KR102188011B1 - Glass fiber reinforced polypropylene-polyamide resin composition - Google Patents

Abstract

The present invention relates to a polypropylene-polyamide glass fiber reinforced resin composition,
Polypropylene comprising 35 to 55 parts by weight of polypropylene, 15 to 25 parts by weight of polyamide, 10 to 45 parts by weight of surface-treated glass fibers of polypropylene and polyurethane emulsion, and 5 to 10 parts by weight of a compatibilizer- As a polyamide glass fiber reinforced resin composition, it has the effect of improving the compatibility that is inferior when developing a glass fiber reinforced resin by mixing polypropylene and polyamide, and has the effect of improving the decrease in mechanical properties due to moisture absorption. The present invention relates to a polypropylene-polyamide glass fiber reinforced resin composition having a weight reduction effect by adding polypropylene compared to the existing polyamide glass fiber reinforced resin.

Description

Polypropylene-polyamide glass fiber reinforced resin composition {Glass fiber reinforced polypropylene-polyamide resin composition}

The present invention relates to a polypropylene-polyamide glass fiber-reinforced resin composition, and to a polypropylene-polyamide glass fiber-reinforced resin composition having improved compatibility, improved physical properties, and improved weight reduction.

Glass fiber reinforced resin products generally refer to composite materials in which a thermoplastic resin is reinforced with glass fiber as a reinforcement material. It is widely used because it has moldability and corrosion resistance of thermoplastic resins, it is light, can reduce cost, and has high strength.

Polyamide resin, along with the development of the automobile industry, has been actively researched because of its superiority due to weight reduction, high mechanical strength, formability, and long-term physical properties.

As reflecting this, as a Korean patent document, 1) Registered Patent No. 101602814 says'

Polyamide 66 resin 27.2 to 49 wt%, dye mixture for coloring 0.2 to 2 wt%, compatibilizer for improving physical properties 0.2 to 2 wt%, 1,3,5-tris (2,6-dimethyl-3-hyde Oxy-4-tert-butylbenzyl) 0.1 to 3% by weight of an antioxidant made of isocyanurate, 0.1 to 3% by weight of a lubricant made of ethylene bis steamide wax, and 50 to 70% by weight of fiberglass strands. The compatibilizer is a zinc-based complex, and the zinc-based complex is a combination of at least some of these, zinc soap, fatty acid zinc, zinc oxide, zinc stearate, zinc borate, zinc laurate, zinc tatarate, zinc oleate, and zinc lactate. At least one selected from one mixture, the polyamide 66 resin has a relative viscosity of 1.5 to 3.5 in a sulfuric acid solution, the glass fiber has an average particle diameter of 6 to 15 and an average length of 2 to 12 mm, and the dye mixture It is a mixture of 10 to 70% by weight of silver dye and 30 to 90% by weight of polyethylene, wherein the dye contains carbon black or nigrosine, characterized in that high tensile strength (tensile strength of 260 MPa or more) glass fiber reinforced polyamide 66 resin composition. '(A) polyamide resin (B) flame retardant that does not contain halogen elements (C) flat glass fiber (D) has a pentaerythritol diphosphite skeleton, and has a molecular weight A phosphorus antioxidant resin composition of 600 or more and less than 800.'

In addition, polypropylene has excellent stiffness and heat resistance due to its high crystallinity, has high tensile strength, and is widely used as a molding material that is easy to form, but it is widely used in various fields, but has a disadvantage of low dimensional stability. I have.

Since higher rigidity or heat resistance is required for a resin composition containing polypropylene as a main component, various attempts have been made to improve the glass fiber-reinforced polypropylene resin composition containing glass fibers in order to improve rigidity, dimensional stability, and heat resistance.

As reflecting this, as a Korean patent document, 3) Patent No. 101587320'(a) 5 to 40% by weight of glass fiber having a fineness within the range of 500 to 1000 and (b) polypropylene resin as the balance, the glass fiber A glass fiber-reinforced polypropylene resin composition, characterized in that the surface is treated with epoxy silane:', but there is a difference in composition from the present invention, and 4) Patent Publication No. 1020180038529'polypropylene resin and A polypropylene resin composition comprising glass fibers, wherein the glass fibers have a mass average fiber length of 200 to 300 μm, and a glass fiber of 60% by mass or more relative to the mass of the glass fibers is within ±100 μm from the mass average fiber length A polypropylene resin composition having a fiber length of and having a content of the glass fiber of 30 to 60% by mass relative to the mass of the polypropylene resin composition.' However, there is a difference in structure from the glass fiber of the present invention.

The high rigidity polyamide glass fiber reinforced resin has a serious problem of deterioration of mechanical properties due to moisture. In addition, polypropylene glass fiber reinforced resin, which is relatively less affected by moisture, increases the glass fiber content in order to increase mechanical properties, but there is a problem that the moldability and appearance become disadvantageous as the glass fiber content increases. Therefore, when developing a glass fiber reinforced resin of a method of mixing polypropylene and polyamide in order to improve the above problems, there is a limitation in that the effect of increasing physical properties is insignificant due to poor compatibility.

1. Korean Patent Registration No. 101602814 (2016.03.07) 2. Korean Patent Registration No. 101175852 (2012.08.14) 3. Korean Patent Registration No. 101587320 (2016.01.14) 4. Republic of Korea Patent Publication No. 1020180038529 (2018.04.16)

In order to solve the problems of the prior art as described above, it is an object of the present invention to simultaneously apply a surface treatment agent having good compatibility with polypropylene and a surface treatment agent having good compatibility with polyamide in a glass fiber surface treatment method. The aim is to provide a polypropylene-polyamide glass fiber-reinforced resin composition capable of realizing excellent mechanical properties because the compatibility is not inferior compared to the method of bonding using a conventional compatibilizer by combining polypropylene and polyamide.

In order to achieve the object of the present invention, the present invention includes glass fibers and compatibilizers surface-treated with polypropylene, polyamide, polypropylene emulsion and polyurethane emulsion.

More specifically, it may include 35 to 55 parts by weight of polypropylene, 15 to 25 parts by weight of polyamide, 10 to 45 parts by weight of glass fibers surface-treated with a polypropylene emulsion and a polyurethane emulsion, and 5 to 10 parts by weight of a compatibilizer. have.

The weight ratio of the polypropylene and the polyamide may be 2:1 to 3:1.

The weight ratio of the polypropylene emulsion and the polyurethane emulsion of the glass fiber surface-treated with the polypropylene emulsion and the polyurethane emulsion may be 7:3 to 8:2.

The polypropylene-polyamide glass fiber reinforced resin composition includes a colorant, a lubricant, an antioxidant, a light stabilizer, a UV stabilizer, a release agent, a pigment, an antistatic agent, a crosslinking agent, an antibacterial agent, a processing aid, a metal deactivator, an anti-friction agent, an antiwear agent, a couple At least one or more may be selected from the group consisting of a ring agent and a coupling reinforcing agent.

The polypropylene-polyamide glass fiber reinforced resin composition includes a colorant, a lubricant, an antioxidant, a light stabilizer, a UV stabilizer, a release agent, a pigment, an antistatic agent, a crosslinking agent, an antibacterial agent, a processing aid, a metal deactivator, an anti-friction agent, an antiwear agent, a couple It may further include 2 to 4 parts by weight of at least one additive selected from the group consisting of a ring agent and a coupling reinforcing agent.

The polyamide may be polyamide 6.

It may be a molded article prepared including the polypropylene-polyamide glass fiber reinforced resin composition.

It may be a tailgate part for automobiles manufactured including the polypropylene-polyamide glass fiber reinforced resin composition.

When the polypropylene-polyamide glass fiber reinforced resin composition according to the present invention is used, the interfacial bonding strength of polypropylene-polyamide glass fibers is improved, and thus the commercial use of the glass fiber reinforced resin of the method of mixing polypropylene and polyamide is lowered when developing There is an effect of improving sex.

Therefore, compared to the existing polyamide glass fiber reinforced resin, the addition of polypropylene has the effect of improving the decrease in mechanical properties due to moisture absorption.

In addition, compared to the existing polyamide glass fiber reinforced resin, there is an effect of reducing weight by adding polypropylene.

In addition, compared to the existing polyamide glass fiber reinforced resin, there is an effect of cost reduction by adding polypropylene.

1 is a photograph of a glass fiber surface treatment process used in the composition of the present invention.
Figure 2 is a schematic diagram of the surface treatment of the glass fibers used in the composition of the present invention.
3 is a comparative photograph showing the result of improved surface activity by glass fibers used in the composition of the present invention.

Hereinafter, the present invention will be described in detail. In this case, when it is determined that a detailed description of known technologies or configurations related to the present invention may unnecessarily obscure the subject matter of the present invention, a detailed description thereof will be omitted.

As a technology related to a resin used to require high strength including tailgate parts such as automobiles, various methods for presenting technologies for using polyamide with high strength have been introduced, but in the present invention, only polyamide is a glass fiber. In order to compensate for the problem of poor mechanical properties due to moisture when used as a reinforcing resin composition, when using a polypropylene glass fiber reinforced resin composition at the same time, in order to solve the inferior compatibility, a surface treatment agent having advantageous compatibility with polypropylene and The technical feature is that the compatibility is improved by simultaneously applying a surface treatment agent with favorable compatibility with polyamide, and polypropylene and polyamide are combined around glass fiber.

The polypropylene-polyamide glass fiber-reinforced resin composition according to an embodiment of the present invention includes polypropylene, polyamide, polypropylene emulsion and polyurethane emulsion surface-treated glass fiber and a compatibilizer.

(1) Polyamide resin

The polyamide-based resin has amino acids, lactams, or diamines and dicarboxylic acids as main components.

Representative examples of its main constituents include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid; lactams such as ε-caprolactam and ω-laurolactam; Tetramethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-/2,4,4-trimethylhexamethylenediamine, 5-methyl Aliphatic, alicyclic, and aromatic diamines such as nonamethylenediamine, metaxylylenediamine, paraxylylenediamine, and aminoethylpiperazine; And adipic acid, sveric acid, azelaic acid, sebacic acid, dodecanoic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoiisophthalic acid, 2 And aliphatic, alicyclic, or aromatic dicarboxylic acids such as ,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid.

In one embodiment of the present invention, nylon homopolymers or copolymers derived from these raw materials may be used alone or in the form of a mixture.

In particular, it is preferable to use PA6, PA66, etc. as a polyamide resin, and PA6 may be preferably used.

The polyamide 6 resin serves to improve mechanical rigidity.

The relative viscosity of the polyamide 6 resin is preferably 2.7 to 3.0.

If the content of the polyamide 6 resin is less than the lower limit, it is not preferable because there is a possibility that it may not be sufficient to improve the stiffness, and if the content of the polyamide 6 resin exceeds the upper limit, it is preferable because there are factors of workability decrease, specific gravity and cost increase. Not.

(2) Polypropylene resin

The polypropylene resin may be selected from the group consisting of a homopolymer of a propylene monomer, a copolymer of a propylene monomer and an alpha-olefin monomer, a terpolymer of a propylene monomer and an ethylene monomer, and an alpha-olefin monomer, and mixtures thereof. have.

The alpha-olefin monomer may be selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, and 3-methyl-1-pentene. have.

The polypropylene is a basic raw material for the polypropylene-polyamide glass fiber-reinforced resin composition according to the present invention, and is preferably a homopolypropylene or a highly crystalline polypropylene polymer in consideration of mechanical properties.

However, polypropylene is not limited to the homo, highly crystalline polypropylene, and other types of polypropylene may be applied.

It is preferable that the homopolypropylene has a melt index of 10 to 60 g/10 min.If the melt index is less than the lower limit, it is not preferable because the moldability may be poor, and if the melt index exceeds the upper limit, the impact strength It is not preferable because there is a concern that physical properties such as may decrease.

When the polypropylene and the polyamide are mixed and used, a weight ratio of 2:1 to 3:1 is the most preferable in terms of specific gravity and water absorption.

(3) Polypropylene emulsion and polyurethane emulsion surface-treated glass fiber

In order to solve the problem of inferior compatibility when polypropylene and fluoramide are applied at the same time, in the present invention, a surface treatment agent having advantageous compatibility with polypropylene and a surface treatment agent having advantageous compatibility with polyamide are simultaneously applied to the glass fiber. Polypropylene emulsion and polyurethane emulsion are simultaneously surface-treated on the fiber.

1 is a photograph of a glass fiber surface treatment process in the present invention.

The melted glass fiber passes through a nozzle of a certain diameter and falls freely to produce a fiber.

In the surface coating method, when the glass fibers are dropped, a polypropylene emulsion and a polyurethane emulsion prepared in advance are sprayed with separate sprays to perform coating.

2 shows a structure in which a polypropylene emulsion and a polyurethane emulsion are simultaneously surface-treated on glass fibers by the above method.

When a surface treatment agent having favorable compatibility with polypropylene and a surface treatment agent having favorable compatibility with polyamide are applied to the glass fiber at the same time, the surface activity of the glass fiber increases compared to the conventional glass fiber reinforcement method.

3A is a photograph in which the interface between the glass fiber and the resin is not attached but is separated, and FIG. 3B is a picture in which the interface between the glass fiber and the resin is strong by the glass fiber surface-treated according to the present invention, so that the resin is attached to the surface of the glass fiber. Show the picture.

Therefore, by combining polypropylene and polyamide around the glass fiber, the result of improved compatibility can be obtained compared to bonding using an existing compatibilizer.

The glass fiber surface-treated with the polypropylene emulsion and the polyurethane emulsion is characterized in that the polypropylene emulsion and the polyurethane emulsion are simultaneously surface-treated, and the surface treatment agent ratio is 7:3 to 8:2, when the polypropylene and It is most preferred in consideration of the weight ratio of 2:1 to 3:1 when the polyamide is mixed and used.

When the ratio of the surface treatment agent is lowered or increased, there is a fear that the rigidity improvement may not be sufficient, which is not preferable.

In particular, the content of the surface-treated glass fibers of polypropylene emulsion (70%) + polyurethane emulsion (30%) is appropriate, and if the content is less than the lower limit, the stiffness and impact strength are low, which is not desirable and exceeds the upper limit. In this case, it is not preferable because there is a concern of a decrease in workability and a decrease in impact strength due to excessive rigidity.

(4) Compatibilizer

The compatibilizer is used to improve the compatibility between polypropylene and polyamide resin.

Usable compatibilizers are as follows.

CM1120H: Polypropylene with a maleic anhydride graft rate of 1% by weight, manufactured by Lotte Chemical

PH200: Polypropylene with a maleic anhydride graft rate of 5% by weight, manufactured by Lotte Chemical

It is preferable that 5 to 10 parts by weight of the compatibilizer be mixed, but when the content of the compatibilizer is less than the lower limit, compatibility may be lowered, which is not preferable, and when the content of the compatibilizer exceeds the upper limit, mechanical properties decrease and cost increases It is not desirable.

(5) additive

The additives include colorants, lubricants, antioxidants, light stabilizers, ultraviolet stabilizers, release agents, pigments, antistatic agents, crosslinking agents, antibacterial agents, processing aids, metal inactivators, antifriction agents, antiwear agents, coupling agents, coupling reinforcing agents, and among them Although it may be selected from the group consisting of two or more mixtures, the present invention is not limited thereto, and additives known in the art may be used as needed or according to the manufacturer's instructions according to the use.

Hereinafter, it will be described in detail as an example to confirm the effect according to the present invention. However, the examples are only exemplified to aid understanding of the present invention, and the scope of the present invention is not limited thereby.

[Example]

According to the composition and content of Table 1 below, the polypropylene-polyamide glass fiber reinforced resin composition (Examples 1 to 2), the polypropylene glass fiber reinforced resin composition (Comparative Example 1), and the polyamide glass fiber reinforced resin composition (Comparative Example) 2) was prepared.

In Examples 1 to 2, the contents of a composition consisting of polypropylene, polyamide 6, polypropylene emulsion (70%) and polyurethane emulsion (30%) surface-treated glass fibers, compatibilizers, and additives were respectively different.

Comparative Example 1 is a polypropylene glass fiber-reinforced resin composition comprising 58.0 parts by weight of polypropylene, 5.0 parts by weight of a compatibilizer, 35.0 parts by weight of polypropylene emulsion surface-treated glass fibers, and 2.0 parts by weight of an additive.

Comparative Example 2 is a polyamide glass fiber-reinforced resin composition consisting of 68.0 parts by weight of polyamide 6, 30.0 parts by weight of polyurethane emulsion surface-treated glass fibers, and 2.0 parts by weight of an additive.

Composition content by example ingredient Content (wt%) Example Comparative example One 2 One 2 Polypropylene 35.5 32.2 58.0 Polyamide 6 17.5 15.8 68.0 Compatibilizer 5.0 5.0 5.0 Polypropylene emulsion surface treatment glass fiber 35.0 Polyurethane emulsion surface treatment glass fiber 30.0 Polypropylene emulsion (70%) + polyurethane emulsion (30%) surface treatment glass fiber 40.0 45.0 Other additives 2.0 2.0 2.0 2.0 system 100 100 100 100

In order to measure the physical properties of the resin compositions prepared according to the above Examples and Comparative Examples, a test piece for measuring physical properties was prepared with a Nikata 180Ton electric injection molding machine.

During injection, the temperature was 180°C/210°C/220°C/220°C in the nozzle order from the fitting hopper, and the injection pressure was 30-100Mpa.

A physical property test was performed with the test pieces prepared according to the above Examples and Comparative Examples.

The measured physical properties and measurement standards are as follows.

That is, the tensile strength was measured according to ASTM D 638, the flexural strength and flexural modulus were ASTM D 790, the impact strength was ASTM D 256, and the moisture absorption rate was determined by ASTM D570.

Example and Comparative Example Results Item Example Comparative example Example 1 Example 2 Comparative Example 1 Comparative Example 2 importance 1.26 1.32 1.18 1.36 Tensile strength (Mpa) 136 139 84 135 Flexural strength (Mpa) 188 190 120 187 Flexural modulus (Mpa) 8,635 8,750 4,350 8,600 Impact strength (J/m) 129 130 63 127 Water absorption rate (%) 0.7 0.7 0.3 1.5 Weight (Kg/m ² ) 1.31 1.31 1.28 1.36

As a result of using a polypropylene-polyamide glass fiber reinforced resin composition including glass fibers in which a polypropylene emulsion and a polyurethane emulsion were simultaneously surface-treated in order to improve the compatibility inferior when using a mixture of polyamide and polypropylene. As can be seen from the results of Table 2, the specific gravity was reduced compared to Comparative Example 2 using only the polyamide glass fiber reinforced resin in Examples 1 to 2 including the polypropylene-polyamide glass fiber reinforced resin composition, while the moisture absorption rate It was confirmed that the silver was reduced by more than 50%, and the weight was reduced, while the stiffness was improved.

In addition, it was confirmed that the improved effect in tensile strength, flexural modulus and impact strength compared to Comparative Example 1 using only polypropylene glass fiber reinforced resin.

In addition, there is a cost reduction effect by mixing polyamide and polypropylene.

In the embodiment of the present composition, the molded article can be suitably used as a material part for various uses, such as for automobiles, machinery industry, industrial materials, and industrial materials.

In particular, it can be suitably used as a tailgate component for automobiles.

The specific embodiments described herein are meant to represent preferred embodiments or examples of the present invention, and the scope of the present invention is not limited thereby. It will be apparent to those skilled in the art that variations and other uses of the present invention do not depart from the scope of the invention described in the claims of this specification.

Claims (9)

In the polypropylene-polyamide glass fiber reinforced resin composition,
Including polypropylene, polyamide, polypropylene emulsion and glass fiber surface-treated with polyurethane emulsion and a compatibilizer,
Polypropylene-polyamide glass fiber reinforced resin composition, characterized in that the weight ratio of the polypropylene emulsion and the polyurethane emulsion of the glass fiber surface-treated with the polypropylene emulsion and the polyurethane emulsion is 7:3 to 8:2. The method of claim 1,
Polypropylene, characterized in that it comprises 35 to 55 parts by weight of polypropylene, 15 to 25 parts by weight of polyamide, 10 to 45 parts by weight of glass fiber surface-treated with polypropylene emulsion and polyurethane emulsion, and 5 to 10 parts by weight of compatibilizer -Polyamide glass fiber reinforced resin composition. The method of claim 1,
Polypropylene-polyamide glass fiber reinforced resin composition, characterized in that the weight ratio of the polypropylene and the polyamide is 2:1 to 3:1. delete The method of claim 1,
The polypropylene-polyamide glass fiber reinforced resin composition includes a colorant, a lubricant, an antioxidant, a light stabilizer, a UV stabilizer, a release agent, a pigment, an antistatic agent, a crosslinking agent, an antibacterial agent, a processing aid, a metal deactivator, an anti-friction agent, an anti-wear agent, and a couple. Polypropylene-polyamide glass fiber reinforced resin composition, characterized in that it further comprises at least one additive selected from the group consisting of a ring agent and a coupling reinforcing agent. The method of claim 2,
The polypropylene-polyamide glass fiber reinforced resin composition includes a colorant, a lubricant, an antioxidant, a light stabilizer, a UV stabilizer, a release agent, a pigment, an antistatic agent, a crosslinking agent, an antibacterial agent, a processing aid, a metal deactivator, an anti-friction agent, an anti-wear agent, and a couple. Polypropylene-polyamide glass fiber reinforced resin composition, characterized in that it further comprises 2 to 4 parts by weight of an additive selected at least one from the group consisting of a ring agent and a coupling reinforcing agent. The method of claim 1,
The polyamide is polyamide 6, characterized in that the polypropylene-polyamide glass fiber reinforced resin composition. A molded article prepared comprising the polypropylene-polyamide glass fiber reinforced resin composition according to any one of claims 1 to 3 and 5 to 7. A tailgate component for an automobile manufactured comprising the polypropylene-polyamide glass fiber reinforced resin composition according to any one of claims 1 to 3 and 5 to 7.

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