JP2009102633A - Masterbatch - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a masterbatch which comprises an organic additive having a melting point lower than that of a thermoplastic resin in a high concentration. <P>SOLUTION: This masterbatch comprises a thermoplastic resin, Fischer-Tropsch wax and an organic additive having a melting point lower than that of the thermoplastic resin, wherein the content of the organic additive is 10-70 mass%. The organic additive is selected from among a surfactant, an antioxidant, a weather-resistant stabilizer, a UV absorber, a slipping agent and a tackifier. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a masterbatch obtained by adding an additive or the like to a thermoplastic resin at a high concentration to form a flake or bead, and a molded product thereof.

  It is generally performed to add various functions to a thermoplastic resin by adding pigments or additives to the thermoplastic resin. There is also known a resin composition called a masterbatch in which pigments and additives are added to a thermoplastic resin at a high concentration to form a flake or bead, and this masterbatch is diluted with a suitable thermoplastic resin. And used for molding. Masterbatches are often used at molding sites and the like because they are suitable for ease of handling and work environment preservation during use.

  In recent years, from the viewpoint of improvement in handling properties and cost reduction, a master batch (hereinafter referred to as “high concentration master batch”) in which the concentration of pigments and additives added to the thermoplastic resin is higher than that of a conventional master batch. ) Is demanded by the market.

  In order to add a pigment to a thermoplastic resin to produce a high-concentration masterbatch, attempts have been made to add various dispersants in order to improve the dispersibility of the pigment in the thermoplastic resin. For example, Patent Document 1 states that a polyolefin wax synthesized with a metallocene catalyst is suitable as a dispersant.

  Since the melting point of the pigment is generally higher than that of the thermoplastic resin, the process of masterbatching the pigment with the thermoplastic resin involves the particles of the pigment remaining solid in the thermoplastic resin that has been plasticized and fluidized. It was a process of dispersing. That is, in order to produce a masterbatch containing a pigment in a high concentration, how to improve the dispersibility of the added pigment has been a problem.

  On the other hand, the melting point of the thermoplastic resin (in the case of a polymer, it is also referred to as a softening point, and in the case of a wax or the like, it is also referred to as a dropping point. In the case of masterbatching an organic additive having a lower melting point (hereinafter referred to as “low-melting point organic additive”), a problem completely different from that in the case of masterbatching a pigment occurred. That is, the kneading of the pigment and the thermoplastic resin is a kneading between the solid and the fluid, but the kneading of the low melting point organic additive and the thermoplastic resin is a kneading of the fluids.

  Low-melting-point organic additives generally have poor compatibility with thermoplastic resins when the temperature is raised to the melting point of the thermoplastic resin, and the difference in viscosity with the thermoplastic resin is too large, making uniform kneading difficult. It was difficult to master batch. Furthermore, when the concentration of the low melting point organic additive is increased, the strand does not solidify and does not become pellets, or the low melting point organic additive added to the strand surface bleeds out or causes blocking even if pelletized. The problem that occurred.

  Typical low melting point organic additives include antistatic agents for the purpose of imparting antistatic functions to thermoplastic resins, and antifogging functions for preventing fogging due to water droplets on the surface of thermoplastic resins. There is an anti-fogging agent. Surfactants are generally used as antistatic agents and antifogging agents. However, it has been difficult to produce a high-concentration masterbatch containing 10% by mass or more of the surfactant with respect to the total amount.

  As a method for producing a master batch containing a surfactant in a thermoplastic resin and containing an antistatic agent at a high concentration, in Patent Document 2, a surfactant is mixed in advance with silicon oxide, and the viscosity with the thermoplastic resin is determined. It proposes kneading after reducing the difference. However, this method has a problem that it is necessary to knead the surfactant and silicon oxide in advance, and there is a problem that unnecessary coloring due to silicon oxide is forced by addition of an unnecessary filler component.

JP 2003-183447 A JP-A-6-322140

  An object of the present invention is to provide a masterbatch containing a high concentration of an organic additive having a melting point lower than that of a thermoplastic resin.

  The present invention has been made in order to solve this problem, and the invention according to claim 1 includes a thermoplastic resin, a Fischer-Tropsch wax, and an organic additive having a melting point lower than that of the thermoplastic resin. A master batch containing the organic batch, wherein the organic additive is 10% by mass or more and 70% by mass or less.

  The invention according to claim 2 is characterized in that the organic additive is one or more organic additives selected from surfactants, antioxidants, weathering stabilizers, ultraviolet absorbers, slip agents and tackifiers. The master batch according to claim 1.

  Invention of Claim 3 is a masterbatch in any one of Claim 1 or 2 whose said thermoplastic resin is polyolefin resin.

  According to a fourth aspect of the invention, the surfactant is one or more surfactants selected from glycerin fatty acid esters, alkyl sulfonates, and amine surfactants. This is the described master batch.

  The invention according to claim 5 is the masterbatch according to any one of claims 1 to 3, wherein the weather stabilizer is a hindered weather stabilizer.

  The invention according to claim 6 is the master according to any one of claims 1 to 3, wherein the ultraviolet absorber is at least one ultraviolet absorber selected from a benzophenone ultraviolet absorber and a triazine ultraviolet absorber. It is a batch.

  The invention according to claim 7 is the master batch according to any one of claims 1 to 3, wherein the tackifier is an alicyclic saturated hydrocarbon.

  The invention according to claim 8 is a thermoplastic resin molded product formed by using the master batch according to any one of claims 1 to 7.

  By adding the Fischer-Tropsch wax according to the present invention, it is possible to produce a masterbatch containing a high concentration of an organic additive having a melting point lower than that of a thermoplastic resin that could not be produced until now.

  By using a masterbatch containing an organic additive having a melting point lower than that of the thermoplastic resin at a high concentration, handling properties can be improved at the molding site.

  A masterbatch containing a low-melting-point organic additive according to the present invention in a high concentration is a masterbatch containing a thermoplastic resin, a Fischer-Tropsch wax, and an organic-based additive having a melting point lower than the melting point of the thermoplastic resin. The organic additive is 10% by mass or more and 70% by mass or less. Note that this embodiment is merely an embodiment for carrying out the present invention, and the present invention is not limited by this embodiment, and various modified embodiments can be made without departing from the gist of the present invention. Is possible.

The Fischer-Tropsch wax used in the present invention is a saturated hydrocarbon wax represented by the general formula C _n H _{2n + 2} produced using carbon monoxide and hydrogen as raw materials by the Fischer-Tropsch method, and has an average molecular weight of 400. ~ 1600. Fischer-Tropsch wax is a wax having a substantially complete linear molecular structure having almost no side branch, and is different from polyethylene wax having a side chain. Fischer-Tropsch wax is added in an amount of about 1% to 15% by weight based on the total amount of the masterbatch. Polyethylene wax does not have a significant effect as in the present invention.

  The thermoplastic resin utilized in the present invention is an olefin resin such as polyethylene, polypropylene, ethylene-α olefin copolymer, propylene-α olefin copolymer, thermoplastic olefin, polystyrene, styrene acrylonitrile copolymer, styrene acrylonitrile. Examples include styrene resins such as butadiene copolymers, acrylic acid ester resins such as methyl methacrylate, nylon 6, nylon 66, nylon 12, polycarbonate, polyethylene terephthalate, and polybutylene terephthalate. A thermoplastic resin can also be used. However, among these, polyolefin resin is particularly preferable.

  The low melting point organic additive used in the present invention is an organic additive having a melting point lower than that of the thermoplastic resin. The melting point here means a temperature at which the organic additive becomes a fluid, and includes a softening point in the case of a polymer and a dropping point in the case of a wax.

  When a masterbatch is produced by adding 10% by mass or more of a low melting point organic additive to the total amount, the strand does not solidify into pellets, or the low melting point organic additive added to the strand surface bleeds out. Even if pelletized, a problem of blocking occurred, and a master batch could not be made. However, by adding about 1 to 15% by mass of Fischer-Tropsch wax with respect to the total amount, the low-melting point organic additive is 10% by mass or more (when using a plurality of low-melting point organic additives, the total is 10 %), A master batch can be produced. However, when the low-melting-point organic additive is 70% by mass or more, the strand does not solidify and become pellets, or the low-melting-point organic additive added to the strand surface bleeds out or causes blocking even if pelletized. Problem occurs, and master batches cannot be made.

  Examples of the low melting point organic additive used in the present invention include, but are not limited to, an antistatic agent, an antifogging agent, an antioxidant, a weathering stabilizer, an ultraviolet absorber, a slip agent, and a tackifier. The present invention is applicable to any organic additive having a melting point lower than that of the thermoplastic resin desired to be made into a high concentration master batch. Moreover, it is also possible to produce a high-concentration masterbatch containing a plurality of types of low-melting-point organic additives by combining these low-melting-point organic additives.

  Surfactants are generally used for antistatic agents and antifogging agents. Examples include glycerin fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, alkyl diethanol amines, hydroxyalkyl monoethanol amines, polyoxyethylene alkyl amines, polyoxyethylene alkyl amine fatty acid esters, alkyl diethanolamides, etc. Nonionic surfactants, anionic surfactants such as alkyl sulfonates, alkylbenzene sulfonates, and alkyl phosphates, cationic surfactants such as tetraalkylammonium salts and trialkylbenzylammonium salts, alkylbetaines, alkylimidazos Although amphoteric surfactants such as lithium betaine can be mentioned, the present invention is applicable to any surfactant.

  The antioxidants generally used include phenolic (hindered phenols, etc.), phosphorus, sulfur, amine, hydroquinone, α-tocopherol, etc., but the present invention is not limited to any antioxidant. It is also applicable to agents.

  Examples of the phenol-based antioxidant include thiobisphenol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-p-cresol, 1,3,5-trimethyl-2,4,6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) benzene, 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], triethyleneglycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) Nenyl) propionate], n-octadecyl-3- (4 ′, 5′-di-t-butylphenol) propionate, n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenol) Propionate, stearyl-2- (3,5-di-t-butyl-4-hydroxyphenol) propionate, distearyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, 2-t-butyl-6 -(3-t-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenyl acrylate, N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrosym Amide), 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethyl ester. L} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl) And hindered phenols such as -4-hydroxy-5-t-butylphenol) butane.

  Examples of the phosphorus antioxidant include triisodecyl phosphite, triphenyl phosphite, trisnonylphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, and 2,2-methylenebis (4,6-di-). -T-butylphenyl) octyl phosphite, 4,4'-butylidenebis (3-methyl-6-t-butylphenyl) ditridecyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (2-t-butyl-4-methylphenyl) phosphite, tris (2,4-di-t-amylphenyl) phosphite, tris (2-t-butylphenyl) phosphite, bis (2-t-butyl) Phenyl) phenyl phosphite, tris [2- (1,1-dimethylpropyl) -phenyl] Phosphites, tris [2,4- (1,1-dimethylpropyl) -phenyl] phosphite, tris (2-cyclohexylphenyl) phosphite, tris (2-tert-butyl-4-phenylphenyl) phosphite Phyto compounds; triethylphosphine, tripropylphosphine, tributylphosphine, tricyclohexylphosphine, diphenylvinylphosphine, allyldiphenylphosphine, triphenylphosphine, methylphenyl-p-anisylphosphine, p-anisyldiphenylphosphine, p-tolyldiphenylphosphine Di-p-anisylphenylphosphine, di-p-tolylphenylphosphine, tri-m-aminophenylphosphine, tri-2,4-dimethylphenylphosphine, tri-2,4,6-trime Tylphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri-o-anisylphosphine, tri-p-anisylphosphine, 1,4-bis (diphenylphosphino ) Phosphine compounds such as butane.

  Examples of the sulfur-based antioxidant include dilauryl thiodipropionate, distearyl thiodipropionate, dimyristyl thiodipropionate, ditridecyl thiodipropionate, dilauryl 3,3′-thiodipropionate, Dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), ditridecyl 3,3'-thiodipropionate It is done.

  Examples of the amine-based antioxidant include phenyl-1-naphthylamine, phenyl-2-naphthylamine, N, N′-diphenyl-1,4-phenylenediamine, and N-phenyl-N′-cyclohexyl-1,4- Examples include phenylenediamine, 4,4′-di (α, α-dimethylbenzyl) diphenylamine, and the like. Examples of the hydroquinone antioxidant include 2,5-di-t-butylhydroquinone.

  Although generally used as a weather stabilizer is a hindered amine system, the present invention is applicable to any weather stabilizer.

  Examples of the hindered amine weathering stabilizer 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, N- (2,2,6,6-tetramethyl-4-piperidyl) dodecylsuccinimide, 1-[(3,5-di-tert-butyl-4 -Hydroxyphenyl) propionyloxyethyl] -2,2,6,6-tetramethyl-4-piperidyl (3,5-tert-butyl-4-hydroxyphenyl) propionate, bis (2,2,6,6-tetra Methyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pe Tamethyl-4-piperidyl) -2-butyl-2- (3,5-di-tert-butyl-4-hydroxybenzyl) hexamethylenediamidine, tetra (2,2,6,6-tetramethyl-4-piperidyl) ) Butenetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidine) ) Di (tridecyl) butanetetracarboxylate, 3,9-bis {1,1, -dimethyl-2- [tris (2,2,6,6-tetramethyl-4-piperidylcarbonyloxy) butylcarbonyloxy] ethyl } -2,4,8,10-tetraoxysaspiro [5,5] undecane, 3,9-bis {1,1-dimethyl-2- [tris (1 2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy] ethyl} -2,4,8,10-tetraoxysaspiro [5,5] undecane, 1,5,8,12 Tetrakis [4,6-bis [N- (2,2,6,6-tetramethyl-4-piperidyl) butylamino] -1,3,5-triazin-2-yl] -1,5,8, 12-tetraazadecane, 1- (2-hydroxyethyl)-, 2,2,6,6-tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tert-octylamino-4,6-dichloro- and s-triazine / N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine / dibromoethane condensed compound.

  Commonly used UV absorbers are benzotriazole, benzophenone, benzoate, salicylate, cyanoacrylate, triazine, and benzoxazine, but the present invention is applicable to any UV absorber. Is possible.

  Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chloro And benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) -5-chlorobenzotriazole, and the like.

  Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, Examples include 2,2′-hydroxy-4,4′-dimethoxybenzophenone and 2-hydroxy-4-methoxy-5-sulfobenzophenone.

  Examples of the benzoate ultraviolet absorber include 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, resorcinol monobenzoate, and the like.

  Commonly used slip agents are fatty acid amides, fatty acid metal salts, fatty acids, and higher alcohols, but the present invention is applicable to any slip agent.

  Examples of the fatty acid amide slip agent include higher fatty acid amides such as lauric acid amide and oleic acid amide.

  Examples of the tackifier generally used include hydrogenated petroleum resins such as alicyclic saturated hydrocarbons, but the present invention is applicable to any tackifier.

  In addition to these low melting point organic additives, pigments can be used in combination. Examples of pigments include titanium oxide, zinc oxide, dial, titanium oxide-based calcined pigment, ultramarine, cobalt aluminate, carbon black and other inorganic pigments, azo-based, quinacridone-based, anthraquinone-based, perylene-based, isoindolinone-based, Organic pigments such as phthalocyanine, quinophthalone, selenium, and diketopyrrolopyrrole, and extender pigments such as barium sulfate, calcium carbonate, and talc can be used.

  Further, if necessary, a heat stabilizer, a light stabilizer, a flame retardant, a plasticizer, a lubricant, a filler and the like can be added.

  The master batch of the present invention is produced by premixing each component with a high-speed mixer or tumbler and then melt-kneading. Further, the low-melting-point organic additive that is liquid at room temperature can be injected from the middle part of the cylinder of the extruder with a liquid addition device without pre-mixing. The melt-kneading step includes a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader, a high-speed rotary intensive mixer, and the like, and any method may be used for melt-kneading. The shape of the masterbatch is determined by the method of taking out from the kneader, and is generally in a granular shape by hot cutting or cold cutting of sheets or strands.

  The masterbatch produced according to the present invention is diluted 1 to 200 times with a thermoplastic resin mainly at the molding site and used for the purpose of producing a molded product.

Examples and comparative examples will be described below, but the present invention is not limited thereto.
Examples 1 to 16 and Comparative Examples 1 to 14 show examples in which polypropylene is used as a thermoplastic resin, and a surfactant used as an antistatic agent or an antifogging agent is used as a low melting point organic additive.

  In Examples 17 to 40 and Comparative Examples 15 to 34, an example was shown in which polyethylene was used as the thermoplastic resin, and a surfactant used as an antistatic agent or an antifogging agent was used as the low melting point organic additive.

  In Examples 41 to 44 and Comparative Examples 35 to 37, examples in which polyethylene was used as the thermoplastic resin and two kinds of surfactants were used in combination as the low melting point organic additive were shown.

  In Examples 45 to 48 and Comparative Examples 38 to 40, examples were shown in which polypropylene was used as the thermoplastic resin, and a hindered amine weathering stabilizer (light stabilizer) was used as the low melting point organic additive.

  In Examples 49 to 60 and Comparative Examples 41 to 49, examples were shown in which polyethylene was used as the thermoplastic resin, and a hindered amine weathering stabilizer (light stabilizer) was used as the low melting point organic additive.

  In Examples 61-68 and Comparative Examples 50-55, examples were shown in which polyethylene was used as the thermoplastic resin and an ultraviolet absorber was used as the low-melting-point organic additive.

  Examples 69 to 72 and Comparative Examples 56 to 61 showed examples using polypropylene as a thermoplastic resin and an alicyclic saturated hydrocarbon as a tackifier as a low melting point organic additive.

  In Examples 73 to 76 and Comparative Examples 62 to 64, polyethylene was used as the thermoplastic resin, a surfactant was used as the low melting point organic additive, and two types of hindered amine weathering stabilizers (light stabilizers) were used in combination. An example is shown.

  In Examples 77 to 80 and Comparative Examples 65 to 67, polyethylene as a thermoplastic resin, two types of hindered amine weathering stabilizers (light stabilizers), and a triazine ultraviolet absorber as low melting point organic additives are combined. The example used is shown.

  Table 1 shows the types, product names, manufacturers, physical properties, and the like of the thermoplastic resins and low-melting-point organic additives used in Examples 1 to 80 and Comparative Examples 1 to 67.

The MFR (* 1) of the thermoplastic resin was in accordance with the JIS K7210 test method.
The melting point (* 2) of the thermoplastic resin was in accordance with the JIS K7121 test method.
The softening point (according to the ring and ball method) is shown in the melting point (* 3) of the tackifier (alicyclic saturated hydrocarbon, Alcon P-125).

For Examples 1 to 80 and Comparative Examples 3, 8, 11, 14, 17, 22, 25, 28, 31, 34, 37, 40, 43, 46, 49, 52, 55, 59, 64, 67 Fischer-Tropsch wax was
Sazol wax H1 (manufactured by Sazol Wax, average molecular weight 750, dropping point: 108 ° C.).

The polyethylene wax used in Comparative Examples 4, 5, 18, 19, 60, 61 is
Allied wax AC-6A (manufactured by Allied Signal, weight average molecular weight 5500, dropping point: 106 ° C.).

  The compositions of Examples 1 to 80 and Examples 1 to 67 are shown in Tables 2 to 21.

  Masterbatches having the compositions shown in Tables 2 to 12 and Tables 15 to 21 were produced through the following steps. The mixture of the composition described in each table | surface was mixed with the Henschel mixer (Mitsui FM mixer by Mitsui Mining Co., Ltd.), and the mixture was produced. The mixture was melt kneaded using a twin screw extruder (30 mmΦ, PCM-30 manufactured by Ikegai Co., Ltd., the set temperature of the maximum temperature setting section is shown in each table), and after forming a strand, cold cut Masterbatching was performed.

Of the compositions shown in Tables 13 and 14, the master batches of the compositions of Examples 45 to 52 and Comparative Examples 40 and 43 were produced through the following steps.
Thermoplastic resin and Fischer-Tropsch wax were mixed with a Henschel mixer (Mitsui FM mixer manufactured by Mitsui Mining Co., Ltd.) to prepare a mixture. The mixture was introduced from the feeder part of a twin screw extruder (30 mmΦ, PCM-30 manufactured by Ikegai Co., Ltd., the set temperature of the maximum temperature setting section is shown in each table), and then Tinuvin 765, which is liquid at room temperature, was placed in the middle of the cylinder. After injecting with a liquid addition apparatus from the part, melt-kneading was performed, strands were formed, and master batching was performed by cold cutting.

Of the compositions shown in Tables 13 and 14, master batches having the compositions of Comparative Examples 38, 39, 41, and 42 were produced through the following steps.
After the thermoplastic resin is charged from the feeder part of a twin screw extruder (30 mmΦ, PCM-30 manufactured by Ikegai Co., Ltd., the setting temperature of the maximum temperature setting section is shown in each table), Tinuvin 765, which is liquid at room temperature, is placed in the cylinder. After injecting from an intermediate part with a liquid addition apparatus, melt kneading, forming a strand, a master batch was formed by cold cutting.

The obtained master batch was evaluated as follows.

1) Masterbatch formation The process of masterbatch formation by a twin screw extruder was visually determined.
○: No bleed-out of low melting point organic additive on the strand surface △: Slight bleed-out of low melting point organic additive on the strand surface ×: Unstable ejection from the extruder, making a masterbatch Can not

2) Blocking evaluation Blocking of the granulated masterbatch was visually evaluated.
○: Blocking is not observed at all Δ: Blocking is slightly observed ×: Blocking —: Master batch is not obtained (granulation cannot be performed) and cannot be evaluated.

3) Measurement of surface resistance value About Examples 1-44, 73-76 and Comparative Examples 1-37, 62-64 which added surfactant as a low melting-point organic additive, the film was produced and the surface resistance value was measured. .
The obtained master batch is diluted with the same kind of thermoplastic resin so that the surfactant concentration becomes 0.7% by mass, and an inflation molding machine (manufactured by Yamaguchi Seisakusho Co., Ltd. for polypropylene, Tommy Industries Ltd. for polyethylene) A film having a thickness of 50 μm was produced.
The obtained film was stored under constant temperature and humidity conditions (25 ° C. × 40%) for 7 days, and then the resistance value of the film surface was measured with an applied voltage of 500 V using a Hirester UP type resistance measuring device manufactured by Mitsubishi Chemical. . In addition, "-" in a table | surface showed the state which cannot evaluate and cannot produce a film.

4) Weather resistance evaluation Films were prepared and weather resistance stability was evaluated for Examples 45 to 60 and 73 to 80 and Comparative Examples 38 to 49 and 62 to 67 to which a weather stabilizer was added as a low melting point organic additive.
The resulting masterbatch is diluted with the same kind of thermoplastic resin so that the concentration of the weather stabilizer is 0.5% by mass, and an inflation molding machine (manufactured by Yamaguchi Seisakusho Co., Ltd. for polypropylene, Tommy Industries Ltd. for polyethylene) A film having a thickness of 50 μm was produced.
The prepared film was irradiated with a sunshine weather meter (black panel temperature = 63 ± 3 ° C., rainfall 18 minutes / 120 minutes) for 800 hours for an accelerated weathering test. The film was subjected to a tensile test after irradiation to measure the elongation retention.
○: Retention rate> 80%
Δ: 50 <retention rate <80
×: Retention rate <50%
―: The film cannot be obtained and cannot be evaluated.

5) Ultraviolet absorption evaluation About Examples 61-68, 77-80 and Comparative Examples 50-55, 65-67 which added the ultraviolet absorber as a low melting-point organic additive, the film was produced and ultraviolet absorption was evaluated.
The obtained master batch was diluted with the same kind of thermoplastic resin so that the ultraviolet absorber concentration was 0.5% by mass, and a film having a thickness of 50 μm was produced with an inflation molding machine (manufactured by Tommy Industries, Ltd.).
The prepared film was measured for ultraviolet absorption with an ultraviolet-visible spectrophotometer (manufactured by Perkin Elmer, RAMBDA950).
The evaluation criteria are as follows.

a) In the case of UV absorber Cyasorb UV-531 (Examples 61 to 64, Comparative Examples 50 to 52) ○: The transmittance at a maximum absorption wavelength of 330 nm is 30% or less ×: The transmittance at a maximum absorption wavelength of 330 nm is from 30% Large-: The film cannot be obtained and cannot be evaluated.

b) In the case of UV absorber Cyasorb UV-1164 (Examples 65 to 68, Examples 77 to 80, Comparative Examples 53 to 55, Comparative Examples 65 to 67) ○: The transmittance at a maximum absorption wavelength of 340 nm is 20% or less. : The transmittance at a maximum absorption wavelength of 340 nm is greater than 20%.-: A film cannot be obtained and cannot be evaluated.

In Table 2, the evaluation result of Examples 1-4 and Comparative Examples 1-5 was shown.
The surface resistance values of Examples 1 to 4 were comparable to the surface resistance value of Comparative Example 1, and it was confirmed that the antistatic effect was sufficient.

In Table 3, the evaluation result of Examples 5-8 and Comparative Examples 6-8 was shown.
The surface resistance values of Examples 5 to 8 were comparable to the surface resistance value of Comparative Example 6, and it was confirmed that the antistatic effect was sufficient.

In Table 4, the evaluation result of Examples 9-12 and Comparative Examples 9-11 was shown.
The surface resistance values of Examples 9 to 12 were comparable to the surface resistance value of Comparative Example 9, and it was confirmed that the antistatic effect was sufficient.

In Table 5, the evaluation result of Examples 13-16 and Comparative Examples 12-14 was shown.
The surface resistance values of Examples 13 to 16 were comparable to the surface resistance value of Comparative Example 12, and it was confirmed that the antistatic effect was sufficient.

In Table 6, the evaluation result of Examples 17-20 and Comparative Examples 15-19 was shown.
The surface resistance values of Examples 17 to 20 were comparable to the surface resistance value of Comparative Example 15, and it was confirmed that the antistatic effect was sufficient.

In Table 7, the evaluation result of Examples 21-24 and Comparative Examples 20-22 was shown.
The surface resistance values of Examples 21 to 24 were comparable to the surface resistance value of Comparative Example 20, and it was confirmed that the antistatic effect was sufficient.

In Table 8, the evaluation result of Examples 25-28 and Comparative Examples 23-25 was shown.
The surface resistance values of Examples 25 to 28 were comparable to the surface resistance value of Comparative Example 23, and it was confirmed that the antistatic effect was sufficient.

Table 9 shows the evaluation results of Examples 29 to 32 and Comparative Examples 26 to 28.
The surface resistance values of Examples 29 to 32 were comparable to the surface resistance value of Comparative Example 26, and it was confirmed that the antistatic effect was sufficient.

In Table 10, the evaluation result of Examples 33-36 and Comparative Examples 29-31 was shown.
The surface resistance values of Examples 33 to 36 were comparable to the surface resistance value of Comparative Example 29, and it was confirmed that the antistatic effect was sufficient.

In Table 11, the evaluation result of Examples 37-40 and Comparative Examples 32-34 was shown.
The surface resistance values of Examples 37 to 40 were comparable to the surface resistance value of Comparative Example 32, and it was confirmed that the antistatic effect was sufficient.

Table 12 shows the evaluation results of Examples 41 to 44 and Comparative Examples 35 to 37.
The surface resistance values of Examples 41 to 44 were comparable to the surface resistance value of Comparative Example 35, and it was confirmed that the antistatic effect was sufficient.

In Table 13, the evaluation result of Examples 45-48 and Comparative Examples 38-40 was shown.

In Table 14, the evaluation result of Examples 49-52 and Comparative Examples 41-43 was shown.

In Table 15, the evaluation result of Examples 53-56 and Comparative Examples 44-46 was shown.

Table 16 shows the evaluation results of Examples 57 to 60 and Comparative Examples 47 to 49.

In Table 17, the evaluation result of Examples 61-64 and Comparative Examples 50-52 was shown.

Table 18 shows the evaluation results of Examples 65 to 68 and Comparative Examples 53 to 55.

In Table 19, the evaluation result of Examples 69-72 and Comparative Examples 56-61 was shown.

In Table 20, the evaluation result of Examples 73-76 and Comparative Examples 62-64 was shown.
The surface resistance values of Examples 73 to 76 were comparable to the surface resistance value of Comparative Example 62, and it was confirmed that the antistatic effect was sufficient.

In Table 21, the evaluation result of Examples 77-80 and Comparative Examples 65-67 was shown.

  By adding the Fischer-Tropsch wax of the present invention, it becomes possible to produce a masterbatch containing a high concentration of an organic additive having a melting point lower than the melting point of a thermoplastic resin that could not be produced until now, The handling property at the molding site can be improved.

Claims (8)

  A masterbatch containing a thermoplastic resin, a Fischer-Tropsch wax, and an organic additive having a melting point lower than the melting point of the thermoplastic resin, the organic additive being 10% by mass or more and 70% by mass or less A masterbatch characterized by being.   The masterbatch according to claim 1, wherein the organic additive is at least one organic additive selected from a surfactant, an antioxidant, a weathering stabilizer, an ultraviolet absorber, a slip agent, and a tackifier. .   The master batch according to claim 1, wherein the thermoplastic resin is a polyolefin resin.   The master batch according to any one of claims 1 to 3, wherein the surfactant is one or more surfactants selected from glycerin fatty acid esters, alkyl sulfonates, and amine surfactants.   The masterbatch according to any one of claims 1 to 3, wherein the weathering stabilizer is a hindered weathering stabilizer.   The masterbatch according to any one of claims 1 to 3, wherein the ultraviolet absorber is one or more ultraviolet absorbers selected from a benzophenone ultraviolet absorber and a triazine ultraviolet absorber.   The masterbatch according to any one of claims 1 to 3, wherein the tackifier is an alicyclic saturated hydrocarbon.   A thermoplastic resin molded product formed by using the master batch according to any one of claims 1 to 7.