JP5224497B2 - Resin composition - Google Patents

Description

  The present invention relates to a resin composition, and particularly relates to a resin composition having excellent weather resistance in a synthetic resin having an acidic group such as maleic acid-modified polypropylene.

  A hindered amine compound is known to deactivate a catalyst in the production process of a synthetic resin (Patent Document 1) and to suppress photodegradation of organic substances such as a synthetic resin, and has a stabilizing effect due to a difference in amine structure. Due to the difference and the influence from the usage environment, structures having active hydrogen, tertiary amine structures having no active hydrogen, and alkyloxyamine structures having a lower basicity than tertiary amine structures have been studied. In addition, studies have been made to introduce a triazine skeleton for the purpose of improving compatibility with a synthetic resin to be stabilized and extraction resistance.

  For example, when a conventional hindered amine compound is used in a polyolefin resin as in Patent Document 2, there is a problem in that the compatibility with the resin is low and the stabilization effect is not sustained because it evaporates from the resin. Moreover, in the use which contacts acid rain and agrochemicals, there also existed a problem extracted with an acid.

  Accordingly, as a low basic hindered amine compound, a compound having an alkyloxyamine structure is proposed in Patent Document 3, and a low basic hindered amine compound having various skeletons is proposed in Patent Document 4, and a carboxylate structure and an amide structure are proposed. In addition, hindered amines having a carbamate structure and an acetal structure have been proposed.

  Since these low basic hindered amine compounds exhibit excellent resistance to acid extraction, Patent Document 5 and the like propose use of the film for polyolefin agricultural films.

In addition, non-polar resins such as polypropylene that have been modified with maleic acid to improve compatibility and adhesion with other resins, water-based urethanes that have been rendered water-soluble by dimethylolpropionic acid, and adhesion to metal surfaces Copolymers using (meth) acrylic acid with excellent properties as a part of the monomer have an acidic group in the resin and are expected to be excellent in retention of basic additives such as hindered amines. It was.
JP-A-63-75019 JP 62-273239 A Japanese Patent Publication No.49-40557 Japanese Unexamined Patent Publication No. 1-1113368 Japanese Patent Laid-Open No. 2001-139821

  However, with maleic acid-modified polypropylene, a resin composition with satisfactory weather resistance can be obtained, although it shows the expected affinity, such as no bleeding even when blended with a large amount of hindered amine, compared to unmodified polypropylene. It wasn't.

  Accordingly, an object of the present invention is to provide a resin composition having excellent weather resistance in a synthetic resin having an acidic group such as maleic acid-modified polypropylene.

  As a result of intensive studies in view of the present situation, the present inventors have found that a hindered amine compound having a specific partial structure is excellent in the long-term weather resistance stabilizing effect of the resin, and have completed the present invention.

  That is, the resin composition of the present invention is a hindered amine compound represented by the following general formula (II) with respect to 100 parts by mass of the resin component in a resin composition containing a maleic acid-modified polyolefin having an acidic group as a resin component. 0.0005 to 30 parts by mass are blended.

（式中、Ｒ^５は炭素原子数１〜１８のアルキル基、ヒドロキシ基で置換されたアルキル基または炭素原子数５〜８のシクロアルキル基を表す。）

(In the formula, R ⁵ represents an alkyl group having 1 to 18 carbon atoms, an alkyl group substituted with a hydroxy group, or a cycloalkyl group having 5 to 8 carbon atoms.)

  In the resin composition of the present invention, the maleic acid-modified polyolefin is preferably 3 parts by mass or more with respect to 100 parts by mass of the resin component.

  According to the present invention, it is possible to provide a resin composition having excellent weather resistance in a synthetic resin having an acidic group such as maleic acid-modified polypropylene.

  Hereinafter, the resin composition imparted with excellent weather resistance according to the present invention will be described in detail.

  As the synthetic resin having an acidic group in the present invention, maleic acid-modified polypropylene, maleic acid-modified polybutadiene, urethane imparted with water solubility by dimethylolpropionic acid, and co-polymer using (meth) acrylic acid as a part of the monomer. Examples include coalescence. In particular, maleic acid-modified polypropylene is preferable because the hindered amine having a specific partial structure of the present invention is remarkably effective in imparting weather resistance. These may be used alone or mixed with other resins.

  Examples of the other resin include α such as polypropylene, low density polyethylene, linear low density polyethylene, high density polyethylene, polybutene-1, poly-3-methylpentene, poly-4-methylpentene, and ethylene-propylene copolymer. -Monomers or copolymers of olefins, copolymers of these α-olefins with polyunsaturated compounds such as conjugated or nonconjugated dienes, acrylic acid, methacrylic acid, vinyl acetate, polyethylene terephthalate, polyethylene terephthalate・ Linear polyester such as isophthalate, polyethylene terephthalate, paraoxybenzoate, polybutylene terephthalate, acid-modified polyester, polyamide such as polycaprolactam and polyhexamethylene adipamide, polyimide, polystyrene, styrene and / or Is a copolymer of α-methylstyrene and other monomers (eg, maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.) (eg, AS resin, ABS resin, MBS resin, heat-resistant ABS resin) Etc.), polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer Halogenated resins such as polymers, vinyl chloride-vinylidene chloride-vinyl acetate terpolymers, vinyl chloride-acrylic acid ester copolymers, vinyl chloride-maleic acid ester copolymers, vinyl chloride-cyclohexyl maleimide copolymers, (Meth) methyl acrylate, (meth) ethyl acrylate, (meth ) Polymers of (meth) acrylic acid esters such as octyl acrylate, polyether ketone, polyvinyl acetate, polyvinyl formal, polyvinyl butyral, polyvinyl alcohol, linear or branched polycarbonate, petroleum resin, coumarone resin, polyphenylene oxide, polyphenylene sulfide , Thermoplastic resins such as polyurethane and fiber-based resins, thermosetting resins such as epoxy resins, phenol resins, urea resins, melamine resins, unsaturated polyester resins, isoprene rubber, butadiene rubber, butadiene-styrene copolymer rubber , Butadiene-acrylonitrile copolymer rubber, acrylonitrile-butadiene-styrene copolymer rubber, copolymer rubber of ethylene and α-olefin such as propylene, butene-1, and ethylene-α-ole It may be an elastomer such as a terpolymer rubber with a non-conjugated diene such as tin and ethylidene norbornene or cyclopentadiene, a silicon resin, etc., and these resins and / or elastomers may be alloyed or blended. May be.

  When mixed with other resins, the synthetic resin having an acidic group preferably contains 3 parts by mass or more, more preferably 10 parts by mass or more, based on 100 parts by mass of the entire resin component. When the content is low, the effect of selecting a hindered amine compound having a specific structure according to the present invention is small, and the composition may not be superior to a composition using a less expensive general-purpose hindered amine compound. is there.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ in the general formula (I) of the present invention include methyl, ethyl, propyl, isopropyl, n-butyl and sec-butyl. And tertiary butyl.

  Examples of the alkyl group having 1 to 18 carbon atoms represented by R in the general formula (I) of the present invention include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl Octyl, 2-ethylhexyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and the like. Examples of the alkyl group substituted with a hydroxyl group include groups corresponding to the above alkyl groups such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxy-2-methylpropyl and the like.

  Examples of the cycloalkyl group having 5 to 8 carbon atoms represented by R in the general formula (I) of the present invention include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like.

  As the hindered amine compound having a group represented by the general formula (I) of the present invention, more specifically, the following no. The compound of 1-6 is mentioned. However, the present invention is not limited by the following compounds.

  The method for synthesizing the compound having the group represented by the general formula (I) is not particularly limited, and may be used alone or as a mixture, and is blended in an amount of 0.005 to 30 parts by mass with respect to 100 parts by mass of the resin component. The If the blending amount is less than the above-mentioned amount, a sufficient stabilizing effect cannot be obtained. Even if the blending amount exceeds the above-mentioned blending amount, the accumulation of the stabilizing effect is small, and the appearance may be impaired by bleeding from the resin.

  Among the compounds specifically shown above, no. The compound 1 is preferable because it has a particularly large weather resistance imparting effect.

  In the resin composition of the present invention, various compounding agents usually used for each resin are used as necessary. For example, phenolic antioxidants, sulfur antioxidants, phosphorus antioxidants, UV absorbers, other hindered amine compounds, nucleating agents, flame retardants, flame retardant aids, lubricants, fillers, fibrous fillers Metal soaps, hydrotalcites, antistatic agents, pigments, dyes and the like.

  Examples of the phenol type include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditert-butyl-4-hydroxybenzyl). ) Phosphonate, 1,6-hexamethylene bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-tert-butyl-m-cresol), 2 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis (6-tert-butyl-m-) Cresol), 2,2'-ethylidenebis (4,6-ditert-butylphenol), 2,2'-ethylidenebis (4-secondarybutyl-6-tert-butylphenol) 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) Isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5-ditertiary Butyl-4-hydroxyphenyl) propionate, thiodiethylene glycol bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis [ 3,5-ditert-butyl-4-hydroxyphenyl) propionate], bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, bis [2-tert-butyl -4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) Propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8, 10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propione The amount is 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the resin.

  Examples of the sulfur antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and pentaerythritol tetra (β-dodecyl mercaptopropionate). Β-alkyl mercaptopropionic acid esters of polyols such as 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the resin.

  Examples of the phosphorus antioxidant include trisnonylphenyl phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl]. Phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di Tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite Phosphite, bis (2,4-dicumylphenyl) penta Rithritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)- 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide, 2,2′-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2′-methylenebis (4,6- Tert-butylphenyl) -octadecyl phosphite, 2,2′-ethylidenebis (4 -Di-tert-butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphine-6- Yl) oxy] ethyl) amine, phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tritert-butylphenol, etc., and 0.001 to 10 mass per 100 mass parts of resin Parts, more preferably 0.05 to 5 parts by weight.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones; 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2- 2- (2′-hydroxyphenyl) benzotriazoles such as 2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl) benzotriazole; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butyl Phenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, hexadecyl-3,5-ditert-butyl Benzoates such as -4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2′-ethoxyoxanilide and 2-ethoxy-4′-dodecyloxanilide; ethyl-α-cyano-β, β-diphenyl Acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate, etc. Anoacrylates; 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-ditert-butylphenyl) -s-triazine, 2- (2-hydroxy-4-methoxyphenyl) ) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4,6-bis (2,4-ditert-butylphenyl) -s-triazine, etc. These are triaryltriazines, and 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the resin.

Examples of the other hindered amine compounds include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, and 2,2,6. , 6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Tetrakis (2,2,6,6-tetramethyl-4-piperidylbutanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidylbutanetetracarboxylate, bis (2,2,6 , 6-tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2, , 6,6-pentamethyl-4-piperidyl) .di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2 -Butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate Condensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl- 4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2 4- Chloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl- 4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2 , 4-Bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-ylaminoundecane, 1,6,11-tris [2, 4-Bis (N-butyl-N- (1,2,2,6,6-pentamethyl And hindered amine compounds such as -4-piperidyl) amino) -s-triazin-6-ylaminoundecane.

  Examples of the nucleating agent include aromatic carboxylic acid metal salts such as aluminum pt-butylbenzoate and sodium benzoate; sodium bis (2,4-ditert-butylphenyl) phosphate, bis (2,4- Acid phosphate metal salts such as ditertiarybutylphenyl) lithium phosphate and sodium-2,2′-methylenebis (4,6-ditertiarybutylphenyl) phosphate; dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, etc. And polyhydric alcohol derivatives thereof.

  Examples of the flame retardant include halogen flame retardants, red phosphorus, melamine phosphate, guanidine phosphate, phosphorus ester compounds, phosphorus flame retardants such as phosphazene compounds, nitrogen flame retardants such as melamine cyanurate, magnesium hydroxide, Examples of flame retardant aids include metal hydroxides such as aluminum hydroxide, inorganic compounds such as antimony trioxide and zinc borate, and anti-drip agents such as polytetrafluoroethylene.

  Hydrotalcites may be natural products or synthetic products, and can be used regardless of the presence or absence of surface treatment or the presence or absence of crystal water. Examples thereof include basic carbonates represented by the following general formula (III).

M _x Mg _y Al _z CO ₃ (OH) _{xp + 2y + 3z-2}・ nH ₂ O (III)
(Wherein M is an alkali metal or zinc, x is a number from 0 to 6, y is a number from 0 to 6, z is a number from 0.1 to 4, p is a valence of M, and n is Represents the number of water of crystallization from 0 to 100.)

  Lubricants include fatty acid amides such as lauryl amide, myristyl amide, stearyl amide and behenyl amide, metal soaps such as ethylene bisstearyl amide, polyethylene wax, calcium stearate, magnesium stearate, magnesium stearate phosphate, stearyl phosphate Examples include phosphate metal salts such as ester magnesium.

  As filler, inorganic particles such as talc, silica, calcium carbonate, glass fiber, potassium titanate, potassium borate, etc. are appropriately selected for the particle size in the case of spherical materials, and the fiber diameter, fiber length and aspect ratio in the case of fibrous materials Used. Moreover, it is preferable to use what was surface-treated as needed for the filler.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples.

95 parts by mass of block polypropylene (MFR = 25, density = 0.9 g / cm ³ , flexural modulus 950 MPa), maleic acid-modified polypropylene (YUMEX 1001, manufactured by Sanyo Chemical Industries, acid value 26 mgKOH / g, softening point 154 ° C.) 5 parts by mass, 0.05 part by mass of calcium stearate, 0.1 part by mass of tetrakis (3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxymethyl) methane, tris (2,4- Ditertiary butylphenyl) phosphite 0.1 parts by weight and hindered amine compounds (parts by weight) listed in Table 1 were added, and the resulting mixture was injection molded at 230 ° C. as pellets at 230 ° C. by extrusion at 60 mm × 20 mm × 2 mm. A specimen was obtained.

  The yellowness of the obtained test piece was measured to evaluate the initial colorability, and the weather resistance was evaluated by the time until the occurrence of cracks under microscopic observation under the conditions of 83 ° C. and no rain with a sunshine weather meter. Moreover, the surface gloss after 500 hours was also measured only for each 0.3 parts by mass. The results are shown in Table 1.

＊１：

＊２：ビス（２，２，６，６−テトラメチル−４−ピペリジル）セバケート
＊３：テトラキス（１，２，２，６，６−ペンタメチル−４−ピペリジルブタンテトラカルボキシレート
＊４：試験片の劣化が激しく測定不可

* 1:

* 2: Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate * 3: Tetrakis (1,2,2,6,6-pentamethyl-4-piperidylbutanetetracarboxylate * 4: Test piece Measurement is impossible due to severe deterioration

  From Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-7, the hindered amine compound having a specific structure according to the present invention is compared to other hindered amine compounds with respect to the resin having an acidic group. It can be seen that the initial coloring is excellent and the weather resistance is also excellent. Further, as compared with Comparative Examples 1-1 to 1-3 and Comparative Examples 1-4 to 1-6, the hindered amine compound having an NH structure is a hindered amine compound having an N-methyl structure with respect to the resin having an acidic group. It can be seen that the initial coloration is inferior to that of, but the weather resistance is excellent. From this result, it can be seen that the present invention can provide a resin composition having both unexpectedly excellent colorability and weather resistance.

Claims (2)

In a resin composition containing a maleic acid-modified polyolefin having an acidic group as a resin component, 0.005 to 30 parts by mass of a hindered amine compound represented by the following general formula (II) is blended with respect to 100 parts by mass of the resin component. A resin composition characterized by comprising:

(In the formula, R ⁵ represents an alkyl group having 1 to 18 carbon atoms, an alkyl group substituted with a hydroxy group, or a cycloalkyl group having 5 to 8 carbon atoms.) The resin composition according to claim 1, wherein the maleic acid-modified polyolefin is 3 parts by mass or more with respect to 100 parts by mass of the resin component.