polymer. .

The method according to claim 1,
And at least one conventional additive selected from the group consisting of light stabilizers, nucleating agents, antioxidants, antifade agents, dispersants, lubricants, antistatic agents, slip agents, metal deactivators, coupling agents, flame retardants, By weight based on the total weight of the thermoplastic resin composition.

A long-fiber reinforced plastic produced by using the composition of any one of claims 1 to 10 as a raw material.

12. The method of claim 11,
Long-fiber reinforced plastic used as a core component of crash pad or polymer composite material of cow cross member.