KR20060020087A - Thermoplastic resin composition having excellent impact strength - Google Patents

Abstract

The thermoplastic resin composition of the present invention comprises 40 to 70 parts by weight of 40 to 70 parts by weight of (A) polyamide resin and 10 to 60 parts by weight of (B) rubbery polymer (b ₁ ) and cyanized with aromatic vinyl monomer (b ₂₁ ). 10 to 50 parts by weight of a styrene-containing graft polymer obtained by graft polymerization by adding 95 to 20 parts by weight of a mixture of monomers (b ₂ ) consisting of 10 to 60% by weight of a vinyl monomer (b ₂₂ ), (C) an aromatic vinyl monomer ( c ₁ ) 30 to 70 parts by weight, maleimide monomer (c ₂ ) 30 to 50 parts by weight, unsaturated carboxylic anhydride monomer (c ₃ ) 1 to 20 parts by weight and copolymerizable monomer (c ₄ ) 0 to 50 parts by weight 1 to 20 parts by weight of the maleimide copolymer copolymerized into parts, (D) 0.1 to 10 parts by weight of a compound having a triglyceride structure, based on 100 parts by weight of the base resin (A) + (B) + (C), and (E) 5 to 100 parts by weight of glass fiber relative to 100 parts by weight of the base resin (A) + (B) + (C) Characterized in that eojineun.

Polyamide resin, graft polymer, maleimide copolymer, triglyceride, glass fiber, impact resistance

Description

Thermoplastic Resin Composition Having Excellent Impact Strength

Field of invention

The present invention relates to a thermoplastic resin composition excellent in impact resistance. More specifically, the present invention relates to a styrene-based thermoplastic resin composition prepared by adding a compound having a triglyceride structure into a polyamide resin, a styrene-containing graft copolymer resin, and a maleimide-based resin blend and reinforcing with glass fiber. will be.

Background of the Invention

In general, thermoplastic resins have disadvantages that are not suitable for use as a material for parts requiring high strength and precision because they have low dimensional stability, creep resistance, heat resistance, and rigidity. In order to compensate for this problem, it is known to use an inorganic filler such as glass fiber as a reinforcing material. In general, when the glass fiber is reinforced, the rigidity is greatly improved. However, when the inorganic filler is used, the rigidity can be improved, but the appearance and the impact strength of the molded article are deteriorated.

Thus, one of the most important techniques in making such thermoplastic composites is to increase the interfacial bond between the reinforcement and the resin. When the interfacial bond between resin and stiffener decreases, the stress applied to the thermoplastic composite material acts on the interface between resin and stiffener, and the fracture progresses around the interface, so that the target stiffness cannot be obtained. Have a problem

On the other hand, polyamide resins are widely used in industrial fields such as automobile parts, electrical and electronic parts, because of their excellent chemical resistance and moldability. However, there is a drawback of low impact resistance, particularly notch impact strength.

Therefore, by blending the polyamide resin with a rubbery polymer containing a diacid anhydride, it is possible to improve the workability and to significantly improve the impact strength of the resin.

However, even when blending a rubbery polymer and a polyamide resin containing a dihydric anhydride, there is a limit in improving the impact strength if the compatibility problem between the resins and the interfacial bonding strength between the resin and the reinforcing material is lowered.

Therefore, in order to overcome the above problems, the inventors have blended a rubbery polymer containing a polyamide resin and a diacid anhydride, and then improved the bonding strength between the mixture and the reinforcing material by using a compound having a triglyceride structure. It is early to develop an excellent thermoplastic resin composition.

An object of the present invention is to provide a thermoplastic resin composition excellent in impact strength.

Another object of the present invention is to provide a thermoplastic resin composition having excellent interfacial bonding force between the reinforcing material and the resin.

The above and other objects of the present invention can be achieved by the present invention described in detail below.

Summary of the Invention

The thermoplastic resin composition of the present invention comprises (A) 40 to 70 parts by weight of a polyamide resin; (B) Monomer (b ₂ ) consisting of 40 to 90% by weight of an aromatic vinyl monomer (b ₂₁ ) and 10 to 60% by weight of a vinyl cyanide monomer (b ₂₂ ) in 10 to 60 parts by weight of the rubbery polymer (b ₁ ). 10 to 50 parts by weight of a styrene-containing graft copolymer obtained by adding 95 to 20 parts by weight of the mixture to graft polymerization; (C) 30 to 70 parts by weight of the aromatic vinyl monomer (c ₁ ), 30 to 50 parts by weight of the maleimide monomer (c ₂ ), 1 to 20 parts by weight of the unsaturated carboxylic anhydride monomer (c ₃ ) and a copolymerizable monomer ( c ₄ ) 1 to 20 parts by weight of maleimide copolymer copolymer copolymerized to 0 to 50 parts by weight; (D) 0.1 to 10 parts by weight of a compound having a triglyceride structure with respect to 100 parts by weight of the base resin (A) + (B) + (C); And (E) 5 to 100 parts by weight of glass fibers based on 100 parts by weight of the base resin (A) + (B) + (C).

Hereinafter, the detailed description of each of these components is as follows.

Detailed Description of the Invention

(A) polyamide resin

Polyamide resin used in the present invention is poly caprolactam (nylon 6), poly (11-amino undecanoic acid) (nylon 11), polylauryl lactam (nylon 12), poly hexamethylene adipamide (nylon 6) 9), nylon 6, such as polyhexamethylene sebacamide (nylon 6, 10), polyhexamethylene dodecanodiamide (nylon 6, 12), and copolymers thereof such as nylon 6 / nylon 6, 10 , nylon 6 / nylon 66, nylon 6 / nylon 12 and mixtures thereof.

In the present invention, a polyamide resin having a melting point of 200 ° C or higher and a relative viscosity (measured at 25 ° C by adding 1% by weight of polyamide resin to m-cresol) in consideration of the mechanical properties and heat resistance of the resin composition is selected. It is preferable.

(B) styrene-containing graft copolymer resin

The styrene-containing graft copolymer resin of the present invention is added to 10 to 60 parts by weight of a rubbery polymer, 95 to 20 parts by weight of a monomer mixture composed of 40 to 90% by weight of an aromatic vinyl monomer and 10 to 60% by weight of a vinyl cyanide monomer. It is prepared by graft polymerization.

Rubber used for the graft copolymer resin of the present invention is a diene-based rubber such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), and saturated rubber and iso containing hydrogenated diene rubber. At least one selected from the group consisting of acrylic rubbers such as propylene rubber chloroprene rubber and butyl polyacrylate and ethylene-propylene-diene monomer terpolymer (EPDM) rubber. Among them, diene rubber is particularly preferred, and butadiene rubber is more preferable.

The content of the rubber used in the graft copolymer resin of the present invention is 10 to 60 parts by weight in the weight of the graft copolymer resin. If the content of butadiene-based rubber is less than 10 parts by weight, the impact reinforcing effect is lowered, and if it is more than 60 parts by weight, there is a disadvantage in that a large decrease in modulus occurs.

As the aromatic vinyl monomer in the graft polymerizable monomer mixture, styrene, α-methylstyrene, p-methylstyrene, and the like may be added, of which styrene is most preferred.

The method for preparing the graft copolymer is well known to those skilled in the art, and any one of emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization may be used. As the production method, it is preferable to add the above-described vinyl monomer in the presence of a rubbery polymer and to perform emulsion polymerization or bulk polymerization as a polymerization initiator.

The graft copolymer of the present invention may include one or more types of monomers copolymerizable with the aromatic vinyl monomers. As a monomer which can be introduced, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile are preferable.

The weight ratio of the rubber in the graft copolymer as a whole component is 10 to 60 parts by weight, graft copolymerized by adding 95 to 20 parts by weight of the monomer mixture to be grafted to the rubber. At this time, if the content of butadiene rubber is less than 10 parts by weight, the impact reinforcing effect is lowered, and if it is more than 60 parts by weight, there is a disadvantage that a large decrease in modulus.

The monomer mixture is 90 to 40% by weight of aromatic vinyl monomers such as styrene, and 10 to 60% by weight of unsaturated nitrile monomers. At this time, if the aromatic vinyl monomer is less than 40% by weight, moldability is lowered, and if it is more than 90% by weight, rigidity is deteriorated. In addition, the unsaturated nitrile-based monomer has a disadvantage in that the chemical resistance of the resin is lowered if it is less than 10% by weight, and gloss and moldability are lowered if it is more than 60% by weight.

In consideration of the impact strength and appearance at the time of preparing the graft copolymer, the average size of the rubber particles is suitably in the range of 0.1 to 0.5 μm. If the average particle diameter of the rubber particles is less than 0.1 ㎛ has a disadvantage of lowering the impact strength, if more than 0.5 ㎛ has a disadvantage that the gloss is reduced.

(C) maleimide copolymer

The maleimide copolymer of the present invention comprises 30 to 70 parts by weight of an aromatic vinyl monomer, 30 to 50 parts by weight of a maleimide monomer, 1 to 20 parts by weight of an unsaturated carboxylic anhydride monomer and 0 to 50 parts by weight of a copolymerizable monomer. If the content of the maleimide monomer is less than 30 parts by weight has a disadvantage that the heat resistance is lowered, if more than 50 parts by weight will be lowered the fluidity. In addition, when the content of unsaturated carboxylic anhydride is less than 1 part by weight, the reactivity with nylon is reduced, and phase separation with nylon is caused. When the amount is greater than 20 parts by weight, crosslinking between polymer chains is caused, resulting in very high physical properties. It has a disadvantage of deterioration.

Among the maleimide-based copolymers used in the present invention, aromatic vinyl monomers include styrene, α-methylstyrene, vinyltoluene, and t-butylstyrene.

As the maleimide monomer, maleimide N-methyl maleimide, N-butyl maleimide, N-hexyl maleimide, N-dichlorohexyl maleimide, N-phenylmaleimide, or N-trimaleimide can be used.

As said unsaturated carboxylic anhydride monomer, maleic anhydride, methyl maleic anhydride, 1,2-dimethyl maleic anhydride, ethyl maleic anhydride, phenyl maleic anhydride, etc. can be used.

As a monomer which can be copolymerized, acrylonitrile, methyl methacrylate, ethyl (meth) acrylate. Butyl methacrylate, hexyl methacrylate. At least one selected from the group consisting of digrohexyl methacrylate, decyl (meth) acrylate, octadecyl methacrylate, hydroxyethyl (meth) acrylate, greenyl methacrylate monomers, and mixtures thereof.

The method for producing these monomers is capable of reacting an aromatic vinyl monomer, an unsaturated carboxylic anhydride monomer, and other copolymerizable monomers with ammonia or a primary amine to imidize the anhydride acid. There are many known imidization reactions between amine compounds and polymers having anhydride acid groups in the polymer chain.

(D) triglyceride structure compounds

In the present invention, the compound of the triglyceride structure used as an impact modifier is represented by the following formula:

In the formula, R is hydrogen or an alkyl group having 1 to 32 carbon atoms.

The method for preparing a compound having a triglyceride structure is well known to those skilled in the art and is used in the present invention to improve the interfacial adhesion between the resin and the reinforcing material.

In 100 parts by weight of the thermoplastic resin composition ((A) + (B) + (C)) of the present invention, the compound having the triglyceride structure is added at 0.1 to 10 parts by weight. When the compound having a triglyceride structure is added in less than 0.1 part by weight, the effect of improving the impact strength is insignificant, and when it is added in excess of 10 parts by weight, the improvement of the impact strength is not increased and other physical properties may be reduced. Can be.

(E) Glass Fiber

Glass fiber used in the present invention is a kind used commercially. For example, 촙 glass fiber having a length of about 2.5 to 6 mm. The glass fiber used for the injection molded product is E-glass, and the diameter of the glass fiber generally used is 8 to 20 µm.

Glass fiber sizing compositions are generally treated during fabrication or in post processing. Lubricating agents, coupling agents, surfactants and the like are used as the glass fiber treating agent. Lubricants use suitable additives to form good strands in the manufacture of glass fibers. The coupling agent serves to give good adhesion between the glass fiber and the resin. When various glass fiber treatment agents are appropriately selected and used according to the type of resin and glass fiber used, the glass fiber reinforcement material has good physical properties.

In general, the coupling agent treated on the glass fiber is a silane coupling agent and has a structural formula such as YRSiX ₃ . Y is an organic functional group which can react with a matrix resin here. Organic functional groups are generally a vinyl group, an epoxy group, a merketane group, an amine group, and an acryl group. R is hydrogen or a general alkyl group. X consists of an ethoxy group, a methoxy group, a halogen group, etc. It combines with the moisture in air or an inorganic material, and forms hydrolyzed silanol. This silanol is combined with an inorganic filler. Therefore, the silane coupling agent has a structure capable of reacting with the dendritic and the inorganic filler to bind. The treatment of the silane coupling agent on the glass fibers is generally used without any particular limitation. The use method of a silane coupling agent includes the method of directly processing to an inorganic filler, the method of adding to an organic matrix, etc. In order to fully demonstrate the performance of the silane coupling agent, the selection and the content of the coupling agent suitable for the inorganic filler and the organic matrix are important.

Glass fibers used in the present invention are amine-, acryl-based, epoxy-based γ-amino propyltriethoxy silane (γ-amino propyltriethoxy silane), γ-amino propyltrimethoxy silane (γ-amino propyltrimethoxy silane), N- ( Beta-aminoethyl) γ-amino propyltriethoxy silane (N- (β-amino ethyl) γ-amino propyltriethoxy silane), γ-methacryloxy propyltriethoxy silane, γ-methoxy Γ-methacryloxy propyltrimethoxy silane, γ-glycidoxy propyltriethoxy silane, beta (3,4-epoxyethyl) γ-amino propyltrimethoxy silane (β ( 3,4-epoxyethyl) γ-amino propyltriethoxy silane) and the like.

In the present invention, the glass fiber (E) is used in an amount of 5 to 100 parts by weight based on 100 parts by weight of the base resin ((A) + (B) + (C)).

In the thermoplastic resin manufacturing method of the present invention, flame retardants, lubricants, antibacterial agents, mold release agents, nucleating agents, plasticizers, heat stabilizers, antioxidants, light stabilizers, compatibilizers, pigments, dyes and inorganic additives may be further added according to the respective uses. .

The present invention will be further illustrated by the following examples, which are only specific examples of the present invention and are not intended to limit or limit the protection scope of the present invention.

Example

(A) polyamide resin, (B) styrene-containing graft copolymer resin, (C) maleimide-based resin, (D) triglyceride structure compound (E) used in Examples and Comparative Examples below (E) ) Specifications of glass fiber are as follows.

(A) polyamide resin

Nylon 6 product (trade name KN-170) was used.

(B) styrene-containing graft copolymer resin

In a composition consisting of 150 g of polybutadiene latex (based on solids), 510 g of α-methylstyrene, 90 g of styrene, and 250 g of acrylonitrile, 2 g of t-dodecylmetcaptan, 5 g of calcium persulfate, 5 g of sodium maleate Emulsion polymerization was carried out to prepare a graft copolymer was used.

(C) maleimide resin

A product of DENKA-IP (trade name NA, styrene / rubber / = 28/72 weight ratio maleic anhydride added amount 1% by weight) was used.

(D) triglyceride structure compounds

A product (trade name 85P) from KAO CORPORATION was used.

(E) glass fiber

Nitto boseki Co., Ltd. has a diameter of 13 ㎛, chop (length) of 3 mm, and used a glass fiber treated with a coupling agent, such as amino silane and metaoxy silane, and a lubricant and binding agent.

Example 1-2

Each component was added to the contents shown in Table 1 below to prepare pellets using a conventional twin screw extruder, and then a specimen for measuring physical properties was prepared using an injection machine. The impact strength of the prepared specimens was measured in accordance with ASTM D256. The physical properties are shown in Table 1.

Comparative Example 1-3

Comparative Examples 1 and 2 do not add a compound having a triglyceride structure, and Comparative Example 3 does not add a compound having a maleimide resin and a triglyceride structure.

The compositions and physical properties of the resins prepared in Examples 1-3 and Comparative Examples 1-3 are shown in Table 1 below.

Example Comparative Example One 2 One 2 3 (A) polyamide resin 60 55 60 55 60 (B) styrene graft copolymer 10 10 10 10 10 (C) maleimide resin 10 5 10 5 - (D) a compound of triglyceride structure 0.5 0.5 - - - (E) glass fiber 20 30 20 30 20 IZOD impact strength (kgfcm / cm) 20 17 15 13 12

From the results of Table 1, in the case of Example 1-2 to which the compound of triglyceride (triglyceride) is added, the interfacial bonding force between the resin and the reinforcing agent is improved, compared with Comparative Example 1-3, which is not added excellent impact strength It can be seen that.

The present invention has excellent impact strength by blending a rubbery polymer comprising a polyamide resin and a diacid anhydride, and then improving the interfacial adhesion between the glass fiber (triglyceride) and the compound using a triglyceride structure It has the effect of providing a thermoplastic resin composition.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (5)

(A) 40-70 weight part of polyamide resins; (B) Monomer (b ₂ ) consisting of 40 to 90% by weight of an aromatic vinyl monomer (b ₂₁ ) and 10 to 60% by weight of a vinyl cyanide monomer (b ₂₂ ) in 10 to 60 parts by weight of the rubbery polymer (b ₁ ). 10 to 50 parts by weight of a styrene-containing graft polymer obtained by adding 95 to 20 parts by weight of the mixture to graft polymerization; (C) 30 to 70 parts by weight of the aromatic vinyl monomer (c ₁ ), 30 to 50 parts by weight of the maleimide monomer (c ₂ ), 1 to 20 parts by weight of the unsaturated carboxylic anhydride monomer (c ₃ ) and a copolymerizable monomer ( c ₄ ) 1 to 20 parts by weight of maleimide copolymer copolymerized to 0 to 50 parts by weight; (D) 0.1 to 10 parts by weight of a compound having a triglyceride structure represented by the following formula with respect to 100 parts by weight of the base resin (A) + (B) + (C); [Formula]

(In the formula, R is hydrogen or an alkyl group having 1 to 32 carbon atoms.) And (E) 5 to 100 parts by weight of glass fiber with respect to 100 parts by weight of the base resin (A) + (B) + (C); A thermoplastic resin composition, characterized in that consisting of. The polyamide resin according to claim 1, wherein the polyamide resin has a melting point of 200 ° C. or higher and a relative viscosity (measured at 25 ° C. by adding 1% by weight of polyamide resin to m-cresol), and the rubbery polymer (b _1). ) Is selected from the group consisting of diene rubber, acrylic rubber, ternary copolymer of ethylene propylene diene monomer and mixtures thereof, wherein the aromatic vinyl monomers (b _21, c ₁ ) are styrene, α-methylstyrene , at least one selected from the group consisting of p-methylstyrene, and the maleimide monomer (c ₂ ) is maleimide N-methyl maleimide, N-butyl maleimide, N-hexyl maleimide, N-dichlorohexyl maleimide, N- phenylmaleimide, N- tree and select at least one from the group consisting of maleimide, wherein the unsaturated carboxylic acid anhydride monomer (c ₃₎ are maleic anhydride, methyl maleic anhydride, anhydrous 1,2 Methyl maleate, and select at least one from the group consisting of anhydrous ethyl maleic acid, the copolymerizable monomer (c ₄₎ acrylonitrile, methyl (meth) acrylate. Ethyl (meth) acrylate. Butyl (meth) acrylate, hexyl (meth) acrylate. At least one selected from the group consisting of digrohexyl methacrylate, decyl (meth) acrylate, octadecyl (meth) acrylate, hydroxyethyl (meth) acrylate, greenyl methacrylate, and mixtures thereof A thermoplastic resin composition. The styrene-based thermoplastic resin composition according to claim 1, wherein the glass fiber is treated with a silane coupling agent. The silane coupling agent of claim 3, wherein the silane coupling agent is an amine-based, acryl-based, or epoxy-based γ-amino propyltriethoxy silane or γ-amino propyltrimethoxy silane. , N- (beta-aminoethyl) γ-amino propyltriethoxy silane (N- (β-amino ethyl) γ-amino propyltriethoxy silane), γ-methacryloxy propyltriethoxy silane, γ-methacryloxy propyltrimethoxy silane, γ-glycidoxy propyltriethoxy silane, beta (3,4-epoxyethyl) γ-amino propyltrimethoxy Silane (β (3,4-epoxyethyl) γ-amino propyltriethoxy silane) The thermoplastic resin composition, characterized in that at least one selected from the group consisting of. The thermoplastic resin of claim 1, wherein the resin composition further comprises a flame retardant, a lubricant, an antibacterial agent, a mold release agent, a nucleating agent, a plasticizer, a heat stabilizer, an antioxidant, a light stabilizer, a compatibilizer, a pigment, a dye, and an inorganic additive. Composition.