JPH04120170A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition, excellent in heat resistance, mechanical, water absorption and dimensional characteristics with a low specific gravity by blending nylon 46 resin with a specific modified polymethylpentene in a specified amount. CONSTITUTION:A resin composition is obtained by blending (A) 100 pts.wt. nylon 46 resin having 0.8-1.9, preferably 1-1.5 intrinsic viscosity with (B) 2-100 pts.wt. modified polymethylpentene which is a crystalline polymer, having 230 deg.C melting point and 0.5-2.5 intrinsic viscosity and containing carboxylic acid groups or derivatives thereof in the molecular chain thereof.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a resin composition, and more specifically, a polytetramethylene azimuth resin composition that exhibits excellent heat resistance, mechanical properties, water absorption properties, and dimensional properties and has a low specific gravity. The present invention relates to a pamid (nylon 46) resin composition.

[Prior art] Nylon 46 obtained from tetramethylene diamine or its functional derivative and adipic acid or its functional derivative
resin is known.

This nylon 46 resin has excellent heat resistance, tensile strength,
Because it has excellent mechanical properties such as bending strength and sliding properties, it is considered to have great value as a useful engineering plastic.

However, this nylon 46 resin has a higher proportion of amide groups than ordinary polyamide resins such as nylon 6 resin and nylon 66 resin, and therefore has a drawback in that its water absorption rate is higher than those. This means that although nylon 46 resin has better heat resistance and mechanical properties than ordinary polyamide resins in the dry state immediately after molding, it has a higher water absorption rate than ordinary polyamide resins during actual use. Although the properties are further improved, the decrease in heat resistance and mechanical properties is greater than the above, and in some cases, the superiority of nylon 46 resin may be lost. Also, like ordinary polyamide resins, the dimensions of molded products of nylon 46 resins change due to water absorption.

Nylon 46 resin has a high degree of crystallinity, so the rate of dimensional change per water absorption rate is smaller than that of normal polyamide resin, but the degree of dimensional change due to water absorption is not at a satisfactory level due to its high water absorption rate. .

As a means to improve the water absorption of polyamide resins, it is widely used to add non-water absorbing polymers, reinforcing materials, fillers, etc. However, an important advantage of using plastics such as polyamide resin for various U43TI parts is that their specific gravity is low, and as well as the addition of reinforcing materials and fillers mentioned above, polyamide resin is an aliphatic polymer. Therefore, even when other polymers are blended, the specific gravity often increases. There is a great demand for weight reduction in the field of various structural parts, and it is necessary to reduce the specific gravity of nylon 46 resin and improve its water absorption.

When an olefin polymer is blended with polyamide resin, its water absorption is improved and its specific gravity is also reduced. nylon 4
Regarding 681 fat, a composition containing an olefin polymer, mainly a copolymer using ethylene or α-olefin, is disclosed in JP-A-61-188461.62-179562.
．． 63-75047, Japanese Unexamined Patent Publication No. 2-28256, etc. However, nylon 46 resin is nylon 6
, has a higher melting point than ordinary polyamides such as nylon 66, and has a molding temperature of 300° C. or higher, so there is a problem that the heat resistance of olefin-based polymers is insufficient.

[Object of the invention] The present invention was made in the light of the above-mentioned circumstances, and
The purpose is to maintain the excellent heat resistance and mechanical properties of nylon 46 resin, improve its water absorption properties and dimensional properties, and lower its specific gravity.

[Structure of the Invention] The present inventors have conducted extensive research to achieve the above-mentioned objects, and have discovered that a composition in which a specific polymer is blended with nylon 4681 resin satisfies the above-mentioned objects, and have thus arrived at the present invention. did.

That is, the resin composition of the present invention comprises (A) nylon 46
<8 per 100 weight M parts of resin Modified polymethylpente containing a carboxylic acid group or its derivative in the molecular chain 22-10
This is a resin composition containing 0 parts by weight.

The present invention will be explained.

The nylon 46 resin as component (A) used in the present invention is mainly a polyamide obtained by a synthesis reaction using adipic acid or its functional Xs form as an acid component and tetramethylene diamine or a functional derivative thereof as an amine component. However, a part of the adipic acid component or tetramethylenediamine component may be replaced with a copolymerized component of Haku.

A preferred embodiment of the nylon 46 resin is disclosed in Japanese Patent Application Laid-Open No. 561494.
30 and Japanese Unexamined Patent Publication No. 149431/1983.

The intrinsic viscosity of the nylon 46 resin used in the present invention is -
0.80 to 1 when measured at 35°C using monocresol
．． 90, more preferably in the range of 1.00 to 1.50.

If a nylon 46 resin with an intrinsic viscosity exceeding 1.90 is used, the fluidity of the composition in the molten state will be poor, and the resulting molded product will not only lose its glossy appearance, but also have poor mechanical and thermal properties. This is not preferable because the variation becomes large.

An intrinsic viscosity lower than 0.80 has the disadvantage that the mechanical strength of the composition is reduced.

Even if attempts were made to blend polymethylbentene into Nine 46 resin, the compatibility between the two was extremely poor and good molded products could not be obtained. However, when modified polymethylpentene containing a carboxyl M group or its derivative in the molecular chain as component (B) of the present invention is used, both can be mixed uniformly, and the resulting nylon 46 resin composition has a heat resistant While maintaining the properties and mechanical properties, the water absorption properties and dimensional properties are improved, and the specific gravity is also lowered.

This component (B), a modified polymethylbentene containing carbon MW or its derivative in the molecular chain, is produced by homopolymerization of 4-methyl-1-pentene or by combining 4-methyl-1-pentene with other α-olefins, such as ethylene and propylene. , 1-
Butene, 1-hexene, 1-octene, 1-decene, 1
- 2 to 2 carbon atoms such as tetradecene, 1-octadecene, etc.
It is a copolymer with 0 α-olefin, and the main component is a polymer mainly composed of 4-methyl-1-pentene, which usually contains 85 mol% or more of 4-medyl-1-pentene, and carbon Ill and its derivatives. , for example, represents a copolymer into which a monomer component having at least one functional group selected from a carboxylic acid metal base, a carboxylic ester group, an acid anhydride group, and an acid amide group is introduced, Preferably melting point is 230°C, intrinsic viscosity (decalin, 135°C)
It is a crystalline polymer with a diameter of 0.5 to 2.5.

A method for modifying polymethylpentene by introducing an 11m component having a carboxylic acid group or its derivative is a method of copolymerizing it with 4-methyl-1-pentene, or a method of copolymerizing polymethylpentene with 4-methyl-1-pentene;
-Methyl-1-pentene).

Examples of monomers with functional groups that can be copolymerized include:
Maleic anhydride, maleic acid, fumaric acid, maleimide,
Maleic acid hydrazide, reaction product of maleic anhydride and diamine, maleic acid amide, soybean oil, sesame oil, rapeseed oil,
Natural oils and fats such as peanut oil, camellia oil, olive oil, coconut oil, sardine oil, acrylic acid, crotonic acid, butenoic acid, vinyl acetic acid, methacrylic acid, pentenoic acid, angelic acid,
Tiburic acid, 2-pentenoic acid, 3-pentenoic acid, α-ethyl acrylic acid, β-methylcrotonic acid, 4-pentenoic acid, 2-hexenoic acid, 2-methyl-2pentenoic acid, α-
edylcrotonic acid, 2,2-dimethyl-3-butenoic acid,
2-heptenoic acid, 2-octenoic acid, 4-decenoic acid, 9-
undecenoic acid, 10-undecenoic acid, 4-dodecenic acid,
5-dodecenoic acid, 4-tetradecenoic acid, 9-tetradecenoic acid, 9-hexadenoic acid, 2-octadecenoic acid, 9-
Octadecenoic acid, icosenoic acid, tocosenoic acid, erucic acid, tetracosenoic acid, mycolipenic acid, 2.4-pentadienoic acid, 2.4-hexadienoic acid, diallylacetic acid, geranic acid, 2.4-decadienoic acid, 2.4- Dodecadienoic acid, 9.12-hexadecadienoic acid, 9.12-octadecadienoic acid, hexadecatrienoic acid, linoleic acid,
lyrinic acid, octadecatrienoic acid, icosadienoic acid,
Icosatrienoic acid, icosatetraenoic acid, ricinoleic acid, eleostearic acid, oleic acid, icosapentaenoic acid, erucic acid, docosadienoic acid, docosatrienoic acid, docosatetraenoic acid, docosapentaenoic acid, tetracosenoic acid, hexacosanoic acid 1. Examples thereof include unsaturated carboxylic acids such as hexacosenoic acid, octacosanoic acid, and traalonthenic acid, and their esters, acid amides, and anhydrides. Two or more kinds of compounds may be used simultaneously for modifying polymethylpentene.

In addition, the introduction ω of the monomer component having a functional group is 0.001 to 10 mol%, preferably 0.01 to 10% by mole based on the total constituent components.
It is 5 mol%. If the amount introduced is less than 0.001 mol%, the effect of compatibilizing the nylon 46 resin and polymethylpentene will not be sufficient, and if it is more than 10 mol%, the stability of the modified polymethylpentene will decrease, resulting in gelation, etc. This is not preferred because side reactions are likely to occur.

A method for modifying polytetramethylpentene by grafting can be carried out using poly(4-methyl-1-pentene), a monomer component having the above-mentioned functional group, and a radical-generating compound. One method can be used, such as a method of homogeneously mixing with a mixer etc. and kneading with nylon 46 resin, or a method of melt-kneading with an extruder and pelletizing in advance.
A method of pelletizing the poly(4-methyl-1-pentene) in advance using an extruder is effective because of the uniformity of modification of the poly(4-methyl-1-pentene).

As the radical-generating compound, known compounds used for generating radical species can be used. In this case, it is necessary that the radical-generating compound has a sufficient half-life for effective R to remain until the poly(4-methyl-1-pentene) melts. Examples of radical-generating compounds include peroxides and the following general formula <I) I R4 (R+ to R6 each independently represent an alkyl group having 1 to 8 carbon atoms,
These are alkoxy groups and aryl groups having 1 to 8 carbon atoms, and they may further have functional groups such as carboxyl groups, hydroxyl groups, amide groups, thiol groups, and glycidyl groups. ) can be mentioned. As peroxides, di(2,4-dichlorobenzoyl) peroxide, t-butyl peroxide, di(3,5,5-trimethylhexanol) peroxide, dilauroyl peroxide, didecanoyl peroxide, Dibenzoyl peroxide, t-butylperoxy-2-ethylhexoate, t-butylperoxydiethyl acetate, t-butylperoxyisobutyrate, 1.1-
Di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylperoxyisopropol carbonate, t-butylperoxy-3,3,5-trimethylhexoate, t-butylperacetate, t-butylperoxy-3,3,5-trimethylhexoate, t-butylperoxy-3,3,5-trimethylcyclohexane -Butyl perbenzoate, 4.4-di-t-butylperoxyparerianic acid butyl ester, 2.2-di-t-butylperoxybutane, dicumyl peroxide, t-
Butylcumyl peroxide, 1,3-di(t-butylperoxyisopropyl)penzole, diisopropylpenzole monohydroperoxide, cumol hydroperoxide, t-butylhydroperoxide, p
-menthyl hydroperoxide, vinylane hydroperoxide, etc., and examples of the compound represented by the above general formula (I) include 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4 -Diphenylhexane, 2,2,3,3-thiedraphenylbutane, etc. are examples, but the reaction starts at a relatively high temperature of 200°C or higher, so the efficiency of modification is high, and there is less excessive attack on the polymer, so crosslinking , 2,3-dimethyl-2,3-diphenylbutane is preferred because it does not cause gelation or the like.

The blending amount of the monomer component having a carboxylic acid group or its derivative and the radical-generating compound used for the modification of poly(4-methyl-1-pentene) is as follows:
- pentene) per 100 executives, the former is 0.05 to 10
The important part is 0.005 to 2 parts by weight. When the amount of the former compound is less than 0.05 parts by weight, the effect of modification is small, and when it exceeds 10 parts by weight, the molecular weight of the polymer, including poly(4-methyl 1-pentene) and nylon 46 resin, is reduced. This is undesirable as it causes a decline.

Furthermore, when the amount of the radical-generating compound blended is 0.005 parts by weight without swirling, sufficient denaturation is not achieved, and when it exceeds 2 parts by weight, not only is the effect no longer promoted by increasing the amount blended, but the polymer This is not desirable because it increases the excessive reaction to

The amount of modified polymethylpentene containing a carboxylic acid group or a derivative thereof in the molecular chain of component (B) in nylon 46 resin is 2 to 100 parts by weight per 100 parts by weight of nylon 46 resin.
It is 100 parts by weight. When this blending amount is less than 21 parts, the desired effect of improving water absorption properties etc. is not sufficient.
If the amount exceeds 100 parts by weight, the excellent heat resistance of nylon 46 resin can no longer be maintained.

Pigments and other compounding agents may be added to the resin composition of the present invention in the desired amount. Such compounding agents include fillers such as glass fibers, aramid fibers, and carbon! Miscellaneous, steel fiber, asbestos, ceramic fiber,
Fibrous materials such as potassium titanate whiskers and boron whiskers, powdered, granular or plate-like inorganic fillings such as kaolin, clay, wollastonite, tar, mica, calcium carbonate, barium sulfate, glass peas, glass peaks, etc. An example is wood.

These fillers are usually blended as reinforcing materials, surface modifiers, or for the purpose of modifying electrical and thermal properties. It should be blended at a moderate amount without losing its excellent properties and molding advantages.

In addition, flame retardants such as brominated polystyrene, brominated polyphenylene ether, brominated epoxy, brominated bisphenol-A-diglycidyl ether and its oligomers, polycarbonate oligomers produced using brominated bisphenol-8 as raw materials, brominated biphenyl ether, Brominated cyphthalimide compound, 2f of chlorinated hexapentadiene! Halogen-containing compounds such as red phosphorus and triphenyl phosphate; phosphorus-nitrogen compounds such as phosphonic acid amide; triazine compounds such as melamine, melam, melem, melon, cyanuric acid, and melamine cyanurate; hydroxide Metal hydroxides such as aluminum, magnesium hydroxide, dawsonite, and gypsum dihydrate, and flame retardant aids used in combination with or alone with the above halogen-containing compounds, such as antimony compounds such as antimony trioxide, boron oxide, oxidized It is possible to mix metal oxides such as iron.

Furthermore, copper compounds such as copper iodide,
Antioxidants or heat stabilizers such as hindered phenol compounds, aromatic amine compounds, organic phosphorus compounds, and sulfur compounds may also be added. Furthermore, various epoxy compounds, oxazoline compounds, etc. may be added for the purpose of improving melt viscosity stability and hydrolysis resistance. Examples of epoxy compounds include bisphenol-A type epoxy compounds obtained by reacting bisphenol-A and epichlorohydrin, aliphatic glycidyl ethers obtained by reacting various glycols or glycerol with epichlorohydrin, novolak-type epoxy compounds, aromatic Preferred are group or aliphatic carboxylic acid type epoxy compounds, alicyclic compound type epoxy compounds, etc. As the oxazoline compound, aromatic or aliphatic bisoxazolines, especially 2.2'-
Bis(2-oxazoline) and 2,2′-a-phenylenebis(2-oxazoline) are preferred.

Other stabilizers, colorants, lubricants, ultraviolet absorbers, and antistatic agents can also be added.

Furthermore, in small proportions other thermoplastic resins, such as other polyamide resins, polyesters, polyphenylene sulfide resins, polyphenylene ether resins, polycarbonate resins, phenoxy resins, polyethylene and its copolymers, polypropylene and its copolymers , polystyrene and its copolymers, acrylic resins and acrylic copolymers, polyamide elastomers, polyester elastomers, etc.; thermosetting resins, such as enol resins, melamine resins, unsaturated polyester resins, silicone resins, etc. good.

Any blending method can be used to obtain the resin composition of the present invention.

Generally, it is preferable to disperse these ingredients more uniformly, and there are methods in which all or part of them are mixed simultaneously or separately in a mixer such as a blender, kneader, roll, extruder, etc. to homogenize, or in a mixing part. A method can be used in which a part of the components are mixed simultaneously or separately using, for example, a blender, kneader, roll, extruder, etc., and then the remaining components are mixed and homogenized using these mixers or extruders. Furthermore, there is a method of melt-kneading a pre-triblended composition in a heated extruder to homogenize it, extruding it into a wire shape, and then cutting it into a desired length and granulating it.

The molding composition thus prepared is normally kept in a sufficiently dry state and then put into a molding machine hopper and subjected to molding. Furthermore, it is also possible to tri-blend the constituent raw materials of the composition, directly charge the mixture into the hopper of a molding machine, and melt-knead the mixture in the molding machine.

[Examples] The present invention will be explained in detail below using Examples. In addition, various characteristics in the examples were measured by the following methods.

(1) Mechanical strength: Tensile test: Based on ASTM D638.

Impact test: 8 STM D256 (Izot, with notch, thickness 3.2 mm) (2 Heat distortion temperature: Compliant with ASTM D 648. (Load m 4.6)
kMcd) (3) Water absorption characteristics, dimensional characteristics: Calculated from the amount change and dimensional change after being left in an atmosphere of 80°C and 95% relative humidity for 5 hours. (molded product; flow direction 1
000111X Right angle direction 60emx Thickness 1.51Il1
1 film gate) (4) Specific gravity: Based on JIS K7112. (Method A: Substitution method in water) (5) Intrinsic viscosity: Measured at 35° C. using an Ostold viscometer using ■-cresol as a solvent.

Modification of polymethylpentene Poly(4-methyl 1-pentene) dried at 130°C for 5 hours (“TPX MxOO4” manufactured by Mitsui Petrochemicals ■)
100 parts anhydrous maleic MO, 3 parts by weight and 2.3 parts
-Dimethyl-2,3-diphenylbutane (0.03 portions) was melt-kneaded at 280° C. using a vented twin-screw extruder with screw diameters of 44 g+m each, and then pelletized.

Examples 1 to 2, Comparative Examples 1 to 3 Nylon 46 resin (rsTANYL
MXOO
4J (manufactured by Mitsui Petrochemical @) at the proportions shown in Table 1.
After uniformly mixing with a tumbler in advance, screw diameter 44
Using a vented twin-screw extruder (No. 1), vacuum the cylinder temperature at 330°C and screw rotation speed at 160 rE).
The mixture was melt-kneaded at LDffi output H140 ko/h, and the thread discharged from the die was cooled and cut to obtain a pellet for molding.

Next, using this pellet, the cylinder temperature was 300°C, the mold temperature was 120°C, and an injection molding machine with an injection capacity of 5 ounces was used.
Molded articles for each property measurement were molded under the conditions of an injection pressure of 800 k (1/l:i), a cooling time of 15 seconds, and a total molding cycle of 40 seconds.

Each characteristic was measured using these molded products. Molded products should be kept at 23℃ and relative humidity 1 in accordance with JIS K7100 before measurement.
! ! Conditioning was carried out in a 50% atmosphere for 88 hours.

The results are shown in Table-1. Nylon 46 resin is a resin with excellent mechanical properties such as impact strength and heat resistance expressed by HDT, but has the disadvantage of high water absorption and a large dimensional change rate (Comparative Example 1). In order to improve the water absorption and dimensional properties of this resin, poly(4-methyl-
Even if 1-pentene) is blended, kneading is difficult due to poor compatibility between the two, and the mechanical properties of the resulting molded product are also extremely low (Comparative Example 2). However, when poly(4-methyl-1-pentene) modified by the above method is blended with nylon 46 resin, the compatibility between the two is greatly improved and extrusion and molding can be performed in good condition, resulting in a molded product. The characteristics of
It shows good tensile elongation, and the impact strength and HDT well maintain the values of the nylon 46 resin itself (Example 1
~2). Its water absorption and dimensional characteristics are also greatly improved compared to nylon 46 resin, and its specific gravity is also lower.
It can be seen that the composition is the object of the present invention.

Claims (1)

[Claims] 1. A resin composition comprising (A) 2 to 100 parts by weight of modified polymethylpentene containing a carboxylic acid group or a derivative thereof in its molecular chain per 100 parts by weight of nylon 46 resin. thing.