JPH0657062A - Resin composition and molded article using the same - Google Patents

Abstract

PURPOSE:To provide a heat reversible crosslinkable resin composition having an extremely high crosslinking formation reaction rate and crosslinking dissociation reaction rate and a molded article using the same composition. CONSTITUTION:A resin composition comprises (a) a modified polyolefin which is a modified polyolefin onto which at least one unsaturated carboxylic anhydride is grafted wherein the component concentration of an unsaturated carboxylic anhydride group in the modified polyolefin is 0.1-20wt.%, (b) a polyhydric alcohol compound containing at least two hydroxyl groups in the molecule and (c) a reaction promoter wherein the molar ratio of the hydroxyl group unit in the polyhydric alcohol compound to the unit derived from the unsaturated carboxylic anhydride in the modified polyolefin is 0.01-10 and the amount of the reaction promoter is 0.001-20 pts.wt. based on 100 pts.wt of the modified polyolefin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a crosslinkable resin composition and a thermoreversible crosslinkable molded article using the composition.

[0002]

2. Description of the Related Art For the purpose of improving the practical physical properties of resins, it is generally frequently used to improve the physical properties such as heat resistance and mechanical strength by introducing a cross-linking structure into the resin to increase the cohesive force of the resin. ing. However, the resin having the cross-linked structure introduced therein easily gels and has a problem in moldability. Therefore, conventionally, the crosslinking step has been performed after the molding is completed. Specific methods include irradiation with radiation and application of a reaction utilizing water in the air. However, these methods have problems in that they are not crosslinked immediately after molding and in terms of cost. Also, from the standpoint of environmental protection and resource saving, it is becoming more and more required to recycle molded products, molded punched parts and burrs.
The resin once the cross-linked structure has been introduced is extremely difficult to recycle and has been a problem.

Various methods have been proposed so far in order to solve these problems. Most of them are resins in which the crosslinking is dissociated during molding, and the crosslinking is carried out upon cooling and solidification after molding. For example, US Pat. No. 3,264,272.
No. 3267083, No. 3789035 and No. 3
As described in Japanese Patent No. 997487, a resin is quasi-crosslinked by introducing a carboxylic acid group into the resin, and using this as a metal salt, and US Pat. No. 3,328,36.
As described in No. 7 and No. 3471460, it has been proposed to introduce a carboxylic acid group into a resin and form a salt with this to form a salt with an organic diamine to pseudo-crosslink the resin. Alternatively, one using the Diels-Alder reaction [J. Pee. Kennedy, K. F. Cassner, Journal of Polymer Science Polymer Chemistry, Edition 17
Vol. 2055 (1979) and J. Pee. Kennedy, Gee. M. Carlson, ibid, vol.21, 29
73 (1983)] and those utilizing the reaction of nitroso group (US Pat. No. 3,872,057) have been proposed.

Further, a method utilizing the reaction of an acid anhydride group with an alcohol or an amine [US Pat. No. 3,299,184]
And 3678016, J. et al. C. DeCroy et al., Journal of Polymer Science, Polymer Symposium, 52, 299 (1975).
Year)] or a resin using a transesterification reaction of a hydroxyl group-containing resin and a diester [D. S. Campbell, Chemistry and Industry (London), Volume 7,
279 (1974)] and the like.

However, the pseudo-crosslinked resin is insufficient in heat resistance because the crosslinking is dissociated immediately when the temperature of the resin rises, and a system utilizing the Diels-Alder reaction is not available. Actually, it is difficult to manufacture, and the cross-linking is not completely dissociated even at high temperature, which causes a problem in moldability. Further, a system utilizing a reaction between an acid anhydride and an alcohol or an amine or a transesterification reaction is not suitable for practical use because the progress of cross-linking is slow during cooling and solidification or the reaction of cross-linking / dissociation cannot be controlled. There wasn't.

[0006]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, can be melt-molded at a processing temperature without forming a crosslinked structure, and can be rapidly crosslinked in a cooling and solidifying process after molding. Can be formed, and crosslinking can be completely dissociated by heating again to the molding temperature, that is, a thermoreversible crosslinkable resin composition having a very high crosslink formation reaction rate and a high crosslinking dissociation reaction rate, and a molded article using the same. The purpose is to provide.

[0007]

The present invention has achieved the above object by incorporating a reaction accelerator into a composition comprising a specific modified polyolefin and a polyhydric alcohol. That is, the present invention is (a) a modified polyolefin grafted with at least one unsaturated carboxylic acid anhydride, wherein the unsaturated carboxylic acid anhydride group component concentration in the modified polyolefin is 0.1 to 20% by weight. Derived from the unsaturated carboxylic acid anhydride in the modified polyolefin of the component (a), which contains the modified polyolefin of (b), the polyhydric alcohol compound having at least two hydroxyl groups in the molecule, and (c) the reaction accelerator. The molar ratio of the unit of the hydroxyl group in the polyhydric alcohol compound as the component (b) to the unit is 0.1.
A resin having a range of 01 to 10 and a range of 0.001 to 20 parts by weight with respect to 100 parts by weight of the modified polyolefin as the component (a) of the reaction accelerator as the component (c). The present invention provides a thermoreversible crosslinkable molded article, which is characterized in that the resin composition is melt-molded and a crosslinked structure is formed in the cooling process.

Next, each component of the resin composition of the present invention will be described. First, the component (a) is a modified polyolefin grafted with at least one unsaturated carboxylic acid anhydride. The polyolefins used to produce this modified polyolefin include homopolymers of olefins such as ethylene, propylene, 1-butene, 1-hexene and 4-methyl-1-pentene, or two or more of these olefins. Random or block copolymers of
Alternatively, it is a binary or multi-component copolymer with vinyl acetate, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, etc., containing these olefins as main components. Specifically, high density polyethylene, low density polyethylene,
Polypropylene, ethylene-propylene random copolymer, ethylene-vinyl acetate copolymer, ethylene-butene-1 copolymer, propylene-butene-1 copolymer, ethylene-acrylic acid ester copolymer, ethylene-maleic anhydride -Acrylic acid ester copolymer, zinc salt of ethylene-methacrylic acid copolymer, and the like. You may use these individually or in mixture of 2 or more types.

As the unsaturated carboxylic acid anhydride used as the grafting monomer, for example, maleic anhydride,
Itaconic anhydride, endic acid anhydride, citraconic anhydride, 1-butene-3,4-dicarboxylic acid anhydride, alkenyl succinic anhydride having a double bond at the end having at most 18 carbon atoms, many carbon atoms Examples thereof include alkadienyl succinic anhydride having a double bond at the end which is 18. These may be used alone or in combination of two or more kinds at the same time. Of these, maleic anhydride and itaconic anhydride are preferred.

The unit derived from the unsaturated carboxylic acid anhydride in the modified polyolefin which is the component (a) is 0.1 to 20.
Must be in the range of 1% by weight, 1-10% by weight
The range is preferably. When the unit derived from the acid anhydride is less than 0.1% by weight, the crosslinking density, which is the object of the present invention, becomes insufficient, which is not preferable. Also, 20% by weight
If it exceeds, the properties such as flexibility and mechanical strength expected of the modified polyolefin are impaired, which is not preferable. Furthermore, the modified polyolefin MFR (JI
(Condition 14 of Table 1 of SK-7210) is 0.1 to
A range of 1000 g / 10 minutes is preferred. Outside this range, a resin composition that meets the object of the present invention cannot be obtained.

In order to produce the modified polyolefin used in the present invention, any known method can be adopted.
That is, in a solution of polyolefins dissolved in a solvent,
A solution grafting method in which a radical initiator and an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride are mixed and reacted, a melt grafting method that modifies in an extruder in the absence of a solvent, a radiation grafting method using an electron beam, etc. Can be used. Furthermore, after graft modification by these methods, it is preferable to remove unreacted substances, reaction by-products and the like by washing with a solvent.

The polyhydric alcohol compound having at least two hydroxyl groups in the molecule of the component (b) of the resin composition of the present invention includes, for example, glycols such as ethylene glycol, diethylene glycol and triethylene glycol; Alcohol compounds such as 4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, trimethylolethane, trimethylolpropane and pentaerythritol; arbitol, sorbitol, xylose, arabinose, Glucose, galactose, sorbose, fructose,
Sugars such as palatinose, maltotriose, and malezitose; saponification products of ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyolefin oligomers having a plurality of hydroxyl groups, ethylene-hydroxyethyl (meth) acrylate [(meth) acrylate is methacrylate. And acrylate. The same shall apply hereinafter] A polymer having a plurality of hydroxyl groups in the molecule such as a copolymer; 1,3-dihydroxypropane, 2,2-dimethyl-1,3-dihydroxypropane, trimethylolethane, 1,1,1 −
Trimethylolpropane, 1,1,1-trimethylolhexane, 1,1,1-trimethyloldodecane, 2-
Cyclohexyl-2-methylol-1,3-dihydroxypropane, 2- (p-methylphenyl) -2-methylol-1,3-dihydroxypropane, pentaerythritol, glycerin, diglycerin, hexadiglycerin, octaglycerin, decaglycerin Polyoxyalkylene compound obtained by addition reaction of ethylene oxide or propylene oxide with glycerin monostearate, glycerin monooleate, glycerin monolaurate, glycerin monocaprylate, glycerin monohexanoate, glycerin monophenethyl ester, glycerin monopro Pionate, diglycerin monostearate, diglycerin distearate, diglycerin monooleate, diglycerin monohexanoate, diglycerin diocta Ate, tetraglycerin monostearate, tetraglycerin tristearate, tetraglycerin tetrastearate, tetraglycerin trihexanoate, tetraglycerin monophenethyl ester, hexaglycerin monostearate, hexaglycerin distearate, hexaglycerin pentastearate , Hexaglycerin trioleate, hexaglycerin monolaurate, hexaglycerin pentalaurate, decaglycerin monostearate, decaglycerin octastearate, decaglycerin pentaoleate, decaglycerin dilaurate, pentadecaglycerin distearate, pentadecaglycerin Polyglycerin alkyl esters such as decaoleate and octadecaglycerin tetrastearate; Sol Monostearate, sorbitan monooleate, sorbitan monolaurate, sorbitan monocaprylate, sorbitan mono-hexanoate, sorbitan mono-phenethyl ester,
Examples thereof include sorbitan alkyl esters such as sorbitan monopropionate, sorbitan tristearate and sorbitan tetrastearate. The melting point of these polyhydric alcohol compounds is preferably 300 ° C. or lower in consideration of the thermal deterioration of the modified polyolefin of the component (a). In addition, these polyhydric alcohol compounds may be used alone or in combination of two or more kinds.

The amount of the polyhydric alcohol used as the component (b) in the resin composition of the present invention is such that the polyhydric alcohol is used based on the unit derived from the unsaturated carboxylic acid anhydride contained in the modified polyolefin of the component (a). The molar ratio of hydroxyl groups contained in the alcohol compound is preferably in the range of 0.01 to 10,
It is more preferable that the range is from 05 to 5. This molar ratio is
When it is less than 0.01, it is insufficient to introduce the crosslinked structure into the composition in an effective amount, and when it exceeds 10, the crosslinked structure may be completely dissociated at a processing temperature during molding. However, this is not preferable because molding becomes extremely difficult. When the unit derived from the unsaturated carboxylic acid anhydride contained in the modified polyolefin is in the range of 0.1 to 1% by weight, the molar ratio of the hydroxyl groups contained in the polyhydric alcohol compound is 0.1 to 1. The range of 5 is more preferable.

The reaction accelerator as the component (c) in the resin composition of the present invention is a carbonyl group contained in the unit derived from the unsaturated carboxylic acid anhydride contained in the modified polyolefin to activate the hydroxyl group and the acid anhydride. It is a compound that accelerates the reaction with a physical group. There are various kinds of such reaction accelerators, and one example thereof is a metal salt of an organic carboxylic acid. As a metal salt of an organic carboxylic acid,
Metal salts of fatty acids having 1 to 30 carbon atoms, such as acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid,
Oleic acid, behenic acid, etc.
IIB group and IIIB group metals (eg, Li, Na, K, M
g, Ca, Zn, Al, etc.). More specific examples are lithium acetate, sodium acetate, magnesium acetate, aluminum acetate, potassium butyrate, calcium butyrate, zinc butyrate, sodium octanoate, calcium octanoate, potassium decanoate, magnesium decanoate, zinc decanoate, and lauric acid. Lithium, sodium laurate, calcium laurate, aluminum laurate, potassium myristate, sodium myristate, aluminum myristate, sodium palmitate, zinc palmitate, magnesium palmitate, sodium stearate, potassium stearate, calcium stearate, stearic acid Examples include zinc, sodium olein sulfate, and sodium behenate. Of these, lithium laurate, sodium laurate, calcium laurate, aluminum laurate,
Preferred are potassium myristate, sodium myristate, aluminum myristate, sodium palmitate, zinc palmitate, magnesium palmitate, sodium stearate, potassium stearate, calcium stearate, zinc stearate, sodium oleate, and the like.

Another example of the metal salt of an organic carboxylic acid is a resin having a metal salt structure of a carboxylic acid. Examples of such a resin include metals of IA group, IIA group, IIB group, and IIIB group of ethylene and radically polymerizable unsaturated carboxylic acid (for example, Li, Na, K, Mg, Ca, Zn, Al, etc.).
Examples thereof include those having a structure in which a salt is copolymerized, or those having a structure in which ethylene and a metal salt of a radical-polymerizable carboxylic acid and another radical-polymerizable unsaturated carboxylic acid and / or a derivative thereof are multi-component copolymerized. .

Further, polyethylene, polypropylene,
A structure obtained by graft-polymerizing a metal salt of a radical-polymerizable unsaturated carboxylic acid (which may be polymerized from a free unsaturated carboxylic acid and then neutralized) onto a polyolefin resin such as a free ethylene-propylene copolymer And those having a structure in which a metal salt of a radically polymerizable carboxylic acid and another radically polymerizable unsaturated carboxylic acid and / or a derivative thereof are simultaneously co-grafted with a polyolefin resin. The radical-polymerizable unsaturated carboxylic acid and its derivative used here include (meth) acrylic acid, maleic acid, fumaric acid, monomethyl maleate, monomethyl fumarate, monoethyl maleate, monoethyl fumarate, monobutyl maleate, and fumarate. Monobutyl acid, methyl (meth) acrylate, dimethyl maleate, dimethyl fumarate, diethyl maleate, diethyl fumarate, dibutyl maleate, dibutyl fumarate and the like.

Another example of the reaction accelerator used in the resin composition of the present invention is a tertiary amine compound. Specific examples of the tertiary amine compound used here include trimethylamine, triethylamine, triisopropylamine, trihexylamine, trioctylamine, trioctadecylamine, dimethylethylamine,
Methyldioctylamine, dimethyloctylamine, diethylcyclohexylamine, N, N-diethyl-4-
Methylcyclohexylamine, diethylcyclododecylamine, N, N-diethyl-1-adamantamine, 1-
Methylpyrrolidine, 1-ethylpiperidine, quinuclidine, triphenylamine, N, N-dimethylaniline,
N, N-diethylaniline, N, N-dimethyl-m-phenetidine, 4-t-butyl-N, N-dimethylaniline and the like can be mentioned.

Another example of the reaction accelerator is a quaternary ammonium salt. Examples of the quaternary ammonium salt used here include tetramethylammonium tetrafluoroborate, tetramethylammonium hexafluorophosphate, tetramethylammonium bromide, tetraethylammonium bromide, tetraethylammonium iodide, methyltri-n-butylammonium chloride and tetramethylammonium tetrachloride. Butyl ammonium bromide, tetrahexyl ammonium bromide, tetraheptyl ammonium bromide, phenyl trimethyl ammonium bromide, benzyl triethyl ammonium chloride, etc. are mentioned.

Further, a hydroxide of a metal of group IIA, IIB or IIIB or a halide of a metal of group IIA or IIB can be used as a reaction accelerator. Where IIA
Examples of the metal hydroxides of the genus, IIB group and IIIB group include calcium hydroxide, magnesium hydroxide and aluminum hydroxide, and the halides of the IIA group and IIB group metals include, for example, Examples include calcium chloride, calcium bromide, magnesium chloride and the like.

Further, oxo acid and IA, IIA, IIB
A salt of a metal of Group IIIB can be used as a reaction accelerator. Specific examples thereof include aluminum nitrate, calcium nitrate, zinc nitrate, magnesium nitrate, aluminum nitrate, sodium phosphate, calcium phosphate, sodium carbonate, calcium carbonate, magnesium carbonate, sodium sulfate, zinc sulfate, magnesium sulfate, aluminum sulfate, and chloric acid. Examples thereof include sodium, potassium chlorate, and sodium iodate.

In addition, Li BF ₄ , Na BF ₄ , KBF
₄ , Na PF ₆ , KPF ₆ , Na PCl ₆ , Na Fe C
_{l 4, Na Sn Cl 4,} Na Sb F 6, KSb F 6, Na A
Alkali metal salts of Lewis acids such as s F ₆ and Na As Cl ₆ can also be used as reaction accelerators.

Among the above-exemplified reaction accelerators, metal salts of organic carboxylic acids are preferably used. Further, two or more of the above-mentioned various reaction accelerators can be used in combination, if necessary. The amount of these reaction accelerators used depends on the amount of component (a).
0.001 to 100 parts by weight of modified polyolefin of
20 parts by weight, more preferably 0.01 to 15 parts by weight. If this amount is less than 0.001 parts by weight,
The reaction becomes too slow and it becomes difficult to effectively introduce the crosslinked structure into the composition. When it exceeds 20 parts by weight, not only is it meaningless in improving the reaction rate, but also economically preferable. Absent.

Further, the resin composition of the present invention may contain various additives, compounding agents, fillers and the like within a range that does not impair the characteristics of the composition. Specific examples of these include antioxidants (heat stabilizers), ultraviolet absorbers (light stabilizers), antistatic agents, antifogging agents, flame retardants, lubricants (slip agents, antiblocking agents), glass fillers, etc. Inorganic fillers, organic fillers, reinforcing agents, colorants (dye, pigment),
Examples include foaming agents and fragrances. Furthermore, the resin composition of the present invention may be blended with a polyolefin resin other than the component (a) depending on its use and purpose.

To produce the resin composition of the present invention,
The modified polyolefin (a), the polyhydric alcohol (b) and the reaction accelerator (c) may be mixed by various means. As the mixing method, dry blending may be performed using a mixer such as a Henschel mixer or a tumbler generally used in the field of olefin polymers, and kneading such as a Banbury mixer, a kneader, an extruder or a roll mill. Examples of the method include melt kneading using a machine. On this occasion,
It is possible to obtain a uniform mixture by dry-blending in advance and melt-kneading the obtained mixture. Further, each component may be melt-mixed at the time of molding the resin composition of the present invention. That is, the components may be mixed (dry blended) in the form of pellets or powder, and melt-mixed in the extruder or injection molding machine at the stage of producing a film or the like.

The resin composition of the present invention is melt-kneaded and molded, but a crosslinked structure is not formed during this molding process. Then, after it is molded into pellets, plates, films or various molded products by injection molding, in the cooling and solidifying process, a crosslinked structure is formed, the cohesive force is increased, and the mechanical strength is improved. In addition, even if a crosslinked structure is formed once, the structure is dissociated by melting to recover the moldability, and the crosslinked structure is formed again in the cooling and solidification process after newly molding to form a high-strength molded product. Occurs.

To give a concrete example of molding conditions, the extruder and die temperatures are set so that the resin temperature is 230 ° C. or higher and the melting point of the polyhydric alcohol used is not lower than that in the composition. Cross-linking is dissociated and melt molding becomes possible. Then, upon cooling and solidification, the crosslinking reaction proceeds rapidly due to the curing of the reaction accelerator, resulting in a resin composition molded article having a crosslinked structure introduced therein. Therefore, the strength of the resin is improved, and a molded product that can be used for various purposes can be obtained. As the molded product, for example, a film, a blow molded product, an injection molded product, a laminated molded product, etc., can be used as various packaging materials, containers, machine parts, daily necessities and the like. Also,
It can also be used as a resin modifier that improves environmental stress crack resistance (ESCR), mechanical strength, and the like.

[0027]

The acid anhydride group contained in the modified polyolefin used in the resin composition of the present invention reacts with the hydroxyl group contained in the polyhydric alcohol to form a monoester, thereby forming a crosslinked structure in the composition. It is considered to be introduced. The composition composed of two components, a modified polyolefin containing an acid anhydride group and a polyhydric alcohol, exhibits the property as a so-called thermoreversible crosslinkable resin which dissociates the crosslinked structure at high temperature and forms the crosslinked structure again on cooling. However, the crosslinking formation reaction rate and the crosslinking dissociation reaction rate are extremely slow, and sufficient physical properties cannot be expressed under general thermoforming processing conditions.

However, in the present invention, by further adding a reaction accelerator to this composition, the crosslinking reaction rate and the crosslinking dissociation reaction rate are increased, and the composition is practically ready for use. This is considered to be because, for example, the metal ion of the organic carboxylic acid metal salt as the reaction accelerator enhances the reaction rate between the acid anhydride group contained in the modified polyolefin and the hydroxyl group of the polyhydric alcohol. Only by adding the acid metal salt, a thermoreversible crosslinkable resin composition exhibiting sufficient physical properties even under general thermoforming processing conditions can be obtained. It is considered that other reaction accelerators have the same action.

The resin composition of the present invention varies depending on the modified polyolefin, but by selecting an appropriate molding temperature, the ester bond is dissociated and good moldability can be exhibited. It is presumed that the ester bond is rapidly re-formed during the solidification by cooling and the cross-linking reaction proceeds, and the resulting molded article has a cross-linking structure introduced therein to exert its action of increasing the strength. However,
This mechanism has not been completely elucidated, and the present invention is not bound by this.

[0030]

EXAMPLES Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 A modified polyolefin was prepared by grafting maleic anhydride onto polypropylene. The obtained modified polyolefin [hereinafter, abbreviated as modified polyolefin (A)] is
MFR (JIS K7210, Table 1, Condition 14) 70 g /
After 10 minutes, the unit derived from maleic anhydride was 0.5% by weight. The composition of the modified polyolefin was determined by infrared absorption spectrum. Furthermore, the tensile strength was measured according to JIS-K6760, which was 310 kg.
The fracture strength was / cm ² . The growth rate at that time is 40
%Met.

Modified polyolefin (A) 95% by weight, trimethylolpropane 0.2% by weight (hydroxyl group / anhydride group = 0.40), MFR as a metal salt of an organic carboxylic acid.
(JIS-K7210, Table 1, Condition 4) 3.0 g / 10 minutes,
Partially neutralized ethylene-methacrylic acid copolymer having a density of 0.94 g / cm ³ (hereinafter, abbreviated as metal salt (a))
(Copolymer in which the content of methacrylic acid is 18% by weight and about 10% of the methacrylic acid is neutralized with sodium ion) 1
% By weight (metal atom / acid anhydride group = 0.40) and 0.1% by weight of 2,6-di-t-butyl-p-cresol as an antioxidant were mixed. Upon mixing, the three components were dry blended with a tumbler, and then melt-kneaded at 250 ° C. using a 30 mmφ twin-screw extruder to form pellets. The composition has an MFR of 3.2 g (condition 14 in Table 1 of JIS-K7210).
/ 10 minutes.

The tensile strength of this composition was measured. The molding temperature for sample production was 250 ° C., and molding could be carried out without any particular problems. The obtained sample was conditioned for 24 hours at 23 ° C. and a relative humidity of 50%, and the tensile strength was measured. As a result, a breaking strength of 410 kg / cm ² was observed, and improvement in mechanical strength was confirmed.
The elongation at this time was 590%. The gel fraction of this sample was measured by the extraction method. Sample 4
When placed in a 00 mesh stainless wire mesh bag and subjected to Soxhlet extraction for 6 hours at the boiling point of toluene, the extraction residue (gel fraction) showed a value of 74%.

A film was formed using this composition. For the molding, a 25 mmφ extruder and a film molding machine having a 200 mm wide T-die are used, and the resin temperature is set to 255.
A film having a thickness of 75 μm was produced at a temperature of 3 ° C. and a take-up speed of 3 m / min. The molding could be carried out without any problems. The obtained film had good appearance and transparency, and its gel fraction measured by the above method was 65%. From the above results, it is understood that the resin composition of the present invention can be melt-molded and has a crosslinking component.

Examples 2 to 11 and Comparative Examples 1 to 6 Various modified polyolefins were produced in the same manner as in Example 1 using various olefin polymers, and the modified polyolefin, polyhydric alcohol and reaction accelerator were added. A crosslinkable resin composition shown in Table 1 was produced using the
The results are shown in Table 2. The materials used for producing the modified polyolefin and the resin composition are as follows.

Polypropylene MFR 22 g / 10 min, breaking strength 330 kg / cm ² ,
Elongation at break 500% Low density polyethylene MFR 9.5g / 10 minutes, breaking strength 120kg / cm ² ,
Elongation at break 580% High density polyethylene MFR 0.7g / 10 minutes, breaking strength 230kg / cm ² ,
Elongation at break 810% Linear polyethylene MFR 5.0 g / 10 min, breaking strength 140 kg / cm ² ,
Elongation at break 820% r-PP propylene-ethylene (7% by weight) random copolymer,
MFR (14 condition in Table 1 of JIS-K7210) 10 g /
10 minutes, breaking strength 360 kg / cm ² , elongation at break 730% EVA ethylene-vinyl acetate (30% by weight) copolymer, MFR
(JIS-K7210, Table 1, Condition 4) 7.0 g / 10 min,
Breaking strength 210 kg / cm ² , elongation at break 860% E-MAh Ethylene-maleic anhydride (2.5 wt%) copolymer, M
FR (Table 1 condition 4 of JIS-K7210) 10 g / 10
Min, breaking strength 110 kg / cm ² , elongation at break 69
0% EMMA ethylene-methyl acrylate (18 wt%) copolymer, MFR (condition 1 in Table 1 of JIS-K7210) 7.0 g
/ 10 minutes, breaking strength 90 kg / cm ² , elongation at break 650% Terpolymer Copolymer ethylene-maleic anhydride (3% by weight) -methyl acrylate (18% by weight), MFR (JIS-K7
210 Table 1 condition 4) 15 g / 10 minutes, breaking strength 120
kg / cm ² , elongation at break 840% EPR ethylene-propylene (45% by weight) copolymer, MFR
(JIS-K7210, Table 1, Condition 14) 4.0 g / 10
Min, breaking strength 60 kg / cm ² , elongation at break 880
% HIPP propylene-EPR (16% by weight) copolymer, MFR
(JIS-K7210, Table 1, Condition 14) 6.0 g / 10
Min, breaking strength 340 kg / cm ² , elongation at break 71
0% TMP: trimethylolpropane 1,10DEC: 1,10-decanediol E-HEA ethylene-2-hydroxyethyl acrylate (8% by weight) copolymer, MFR (JIS-K7210, Table 1, Condition 4) 30 g / 10 Min, breaking strength 110 kg / cm ² , elongation at break 720% Na stearate: sodium stearate Ca stearate: calcium stearate metal salt (a) ethylene-methacrylic acid (18% by weight) copolymer Na
Salt (neutralized with methacrylic acid 10 mol%), MFR (JIS-
K7210 Table 1 condition 4) 3.0 g / 10 min, breaking strength 3
60 kg / cm ² , elongation at break 440% Metal salt (b) Zn of ethylene-methacrylic acid (18 wt%) copolymer Zn
Salt (neutralized with methacrylic acid 10 mol%), MFR (JIS-
K7210 Table 1 condition 4) 4.0 g / 10 min, breaking strength 2
50 kg / cm ² , elongation at break 580% BHT: 2,6-di-t-butyl-p-cresol

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

[0040]

[Table 4]

[0041]

[Table 5]

[0042]

The resin composition of the present invention is easy to produce,
The resulting molded article is inexpensive, has excellent melt moldability, has a high crosslinking formation reaction rate and a high crosslinking dissociation reaction rate, has an excellent appearance, and has various properties such as mechanical strength greatly improved. Further, since the resin composition of the present invention is thermoreversible crosslinkable,
Burrs generated during the molding process, off-spec molded products, punched parts, etc. can be recycled for use.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical indication location C08L 101: 08) (72) Inventor Takashi Nagaoka 2 Nakanosu, Oita-shi, Oita Showa Denko Oita Co., Ltd. In the laboratory (72) Inventor Shintaro Inazawa 2 Nakanosu, Oita City, Oita Prefecture Showa Denko Oita Laboratory

Claims (3)

[Claims] 1. A modified polyolefin grafted with (a) at least one unsaturated carboxylic acid anhydride, wherein the unsaturated carboxylic acid anhydride group component concentration in the modified polyolefin is 0.1 to 20% by weight. It contains a modified polyolefin, (b) a polyhydric alcohol compound having at least two hydroxyl groups in the molecule, and (c) a reaction accelerator, and is derived from the unsaturated carboxylic acid anhydride in the modified polyolefin of the component (a). The molar ratio of the unit of the hydroxyl group in the polyhydric alcohol compound as the component (b) to the unit is 0.01 to 10.
And the reaction accelerator which is the component (c) is 100 parts by weight of the modified polyolefin which is the component (a).
A resin composition having a range of 0.001 to 20 parts by weight. 2. The resin composition according to claim 1, wherein the reaction accelerator as the component (c) is a metal salt of a polymer containing a carboxyl group or a metal salt of an organic carboxylic acid. 3. A thermoreversible crosslinkable molded article, which is obtained by melt-molding the resin composition according to claim 1 or 2 and forming a crosslinked structure in the cooling process.