JP3473183B2 - Polyolefin molded products - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to a polyolefin molded article,
More specifically, it relates to a polyolefin molded article having an ultraviolet curable resin layer and having no yellowing.

[0002]

2. Description of the Related Art Generally, polyolefin is relatively inexpensive and has excellent mechanical properties, and therefore it is used for producing various molded products such as injection molded products, hollow molded products, films, sheets and fibers. However, polyolefins, especially propylene-based polymers, have the disadvantage that they are susceptible to thermal oxidative deterioration during molding and practical use because they have tertiary carbons that are susceptible to oxidation. Therefore, various antioxidants such as phenol-based, phosphorus-based, and thioether-based antioxidants have been widely used for the purpose of preventing thermal oxidative deterioration. However, when a polyolefin composition formed by blending various antioxidants is molded and the resulting molded article is subjected to surface treatment such as printing or painting with an ultraviolet curable ink or paint, it is blended in the molded article. There is a problem in that the antioxidants turned yellow due to the irradiation of ultraviolet rays and the commercial value of the molded products was significantly reduced.

Therefore, it has been proposed in the past to incorporate a specific antioxidant for the purpose of preventing yellowing at the time of ultraviolet curing printing or coating of a polyolefin molded article.
For example, in Japanese Patent Laid-Open No. 6-100737, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite and pentaerythrityl-tetrakis [3- ( 3,5-
It is described that an antioxidant selected from the group consisting of di-t-butyl-4-hydroxyphenyl) propionate] is added. In addition, Japanese Patent Laid-Open No.
JP-A-313076 describes blending a crystalline polypropylene resin with a phosphorus-based antioxidant having a melting point of 175 ° C. or higher.

On the other hand, Japanese Patent Laid-Open No. 63-95246 discloses a polypropylene composition as an antioxidant for polypropylene for the purpose of obtaining a polypropylene composition which does not discolor under a high temperature or under a high temperature humidification after contact with a printing ink. a) a phenolic antioxidant in which the 2- and 6-positions of the phenol group are substituted with at least one substituent having 1 or more carbon atoms,
One or a mixture of two or more selected from bis, tris or tetrakisphenol type antioxidants, (b) thioether type antioxidants and (c) phosphite, phosphonite type and phosphonic acid type antioxidants. It has been proposed to blend.

[0005]

However, Japanese Patent Application Laid-Open No. 63-95246 mentions problems and solutions when a polypropylene sheet is used as a printing ink, especially when an ultraviolet curable ink is used for printing. Not not.

The present inventors were not satisfied with the molded products proposed in Japanese Patent Laid-Open Nos. 6-100737 and 6-313076, and further, polyolefin molding without yellowing during ultraviolet curing printing or coating. As a result of studying to obtain a product, it was found that the above-mentioned drawbacks of the conventional polyolefin molded product can be solved by blending a specific amount of a specific phosphorus compound and a specific amount of a phenolic compound with a polyolefin, and the present invention has been accomplished. Therefore, an object of the present invention is to provide a polyolefin molded article having an ultraviolet curable resin layer and having no yellowing.

[0007]

According to the present invention, one or more compounds selected from the following groups (1) to (10) are added to 0.01 to 100 parts by weight of polyolefin. 1
There is provided a polyolefin molded article having an ultraviolet curable resin layer, which is obtained by molding a composition containing parts by weight. (1) Bis (2,4-di-t-butyl-5-methylphenyl) -pentaerythritol-diphosphite, (2)
Tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylene-di-phosphonite, (3) a phosphorus compound represented by the following general formula (I)

[Chemical 2] (In the formula, R ₁ represents a direct bond or an alkylidene group having 1 to 4 carbon atoms, Ar ₁ and Ar ₂ each represent an alkylarylene group, n represents an integer of 1 to 4, and n represents 1. , R ₂ represents an alkyl group having 1 to 28 carbon atoms,
And when n represents an integer of 2 to 4, R ₂ represents a polyol residue), (4) n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) Propionate, (5) Tris (3,5-di-t-butyl-4)
-Hydroxybenzyl) isocyanurate, (6) tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, (7) tris [3- (3,
5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, (8) N, N ′
-Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, (9) N, N '
-Bis [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide, (10) 2,2'-alkylidene-bis (4,6-di-t) -Alkylphenol). The compounds (1) to (10) used in the present invention are hereinafter abbreviated as "compound A" for convenience of explanation.

The polyolefin used in the present invention is
Ethylene, propylene, butene-1, pentene-1, 4
-Methyl-pentene-1, hexene-1, octene-1
And the like, crystalline homopolymers of α-olefins, crystalline, low crystalline or amorphous random copolymers or crystalline block copolymers of these two or more α-olefins, amorphous ethylene-propylene- Non-conjugated diene terpolymer,
Polyolefin such as amorphous ethylene-cyclic alkene copolymer (for example, amorphous ethylene-tetracyclododecene copolymer), copolymer of the above-mentioned α-olefin and vinyl acetate or acrylic ester, Saponified polymers, copolymers of these α-olefins with unsaturated silane compounds, copolymers of these α-olefins with unsaturated carboxylic acids or their anhydrides, between these copolymers and metal ion compounds A reaction product, a modified polyolefin obtained by modifying the above-mentioned polyolefin with an unsaturated carboxylic acid or a derivative thereof, a silane-modified polyolefin obtained by modifying the above-mentioned polyolefin with an unsaturated silane compound, and the like can be exemplified. That is, two or more kinds of polyolefins can be mixed and used.

In addition to the above-mentioned polyolefins, various synthetic rubbers (for example, polybutadiene, polyisoprene, polychloroprene, chlorinated polyethylene, chlorinated polypropylene, fluororubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, styrene-butadiene-styrene). Block copolymer, styrene-isoprene-
Styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-propylene-butylene-styrene block copolymer, ethylene-
Ethylene-butylene-ethylene block copolymer, ethylene-propylene-butylene-ethylene block copolymer, etc.) or thermoplastic synthetic resin (for example, polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide,
Polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycarbonate, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, fluororesin, petroleum resin (for example, C ₅ petroleum resin, water Appendix C ₅ petroleum resins, C ₉ petroleum resins, hydrogenated C ₉ petroleum resin, C ₅ -C ₉ copolymer petroleum resin, hydrogenated C ₅ -C ₉ copolymer petroleum resin, acid-modified C ₉ petroleum resin Softening point of 80 to 2
00 ° C petroleum resin), DCPD resin (for example, cyclopentadiene-based petroleum resin, hydrogenated cyclopentadiene-based petroleum resin, cyclopentadiene-C ₅ copolymerized petroleum resin, hydrogenated cyclopentadiene-C ₅ copolymerized petroleum resin, cyclopentadiene- C ₉ copolymer petroleum resin, hydrogenated cyclopentadiene -C ₉ copolymer petroleum resin, cyclopentadiene -C ₅ -C
₉ copolymer petroleum resin, hydrogenated cyclopentadiene -C ₅ -C ₉
DCPD with a softening point of 80-200 ° C, such as copolymerized petroleum resin
It is also possible to use a mixture of (resin) and the like. A crystalline propylene homopolymer, a crystalline propylene copolymer containing 70% by weight or more of a propylene component, which is a crystalline ethylene-propylene random copolymer, a crystalline ethylene-
Propylene block copolymer, crystalline propylene-butene-1 random copolymer, crystalline ethylene-propylene-butene-1 terpolymer, crystalline propylene-hexene-butene-1 terpolymer and these A mixture of two or more kinds is particularly preferably used.

Among the compounds A used in the present invention, in the general formula (I), the alkylidene group having 1 to 4 carbon atoms represented by R ₁ includes methylene, ethylidene, propylidene, i-propylidene, butylidene and the like. Examples of the alkylarylene group represented by Ar ₁ and Ar ₂ include 4,6-dialkylphenyl-2-yl (wherein the alkyl group is the same or different alkyl group, methyl, ethyl, propyl, i- Propyl, butyl, s-butyl, t-butyl, amyl, t-amyl, hexyl, heptyl, octyl, i-octyl, t-octyl, 2-ethylhexyl, nonyl, i-nonyl, decyl, i-decyl, undecyl, dodecyl, t-dodecyl), and the like, the alkyl group having a carbon number of 1 to 28 represented by R _2, methyl Ethyl, propyl, i-
Propyl, butyl, s-butyl, t-butyl, amyl,
t-amyl, hexyl, heptyl, octyl, i-octyl, t-octyl, 2-ethylhexyl, nonyl, i
-Nonyl, decyl, i-decyl, undecyl, dodecyl, t-dodecyl, pentadecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, hexacosyl, octacosyl and the like, and the polyol residue is ethylene glycol, 1,4-butane. Diol, 1,6-hexanediol, spiroglycol, bis (2-hydroxyethyl) oxamide, glycerin,
Examples thereof include residues of polyols such as trimethylolethane, trimethylolpropane, triethanolamine, tris (2-hydroxyethyl) isocyanurate, erythritol, and pentaerythritol.

Therefore, the preferable phosphorus compound represented by the general formula (I) is 2,2'-methylene-bis (4,6-di-t-butylphenyl) -2-ethylhexylphosphite, 2'-methylene-bis (4,6
-Di-t-amylphenyl) -2-ethylhexyl phosphite, 2,2'-ethylidene-bis (4,6-di-
t-butylphenyl) octadecyl phosphite,
2,2'-ethylidene-bis (4,6-di-t-amylphenyl) octadecyl phosphite, bis [2,2 '
-Methylene-bis (4,6-di-t-butylphenyl)]-ethylene glycol-diphosphite, bis [2,2'-methylene-bis (4,6-di-t-butylphenyl)]-1 , 4-Butanediol-diphosphite, bis [2,2'-methylene-bis (4,6-di-t-
Butylphenyl)]-1,6-hexanediol-diphosphite, bis [2,2'-methylene-bis (4-
Methyl-6-t-butylphenyl)]-3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,
8,10-Tetraoxaspiro [5.5] undecane-diphosphite, bis [2,2'-methylene-bis (4,
6-di-t-butylphenyl)]-3,9-bis (1,1
-Dimethyl-2-hydroxyethyl) -2,4,8,10
-Tetraoxaspiro [5.5] undecane-diphosphite, bis [2,2'-methylene-bis (4,6-di-t-amylphenyl)]-3,9-bis (1,1-dimethyl) 2-Hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane-diphosphite, bis [2,2'-ethylidene-bis (4-methyl-)
6-t-butylphenyl)]-3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane-diphosphite, bis [2,2'-ethylidene-bis (4,6-di-
t-Butylphenyl)]-3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane-diphosphite, bis [2 2,2'-ethylidene-bis (4,6-di-t
-Amylphenyl)]-3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane-diphosphite,
Bis [2,2'-methylene-bis (4,6-di-t-butylphenyl)]-N, N'-bis (2-hydroxyethyl) oxamide-diphosphite,

Tris [2,2'-methylene-bis (4,6)
-Di-t-butylphenyl)]-glycerin-triphosphite, tris [2,2'-methylene-bis (4,6)
-Di-t-butylphenyl)]-trimethylolethane-triphosphite, tris [2,2'-methylene-
Bis (4,6-di-t-butylphenyl)]-trimethylolpropane-triphosphite, tris [2,
2'-bis (4,6-di-t-butylphenyl)]-triethanolamine-triphosphite, tris [2,2'-bis (4,6-di-t-amylphenyl)]
-Triethanolamine-triphosphite, tris [2,2'-methylene-bis (4,6-di-t-butylphenyl)]-triethanolamine-triphosphite, tris [2,2'-methylene- Bis (4,6-di-t
-Amylphenyl)]-triethanolamine-triphosphite, tris [2,2'-ethylidene-bis (4,6-di-t-butylphenyl)]-triethanolamine-triphosphite, Tris [2, 2'-ethylidene-bis (4,6-di-t-amylphenyl)]
-Triethanolamine-triphosphite, tris [2,2'-methylene-bis (4,6-di-t-butylphenyl)]-N, N ', N "-tris (2-hydroxyethyl) isocyanurate -Triphosphite, tetrakis [2,2'-methylene-bis (4,6-di-t-butylphenyl)]-erythritol-tetraphosphite, tetrakis [2,2'-methylene-bis (4,6-) Examples thereof include di-t-butylphenyl)]-pentaerythritol-tetraphosphite.

Further, among the compound A, in 2,2'-alkylidene-bis (4,6-di-t-alkylphenol), examples of the alkylidene group include methylene, ethylidene, propylidene, i-propylidene and butylidene. Examples of the t-alkyl group include t-butyl, t
-Amyl, t-octyl, t-nonyl, t-dodecyl and the like. 2,2'-Alkylidene-bis (4,6
Preferred as (di-t-alkylphenol) are 2,2'-methylene-bis (4,6-di-t-butylphenol) and 2,2'-ethylidene-bis (4,6-di-t-butylphenol). ) 2,2'-ethylidene-bis (4,6-di-t-amylphenol) and the like.

Therefore, as the compound A used in the present invention, particularly, bis (2,4-di-t-butyl-5-methylphenyl) -pentaerythritol-diphosphite and tetrakis (2,4-di-t) are used. -Butyl-5-methylphenyl) -4,4'-biphenylene-di-phosphonite, 2,2'-methylene-bis (4,6-di-t-butylphenyl) -2-ethylhexylphosphite,
Bis [2,2'-ethylidene-bis (4,6-di-t-amylphenyl)]-3,9-bis (1,1-dimethyl-2)
-Hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane-diphosphite, tris [2,2'-bis (4,6-di-t-butylphenyl)]-tri Ethanolamine-triphosphite,
n-octadecyl-β- (4′-hydroxy-3 ′,
5'-di-t-butylphenyl) propionate, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, tris (4-t-butyl-3-)
Hydroxy-2,6-dimethylbenzyl) isocyanurate, tris [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, N, N'-bis [3- (3 , 5-Di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, N, N'-bis [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy]
Ethyl] oxamide, 2,2'-methylene-bis (4,6
-Di-t-butylphenol), 2,2'-ethylidene-bis (4,6-di-t-butylphenol) and 2,
2'-Ethylidene-bis (4,6-di-t-amylphenol) is preferred. These compounds A may be used alone or in combination of two or more kinds. The compounding ratio of the compound A is 0.01 to 1 part by weight, preferably 0.05 to 100 parts by weight of the polyolefin.
0.5 parts by weight. If the amount is less than 0.01 parts by weight, the effect of preventing yellowing of the polyolefin molded article will not be sufficiently exhibited.
Although it may be added in an amount of more than 1 part by weight, further yellowing prevention effect cannot be expected, which is impractical and uneconomical.

The UV-curable resin layer contained in the polyolefin molded article of the present invention includes, for example, a hard coat layer made of only the UV-curable resin for imparting high gloss and scratch resistance, or a UV-curable ink layer containing the UV-curable resin. Although a paint layer and the like are included, here, the UV curable ink layer will be specifically described below as an example. UV-curable inks containing UV-curable resins include colorants (organic and inorganic pigments), vehicles and auxiliaries (surfactants,
Diluent, varnish, toner, Victoria, etc.),
The vehicle, that is, the ultraviolet curable resin, comprises a photosensitive prepolymer (oligomer), a photosensitive monomer and a photopolymerization initiator (sensitizer).

As the photosensitive prepolymer, for example, pentaerythritol tri (meth) acrylate [(meth) acrylate in the present specification is a general term for acrylate and methacrylate. ], Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, epoxidized drying oil (Meth) acrylate, bisphenol A diglycidyl ether (meth) acrylate, modified bisphenol A epoxy (meth) acrylate, aliphatic epoxy (meth) acrylate, poly (meth) acrylate carbamate,
Hydroxy group-containing (meth) acrylate, diisocyanurate and hydroxy group-containing resin or drying oil
Examples include reaction products composed of components, polyester / (meth) acrylate, polyether / (meth) acrylate, poly (meth) acrylate / alkyd, and melamine / (meth) acrylate.

Examples of the photosensitive monomer include hydroxybutyl (meth) acrylate, dicyclopentadiene (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, cyclohexyl (meth) acrylate and 1,6-hexanediol diacrylate. (Meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate,
Examples thereof include ethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate.

Examples of the photopolymerization initiator include anthraquinone, benzoin ethers, benzyl, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (trichloromethyl) benzophenone and 2-chloro. Thioxanthenone, dibutylphenylphosphine, α, α-diethoxyacetophenone, p
-Dimethylaminobenzaldehyde, 2-ethylanthraquinone, xanthenone, 2-benzoylbenzoates, benzoylbiphenyl, 1-benzoylnaphthalene, 4-benzoylpyridine, 2-chloroanthraquinone, chlorobenzophenone, 1-hydroxycyclohexyl-phenylketone, ( η ⁵ -2,4-Cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1
- methylethyl) benzene] - Iron (I ⁺⁾ - hexafluorophosphate ^(I -), 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl -
1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,
2-Hydroxy-2-methyl-1-phenyl-propan-1-one, 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy 2-Methyl-1-propan-1-one, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pyr-1
Examples include -yl) -phenyl] titanium and the like.

The ultraviolet curable resin layer can be formed, for example, by the following method. That is, after forming a coating film of the above-mentioned ultraviolet curable resin composition on the surface of a polyolefin molded article, the ultraviolet curable resin is irradiated with ultraviolet rays using an ultraviolet irradiation device to cure the ultraviolet curable resin to form an ultraviolet curable resin layer. Examples of the ultraviolet irradiation device include a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp,
Examples include carbon arc lamps, tungsten lamps and halogen lamps.

In the polyolefin molded article of the present invention, various additives usually added to polyolefins such as phenol type (excluding compound A), thioether type, phosphorus type (excluding compound A), etc. Antioxidants, light stabilizers, heavy metal deactivators (copper damage inhibitors;
However, except compound A), a clarifying agent, a nucleating agent, a lubricant, an antistatic agent, an antifogging agent, an antiblocking agent, a non-dropping agent, a radical generating agent such as a peroxide, a flame retardant, a flame retardant auxiliary agent, Pigments, halogen scavengers, dispersants or neutralizers for metallic soaps, organic or inorganic antibacterial agents, inorganic fillers (eg talc, mica, clay, wollastonite, zeolite, kaolin, bentonite, perlite) , Diatomaceous earth, asbestos, calcium carbonate, magnesium hydroxide, aluminum hydroxide, hydrotalcite, basic aluminum lithium hydroxycarbonate
Hydrate, silicon dioxide, titanium dioxide, zinc oxide, calcium oxide, magnesium oxide, zinc sulfide, barium sulfate, magnesium sulfate, calcium silicate, aluminum silicate, glass fiber, potassium titanate, carbon fiber, carbon black, graphite and The inorganic filler or the organic filler (eg, silane-based, titanate-based, boron-based, aluminate-based, zirco-aluminate-based) surface-treated with a surface-treating agent such as a metal fiber). Wood flour, pulp, waste paper,
Synthetic fibers, natural fibers, etc.) can be used in combination with Compound A as long as the object of the present invention is not impaired.

The polyolefin molded article of the present invention can be obtained, for example, by the following production method. That is, a predetermined amount of each of the above-mentioned compound A and the above-mentioned various additives usually added to a polyolefin is mixed with a polyolefin by using an ordinary mixing device such as a Henschel mixer (trade name), a super mixer, a ribbon blender, or a Banbury mixer. Then, the composition is prepared by melt-kneading and pelletizing at a melt-kneading temperature of 150 ° C. to 320 ° C., preferably 180 ° C. to 290 ° C. with a normal single-screw extruder, twin-screw extruder, Brabender or roll. By various molding methods such as injection molding method, extrusion molding method, and blow molding method, the product is formed into a single-layered product or a laminated product depending on the intended use, and the above-mentioned UV-curable resin layer is formed on the surface of this molded product. It is possible to obtain a polyolefin molded article by providing, and it is put to practical use.

[0022]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The evaluation methods used in Examples and Comparative Examples were as follows. UV yellowing: 50 mm length using the obtained pellets,
A test piece having a width of 50 mm and a thickness of 2 mm was prepared by an injection molding method, and 0.3 ml of ultraviolet curable ink manufactured by Toyo Ink Mfg. Co., Ltd. was placed on the test piece and an ultraviolet irradiation device (UVC manufactured by Ushio Inc.) -181) with an ultraviolet wavelength of 30
The UV-curable ink layer (UV-curable resin layer) is exposed by UV irradiation under the conditions of 0 nm, UV irradiation intensity of 80 w / cm, irradiation time of 3 seconds, and distance of 100 mm between the UV source and the test piece to be irradiated. A test piece having the above was obtained. The degree of yellowing of the obtained test piece having the ultraviolet curable ink layer was visually determined and evaluated according to the following criteria. ○: No yellowing ×: Yellowing

The various additives shown in the following Tables 1 to 4 used in the following Examples and Comparative Examples are as follows. Compound A [1]: Bis (2,4-di-t-butyl-5-
Methylphenyl) -pentaerythritol-diphosphite, compound A [2]: tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylene-di-phosphonite, compound A [3]: 2,2'-methylene-bis (4,6-di-t-butylphenyl) -2-ethylhexyl phosphite, Compound A [4]: 2,2'-ethylidene-bis (4,6-
Di-t-amylphenyl) octadecyl phosphite, compound A [5]: bis [2,2'-methylene-bis (4
-Methyl-6-t-butylphenyl)]-ethylene glycol-diphosphite, Compound A [6]: bis [2,2'-methylene-bis (4,
6-di-t-butylphenyl)]-1,4-butanediol-diphosphite, Compound A [7]: bis [2,2'-ethylidene-bis (4,6-di-t-octylphenyl) ] -1,6-Hexanediol-diphosphite, Compound A [8]: bis [2,2'-methylene-bis (4,
6-di-t-butylphenyl)]-3,9-bis (1,1
-Dimethyl-2-hydroxyethyl) -2,4,8,10
-Tetraoxaspiro [5.5] undecane-diphosphite, Compound A [9]: bis [2,2'-ethylidene-bis (4,6-di-t-amylphenyl)]-3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,
8,10-Tetraoxaspiro [5.5] undecane-diphosphite, Compound A [10]: Bis [2,2'-methylene-bis (4,6-di-t-butylphenyl)]-N, N'-bis (2-hydroxyethyl) oxamide-diphosphite, compound A [11]: tris [2,2'-propylidene-
Bis (4,6-di-nonylphenyl)]-glycerin-
Triphosphite, Compound A [12]: Tris [2,2'-i-propylidene-bis (4,6-di-t-dodecylphenyl)]-trimethylolethane-triphosphite, Compound A [13]: Tris [2,2'-butylidene-bis (4-ethyl-6-t-butylphenyl)]-trimethylolpropane-triphosphite, Compound A [14]: Tris [2,2'-bis (4,6) -Di-t-butylphenyl)]-triethanolamine-triphosphite, compound A [15]: tris [2,2'-methylene-bis (4,6-di-t-butylphenyl)]-triethanol. Amine-triphosphite, compound A [16]: tris [2,2'-methylene-bis (4,6-di-t-butylphenyl)]-N, N ', N "
-Tris (2-hydroxyethyl) isocyanurate-
Triphosphite, Compound A [17]: Tetrakis [2,2'-methylene-
Bis (4,6-di-t-butylphenyl)]-erythritol-tetraphosphite, compound A [18]: tetrakis [2,2'-methylene-
Bis (4,6-di-t-butylphenyl)]-pentaerythritol-tetraphosphite,

Compound A [19]: n-octadecyl-β
-(4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate, compound A [20]: tris (3,5-di-t-butyl-
4-hydroxybenzyl) isocyanurate, compound A [21]: tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, compound A [22]: tris [3- (3,5) -Di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, compound A [23]: N, N'-bis [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionyl]
Hydrazine, compound A [24]: N, N'-bis [2- [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide, compound A [25]: 2,2'-methylene-bis (4,6-
Di-t-butylphenol), Compound A [26]: 2,2'-ethylidene-bis (4,6)
-Di-t-butylphenol), Compound A [27]: 2,2'-ethylidene-bis (4,6)
-Di-t-amylphenol), Compound A [28]: 2,2'-butylidene-bis (4,6)
-Di-t-dodecylphenol), phosphorus-based antioxidant 1: bis (2,4-di-t-butylphenyl) -pentaerythritol-diphosphite, phosphorus-based antioxidant 2: tetrakis (2,4- Di-t-butylphenyl) -4,4'-biphenylene-di-phosphonite, phosphorus-based antioxidant 3: 2,2'-ethylidene-bis (4,
6-di-t-butylphenyl) fluorophosphite, phenolic antioxidant 1: 1,3,5-trimethyl-
2,4,6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, phenolic antioxidant 2: 3,9-bis [1,1-dimethyl-2- {β- ( 3-t-butyl-4-hydroxy-
5-Methylphenyl) propionyloxy} ethyl]-
2,4,8,10-Tetraoxaspiro [5.5] undecane, Ca-St: calcium stearate.

Examples 1 to 14 Melt flow rate as a polyolefin (a discharge amount of a molten resin for 10 minutes when a load of 21.18N at 230 ° C. is applied, hereinafter abbreviated as MFR) 6.0 g / 10
To 100 parts by weight of powdery crystalline propylene homopolymer which is not stabilized, and each compound and additive (Ca-St) shown in Table 1 below are mixed at a predetermined mixing ratio, and a Henschel mixer (commercial product) After mixing with stirring for 3 minutes, the mixture was melt-kneaded at 200 ° C. with a single screw extruder having a diameter of 40 mm to form pellets. Using the obtained pellets to evaluate ultraviolet yellowing by the above test method,
The results are shown in Table 1.

Comparative Examples 1 to 5 100 parts by weight of an unstabilized powdery crystalline propylene homopolymer having an MFR of 6.0 g / 10 min were added to Table 1 below.
Predetermined amounts of the respective antioxidants and additives (Ca-St) shown in (1) were blended and melt-kneaded according to Examples 1 to 14 to obtain pellets. The obtained pellets were used to evaluate ultraviolet yellowing by the above test method, and the results are shown in Table 1.

Examples 15 to 28 99% by weight of an unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 4.0% by weight) as MFR 1.0 g / 10 min as polyolefin
And melt index (load 21.
Discharge amount of molten resin for 10 minutes when 18N was added; hereinafter abbreviated as MI. ) 7.0 g / 10 min unstabilized powdered linear low density polyethylene (ethyl branch 3
0 parts / 1000 carbons) and 1% by weight, in total 100 parts by weight, each compound and additive (Ca-
St) is mixed at a predetermined mixing ratio into a Henschel mixer (trade name) and mixed for 3 minutes with stirring.
The mixture was melt-kneaded at 200 ° C. with a single screw extruder having a diameter of 40 mm to form pellets. The obtained pellets were used to evaluate the yellowing of ultraviolet rays by the above-mentioned test method, and the results are shown in Table 2.

Comparative Examples 6 to 10 99% by weight of powdery crystalline ethylene-propylene random copolymer (ethylene content 4.0% by weight) having an MFR of 1.0 g / 10 min and an MI of 7 0.0 g /
A total of 100 parts by weight of unstabilized powdered linear low-density polyethylene (30 ethyl branches / 1000 carbons) for 10 minutes was added to 100 parts by weight of each antioxidant and additive shown in Table 2 below. Add a predetermined amount of (Ca-St),
Melt-kneading processing was performed according to Examples 15 to 28 to obtain pellets. The obtained pellets were used to evaluate the yellowing of ultraviolet rays by the above-mentioned test method, and the results are shown in Table 2.

Examples 29 to 42 100 parts by weight of an unstabilized powdery crystalline ethylene-propylene block copolymer having an MFR of 4.0 g / 10 min as a polyolefin (ethylene content 8.5% by weight) were added as described below. Each compound and additive (Ca-
St) was mixed at a predetermined mixing ratio, put into a Henschel mixer (trade name), stirred and mixed for 3 minutes, and then melt-kneaded at 200 ° C. in a single screw extruder having a diameter of 40 mm to form pellets. The obtained pellets were used to evaluate the ultraviolet yellowing by the above test method, and the results are shown in Table 3.
Shown in.

Comparative Examples 11-15 100 parts by weight of an unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight) having an MFR of 4.0 g / 10 min. Predetermined amounts of the respective antioxidants and additives (Ca-St) shown in Table 3 were mixed and melt-kneaded according to Examples 29 to 42 to obtain pellets. The obtained pellets were used to evaluate ultraviolet yellowing by the test method described above, and the results are shown in Table 3.

Examples 43-56 Unstabilized powdery crystalline ethylene-propylene-butene-1 terpolymers with an MFR of 7.0 g / 10 min as polyolefin (ethylene content 2.5% by weight, butene- 1 content 4.5% by weight) 80% by weight, MI 7.0 g
Unstabilized powdery amorphous ethylene of 10% by weight of unstabilized powdery linear low-density polyethylene (30 ethyl branches / 1000 carbons) and Mooney viscosity ML1 + 4 (100 ° C.) of / 10 min -Propylene random copolymer (propylene content 25% by weight) 10% by weight and a total of 100 parts by weight, each compound shown in Table 4 below and the additive (Ca-St) are mixed at a predetermined mixing ratio. Put it in a Henschel mixer (trade name),
After stirring and mixing for 3 minutes, 2 with a single-screw extruder with a diameter of 40 mm.
The mixture was melt-kneaded at 00 ° C. and pelletized. The obtained pellets were used for evaluation of ultraviolet yellowing by the above test method, and the results are shown in Table 4.

Comparative Examples 16 to 20 Unstabilized powdery crystalline ethylene-propylene-butene-1 terpolymer having an MFR of 7.0 g / 10 min (ethylene content 2.5% by weight, butene- 1 content 4.5
80% by weight, MI of 7.0 g / 10 min, unstabilized powdery linear low-density polyethylene (30 ethyl branches / 1000 carbons) and Mooney viscosity ML1 + 4 (100 ° C). 30 parts by weight of non-stabilized powdery amorphous ethylene-propylene random copolymer (propylene content 25% by weight) and 100% by weight in total were added to the antioxidants shown in Table 4 below. Add predetermined amount of each additive (Ca-St),
Melt-kneading processing was performed according to Examples 43 to 56 to obtain pellets. The obtained pellets were used for evaluation of ultraviolet yellowing by the above test method, and the results are shown in Table 4.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

[Table 3]

[0036]

[Table 4]

The examples and comparative examples shown in Table 1 are the cases where a crystalline propylene homopolymer was used as the polyolefin. As can be seen from Table 1, Examples 1 to 14 contain the compound A according to the present invention.
14 to Comparative Examples 1 to 5 show that Examples 1 to 14 have no ultraviolet yellowing, whereas Comparative Examples 1 to 5 have ultraviolet yellowing. That is, a phosphorus-based antioxidant 1 in which the 2,4-di-t-butyl-5-methylphenyl group of Compound A [1] and Compound A [2] is replaced with a 2,4-di-t-butylphenyl group And phosphorus-based antioxidant 2, phosphorus-based antioxidant 3 in which the alkoxy groups of Compounds A [3] to [4] are substituted with fluorine, and β-
(3,5-di-t-butyl-4-hydroxyphenyl)
-Phenolic antioxidants 1 and 2 which do not satisfy various requirements of a propionic acid derivative, a phenol compound having an isocyanurate ring, and 2,2'-alkylidene-bis (4,6-di-t-alkyl-substituted phenol) are It can be seen that there is no effect of preventing the yellowing of ultraviolet rays of the molded product. Therefore, it is apparent that the comparative examples containing no compound A according to the present invention do not exhibit the effects of the present invention. That is, it can be said that the effect of preventing ultraviolet yellowing of the molded article obtained by the present invention is a peculiar effect that is first seen by the inclusion of the compound A according to the present invention.

Tables 2 to 4 show a mixture of a crystalline ethylene-propylene random copolymer and a linear low-density polyethylene as the polyolefin, and a crystalline ethylene-polyethylene.
A mixture of a propylene block copolymer or a crystalline ethylene-propylene-butene-1 terpolymer, a linear low density polyethylene and an amorphous ethylene-propylene random copolymer is used, and these are also used. The same effect as the above was confirmed.

[0039]

INDUSTRIAL APPLICABILITY The polyolefin molded article of the present invention has no yellowing due to UV irradiation and has a predetermined color tone and decoration, as compared with a polyolefin molded article having an ultraviolet curable resin layer containing various conventionally known antioxidants. The effect and the like can be maintained. Further, the effect of preventing ultraviolet yellowing according to the present invention is considered to be based on the result of the photochemical reaction between the antioxidant and ultraviolet light, regardless of the kind of the ultraviolet curable resin used in the ultraviolet curable resin layer.

─────────────────────────────────────────────────── --- Continuation of front page (56) Reference JP-A-6-313076 (JP, A) JP-A-6-128450 (JP, A) JP-A-6-100737 (JP, A) JP-A-6- 87984 (JP, A) JP 4-220446 (JP, A) JP 63-95246 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08J 7/04 C08L 23 / 00-23/36 C08K 3/00-13/08

Claims (2)

(57) [Claims] 1. With respect to 100 parts by weight of polyolefin,
A polyolefin molded article having an ultraviolet curable resin layer, which is obtained by molding a composition containing 0.01 to 1 part by weight of one or more compounds selected from the group consisting of (1) to (10) below: (1) Bis (2,4-di-t-butyl-5-methylphenyl) -pentaerythritol-diphosphite, (2) tetrakis (2,4-di-t-butyl-5-methylphenyl) -4 , 4'-biphenylene-di-phosphonite, (3) a phosphorus compound represented by the following general formula (I): (In the formula, R ₁ represents a direct bond or an alkylidene group having 1 to 4 carbon atoms, Ar ₁ and Ar ₂ each represent an alkylarylene group, n represents an integer of 1 to 4, and n represents 1. , R ₂ represents an alkyl group having 1 to 28 carbon atoms,
And when n represents an integer of 2 to 4, R ₂ represents a polyol residue), (4) n-octadecyl-β- (4'-hydroxy-
3 ', 5'-di-t-butylphenyl) propionate, (5) tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, (6) tris (4-t-butyl-3) -Hydroxy-2,6
-Dimethylbenzyl) isocyanurate, (7) tris [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, (8) N, N'-bis [3- ( 3,5-di-t-butyl-4
-Hydroxyphenyl) propionyl] hydrazine, (9) N, N'-bis [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide, (10) 2 , 2'-Alkylidene-bis (4,6-di-t-alkylphenol). 2. The molded article according to claim 1, wherein the ultraviolet curable resin layer is an ultraviolet curable ink layer.