JPH101606A - Resin composition excellent in light resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition excellent in light resistance and surface beautifying property and obtain a molding composed of a resin composition. SOLUTION: This resin composition is obtained by blending 100 pts.wt. polyketone resin (I) with 0.1-20 pts.wt. block copolymer (III) composed of a polymer block (A) comprising 0.1-5 pts.wt. amino group-containing hindered amine-based compound (II), 30-100mol% aromatic vinyl-based monomer unit and 70-0mol% vinyl-based monomer unit copolymerizable therewith and a polymer block (B) comprising 0.1-100mol% vinyl-based monomer unit having at least one kind of functional group selected from carboxyl groups, epoxy groups and carboxylic acid anhydride groups and 99.9-0mol% vinyl-based monomer unit copolymerizable therewith. This molding is obtained from the resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyketone resin,
The present invention relates to a resin composition comprising an amino group-containing hindered amine compound and a block copolymer having a specific functional group, and a molded article comprising the resin composition. The molded article produced from the resin composition of the present invention has excellent light resistance and surface beauty, and can be suitably used as a molding material for industrial materials, industrial materials, household goods, and the like.

[0002]

2. Description of the Related Art Polyketone resins are excellent in mechanical properties, water resistance, paintability, printability and abrasion resistance, and have recently been receiving attention as resins for molding materials and fibers. However, polyketone resins have poor light resistance, and have the drawback that when exposed to sunlight or fluorescent light transmitted through a window glass for a long time, the surface is discolored or the surface tone is impaired. I have. In recent years, with the spread of OA equipment such as a personal computer and a facsimile, a polyketone resin is used as a housing material. However, since the light resistance is insufficient, it is desired to improve the light resistance of this resin. .

[0003]

SUMMARY OF THE INVENTION Hindered amines,
Benzotriazole, benzophenone, salicylic acid ester-based light fastness improver in the method of simply blending into the polyketone resin, it is necessary to melt and knead at a high temperature, the light resistance improver decomposed during melt kneading, They are scattered and the light resistance is not effectively improved. Furthermore, when a molded article is manufactured using the resin composition containing the light resistance improver, the light resistance improver bleeds out and contaminates the mold of a molding machine, and thus the appearance of the molded article surface is poor. And it is virtually impossible to continuously produce a molded article having a clean surface.

[0004] It is an object of the present invention to provide a resin composition which gives a molded article excellent in light resistance and surface aesthetics, and a molded article comprising the resin composition.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a polymer block (A) containing an aromatic vinyl monomer unit in an amount of 30 mol% or more, A block copolymer composed of a polymer block (B) containing 0.1 to 100 mol% of a vinyl monomer having at least one functional group selected from a carboxyl group, an epoxy group and a carboxylic anhydride group And the amino group-containing hindered amine compound are blended with the polyketone resin in a specific amount, whereby a molded article excellent in light resistance and surface aesthetics can be obtained without impairing the properties of the polyketone resin. Was completed.

That is, the present invention provides the following general formula (1)
Polyketone resin (I) 10 comprising a structural unit represented by
0.1 to 5 parts by weight of an amino group-containing hindered amine compound (II), 30 to 100 mol% of an aromatic vinyl monomer unit and a vinyl monomer copolymerizable therewith with respect to 0 part by weight A polymer block (A) consisting of 70 to 0 mol% of a unit, and 0.1 to 100 mol of a vinyl monomer unit having at least one kind of functional group selected from a carboxyl group, an epoxy group and a carboxylic anhydride group. % And a vinyl monomer unit copolymerizable therewith from 99.9 to
The present invention relates to a resin composition comprising 0.1 to 20 parts by weight of a block copolymer (III) composed of a polymer block (B) of 0 mol%. Further, the present invention relates to a molded article comprising the above polyketone resin composition.

[0007]

Embedded image

Wherein A represents a unit derived from an olefin.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The polyketone resin used in the present invention comprises a structural unit represented by the general formula (1), wherein a unit derived from carbon monoxide and a unit derived from olefin alternate. Is a linear alternating copolymer.

Examples of the olefin include ethylene,
Examples thereof include propylene, butene, isobutene, pentene, hexene, heptene, octene, nonene, and dodecene, and one or more of these can be used. Among these, it is preferable to use ethylene and propylene, and particularly preferable to use ethylene. Further, in addition to the above monomers, if necessary, styrene, methyl acrylate, methyl methacrylate, vinyl acetate, undecenoic acid, undecenol, 6-chlorohexene, N-vinylpyrrolidone, diethyl ester of sulfonylphosphonic acid, etc. They can be used together.

The polyketone resin is, for example, palladium,
In the presence of a catalyst composition formed from a cobalt or nickel compound, a non-hydrohalic acid anion having a pKa of 6 or less, preferably 2 or less, and phosphorus, arsenic or antimony, carbon monoxide and an olefin are converted. Obtained by contact.

In the polyketone resin used in the present invention, m
Solution viscosity measured in cresol at 60 ° C. (hereinafter LV
N) is 0.5 to 10.0 dl / g.
Is preferably within the range. When the LVN is less than 0.5, the mechanical strength of the obtained resin composition becomes insufficient.

The amino group-containing hindered amine compound (II) used in the present invention is preferably a compound represented by the following general formula (2).

[0014]

Embedded image

(In the formula, X represents a hydrogen atom or a hydrocarbon group.)

The hydrocarbon group represented by X in the general formula (2) is preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably an alkyl group, an aryl group or an aralkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group,
t-butyl group, pentyl group, hexyl group, octyl group,
Examples include a nonyl group, a decyl group, and a dodecyl group. Examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group. Examples of the aralkyl group include a benzyl group.

Examples of the amino group-containing hindered amine compound (II) include, for example, 4-amino-2,2,6,6
-Tetramethylpiperidine, N-methyl-4-amino-
2,2,6,6-tetramethylpiperidine, N-ethyl-4-amino-2,2,6,6-tetramethylpiperidine, N-propyl-4-amino-2,2,6,6-tetramethyl Piperidine, N-isopropyl-4-amino-
2,2,6,6-tetramethylpiperidine, Nn-butyl-4-amino-2,2,6,6-tetramethylpiperidine, Nt-butyl-4-amino-2,2,6, 6
-Tetramethylpiperidine, N-pentyl-4-amino-2,2,6,6-tetramethylpiperidine, N-hexyl-4-amino-2,2,6,6-tetramethylpiperidine, N-octyl-4 -Amino-2,2,6,6-
Tetramethylpiperidine, N-nonyl-4-amino-
2,2,6,6-tetramethylpiperidine, N-decyl-4-amino-2,2,6,6-tetramethylpiperidine, N-dodecyl-4-amino-2,2,6,6-tetramethyl Piperidine, N-phenyl-4-amino-2,
2,6,6-tetramethylpiperidine, N-tolyl-4
-Amino-2,2,6,6-tetramethylpiperidine,
N-naphthyl-4-amino-2,2,6,6-tetramethylpiperidine, N-benzyl-4-amino-2,2,2
6,6-tetramethylpiperidine and the like can be mentioned, and one or more of these can be used. Among these, 4-amino-2,2,6,6
Preference is given to using tetramethylpiperidine.

The block copolymer (II) used in the present invention
I) is composed of a polymer block (A) and a polymer block (B) described below, and includes, for example, an AB-type diblock copolymer, an ABA-type triblock copolymer,
BAB type triblock copolymers can be mentioned. Of these, AB-type diblock copolymers are preferred.

The block copolymer (II) used in the present invention
The polymer block (A) constituting I) contains an aromatic vinyl monomer unit in an amount of 30 to 100 mol%, preferably 55 to 100 mol%, based on all structural units. Preferably, it is contained in an amount of 70 to 100 mol%, more preferably 95 to 100 mol%. As the aromatic vinyl monomer unit, for example,
Styrene; α-methylstyrene, p-methylstyrene,
Examples include units derived from alkyl-substituted styrenes such as p-tert-butylstyrene and 3,4-dimethylstyrene; halogen-substituted styrenes such as chlorostyrene; and hydroxystyrenes such as p-hydroxystyrene. One or more kinds can be used. Of these, units derived from styrene are preferred.

As the structural unit of the polymer block (A),
If necessary, 70 mol% or less, preferably 45 mol% or less, more preferably 30 mol% or less, and still more preferably 5 mol%, of a vinyl monomer unit copolymerizable with an aromatic vinyl monomer. The following ratio may be included. Examples of the vinyl monomer unit copolymerizable with the aromatic vinyl monomer include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, Examples include units derived from N, N-dimethylacrylamide and the like.

The block copolymer (II) used in the present invention
The polymer block (B) constituting I) includes a vinyl monomer unit having at least one functional group selected from a carboxyl group, an epoxy group and a carboxylic anhydride group,
The content is 0.1 to 100 mol%, preferably 0.1 to 50 mol%, based on all structural units,
More preferably, the content is 0.1 to 30 mol%.

Examples of the vinyl monomer unit having a carboxyl group include units derived from acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, maleic acid and the like. One or two or more of them can be used. Of these, units derived from acrylic acid and methacrylic acid are preferred.

Examples of the vinyl monomer unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl itaconate, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, and 3,4. −
Epoxybutene, 3,4-epoxy-3-methyl-1-
Units derived from butene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide, p-glycidylstyrene and the like can be mentioned. One or more kinds can be used. Of these, units derived from glycidyl acrylate and glycidyl methacrylate are preferred.

Examples of the vinyl monomer unit having a carboxylic anhydride group (—CO—O—CO—) include maleic anhydride, itaconic anhydride, citraconic anhydride, butenyl succinic anhydride, and tetrahydrophthalic anhydride. And the like. One or more of these units can be used. Of these, units derived from maleic anhydride are preferred.

The polymer block (B) may be, if necessary,
A vinyl monomer unit copolymerizable with the vinyl monomer unit having the above functional group is used in an amount of 0 to 9 with respect to all structural units.
9.9 mol%, preferably 50 to 99.9 mol%, more preferably 70 to 99.9 mol% can be contained. Examples of the vinyl monomer units that can be used in combination include styrene monomers such as styrene, p-styrenesulfonic acid, and sodium and potassium salts thereof; (meth) acrylonitriles; vinyl acetate, vinyl pivalate, and the like. Vinyl esters; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) (Meth) acrylic acid such as 2-hydroxyethyl acrylate and its esters; (meth) acrylamide; units derived from N-vinyl-2-pyrrolidone; The above can be used. Of these, units derived from methyl acrylate, methyl methacrylate, styrene, and acrylonitrile are preferred.

The number average molecular weight of the polymer block (A) is
It is preferably from 1,000 to 100,000,
More preferably, it is 500 to 50,000. The number average molecular weight of the polymer block (B) is 1,000 to 10
0000, preferably 2,500 to 50,000.
More preferably, it is 00. Block copolymer (II
The number average molecular weight of I) is preferably from 2,000 to 200,000, more preferably from 5,000 to 100,000. The number average molecular weight referred to in the present specification is determined by gel permeation chromatography (GP).
It is a value obtained from a standard polystyrene calibration curve by the method C).

The method for producing the block copolymer (III) is not particularly limited. For example, a monomer component constituting the polymer block (A) [or the polymer block (B)] is converted to thio-S Radical polymerization in the presence of a compound containing a thioester group and a mercapto group in the molecule such as carboxylic acid, 2-acetylthioethylthiol, and 10-acetylthiodecanethiol, and the obtained polymer is subjected to sodium hydroxide, ammonia And a polymer having a mercapto group at one end by treatment with an alkali such as hydrochloric acid, sulfuric acid, or the like. In the presence of the polymer, a polymer block (B) [or a polymer block (A) The method for producing a block copolymer (III) by radical polymerization of a monomer component constituting the above copolymer has a desired number average molecular weight and molecular weight distribution. Preferred can be obtained lock copolymer (III) easily and efficiently.

The resin composition of the present invention can be obtained by blending a block copolymer (III) with the polyketone resin (I) and the hindered amine compound containing an amino group (II). Although there is no particular limitation on the blending method,
A method in which a mixture of an amino group-containing hindered amine compound (II) and a block copolymer (III) is prepared in advance, and then the mixture is mixed with a polyketone resin (I); a block copolymer (III) and a polyketone resin are prepared in advance. A method of preparing a mixture with (I) and then mixing the mixture with an amino group-containing hindered amine compound (II); previously preparing a mixture of an amino group-containing hindered amine compound (II) and a polyketone resin (I). Thereafter, a method of mixing the block copolymer (III) with the mixture; polyketone resin (I), hindered amine compound containing amino group (II)
Any method such as a method of simultaneously mixing the block copolymer (III) and the block copolymer (III) can be employed.

The compounding ratio of the amino group-containing hindered amine compound (II) is 0.01 to 5 parts by weight, preferably 0.05 to 2 parts by weight, per 100 parts by weight of the polyketone resin (I).
It is preferably in parts by weight. Block copolymer (III)
Is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the polyketone resin (I). When the mixing ratio of the block copolymer (III) exceeds 20 parts by weight, the heat resistance of the obtained resin composition decreases. On the other hand, when the amount is less than 0.1 part by weight, the light resistance of the resin composition is not sufficiently improved.

The resin composition of the present invention comprises the above-mentioned polyketone resin (I), the hindered amine compound containing amino group (II) and the block copolymer (III) as essential components. May be contained. Examples of other optional components include an action that promotes the reaction between the functional group (carboxyl group, epoxy group, and carboxylic anhydride group) of the block copolymer (III) and the amino group-containing hindered amine compound (II). Compounds. By adding the compound, a resin composition having more excellent light resistance can be obtained. In particular, even if the amount of the block copolymer (III) used is reduced, the light resistance of the resin composition is sufficiently improved. Examples of the compound include tertiary amines such as triphenylamine and 2,4,6-tris (dimethylaminomethyl) phenol; tetrabutylammonium fluoride, triethylbenzylammonium chloride, tetramethylammonium chloride, trioctylammonium chloride , Tributylbenzylammonium chloride, N-laurylpyridinium chloride,
Ammonium compounds such as tetramethylammonium bromide, tetraethylammonium bromide and n-butylammonium bromide; phosphites such as triphenyl phosphite and triisodecyl phosphite; alkyltriphenylphosphonium halogen compounds (for example, Phosphonium compounds such as ethyltriphenylphosphonium bromide and n-butyltriphenylphosphonium bromide), alkenyltriphenylphosphonium halogen compounds and tetraalkylphosphonium halogen compounds (eg tetrabutylphosphonium bromide); tertiary such as triphenylphosphine Phosphine; metal sulfonic acid salts such as sodium dodecylbenzenesulfonate and sodium 3,5-dicarbomethoxybenzenesulfonate; sodium lauryl sulfate Mention may be made of sulfuric acid esters such as. The compounding ratio of the above compound is usually about 0.001 to 1: 1 with respect to 100 parts by weight of the block copolymer (III).
It is preferably 0 parts by weight.

The resin composition of the present invention may optionally contain a known ultraviolet absorber as long as the effects of the present invention are not impaired. It is preferable to use these ultraviolet absorbers in combination, since a resin composition having more excellent light resistance can be obtained. Known UV absorbers include, for example, 2,4-
Dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2,2′-dihydroxy-4 Benzophenone ultraviolet absorbers such as -methoxybenzophenone and 2,2 ', 4,4'-tetrahydroxybenzophenone; 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole, 2- (2'-hydroxy −
3 ′, 5′-di-t-butylphenyl, 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) -benzotriazole, 2- (2′-hydroxy-3 ′,
5'-di-t-butylphenyl) -benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) -benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5 '-Methylphenyl) -5-chlorobenzotriazole, 2- [2'-hydroxy-
3 ', 5'-bis- (α, α-dimethylbenzyl) phenyl] benzotriazole, methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl)-
Benzotriazole UV absorbers such as condensates of [4-hydroxyphenyl] propionate and polyethylene glycol (molecular weight 300); salicylates such as p-octylphenyl salicylate, phenyl salicylate and t-butylphenyl salicylate UV absorbers; resorcinol monobenzoate, hexadecyl 3,5-di-t-butyl-4-hydroxybenzoate, 5
-T-butyl-2-ethoxy-2 ', 2'-ethyl oxide, 5-dihexylamino-2-cyano-2,4-
Pentadiene nitrile and the like can be mentioned.

The resin composition of the present invention may further comprise, if necessary, additives such as a pigment, a nucleating agent, an antioxidant, a thermal deterioration inhibitor, an antiblocking agent, a lubricant, etc. Fibrous fillers such as carbon fibers and polyamide fibers; powdered fillers such as silica, aluminum hydroxide, calcium carbonate, talc, mica, titanium oxide, carbon black, potassium titanate; and other polymers Is also good.

The resin composition of the present invention comprises the above-mentioned polyketone resin (I), an amino group-containing hindered amine compound (II), a block copolymer (III) and, if necessary, other components described above. Then, it can be produced by a usual polymer blending technique. For example, melt kneading may be performed using a melt kneader such as a single-screw extruder, a twin-screw extruder, a Brabender, a kneader, or a Banbury mixer, or may be simply dry-blended. When the resin composition is manufactured by melt-kneading, the block copolymer (II
The reaction between the functional group of I) and the amino group of the amino group-containing hindered amine compound (II) proceeds, and in the resulting resin composition, the amino-containing hindered amine compound (II) in the polyketone resin (I) matrix
Is preferred because it is in a state of being finely dispersed, and more excellent in light resistance and surface aesthetics can be obtained. Further, at the time of melt-kneading, the hindered amine compound having a functional group and an amino group contained in the block copolymer (III) (I)
When a compound having a function of accelerating the reaction with the amino group of I) is present, the functional group of the block copolymer (III) and the amino group of the amino group-containing hindered amine compound (II) during kneading may be present. The reaction with a group is further promoted, and a compound having more excellent light resistance and surface aesthetics can be obtained. Melt kneading conditions are not particularly limited, but usually kneading is preferably performed at a temperature of about 180 to 300 ° C. for about 3 to 30 minutes.

The resin composition of the present invention can be melt-molded or heat-processed, and can smoothly produce various molded articles by any molding method such as injection molding, extrusion molding, blown film molding, blow molding and the like. Can be.

The resin composition of the present invention can be used for automobile-related parts such as electric tools, general industrial parts, mechanical parts such as gears and cams, interior and exterior parts of automobiles, electric parts of automobiles, and parts in the engine room of automobiles. It is useful as a molding material for various applications such as housing parts for home appliances and OA equipment or electronics-related parts.

[0036]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited to these Examples. In the following Examples and Comparative Examples, the light discoloration resistance, the surface state of the molded product, the Izod impact strength, and the thermal deformation temperature were measured or evaluated by the following methods.

[Light discoloration resistance] Using a xenon arc type fade meter (manufactured by Atlas Co., Ci65 type) [Filter used: Perlex glass, clear glass, black panel temperature: 60 ° C, rain spray: none], 12.7
300 × 300 mm × 63.6 mm × 3.2 mm
Irradiated for hours. The color tone of the test piece before and after light irradiation was measured using a color difference meter (（-80, manufactured by Nippon Denshoku Industries Co., Ltd.), and the difference in the color tone was expressed as a ΔYI value. The larger the value of the ΔYI value, the lower the light resistance.

[Surface State of Molded Article] The surface of the molded article was visually observed, and the one having a good surface state was indicated by “、”, and the one having a scratch or silver streak on the surface and having a poor surface state was indicated by “x”. .

[Izod impact strength] ASTM D25
6 (notched).

[Heat deformation temperature] Measured according to ASTM D648 (load: 18.6 kg / cm ² ).

Reference Example 1 [Synthesis of block copolymer containing carboxyl group] 75 kg of styrene was charged into a 90-liter polymerization tank, and the temperature was raised until the internal temperature reached 90 ° C under a nitrogen atmosphere. After 30 minutes, 32 g of thio-S-acetic acid was added into the polymerization tank, and a radical polymerization initiator (V-65, manufactured by Wako Pure Chemical Industries, Ltd., 7 g) was immediately added.
Wt% toluene solution) at a rate of 430 ml / hour,
Further, thio-S-acetic acid (6% by weight toluene solution) was added to 7
It was added to the polymerization tank at a rate of 50 ml / hour to initiate polymerization. When the polymerization rate (polymer conversion rate) reached 40%, the polymerization was stopped and the internal temperature was cooled. By removing the solvent and the unreacted monomer of the obtained viscous liquid, a number average molecular weight of 1 having a thio-S-acetate group at a terminal is obtained.
1,000 polystyrenes were obtained. This polystyrene 3
0 kg, 30 kg of toluene and 15 kg of butanol were charged into a 90-liter reaction vessel, and heated to 70 ° C. under a nitrogen atmosphere.
10% by weight sodium hydroxide / methanol solution 13
5 ml was added, and a transesterification reaction of the thio-S-acetic acid ester group at the end of the polystyrene was performed. Two hours later, 30 g of acetic acid was added to the reaction vessel to complete the reaction. By distilling off the solvent from the obtained reaction solution, polystyrene having a mercapto group at a terminal was obtained. 28.2 kg of methyl methacrylate, 1.8 kg of methacrylic acid, toluene 4
8 kg and 30 kg of polystyrene having a mercapto group at the end were charged into a 200-liter polymerization tank, and the inside thereof was sufficiently purged with nitrogen at 90 ° C., and then a radical polymerization initiator (V-
65, 10% by weight toluene solution manufactured by Wako Pure Chemical Industries, Ltd.)
Was added to the polymerization vessel at a rate of 54 ml / hour to initiate polymerization. When the polymerization rate (polymer conversion rate) reaches 95%, the polymerization is stopped, and a polystyrene block (A) and a methyl methacrylate-methacrylic acid copolymer (methyl methacrylate: methacrylic acid = 94: 6 (molar ratio)) block. An AB-type diblock copolymer (hereinafter, referred to as block copolymer 1) composed of (B) was obtained. The number average molecular weight of the polymer block (A) of the obtained block copolymer 1 was 11,000, the number average molecular weight of the polymer block (B) was 10,000, and the number average molecular weight of the block copolymer 1 was 21. 2,000.

Reference Example 2 [Synthesis of Epoxy Group-Containing Block Copolymer] 75 kg of styrene was charged into a 90-liter polymerization tank, and the temperature was raised to 90 ° C. in a nitrogen atmosphere until the internal temperature reached 90 ° C. After 30 minutes, 32 g of thio-S-acetic acid was added into the polymerization tank, and a radical polymerization initiator (V-65, manufactured by Wako Pure Chemical Industries, Ltd., 7 g) was immediately added.
Wt% toluene solution) at a rate of 430 ml / hour,
Further, thio-S-acetic acid (6% by weight toluene solution) was added to 7
It was added to the polymerization tank at a rate of 50 ml / hour to initiate polymerization. When the polymerization rate (polymer conversion rate) reached 40%, the polymerization was stopped and the internal temperature was cooled. By removing the solvent and the unreacted monomer of the obtained viscous liquid, a number average molecular weight of 1 having a thio-S-acetate group at a terminal is obtained.
1,000 polystyrenes were obtained. This polystyrene 3
0 kg, 30 kg of toluene and 15 kg of butanol were charged into a 90-liter reaction vessel, and heated to 70 ° C. under a nitrogen atmosphere.
10% by weight sodium hydroxide / methanol solution 13
5 ml was added, and a transesterification reaction of the thio-S-acetic acid ester group at the end of the polystyrene was performed. Two hours later, 30 g of acetic acid was added to the reaction vessel to complete the reaction. By distilling off the solvent from the obtained reaction solution, polystyrene having a mercapto group at a terminal was obtained. Methyl methacrylate 29.1kg, glycidyl methacrylate 0.9K
g, 48 kg of toluene and 30 kg of polystyrene having a mercapto group at a terminal were charged into a 200-liter polymerization tank, and the inside thereof was sufficiently purged with nitrogen at 90 ° C., and then a radical polymerization initiator (V-65, manufactured by Wako Pure Chemical Industries, Ltd. (A 10% by weight toluene solution) was added to the polymerization tank at a rate of 54 ml / hour to initiate polymerization. Polymerization rate (polymer conversion rate) is 95
%, The polymerization was stopped, and a polystyrene block (A) and a methyl methacrylate-glycidyl methacrylate copolymer (methyl methacrylate: glycidyl methacrylate = 97: 3 (molar ratio)) block (B)
AB-type diblock copolymer (hereinafter, referred to as block copolymer 2). The number average molecular weight of the polymer block (A) of the obtained block copolymer 2 is 1
1,000, the number average molecular weight of the polymer block (B) is 8,000, and the number average molecular weight of the block copolymer 2 is 1
It was 9,000.

Reference Example 3 [Synthesis of Block Copolymer Having Carboxylic Anhydride Group] 45 kg of styrene was charged into a 60-liter polymerization tank, and the temperature was raised to 90 ° C. under a nitrogen atmosphere. 30 minutes later, 19.2 g of thio-S-acetic acid was added to the polymerization tank, and immediately a radical polymerization initiator (V-65, Wako Pure Chemical Industries, Ltd.)
Was added to the polymerization vessel at a rate of 260 ml / hour and thio-S-acetic acid (3% by weight toluene solution) at a rate of 900 ml / hour to initiate polymerization. When the polymerization rate (polymer conversion rate) reached 40%, the polymerization was stopped and the internal temperature was cooled. By removing the solvent and the unreacted monomer of the obtained viscous liquid, polystyrene having a number average molecular weight of 11,000 having a thio-S-acetate group at a terminal was obtained. This polystyrene 10 kg, toluene 10 kg and butanol 5
kg into a 30 liter reactor, under a nitrogen atmosphere,
At 70 ° C., 45 ml of a 10% by weight sodium hydroxide / methanol solution was added to carry out transesterification of the thio-S-acetic acid ester group at the end of polystyrene. Two hours later,
10 g of acetic acid was added to the reaction vessel to terminate the reaction. By distilling off the solvent from the obtained reaction solution, polystyrene having a mercapto group at a terminal was obtained. Styrene 8.0
kg, 2.6 kg of acrylonitrile, 0.6 kg of maleic anhydride, 5.3 kg of toluene, and 3.3 kg of polystyrene having a mercapto group at the end were charged into a 50-liter polymerization tank, and the inside was sufficiently purged with nitrogen at 90 ° C.
Radical polymerization initiator (V-65, manufactured by Wako Pure Chemical Industries, Ltd., 1
0% by weight toluene solution) at a rate of 30 ml / hour.
Furthermore, polystyrene having a mercapto group at the terminal (40
% By weight of a toluene solution) was added to the polymerization tank at a rate of 2.4 kg / hour to initiate polymerization. When the polymerization rate (polymer conversion rate) reached 65%, the polymerization was stopped, and the polystyrene block (A) and styrene-acrylonitrile-
AB type diblock copolymer (hereinafter referred to as block copolymer 3) composed of block (B) maleic anhydride terpolymer (styrene: acrylonitrile: maleic anhydride = 71: 24: 5 (molar ratio)) ). The number average molecular weight of the polymer block (A) of the obtained block copolymer 3 was 11,000, the number average molecular weight of the polymer block (B) was 10,000, and the number average molecular weight of the block copolymer 3 was 21. 2,000.

Reference Example 4 [Synthesis of polyketone resin] Carbon monoxide, ethylene and propylene were dissolved in methanol in palladium acetate, trifluoroacetic acid and 1,3-
By contacting with bis [bis (2-methoxyphenyl) phosphino] propane, a polyketone resin of a linear alternating copolymer was produced. The melting point of this polyketone resin is 22
0 ° C, LVN 1.78 dl / g (in m-cresol,
(Measured at 60 ° C.).

Examples 1 to 4 The polyketone resin obtained in Reference Example 4 was added to 4-amino-
2,2,6,6-tetramethylpiperidine (manufactured by Wako Pure Chemical Industries, Ltd.) and the block copolymers 1 to 3 obtained in Reference Examples 1 to 3 were blended in the proportions shown in Table 1 below. After mixing using a Brabender, the mixture was melt-extruded using a twin-screw extruder to obtain a resin composition. Test pieces were prepared from the obtained resin composition using an injection molding machine, and various physical properties were evaluated. The results are shown in Table 1 below.

Examples 5 and 6 The polyketone resin obtained in Reference Example 4 was added to 4-amino-
2,2,6,6-tetramethylpiperidine [manufactured by Wako Pure Chemical Industries, Ltd.], 2- (hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzothiazole [Sumitomo Chemical Co., Ltd. ) "Sumisorb 300"] and the block copolymer 3 obtained in Reference Example 3 were prepared according to Table 1 below.
After blending using a Brabender, the mixture is melt-extruded using a twin-screw extruder,
A resin composition was obtained. Test pieces were prepared from the obtained resin composition using an injection molding machine, and various physical properties were evaluated. The results are shown in Table 1 below.

Comparative Example 1 Test pieces were prepared from the polyketone resin obtained in Reference Example 4 using an injection molding machine, and the test pieces were evaluated in the same manner as in Examples 1 to 6. The results are shown in Table 1 below.

Comparative Example 2 The polyketone resin obtained in Reference Example 4 was added to 4-amino-
Table 1 below shows 2,2,6,6-tetramethylpiperidine.
The resin compositions were prepared in the same manner as in Examples 1 to 6, except that the block copolymer was not compounded, and various physical properties were evaluated. The results are shown in Table 1 below.

Comparative Examples 3 to 5 Bis- (2,2) was added to the polyketone resin obtained in Reference Example 4.
2,6,6-tetramethyl-4-piperidinyl) sebacate (“Sumisorb 577” manufactured by Sumitomo Chemical Co., Ltd.) and / or 2- (hydroxy-3-tert-butyl-)
Example 1 was repeated except that 5-methylphenyl) -5-chlorobenzothiazole (“Sumisorb 300” manufactured by Sumitomo Chemical Co., Ltd.) was blended in the ratio shown in Table 1 below, and that no block copolymer was blended. In the same manner as in Examples 6 to 6, resin compositions were prepared and various physical properties were evaluated. The results are shown in Table 1 below.

[0050]

[Table 1]

[0051]

The molded article produced from the resin composition of the present invention is excellent in light resistance and surface aesthetics and can be suitably used as a molding material for industrial materials, industrial materials, household goods and the like. .

Claims (4)

[Claims] 1. A polyketone resin (I) comprising a structural unit represented by the following general formula (1):
0.1% amino-containing hindered amine compound (II)
-5 parts by weight, and aromatic vinyl monomer unit 30-1
A polymer block (A) comprising 00 mol% and 70 to 0 mol% of a vinyl monomer unit copolymerizable therewith, and at least one functional group selected from a carboxyl group, an epoxy group and a carboxylic anhydride group Block copolymer composed of a polymer block (B) consisting of 0.1 to 100 mol% of a vinyl monomer unit having the following formula and 99.9 to 0 mol% of a vinyl monomer unit copolymerizable therewith. A resin composition comprising 0.1 to 20 parts by weight of the compound (III). Embedded image (In the formula, A represents a unit derived from an olefin.) 2. The resin composition according to claim 1, wherein the amino group-containing hindered amine compound (II) is a compound represented by the following general formula (2). Embedded image (In the formula, X represents a hydrogen atom or a hydrocarbon group.) 3. Constituting a block copolymer (III),
The number average molecular weight of the polymer block (A) is 1,000 to 1
The resin composition according to claim 1, wherein the number average molecular weight of the polymer block (B) is 1,000 to 100,000. 4. A molded article comprising the resin composition according to claim 1.