JPH04323239A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition having improved compatibility between a polyolefin and an engineering plastics, and having good impact resistance, good rigidity, etc. CONSTITUTION:A resin composition comprises (A) a hydroxyl group-modified polyolefin resin prepared by introducing hydroxyl groups to a crystalline olefinic copolymer comprising at least one of ethylene and a 3-8C alpha-olefin and at least one of chained non-conjugated dienes, and (B) a polyamide resin or a saturated polyester resin.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition of a polyolefin resin and an engineering resin. More specifically, the present invention provides impact resistance, rigidity, heat resistance, moldability, and moisture resistance required for molding materials for automobile parts, electrical product parts, etc., which are made of a specific hydroxyl-modified polyolefin resin and polyamide resin or saturated polyester resin. sex,
The present invention relates to a resin composition having good basic properties of chemical resistance.

0002

[Prior Art] Polyolefin resins are widely used as molding materials because they are inexpensive and have excellent mechanical strength, moldability, and moisture resistance. For the purpose of improving heat resistance and rigidity, attempts have been made to blend engineering plastics such as polyamide resin into this material. Generally, polyamide, polyester and polyolefin are
They have poor compatibility, and simply mixing them in an extruder or molding machine will not result in a fine and homogeneous mixed state, resulting in a decrease in impact strength and the like, making it impossible to achieve the above objective. Therefore, as a method to improve compatibility, functional groups such as carboxylic acid and epoxy groups, which are expected to undergo bonding reactions with polyamides and polyesters, are introduced into polyolefins that have poor reactivity.
It has been proposed to blend this into polyamide or polyester as a modified polyolefin (for example, Japanese Patent Publication No. 30945/1983). Further, as a method for producing such modified polyolefin, for example, Japanese Patent Application Laid-Open No. 59-62613
The publication discloses a method of melt-kneading a polyolefin, an epoxy group-containing unsaturated compound, and an organic peroxide. However, in general, the radical grafting method does not have a sufficiently high grafting rate or grafting efficiency, and when trying to improve the degree of modification, there are problems such as undesirable reactions such as molecular cleavage and crosslinking of the backbone polymer to be grafted. There are some spots, and highly denatured products cannot be obtained. Compositions of modified polyolefin and polyamide or polyester obtained by these methods achieve a certain degree of fine dispersion and achieve the purpose of improving the balance of performance such as impact strength and heat resistance stiffness. The current situation is that further improvements are desired.

0003

SUMMARY OF THE INVENTION An object of the present invention is to provide a composition comprising a polyolefin resin and a polyamide resin or a saturated polyester resin, which has improved impact strength. Specifically, the objective is to find a new hydroxyl-modified polyolefin that has further improved compatibility with polyamide or polyester, and to obtain a composition with good miscibility that could not be achieved using conventional techniques.

0004

[Means for Solving the Problems] That is, the present invention provides a resin composition comprising the following components (A) and (B): component (A) at least one of ethylene or an α-olefin having 3 to 8 carbon atoms; at least one of a species and a linear nonconjugated diene
The present invention provides 90 to 10 parts by weight of a hydroxyl group-modified polyolefin resin in which hydroxyl groups are introduced into a crystalline olefin copolymer consisting of seeds; and 10 to 90 parts by weight of component (B) polyamide resin or saturated polyester resin. The specific hydroxyl-modified polyolefin resin used in the present invention is
Although it is not clear why the composition exhibits better performance than unmodified polyolefin resins or known hydroxyl-modified polyolefins, it is thought that it can be obtained as a highly modified product without significantly impairing the original performance of polyolefin resins. .

The present invention will be explained in more detail below. [Crystalline olefin copolymer] The crystalline olefin copolymer used in the present invention is ethylene or α having 3 to 8 carbon atoms.
- at least one olefin and the following general formula:

000
6]

[Formula 1] (wherein R1 is an alkyl group having 1 to 8 carbon atoms, R2, R3,
R4 and R5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and n is a number of 1 to 10. If the diene content of the copolymer is 0.
It is 1 to 30 mol%, preferably 0.5 to 15 mol%. The copolymer has crystallinity. The degree of crystallinity at room temperature measured by X-ray diffraction is preferably 10% or more, more preferably 20% or more, and has a melting point of 40° C. or more. A decrease in crystallinity results in a decrease in the modulus of the final composition. Further, this copolymer should have a sufficient molecular weight to be called a resin at room temperature. For example, if propylene is the main component, JIS-K-
If the melt flow rate measured in accordance with 6758 is 0.
01-500g/10min, preferably 0.05-100
The molecular weight corresponds to g/10 minutes, JIS-K-72
It is desirable that the elastic modulus according to 03 is 500 kg/cm2 or more. Examples of the above-mentioned ethylene and α-olefin that are constituent components of the copolymer include ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, and 4-methyl. -1-pentene, 3,3-dimethyl-1-butene, 4,4-dimethyl-1-pentene, 3-methyl-1-hexene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene ,
5-methyl-1-hexene, allylcyclopentane, allylcyclohexane, allylbenzene, 3-cyclohexyl-1-butene, vinylcyclopropane, vinylcyclohexane, 2-vinylbicyclo[2,2,1]-heptane, etc. Can be done. Among these, preferable examples include ethylene, propylene, 1-butene, 1-
hexene, 3-methyl-1-butene, 3-methyl-1-
Pentene, 4-methyl-1-pentene, 3-methyl-1
- hexene, etc., in particular ethylene,
Propylene, 1-butene, 3-methyl-1-butene, and 4-methyl-1-pentene are preferred. These α
- One type of olefin may be used, or two or more types may be used. In particular, when the α-olefin is 1-hexene, it is preferably used in combination with at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene, and 3-methyl-1-butene. When two or more types of α-olefins are used, the α-olefins may be randomly distributed in the unsaturated copolymer resin or may be distributed in blocks. In the linear nonconjugated diene represented by formula (1), preferably n is 5 or less, R4 and R5 are hydrogen atoms, and R1, R2, and R
Each of 3 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and not all of them are hydrogen atoms. Specific examples of preferred diene compounds are as follows. 4-
Methyl-1,4-hexadiene, 5-methyl-1,4-
1,4-dienes such as hexadiene, 1,5-heptadiene, 1,5-octadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, etc.
, 5-dienes, 1,6-octadiene, 6-methyl-
1,6-octadiene, 7-methyl-1,6-octadiene, 2-methyl-1,6-octadiene, 6-methylidene-1-octene, 6-ethyl-1,6-octadiene, 6,7-dimethyl- 1,6-octadiene, 1,6
-1,6-dienes such as nonadiene, 1,7-nonadiene, 7-methyl-1,7-nonadiene, 8-methyl-1
, 1,7-dienes such as 7-nonadiene, 8-methyl-
1,8-dienes such as 1,8-decadiene and 9-methyl-1,8-decadiene. Particularly preferred examples include 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 6-methyl-1, 6-octadiene and 7-methyl-1,6-octadiene. These dienes may be used alone or in combination of two or more. The crystalline olefin copolymer to be modified according to the present invention is produced by combining these ethylene or α-olefin with a linear non-conjugated diene using a Ziegler-Natta catalyst for α-olefin polymerization to produce an α-olefin polymer. Copolymerization can be carried out using similar methods and equipment. These chain nonconjugated dienes may be distributed randomly or in blocks in the copolymer. The content of non-conjugated diene is preferably 0.1 to 30 mol%, and 0.5
-15 mol% is more preferable. If the diene content is less than 0.1 mol%, a high degree of modification cannot be obtained when subjected to a hydroxyl group modification reaction. When the diene content exceeds 30 mol%, the reaction rate decreases and the production of low-crystalline by-product polymers increases, resulting in production problems such as decreased productivity. . Furthermore, when subjected to a hydroxyl group modification reaction, the performance of the final product deteriorates, probably because side reactions such as crosslinking and molecular scission of the copolymer itself tend to occur.

[Hydroxyl group-modified polyolefin resin] The hydroxyl group-modified polyolefin resin used in the present invention is obtained by introducing a hydroxyl group into the above crystalline olefin copolymer. The method of introduction is not particularly limited, but
For example, (1) the above olefin copolymer and a compound having an ethylenic double bond and a hydroxyl group in the same molecule, specifically 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, or 2-hydroxypropyl acrylate, etc. coexist. (2) a method of oxidizing the unsaturated bonds contained in the above olefin copolymer to convert them into hydroxyl groups; Oxidation via peracid with hydrogen oxide water and organic acid such as formic acid, oxidation with permanganate etc. in the presence or absence of a phase transfer catalyst, catalyzed by oxides such as osmium, ruthenium, tungsten etc. Oxidation with hydrogen peroxide, permanganate, etc., hydrolysis of adducts of hydrogen halides such as bromine,
(3) There are methods such as hydrolysis of epoxy groups introduced by various reactions. These reactions are generally carried out in a dissolved or molten state, but they can also be carried out in a swollen or suspended state. The content of hydroxyl groups is 0.1% by weight in terms of 2-hydroxyethyl methacrylate.
The content is preferably 0.5% by weight or more. In the present invention, the hydroxyl group-modified polyolefin resin can contain the above crystalline olefin copolymer that has been subjected to modification conditions or unmodified without being subjected to modification conditions. Other olefin polymers having the same main components as the crystalline olefin copolymer can be included. Typical examples of other olefin polymers include polypropylene resins from the viewpoints of moldability, rigidity, and economic efficiency.

[Polyamide resin or saturated polyester resin] The polyamide resin used in the present invention includes hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2,2,4- or 2,4,4-trimethylhexamethylene diamine, 1 , 3- or 1,4-bis(aminomethyl)cyclohexane, bis(p-aminocyclohexylmethane), m- or p-xylylenediamine, and aliphatic, alicyclic or aromatic diamines, adipic acid, suberin. polyamide obtained by polycondensation with a dicarboxylic acid such as sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, or a derivative thereof, polyamide obtained from a lactam such as ε-caprolactam, ω-laurolactam, ε-aminocaproic acid, 11 - polyamide obtained by condensation of aminoundecanoic acid,
Examples include mixtures of these polyamides. Specifically, they are polycaproamide, polyhexamethylene adipamide, polyhexamethylene sebamide, polydodecanamide, and copolyamides containing these as main components. Preferred are polycaproamide (nylon 6) and polyhexamethylene adipamide (nylon 66), which have excellent melting point, rigidity, and moldability, and have a large improvement effect on polyolefins. There is no particular restriction on molecular weight, but it is usually determined by relative viscosity (JIS
K-6810) A polyamide in the range of 2 to 5 is used. Elastomer-reinforced polyamides, such as those known as tough nylons, can also be used if desired. Further, polyamides containing various fibers such as glass fibers and various inorganic fillers such as talc can be used.

The saturated polyester resin used in the present invention is a thermoplastic saturated polyester obtained by polycondensation of dicarboxylic acid or its lower alkyl ester, acid halide, or acid anhydride derivative with glycol. Specific examples of dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, sebacic acid, terephthalic acid, isophthalic acid, p-carboxyphenoxyacetic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, etc. Can be mentioned. As a specific example of glycol, carbon number 2
~12 linear alkylene glycols, such as ethylene glycol, 1,3-propylene glycol, 1,4-butene glycol, 1,6-hexene glycol, pyrocatechol, resorcinol, hydroquinone, cyclohexanedimethanol, or alkyls of these compounds There are substituted derivatives. Suitable polyesters include polyethylene terephthalate, polybutylene terephthalate,
Examples include polynaphthalene terephthalate and poly(1,4-cyclohexane dimethylene terephthalate). Liquid crystalline polyester, such as Eastman Kodak's X
Also preferred are those commercially available under trade names such as 7G, Hoechst Celanese's Vectra, and Sumitomo Chemical's Econol. Elastomer-reinforced polyester can also be used if desired. Further, polyester containing various fibers such as glass fibers and various inorganic fillers such as talc can also be used. Polyamide resin or polyester resin is
It can be selected from the viewpoints of heat resistance, rigidity, moldability, moisture resistance, etc., or economic efficiency. It is also possible to use both together.

[Additional Components] The resin composition according to the present invention may contain other additional components. for example,
Well-known additives such as antioxidants, weatherability improvers, crystallization promoters, flame retardants, plasticizers, and fluidity improvers can be used for each component. Furthermore, addition of organic or inorganic fillers, particularly glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate, and silica, is effective in improving rigidity, heat resistance, and dimensional accuracy. Furthermore, various elastomers can be added for the purpose of reinforcing impact resistance. Examples include styrene-butadiene block or random copolymers and their hydrides, ethylene propylene (diene) copolymers, polyester elastomers, polyamide elastomers, and nitrile rubber. In order to improve the lack of affinity with the constituent components, they can be used after being modified by known methods such as acid modification, hydroxyl modification, and epoxy modification. The blending amount of the elastomer varies depending on the target performance, but when the objective of the present invention is to achieve a balance between rigidity and impact strength, the resin component of the composition 100%
It is preferable to limit the content to 20 parts by weight or less.

[Composition ratio of constituent components] The composition ratio of component (A) hydroxyl-modified polyolefin resin and component (B) polyamide resin or saturated polyester resin in the present invention is as follows:
They mix well no matter what the value is, but in general, when a hydroxyl group-modified polyolefin resin is the main component, the heat resistance of the polyolefin is improved. Furthermore, when polyamide or polyester is the main component, moisture resistance and moldability are improved. A component obtained by harmonizing the features of both of these components (A
) The ratio of the hydroxyl-modified polyolefin resin to the component (B) polyamide resin or saturated polyester resin is 90:10 to 10:90, preferably 70:30 to 30 by weight.
It is in the range of 70 vs.

[Production method of resin composition] The mixing method for obtaining the resin composition of the present invention is not particularly limited, and any known method that is generally put into practical use can be adopted. . For example, powdered, granular, and fibrous components are uniformly mixed with a mixer such as a Henschel mixer, if necessary, along with the formulations described in the additional components section, and then mixed using a single-screw or multi-screw extruder. A typical method is melt-kneading. Moreover, the final composition can be obtained by not mixing each component all at once, but by sequentially mixing them according to a designed blending ratio. This method is effective when it is necessary to control deterioration or alteration of the resin by controlling miscibility and adjusting the kneading history of specific components. Furthermore, mixing all or some of the constituent components in a solution state is also an effective method for the same purpose.

[0013]

[Examples] The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples unless the spirit thereof is exceeded. The properties of the compositions of Examples and Comparative Examples were measured and evaluated by the following methods. (1) Manufacture of composition: dry ingredients in a predetermined amount,
Using a Labo Plast Mill kneading machine manufactured by Toyo Seiki Seisakusho, 26
After melt-kneading at 0° C., the mixture was pulverized to obtain a powdered sample. (2) Preparation of sample piece: After obtaining a sheet by pressure forming at 280° C. using a hydraulic press molding machine manufactured by Toyo Seiki Seisakusho, predetermined test pieces were cut out. (3) MFR (melt flow rate): JIS K-
6758. (4) Impact resistance strength: ISO R180-1969 (J
According to IS K7110) non-notched Izod impact strength, three 2 mm thick test pieces were stacked and fixed with cellophane tape, and measured using an Izod impact tester manufactured by Toyo Seiki Seisakusho. (5) Evaluation of mixed state: A part of the test piece obtained in (2) above was cut out, ion-etched, and then the dispersed particle size was observed using a scanning electron microscope (manufactured by Hitachi, Ltd., S-2400).

Reference Example 1 Production of Crystalline Olefin Copolymer After purging an autoclave with a capacity of 1 liter with propylene, 330 ml of n-heptane was introduced, and 0.1 g of triethylaluminum and 0.07 g of magnesium-containing solid titanium were added in this order. I added it. Then 125Nml of hydrogen
After adding the
/cm2G, and further 7-methyl-1,
Add 70 ml of 6-octadiene, and while pressurizing propylene, maintain at 65°C and 5.5 kg/cm2G.
Time polymerization was performed. Thereafter, the catalyst was inactivated with n-butanol, the catalyst residue was extracted with water, and the copolymer was collected by centrifugation and dried. MFR at 230℃ is 1.7
g/10 min, 7-methyl-1,6-octadiene content 2
．． 7 mol%, mainly 1,2 addition bonds (H-NM
A crystalline propylene copolymer with a crystallinity of 45% (X-ray diffraction method) was obtained.

Reference Example 2 Synthesis of hydroxyl group-modified polyolefin resin (A-1) 250 g of the crystalline olefin copolymer obtained in Reference Example 1 and 2
- 75 g of hydroxyethyl methacrylate in xylene 5 g in a 10 liter stirred flask, which had been previously purged with nitrogen.
000 ml and stirred and dissolved at 110°C. Furthermore, 25g of benzoyl peroxide and 500ml of xylene
1 solution was added dropwise over 2 hours, and the mixture was reacted at 110° C. for 3 hours. The obtained product was poured into cold acetone to precipitate, filtered, washed, and dried to obtain a 2-hydroxyethyl methacrylate graft-modified polypropylene resin. The 2-hydroxyethyl methacrylate content of this resin was 2.0% by weight (infrared absorption method), and the MFR at 230°C was 4.1 g/10 minutes.

Reference Example 3 Synthesis of hydroxyl group-modified polyolefin resin (A-2) In Reference Example 2, the amount of benzoyl peroxide was 40%.
A hydroxyl-modified polypropylene resin was obtained in the same manner as in Reference Example 2, except that g was used instead. 2-hydroxyethyl methacrylate content 3.2% by weight, MFR 1.8g/10
It was a minute.

Reference Example 4 Synthesis of hydroxyl-modified polypropylene (A-3) In Reference Example 2, instead of the crystalline olefin copolymer,
Polypropylene (manufactured by Mitsubishi Yuka, product name TA8, MF
A hydroxyl-modified polypropylene was obtained in the same manner as in Reference Example 2 except that R was 0.9 g/10 min). 2-hydroxyethyl methacrylate content 0.9% by weight, MFR
was 17.4 g/10 minutes.

Example 1 Hydroxyl-modified polyolefin resin (A-1) obtained in Reference Example 2
) and 22.5 g of polycaproamide (polyamide-6 manufactured by BASF, trade name Ultramid KR4411), which had been previously vacuum-dried at 80°C for 15 hours, were melt-kneaded using a Labo Plus Mill to obtain a composition. . The resulting composition exhibited an impact strength of 5.0 kgf·cm/cm 2 , and it was observed that the polyamide existed uniformly as a fine dispersed phase of 1 to 2 microns.

Comparative Examples 1 and 2 Hydroxyl group-modified polyolefin resin (A-
1) Polypropylene (manufactured by Mitsubishi Yuka, trade name
MA4, MFR 12g/10min)
A composition was obtained in the same manner as in Example 1. The impact strength of the resulting composition was as low as 2.5 kgf·cm/cm2, and it was observed that the polyamide existed as coarse particles of 10 microns or more. Moreover, the impact strength of the composition obtained in the same manner as in Example 1 except that the hydroxyl-modified polypropylene (A-3) obtained in Reference Example 4 was used in place of the resin (A-1) was 3. 0 kgf·cm/cm2, and the size of the polyamide dispersed phase was about 3 microns.

Example 2 Hydroxyl-modified polyolefin resin (A-2) obtained in Reference Example 3
) A composition was obtained in the same manner as in Example 1 except for using the following. The resulting composition has an impact strength of 4.7 kgf・cm/c
m2, and the polyamide was found to exist uniformly as a fine dispersed phase of about 1 micron.

Example 3 Hydroxyl-modified polyolefin resin (A-2) obtained in Reference Example 3
)9g, polypropylene (manufactured by Mitsubishi Yuka, trade name MA
4) A composition was obtained by melt-kneading 13.5 g and 22.5 g of polycaproamide (polyamide-6 manufactured by BASF, trade name Ultramid KR4411), which had been previously vacuum-dried at 80° C. for 15 hours, using a laboplasto mill. Ta. The resulting composition exhibited an impact strength of 8.1 kgf·cm/cm 2 , and it was observed that the polyamide existed uniformly as a fine dispersed phase of 1 to 3 microns.

Example 4 Hydroxyl group-modified polyolefin resin (A-1) obtained in Reference Example 2
) 22.5g and polybutylene terephthalate (manufactured by Mitsubishi Kasei Corporation, trade name
A composition was obtained by melt-kneading 22.5 g of Novadol 50101) using a Labo Plasto Mill. The resulting composition exhibited an impact strength of 7.5 kgf·cm/cm 2 , and it was found that the polyester component existed uniformly as a finely dispersed mixture of about 1 micron.

Comparative Example 3 Hydroxyl-modified polyolefin resin (A-
1) Polypropylene (manufactured by Mitsubishi Yuka, trade name
MA4, MFR 12g/10min)
A composition was obtained in the same manner as in Example 4. The impact strength of the resulting composition was as low as 2.4 kgf·cm/cm2, and the polyester component was observed to exist as coarse particles of 50 microns or more.

[0024]

Effects of the Invention As shown in the Examples and Comparative Examples, component (A) a crystalline olefin consisting of ethylene or at least one α-olefin having 3 to 8 carbon atoms and at least one chain nonconjugated diene; Hydroxyl-modified polyolefin resin, which has hydroxyl groups introduced into the copolymer, has good miscibility when blended with component (B) polyamide resin or saturated polyester resin, which is expected from the composition of component (A) and component (B). In addition to good mechanical performance, it has good impact resistance, so it can be used in a wide range of applications such as automobile parts and electrical parts.

Claims (1)

[Claims] [Claim 1] A resin composition comprising the following components (A) and (B): component (A) ethylene or 3 carbon atoms;
90 to 10 parts by weight of a hydroxyl-modified polyolefin resin in which a hydroxyl group has been introduced into a crystalline olefin copolymer consisting of at least one α-olefin of ~8 and at least one chain nonconjugated diene; Component (B) polyamide 10 to 90 parts by weight of resin or saturated polyester resin.