JPH0453870A - Automobile underhood component - Google Patents

Abstract

PURPOSE:To obtain a composition desirable for an automobile underhood component which is inexpensive and has a good resistance to a road antifreezer and excellent impact resistance, rigidity and heat resistance by mixing a specified (co)polyamide with a modified polyolefin and a filler. CONSTITUTION:This automobile underhood component is formed by molding a composition prepared by mixing 100 pts.wt. (co)polyamide comprising recurring units (I) of formula I and either recurring units (II) of formula II or recurring units (III) of formula III (wherein R is a 6-18C aliphatic group; R' is a 4-18C aliphatic group of formula IV; and n is an integer of 5-18) and having a weight ratio of (I)/[(II) or (III)] of 10/90-100/0 with 1-100 pts.wt. modified polyolefin and 1-100 pts.wt. filler.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention has good resistance to road surface antifreeze agents whose main ingredients are metal halide compounds such as Cal/Rum chloride, Magnenium chloride, and zinc chloride, and has good impact resistance. This invention relates to underhood parts for automobiles made of polyamide, which have excellent properties such as strength, rigidity, and heat resistance.

<Conventional technology> In recent years, the automobile industry has been promoting weight reduction and F/J to improve fuel efficiency.
There is a noticeable trend of replacing conventional metal parts with resin for purposes such as rust resistance and sound insulation. Among these, polyamide resin has excellent heat resistance, oil resistance, moldability, and toughness, so it is used in automobile underhood parts such as cooling fans, radiator tank tops and paces, engine cylinders, door covers, etc. oil pan, gear,
It is being applied to various functional parts such as valves, brake piping, fuel piping chicoves, exhaust gas system parts, and electrical system parts such as connectors.

In general, roads in cold regions are sprayed with large amounts of antifreeze agents containing calcium/lamb chloride, chloride*/umum chloride, zinc chloride, etc. in large quantities to prevent road surfaces from freezing, especially in the winter. There is a need for materials that are highly resistant to road deicing agents.

On the other hand, nylon 6, nylon 66 and nylon]
Polyamide resin compositions blended with I and nylon 12 and their reinforced products (JP-A-608-8066, JP-A-57
-212252, etc.), polyamide resin compositions prepared by blending aliphatic polyamide and aromatic polyamide, and their reinforced products (JP-A-58-120665, JP-A-58-53)
950, etc.), resin compositions made by blending polyamide with phenol resin or modified polyolefin, and reinforced products thereof (JP-A-60-188456, JP-A-61-76540)
), and many others have been proposed.

<Problems to be Solved by the Invention> With the rise in temperature in automobile engineering/generator rooms due to recent technological innovations and advances in microelectronics, there has been a demand for molded product materials that can sufficiently withstand use in even higher temperature environments.

However, these resin compositions lack the mechanical properties such as tensile strength and flexural modulus as well as heat resistance as metal substitute materials, and their material costs are high, so their uses are extremely limited. Not applicable.

Means for Solving the Problems> In view of the above circumstances, the present inventors have developed an underhood part for automobiles that is inexpensive, has good resistance to road antifreeze agents, and has excellent impact resistance, rigidity, and heat resistance. As a result of investigation, it was discovered that a specific terephthalic acid-containing polyamide resin composition could solve all the problems, and the present invention was achieved.

That is, the present invention provides repeating units and repeating units (rl), any unit of (+17), ν (m) -NH-(CRz)h-C- (wherein R is an aliphatic group having 6 to 18 carbon atoms) group, R', n represents an integer from 5 to 18), and the weight of (1)/[(It) or (m)]! 1 part of (co)polymerized polyamide CAE 100] 1j with a ratio of 10/90 to 10010 to 1 part of modified polyolefin CB] 1 to 1ooffif
This is an automotive anode hood part formed by molding a blend containing fi part and filler (C) 1 to 100111 [m parts.

What is the copolyamide resin (A) of the present invention? (1) 1 g of charcoal
Aliphatic alkylene terephthalamide synthesized from number 6 to 18 aliphatic alkylene diamine and terephthalic acid,
(It) Aliphatic alkylene/isophthalamide synthesized from aliphatic alkylene diamino having 6 to 18 carbon atoms and isophthalic acid or aliphatic alkylene diamine having 6 to 18 carbon atoms and aliphatic alkylene carboxylic acid having 4 to 18 carbon atoms It is a condensate formed from Specific examples of aliphatic alkylene diamines having 6 to 18 carbon atoms include 1.4-v amino-], ]-; methylbutano, ], 4-diamino-1
-Ethylbutane, I, 4-diamino-1゜2-dimethylbutane, l 4-diamino-13dimethylbutane/,
I, 4-diamino-1,4 dimethylbuta/, l
4-diamino-23-; methylbutane, 12-di-7-1-butylethane, I, 6-tsami/hegyusan, + 7-diaminohebutane, 1.8-noaminooctano, 16-noamino-2,5 -trimethylhexane/, ]16-cyami2.4-trimethylhexane, 1
6-Diami2-3,3-dimethylhexano, 116-
Diami2-2.2-methyl-beef san, 19-noaminononane, I, 6-tami/-2,24-trimethyl-beef san, 1,6-cyami-2゜44-trimethylhexane, 1,7-diamino-23-trimethylhexano , 1,7-diamino=24-dimethylbuta7.1.
7-diamino25-tmethylhebutano, 1,7-noamino22-. ; Methylhebutane, l, 10-diaminodecane, 1,8-+; Amino/-1,3-dimethyloctane 18-diamino-1,4-U aminooctano,
18-diamino-2,4-dimethylocta/, 1.8
-Diamino-3,4-dimethyloctane, l 8-diamino-4,5-dimethyloctane, l, 8-diamino-2,2-dimethyloctane, I, 8-noamino-3,3-dimethyloctane, l , 8-diamine-4,4-dimethyloctane, 16-diamino-2,4-dimethyl-beef san, l 9-diamino-5
-Methyl 7 nano, 111-diaminoundecano, l,
Examples include 12-diaminododecane. Among these alkylene diamine components, 1.6
-Diamine to beef san, 1.8-diaminooctane, 1,
Preferably, it is 10-noaminodeca/, 1,12-diaminododecane or a mixture thereof. Specific examples of aliphatic alkylene dicardiic acid component units having 4 to 18 carbon atoms include phosphoric acid, glutaric acid, adipic acid, pimelic acid, superic acid, azelaic acid, sepanonic acid, undecane acid, Dodecanniic acid, puranphosphoric acid,
Examples include tetradecanoic acid, beta/tadecanoic acid, and octadecanoic acid. Among these aliphatic alkylene dicarzonic acid components, adipic acid, sepanonic acid, undecanoic acid, and dodeca/diacid are preferred. (m) is a lactam or a condensate formed from an aliphatic aminocarboxylic acid component having 5 to 18 carbon atoms.

Specific examples of lactams include ε-caprolactam, ζ-
Examples include enantholactam, η-capryllactam, and ω-laurolactam, with ε-caprolactam being particularly preferred. Specific examples of the aliphatic aminocarboxylic acid component having 5 to 18 carbon atoms include 6-amitsukabronoic acid,
Examples include 11-aminoundecanoic acid and 12-aminododecanoic acid.

The copolymerization ratio of the (co)polymerized polyamide of the present invention is (1)/[(n) or x)] in a weight ratio of lO/90 to too
It needs to be in the range of 10, preferably 20/
80-90/10, more preferably 30/70-90/
It is 10. If the copolymerization ratio is less than 1O/90, the resistance to the compound of sulfur chloride and road antifreeze agents will be lowered, which is not preferable. There is no particular restriction on the degree of polymerization of the polyamide used here, and the relative viscosity (ηr) of a 1% sulfuric acid solution at 25°C is usually
can be arbitrarily used.

The method for producing the (co)polymerized polyamide of the present invention is not particularly limited, but an aqueous solution of monomers or salts of the (+) to (m) constituent components is stirred at a water vapor pressure of 20 kg/cw+'-G or less at +50-320°C. Heating at ηr=101~1
．． Simple methods include producing a low-order condensate of No. 6 and then solid-phase polymerizing it at a temperature below the melting point, or using a single-screw screw or two-wheel screw extruder with a pentro to increase the degree of polymerization. .

According to the present invention, the presence of a phosphorus catalyst is effective in obtaining pellets with a good degree of polymerization in one kneading process of melt extrusion, and the amount added is 0.02 to 2 wt% based on the lower condensate. Preferably, it is more preferably 0.05 to 1.2 wt%. Specific examples of phosphorus compounds include H3P0a, 113P
03, R3PO2, H4P20v, Na II 2
P Ot4H20+Na211POa12H20,1l
a3POa・121120, Na42O7・R20, N
a4P2O7・1OH20, N a 2 H2P 20
7 ・6 II 20, Na5P30+s, C6116
P(011)2, Cs116PO(ONa)a, Ce1
1aPO (Oll)? , Mn(I12PO2)2, (C
6H5O)3P, etc. can be mentioned. Preferred are H3P Oa and H4P2O7. There are no particular restrictions on the method of adding the phosphorus compound, and methods such as when preparing a low-order condensate or blending it in advance with a low-order condensate and melt-extruding it are convenient and convenient.

The modified polyolefin [B] of the present invention refers to ethylene, propylene, butene-11 pennotene-1,4 methylpentene-1, inobutylene, l,4 hexadiene, di/clobe/tadiene, 2,5-flubornadiene, 5-ethylidenenor A polyolefin obtained by radical combination of at least one refine selected from the group consisting of irne/, 5-ethyl-25-norbornadiene, 5-()C+benyl)-2-norbornene, butadiene/, isoprene, and styrene. and a small number of functional groups selected from carboxylic acid groups, carbo/acid ester groups, carboxylic acid metal groups, carboxylic acid anhydride groups, carboxylic acid amide groups, imide groups, and aminohydroquinoethyl groups. Lyolefin is a modification obtained by introducing a monomer component (hereinafter referred to as a functional group-containing component).

Examples of functional group-containing components include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconoic acid, crotonic acid, methylmaleic acid, methylfumaric acid, mesaconoic acid,
/traconoic acid, glutaconic acid and their carboxylic acid metal salts, methyl hydrogen maleate, methyl hydrogen itaconate, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, (meth)
2-ethylamine acrylate, hydroxyethyl (meth)acrylate, akodimethyl (meth)acrylate,
Dimethyl maleate, dimethyl itaconoate, maleinoic anhydride, itafluoric anhydride, anhydride/drafonic acid, Entobi/
Claw[22,11-5-heptene-23-dicarboxylic acid, Entobi/Clo[2211-5-hebutene-2,3
- α, β-unsaturated carboxylic acid conductors such as dicarboxylic acid anhydrides, as well as α, β-unsaturated carboxylic acids mentioned here, their esters, their anhydrides, (meth)acrylic acid glyc/nor, (meth) ) acrylic glycol ether,
Vinyl glycol/Norether etc./containing-free T8
m Compounds include ammonia, methylamine, ethylamine, butylamine, bex/ruamino, dov/ruamino,
Oleylamine, stearylamine, / clohequinylamine, benzylamine, aniline, naphthylamino, dimethylamine, diethylamino, methylathiamine, dibutylamine, distearylamine, clohequinylamine, ethylamine hequinylamine, methylanilino, phenylnaphthylamine , melamine, etha/-ruamino, 3-amino-1-propatur, noethanolamine, morpholine, α-amino-2-viclidone, α-amino-e-caprolactam, α-monomethylamino-ε-
caprolactam, α-monoethylamino-ε-caprolactam, α-monobenzylamino-ε-caprolactam,
These include N-substituted amide compounds, N-11-substituted imide compounds, and N-substituted hydroxyethyl compounds obtained by adding nylon oligomers with terminal amino groups.

The method of introducing these functional group-containing components is not particularly limited, and methods such as mixing with the main component olefins and copolymerizing them, or grafting them into polyolefins using a radical initiator can be used. . The amount of the functional group-containing component introduced is usually 0.001 to 40 mol%, preferably 0.01 to 35% by mole, based on the entire modified polyolefin.
Suitably, the amount is within the range of mol %. If the amount of functional group-containing components is less than 0.001 mol%, modified polyolefin/
There is a tendency for the affinity of the co-polyamide to be insufficient and the effect of imparting k41i impact properties to be insufficient. On the other hand, if the amount of functional group-containing components exceeds 40 mol %, side reactions such as gelation tend to occur more easily.

Specific examples of modified polyolefins particularly useful in the present invention include ethylene/(meth)acrylic acid copolymers, and some or all of the carboxylic acid moieties in these copolymers replaced with sodium, lithium, zinc, carunium, or potassium. etc., ethylene/ethyl (meth)acrylate copolymer, ethylene/ethyl (meth)acrylate copolymer, ethyl 1/7/ethyl (meth)acrylate-g-maleinoic anhydride copolymer (g" represents a graft. The same applies hereinafter), ethylene/methyl(meth)acrylate-g-maleic anhydride copolymer, ethylene/methyl(meth)acrylate copolymer, ethylene/ethyl acrylate-g -maleimide copolymer, ethylene/ethyl acrylate-g-phenylmaleimide copolymer and partially saponified products of these copolymers, ethylene/propylene-g-maleinoic anhydride copolymer, ethylene/butene-1-g-anhydride Malei/acid copolymer 1iF, ethylene/propylene/1.4-hexene-g-maleic anhydride copolymer, J tileno/propylene/synchropentadiene-g maleic anhydride copolymer, ethylene/propylene /2,5-norbornadiene-g-maleic anhydride copolymer, ethylene, /propylene-g-N-phenyl 7-reimide copolymer, ethylene/butene 1-g-N-phenylmaleimide co-IT [combined L water lily/' Examples include butageno g-maleic anhydride copolymer, styrene/maleic anhydride copolymer, and the like.

The blending amount of the modified polyolefin is 11% polyamide 10%
1 to 10011 parts per 011 parts, preferably 5 to 90f! Within the range of quantitative parts. If the amount is less than 1 part by weight, the resulting molded product will lack impact resistance, which is undesirable, and if it exceeds 100 parts by weight, the molded product will have insufficient heat resistance, which is undesirable.

The filler [C) in the present invention refers to glass fibers or beads, talc, kaolin, wollastonite, mica 2, lyca, alumina, diatomaceous earth, clay, Seifu, red iron, graphai 1, Examples include powdered or plate-like inorganic compounds such as titanium dioxide, zinc oxide, copper, and stainless steel, other polymer fibers (cooked fibers), and preferably glass fibers. Particularly preferable glass fibers include glass fiber strands and glass threads having a diameter of about 3 to 20 μm. The blending ratio of such filler needs to be in the range of 1 to 100 parts by weight, preferably in the range of 5 to 90 parts by weight, and particularly preferably in the range of 10 to 90 parts by weight, based on 1 part of copolymerized polyamide + ooffij. .

If the blending amount of the filler exceeds 100 parts, the fluidity during melting will deteriorate, making it difficult to injection mold the molded product, and the appearance of the molded product will also deteriorate, which is not preferred.

There is no particular restriction on the method of blending the filler into the copolyamide of the present invention, and any known method can be used. A specific example of the blending method is a method in which copolyamide pellets are triblended with a modified polyolefin and a filler, and this is melt-kneaded in a single screw or two-wheel screw extruder.

The automotive aredal hood parts of the present invention are molded by subjecting the boria 2-do compound to known molding methods such as injection molding, extrusion molding, blow molding, and vacuum forming. Examples of molded products include cooling pipes, lanator tanks, cylinder covers, oil pans, gears, valves, brake piping, fuel piping, other tubes, pipes, other exhaust gas system parts, connectors, etc. I can do it.

In addition, the molded parts obtained in this way are coated, steamed,
Secondary processing such as lamination can also be performed.

In addition, other ingredients such as pigments, dyes, heat resistant agents, catalysts, antioxidants, weathering agents, A lubricant, a crystal nucleating agent, an antistatic agent, a phasifying agent, other polymers, etc. can be added.

<Example> EXAMPLES The present invention will be explained in more detail with reference to Examples below.

The properties in the Examples and Comparative Examples were measured by the following method.

l) Melting point (Tm) Using DSC (PERKIN-ELMER7 pear),
Sample 8~I Omg heating rate 20℃/mI
The temperature showing the maximum value of the melting curve obtained by measuring n is (
r). Temperature increase rate of 8~lomg to 20'C
/mln and held at T+20°C for 5 minutes 1-1 Next,
Cool down to 30°C at a cooling rate of 20°C/min,
After holding at 30 °C for 5 min, again at 20 °C/m I
The sample was heated to T+20''C at a heating rate of n. The maximum value of the melting curve at this time was defined as the melting point (Tm).

2) Metal halide resistance test The underhood molded product was soaked in hot water at 90"C for 24 hours, and then left in a gear oven at 100"C.
One cycle consisted of spraying a 50% calumium chloride solution in the form of water droplets every hour, and the number of cycles until cracks appeared in the molded product was measured.

3) Appearance of molded product Inspect the surface of the molded product for roughness, air bubbles, color tone, gloss, etc. ○: Glossy and smooth surface.

△: The gloss is reduced, but the surface is smooth.

×: There is no gloss and the surface is rough.

4) Physical properties of the molded product were measured by the following method.

Tensile strength: ASTM-D638 Bending strength: ASTM-D790 Flexural modulus
: ASTM-D7') O1zod impact strength : ASTM-D256 Thermal Distortion Temperature (HDT)+
ASTM-D648 load 114.6kgf/am? Load: 8 kgr/cm2 <Implementation IFIII> 7.21 kg of terephthalic acid, 7.80 kg of a 64.5 wt% aqueous solution of hexamethylene diamine.

- 5.25 kg of caprolactam and ion-exchanged water 6.
After charging 10 kg into a 0.05 m' batch pressure polymerization strainer and thoroughly purging with nitrogen, the water vapor pressure was 17.5 kg.
Heating was continued under a pressure of /cm2-G. The temperature was raised to 230°C over 5 hours with stirring, and then further heated to 230°C to 245°C.
After allowing the reaction to proceed for 30 ml, the stirring was stopped and the lower order condensate was drawn out from the bottom of the polymerization vessel into water at a differential pressure of 17.5 kg/cm"G.The obtained lower order condensate was Tm- 303℃
, ηr=1. It was 21°. This lower condensate is 10
After vacuum drying at 0° C. for 24 hours, solid phase polymerization was carried out at 250° C. for 3 hours in an N2 blowing atmosphere using a Ni-Goo with a content edge of 301. The obtained dillimer is ηr-2.7
5, Tm = 303°C. This polymer tooj
Glass fiber tip strand 43ffN with a length of 3mm and a true diameter of 13μφ for the i placement part! 1 part and 2 moles of aquatic maleic acid, with a melt index of 0.
4g/10min ethylene/propyleno/butene-1-g
- After triblending 20ii parts of maleic anhydride copolymer, T
The mixture was melt-kneaded and pelletized at a temperature of m+20°C.

After vacuum-drying the pellets, they were molded using an injection molding machine under conditions of temperature Tm + 20°C and mold temperature 80°C.
TM standard physical property test piece, length 450mm, width 2
00 crystal m1 height 80mm, wall thickness a, 5mm
0) W/cylinder head cover was molded.

Using the molded piece obtained here, mechanical properties, heat distortion temperature,
Table 1 shows the results of evaluating resistance to metal halides.

<Implementation F12> 115.89 kg of terephthal, 6.37 kg of 64.5 wt% aqueous solution of hexamethylene diamine, hexamethylene ammonium (66 salt)] 0.00
kg and 6.66 kg of ion-exchanged water were charged into a 0.05 m' batch pressurized kettle, and a lower condensate was prepared in the same manner as in Example 1. The obtained lower condensate is Tm-296
℃, Qr-1,26. This lower condensate is 10
After vacuum drying at 0°C for 24 hours, melt extrusion was performed using a 30 mmφ vented two-wheel screw extruder at a temperature of +20°C to obtain a pellet with nr=3.25 and Tm=295°C. This beret, y) 1 part of 100ffii, glass fiber with a length of 3 mm, I [diameter of 13 μΦ, glass fiber strand 4311] containing 2 mole % of maleic anhydride, Meltoy/dexfug/10 minutes of ethylene /ethyl acrylate/m water maleic acid copolymer 20
tf1! After triblending the lt part, a molded article was made by the method of Example 1, and the results of evaluation are shown in Table 1.

<Examples 3 to 10> Example 1 or Example 11 was carried out by changing the Fi of the polyamide, the type of modified polyolefin, the type of filler, the blending amount, etc.
Table 1 shows the results of evaluating the characteristics of test pieces and molded products obtained by performing the same operations as in No. 112.

Comparative Example 1> Glass fiber reinforced nylon 66 Beregut (CM3001G
30: Toshi ■Product) 100ff [4311111 parts of glass fiber Cheebut strands with a length of 3 mm and a diameter of 13 μΦ were dry-breaded in the same manner as in Example 1 to prepare a test piece and a Linder head cover. Created. The chloride resistance of this molded article was 20M using Triblend L, and the fPI+ property was poor.

Table 1 shows the results of moldings made and evaluated.

Comparative example 2> Flexural modulus was low.

Nylon 12,100! A test piece and an underhood part were prepared in the same manner as in Example 1 by triblending 65 parts by weight of glass fiber strands with respect to 1 part by weight. When the physical properties of the obtained test piece were evaluated, it was found that the rigidity and heat distortion temperature were insufficient.

Comparative Example 3> 4311 parts of glass fiber strands having a length of 3 mm and a diameter of 13 μΦ were dry-breaded to 1 part of the highly polymerized pellet of Example 1, and a molded product was prepared by the method of Example 1. Table 1 shows the results of the evaluation. Impact resistance was low.

<Comparative Example 4> Contains 2 mol% of maleic anhydride based on 100 parts by weight of the highly polymerized peleb of Example 1, and has a melt index of 0.
4g/10min ethylene/propylene/butene-1-g
-Maleic anhydride copolymer <Effects of the invention> The gamma nodder hood parts for automobiles of the present invention have high rigidity and lit resistance.
It has high hardness and heat resistance, and also has good resistance to road antifreeze agents whose main ingredients are metallogen compounds such as carunium chloride and zinc chloride.

Claims (1)

[Claims] Repeating unit (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ And repeating units (II), (III), (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III)▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R is an aliphatic group with 6 to 18 carbon atoms, R' is a carbon number 4
~18 aliphatic groups or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ where n represents an integer from 5 to 18. ) and the weight ratio of (I)/[(II) or (III)] is 10/90 to 100/0.
An automobile underhood part formed by molding a mixture containing 1 to 100 parts by weight of B] and 1 to 100 parts by weight of filler [C].