JP2002241556A - Olefin-based polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an olefin-based polymer composition having high crosslinkability at a low temperature and crosslinking release at a high temperature and excellent thermally reversible crosslinkability. SOLUTION: This olefin-based composition comprises (A1) a modified olefin-based polymer modified with an ethylenic unsaturated carboxylic anhydride and an acryloxy group-containing ethylenic unsaturated compound having the average number of bonds of carboxylic anhydride groups per molecule of >=1 and the ratio of the number of acryloxy groups to the number of carboxylic anhydride groups in the modified olefin- based polymer of 0.5-20, or (A2) a modified olefin-based polymer which is a modified olefin-based polymer modified with an ethylenic unsaturated carboxylic anhydride and an acryl group-containing ethylenic unsaturated compound having the average number of bonds of carboxylic anhydride groups per molecule of >=1 and the ratio of the number of acyl groups to the number of carboxylic anhydride groups in the modified olefin-based polymer of 0.5-20, and (B1) a hydroxy group-containing compound containing two or more hydroxy groups or/and (B2) a hydroxy group-containing polymer having the average number of bonds of hydroxy groups per molecule of >=1 and has the ratio of the number of groups of the component (B1) and/or the component (B2) to the number of carboxylic anhydride groups of the component (A1) or the component (B2) is 0.1-5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin polymer composition, and more particularly, to a so-called thermoreversible crosslinkable olefin polymer which can repeatedly form crosslinks at low temperatures and dissociate crosslinks at high temperatures. It relates to a polymer composition.

[0002]

2. Description of the Related Art Olefinic resins such as polyethylene and polypropylene are excellent in moldability, mechanical strength, transparency, chemical resistance, etc., and are variously molded such as extrusion molding, injection molding, hollow molding, compression molding, and rotational molding. It is shaped into a desired shape in the molten state by the method and is widely used in various fields. Also, in order to impart heat resistance and improve mechanical strength at high temperatures, etc., compounding of organic peroxide, irradiation of radiation Alternatively, it is often used as a crosslinked body which has been subjected to a crosslinking treatment by utilizing a silanol condensation reaction or the like.

[0003] On the other hand, from the standpoint of environmental protection and resource saving, it has become increasingly necessary to reuse used resins. However, this crosslinked resin is no longer used. Since it does not have thermoplasticity and cannot be reused by melt molding, compatibility between this crosslinked product and thermoplasticity is strongly desired.

On the other hand, at low temperatures, crosslinks are formed,
In contrast to some conventional techniques as a method of dissociating the crosslinks at high temperature to impart thermoplasticity, an olefin resin composition having excellent thermoreversible crosslinkability, particularly high crosslink formation reaction rate and crosslink dissociation reaction rate JP-A-6-5
Nos. 7062 and 7-94029 disclose unsaturated carboxylic anhydride-modified olefin resins, polyhydric alcohol compounds or polymers having at least two hydroxyl groups in the molecule, and metals of organic carboxylic acids. An olefin resin composition comprising a reaction accelerator such as a salt is disclosed.

According to studies by the present inventors, a thermoreversible crosslinkable composition based on the reaction between a carboxylic acid anhydride group and a hydroxyl group basically comprises one molecule of a carboxylic acid anhydride group. And one molecule of hydroxyl group reacts to form a carboxylic acid monoester, and one reaction of the generated carboxylic acid monoester and one molecule of hydroxyl group further reacts to form a carboxylic acid diester. The former carboxylic acid monoester formation reaction has good thermoreversibility, but the latter carboxylic acid diester formation reaction has poor heat reversibility, and further, in the above-mentioned prior art, acid anhydrides are used. Although the initial cross-linking degree is high because the metal salt formation reaction between the group and the organic carboxylic acid metal salt also occurs at the same time, the formation of the subsequent cross-links is extremely slow,
In addition, the metal salt formation reaction is easily dissociated at a high temperature, and since the ester formation reaction is reduced by the reaction, the degree of heat-resistant cross-linking is reduced as a whole. It was found that there were problems such as poor heat resistance.

On the other hand, the present inventors have made a specific modification with an ethylenically unsaturated carboxylic anhydride without substantially using a metal salt of an organic carboxylic acid, based on the results of the above-mentioned study on the prior art. Olefin polymer, or, a specific modified olefin polymer by ethylenically unsaturated carboxylic anhydride and ethylenically unsaturated carboxylic acid ester, and a specific hydroxyl group-containing compound, or a specific hydroxyl group-containing polymer The inventors filed a patent application for finding out that the above problem can be solved by an olefin-based polymer composition (JP-A-11-106578, JP-A-2000-34376).
And Japanese Patent Application Laid-Open No. 2000-204204. ).
However, these compositions still leave room for solution in crosslinking dissociation at high temperatures.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and has an excellent thermoreversible cross-linking property, which has high cross-linkability at low temperatures and high cross-link dissociation at high temperatures. It is an object of the present invention to provide an olefin polymer composition having a property.

[0008]

The present invention comprises the following component (A ₁ ) and component (B ₁ ) and / or component (B ₂ ), and the carboxylic acid component (A ₁ ) (B ₁ ) component and / or (B ₂ ) based on the number of anhydride groups
An olefin polymer composition in which the ratio of the number of hydroxyl groups of the components is 0.1 to 5 is summarized.

(A ₁ ) A modified olefin polymer modified by an ethylenically unsaturated carboxylic acid anhydride and an acyloxy group-containing ethylenically unsaturated compound, wherein the average bond of carboxylic acid anhydride groups per molecule The number is one or more, and the ratio of the number of acyloxy groups to the number of carboxylic anhydride groups in the modified olefin polymer is 0.5 to 20.
(B ₁ ) a hydroxyl group-containing compound having two or more hydroxyl groups (B ₂ ) a hydroxyl group-containing polymer having an average number of hydroxyl groups of 1 or more per molecule

Further, the present invention comprises the following component (A ₂ ) and the component (B ₁ ) and / or the component (B ₂ ), wherein the component (A ₂ ) has a carboxylic acid anhydride group of: (B
₁ ) The ratio of the number of hydroxyl groups of the component and / or the component (B ₂ ) is 0.
An olefin polymer composition of 1 to 5 is summarized.

(A ₂ ) A modified olefin polymer modified with an ethylenically unsaturated carboxylic anhydride and an acyl group-containing ethylenically unsaturated compound, wherein the average bond of carboxylic anhydride groups per molecule A modified olefin polymer having a number of one or more, and a ratio of the number of acyl groups to the number of carboxylic anhydride groups in the modified olefin polymer of 0.5 to 20 (B ₁ ) having two or more hydroxyl groups Hydroxyl-containing compound (B ₂ ) Hydroxyl-containing polymer having an average number of hydroxyl groups of 1 or more per molecule

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Modified olefin modified with an ethylenically unsaturated carboxylic anhydride and an acyloxy group-containing ethylenically unsaturated compound as the component (A ₁ ) constituting the olefin polymer composition of the present invention Basically, terpolymers of an α-olefin, an ethylenically unsaturated carboxylic anhydride and an acyloxy group-containing ethylenically unsaturated compound, and an α-olefin and an ethylenically unsaturated Grafted product of a binary copolymer with a carboxylic anhydride with an acyloxy group-containing ethylenically unsaturated compound, and ethylenically unsaturated carboxylic acid of a binary copolymer of an α-olefin and an acyloxy group-containing ethylenically unsaturated compound Grafts with anhydrides, and ethylenically unsaturated carboxylic anhydrides of α-olefin-based polymers and acyloxy group-containing ethylene Graft body and the like due to the sexual unsaturated compound.

Further, a modified olefin polymer modified by the ethylenically unsaturated carboxylic anhydride and the acyl group-containing ethylenically unsaturated compound as the component (A ₂ ) constituting the olefin polymer composition of the present invention. A terpolymer obtained by substituting the acyloxy group-containing ethylenically unsaturated compound in the above-mentioned component (A ₁ ) with an acyl group-containing ethylenically unsaturated compound, and a graft copolymer of the same binary copolymer, Also, a similar α-olefin polymer graft may be used.

The α-olefin in the terpolymer and the terpolymer is, for example, ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl -1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1
-Decene and the like, among which ethylene is preferred in the present invention.

The terpolymer and the binary copolymer,
As the ethylenically unsaturated carboxylic anhydride in the graft, for example, 2-octene-1-succinate
Yl anhydride, 2-dodecene-1-yl succinate anhydride,
2-octadecene-1-yl succinate anhydride, maleic anhydride, 2,3-dimethylmaleic anhydride, bromomaleic anhydride, dichloromaleic anhydride, citraconic anhydride, itaconic anhydride, 1 -Butene-3,4
-Dicarboxylic anhydride, 1-cyclopentene-1,2-
Dicarboxylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydro Phthalic anhydride, 5-norbornene-2,3
-Dicarboxylic anhydride, methyl-5-norbornene-
2,3-dicarboxylic anhydride, endo-bicyclo [2.
2.2] oct-5-ene-2,3-dicarboxylic anhydride, bicyclo [2.2.2] oct-7-ene-2,
Examples thereof include 3,5,6-tetracarboxylic anhydride, and among them, maleic anhydride is preferable in the present invention.

The acyloxy group-containing ethylenically unsaturated compound is preferably one having an acyl group of about 1 to 20 carbon atoms, for example, vinyl formate, vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, Vinyl decanoate, vinyl laurate, vinyl palmitate,
Vinyl esters of aliphatic saturated carboxylic acids such as vinyl stearate, vinyl esters of aromatic carboxylic acids such as vinyl benzoate and vinyl naphthoate, allyl chloroformate, allyl acetate, allyl propionate, allyl butyrate, allyl decanoate And allyl esters of aromatic carboxylic acids such as allyl benzoate. Among them, in the present invention, vinyl esters of aliphatic saturated carboxylic acids are preferable.

As the acyl group-containing ethylenically unsaturated compound, those having an acyl group of about 1 to about 20 carbon atoms are preferable, for example, alkyl vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, and butyl vinyl ketone. And aryl vinyl ketones such as phenyl vinyl ketone, and alkyl allyl ketones such as methyl allyl ketone, ethyl allyl ketone and butyl allyl ketone. Among them, in the present invention, alkyl vinyl ketones are preferable.

The above terpolymer and binary copolymer further include, for example, (meth) acrylic acid [here, “(meth) acryl” means acryl and methacryl. Shall be. ], Ethylenically unsaturated carboxylic acid esters such as (meth) acrylic acid ester, (meth) acrylamide, N
Monomers such as ethylenically unsaturated amides such as -methyl (meth) acrylamide, ethylenically unsaturated nitriles such as (meth) acrylonitrile, and other ethylenically unsaturated compounds such as aromatic vinyl such as styrene. It may be a quaternary or higher or ternary or higher multi-component copolymer. In addition, these copolymers are produced by conventionally known polymerization methods such as bulk, solution, suspension, and gas phase.

As the α-olefin polymer in the graft, for example, a homopolymer of ethylene such as low density / medium density / high density polyethylene (branched or linear), ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,
-Copolymers with other α-olefins such as octene and 1-decene, ethylene and ethylenically unsaturated carboxylic acids such as (meth) acrylic acid, and ethylenically unsaturated carboxylic acids such as (meth) acrylic acid ester Other ethylenically unsaturated compounds such as esters, (meth) acrylamide, ethylenically unsaturated amides such as N-methyl (meth) acrylamide, ethylenically unsaturated nitriles such as (meth) acrylonitrile, aromatic vinyls such as styrene, etc. -Based polymers such as copolymers with monomers of the following, propylene homopolymers, propylene and ethylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene , 4-
Methyl-1-pentene, 1-hexene, 1-octene,
Copolymer with other α-olefin such as 1-decene, propylene, isoprene, 1,3-butadiene, 1,3-
Propylene-based polymers such as copolymers with other monomers such as diene such as pentadiene, 1,4-hexadiene, 1,5-hexadiene, and 1,9-decadiene; and other 1-butene and 4-methyl-1 Α- such as pentene and 1-hexene
Examples thereof include olefin homopolymers and copolymers.

The grafted product is produced by a conventionally known grafting method such as melt kneading in the presence of a radical generator, solution, suspension, etc. , T-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethyl-2,
Hydroperoxides such as 5-di (hydroperoxy) hexane, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 2,
5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,1,3-bis (t-butylperoxy) (Oxyisopropyl) benzene and other dialkyl peroxides, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, benzoyl peroxide, o-methylbenzoyl peroxide,
Diacyl peroxide such as 2,4-dichlorobenzoyl peroxide, t-butyl peroxyacetate,
t-butylperoxy-2-ethylhexanoate, t
-Butylperoxypivalate, t-butylperoxybenzoate, di-t-butyldiperoxyphthalate, t-butylperoxyisopropyl carbonate,
Peroxyesters such as 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexyne-3, methyl ethyl ketone peroxide, and cyclohexanone peroxide Organic peroxides such as ketone peroxides; inorganic peroxides such as potassium peroxide and hydrogen peroxide; 2,2′-azobisisobutyronitrile;
2′-azobis (isobutylamide) dihalide, 2,
Examples include azo compounds such as 2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] and azodi-t-butane, and carbon radical generators such as dicumyl. These radical generators are appropriately selected according to the type of the monomer used, the graft reaction conditions, and the like, and two or more types may be used in combination.

In the present invention, the modified olefin polymer of the component (A ₁ ) or (A ₂ ) includes:
When the tertiary or binary copolymerization of the α-olefin, the ethylenically unsaturated carboxylic acid, the acyloxy group-containing ethylenically unsaturated compound or the acyl group-containing ethylenically unsaturated compound, each monomer thereof is used. Polymerizability of
Various factors such as copolymerizability, polymerization catalyst selectivity and poisoning affect the molecular weight of the resulting modified olefin polymer,
While it is difficult to control various physical properties such as crystallinity and melting point, by grafting each monomer onto the α-olefin polymer, it is relatively easy to control those physical properties. Thus, a graft-modified olefin polymer is preferred.

As the graft, the above α
-An olefin polymer, a co-graft of the ethylenically unsaturated carboxylic anhydride and the acyloxy group-containing ethylenically unsaturated compound or the acyl group-containing ethylenically unsaturated compound, the α-olefin and the acyloxy group-containing A graft of the ethylenically unsaturated compound or the copolymer with the acyl group-containing ethylenically unsaturated compound by the ethylenically unsaturated carboxylic anhydride is preferable, and the ethylenically unsaturated compound of the α-olefin-based polymer is preferably A co-graft of a saturated carboxylic anhydride and the acyloxy group-containing ethylenically unsaturated compound or the acyl group-containing ethylenically unsaturated compound is particularly preferable.

In the present invention, the modified olefin polymer of the component (A ₁ ) or the component (A ₂ ) has a content of the ethylenically unsaturated carboxylic anhydride unit of from 0.1 to 0.1.
It is preferably at least 1% by weight, particularly preferably at least 0.5% by weight, and is based on the number-average molecular weight of the modified olefin polymer and a multiplier of this content, and is calculated per molecule of the modified olefin polymer. It is essential that the average number of bonds of the carboxylic acid anhydride group is one or more, and preferably 1.5 or more. When the average number of carboxylic acid anhydride groups is less than 1, the crosslinkability of the composition itself is poor.

Further, in the present invention, the modified olefin polymer of the component (A ₁ ) or the component (A ₂ ) is characterized in that the acyloxy group is based on the number of carboxylic acid anhydride groups derived from the ethylenically unsaturated carboxylic acid anhydride. It is essential that the ratio of the number of acyloxy groups derived from the containing ethylenically unsaturated compound or the number of acyl groups derived from the acyl group-containing ethylenically unsaturated compound is 0.5 to 20,
It is preferably 15. When the ratio of the number of acyloxy groups or the number of acyl groups to the number of carboxylic acid anhydride groups is less than the above range, the crosslink dissociation itself as a composition is inferior.On the other hand, when the ratio exceeds the above range, the crosslinkability itself as a composition is inferior. Becomes

In the present invention, the component (A ₁ ) or (A
₂ ) As the component, a modified olefin that does not satisfy the above range, as long as the average number of carboxylic anhydride groups per molecule and the ratio of the number of acyloxy groups or the number of acyl groups to the number of carboxylic anhydride groups satisfy the above range. It may be diluted with a polymer or an unmodified olefin polymer.

The hydroxyl group-containing compound (B ₁ ) constituting the olefin polymer composition of the present invention, and / or
The hydroxyl group-containing polymer of the component (B ₂ ) has a function of forming a crosslink by bonding to the carboxylic acid anhydride group of the component (A ₁ ) or the modified olefin polymer of the component (A ₂ ). .

It is essential that the hydroxyl group-containing compound as the component (B ₁ ) has at least two hydroxyl groups, and if the number of hydroxyl groups is less than 2, the crosslinkability itself of the composition is inferior. Become.

In the present invention, examples of the hydroxyl group-containing compound include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol and 2,2-dimethyl-
1,3-propanediol, 1,4-butanediol,
2,3-butanediol, 1,5-pentanediol,
Aliphatic diols such as 2,4-pentanediol, 1,6-hexanediol, 2,5-hexanediol, 1,8-octanediol, 1,10-decanediol and neopentyl glycol; , 4-tetramethyl-1,3-cyclobutanediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol,
1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,
4-cyclooctanediol, 1,5-cyclooctanediol, 1,2-cyclohexane dimethylol, 1,
4-cyclohexane dimethylol, 4,4′-isopropylidene-dicyclohexanol, α, α′-bis (4
-Hydroxycyclohexyl) -1,4-diisopropylbenzene, α, α′-bis (4-hydroxycyclohexyl) -1,4-diisopropylcyclohexane,
4,4'-methylenebis (cyclohexanol), 2,
2'-methylenebis (4-methylcyclohexanol)
Fats such as alicyclic diols such as trimethylolethane, trimethylolpropane, trimethylolhexane, trimethyloldodecane, glycerol, diglycerol, tetraglycerol, hexaglycerol, octaglycerol, decaglycerol, pentaerythritol, and dipentaerythritol Polyhydric alcohols, 1,
Alicyclic polyhydric alcohols such as 3,5-cyclohexanetriol and inositol, ethylene of aliphatic polyhydric alcohols such as glycerol, diglycerol, tetraglycerol, hexaglycerol, octaglycerol, decaglycerol, pentaerythritol and dipentaerythritol Carboxylic acids such as propionate, pivalate, caproate, caprylate, caprate, laurate, palmitate, stearate, and oleate such as oxide or / and propylene oxide adducts, glycerol, (poly) glycerol such as mono, di, tri, and tetra. Esters, sorbitol mono, di, tri,
Tetraose such as tetrapionate, pivalate, caproate, caprylate, caprate, laurate, palmitate, stearate, carboxylic acid esters such as oleate, erythrose, and erythrulose;
Saccharides such as hexoses such as pentoses such as arabinose and xylose, glucose, fructose, mannose, sorbose and galactose, and pentitols such as erythritol and threitol derived therefrom, pentitols such as arabitol and xylitol, sorbitol, mannitol and iditol , Sugar alcohols such as hexitol such as dulcitol, and the like.
2-cyclohexane dimethylol, 1,4-cyclohexane dimethylol, and pentaerythritol are preferred.

The hydroxyl group-containing polymer as the component (B ₂ ) may be a hydroxyl group per one molecule of the hydroxyl group-containing polymer, which is determined based on a multiplier of the number average molecular weight of the hydroxyl group-containing polymer and the content of the hydroxyl group. It is essential that the average number of bonds is 1 or more, and preferably 1.5 or more.
If the average number of hydroxyl groups bonded per molecule is less than 1, the crosslinkability itself of the composition will be poor. As the component (B ₂ ) in the present invention, as long as the average number of hydroxyl groups per molecule satisfies the above range, it is diluted with a polymer containing or not containing a hydroxyl group having an average number of hydroxyl groups of less than 1 or the like. May be done.

Examples of the hydroxyl group-containing polymer of the component (B ₂ ) in the present invention include ethylene- (meth) acrylic acid 2-hydroxyethyl copolymer, 2- (meth) acrylic acid 2-hydroxyethyl graft polyethylene, ethylene -Saponified vinyl acetate copolymer, polyvinyl alcohol, low molecular weight polyolefin polyols, polyalkylene ether glycols, polyoxyalkylene polyols, hydroxyl-terminated diene polymers and their hydrogenated products or adipates, hydroxyl-terminated polycaprolactone, etc. These have a number average molecular weight of 500
It is preferably from 10,000 to 10,000. Among them, low molecular weight polyolefin polyols, polyalkylene ether glycols, polyoxyalkylene polyols, hydroxyl-terminated diene polymers and hydrogenated products thereof are preferred.

In the olefin polymer composition of the present invention, the modified olefin polymer of the component (A ₁ ) or (A ₂ ) and the hydroxyl group-containing compound of the component (B ₁ ), and / or (B) ₂ ) The composition ratio of the component to the hydroxyl group-containing polymer is the ratio of the number of hydroxyl groups of the component (B ₁ ) or / and the number of hydroxyl groups of the component (B ₂ ) to the number of carboxylic anhydride groups of the component (A ₁ ) or (A ₂ ). It is essential that the ratio be from 0.1 to 5, and preferably from 0.1 to 3. If the ratio of the number of hydroxyl groups to the number of carboxylic anhydride groups is less than the above range, the crosslinkability of the composition itself will be poor, while if the ratio is more than the range, the crosslink dissociation itself of the composition will be inferior. In this case, the object of the present invention cannot be achieved.

The olefin polymer composition of the present invention may contain other polymers as long as the effects of the present invention are not impaired, and various commonly used additives such as oxidizing agents may be used. Inhibitors, UV absorbers, light stabilizers, nucleating agents,
Neutralizing agent, antistatic agent, lubricant, antiblocking agent, dispersant, flow improver, release agent, flame retardant, colorant, filler,
A foaming agent or the like may be added.

The olefin polymer composition of the present invention is used together with the component (A ₁ ) or the component (A ₂ ), and the component (B ₁ ) and / or (B ₂ ), if necessary. And other optional components are uniformly mixed with a Henschel mixer, a ribbon blender, a V-type blender, etc. and melt-molded, or after uniformly mixed, a single-screw or multi-screw extruder, roll, Banbury mixer, kneader , Melt kneading with a Brabender, etc., pelletizing and then melt molding, or a method other than the component (A ₁ ) or the component (A ₂ ) and the component (B ₁ ) or / and (B ₂ ) The components are mixed and melt-kneaded by the method described above, and separately, the component (B ₁ ) or / and (B ₂ ) and the component (A ₁ ) or the component other than the component (A ₂ ) Mix by method Melt-kneaded, then mixed together by a method such as melt molding, can be prepared.

The olefin polymer composition of the present invention as described above can be obtained by molding methods usually used for thermoplastic resins, namely, injection molding, extrusion molding, hollow molding, compression molding, and the like.
It can be formed into a desired shape in a molten state by various molding methods such as rotational molding and crosslinked to form a crosslinked molded article,
Even when the used molded article is reused, it can be formed into a desired shape again in a molten state by a similar molding method and subjected to a crosslinking treatment to obtain a crosslinked molded article.

In order to form crosslinks in the olefin polymer composition of the present invention and its molded product, it is preferable to heat the olefin polymer composition to a temperature higher than the glass transition temperature and lower than the melting point of the olefin polymer composition. In order to dissociate the formed crosslinks, it is preferable to heat the olefin polymer composition to a temperature higher than the melting point of the olefin polymer composition. As the thermoreversible crosslinkability, the heat deformation rate after the crosslinking treatment is preferably 35% or less, particularly preferably 30% or less, and the heat deformation rate after the crosslink dissociation treatment is 65% or more, particularly 80%. It is preferable that this is the case.

[0036]

The present invention will now be described in more detail with reference to examples.
However, the present invention will be described below without departing from the gist thereof.
It is not limited to the embodiment. Examples and Comparative Examples
(A₁) Component or (A)_Two) Ingredient modified olefin
Polymer, and (B ₁) Component of hydroxyl group-containing compound
Or / and (B_TwoThe hydroxyl group-containing polymer of the component)
This is shown below.

(A ₁ ) or (A ₂ ) modified olefin-based weight
Coalescing A ₁ -1; ethylene - vinyl acetate copolymer (vinyl acetate unit content of 10 wt%, density 0.933 g / cm ^3, 1
Melt flow rate at 90 ° C. 9 g / 10 min, “LV360” manufactured by Nippon Polychem Co., Ltd.) 100 parts by weight, maleic anhydride 1.0 part by weight, 2,5-dimethyl-2,5-bis (t-butyl par) After uniformly mixing 0.06 parts by weight of (oxy) hexane with a Henschel mixer, a twin-screw extruder (cylinder diameter 30 mm, L / D32, manufactured by Ikegai Co., Ltd., “PCM-
30 ") and melt-kneaded to carry out a graft reaction to obtain a modified olefin polymer of maleic anhydride of an ethylene-vinyl acetate copolymer. The resulting modified olefin polymer was obtained by removing the ungrafted product by reprecipitation purification treatment, and then measuring 0.7% by weight of maleic anhydride units and measuring the number of acyloxy groups based on the number of carboxylic anhydride groups by infrared absorption spectrum. (Acetyloxy group) number ratio of 16.3, number average molecular weight measured by gel permeation chromatography of 28,000, modified olefin polymer obtained based on the number average molecular weight and a multiplier of maleic anhydride unit content The average number of carboxylic anhydride groups bonded per molecule was 2.0, and the melt flow rate at 190 ° C. was 2.9 g / 10 min.

A _1-2 : Ethylene-1-butene copolymer (density 0.926 g / cm ³ , melt flow rate at 190 ° C. 20 g / 10 min, “UJ58” manufactured by Nippon Polychem Co., Ltd.
0 ") 70 parts by weight, ethylene-1-butene copolymer (density 0.925 g / cm ³ , melt flow rate at 190 ° C. 9 g / 10 min,“ Z-50M ”manufactured by Nippon Polychem Co., Ltd.
G ") 15 parts by weight, ethylene-propylene random copolymer (propylene content 27% by weight, density 0.865 g)
/ Cm ³ , melt flow rate at 230 ° C. 0.7 g /
10 minutes, 15 parts by weight of "EP07P" manufactured by JSR Co., Ltd., 1.0 part by weight of maleic anhydride, 3.4 parts by weight of vinyl laurate, 2,5-dimethyl-2,5-bis (t
-Butylperoxy) hexane 0.13 parts by weight,
Perform graft reaction in the same manner as in the case of the A ₁ -1,
An olefin polymer modified with maleic anhydride and vinyl laurate of an ethylene copolymer mixture was obtained. The unmodified grafted olefin polymer obtained was subjected to reprecipitation purification treatment to remove ungrafted products, and thereafter, the maleic anhydride unit content was 0.8% by weight and the vinyl laurate unit content was 1. 3% by weight, ratio of the number of acyloxy groups (lauroyloxy groups) to the number of carboxylic anhydride groups, 0.7, the number average molecular weight measured by gel permeation chromatography, 29,000, the number average molecular weight and the maleic anhydride unit content The average number of carboxylic acid anhydride groups per molecule of the modified olefin polymer determined by the multiplier of 2.4 was 2.4, and the melt flow rate at 190 ° C. was 2.4 g / 10 minutes.

A _1-3 (for comparative example); ethylene-1-butene copolymer (density 0.926 g / cm ³ , melt flow rate at 190 ° C. 20 g / 10 min, “UJ580” manufactured by Nippon Polychem Co., Ltd.) 70 parts by weight of an ethylene-1-butene copolymer (density 0.925 g / cm ³ , melt flow rate at 190 ° C. 9 g / 10 min, “Z” manufactured by Nippon Polychem Co., Ltd.
-50MG "), 15 parts by weight of ethylene-propylene random copolymer (propylene content: 27% by weight, density: 0.1%).
865 g / cm ³ , melt flow rate at 230 ° C. 0.7 g / 10 min, “EP07” manufactured by JSR Co., Ltd.
P ") 15 parts by weight, maleic anhydride 1.0 part by weight, vinyl laurate 1.0 part by weight, 2,5-dimethyl-2,
Using 5-bis (t-butylperoxy) hexane 0.08 parts by weight, subjected to graft reaction in the same manner as in the case of the A ₁ -1, maleic anhydride ethylene copolymer mixture and a vinyl laurate To obtain a modified olefin polymer. The resulting modified olefin-based polymer had a maleic anhydride unit content of 0.7% by weight and a vinyl laurate unit content of 0. 4% by weight, a ratio of the number of acyloxy groups (lauroyloxy groups) to the number of carboxylic anhydride groups of 0.25, and a number average molecular weight of 31,00 as measured by gel permeation chromatography.
0, average number of carboxylic anhydride groups per one molecule of the modified olefin-based polymer obtained based on the multiplier of the number average molecular weight and the maleic anhydride unit content: 2.2, 190 ° C.
At a melt flow rate of 1.9 g / 10 min.

[0040] A ₂ -1; ethylene-1-butene copolymer (density of 0.926g / cm ^3, 190 melt flow rate 20 g / 10 min at ° C., Nippon Polychem Co., Ltd., "UJ58
0 ") 70 parts by weight, ethylene-1-butene copolymer (density 0.925 g / cm ³ , melt flow rate at 190 ° C. 9 g / 10 min,“ Z-50M ”manufactured by Nippon Polychem Co., Ltd.
G ") 15 parts by weight, ethylene-propylene random copolymer (propylene content 27% by weight, density 0.865 g)
/ Cm ³ , melt flow rate at 230 ° C. 0.7 g /
10 minutes, 15 parts by weight of "EP07P" manufactured by JSR Corporation), 1.1 parts by weight of maleic anhydride, 1.8 parts by weight of ethyl vinyl ketone, 2,5-dimethyl-2,5-bis (t-butyl par) using oxy) hexane 0.13 parts by weight, the as in the case of a ₁ -1 perform graft reaction, obtain an ethylene copolymer mixture maleic anhydride with ethyl vinyl ketone by the modified olefinic polymer Was. The unmodified grafted olefin polymer obtained was subjected to reprecipitation purification treatment to remove ungrafted products, and then the maleic anhydride unit content was 0.6% by weight and the ethyl vinyl ketone unit content was 0.3% as measured by infrared absorption spectrum. 4% by weight, ratio of the number of acyl groups (ethylcarbonyl groups) to the number of carboxylic anhydride groups 0.8, number average molecular weight 28,000 measured by gel permeation chromatography, number average molecular weight and maleic anhydride unit content The average number of carboxylic acid anhydride groups per molecule of the modified olefin-based polymer determined by the multiplier of 1.7 was 1.7 and the melt flow rate at 190 ° C. was 2.8 g / 10 minutes.

[0041] A ₂ -2 (comparative example), ethylene-1-butene copolymer (density of 0.926g / cm ^3, 190 melt flow rate 20 g / 10 min at ° C., Nippon Polychem Co., Ltd., "UJ580") 70 parts by weight of an ethylene-1-butene copolymer (density 0.925 g / cm ³ , melt flow rate at 190 ° C. 9 g / 10 min, “Z” manufactured by Nippon Polychem Co., Ltd.
-50MG "), 15 parts by weight of ethylene-propylene random copolymer (propylene content: 27% by weight, density: 0.1%).
865 g / cm ³ , melt flow rate at 230 ° C. 0.7 g / 10 min, “EP07” manufactured by JSR Co., Ltd.
P ") 15 parts by weight, 1.1 parts by weight of maleic anhydride, 0.6 parts by weight of ethyl vinyl ketone, 2,5-dimethyl-
2,5-bis (t-butylperoxy) hexane 0.0
With 8 parts by weight, the perform graft reaction in the same manner as in the A ₁ -1, to obtain an ethylene-based copolymer mixture modified olefinic polymer by maleic anhydride and ethyl vinyl ketone. The unmodified grafted olefin polymer obtained was subjected to reprecipitation purification treatment to remove ungrafted products, and then the maleic anhydride unit content was 0.7% by weight and the ethyl vinyl ketone unit content was 0.2% as measured by infrared absorption spectrum. 1% by weight, a ratio of the number of acyl groups (ethylcarbonyl groups) to the number of carboxylic anhydride groups of 0.17, a number average molecular weight of 30, measured by gel permeation chromatography,
000, the average number of carboxylic anhydride groups per molecule of the modified olefin-based polymer determined by a multiplier of the number average molecular weight and the maleic anhydride unit content of 2.1, 19
The melt flow rate at 0 ° C. was 2.3 g / 10 minutes.

A-1 (for Comparative Example); Ethylene-1-butene copolymer (density 0.926 g / cm ³ , melt flow rate at 190 ° C. 20 g / 10 min, “UJ580” manufactured by Nippon Polychem Co., Ltd.) 70 Parts by weight, ethylene-1-butene copolymer (density 0.925 g / cm ³ , melt flow rate at 190 ° C. 9 g / 10 min, “Z-
50MG ") 15 parts by weight, ethylene-propylene random copolymer (propylene content 27% by weight, density 0.8
65 g / cm ³ , melt flow rate at 230 ° C.
7 g / 10 minutes, "EP07P" manufactured by JSR Co.)
15 parts by weight, maleic anhydride 1.0 part by weight, n-butyl acrylate 1.2 parts by weight, 2,5-dimethyl-2,5
- bis (t-butylperoxy) using hexane 0.12 parts by weight, subjected to graft reaction in the same manner as in the case of the A ₁ -1, maleic anhydride ethylene copolymer mixture and acrylic acid n- An olefin polymer modified with butyl was obtained. The resulting modified olefin polymer had a maleic anhydride unit content of 0.8 as measured by infrared absorption spectrum after removing ungrafted products by reprecipitation purification treatment.
% By weight, n-butyl acrylate unit content 0.8% by weight, ratio of the number of carboxylic acid ester groups to the number of carboxylic acid anhydride groups 0.8, the number average molecular weight measured by gel permeation chromatography 27,000, the number average The average number of carboxylic acid anhydride groups per molecule of the modified olefin polymer was 2.2, determined based on the molecular weight and the multiplier of the maleic anhydride unit content, and the melt flow rate at 190 ° C was 3.3 g / g. It was 10 minutes.

[0043] (B ₁₎ hydroxyl group-containing compound B ₁ -1; 1,4-cyclohexane dimethylol 10 parts by weight of ethylene homopolymer (density 0.919 g / c
m ³ , melt flow rate at 190 ° C. 2 g / 10 min,
90 parts by weight of "PH-30" manufactured by Nippon Polychem Co., Ltd.) and tetrakis [methylene-3- (3 ',
5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane ("IRG" manufactured by Ciba-Geigy Japan)
ANOX1010 ") and 2.0 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (" IRGAFOS168 "manufactured by Ciba-Geigy Japan) were added, and the mixture was uniformly mixed with a Henschel mixer. It is supplied to a screw extruder (cylinder diameter 45 mm, L / D34, “PCM-45” manufactured by Ikegai Co., Ltd.) and melt-kneaded to obtain a master batch of a hydroxyl-containing compound (melt flow rate at 190 ° C. 4.3 g / 10). Min).

[0044] (B ₂₎ a hydroxyl group-containing polymer B ₂ -1; hydrogenated polybutadiene polyol (hydroxyl group content 1.4 wt%, number average molecular weight of 2,700, calculated on the basis of the multiplier having a number average molecular weight and hydroxyl content (Average number of hydroxyl groups per 2.2 molecules per molecule of hydroxyl group-containing polymer) 50
Parts by weight and ethylene homopolymer (density 0.919 g / cm
³ , 50 parts by weight of a melt flow rate at 190 ° C. of 2 g / 10 min, “PH-30” manufactured by Nippon Polychem Co., Ltd.) and tetrakis [methylene-3- (3 ′,
5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane ("IRG" manufactured by Ciba-Geigy Japan)
ANOX1010 ") and 0.6 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (" IRGAFOS168 "manufactured by Ciba-Geigy Japan Co., Ltd.) were added, and the mixture was uniformly mixed with a Henschel mixer. By supplying to a screw extruder (cylinder diameter 45 mm, L / D34, “PCM-45” manufactured by Ikegai Co., Ltd.) and melt-kneading, a master batch of a hydroxyl group-containing polymer (melt flow rate at 190 ° C. 210 g / 10 min. ) Was prepared.

Examples 1 to 4 and Comparative Examples 1 to 4 The components (A ₁ ) or (A ₂ ) shown in Table 1 and (B)
₁ ) After dry blending with the Henschel mixer using the component (B) or the component (B ₂ ), the extruder (cylinder diameter 20) is used.
mm, L / D20) and melt-extruded into a sheet to form a 2 mm thick sheet.

The obtained sheets were evaluated for crosslinkability and crosslink dissociation by the following methods. The results are shown in Table 1. The crosslinked sheet was subjected to heat treatment at 80 ° C. for 24 hours to crosslink, and then the heat deformation rate was measured at 140 ° C. and 1 kgf in accordance with JIS C3005 (heat deformation). The crosslinked dissociatively molded sheet was heat-treated at 80 ° C for 24 hours to crosslink, and then the heat deformation rate was measured at 230 ° C and 1 kgf in accordance with JIS C3005 (heat deformation).

[0047]

[Table 1]

[0048]

According to the present invention, it is possible to provide an olefin-based polymer composition having high crosslinking property at low temperature and high crosslinking dissociation property at high temperature, and excellent thermoreversible crosslinking property.

Claims (4)

[Claims] (1) The following (A)₁) Component and (B)₁)
Component or / and (B _Two) Component, and (A)₁)
(B) based on the number of carboxylic anhydride groups of the component₁) Components or
/ And (B_Two) The ratio of the number of hydroxyl groups of the component is from 0.1 to 5.
An olefin-based polymer composition, comprising: (A₁) Ethylenically unsaturated carboxylic anhydrides and acylo
Modified with an ethylenically unsaturated compound containing a xy group
Modified olefin polymer, the power per molecule
The average number of bonds of the rubonic anhydride group is 1 or more;
For the number of carboxylic anhydride groups in the modified olefin polymer
Wherein the ratio of the number of acyloxy groups to be
Lefin polymer (B₁) A hydroxyl-containing compound having two or more hydroxyl groups (B_Two) The average number of hydroxyl groups bonded per molecule is 1 or more
Is a hydroxyl group-containing polymer 2. The modified olefin polymer of the component (A ₁ ) wherein the ethylenically unsaturated carboxylic anhydride is maleic anhydride and the acyloxy group-containing ethylenically unsaturated compound is a vinyl ester of an aliphatic saturated carboxylic acid. The olefin polymer composition according to claim 1, wherein 3. The following (A)_Two) Component and (B)₁)
Component or / and (B _Two) Component, and (A)_Two)
(B) based on the number of carboxylic anhydride groups of the component₁) Components or
/ And (B_Two) The ratio of the number of hydroxyl groups of the component is from 0.1 to 5.
An olefin-based polymer composition, comprising: (A_Two) Ethylenically unsaturated carboxylic anhydrides and acyl groups
Modified by Containing Ethylenically Unsaturated Compound
An olefin-based polymer comprising
The acid anhydride group has an average bond number of 1 or more, and
A for the number of carboxylic anhydride groups in the olefin polymer
Modified olefin-based weight having a ratio of the number of sil groups of 0.5 to 20
Coalescing (B₁) A hydroxyl-containing compound having two or more hydroxyl groups (B_Two) The average number of hydroxyl groups bonded per molecule is 1 or more
Is a hydroxyl group-containing polymer 4. The modified olefin polymer of the component (A ₂ ) wherein the ethylenically unsaturated carboxylic anhydride is maleic anhydride and the acyl group-containing ethylenically unsaturated compound is an alkyl vinyl ketone. 4. The olefin polymer composition according to 3.