Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3432—Six-membered rings
  • C08K5/3435—Piperidines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
  • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/346—Clay
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
  • C08K5/134—Phenols containing ester groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3472—Five-membered rings
  • C08K5/3475—Five-membered rings condensed with carbocyclic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
  • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/527—Cyclic esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2423/10—Homopolymers or copolymers of propene
  • C08J2423/12—Polypropene

Definitions

• the present invention relates to a resin additive masterbatch and a polyolefin resin composition containing the resin additive masterbatch (hereinafter, also simply referred to as “masterbatch” and “resin composition”). Specifically, the melting point is 65 ° C.
• the present invention relates to a polyolefin masterbatch containing the following resin additives in high concentration and a polyolefin resin composition using the same.
• Resin additives such as phenolic antioxidants, ultraviolet absorbers, hindered amine compounds, etc. are generally known in order to suppress deterioration of organic substances such as synthetic resins due to light and heat.
• resin additives include tetrakis (3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxymethyl) methane, tris (2,4-ditert-butylphenyl) phosphite, etc.
• a compound having a high melting point and low plasticization of the resin and low volatilization from the resin is preferable.
• the stabilizing effect tends to be small because the additive cannot move in the resin.
• low molecular weight compounds such as stearyl (3,5-ditert-butyl-4-hydroxyphenyl) propionate and bis (2,2,6,6-tetramethylpiperidyl) sebacate have a relatively small molecular weight. Although it is excellent in the initial stabilization effect, it tends to be volatilized from the resin, so that the long-term stabilization effect is poor. In addition, liquid, viscous, or powdery powders are poorly handled due to mutual adhesion during storage, and need to be masterbatched to improve handling. was there.
• a hindered amine compound obtained by reacting 2,2,6,6-tetramethylpiperidinols with a fatty acid exhibits an excellent weather resistance-imparting effect, but tends to be liquid at a low molecular weight, and is easy to handle.
• the additive oozes out on the surface of the resin composition that has been made into a masterbatch and it becomes easy to show adhesiveness.
• Patent Document 1 discloses a master batch composition in which talc is blended at a high concentration of 80 to 40 parts by mass with respect to 20 to 60 parts by mass of resin.
• Patent Document 2 proposes a method for suppressing stickiness by forming a masterbatch using an organic metal salt. Has been.
• Patent Document 1 The purpose of the invention described in Patent Document 1 is to improve mechanical properties and reduce costs, and there is no mention of making a master batch together with a low melting point additive.
• a masterbatch containing a large amount of talc is blended together with a masterbatch containing a large amount of talc as in the invention described in Patent Document 1
• a large amount of talc is added to the resin molded product.
• the transparency of the resin molded product is lowered, and the use is restricted.
• master batch production of both low-melting-point additive and talc together at a high concentration has not been put into practical use because the degree of freedom in product design as a resin composition of the final product is poor.
• a masterbatch that contains talc together at a high concentration is a masterbatch that is not suitable for normal final products that do not use talc because talc affects the physical properties of the final product, such as transparency and elongation. It is.
• Patent Document 2 it has become possible to suppress stickiness by making a masterbatch using an organometallic salt, but at present, further improvement in performance is desired.
• the object of the present invention is that a low-melting-point additive can be blended at a high concentration, can be continuously produced without strand breakage, and exudation from the pellet is suppressed, and is excellent in blocking resistance.
• the object is to provide a resin additive masterbatch with less application restrictions, and a polyolefin resin composition containing the resin additive masterbatch.
• the present inventors have formulated the above-mentioned problems by blending a predetermined amount of an inorganic layered compound in a master batch in which a resin additive having a low melting point (melting point is 65 ° C. or less) is blended. As a result, the present invention has been completed.
• the resin additive masterbatch of the present invention comprises (A) 100 parts by mass of polyolefin resin, (B) 50 to 200 parts by mass of resin additive having a melting point of 65 ° C. or less, and (C) 10 to 10 parts of inorganic layered compound. 20 mass parts is mix
• the (B) resin additive having a melting point of 65 ° C. or lower is preferably at least one kind of hindered amine compound, and the hindered amine compound represented by the following general formula (1) More preferably, it is one or more.
• R 1 represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 30 carbon atoms, a hydroxyalkyl group, an alkoxy group, a hydroxyalkoxy group or an oxy radical
• R 2 represents an alkyl having 7 to 31 carbon atoms. Represents a group or an alkenyl group having 2 to 30 carbon atoms.
• the resin additive (B) having a melting point of 65 ° C. or less is at least one benzoate compound represented by the following general formula (2).
• R 3 and R 4 each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms, and R 5 represents an alkyl group having 8 to 30 carbon atoms.
• the resin additive (B) having a melting point of 65 ° C. or lower is one or more of the hindered amine compounds represented by the general formula (1), and the general formula (2 It is preferable that the content ratio of the hindered amine compound and the benzoate compound is within a range of 1: 1 to 4: 1.
• the (C) inorganic layered compound is preferably talc.
• the resin additive masterbatch of the present invention preferably further contains 0.3 to 5 parts by mass of one or more aromatic phosphate metal salts represented by the following general formula (3).
• R 6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
• R 7 represents an alkyl group having 4 to 8 carbon atoms
• R 8 represents an alkylidene group having 1 to 4 carbon atoms.
• X 1 represents an alkali metal atom, an alkaline earth metal atom or an aluminum atom, and when X 1 is an alkali metal atom, n is 1, and m is 0, and X 1 is an alkaline earth metal. In the case of an atom, n is 2 and m is 0, and when X 1 is an aluminum atom, n is 1 or 2 and m is 3-n.
• the resin additive masterbatch of the present invention contains 0.5 to 50 of at least one selected from the group consisting of benzotriazole ultraviolet absorbers represented by the following general formula (4) and the following general formula (5). It is preferable to be blended in parts by mass.
• R 9 and R 10 each independently represents a hydrogen atom, a chlorine atom, or an alkyl group having 1 to 4 carbon atoms
• R 11 and R 12 each independently represents a hydrogen atom or 1 carbon atom
• R 13 and R 14 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• R 15 represents a hydrogen atom, a chlorine atom, or an alkyl group having 1 to 4 carbon atoms
• R 16 and R 17 each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, Or an aralkyl group having 7 to 18 carbon atoms.
• the polyolefin resin composition of the present invention is characterized in that the resin additive masterbatch is blended with a polyolefin resin.
• the polyolefin resin (A) used in the present invention is not particularly limited as long as it is a polyolefin, and can be used as polypropylene, isotactic polypropylene, syndiotactic polypropylene, hemiisotactic polypropylene, stereoblock polypropylene.
• Cycloolefin polymer polyethylene, low density polyethylene, linear low density polyethylene, high density polyethylene, polybutene-1, poly-3-methylbutene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene And an ⁇ -olefin homopolymer or copolymer such as an ethylene-propylene copolymer.
• Particularly preferable (A) polyolefin resin includes polypropylene.
• Examples of the resin additive (B) having a melting point of 65 ° C. or lower used in the present invention include antioxidants, ultraviolet absorbers, light stabilizers, and mixtures thereof.
• antioxidant having a melting point of 65 ° C. or lower examples include phosphorus-based antioxidants such as phenol-based antioxidants and phosphite-based antioxidants, and sulfur-based antioxidants such as thioether-based antioxidants.
• UV absorber having a melting point of 65 ° C. or lower examples include salicylic acid UV absorbers, benzophenone UV absorbers, benzotriazole UV absorbers, and cyanoacrylate UV absorbers.
• Examples of the light stabilizer having a melting point of 65 ° C. or lower include hindered amine compounds.
• examples of the phenolic antioxidant having a melting point of 65 ° C. or lower include stearyl (3,5-ditert-butyl-4-hydroxyphenyl) propionate, thiobis (3- (3,5-ditertiary).
• Tributyl-4-hydroxyphenyl) propionyloxy) ethyl triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 2,4-bisoctylthio-6- (3 5-Ditert-butyl-4-hydroxyanilino) -s-triazine, 2-methyl-4,6-bis (octylthiomethyl) phenol, 2,4-dimethyl-6- (1-methylpentadecyl) phenol
• Examples of the phosphite antioxidant having a melting point of 65 ° C. or lower include triphenyl phosphite, trisnonylphenyl phosphite, distearyl pentaerythritol diphosphite, bisnonylphenyl pentaerythritol diphosphite, bisphenol A and carbon atom.
• Examples of the thioether antioxidant having a melting point of 65 ° C. or lower include dilauryl thiodipropionate, ditridecyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis (3-dodecyl thiopropionate), Examples include 4,4-thiobis (2-tert-butyl-5-methylphenol) bis-3- (dodecylthio) propionate.
• Examples of the ultraviolet absorber having a melting point of 65 ° C. or lower include phenyl salicylate, hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxy Benzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 4- (2-acryloyloxy) ethoxy-2-hydroxybenzophenone polymer, 2- (2-hydroxy-4 -Octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (4-isooctyloxyphenyl) -4,6-bis (2,4-dimethyl) Phenyl) -1,3,5-triazine, 2- (2-hydroxy-4- (3- (2 Ethylhexyl-1-oxy) -2-hydroxypropyl
• hindered amine compounds having a melting point of 65 ° C. or lower examples include 2,2,6,6-tetramethyl-4-piperidinol fatty acid ester, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and the like.
• Tetraester 2,2,6,6-tetramethylpiperidinol and tridecyl alcohol mixed alcohol and butanetetracarboxylic acid tetraester, bis (1-octyloxy-2,2,6,6-pentamethyl-4 -Piperidyl) sebacate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-pi Lizinol and butanedioic acid polyester, 2,2,6,6-tetramethyl-4- (2-propenyloxy) piperidine and methylhydrogensiloxane reaction product, dodecyl-3- (2,2,4,4 -Tetramethyl-21-oxo-7-oxa-3,20-diazodispiro (5.1.11.2) henicosane-20-yl) propionate and tetradecyl-3- (2,2,4,4-tetramethyl- Mixture of 21-oxo-7-oxa-3,20-diazodispir
• the resin additive (B) having a melting point of 65 ° C. or lower has a melting point of 65 ° C. or lower, and includes those that are liquid at room temperature.
• a hindered amine compound is preferable and the hindered amine compound represented by following General formula (1) is more preferable.
• R 1 represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 30 carbon atoms, a hydroxyalkyl group, an alkoxy group, a hydroxyalkoxy group or an oxy radical
• R 2 represents an alkyl having 7 to 31 carbon atoms. Represents a group or an alkenyl group having 2 to 30 carbon atoms.
• examples of the alkyl group having 1 to 30 carbon atoms that R 1 can take include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec Examples include pentyl, tertiary pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and the like.
• alkyl group having 7 to 31 carbon atoms which R 2 can take include, for example, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl , Hexadecyl, heptadecyl, octadecyl and the like.
• R 1 or R 2 is a mixture of alkyl groups having different numbers of carbon atoms, the melting point tends to be low, so that the present invention is also suitably used in a mixture.
• examples of the hydroxyalkyl group having 1 to 30 carbon atoms that R 1 can take in the general formula (1) include hydroxy-substituted products of the above alkyl groups such as hydroxyethyl, 2-hydroxypropyl, and 3-hydroxypropyl. Can be mentioned.
• examples of the alkoxy group having 1 to 30 carbon atoms that R 1 can take in the general formula (1) include methoxy, ethoxy, propoxy, isopropoxy, butoxy, octoxy, 2-ethylhexyloxy and the like corresponding to the above alkyl group. Can be mentioned.
• examples of the hydroxyalkoxy group having 1 to 30 carbon atoms that R 1 can take in the general formula (1) include hydroxyethyloxy, 2-hydroxypropyloxy, 3-hydroxypropyloxy, 4 -Hydroxybutyloxy, 2-hydroxy-2-methylpropyloxy, 6-hydroxyhexyloxy and the like.
• examples of the alkenyl group having 2 to 30 carbon atoms that R 2 can take in the general formula (1) include vinyl, propenyl, butenyl, hexenyl, oleyl and the like.
• the position of the double bond may be the ⁇ -position, the inside, or the ⁇ -position.
• examples of the compound represented by the general formula (1) include the compound No. 1 shown below. 1-No. 6 compounds.
• the present invention is not limited by the following compounds.
• the melting point is 60 ° C. or less, which is particularly preferable.
• the method for synthesizing the compound represented by the general formula (1) is not particularly limited, and can be synthesized by a normal organic synthesis method.
• a normal organic synthesis method For example, direct esterification of acid and alcohol, acid halide and alcohol can be synthesized. Esterification is possible by reaction, transesterification reaction, etc., and as a purification method, distillation, recrystallization, reprecipitation, a method using a filtering agent / adsorbent, and the like can be used as appropriate.
• a benzoate compound is preferable and the compound represented by following General formula (2) is more preferable.
• R 3 and R 4 each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms, and R 5 represents an alkyl group having 8 to 30 carbon atoms.
• examples of the alkyl group having 1 to 12 carbon atoms that R 3 and R 4 can take include, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, Hexyl, octyl, etc., cycloalkyl groups such as cyclopentyl, cyclohexyl and the like, and arylalkyl groups having 7 to 30 carbon atoms include benzyl, phenylethyl, 1-methyl-1-phenylethyl and the like.
• examples of the alkyl group that R 5 may have 8 to 30 carbon atoms include octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, and the like.
• R 5 is a single alkyl group, the melting point increases as the number of carbon atoms increases, but the melting point of the mixture decreases, so even a single alkyl group compound that is not applicable can be used in the present invention. .
• examples of the compound represented by the general formula (2) include the following compound Nos. 7 to 8.
• the present invention is not limited by the following compounds.
• the method for synthesizing the compound represented by the general formula (2) is not particularly limited, and can be synthesized by a general organic synthesis method.
• a general organic synthesis method For example, direct esterification of acid and alcohol, acid halide and alcohol can be synthesized. Esterification can be performed by reaction, transesterification, and the like.
• As a production method distillation, recrystallization, reprecipitation, a method using a filtering agent or an adsorbent, and the like can be appropriately used.
• (B) 1 or more types of the hindered amine compound represented by the said General formula (1), and 1 or more types of the benzoate compound represented by the said General formula (2) are resin additives whose melting
• the content ratio of the hindered amine compound and the benzoate compound is preferably 1: 1 to 4: 1 by mass ratio.
• the resin additive having a melting point of 65 ° C. or less is blended in an amount of 50 to 200 parts by mass with respect to 100 parts by mass of (A) polyolefin resin. Preferably, 70 to 150 parts by mass is blended with 100 parts by mass of (A) polyolefin resin.
• the blending amount of the resin additive having a melting point of 65 ° C. or less is less than 50 parts by mass, it is necessary to add a large amount of master batch, and the merit as a high concentration master batch is reduced. When it exceeds the part, the additive tends to ooze out, the pellets adhere to each other, and the blocking resistance is lowered.
• the (C) inorganic layered compound used in the present invention may be a natural product or a synthetic product, and can be used regardless of the presence or absence of surface treatment and the presence or absence of crystal water. Examples include talc, mica, kaolin, hydrotalcite, and various clays. These (C) inorganic layered compounds can be used alone or in combination of two or more.
• the (C) inorganic layered compound is blended in an amount of 10 to 20 parts by mass with respect to 100 parts by mass of the (A) polyolefin resin.
• (C) Blocking resistance falls that the compounding quantity of an inorganic layered compound is less than 10 mass parts, and on the other hand, when a compounding quantity exceeds 20 mass parts, transparency etc. will fall and a use will be restrict
• the resin additive masterbatch of the present invention uses at least one aromatic phosphate metal salt represented by the following general formula (3) in order to further improve the blocking resistance (storage stability).
• Can do (Wherein R 6 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R 7 represents an alkyl group having 4 to 8 carbon atoms, and R 8 represents an alkylidene group having 1 to 4 carbon atoms.
• X 1 represents an alkali metal atom, an alkaline earth metal atom or an aluminum atom, and when X 1 is an alkali metal atom, n is 1, and m is 0, and X 1 is an alkaline earth metal. In the case of an atom, n is 2 and m is 0, and when X 1 is an aluminum atom, n is 1 or 2 and m is 3-n.
• examples of the alkyl group having 1 to 8 carbon atoms represented by R 6 include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, tertiary Examples include pentyl, hexyl, cyclohexyl, heptyl, octyl, isooctyl, and tertiary octyl.
• alkyl group having 4 to 8 carbon atoms represented by R 7 examples include butyl, sec-butyl, tert-butyl, pentyl, tert-pentyl, hexyl, cyclohexyl, heptyl, octyl, isooctyl, and tertiary octyl. Etc.
• Examples of the alkylidene group having 1 to 4 carbon atoms represented by R 8 include methylene, ethylidene, 1,1-propylidene, 2,2-propylidene, butylidene and the like.
• the metal represented by X 1 lithium, sodium, alkali metals such as potassium, magnesium, alkaline earth metals such as calcium, and aluminum. Of these, alkali metals are preferable.
• examples of the compound represented by the general formula (3) include the following compound Nos. 9-No. 26 compounds are mentioned.
• the present invention is not limited by the following compounds.
• the blending amount of the aromatic phosphate metal salt is 0.3 to 5 with respect to 100 parts by mass of the (A) polyolefin resin. It is preferable to include parts by mass. If the amount is less than 0.3 parts by mass, a sufficient effect may not be obtained. On the other hand, if the amount exceeds 5 parts by mass, the crystallinity of the resin to which the masterbatch is added is affected, and the resin physical properties are reduced. End up.
• the resin additive masterbatch of the present invention can use one or more benzotriazole ultraviolet absorbers.
• benzotriazole ultraviolet absorber used in the present invention include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- ( 2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-yl-phenol], Polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole 2- [2-hydroxy-3- (2-acryloyloxyeth
• the benzotriazole-based ultraviolet absorber contains at least one selected from the group consisting of compounds represented by the following general formula (4) and the following general formula (5) from the viewpoint of blocking resistance (storage stability) of the pellet. It is preferable to use it.
• R 9 and R 10 each independently represents a hydrogen atom, a chlorine atom, or an alkyl group having 1 to 4 carbon atoms
• R 11 and R 12 each independently represents a hydrogen atom or 1 carbon atom
• R 13 and R 14 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• R 15 represents a hydrogen atom, a chlorine atom, or an alkyl group having 1 to 4 carbon atoms
• R 16 and R 17 each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, Or an aralkyl group having 7 to 18 carbon atoms.
• Examples of the alkyl group having 1 to 18 carbon atoms represented by R 11 and R 12 include, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, sec-pentyl, and tertiary pentyl.
• examples of the compound represented by the general formula (4) include the compound No. 1 shown below. 27-No. There are 31 compounds. However, the present invention is not limited by the following compounds.
• the compound No. 27 is particularly preferred.
• the alkyl group having 1 to 4 carbon atoms that R 15 can take and the alkyl group having 1 to 18 carbon atoms that R 16 and R 17 can take are the same as those described above.
• the aralkyl group having 7 to 18 carbon atoms that can be taken by R 16 and R 17 is one in which the hydrogen atom of the alkyl group is substituted with an aryl group such as a phenyl group, and for example, an ⁇ , ⁇ -dimethylbenzyl group is Can be mentioned.
• Examples of the compound represented by the general formula (5) include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2,4-bis ( ⁇ , ⁇ -dimethylbenzyl) -6- ( 2H-benzotriazol-2-yl) phenol, 2- (5-chloro-2H-benzotriazol-2-yl) -4-methyl-6-tert-butylphenol, 4,6-bis (1,1-dimethylpropyl) ) -2- (2H-benzotriazol-2-yl) phenol, 2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole.
• the benzotriazole-based ultraviolet absorber is blended in an amount of 0.5 to 50 parts by mass with respect to 100 parts by mass of the (A) polyolefin resin. Preferably, 1.0 to 25 parts by mass is blended with 100 parts by mass of (A) polyolefin resin.
• the blending amount of the benzotriazole ultraviolet absorber is less than 0.5 parts by mass, the pellets are attached to each other and the blocking resistance is lowered. On the other hand, when it exceeds 50 parts by mass, the melt viscosity is lowered and pelletization is difficult. It may become.
• the method for producing the resin additive master batch of the present invention is not particularly limited, and can be performed by a conventionally known method.
• the blended components may be mixed using a Henschel mixer, mill roll, Banbury mixer, super mixer, etc., kneaded using a single screw or twin screw extruder, and pelletized.
• Resins stabilized by the resin additive masterbatch of the present invention include thermoplastic resins, thermosetting resins, crystalline resins, non-crystalline resins, biodegradable resins, non-biodegradable resins, synthetic resins, natural resins Any kind of resin such as production resin, general-purpose resin, engineering resin, and polymer alloy may be used.
• Synthetic resins include ⁇ -olefins such as polypropylene, low density polyethylene, linear low density polyethylene, high density polyethylene, polybutene-1, poly-3-methylpentene, poly-4-methylpentene, and ethylene-propylene copolymers.
• Copolymer rubbers with ⁇ -olefins, and elastomers such as terpolymer rubbers with ethylene- ⁇ -olefins and non-conjugated dienes such as ethylidene norbornene and cyclopentadiene, silicone resins, etc. may be used. And / or an alloyed or blended elastomer. Among these, polyolefin resin is preferable.
• Naturally-occurring resins include natural rubber, microbial-produced aliphatic polyester such as 3-hydroxybutyrate, microbial-produced aliphatic polyamide, starch, cellulose, chitin / chitosan, gluten / gelatin and the like.
• the resin is a lamella crystal measured by stereoregularity, specific gravity, type of polymerization catalyst, presence / absence or degree of polymerization catalyst removal, degree of crystallization, polymerization conditions such as temperature and pressure, type of crystal, X-ray small angle scattering Size, crystal aspect ratio, solubility in aromatic or aliphatic solvents, solution viscosity, melt viscosity, average molecular weight, degree of molecular weight distribution, how many peaks in molecular weight distribution, Although there are some differences in the expression of the stabilizing effect depending on whether it is block or random, the blending ratio of each monomer, etc., it is applicable when any resin is selected.
• the method of blending the resin additive masterbatch of the present invention into the resin is not particularly limited, and known blending techniques of stabilizers into the resin are used. For example, there is a method of kneading a master batch and resin powder and pellets mixed with a Henschel mixer etc. with an extruder etc., and the type of processing machine used, processing temperature, cooling conditions after processing, etc. The conditions are not limited and it is preferable to select conditions that make the obtained resin properties suitable for the intended use.
• the mass ratio of blending the resin additive masterbatch of the present invention into the resin depends on the concentration of the resin additive in the masterbatch, the final concentration of the resin additive in the resin composition blending the masterbatch, etc.
• a master batch of 0.01 to 20 parts by mass, more preferably 0.05 to 10 parts by mass is added to 100 parts by mass of the resin.
• various compounding agents usually used for each resin are used as necessary. These compounding agents include (B) the resin additive having a melting point of 65 ° C. or less and (C) an inorganic layered compound used in the resin additive masterbatch of the present invention, and an aromatic phosphate metal salt, It may be the same as or different from the triazole ultraviolet absorber.
• Various compounding agents include, for example, phenolic antioxidants, sulfur antioxidants, phosphorus antioxidants, ultraviolet absorbers, hindered amine compounds, nucleating agents, flame retardants, flame retardant aids, lubricants and fillers. , Fibrous fillers, metal soaps, hydrotalcites, antistatic agents, pigments, dyes and the like. These compounding agents may be blended together with the resin additive master batch of the present invention, or may be blended separately. Moreover, as long as it does not affect the storage stability of the resin additive masterbatch of the present invention, it may be incorporated in the masterbatch.
• phenolic antioxidant examples include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditert-butyl-4). -Hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-tert-butyl-m-cresol ), 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-butyl) Eno
• the blending amount is preferably 0.5 to 50 parts by weight, more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the resin.
• the amount is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the resin in the final product. .
• the sulfur antioxidant examples include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and pentaerythritol tetrakis ( ⁇ -dodecylthiopropionate).
• ⁇ -alkylthiopropionic esters of polyols such as
• the blending amount is preferably 0.5 to 50 parts by weight, more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the resin.
• the amount is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the resin in the final product. .
• 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) pe Taerythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphit
• the blending amount is preferably 0.5 to 50 parts by weight, more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the resin.
• the amount is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the resin in the final product. .
• ultraviolet absorber examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone).
• 2-Hydroxybenzophenones such as 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-di-tertiary Butylphenyl-3,5-ditertiarybutyl-4-hydroxybenzoate,
• Cyanoacrylates 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.
• the blending amount is preferably 0.5 to 50 parts by weight, more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the resin.
• the amount is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the resin in the final product. .
• hindered amine compound examples include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 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 (1,2,2 6,6-pentamethyl-4-piperidyl) -di (tridecyl)
• the blending amount is preferably 0.5 to 50 parts by weight, more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the resin.
• the amount is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the resin in the final product. .
• nucleating agent examples include aromatic carboxylic acid metal salts such as aluminum pt-butylbenzoate and sodium benzoate; disodium-bicyclo (2,2,1) heptane-2,3-dicarboxylate Metal salts of alicyclic carboxylic acids such as sodium bis (2,4-ditertiarybutylphenyl) phosphate, lithium bis (2,4-ditertiarybutylphenyl) phosphate, sodium-2,2′-methylenebis Acid phosphate metal salts such as (4,6-ditert-butylphenyl) phosphate; polyhydric alcohol derivatives such as dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (3,4-dimethylbenzylidene) sorbitol, etc. Can be mentioned.
• aromatic carboxylic acid metal salts such as aluminum pt-butylbenzoate and sodium benzoate
• Examples of the flame retardant include halogen-based flame retardant, red phosphorus, ammonium polyphosphate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, guanidine phosphate, and triphenyl.
• Phosphate ester compounds such as phosphate or hydroquinone, resorcinol, bisphenol A, 4,4'-dihydroxybiphenyl, phosphate esters of phenol and phenol, phosphazene compounds, phosphorus flame retardants such as phosphinates, melamine cyanurate
• Nitrogen flame retardants such as metal hydroxides such as magnesium hydroxide and aluminum hydroxide, flame retardant aids include inorganic compounds such as antimony trioxide and zinc borate, and anti-drip agents such as polytetrafluoroethylene Na And the like.
• lubricant examples 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, distearyl phosphate magnesium, stearyl phospho
• metal soaps such as ethylene bisstearyl amide, polyethylene wax, calcium stearate, magnesium stearate, distearyl phosphate magnesium, stearyl phospho
• phosphoric acid ester metal salts such as acid ester magnesium.
• inorganic materials such as talc, silica, calcium carbonate, glass fiber, potassium titanate, potassium borate, etc.
• talc silica
• calcium carbonate glass fiber
• potassium titanate potassium borate
• the filler inorganic materials such as talc, silica, calcium carbonate, glass fiber, potassium titanate, potassium borate, etc.
• a particle size in the case of a spherical material, and a fiber diameter, a fiber length, and an aspect ratio in a fibrous material, as appropriate. Select and use.
• metal soap examples include barium laurate and zinc octylate.
• the hydrotalcites may be, for example, 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.
• 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
• n Represents the number of water of crystallization from 0 to 100).
• a part of the anion may be substituted with a perchlorate anion or the like.
• antistatic agent examples include cationic antistatic agents such as fatty acid quaternary ammonium ion salts and polyamine quaternary salts; higher alcohol phosphate esters, higher alcohol EO adducts, polyethylene glycol fatty acid esters, anionic type Anionic antistatic agents such as alkyl sulfonates, higher alcohol sulfates, higher alcohol ethylene oxide adduct sulfates, higher alcohol ethylene oxide adduct phosphates; polyhydric alcohol fatty acid esters, polyglycol phosphates, poly Nonionic antistatic agents such as oxyethylene alkyl allyl ether; amphoteric antistatic agents such as amphoteric alkylbetaines such as alkyldimethylaminoacetic acid betaine and imidazoline type amphoteric activators. Such an antistatic agent may be used alone, or two or more kinds of antistatic agents may be used in combination.
• cationic antistatic agents such as fatty acid quaternary
• the pigment and dye may be organic or inorganic, for example, carbon black, petal, red lead, basic zinc chromate, chrome vermilion vermilion, cadmium red, rose red, brilliant carmine, brilliant scarlet, quinacridone red , Risor Red, Vermilion, Thioindigo Red, Mingamiya Red, Yellow Lead, Zinc Yellow, Yellow Iron Oxide, Titanium Yellow, First Yellow, Hansa Yellow, Auramin Lake, Benzidine Yellow, Indanthrene Yellow, Beige Pigment, Oxidized Titanium, zinc sulfide, chromium oxide, chrome green, zinc green, copper chloride phthalocyanine green, phthalocyanine green, naphthol green, malachite green lake, ultramarine, bitumen, copper cyanophthaline blue, cobalt blue, silver Russia Nin blue, follower strike Sky Blue, Indanthrene blue, and the like azo pigments.
• organic or inorganic for example, carbon black, petal, red lead, basic zinc
• an ultraviolet absorber is added to control the growth of crops, or an infrared absorber is added to improve heat retention. Since fog may be generated in the house or the film surface may condense and light may not reach the crop sufficiently, an anti-fogging agent or an anti-fogging agent may be added.
• the polyolefin resin composition of the present invention to which the resin additive masterbatch of the present invention is added includes a bumper, a dashboard, an instrument panel, a garnish, a front pillar cover, a side roof cover, a center pillar cover, and a radiator grill.
• Resin parts for automobiles such as side mat guards, aero parts or side protectors; Resin parts for household appliances such as refrigerators, washing machines and vacuum cleaners; Household goods such as tableware, buckets and bathing articles; Resin parts for connection such as connectors ; Miscellaneous goods such as toys; Storage containers such as tanks and bottles; Medical molded products such as medical packs, syringes, catheters and medical tubes; Building materials such as wall materials, flooring materials, window frames and wallpaper; ; Agricultural materials such as houses and tunnels; Includes films and sheets of food packaging materials such as wraps and trays Shaped piece; such fibers can be used in various applications.
• Example 1 to 17 Comparative Examples 1 to 6>
• component (A) a polypropylene resin (Novatech MA3, manufactured by Nippon Polypropylene Co., Ltd.) was used. 1 resin additive and the following compound no. 2 resin additive mixture (manufactured by ADEKA, melting point 33 ° C.) and the following compound No.
• the obtained powder was granulated at 230 ° C. using a twin screw extruder (manufactured by Nippon Steel Works, TEX30 ⁇ ) to obtain pellets.
• a storage stability test (blocking resistance test) was performed using the obtained pellets under the following conditions. The results are also shown in Tables 1 to 3.
• ⁇ Storage stability test (blocking resistance test)> 20 g of the obtained pellets were placed in a 75 ml capacity glass sample bottle having a bottom area of 12.6 cm 2 and a height of 6 cm, and stored in a thermostat bath at 50 ° C. and 60 ° C. After storage for 1 week, the sample bottle was inverted and the blocking resistance was evaluated from the falling state of the pellets.
• the evaluation criteria are as follows. Level 1 has the highest blocking resistance and is inferior to 2, 3, 4 and level 5 is inferior. Level 1: gently invert the sample bottle and the pellet falls. Level 2: If the sample bottle that has not been dropped at Level 1 is inverted from 5 mm above onto a flat table and vibrated, pellets fall.
• Level 3 When the sample bottle which is not dropped at Level 2 and is inverted from 30 mm above is dropped on a flat table and given vibration, the pellet falls.
• Level 4 Level 3 does not fall, and the pellet falls when the bottom of the sample bottle is hit several times.
• Level 5 Even at level 4, pellets do not fall.
• HAZE value in the table, the better the transparency. If the HAZE value is up to 60, the letters of the newspaper placed below can be read, but if the HAZE exceeds 65, the letters of the newspaper placed below cannot be read.

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