JPH07233321A - Fiber-reinforced polyamide resin composition - Google Patents

Abstract

PURPOSE:To obtain a fiber-reinforced polyamide resin composition having improved impact resistance, strength, elastic modulus, etc., by compounding a polyamide resin, a reinforcing fiber and a specific modified polyolefin elastomer at specific ratios. CONSTITUTION:This fiber-reinforced polyamide resin composition contains (A) 100 pts.wt. of a resin composition composed of (i) 99-50wt.% of a polyamide resin composed mainly of nylon 6 and (ii) 1-50wt.% of a reinforcing fiber such as glass fiber preferably surface-treated with a polyurethane composed mainly of a polyether polyol as a collecting agent and (B) l-30 pts. wt. of a modified olefin elastomer produced by graft-polymerizing (i) 100 pts.wt. of a polyolefin elastomer with (ii) 0.1-10 pts.wt. of a glycidyl compound of formula I (R is H or a 1-6C alkyl; Ar is a 6-20C aromatic hydrocarbon group having glycidyloxy group; (n) is 1-4). The compound of formula II is a preferable example of the glycidyl compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber reinforced polyamide resin composition containing a polyolefin elastomer containing a specific modifying group. More specifically, it relates to a fiber-reinforced polyamide resin composition having excellent impact resistance and strength.

[0002]

2. Description of the Related Art Polyamide resins have been used in a wide range of fields because of their excellent properties such as mechanical strength, impact resistance, heat resistance and chemical resistance. However, higher impact resistance may be required due to market demand. In such a case, a method of adding an elastomer component is known. For example, as disclosed in JP-B-55-44108, it is known that the addition of an elastomer having a specific modified group graft-polymerized to improve the affinity and dispersibility with a polyamide resin is extremely effective. There is.

Since polyamide resin is a crystalline resin,
When reinforced with fibers, the mechanical strength is remarkably improved, and most of its uses are reinforced with fibers. The fiber-reinforced polyamide resin has the unique advantage of being superior in toughness and impact resistance as compared with other fiber-reinforced resins such as polyester resins. However, in some fields, higher impact resistance is required. In such a case, it has been attempted to improve the impact resistance of the fiber-reinforced polyamide resin according to the formulation in which the reinforcing fiber is not contained as described above. However, in this case, for example, addition of an acid-modified group-containing elastomer, which shows a very excellent effect with polyamide resin alone, improves impact resistance but significantly reduces other mechanical properties such as strength and elastic modulus. It had the drawback of causing it.
It is considered that this is because the modifying group inhibits the affinity between the polyamide and the reinforcing fiber. Of course, if an elastomer containing no modifying group is used, the strength and elastic modulus will be less reduced, but insufficient performance will be obtained in improving impact resistance. That is, no method has been found for improving the sufficient impact resistance of the fiber-reinforced polyamide resin in balance with other mechanical properties.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a fiber reinforced polyamide resin composition in which excellent mechanical properties such as strength and elastic modulus are improved while maintaining excellent impact resistance. The purpose is to do.

The present inventor has conducted extensive studies to achieve the above object, and as a result, has blended a polyamide resin with a reinforcing fiber and a modified polyolefin elastomer obtained by graft-polymerizing a specific monomer having an acrylamide group and an epoxy group. Then, it was clarified that the strength and elastic modulus of the resulting composition are sufficiently improved while maintaining excellent impact resistance, and further studies were conducted to complete the present invention.

A composition of the modified polyolefin elastomer and a polyamide resin is disclosed in JP-A-4-59857.
Although it is disclosed in the publication, there is no mention in this document of the interaction between the polyamide resin, the reinforcing fiber and the modified polyolefin elastomer.

[0007]

According to the present invention, 100 parts by weight of a resin composition comprising 99 to 50% by weight of a polyamide resin as a component A and 1 to 50% by weight of a reinforcing fiber as a component B is added to a polyolefin as a component C. Elastomer 10
The following general formula (1) is used for 0 part by weight.

[0008]

[Chemical 2]

(Wherein R is H or an alkyl group having 1 to 6 carbon atoms, Ar is an aromatic hydrocarbon group having 6 to 20 carbon atoms and having at least one glycidyloxy group,
n represents an integer of 1 to 4) A fiber-reinforced polyamide resin composition containing 1 to 30 parts by weight of a modified polyolefin elastomer obtained by graft polymerization of 0.1 to 10 parts by weight of a glycidyl compound represented by It is related to.

The present invention will be described in detail below. The polyamide resin used in the present invention essentially contains nylon 6 as a main component and is generally produced by ring-opening polymerization of ε-caprolactam. Further, as widely known, as a plasticizer, a nylon 6/66 copolymer, a nylon 6/12 copolymer in which other polyamide components are copolymerized to the extent of not significantly impairing the physical properties to improve the appearance and fluidity. Those containing a high-melting point nylon oligomer, and those containing a lubricant such as ethylene bis-stearamide type are also included. Specifically, DS
The melting point peak measured by C is 180 to 230 ° C. If it is lower than 180 ° C, the heat resistance is insufficient, and if it is higher than 230 ° C, the moldability is poor. Although the molecular weight is not particularly limited, it is preferable that the relative viscosity η at 20 ° C. in metacresol is 0.7 or more and 1.8 or less.

Next, the reinforcing fibers used as the component B in the present invention include glass fibers and carbon fibers. The fiber is not particularly limited in diameter, cross-sectional shape, surface treatment agent, etc., but particularly preferably, surface-treated polyurethane having a polyether polyol as a main component as a sizing agent is a polyamide resin, a reinforced fiber, or a polyolefin elastomer. It is preferable because the interaction between persons is well balanced. Polyurethane used as a sizing agent is
(1) Organic polyisocyanate, (2) isocyanate-based compound having polyether polyol as a main component, and (3) having 2 to 3 functional groups and having a molecular weight of about 5
The one obtained by the reaction of 0 to 400 chain extenders.

(1) Examples of organic polyisocyanates include methylenebis (phenylisocyanate) [4,
4'-isomer, 2,4-isomer, and mixtures thereof, m- or p-phenylene diisocyanate,
Hexamethylene diisocyanate and methylene bis (cyclohexyl isocyanate) [4.4'-isomer, 2,4-isomer and mixtures thereof] can be mentioned. Among these, hexamethylene diisocyanate and methylene bis (cyclohexyl isocyanate) are preferable in view of heat deterioration and discoloration.

(2) As the polyether polyol,
For example, polyoxyethylene glycol, polyoxypropylene glycol optionally capped with an ethylene oxide residue, a random or block copolymer of ethylene oxide and propylene oxide, glycerin, trimethylolpropane, pentaerythritol, etc. Propoxylated and ethylene oxide capped compounds of trihydric or tetrahydric alcohols, polytetramethylene glycol, random or block copolymers of tetrahydrofuran and ethylene oxide or propylene oxide, and any of the above, 2 or Mention may be made, for example, of polyfunctional carboxylic acids of higher functionality or products derived from the reaction of esters derived from these acids. Among these, polytetramethylene glycol, polyoxyethyne glycol and the like are preferable.

(3) The preferred chain extender is an aliphatic straight chain or branched chain diol including a cycloaliphatic having 2 to 8 carbon atoms in the chain, and the diol to be applied is ethyne. Glycol, 1,2- or 1,
3-propanediol, 1,3-, 1,4- or 2,3-butanediol, 1,3- or 1,5-pentanediol, 1,2- or 1,6-hexanediol, 3-methylpentane -1,5-diol, 1,
4-cyclohexanedimethanol and the like and a mixture of two or more kinds of these diols can be mentioned.

The surface-treated polyurethane as the sizing agent uses the above-mentioned components (1), (2) and (3),
It is manufactured by any commonly known method. For example, each of the components (1), (2) and (3) is 60 to 13
There is a method of heating to 0 ° C. and mixing at substantially the same time. In the case of surface-treating a reinforcing fiber such as glass fiber, a method of attaching the polyurethane as an aqueous emulsion as is generally known is used. The amount of adhesion is preferably 0.2 to 1.2%. If it is less than 0.2%, the bundling property will be insufficient, and if it is more than 1.2%, the unraveling of the reinforcing fibers will be insufficient, and the resin will be adversely affected by decomposition or the like.

Next, the modified polyolefin elastomer used as the component C in the present invention will be described. The glycidyl compound for modifying the polyolefin elastomer is represented by the following general formula (1)

[0017]

[Chemical 3]

(Wherein R is H or an alkyl group having 1 to 6 carbon atoms, Ar is an aromatic hydrocarbon group having 6 to 20 carbon atoms and having at least one glycidyloxy group,
n represents an integer of 1 to 4) is a glycidyl compound.

Preferred glycidyl compounds are:
AXE manufactured by Kanegafuchi Chemical Co., Ltd. represented by the following formula (2)
Is mentioned.

[0020]

[Chemical 4]

The polyolefin elastomer referred to here is a monoolefin such as ethylene, propylene, 1-butene, 1-hexene, butadiene, isoprene, 1,3.
-Copolymer rubber in which two or more kinds of olefin compounds selected from conjugated diolefins such as pentadiene and non-conjugated diolefins such as 1,4-hexadiene and norbornene are copolymerized, or between α-olefin and another kind of monomer It has a copolymerized form. Typically, ethylene-propylene copolymer rubber (EPR) and ethylene-propylene-diene copolymer rubber (EPDM) are mentioned.

Ethylene-propylene copolymer (EPR)
Has a repeating unit content of 5 derived from ethylene.
It is preferable that the content of the repeating unit derived from propylene is 0 to 80 mol% and the content of the repeating unit is 20 to 50 mol%.

The modified polyolefin elastomer used in the present invention is produced by mixing and reacting the above-mentioned glycidyl compound, polyolefin elastomer and, if necessary, a predetermined amount of a catalyst by a method such as a solution method or a melt-kneading method. You can The amount of the glycidyl compound to be reacted is preferably 0.1 to 10 parts by weight per 100 parts by weight of the polyolefin-based elastomer. If it is less than 0.1 part by weight, the reactivity is insufficient and sufficient performance cannot be obtained. If it is 10 parts by weight or more, it is difficult to produce a modified polyolefin elastomer and the thermal stability becomes poor. As the reaction catalyst, a usual radical polymerization catalyst can be used, and examples thereof include benzoyl peroxide, dicumyl peroxide, and dicumyl. When the melt-kneading method is used, a kneading roll, an extruder or the like can be used, and the apparatus is not particularly limited.

The blending amount of each component is such that the polyamide resin 99 to
The modified polyolefin elastomer is 1 to 30 parts by weight to 100 parts by weight of the resin composition consisting of 50% by weight and 1 to 50% by weight of reinforcing fibers, but preferably 85 to 50% by weight of polyamide resin and 15 to 50% by weight of reinforcing fibers. The modified polyolefin-based elastomer is 1 to 15 parts by weight with respect to 100 parts by weight of the resin composition of 1% by weight. When the content of the reinforcing fiber is less than 1% by weight, sufficient strength cannot be obtained, and when the content of the reinforcing fiber is more than 50% by weight, fluidity and appearance are deteriorated, which is not preferable. When the amount of the modified polyolefin elastomer is less than 1 part by weight, the impact resistance is insufficiently improved, and when it is more than 30 parts by weight, the strength and the elastic modulus decrease undesirably.

The composition of the present invention comprises talc,
Inorganic fillers such as titanium oxide, carbon black, stabilizers, release agents, flame retardants, lubricants, nucleating agents, antistatic agents, etc. may be added. The composition of the present invention can be produced by mixing the respective components with a tumbler, a blender, a Nauter mixer, a Banbury mixer, a kneading roll, an extruder or the like.

Since the composition of the present invention is excellent in strength and impact resistance, it is useful for housings of various electric devices, automobile parts such as wheel caps, and mechanical parts such as gears.

[0027]

EXAMPLES The present invention will be further described below with reference to examples. The evaluation in the examples is based on the following methods. (1) Tensile breaking strength: According to ASTM D-638. (2) Flexural modulus: According to ASTM D-790. (3) Impact strength: The impact strength with Izod notch of a 1/8 "-thick test piece was measured according to ASTM D-256.

[Examples 1 to 11, Comparative Examples 1 to 8] The components (A), (B), (C) and (D) shown in Table 1 were mixed in the amounts (parts by weight) shown in Table 1. Pellets were formed at a cylinder temperature of 260 ° C. using a vent type extruder [VSK-30 manufactured by Nakatani Co., Ltd.] having a diameter of 30 mm. This pellet at 80 ℃
After vacuum-drying for 12 hours, the cylinder temperature is 26 by an injection molding machine [IS-150EN manufactured by Toshiba Machine Co., Ltd.].
Physical property test pieces were prepared at 0 ° C. and a mold temperature of 80 ° C., and the evaluation results in an absolutely dry state are shown in Table 1. Each component in Table 1 is as follows.

The DSC melting point peak temperature of the polyamide resin is measured by DS Instruments DSC2910 manufactured by TA Instruments.
The heating rate was 20 ° C./min. Component (A): Polyamide resin [nylon-6, [η]
= 1.10 (solvent m-cresol), DSC melting point peak temperature: 220 ° C.] (A) component: polyamide resin [nylon-6 / 66 copolymer, [η] = 1.10 (solvent m-cresol), D
SC melting point peak temperature: 200 ° C.] (A) component: polyamide resin [nylon-6, [η]
= 1.34 (solvent m-cresol), DSC melting point peak temperature: 216 ° C.) (B) Component: glass fiber [average fiber diameter 11 μ, polyurethane containing polyether polyol as a main component as sizing agent] (B) Component: Glass fiber [with average fiber diameter 11μ, a mixture of polyurethane and bisphenol A type epoxy having polyester polyol as a main component as a sizing agent] (C) Component: Modified EPR containing AXE manufactured by Kanegafuchi Chemical Industry Co., Ltd. [HA-207 (275 manufactured by Tonen Chemical Co., Ltd.)
C, load 2160 g MFR 10 g, modified amount about 6% by weight)] (C) component: Modified EPR containing AXE manufactured by Kaneka Fuchi Chemical Co., Ltd. [manufactured by Tonen Kagaku Co., Ltd. (275 ° C., load 216
0 g MFR 10 g, modification amount about 1.5% by weight)] (C) component: Modified EPR containing AXE manufactured by Kaneka Fuchi Chemical Co., Ltd. [manufactured by Tonen Chemical Co., Ltd. (275 ° C., load 216
0 g MFR150 g, modification amount about 6% by weight)] (C) component: Kanefuchi Chemical Co., Ltd. unmodified EPR containing no AXE [Tonen Chemical Co., Ltd. (275 ° C., load 2
160 g MFR 10 g, modification amount 0%)] (C) component: modified EPR containing carboxylic acid and / or its anhydride group [T-7 manufactured by Nippon Synthetic Rubber Co., Ltd.]
711SP (230 ℃, load 2160g MFR2.5
g, modification amount about 0.8% by weight)] (C) component: modified EPR containing carboxylic acid and / or its anhydride group [manufactured by Exxon, Exzero VA]
-1803]

[0030]

[Table 1]

Claims (1)

[Claims] 1. A resin composition comprising 100 to 100 parts by weight of a polyamide resin as component A and 99 to 50% by weight of polyamide resin and 1 to 50% by weight of reinforcing fiber as component B, and as component C to 100 parts by weight of a polyolefin elastomer: General formula (1) (In the formula, R is H or an alkyl group having 1 to 6 carbon atoms, Ar is an aromatic hydrocarbon group having 6 to 20 carbon atoms having at least one glycidyloxy group, and n is 1 to 4
Represents an integer of 0.1 to 1)
A fiber-reinforced polyamide resin composition containing 1 to 30 parts by weight of a modified polyolefin elastomer obtained by graft polymerization of 0 parts by weight.