JP2002241555A - Weather-resistant olefin-based polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a weather-resistant olefin-based polymer composition having high crosslinkability at a low temperature and crosslinking release at a high temperature, having excellent thermally reversible crosslinkability and controlled bleedout of weather-resistant agent. SOLUTION: This weather-resistant olefin-based polymer composition comprises (A) a modified olefin-based polymer modified with an ethylenic unsaturated carboxylic acid anhydride having one or more average number of bonding carboxylic acid anhydride groups per molecule and the ratio of the total number of groups of the number of carboxylic ester groups, the number of acyloxy groups and the number of acyl groups to the number of carboxylic anhydride groups in the modified olefin-based polymer of 0.5-20, (B) a weather-resistant agent containing a hydroxyalkyl group or a hydroxyalkoxy group and (C) a hydroxy group-containing polymer having the average number of bonds of hydroxy groups per molecule of >=1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light-resistant olefin-based polymer composition, and more particularly, to a so-called thermoreversible crosslinkability capable of repeatedly forming a crosslink at a low temperature and dissociating the crosslink at a high temperature. The present invention relates to a light-resistant olefin-based polymer composition having bleed-out of a light-resistant agent and having significantly suppressed.

[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 widely used in various fields by being shaped into a desired shape in the molten state by the method, and in order to improve heat resistance, mechanical strength, etc., compounding of organic peroxide, irradiation of radiation, or silanol condensation reaction It is also widely used as a crosslinked body which has been subjected to a crosslinking treatment by the use of, for example.

[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.

In order to provide a solution to this point, some conventional techniques for forming a crosslink at low temperature and dissociating the crosslink at high temperature to impart thermoplasticity have been proposed in the prior art.
In particular, as an olefin-based resin composition having excellent thermoreversible crosslinkability, the crosslink formation reaction rate and the crosslink dissociation reaction rate are high.
JP-A-6-57062 and JP-A-7-94029 disclose an unsaturated carboxylic anhydride-modified olefin resin, a polyhydric alcohol compound or polymer having at least two hydroxyl groups in a molecule, and an organic compound. An olefin resin composition comprising a reaction accelerator such as a metal salt of a carboxylic acid is disclosed. However, according to the study of the present inventors, the thermoreversible crosslinkable olefin-based resin composition disclosed herein hardly forms a crosslink enough to exhibit sufficient heat resistance, and dissociation of the crosslink at a high temperature. It was also found that the nature was insufficient.

On the other hand, the inventors of the present invention consisted of a specific modified olefin polymer comprising an ethylenically unsaturated carboxylic anhydride and an ethylenically unsaturated carboxylic acid ester and a specific hydroxyl group-containing polymer. It was found that the above problem could be solved by an olefin polymer composition, and a patent application was filed (Japanese Patent Application Laid-Open No. 2000-34376, Japanese Patent Application Laid-Open No.
See respective publications such as 00-204204. ).

[0006] On the other hand, in the field of olefin resin molded products exposed to the open-air, for example, exterior building materials, building material sheets, agricultural films, etc., not only mechanical strength and the like, but also long-term weather resistance are required. Because it is required, the addition of light stabilizers such as ultraviolet absorbers and light stabilizers is essential, but to a greater or lesser extent, those light stabilizers bleed out of the olefinic resin over time and disappear for a long time. It was difficult to maintain the weather resistance.

[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 a light-resistant olefin-based polymer composition which has a property and suppresses bleed-out of a light-resistant agent.

[0008]

Means for Solving the Problems The present invention provides the following (A)
Component, component (B), and component (C),
The content of the component (B) is 0.01 to 5% by weight based on the total composition, and the number of hydroxyalkyl groups or hydroxyalkoxy groups of the component (B) relative to the number of carboxylic anhydride groups of the component (A) is ( The gist of the present invention is a light-resistant olefin-based polymer composition having a total ratio of the number of hydroxy groups of the component (C) of 0.1 to 5.

(A) selected from the group consisting of ethylenically unsaturated carboxylic anhydrides, ethylenically unsaturated carboxylic acid ester compounds, acyloxy group-containing ethylenically unsaturated compounds, and acyl group-containing ethylenically unsaturated compounds. A modified olefin polymer modified with one or more compounds, wherein the average number of carboxylic anhydride groups per molecule is one or more, and the carboxylic acid in the modified olefin polymer is Modified olefin polymer in which the total ratio of the number of carboxylic acid ester groups, the number of acyloxy groups, and the number of acyl groups to the number of anhydride groups is 0.5 to 20 (B) From a compound having at least one hydroxyalkyl group or hydroxyalkoxy group (C) Hydroxy per molecule Hydroxy group-containing polymer average binding number of groups is 1 or more

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) constituting the light-resistant olefin polymer composition of the present invention, an ethylenically unsaturated carboxylic anhydride (hereinafter sometimes referred to as a first modifier), At least one compound selected from the group consisting of an ethylenically unsaturated carboxylic acid ester compound, an acyloxy group-containing ethylenically unsaturated compound, and an acyl group-containing ethylenically unsaturated compound (hereinafter sometimes referred to as a second modifier) Basically, the modified olefin-based polymer modified with α-olefin, the first modifier, and the second modifier, and the α-olefin and the first modified Of a binary copolymer with a second modifier, a graft of a binary copolymer of an α-olefin and a second modifier with a first modifier, and an α-olefin polymer 1st modifier Cografted products thereof according to the second modifier.

Here, as the α-olefin in the terpolymer and the binary copolymer, 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 terpolymer,
Examples of the ethylenically unsaturated carboxylic anhydride as the first modifier in the graft include 2-octen-1-yl succinate, 2-dodecene-1-succinate
Yl anhydride, 2-octadecene-1-yl succinate, maleic anhydride, 2,3-dimethylmaleic anhydride, bromomaleic anhydride, dichloromaleic anhydride, citraconic anhydride, itaconic acid 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-tetrahydrophthalic 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-2,3,5,6-tetracarboxylic anhydride and the like. In the present invention, maleic anhydride is preferred.

As the ethylenically unsaturated carboxylic acid ester compound of the second modifier, an ester of an alkyl group having about 1 to 20 carbon atoms is preferable, for example, methyl (meth) acrylate, (meth) acrylic acid. Ethyl acid,
Propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate,
Examples include alkyl (meth) acrylates such as lauryl (meth) acrylate and stearyl (meth) acrylate, and methyl crotonate, dimethyl maleate, dimethyl fumarate, and dimethyl itaconate. In the present invention, alkyl (meth) acrylates are preferred. Here, “(meth) acryl” means acryl and methacryl.

The acyloxy group-containing ethylenically unsaturated compound of the second modifier is preferably one having an acyl group of about 1 to 20 carbon atoms, for example, vinyl formate, vinyl acetate, vinyl chloroacetate, and the like. Vinyl propionate, vinyl butyrate, vinyl decanoate, vinyl laurate,
Vinyl esters of aliphatic saturated carboxylic acids such as vinyl palmitate and vinyl stearate, vinyl esters of aromatic carboxylic acids such as vinyl benzoate and vinyl naphthoate, allyl chloroformate, allyl acetate, allyl propionate, allyl butyrate Allyl esters of aliphatic saturated carboxylic acids such as allyl decanoate, allyl esters of aromatic carboxylic acids such as allyl benzoate, etc., among which, in the present invention, vinyl esters of aliphatic saturated carboxylic acids Are preferred.

The acyl group-containing ethylenically unsaturated compound of the second modifier has an acyl group having 1 to 1 carbon atoms.
Those having about 20 are preferred, for example, alkyl vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone and butyl vinyl ketone, aryl vinyl ketones such as phenyl vinyl ketone, methyl allyl ketone, ethyl allyl ketone, butyl allyl ketone and the like. Examples thereof include alkyl allyl ketones. Among them, in the present invention, alkyl vinyl ketones are preferable.

In the present invention, the second modifier is selected from the group consisting of ethylenically unsaturated carboxylic acid ester compounds, acyloxy group-containing ethylenically unsaturated compounds, and acyl group-containing ethylenically unsaturated compounds. As the at least one compound, alkyl (meth) acrylates are particularly preferred.

The terpolymer and binary copolymer further include, for example, (meth) acrylamide, N-
Copolymers of 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 multi-component copolymer of three or more or more. In addition, these copolymers are produced by conventionally known polymerization methods such as bulk, solution, suspension, and gas phase.

Examples of the α-olefin-based polymer in the graft include, 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, (meth) acrylamide, N-methyl (meth) acrylamide and the like. Ethylene-based polymers such as copolymers with monomers such as ethylenically unsaturated amides, ethylenically unsaturated nitriles such as (meth) acrylonitrile, and other ethylenically unsaturated compounds such as aromatic vinyl such as styrene; Homopolymer of propylene, propylene and ethylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene , Copolymers with other α-olefins such as 1-decene, propylene and isoprene, 1,3-butadiene, 1,3-pentadiene,
1,4-hexadiene, 1,5-hexadiene, 1,9
-Propylene polymers such as copolymers with other monomers such as diene such as decadiene, and other 1-butene and 4-methyl-
Examples thereof include homopolymers and copolymers of α-olefins such as 1-pentene and 1-hexene. Among them, in the present invention, an ethylene polymer is preferable.

The above-mentioned 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) includes the α-olefin, the ethylenically unsaturated carboxylic anhydride as the first modifier, and the α-olefin as the second modifier. A ternary or more compound with at least one compound selected from the group consisting of the ethylenically unsaturated carboxylic acid ester compound, the acyloxy group-containing ethylenically unsaturated compound, and the acyl group-containing ethylenically unsaturated compound. A polymer or the α-olefin polymer, the ethylenically unsaturated carboxylic anhydride as a first modifier, the ethylenically unsaturated carboxylic acid ester compound as a second modifier, the acyloxy 1 selected from the group consisting of a group-containing ethylenically unsaturated compound and the acyl group-containing ethylenically unsaturated compound.
It is preferably a co-graft with at least one compound.

In the present invention, the modified olefin polymer of the component (A) has a content of the ethylenically unsaturated carboxylic anhydride unit of 0.1% by weight or more, particularly 0.1% by weight.
It is preferably 5% by weight or more, and the average number of carboxylic acid anhydride groups per molecule of the modified olefin polymer, which is determined based on the number average molecular weight of the modified olefin polymer and a multiplier of this content. However, it is essential that the number is one or more, and it is preferable that the number is one or more. If the average number of carboxylic acid anhydride groups is less than the above range, the crosslinkability of the composition and the bleed-out resistance of the light-resistant agent will be poor.

Further, in the present invention, the modified olefin polymer of the component (A) is based on the number of carboxylic anhydride groups derived from the ethylenically unsaturated carboxylic anhydride.
The number of carboxylic acid ester groups derived from the ethylenically unsaturated carboxylic acid ester compound, the number of acyloxy groups derived from the acyloxy group-containing ethylenically unsaturated compound,
It is essential that the total ratio of the number of acyl groups derived from the acyl group-containing ethylenically unsaturated compound is from 0.5 to 20, and preferably from 0.5 to 15. For the number of carboxylic acid anhydride groups, the number of carboxylic acid ester groups, the number of acyloxy groups, and the ratio of the total number of acyl groups is less than the above range, the cross-linking dissociation properties of the composition will be poor,
On the other hand, when the content is in excess of the above range, the crosslinking property as a composition,
In addition, the bleed-out resistance of the light-resistant agent is inferior.

The component (A) in the present invention includes:
As long as the average number of carboxylic acid anhydride groups per molecule, and the number of carboxylic acid anhydride groups, the ratio of the total number of carboxylic acid ester groups, acyloxy groups, and acyl groups satisfies the above range, the above range is satisfied. It may be diluted with a modified olefin polymer or an unmodified olefin polymer which is not used.

The light-resistant agent containing a hydroxyalkyl group or a hydroxyalkoxy group as the component (B) constituting the light-resistant olefin polymer composition of the present invention comprises a compound having at least one hydroxyalkyl group or hydroxyalkoxy group. Is essential, and is preferably a compound having two or more hydroxyalkyl groups or hydroxyalkoxy groups. If the compound does not have a hydroxyalkyl group or a hydroxyalkoxy group, the bleed-out resistance of the light-fast agent as a composition is inferior, and the object of the present invention cannot be achieved.

In the present invention, examples of the hydroxyalkyl group- or hydroxyalkoxy group-containing light stabilizer of the component (B) include an ultraviolet absorber and a light stabilizer.
In the present invention, any ultraviolet absorber selected from the group consisting of benzophenone-based compounds, benzotriazole-based compounds, and triazine-based compounds is preferable.

As the benzophenone-based compound having at least one hydroxyalkyl group or hydroxyalkoxy group, a compound represented by the following formula (I) is preferable.

[0027]

Embedded image

[R ¹ in the formula (I) represents a hydroxy group or a hydrogen atom, and R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydroxyalkyl group, a hydroxyalkoxy group, an alkyl Group, an alkoxy group, an aryl group, a halogen atom or a hydrogen atom, and at least one of R ^{2 to} R ⁵
One is a hydroxyalkyl group or a hydroxyalkoxy group. ]

Here, when R ^{2 to} R ⁵ are a hydroxyalkyl group or a hydroxyalkoxy group, the alkyl group and the alkoxy group are preferably linear or branched ones having 1 to 4 carbon atoms. As the alkyl group and the alkoxy group, a linear or branched carbon number of 1 to 1
Twelve are preferred. Examples of the aryl group include a phenyl group and a naphthyl group.

Specific examples of these benzophenone compounds include, for example, 2,2'-dihydroxy-
4,4′-di (hydroxymethyl) benzophenone,
2,2'-dihydroxy-4,4'-di (2-hydroxyethyl) benzophenone, 2,2'-dihydroxy-
3,3′-dimethoxy-5,5′-di (hydroxymethyl) benzophenone, 2,2′-dihydroxy-3,
3′-dimethoxy-5,5′-di (2-hydroxyethyl) benzophenone, 2,2′-dihydroxy-3,
3'-di (hydroxymethyl) -5,5'-dimethoxybenzophenone, 2,2'-dihydroxy-3,3'-
Di (2-hydroxyethyl) -5,5′-dimethoxybenzophenone and the like.

The benzotriazole compound having at least one hydroxyalkyl group or hydroxyalkoxy group is preferably a compound represented by the following formula (IIa) or (IIb).

[0032]

Embedded image

[R in the formula (IIa)⁶, R⁷, And R⁸,common
And R in formula (IIb)⁹, R^Ten, R ¹¹, And R¹²Are each
Independently, hydroxyalkyl group, hydroxyalkoxy
Si group, alkyl group, alkoxy group, aryl group, halogen
A hydrogen atom or a hydrogen atom;⁶~ R⁸At least
One is and R⁹~ R¹²At least one of the
A xyalkyl group or a hydroxyalkoxy group,
A in (IIb) is an alkylene bond, an ether bond,
Ether bond, sulfinyl bond, sulfonyl bond,
Shows a mino bond or a direct bond. ]

Here, when R ^{9 to} R ¹² are a hydroxyalkyl group or a hydroxyalkoxy group, the alkyl group and the alkoxy group are preferably linear or branched ones having 1 to 4 carbon atoms. As the alkyl group and the alkoxy group, a linear or branched carbon number of 1 to 1
Twelve are preferred. Examples of the aryl group include a phenyl group and a naphthyl group. The alkylene bond of A may be a straight-chain or branched C1-C6 carbon atom.
Are preferred.

Specific examples of these benzotriazole compounds include 2- [2'-hydroxy-5 '-(hydroxymethyl) phenyl]-as a compound represented by the general formula (IIa). 2H-benzotriazole, 2- [2'-hydroxy-5 '-(2-hydroxyethyl) phenyl] -2H-benzotriazole, 2-
[2'-hydroxy-5 '-(3-hydroxypropyl) phenyl] -2H-benzotriazole, 2-
[2'-hydroxy-3'-methyl-5 '-(hydroxymethyl) phenyl] -2H-benzotriazole, 2
-[2'-hydroxy-3'-methyl-5 '-(2-hydroxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-methyl-5'-
(3-Hydroxypropyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-t-butyl-5 '-(hydroxymethyl) phenyl] -2H-
Benzotriazole, 2- [2'-hydroxy-3'-
t-butyl-5 '-(2-hydroxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-t-butyl-5'-(2-hydroxyethyl) phenyl] -5 Chloro-2H-benzotriazole, 2- [2'-hydroxy-3'-t-butyl-5 '
-(3-hydroxypropyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-t-
Octyl-5 '-(hydroxymethyl) phenyl] -2
H-benzotriazole, 2- [2′-hydroxy-
3'-t-octyl-5 '-(2-hydroxyethyl)
Phenyl] -2H-benzotriazole, 2- [2′-
Hydroxy-3′-t-octyl-5 ′-(3-hydroxypropyl) phenyl] -2H-benzotriazole and the like.

The compounds represented by the general formula (IIb) include 2,2'-methylenebis [6- (2H-benzotriazoly-2-yl) -4- (hydroxymethyl) phenol] and 2,2 ' -Methylenebis [6- (2H-benzotriazoly-2-yl) -4- (2-hydroxyethyl) phenol], 2,2'-methylenebis [6- (5
-Chloro-2H-benzotriazoly-2-yl) -4-
(2-hydroxyethyl) phenol], 2,2′-methylenebis [6- (5-bromo-2H-benzotriazoli-2-yl) -4- (2-hydroxyethyl) phenol], 2,2′-methylenebis [ 6- (2H-benzotriazoly-2-yl) -4- (3-hydroxypropyl) phenol], 2,2'-methylenebis [6- (5
-Chloro-2H-benzotriazoly-2-yl) -4-
(3-hydroxypropyl) phenol], 2,2'-
Methylenebis [6- (5-bromo-2H-benzotriazoli-2-yl) -4- (3-hydroxypropyl) phenol], 2,2'-methylenebis [6- (2H-benzotriazoli-2-yl) -4- (4-hydroxybutyl) phenol], 2,2′-methylenebis [6-
(5-chloro-2H-benzotriazoli-2-yl)-
4- (4-hydroxybutyl) phenol], 2,2 ′
-Methylenebis [6- (5-bromo-2H-benzotriazoly-2-yl) -4- (4-hydroxybutyl) phenol], 3,3- {2,2'-bis [6- (2H-
Benzotriazoly-2-yl) -1-hydroxy-4-
(2-hydroxyethyl) phenyl]） propane, 2,
2- {2,2'-bis [6- (2H-benzotriazoly-2-yl) -1-hydroxy-4- (2-hydroxyethyl) phenyl]} butane, 2,2'-oxybis [6- (2H -Benzotriazoly-2-yl) -4-
(2-hydroxyethyl) phenol], 2,2′-bis [6- (2H-benzotriazoly-2-yl) -4-
(2-hydroxyethyl) phenol] sulfide,
2,2′-bis [6- (2H-benzotriazoly-2-
Yl) -4- (2-hydroxyethyl) phenol] sulfoxide, 2,2′-bis [6- (2H-benzotriazoli-2-yl) -4- (2-hydroxyethyl) phenol] sulfone, 2,2 ′ -Bis [6- (2H-benzotriazoly-2-yl) -4- (2-hydroxyethyl) phenol] amine and the like.

The triazine compound having at least one hydroxyalkyl group or hydroxyalkoxy group is preferably a compound represented by the following formula (III).

[0038]

Embedded image

[R ¹³ , R ¹⁴ and R ¹⁵ in the formula (III) each independently represent a hydroxyalkyl group, a hydroxyalkoxy group, an alkyl group, an alkoxy group, an aryl group, a halogen atom or a hydrogen atom. , at least one of R ¹³ to R ¹⁵ is a hydroxyalkyl group or hydroxyalkoxy groups. ]

When R ^{13 to} R ¹⁵ are a hydroxyalkyl group or a hydroxyalkoxy group, the alkyl group and the alkoxy group are preferably linear or branched ones having 1 to 4 carbon atoms. As the alkyl group and the alkoxy group, a linear or branched carbon number of 1 to 1
Twelve are preferred. Examples of the aryl group include a phenyl group and a naphthyl group.

Specific examples of these triazine compounds include 2- (2-hydroxy-4-hydroxymethylphenyl) -4,6-diphenyl-s-triazine and 2- (2-hydroxy-4 -Hydroxymethylphenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- [2-hydroxy-4-
(2-hydroxyethyl) phenyl] -4,6-diphenyl-s-triazine, 2- [2-hydroxy-4-
(2-hydroxyethyl) phenyl] -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2-
[2-hydroxy-4- (2-hydroxyethoxy) phenyl] -4,6-diphenyl-s-triazine, 2-
[2-hydroxy-4- (2-hydroxyethoxy) phenyl] -4,6-bis (2,4-dimethylphenyl)
-S-triazine, 2- [2-hydroxy-4- (3-
Hydroxypropyl) phenyl] -4,6-diphenyl-s-triazine, 2- [2-hydroxy-4- (3-
Hydroxypropyl) phenyl] -4,6-bis (2,
4-dimethylphenyl) -s-triazine, 2- [2-
Hydroxy-4- (3-hydroxypropoxy) phenyl] -4,6-diphenyl-s-triazine, 2- [2
-Hydroxy-4- (3-hydroxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl)-
s-Triazine, 2- [2-hydroxy-4- (4-hydroxybutyl) phenyl] -4,6-diphenyl-s
-Triazine, 2- [2-hydroxy-4- (4-hydroxybutyl) phenyl] -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- [2-hydroxy-4- (4 -Hydroxybutoxy) phenyl]-
4,6-diphenyl-s-triazine, 2- [2-hydroxy-4- (4-hydroxybutoxy) phenyl]-
4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- (2-hydroxy-4-hydroxymethylphenyl) -4,6-bis (2-hydroxy-4-methylphenyl) -s- Triazine, 2- [2-hydroxy-4- (2-hydroxyethyl) phenyl] -4,6-
Bis (2-hydroxy-4-methylphenyl) -s-triazine, 2- [2-hydroxy-4- (2-hydroxyethoxy) phenyl] -4,6-bis (2-hydroxy-4-methylphenyl)- s-Triazine, 2- [2
-Hydroxy-4- (3-hydroxypropyl) phenyl] -4,6-bis (2-hydroxy-4-methylphenyl) -s-triazine, 2- [2-hydroxy-4-
(3-hydroxypropoxy) phenyl] -4,6-bis (2-hydroxy-4-methylphenyl) -s-triazine and the like.

The hydroxy group-containing polymer as the component (C) constituting the light-resistant olefin polymer composition of the present invention is based on the multiplier of the number average molecular weight of the hydroxy group-containing polymer and the content of the hydroxy group. The average number of bonded hydroxy groups per molecule of the hydroxy group-containing polymer is 1
It is essential that the number be at least 1.5, and preferably at least 1.5. If the average number of hydroxyl groups bonded per molecule is less than 1, the crosslinkability of the composition will be poor. As the component (C) in the present invention, as long as the average number of hydroxy groups per molecule satisfies the above range, a hydroxy group-containing or non-containing polymer having an average number of hydroxy groups of less than 1 can be used. May be used.

The hydroxy group-containing polymer of the component (C) in the present invention includes, for example, ethylene- (meth)
2-hydroxyethyl acrylate copolymer, 2-hydroxyethyl (meth) acrylate-grafted polyethylene,
Saponified ethylene-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 polycaprolactones And those having a number average molecular weight of 5
It is preferably from 00 to 10,000. In, low molecular weight polyolefin polyols, polyalkylene ether glycols, polyoxyalkylene polyols,
Hydroxyl-terminated diene polymers and their hydrogenated products are preferred.

The modified olefin polymer of the component (A) in the light-resistant olefin polymer composition of the present invention,
The composition ratio of the hydroxyalkyl group- or hydroxyalkoxy group-containing light stabilizer of the component (B) and the hydroxy group-containing polymer of the component (C) is determined based on the light resistance of the composition. Of 0.1% of the total composition.
0.01 to 5% by weight, and 0.03 to 3% by weight.
Preferably, it is weight%. Then, the number of hydroxyalkyl groups or hydroxyalkoxy groups derived from component (B) relative to the number of carboxylic anhydride groups derived from component (A) and (C)
It is essential that the total ratio of the number of hydroxy groups derived from the components is from 0.1 to 5, preferably from 0.1 to 3.
If the total ratio of the number of hydroxyalkyl groups or hydroxyalkoxy groups and the number of hydroxy groups to the number of carboxylic acid anhydride groups is less than the above range, the crosslinkability as a composition, and the bleed-out resistance of the light-proof agent will be inferior. Exceeding the range results in poor crosslinking dissociation properties of the composition.

The light-resistant olefin polymer composition of the present invention basically comprises the above components (A), (B) and (C). Components other than those components may be contained as long as the components are not impaired, and various additives generally used, for example, ultraviolet absorbers, light stabilizers, antioxidants other than the component (B), and , A nucleating agent, a neutralizing agent, an antistatic agent, a lubricant, an antiblocking agent, a dispersant, a flow improver, a release agent, a flame retardant, a coloring agent, a filler, a foaming agent, and the like may be added. .

The light-resistant olefin polymer composition of the present invention comprises the components (A), (B) and (C):
A method of uniformly mixing with other optional components used as needed by a Henschel mixer, a ribbon blender, a V-type blender, and melt-molding, or after uniformly mixing, a single-screw or multi-screw extruder, a roll , Melt kneading with a Banbury mixer, a kneader, a Brabender, etc., pelletizing, and then melt molding, or the component (A), a component other than the component (B) and a component other than the component (C). Are mixed and melt-kneaded by the method described above, and separately the component (B) and the component (C)
Mixing the components other than the component (A) with the aforementioned method,
It can be prepared by a method of melt-kneading, then mixing and melt-molding both.

The light-resistant olefin polymer composition of the present invention as described above can be prepared by various molding methods usually used for thermoplastic resins, ie, injection molding, extrusion molding, hollow molding, compression molding, rotational molding and the like. It can be shaped into a desired shape in a molten state by a method and cross-linked to form a cross-linked molded article. Also, when the used molded article is reused, etc., the desired shape in the molten state can be obtained by the same molding method. To form a crosslinked molded article.

In order to form crosslinks in the light-resistant olefin polymer composition of the present invention and its molded product, the composition is heated to a temperature higher than the glass transition temperature and lower than the melting point of the light-resistant olefin polymer composition. In order to dissociate the formed crosslinks, it is preferable to heat to a temperature higher than the melting point of the light-resistant 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.

[0049]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the invention. The modified olefin polymer of the component (A) used in Examples and Comparative Examples, (B)
The hydroxyalkyl group or hydroxyalkoxy group-containing light stabilizer of the component and the hydroxy group-containing polymer of the component (C) are as follows.

(A) Modified olefin polymer A-1; ethylene-maleic anhydride-ethyl acrylate terpolymer (maleic anhydride unit content 2.4% by weight measured by infrared absorption spectrum) Ethyl acrylate unit content 7.5% by weight, ratio of the number of carboxylic acid ester groups to the number of carboxylic acid anhydride groups 3.1, number average molecular weight 19,300 measured by gel permeation chromatography, number average molecular weight and maleic acid 3. Average number of carboxylic acid anhydride groups per molecule of the modified olefin polymer determined based on the multiplier of the anhydride unit content
Seven, "Bondane LX411" manufactured by Sumitomo Chemical Co., Ltd.
0 ").

A-2: 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 ") 20 parts by weight, ethylene-1-butene copolymer (density 0.890 g / cm ³ , melt flow rate at 190 ° C. 18 g / 10 min,“ Tuffmer A200 ”manufactured by Mitsui Chemicals, Inc.
90 ") 80 parts by weight, maleic anhydride 1.0 part by weight,
2.3 parts by weight of 2-ethylhexyl acrylate, 2,5-
After uniformly mixing 0.1 part by weight of dimethyl-2,5-bis (t-butylperoxy) hexane with a Henschel mixer, a twin-screw extruder (cylinder diameter 30 mm, L / D3
2, "PCM-30" manufactured by Ikegai Co., Ltd.) and melt-kneaded to carry out a graft reaction, and a modified olefin-based polymer of maleic anhydride of ethylene-1-butene copolymer and 2-ethylhexyl acrylate. A coalescence was obtained. The resulting modified olefin polymer had a maleic anhydride unit content of 0.8% by weight and a 2-ethylhexyl acrylate unit content measured by infrared absorption spectrum after removing unreacted grafts by reprecipitation purification treatment. 0.9% by weight,
A ratio of the number of carboxylic acid ester groups to the number of carboxylic acid anhydride groups of 0.61, a number average molecular weight of 53,000 measured by gel permeation chromatography, and a modification determined based on a multiplier of the number average molecular weight and the maleic anhydride unit content. The olefin polymer had an average number of carboxylic acid anhydride groups per molecule of 4.3 and a melt flow rate at 190 ° C. of 13 g / 10 min.

A-3 (for Comparative Example); terpolymer of ethylene-maleic anhydride-ethyl acrylate (maleic anhydride unit content 0.8% by weight measured by infrared absorption spectrum, acrylic acid Ethyl unit content 30.0% by weight, ratio of the number of carboxylic acid ester groups to the number of carboxylic acid anhydride groups 36.7, number average molecular weight 18,700 measured by gel permeation chromatography, number average molecular weight and maleic anhydride unit The average number of carboxylic acid anhydride groups per molecule of the modified olefin polymer, which is 1.5 based on the multiplier of the content, "Bondane AX8390" manufactured by Sumitomo Chemical Co., Ltd.).

A-4 (for comparative example); ethylene-1-butene copolymer (density 0.925 g / cm ³ , melt flow rate at 190 ° C. 9 g / 10 min, “Z-50MG” manufactured by Nippon Polychem Co., Ltd.) ) 100 parts by weight, maleic anhydride 1.0 part by weight, 2,5-dimethyl-2,5-bis (t-
After uniformly mixing 0.06 parts by weight of butyl peroxy) hexane with a Henschel mixer, a twin-screw extruder (cylinder diameter 30 mm, L / D32, “PCM-3” manufactured by Ikegai Co., Ltd.
0 "), and the mixture was melted and kneaded to perform a graft reaction, thereby obtaining a modified olefin polymer of maleic anhydride of an ethylene-1-butene copolymer. The resulting modified olefin-based polymer was subjected to reprecipitation purification treatment to remove unreacted grafts, and then to a maleic anhydride unit content of 0.8% by weight, as measured by infrared absorption spectrum, as measured by gel permeation chromatography. The number average molecular weight of 25,000, the average number of carboxylic acid anhydride groups per molecule of the modified olefin polymer determined based on the multiplier of the number average molecular weight and the maleic anhydride unit content of 2.0, 190 Melt flow rate at 2.1 ° C / g
It was 10 minutes.

[0054] (B) a hydroxyalkyl group or a hydroxymethyl
Salkoxy group-containing light stabilizer B-1; 2- [2′-hydroxy-5 ′-(2-hydroxyethyl) phenyl] -2H-benzotriazole. B-2: 2,2'-methylenebis [6- (2H-benzotriazoly-2-yl) -4- (2-hydroxyethyl) phenol]. B-3 (for Comparative Example); 2,2′-methylenebis [6-
(2H-benzotriazoly-2-yl) -4-n-octylphenol].

(C) hydroxy group-containing polymer C-1; low molecular weight polyolefin polyol (hydroxy group content: 1.4% by weight, number average molecular weight: 2,000, based on a multiplier of the number average molecular weight and the hydroxy group content) The obtained average number of hydroxyl group bonds per molecule of the hydroxy group-containing polymer was 1.7, "Polytail HA" manufactured by Mitsubishi Chemical Corporation). C-2: 2-hydroxyethyl methacrylate grafted ethylene-1-butene copolymer (2-hydroxyethyl methacrylate unit content 0.8% by weight measured by infrared absorption spectrum, measured by gel permeation chromatography The number average molecular weight is 20,000, and the average number of hydroxy group bonds per molecule of the hydroxy group-containing polymer is 1.2 based on the multiplier of the number average molecular weight and the content of the 2-hydroxyethyl methacrylate unit. C-3 (for comparative example); hydrogenated polybutadiene (hydroxy group content 0% by weight, number average molecular weight 1,000,
"Nissau PB BI-1000" manufactured by Nippon Soda Co., Ltd.).

Examples 1 to 4 and Comparative Examples 1 to 5 The components (A), (B) and (C) shown in Table 1 were used, and tetrakis [methylene-3-) was used as an antioxidant.
(3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (“IRGANOX1010” manufactured by Ciba-Geigy Japan) and tris (2,4-di-
(t-butylphenyl) phosphite (“IRGAFOS168” manufactured by Ciba-Geigy Japan) was used as the component (A)
0.6 parts by weight with respect to 00 parts by weight, and using a Brabender Plastmill (manufactured by Toyo Seiki Co., Ltd.),
The mixture was melt-kneaded at 0 ° C. and 50 rpm for 10 minutes to obtain a light-resistant olefin polymer composition, and then pelletized. From the obtained composition pellets, using a press molding machine, 23
After preheating at 0 ° C. for 5 minutes, the sheet was heated under a pressure of 100 kg / cm ² for 5 minutes, and cooled under a pressure of 120 kg / cm ² , thereby producing a sheet having a thickness of 1 mm.

Each of the obtained sheets was evaluated for crosslinkability, crosslink dissociation, and bleed-out resistance of the light-proofing agent by the following methods. The results are shown in Table 1. The crosslinked sheet is treated at 23 ° C. for 3 weeks to be crosslinked, and then crosslinked according to JIS C3005 (heat deformation).
The heating deformation rate was measured at 0 ° C. and 1 kgf. The crosslinked dissociatively molded sheet is treated at 23 ° C. for 3 weeks to be crosslinked, and then subjected to a crosslinking process according to JIS C3005 (heat deformation).
The heating deformation rate was measured at 0 ° C. and 1 kgf.

Bleed-out resistance of the light-proofing agent The molded sheet was treated at 23 ° C for 3 weeks to crosslink, and then the sheet surface was visually observed and evaluated according to the following criteria. ；: No ballooning to the surface of the powder was observed. ×: Blowing out of the powder surface is observed.

Separately, a film having a thickness of 100 μm was press-molded from the composition pellets obtained above under the same conditions as described above, and each of the obtained films was subjected to UV absorption by the following method. It was measured. The absorbance of the ultraviolet-absorbing molded film at the maximum absorption wavelength appearing at around 340 nm was measured using an ultraviolet-visible spectrophotometer (“UV-2200” manufactured by Shimadzu Corporation), and the results are also shown in Table 1.

[0060]

[Table 1]

[0061]

Industrial Applicability The present invention provides a light-resistant olefin system which has high crosslinkability at low temperatures and high crosslink dissociation at high temperatures, has excellent thermoreversible crosslinkability, and suppresses bleed-out of a lightfast agent. A polymer composition can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 101/02 C08L 101/02 F-term (Reference) 4J002 BB06X BB08X BB21W BE02X BF03X BG07X BN03X CF19X CH01X CH02X EE036 EU176 EU186 FD056

Claims (6)

[Claims] 1. A composition comprising the following components (A), (B) and (C), wherein the content of the component (B) is 0.01 to 5% by weight based on the whole composition. (A)
A ratio of the total number of hydroxyalkyl groups or hydroxyalkoxy groups of the component (B) to the number of hydroxy groups of the component (C) to the number of carboxylic anhydride groups of the component is 0.1 to 5; Coalescing composition. (A) at least one selected from the group consisting of ethylenically unsaturated carboxylic anhydrides, ethylenically unsaturated carboxylic acid ester compounds, acyloxy group-containing ethylenically unsaturated compounds, and acyl group-containing ethylenically unsaturated compounds Wherein the average number of carboxylic acid anhydride groups per molecule is one or more, and the number of carboxylic acid anhydride groups in the modified olefinic polymer is A modified olefin polymer having a total ratio of the number of carboxylic acid ester groups, the number of acyloxy groups, and the number of acyl groups to 0.5 to 20 (B) hydroxyalkyl comprising a compound having at least one hydroxyalkyl group or hydroxyalkoxy group (C) average number of hydroxy groups per molecule Hydroxy group-containing polymer number is 1 or more 2. The modified olefin polymer of the component (A) has an average number of carboxylic anhydride groups per molecule of 1.
5 or more, and the average number of bonded hydroxy groups per molecule of the hydroxy group-containing polymer of the component (C) is 1.5.
The light-resistant olefin polymer composition according to claim 1, wherein the number is at least one. 3. The modified olefin polymer of the component (A) comprises ethylene, an ethylenically unsaturated carboxylic acid anhydride, an ethylenically unsaturated carboxylic acid ester compound, an acyloxy group-containing ethylenically unsaturated compound, and acyl. The light-resistant olefin polymer composition according to claim 1 or 2, which is a ternary or higher copolymer with one or more compounds selected from the group consisting of group-containing ethylenically unsaturated compounds. 4. The modified olefin polymer of the component (A) is an ethylenically unsaturated carboxylic acid anhydride, an ethylenically unsaturated carboxylic acid ester compound or an acyloxy group-containing ethylenically unsaturated compound of an ethylene polymer. 3. The light-resistant olefin polymer composition according to claim 1, wherein the composition is a co-graft of at least one compound selected from the group consisting of: and an acyl group-containing ethylenically unsaturated compound. 4. 5. The ethylenically unsaturated carboxylic acid anhydride in the modified olefin polymer of the component (A) is maleic anhydride, an ethylenically unsaturated carboxylic acid ester compound, an acyloxy group-containing ethylenically unsaturated compound, The light-resistant olefin polymer composition according to any one of claims 1 to 4, wherein the compound selected from the group consisting of an acyl group-containing ethylenically unsaturated compound is an alkyl (meth) acrylate. 6. The hydroxyalkyl group or hydroxyalkoxy group-containing light stabilizer of the component (B) is any one of a hydroxyalkylalkyl group selected from the group consisting of a benzophenone compound, a benzotriazole compound and a triazine compound. The light-resistant olefin polymer composition according to any one of claims 1 to 5, which is a hydroxyalkoxy group-containing ultraviolet absorber.