JP6427345B2 - Surfactant-containing masterbatch pellet and method for producing the same - Google Patents

Description

The present invention relates to surfactant-containing masterbatch pellets , and methods of making the same. More particularly, surfactant-containing masterbatch pellets, characterized in that the trans crystal crystal layer is present on the interior surface and in the vicinity of the master batch pellets, and a method of manufacturing the same.

  Conventionally, a master batch prepared by kneading a surfactant to a high concentration in a resin is prepared in advance, and the resin batch together with the resin raw material is introduced into a molding apparatus such as an extruder during resin molding to form a surfactant-containing resin. The method of doing is taken.

  The resin molded product obtained by this conventional method exhibits, for example, water repellency, antistatic performance, antifogging performance, etc., by the surfactant contained in the resin molded product being exposed on the surface of the molded product. On the other hand, in the case of a masterbatch containing a high concentration of surfactant, a large amount of surfactant easily migrates (bleeds) to the surface of the masterbatch, and as a result, a blocking phenomenon in which masterbatches are bound to each other. Was apt to occur. Blocking significantly deteriorates molding productivity and workability.

  In order to improve such a defect, for example, in the manufacturing method described in Patent Document 1, a strand obtained from a composition in which a crystalline thermoplastic resin, an antistatic agent and a nucleating agent are blended is subjected to a predetermined air cooling rate It is proposed to reduce the bleeding of the antistatic agent by gradually cooling it.

  In addition, a method of forming a surface crystal layer having fine spherulites in a specific thickness on the surface of a polyester resin pellet is proposed in Reference Document 2 in order to suppress fusion during solid phase polycondensation of the pellet. There is. The surface crystal layer is described as including a trans crystal layer.

  Moreover, in the cited reference 3, in the method for producing a propylene-based resin molded product having a hard coat layer obtained by curing an acrylic UV-curable resin on the surface of a propylene-based resin film or sheet, the propylene-based resin film or sheet is used. Describes a process characterized in that the crystals of the propylene-based resin in the layer to be made into a trans-crystal structure.

JP 2012-72335 A JP, 2006-199830, A Patent No. 2794890

  However, the method disclosed in Patent Document 1 is insufficient as a method for improving blocking, and since the gradually cooled strands are difficult to cut into pellets, uniformity of pellet shape can not be maintained, and variant pellets Problems were likely to occur.

  Further, in the case of a pellet containing a surfactant as a water repellent, an antistatic agent, an antifogging agent, etc., the occurrence of blocking is generally more pronounced than that of a pellet not containing a surfactant, as disclosed in Patent Document 2. Even in the case where the pellet according to the method contains a considerable amount of surfactant, it is not always possible to effectively suppress the occurrence of blocking. Moreover, since none of the pellets described in reference 2 contain additives such as surfactant, reference 2 suggests an effective means to suppress blocking of the pellet containing the surfactant. It is not something to do. In fact, it has been confirmed that the formation of the surface crystal layer described in Patent Document 2 can not sufficiently sufficiently suppress the occurrence of blocking in a pellet containing a considerable amount of surfactant.

  Furthermore, the method disclosed in Patent Document 3 aims to make the gloss of the hard coat layer formed on the surface of the propylene-based resin molded article remarkably inferior. Therefore, the cited reference 3 does not suggest means for suppressing the elution of the molded article surface of the surfactant contained in the propylene-based resin molded article, in particular, the point that the trans crystal structure suppresses the migration of the surfactant. .

The present invention has been made to solve the above-described problems in consideration of the above-described prior art. That is, the present invention suppresses the surface dissolution of the surfactant, and an object thereof is to provide a surfactant-containing masterbatch pellets can suppress the occurrence of blocking of the masterbatch pellets.

Another object of the present invention is to provide a method of producing the surfactant-containing masterbatch pellet .

As a result of intensive investigations to solve the above problems, the inventor of the present invention suppresses the surface elution of the surfactant by forming a trans crystal crystal layer on the surface of the masterbatch pellet and in the vicinity thereof, thereby a masterbatch. It has been found that the occurrence of blocking of pellets can be suppressed, and the present invention has been completed.

In addition, the inventor of the present invention cools a kneaded product obtained by melt-kneading a crystalline thermoplastic resin and a surfactant, and subsequently heats it, whereby crystalline thermoplastic resin can be obtained without using a nucleating agent. It has been found that a transcrystalline layer can be formed on and in the vicinity of the surface of a masterbatch pellet containing a resin and a surfactant, and by further setting the above-mentioned cooling temperature and heating temperature to appropriate temperatures, the master The inventors have found that the formation of a transcrystalline layer can be ensured without causing a significant decrease in the productivity of batch pellets , and the present invention has been accomplished.
That is, the present invention particularly relates to the following [1] to [8].
[1]
A masterbatch pellet comprising a crystalline thermoplastic resin and a surfactant,
Characterized in that a transcrystalline layer is present on the surface of the masterbatch pellet and in the vicinity thereof,
The crystalline thermoplastic resin is a resin selected from the group consisting of a polyolefin resin, a polyamide resin, a polyester resin, a polyacetal resin, a thermoplastic polyurethane resin, a fluorine resin, and a mixture of two or more of them.
Masterbatch pellet.
[2]
The masterbatch pellet according to [1], wherein the thickness of the transcrystalline layer is at least 2 μm.
[3]
The masterbatch pellet according to [1] or [2], wherein the surfactant is an antistatic agent and / or an antifogging agent.
[4]
The masterbatch pellet according to any one of [1] to [3], wherein the crystalline thermoplastic resin is a polyolefin resin.
[5]
A kneading step of melt-kneading the crystalline thermoplastic resin and the surfactant;
A crystallization step in which the kneaded product obtained in the kneading step is cooled and then heated;
After the crystallization step, the method includes a forming step of forming the obtained crystallized product into a master batch in pellet form,
The crystalline thermoplastic resin is a resin selected from the group consisting of a polyolefin resin, a polyamide resin, a polyester resin, a polyacetal resin, a thermoplastic polyurethane resin, a fluorine resin, and a mixture of two or more of them.
A method for producing a masterbatch pellet, comprising
In the crystallization step, the difference between the temperature (T ₁ ) before cooling of the kneaded material and the temperature (T ₂ ) after cooling is T ₂ −T ₁ = −110 to −210 ° C., and A manufacturing method characterized in that a difference between a temperature after cooling (T ₂ ) and a temperature after heating (T ₃ ) is T ₃ −T ₂ = 10 to 90 ° C.
[6]
The manufacturing method according to [5], wherein the cooling in the crystallization step is carried out by a water cooling method.
[7]
The production method according to [5] or [6], wherein the surfactant is an antistatic agent and / or an antifogging agent.
[8]
The method according to any one of [5] to [7], wherein the crystalline thermoplastic resin is a polyolefin resin.

In the present specification, the invention relating to the following is also disclosed.
That is, the present invention relates to a masterbatch comprising a crystalline thermoplastic resin and a surfactant, wherein a transcrystalline layer is present on the surface of the masterbatch and in the vicinity thereof. .

  The invention relates to a masterbatch, characterized in that the thickness of said transcrystalline layer is at least 2 μm.

  The present invention relates to a masterbatch characterized in that the surfactant is an antistatic agent and / or an antifogging agent.

  The present invention relates to a masterbatch characterized in that the crystalline thermoplastic resin is a polyolefin resin.

  The present invention is a method for producing a masterbatch, which comprises a kneading step of melt-kneading a crystalline thermoplastic resin and a surfactant, wherein the kneaded product obtained in the kneading step is cooled and then crystallized. The present invention relates to a manufacturing method characterized by including a step.

In the present invention, in the crystallization step, the difference between the temperature (T ₁ ) before cooling of the kneaded material and the temperature (T ₂ ) after cooling is T ₂ −T ₁ = −110 to −210 ° C. The present invention relates to a method of manufacturing.

The present invention is characterized in that, in the crystallization step, the difference between the temperature (T ₂ ) after cooling of the kneaded material and the temperature (T ₃ ) after heating is T ₃ −T ₂ = 10 to 90 ° C. Related to the manufacturing method.

  The present invention relates to a manufacturing method characterized in that the cooling in the crystallization step is carried out by a water cooling method.

  The present invention relates to a manufacturing method characterized by further comprising a forming step of forming the obtained crystallized product into a master batch in a pellet form after the above-mentioned crystallization step.

  The present invention relates to a method of manufacturing wherein the surfactant is an antistatic agent and / or an antifogging agent.

  The present invention relates to the production method, wherein the crystalline thermoplastic resin is a polyolefin resin.

In the masterbatch pellet of the present invention, since the trans crystal crystal layer is formed on the surface and in the vicinity thereof, the surface elution of the surfactant can be suppressed, and the occurrence of blocking of the masterbatch pellet can be suppressed.

Further, according to the method for producing a masterbatch pellet of the present invention, the kneaded product obtained by melt-kneading the crystalline thermoplastic resin and the surfactant is cooled and then heated to thereby obtain the surface of the masterbatch pellet and Since a transcrystalline layer can be formed in the vicinity thereof, the masterbatch pellet can be efficiently produced.

FIG. 1 is a schematic view of a manufacturing apparatus used in manufacturing the pellets of the example and the comparative example. FIG. 2 is an image of polarized light microscopy of the pellet produced in Example 1. FIG. 3 is an enlarged view of each part of the image shown in FIG. FIG. 4 is an image of polarized light microscopy of the pellet produced in Comparative Example 2. FIG. 5 is an enlarged view of each part of the image shown in FIG. FIG. 6 is an image of cross-sectional TEM observation of the pellets produced in Example 1 and Comparative Example 2. FIG. 7 is an image of a side SEM observation of the pellets produced in Example 1 and Comparative Example 2.

[Masterbatch pellet containing crystalline thermoplastic resin and surfactant]
Master batch pellets of the present invention is a masterbatch pellets containing a crystalline thermoplastic resin and a surfactant, wherein the trans crystal crystal layer is present on the interior surface and in the vicinity of the master batch pellets .

By the presence of the transcrystalline layer on the surface of the master batch pellet and in the vicinity thereof, the surface elution of the surfactant can be suppressed even when the surfactant is contained at a high concentration, and the master Blocking between batch pellets can be suppressed.

Therefore, the thickness of the transcrystalline layer present inside the surface of the masterbatch pellet of the present invention and in the vicinity thereof is, for example, at least 2 μm, preferably at least 2 μm, from the viewpoint of sufficiently suppressing surface elution of the surfactant. It is 10 μm, more preferably at least 30 μm. In addition, even if the entire surface of the masterbatch pellet is not covered with the transcrystalline layer, the blocking resistance is effective.
In the present invention, the thickness of the trans crystalline layer is a value measured using a polarizing microscope.

Examples of the crystalline thermoplastic resin contained in the masterbatch pellet of the present invention include polyolefin resin, polystyrene resin, acrylic resin, vinyl resin, polyamide resin, polyester resin, polyacetal resin, polycarbonate resin, thermoplastic polyurethane resin, fluorocarbon resin And mixtures of two or more of these.

  Examples of polyolefin resins include homopolymers of α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, etc., copolymers of the α-olefins, Copolymers of monomers other than α-olefins which can be copolymerized with the above-mentioned α-olefins and α-olefins, and mixtures thereof can be mentioned. Examples of the monomer other than the α-olefin copolymerizable with the α-olefin include vinyl acetate, maleic acid, methacrylic acid, methyl methacrylate and ethyl methacrylate.

  Examples of the polystyrene resin include homopolymers of styrenes and copolymers of styrenes with monomers copolymerizable with styrenes. Specific examples thereof include polystyrene, acrylonitrile-styrene resin (AS), and acrylonitrile-butadiene-styrene resin (ABS).

  Examples of the vinyl resin include diene polymers such as butadiene resin and polyisoprene resin.

  As a polyamide resin, nylon etc. are mentioned, for example.

  Examples of polyester resins include aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene adipate, polyethylene succinate, polybutylene succinate, polyethylene succinate, polybutylene succinate adipate, polyethylene succinate adipate And aliphatic polyesters such as polycaprolactone and polylactic acid.

  Examples of polyacetal resins include polymers of formaldehyde or trioxane.

  As polycarbonate resin, the condensate of bisphenol A and phosgene, the condensate of bisphenol A and diester carbonate are mentioned, for example.

  As a thermoplastic polyurethane resin, the reaction product of organic diisocyanate and high molecular diol is mentioned, for example.

  As a fluorine resin, the polymer of a fluorine-containing monomer is mentioned, for example.

Among them, as the crystalline thermoplastic resin contained in the masterbatch pellet of the present invention, a polyolefin resin is preferable, and polypropylene and polyethylene having a glass transition point lower than normal temperature are more preferable.

The surfactant used in the masterbatch pellet of the present invention is not particularly limited, and examples thereof include known anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants. These may be used alone or in combination of two or more.

Examples of anionic surfactants include sodium lauryl sulfate, potassium lauryl sulfate, sodium myristyl sulfate, potassium myristyl sulfate, sodium cetyl sulfate, sodium stearyl sulfate, sodium oleyl sulfate, sodium oleyl sulfate, triethanolamine lauryl sulfate, and salts thereof; Sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene cetyl ether sulfate, sodium polyoxyethylene oleyl ether sulfate, polyoxyethylene lauryl ether triethanolamine etc. alkyl ether sulfuric acid such as triethanolamine and salts thereof; sodium polyoxyethylene octyl phenyl ether sulfate Alkyl aryl ether sulfuric acid and its salts such as; sodium polyoxyethylene lauric acid amide ether sulfate; Oxyethylene lauric acid amide ether sulfate triethanolamine, polyoxyethylene myristic acid amide ether sodium sulfate, polyoxyethylene oleic acid amide ether sodium sulfate, polyoxyethylene coconut oil fatty acid amide ether sodium sulfate, oleic acid amide ether sodium sulfate etc. Alkyl amide sulfuric acid and its salt; Cured coconut oil fatty acid sodium sulfate and other acyl ester sulfuric acid and its salt; Sodium lauryl sulfonic acid, sodium myristyl sulfonic acid, coconut oil alkyl sulfonic acid such as sodium alkyl sulfonate and its salt; Dodecyl benzene Alkylbenzene sulfonic acids such as sodium sulfonate, triethanolamine of dodecylbenzene sulfonate and salts thereof; alkyl naphthalenes Fonic acid and its salt; formalin condensation type sulfonic acid and its salt such as formalin polycondensate of naphthalene sulfonate salt and the like; disodium diaryl lauryl sulfosuccinate, sodium di-2-ethylhexyl sulfosuccinate, disodium lauryl polyoxyethylene sulfosuccinate, Sulfosuccinic acid such as oleic acid amide sulfosuccinic acid disodium and its salts; α-olefin sulfonic acid and its salts such as sodium dodecene sulfonate, sodium tetradecene sulfonate, potassium dodecene sulfonate and potassium detradecene sulfonate; α-sulfo fatty acid esters such as α-sulfo lauric acid methyl ester, α-sulfo myritic acid methyl ester, α-sulfo lauric acid (EO) n methyl ester and salts thereof; coconut oil fatty acid acyl-N-methyl tauri Potassium, Lauroyl-N-methyltaurine sodium, Lauroyl-N-methyltaurine potassium, Lauroyl-N-methyltaurinetriethanolamine, myristoyl-N-methyltaurine sodium, myristoyl-N-methyltaurinetriethanolamine, coconut oil fatty acid acyl- N-Acyl-Taurine Sodium, N-Acyl-Taurine Sodium, Coconut Oil Fatty Acid Acyl-N-Methyl Taurine Triethanamine, etc. N-Acyl Methyl-taurine and Its Salts; Coconut Oil Fatty Acid Acyl-Glutamic Acid Potassium, Coconut Oil Fatty Acid Acyl-Glutamic Acid Sodium, Coconut Oil Fatty Acid Acyl -Glutamic acid triethanamine, lauroyl-sodium glutamate, myristoyl- potassium glutamate, myristoyl-sodium glutamate, palm oil fatty acid acyl-glu N-acyl glutamic acid such as sodium tamine acid and salts thereof; N-lauroylglycine sodium, N-myristoylglycine triethanolamine, N-cocoyl fatty acid acyl-glycine sodium, N-cocoyl fatty acid acyl-glycine potassium etc Acyl glycine and its salts; Sodium lauroyl isethionate, sodium myristoyl isethionate, coconut oil fatty acid acyl isethionate and other salts thereof; acyl isethionates and salts thereof; alkyl sulfoacetates; sodium polyoxyethylene lauryl ether phosphate, polyoxyethylene cetyl Ether phosphate sodium, polyoxyethylene myristyl phosphate potassium, polyoxyethylene oleyl ether sodium phosphate, dipolyoxyethylene oleyl ether phosphate sodium Alkyl ether phosphoric acid and salts thereof; alkyl aryl ether phosphoric acid and salts thereof; fatty acid amide ether phosphoric acid and salts thereof such as sodium polyoxyethylene lauryl amide ether phosphate; sodium lauryl phosphate, sodium myristyl phosphate, Coconut oil fatty acid sodium phosphate, potassium myristyl phosphate, triethanolamine lauryl phosphate, triethanolamine of oleyl phosphate and alkylphosphoric acid such as diethanolamine oleyl phosphate and its salts; sodium lauroyl iminodiacetate, triethanolamine lauroyl iminodiacetate, coconut oil fatty acid acyliminodiacetic acid Acyliminodiacetic acid and its salts such as sodium, lauroyl iminodiacetic acid disodium, palm kernel fatty acid iminodiacetic acid sodium, etc .; sodium polyoxyethylene lauryl ether acetate, Ether carboxylic acids and their salts such as potassium oxyethylene myristyl ether acetate, polyoxyethylene palmityl ether acetate triethanolamine, polyoxyethylene stearyl ether acetate sodium, polyglyceryl lauryl ether acetate sodium; Acylation of coconut oil fatty acid silk peptide etc Peptides; Amide ether carboxylic acids and salts thereof, such as sodium polyoxyethylene lauric acid amide ether carboxylate, sodium polyoxyethylene myristate acid amide ether carboxylate, polyoxyethylene coconut oil fatty acid amide ether carboxylic acid triethanolamine, etc .; acyl lactate And alkenyl succinic acid and salts thereof.

  As a cationic surfactant, for example, lauryl trimethyl ammonium chloride, myristyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, oleyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, coconut oil alkyl trimethyl ammonium Monoalkyl quaternary ammonium salts such as chloride, beef tallow alkyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide, coconut oil alkyl trimethyl ammonium bromide, cetyl trimethyl ammonium methyl sulfate; dioctyl dimethyl ammonium chloride, dilauryl dimethyl ammonium chloride Dialkyl quaternary ammonium salts such as lide, distearyl dimethyl ammonium chloride; acylaminoalkyl quaternary ammonium salts such as lanolin fatty acid aminopropylethyl dimethyl ammonium ethyl sulfate, lauroyl aminoethyl methyl diethyl ammonium methyl sulfate; dipalmityl polyetheno Alkyl ethenoxy quaternary ammonium salts such as xylethyl ammonium chloride, distearyl polyethenoxymethyl ammonium chloride; alkyl isoquinolinium salts such as lauryl isoquinolinium chloride; lauryl dimethyl benzyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride Benzalkonium salts such as; benzyldimethyl {2- [2- (p-1,1,3,3-tetramethylbutyl Benzothonium salts such as henoxy) ethoxy] ethyl} ammonium chloride; pyridinium salts such as cetyl pyridinium chloride; imidazolinium salts; N-cocoyl arginine ethyl ester pyrrolidone carboxylate, acyl bases such as N-lauroyl lysine ethyl ester hydrochloride Amino acid alkyl ester salts; primary amine salts such as lauryl amine hydrochloride; secondary amine salts such as dilauryl amine acetate; tertiary amine salts; fatty acid amide guanidinium salts; lauryl triethylene glycol ammonium hydro And alkyltrialkylene glycol ammonium salts such as oxides.

  Examples of nonionic surfactants include POE (polyoxyethylene) octyl ether, POE (2-ethyl-hexyl) ether, POE lauryl ether, POE myristyl ether, POE cetyl ether, POE stearyl ether, POE oleyl ether, POE iso. Polyoxyethylene alkyl ethers such as stearyl ether, POE behenyl ether, polyoxyethylene cetyl stearyl diether; POE • POP (polyoxypropylene) butyl ether, POE • POP lauryl ether, POE • POP cetyl ether, POE • POP glycol, etc. Polyoxyethylene polyoxypropylene glycol type; POE octyl phenyl ether, POE nonyl phenyl ether, POE chlorophenyl ether And polyoxyethylene aryl ethers such as POE naphthyl ether; POE hydrogenated castor oil ether, POE castor oil ether; other POE lanolin alcohol ether, ether such as POE phytosterol; POE glyceryl monostearate, POE glyceryl oleic acid polyoxyethylene glycerin Fatty acid ester; polyoxyethylene sorbitan fatty acid ester such as POE sorbitan monolaurate, POE sorbitan monostearate, POE sorbitan tristearate, POE sorbitan monoisostearate POE sorbitol hexastearate, POE sorbitol tetrastearate, POE sorbitol tetraoleate Polyoxyethylene sorbitol such as sorbitol, monolaurate POE sorbitol Fatty acid esters; polyethylene glycol fatty acid esters such as polyethylene glycol monolauric acid, polyethylene glycol monostearic acid, polyethylene glycol monooleic acid, polyethylene glycol distearic acid, polyethylene glycol dioleic acid, polyethylene glycol diisostearic acid; polyethylene glycol lanolin fatty acid esters Ether ester type: Glyceryl monostearate, Glyceryl monostearate monoglyceryl, Glyceryl monohydroxystearate, Glyceryl fatty acid ester such as glyceryl distearate; Diglyceryl monostearate, Diglyceryl monooleate, Diglyceryl dioleate, Mono Diglyceryl isostearate, tetraglyceryl monostearate, Polyglycerin fatty acid esters such as tetraglyceryl distearate, tetraglyceryl pentastearate, hexaglyceryl monolaurate, hexaglyceryl monomyristate, decaglyceryl distearate, decaglyceryl diisostearate; sorbitan monolaurate, sorbitan monostearate, monoolein Sorbitan fatty acid esters such as sorbitan acid, sorbitan trioleate, sorbitan tristearate, sorbitan monoisostearate; ethylene glycol fatty acid esters such as ethylene glycol monolaurate and ethylene glycol distearate ethylene glycol propylene monostearate, self-emulsifying monostearate Propylene glycol fatty acid ester such as propylene glycol acid; monostearin Pentaerythritol fatty acid esters such as pentaerythritol and pentaerythritol monooleate; sugar derivatives such as maltitol hydroxy fatty acid ether, alkylated polysaccharides, alkyl (poly) glucosides and sugar esters; alkyl glyceryl ethers such as α-monoisostearyl glyceryl ether Organic acid monoglycerides such as acetyl monoglycerides, lactic acid monoglycerides and citric acid monoglycerides; coconut oil fatty acid monoethanolamide, lauroyl monoethanolamide, myristoyl monoethanolamide, lauroyl diethanolamide, coconut oil fatty acid diethanolamide, lauroyl isopropanolamide, myristoyl isopropanol Amide, coconut oil fatty acid isopropanolamide, POE lauroyl monoether Fatty acid alkanolamides such as norylamide, coconut oil fatty acid methyl monoethanolamide, coconut oil fatty acid methyldiethanolamide; POE laurylamine, POE tallow amine, POE palmitylamine, POE stearylamine, POE alkylamines such as POE oleylamine; lauryl dimethylamine Amine oxides such as cocodimethylamine oxide and cocoamidopropyl dimethylamine oxide; esters of POE laurylamine and lauric acid, esters of POE laurylamine and stearic acid, esters of POE palmitylamine and stearic acid, POE stearylamine Examples thereof include esters of palmitic acid and amine esters such as esters of POE stearylamine and stearic acid.

Examples of amphoteric surfactants include lauryl dimethyl betaine, myristyl dimethyl betaine, palmityl dimethyl betaine, stearyl dimethyl betaine, oleyl dimethyl betaine, coconut oil alkyl dimethyl betaine, lauryl methyl ethyl betaine, octadecyloxymethyl dimethyl betaine, lauryl dihydroxyethyl Betaine, stearyldihydroxyethyl betaine, coconut oil alkyldihydroxyethyl betaine, lauric acid amidopropyl dimethyl betaine, myristate amidopropyl dimethyl betaine, stearic acid amidopropyl dimethylbetaine, oleic acid amidopropyl dimethyl betaine, coconut oil fatty acid amidopropyl dimethyl betaine etc carboxymethyl _{^{betaine; RN + H 2 CH 2 COO}} - (R: a Lauryl glycine, stearyl glycine represented by kill), lauryl di aminoethyl sodium glycine, alkyl aminoethyl glycine chloride, cocoyl -N- carboxyethyl ethoxyethyl -N- carboxyethyl ethylenediamine disodium like glycine type; RN ⁺ H ₂ Aminopropionic acid types such as lauryl-β-alanine and stearyl-β-alanine represented by CH ₂ CH ₂ COO ⁻ (R: alkyl); sodium lauryl sulfoacetate, sodium tetradecenesulfonate, di (2-ethylhexyl sulfosuccinate ) Sodium lauryldimethylhydroxypropylsulfobetaine, myristyldimethylhydroxypropyrylsulfobetaine, lauryldimethylpropylsulfobetaine, coconut oil alkyldimethyl propi Sulfobetaine, sulfobetaine type, such as lauric acid amide propyl dimethyl hydroxypropyl _{^{sulfobetaine; RN + H 2 CH 2 CH}} 2 SO 3 -: sulfonic acid type represented by (R _{^{alkyl); RN + H 2 CH 2}} CH 2 OSO ₃ ^-: sulfate-type represented by (R alkyl); sodium lauryl aminopropionic acid, sodium lauryl amino dipropionate acid, N- lauroyl -N- hydroxyethyl -N'- -dicarboxyethyl - ethylenediamine disodium, N- lauroyl - N-Hydroxyethyl-N'-carboxyethyl-ethylenediamine sodium, N-lauroyl-N'-carboxymethyl-N'-hydroxyethylethylenediamine sodium, N-cocoyl fatty acid acyl-N'-carboxyethyl-N'-hydroxyethyl Thiylenediamine sodium, N-lauroyl-N-hydroxyethyl-N'-dicarboxymethyl-ethylenediaminedisodium, N-lauroyl-N-hydroxyethyl-N'-carboxymethyl-ethylenediamine sodium, N-hydroxydodecyl-N-poly Aminocarboxylic acid salt type such as oxyethylene-N'-carboxyethyl-N'-polyoxyethylene ethylenediamine sodium, coconut fatty acid acyl-N-hydroxyethyl ethylenediamine sodium, etc .; 2-lauryl-N-carboxymethyl-N-hydroxyethyl Imidazolinium betaine, 2-myristyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, 2-stearyl-N-carboxymethyl-N-hydroxyethylimidazolinium beta Represented by: (alkyl _{R) - RN + H 2 CH} (CH 3) P (OH) O 2; down, 2-cocoalkyl -N- carboxymethyl -N- hydroxyethyl imidazolinium imidazoline such as betaine Examples include phosphoric acid type; lecithin; aminoacetic acid betaine type such as lauryl dimethylaminoacetic acid betaine, coconut oil fatty acid amidopropyl dimethylaminoacetic acid betaine and the like.

The surfactant contained in the masterbatch pellet of the present invention is preferably used as an antistatic agent or an antifogging agent.

When the surfactant contained in the masterbatch pellet of the present invention is used as the antistatic agent, among the above surfactants, an anionic surfactant having a sulfonic acid group, a cationic surfactant, an ester of glycerin and a fatty acid, POE alkylamine, ester of POE alkylamine and fatty acid, and amide compound which is a reaction product of diethanolamine and fatty acid are preferable.

Moreover, when using surfactant contained in the masterbatch pellet of this invention as an anti-fogging agent, an anionic surfactant, a polyhydric alcohol (or polyhydric alcohol EOA), and a fatty acid also in said surfactant. Reactants etc. are preferred.

The amount of surfactant added to the masterbatch pellet of the present invention is, for example, 1 to 50% by mass, preferably 5 to 40% by mass, and more preferably, to the masterbatch pellet . 8 to 35% by mass.

Moreover, the masterbatch pellet of this invention is a range which does not impair the effect of this invention, and is various additives added to antioxidant, a lubricant, a coloring agent, a compatibilizer, an ionic liquid, a ultraviolet absorber, and other normal resin products. Additives and fillers can also be added as additional components.

[Manufacturing method of master batch pellet ]
The method for producing a masterbatch pellet of the present invention includes a kneading step of melt-kneading a crystalline thermoplastic resin and a surfactant, and a crystallization step of cooling and subsequently heating the kneaded material obtained in the kneading step. It is characterized by including.
Each step will be described below.

<Kneading process>
In this step, the crystalline thermoplastic resin and the surfactant are melt-kneaded.
Examples of the method of melt-kneading the crystalline thermoplastic resin and the surfactant include methods using known melt-kneading apparatuses such as single-screw extruders, twin-screw extruders, Brabenders, open rolls and kneaders. Among them, an extruder such as a twin-screw extruder is preferable in that high shear force can be applied.

  The temperature at which the resin composition is melt-kneaded is appropriately selected depending on the crystalline thermoplastic resin, but in general, a temperature range which is not lower than the melting temperature of the crystalline thermoplastic resin and does not cause coloration due to thermal decomposition of the crystalline thermoplastic resin is preferable. For example, + 20 ° C. to + 80 ° C. with respect to the melting temperature of the crystalline thermoplastic resin.

  The time for melt-kneading is sufficient as long as the surfactant can be uniformly dispersed in the crystalline thermoplastic resin, and varies depending on the screw shape of a twin-screw extruder or the like, but is, for example, 30 seconds to 10 minutes.

The crystalline thermoplastic resin and surfactant used in this step are as described above. The amount of the surfactant to be blended in the master batch pellets, the master batch pellets, for example, from 1 to 50 wt%, preferably 5 to 40 wt%, more preferably 8 to 35 It is mass%.

<Crystallization process>
In the present step, the kneaded material obtained in the above-mentioned kneading step is cooled and subsequently heated.
Thereby, a trans crystal crystal layer can be formed on the surface of the masterbatch pellet and in the vicinity thereof.

  As a method for cooling the kneaded material obtained in the above-mentioned kneading step, a known method can be mentioned, and among them, from the viewpoint of safety and environmental aspect, it is preferable to carry out by a water cooling method.

  Moreover, as a method of heating the cooled kneaded material, there are known methods such as heating using an electric heating oven, an oil bath, a far infrared heater, a near infrared heater, a halogen heater, dielectric heating, hot air heating, and hot plate heating. The method etc. which used the heating apparatus are mentioned.

In the crystallization step, the difference between the temperature (T ₁ ) before cooling of the kneaded material and the temperature (T ₂ ) after cooling is, for example, T ₂ −T ₁ = −110 to −210 ° C., preferably T is ₂ -T ₁ = -140 to -190 ° C., more preferably _T 2 _-T 1 = -150 to -180 ° C.. When the difference (T ₂ −T ₁ ) between the temperature (T ₁ ) before cooling of the kneaded material and the temperature (T ₂ ) after cooling is less than −110 ° C., the inside of the kneaded material is not fully solidified, In the forming step, it may be difficult to form the crystallized product into a predetermined form of master batch pellet . On the other hand, when the difference (T ₂ −T ₁ ) exceeds −210 ° C., the load of the subsequent heat treatment may be increased, which may lower the operation efficiency.

The time for cooling the kneaded material is such that the difference between the temperature (T ₁ ) before cooling of the kneaded material and the temperature (T ₂ ) after cooling is T ₂ −T ₁ = −110 to −210 ° C. It is appropriately selected, for example, 0.1 to 10 seconds.

In the crystallization step, the difference between the temperature (T ₂ ) after cooling of the kneaded material and the temperature (T ₃ ) after heating is, for example, T ₃ −T ₂ = 10 to 90 ° C., preferably T _3. -T ₂ = a 20 ° C. to 70 ° C.. When the difference (T ₃ -T ₂ ) between the temperature (T ₂ ) after cooling of the kneaded material and the temperature (T ₃ ) after heating is less than 10 ° C., sufficient trans crystal may not be formed. . On the other hand, if the difference (T ₃ -T ₂ ) exceeds 90 ° C., deformed pellets may be generated.

Although the time for heating the kneaded material varies depending on the apparatus used, the difference between the temperature (T ₂ ) after cooling of the kneaded material and the temperature (T ₃ ) after heating is T ₃ −T ₂ = 10 to 90 ° C. It is appropriately selected to be, for example, 0.1 second to 10 hours.

In the present invention, the temperature (T ₁ ) before cooling of the kneaded material means the surface temperature of the kneaded material obtained by melt-kneading the crystalline thermoplastic resin and the surfactant, for example, from the melt-kneading apparatus The surface temperature of the discharged kneaded material.
Further, the temperature (T ₂ ) after cooling of the kneaded material means the surface temperature of the cooled kneaded material, and for example, the surface temperature of the kneaded material discharged from the cooling device.
Furthermore, the temperature (T ₃ ) after heating of the kneaded material means the surface temperature of the heated kneaded material, and, for example, not only the surface temperature of the kneaded material discharged from the heating device but also the kneading discharged from the cooling device It also refers to the surface temperature of a molded article obtained by forming an article into a predetermined form and heating it.
In the present invention, the surface temperature of each of the above-mentioned kneaded materials is measured by an infrared radiation thermometer.

Further, in the crystallization step in the production method of the present invention, before heating the cooled kneaded material, the kneaded material may be molded into a predetermined form, and the molded article may be heated. In that case, the difference between the temperature after cooling (T ₂ ) and the temperature after heating (T ₃ ) is the same as the matters described in paragraphs [0063] and [0064].
As a method of heating, in addition to the above-described heating method, a method of packing the kneaded product formed into a predetermined form in a flexible container, a drum or the like and storing it in a thermostatic chamber may be mentioned.

<Molding process>
The method for producing a masterbatch pellet of the present invention can further include a forming step.
In this step, after the above-mentioned crystallization step, the obtained crystallized product is formed into a master batch in the form of pellets (master batch pellets) .
As a method of shaping the crystallized product, for example, a known method such as cutting the crystallized product can be used. In addition, according to this process, the pellet form to be formed can be appropriately set depending on the purpose of use etc. For example, flat plate, flat column, flat column, flat square column, block, powder and the like may be mentioned. it can. Moreover, there is no restriction in particular also about the size.

  In the production method of the present invention, a pigment, an antioxidant, a plasticizer, an ultraviolet light absorber, a lubricant, a crystal nucleating agent and the like can be added at an arbitrary ratio within the range not impairing the effects of the present invention.

  EXAMPLES The present invention will next be described in detail by way of examples and comparative examples, but the present invention is not limited to these examples.

Example 1
In the production apparatus shown in FIG. 1, polypropylene [prime polypro F-300 SP made by Prime Polymer Co., Ltd.] as a crystalline thermoplastic resin (hereinafter also abbreviated as resin) (a) and anth as a surfactant (b) Tex SA-300F (manufactured by Toho Chemical Industry Co., Ltd.) and Irganox 1010 (manufactured by BASF) as an antioxidant (c) in a mass ratio (d) [(a) / (b) / (c) = 90 / It knead | mixed with a twin-screw extruder by 10 / 0.05], and after producing a strand, it cut and produced the pellet of diameter 2-7 mm.
Resin temperature (e) of the strand that came out is 230 ° C, water bath temperature (f) is 30 ° C, resin temperature (g) after cooling is 60 ° C, heater temperature (h) is 150 ° C, pellet temperature after cutting ( The i) was 100 ° C., the tank temperature (j) was 90 ° C., and the pellet temperature (k) after passing through the tank was 80 ° C.

[Examples 2 to 7]
Pellets were produced in the same manner as in Example 1 except that the conditions of Example 1 were changed to the conditions shown in Table 1 below.

Comparative Example 1
Polypropylene [Prime PolyPro F-300SP made by Prime Polymer Co., Ltd.] as the crystalline thermoplastic resin (a) in the production apparatus shown in FIG. 1 and Anstex SA-300F (Toho Chemical Industries, Ltd.) as the surfactant (b) Manufactured by Co., Ltd., as an antioxidant (c), at a mass ratio (d) [(a) / (b) / (c) = 80/20 / 0.05] as Irganox 1010 (manufactured by BASF) It knead | mixed with a twin-screw extruder, and after producing a strand, it cut and produced the pellet of diameter 2-7 mm.
The resin temperature (e) of the strand that came out was 230 ° C., and cooling was performed with air cooling at room temperature of 20 ° C. without using a water tank. The resin temperature (g) after cooling was 135 ° C., the pellet temperature (i) after cutting was 120 ° C., the tank temperature (j) was 90 ° C., and the pellet temperature (k) after passing through the tank was 80 ° C.

[Comparative Example 2 to Comparative Example 4]
Pellets were produced in the same manner as in Example 1 except that the conditions of Example 1 were changed to the conditions shown in Table 1 below.

The “surface elution rate”, “blocking property”, “trans crystal crystal” and “shape of pellet” were evaluated for the pellets produced in each example and each comparative example.
Moreover, about the pellet manufactured by Example 1 and Comparative Example 2, cross-sectional TEM observation and side surface SEM observation were performed.

"Surface dissolution rate"
The pellet produced in Example 1 was stored in a thermostat at 60 ° C. for 24 hours, weighed 100 g (1), placed in a 300 mL beaker, and poured 100 mL of isopropyl alcohol (IPA). After adding IPA, it stirred for 1 minute with a glass rod, and filtered. The filtrate was put in an eggplant flask, IPA was distilled off, dried in an oven at 100 ° C. for 1 hour, and then the eluate was weighed (2). And the surface elution rate of surfactant was computed by the following formula.
Surface elution rate (%) = (2) / (1) x 100

"Blocking"
70 g of the pellets produced in Example 1 were placed in a 100 mL plastic container and left at 60 ° C. for 12 hours and at 10 ° C. for 12 hours. After standing at room temperature for 3 hours, if the pellet flows out by turning the container upside down, it is regarded as ○ because there is no blocking property. The state of not flowing out is indicated by x, and the state of flowing a little is indicated by Δ.

"Trans Crystal"
Using a microtome, longitudinal cross-sectional sections of the pellet were prepared, and the surface of the pellet and its vicinity were observed with a polarizing microscope under crossed nicols. O was observed if trans crystal was observed, and x was not observed.

  Moreover, the image of polarization microscope observation in the pellet manufactured in Example 1 is shown in FIGS. 2 and 3, and the image of polarization microscope observation in the pellet manufactured in Comparative Example 2 is shown in FIG. 4 and FIG. 5, respectively. From FIG. 3, it was possible to confirm the presence of a transcrystalline layer on the surface of the pellet produced in Example 1 and in the vicinity thereof. On the other hand, as shown in FIG. 5, the presence of the transcrystalline layer was not confirmed on the surface of the pellet produced in Comparative Example 2 and in the vicinity thereof.

"Shape of pellet"
After cutting the pellets, they were visually confirmed, and if there were burrs or whiskers, crushed pellets or irregularly shaped pellets that were not cut finely, they were marked x, and if not, they were marked ○.

[Section TEM observation]
The cross sections of the pellets produced in Example 1 and Comparative Example 2 were observed using a transmission electron microscope (TEM). The results are shown in FIG.

  From FIG. 6, compared to the pellet produced in Comparative Example 2, there were less amorphous streaks on the surface of the pellet produced in Example 1 and in the vicinity thereof.

[Side SEM observation]
The side of the pellet produced in Example 1 and Comparative Example 2 was observed using a scanning electron microscope (SEM). The results are shown in FIG.

  From FIG. 7, the surfactant was thinly dispersed in the pellet manufactured in Example 1, while the surfactant was thickly raised in the pellet manufactured in Comparative Example 2. In addition, when the pellet surface was washed with isopropyl alcohol (IPA) and the surfactant was removed to observe the pellet surface, the pellet produced in Example 1 had a smooth surface, while the surface was smooth in Comparative Example 2. In the manufactured pellet, spherulites and amorphous parts were seen like a turtle shell, and surfactant was starting to precipitate from the amorphous parts.

  The temperature conditions in each example and each comparative example are shown in Table 1. Moreover, the evaluation result of "surface elution rate", "blocking property", "trans crystal crystal", and "shape of pellet" in each Example and each comparative example is shown in Table 2.

A: Prime Polymer Co., Ltd .: Prime Polypro F-300SP (polypropylene)
B: Toho Chemical Industry Co., Ltd. product: Anstex SA-300F (ester of stearyldiethanolamine and stearic acid)
C: made by BASF: Irganox 1010
D: Japan Polypropylene Corp. product: Novatec PP FB3 EBT (polypropylene)
E: Toho Chemical Industry Co., Ltd. product: Anstex SA-35 (alkyl diethanolamine)
F: Made by Adeka Co., Ltd .: Adeka Stub 2112
G: Nippon Polyethylene Co., Ltd. product: Novatec LL UF 442 (polyethylene)
H: BASF: Irganox 1076
I: Toho Chemical Industry Co., Ltd. product: Anstex SA-8 MB (surfactant composition)
J: Toho Chemical Industry Co., Ltd. product: Sorbon S-40 (Sorbitan monopalmitate)

  The pellets produced in Examples 1 to 7 of Table 2 have cooling temperatures and heating temperatures when the kneaded material obtained by melt-kneading the crystalline thermoplastic resin and the surfactant is cooled and subsequently heated. By setting the temperature to a suitable temperature, the surface exposed amount of surfactant was suppressed as compared to the pellets produced in Comparative Examples 1 to 4, and the occurrence of blocking was suppressed. Besides, the shape of the pellet was also good.

1: Raw material resin tank 2: Feeder 3: Twin screw extruder 4: Pump for adding liquid 5: Surfactant 6: Water tank 7: Dewatering machine 8: Heater 9: Cutter 10: Sifter 11: Sieve 11: Pressure feeder 12: Tank

Claims (8)

A masterbatch pellet comprising a crystalline thermoplastic resin and a surfactant,
Characterized in that a transcrystalline layer is present on the surface of the masterbatch pellet and in the vicinity thereof ,
The crystalline thermoplastic resin is a resin selected from the group consisting of a polyolefin resin, a polyamide resin, a polyester resin, a polyacetal resin, a thermoplastic polyurethane resin, a fluorine resin, and a mixture of two or more of them.
Masterbatch pellet . A masterbatch pellet according to claim 1 , characterized in that the thickness of the transcrystalline layer is at least 2 μm. The masterbatch pellet according to claim 1 or 2, wherein the surfactant is an antistatic agent and / or an antifogging agent. The masterbatch pellet according to any one of claims 1 to 3, wherein the crystalline thermoplastic resin is a polyolefin resin. A kneading step of melt-kneading the crystalline thermoplastic resin and the surfactant ;
A crystallization step in which the kneaded product obtained in the kneading step is cooled and then heated ;
After the crystallization step, the method includes a forming step of forming the obtained crystallized product into a master batch in pellet form,
The crystalline thermoplastic resin is a resin selected from the group consisting of a polyolefin resin, a polyamide resin, a polyester resin, a polyacetal resin, a thermoplastic polyurethane resin, a fluorine resin, and a mixture of two or more of them.
A method for producing a masterbatch pellet , comprising
In the crystallization step, the difference between the temperature (T ₁ ) before cooling of the kneaded material and the temperature (T ₂ ) after cooling is T ₂ −T ₁ = −110 to −210 ° C., and A difference between a temperature after cooling (T ₂ ) and a temperature after heating (T ₃ ) is T ₃ −T ₂ = 10 to 90 ° C.,
Production method. The method according to claim 5, wherein the cooling in the crystallization step is carried out by a water cooling method. The method according to claim 5 or 6 , wherein the surfactant is an antistatic agent and / or an antifogging agent. The method according to any one of claims 5 to 7 , wherein the crystalline thermoplastic resin is a polyolefin resin.