JPH09194628A - Thermoplastic polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic polymer compsn. which is suitable as a cleaner for a molding machine for a thermoplastic polymer by incorporating a particular complex of an org. complex with an inorg. complex and a particular metallic compd. into a thermoplastic polymer. SOLUTION: This compsn. comprises a thermoplastic polymer (A) and, incorporated therein, an ester type complex (B) of a partial ester of a higher fatty acid with a polyol with boric acid, and at least one metallic compd. (C) selected among a metal oxide, a metal hydroxide (wherein the metal is Mg, Ca, Zn, or Al), a metal carbonate, a metal phosphate (wherein the metal is Li, Na, K, Mg, Ca, or Zn), a metal silicate (wherein the metal is Li, Na, K, or Mg), a hydrotalcite or a lithium aluminum composite hydroxide salt, a metal salt of a fatty acid, a metal salt of an aliphatic hydroxy acid, a metal salt of an aliph. phosphoric acid (wherein the metal is Li, Na, K, Mg, Ca, Zn, or Al). The amts. of the components (B) and (C) incorporated are pref. 1 to 90wt.% and 0.01 to 50wt.%, respectively, based on the component (A).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic polymer composition suitable as a detergent for a molding machine of a thermoplastic polymer.

[0002]

2. Description of the Related Art In molding of plastics, some kinds of treatments are taken in order to eliminate the influence of the preceding product when switching the product. Especially in the processing of colored products, when changing the color from dark colors such as blue and black to lighter grades such as white and natural colors, cleaning the inside of the molding machine with cleaning resin, disassembling and cleaning the molding machine, etc. The actual situation is that the complicated work of and the production stoppage accompanying it is inevitable.
For example, in the case of color change in extrusion granulation, it is necessary to stop the extruder, extract the screw, clean the inside of the screw and the cylinder by a method such as brushing, and then install the screw again. In the process of replacing the preceding product with resin without removing the screw, a large amount of resin is required for cleaning, and stains on the complicated structure inside the extruder cannot be removed. I have a problem.

In order to solve these problems, a method of using a cleaning compound has been developed. This method is intended to facilitate the removal of the residue in the extruder with a cleaning compound and to switch the product type by using a small amount of the replacement resin. Cleaning compounds include those that contain a lubricant such as stearic acid and those that use acrylic resin with high melt viscosity, but the former is not effective enough and the latter has a strong odor. In addition, since the melt viscosity is high, there is a drawback that complicated work such as the use of a cleaning compound after removing the die, breaker plate, wire net, etc. is required. In addition, cleaning compounds containing glass fibers and the like have the drawback of abrading the screw and cylinder of the extruder.

On the other hand, in JP-B-39-12457, an appropriate amount of a boron complex compound is added to 20 to 600 parts (by weight) of a solid filler selected from asbestos, clay, calcium carbonate, gypsum and mica. A method for stabilizing a chlorine-containing resin against heat and light characterized in that, in JP-A-48-85634, a filler-containing polyolefin polymer, bismuth or boron phosphate, acid phosphate or Polyolefin polymer composition obtained by adding at least one selected from phosphite, or a mixture of phosphoric acid, at least one of acidic phosphoric acid or phosphorous acid, and bismuth acid, boric acid, or an ester compound thereof. However, in JP-A-55-157635, borate ester of higher fatty acid monoglyceride is added to 100 parts by weight of polyolefin.
A polyolefin composition having an improved antistatic property, which is obtained by blending 05 to 0.4 parts by weight and 0.01 to 1.0 parts by weight of a higher fatty acid, and has an excellent antistatic effect even when used in combination with a metal salt of a higher fatty acid. JP-A-58-129030 discloses that a combination of a stable halogenated organic compound and a boron-containing salt or ester further contains a filler and / or a reinforcing agent, imparts flame resistance to a polymer and prevents discoloration thereof. The flame retardant composition contains an internal particle formed by adding a boron compound, an alkali metal compound and / or an alkaline earth metal compound during polyester synthesis in JP-A-59-126456, and A fiber characterized by having an average diameter of 3 μm or less, substantially no coarse particles of 10 μm or more, a solution haze of 5% or more, and a transparency of a molten polymer of 30 ppm or less. Upon polyester composition having a film forming ability, Japanese Patent Publication No. Sho 59-219357 stabilizing halogen-containing resin with lead-based stabilizers,
A stabilized halogen-containing resin composition comprising a polyhydric alcohol and a boron compound esterified with at least one fatty acid and at least one boric acid, and the halogen-containing resin composition Discloses that a metal soap other than a lead-based metal, an oxide or hydroxide of an alkaline earth metal, and the like can be contained if necessary.

Further, in JP-A-60-13839, a styrene-butadiene block copolymer or a styrene-based resin composition containing 10% by weight or more of a styrene-butadiene block copolymer is blended with an inorganic filler. Resin-inorganic filler mixture 100 parts by weight, glycerin monofatty acid ester borate ester and / or glycerin difatty acid ester borate ester is blended 0.1 to 20 parts by weight inorganic filler containing, characterized in that The resin composition is disclosed in JP-A-60
JP-A-86143 discloses that a hydrotalcite and a polyhydric alcohol are used in combination with a halogen-containing flame retardant-containing styrene resin composition in which a boron compound esterified with at least one fatty acid and at least one boric acid is used. Stabilization method of halogen-containing flame retardant-containing styrene resin composition, which is characterized by adding, to the halogen-containing flame retardant-containing styrene resin composition in JP-A-60-86144,
Aluminum carboxylate and polyhydric alcohol
A method for stabilizing a styrene-based resin composition containing a halogen-containing flame retardant, characterized in that a boron compound esterified with at least one fatty acid and at least one boric acid is added in combination, is disclosed in Japanese Patent Laid-Open No. In Japanese Patent Application Laid-Open No. 125542, a polyolefin resin composition containing a phenolic stabilizer is used, and in a molded article used for the purpose of contacting with an alkali metal ion, the polyolefin resin composition further comprises a polyhydric alcohol having a valence of 3 or more. A molded article excellent in yellowing resistance, which is characterized by containing a reaction product of a mono- or diester and boric acid, discloses a thermoplastic synthetic polymer and decomposed starch in JP-A-5-505416. In a polymer blend useful for making biodegradable films, sheets and fibers that can be prepared from a melt containing the melt Polymer blend, characterized in that it contains a starch-degrading agents such as boron-containing compounds and alkaline earth metal hydroxides, and JP-A-6
-136112 discloses [A] copolycarbonate,
[B] The additive is (a) a sulfur-containing acidic compound having a pKa value of 3 or less and / or a derivative formed from the acidic compound, (b) phosphorus compound, (c) epoxy compound, (d) phenol-based compound Stabilizer, (e) mold release agent, (f) boron compounds such as boric acid ester, (to) calcium carbonate, hydrated alumina, an additive selected from the group consisting of fillers such as talc Characteristic copolycarbonate compositions have been proposed respectively.

[0006]

[Problems to be solved by the invention] Japanese Patent Publication No. 39-12457
JP, JP-A-48-85634, JP-A-55-157635, JP-A-58-129030, JP-A-59-126456, JP-A-59-219357, JP-A-60-13839, JP-A-60-86143, JP-A-60-86144,
JP-A-63-125542, JP-A-5-505416, and JP-A-6-136112 disclose an ester-type complex of a higher fatty acid partial ester of a polyol and boric acid in a thermoplastic polymer and a specific polymer. There is no description or suggestion that a thermoplastic polymer composition containing a metal compound is a composition suitable as a detergent for a molding machine of a thermoplastic polymer.

The present inventors have found that the above-mentioned problems relating to the cleaning compound, that is, after cleaning with the cleaning thermoplastic polymer composition, the use of a small amount of the replacement polymer leaves the former type product remaining in the molding machine. The present inventors have earnestly studied to obtain a thermoplastic polymer composition suitable as a detergent for a molding machine of a thermoplastic polymer, which enables removal of the polymer by a simple operation in a short time.

As a result, the present inventors have found that a thermoplastic polymer composition obtained by blending a thermoplastic polymer with an ester type complex of a higher fatty acid partial ester of a polyol and boric acid and a specific metal compound is a thermoplastic polymer. It was found that the composition is suitable as a detergent for a polymer molding machine, and the present invention was completed based on this finding. As is clear from the above description, an object of the present invention is to provide a thermoplastic polymer composition suitable as a detergent for a molding machine of a thermoplastic polymer.

[0009]

The present invention has the following arrangement. (1) An ester-type complex of a higher fatty acid partial ester of polyol and boric acid (hereinafter referred to as compound A) in a thermoplastic polymer, and one or more metal compounds (hereinafter referred to as compound) selected from the following: A thermoplastic polymer composition obtained by blending B). Metal oxide (however, metal is magnesium, calcium, zinc or aluminum.) Metal hydroxide (however, metal is magnesium, calcium, zinc or aluminum) Carbonate metal salt (however, metal is lithium or sodium) ,
Indicates potassium, magnesium, calcium or zinc. ) Metal phosphate (provided that metal represents lithium, sodium, potassium, magnesium, calcium or zinc) Metal silicate (provided that metal represents lithium, sodium, potassium or magnesium) Hydrotalcites or Lithium aluminum complex hydroxide salt Fatty acid metal salt (provided that the metal is lithium, sodium, potassium, magnesium, calcium, zinc or aluminum.) Aliphatic hydroxy acid metal salt (provided that the metal is lithium, sodium, potassium, magnesium) , Calcium, zinc, or aluminum.) Aliphatic metal phosphate (provided that the metal is lithium, sodium, potassium, magnesium, calcium, zinc, or aluminum.) (2) Compound with a thermoplastic polymer A 1 to 90% by weight and Compound B 0.01 to 50 wt% blended comprising the thermoplastic polymer composition described in (1).

The thermoplastic polymer used in the present invention includes ultra low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, ultra high molecular weight polyethylene and the like, amorphous ethylene- Cyclic alkene copolymer (for example, amorphous ethylene-tetracyclododecene copolymer), isotactic polypropylene, syndiotactic polypropylene, polybutene, poly-4-methylpentene-1
Polyolefin, atactic polystyrene, etc.
Syndiotactic polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, methacryl-butadiene-styrene copolymer, polyacrylonitrile, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate Such as polyester, polyacetal, polycarbonate,
Polyphenylene oxide, polyphenylene sulfide, polyvinyl chloride, polyvinyl acetate, fluororesin, petroleum resin, DCPD resin, amorphous ethylene-propylene random copolymer, amorphous ethylene-propylene-nonconjugated diene terpolymer, Low crystalline ethylene-butene-1 random copolymer, low crystalline propylene-butene-1 random copolymer, low crystalline ethylene-hexene-1 random copolymer, low crystalline ethylene-octene-1 random copolymer Coalescing,
Ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polybutadiene, polyisoprene, polychloroprene, chlorinated polyethylene, chlorinated polypropylene, fluororubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, styrene-butadiene -Styrene block copolymer, styrene-isoprene-
Styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-propylene-
Butylene-styrene block copolymer, ethylene-ethylene-butylene-ethylene block copolymer, ethylene-propylene-butylene-ethylene block copolymer and the like can be exemplified, not to mention the use alone of these thermoplastic polymers. That is, two or more kinds of thermoplastic polymers can be mixed and used.

Examples of the compound A used in the present invention include polyglycerin higher fatty acid monoesters such as glycerin higher fatty acid monoester and diglycerin higher fatty acid monoester, sorbitan higher fatty acid monoester, sucrose higher fatty acid monoester, pentaerythritol higher fatty acid. Mono or diester, polypentaerythritol higher fatty acid mono or diester such as dipentaerythritol higher fatty acid mono or diester, trimethylolethane higher fatty acid monoester, trimethylolpropane higher fatty acid monoester, polyoxyethylene glycerin higher fatty acid monoester, polyoxy Higher fatty acid partial esters of polyols such as ethylene sorbitan higher fatty acid monoesters (higher fatty acids include hexanoic acid and octane , 2-ethylhexanoic acid, nonanoic acid,
Decanoic acid, lauric acid, myristic acid, palmitic acid,
Stearic acid, behenic acid, montanic acid, oleic acid, erucic acid, 12-hydroxystearic acid, ricinoleic acid,
Examples thereof include ester type complexes of dodecanoyl lactic acid, tetradecanoyl lactic acid, hexadecanoyl lactic acid, octadecanoyl lactic acid) and boric acid. Particularly preferred are ester-type complexes of glycerin higher fatty acid monoester and boric acid, and ester-type complexes of pentaerythritol higher fatty acid mono- or diester and boric acid. The ester-type complex in the compound A means a compound formed by reacting four hydroxyl groups of one or more molecules of a higher fatty acid partial ester of a polyol with boric acid.
The complex represented by These compounds A may be used alone or in combination of two or more kinds. The compounding ratio of the compound A is not particularly limited with respect to the thermoplastic polymer, but is preferably 1 to 90% by weight,
More preferably, it is 1 to 20% by weight.

[0012]

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The compound B used in the present invention includes metal oxides such as magnesium oxide, calcium oxide, zinc oxide and aluminum oxide, and metal hydroxides such as magnesium hydroxide, calcium hydroxide, zinc hydroxide and aluminum hydroxide. , Lithium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, zinc carbonate and other metal carbonates, lithium phosphate, sodium phosphate, disodium hydrogen phosphate, potassium phosphate, magnesium phosphate, Calcium phosphate,
Metal phosphates such as zinc phosphate, lithium silicate, sodium silicate, potassium silicate, magnesium silicate,
Silicic acid metal salts such as talc, hydrotalcites, lithium aluminum composite hydroxide salts such as basic aluminum lithium lithium hydroxy carbonate hydrate, basic aluminum lithium lithium hydroxy sulfate sulfate hydrate,

Fatty acid metal salts (eg acetic acid, propionic acid, butyric acid, valeric acid, α-methylbutyric acid, hexanoic acid, sorbic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid,
Decanoic acid, caproic acid, undecanoic acid, undecylenic acid, lauric acid, linderic acid, myristic acid, fizeteric acid, myristoleic acid, palmitic acid, palmitoleic acid, hiragoic acid, stearic acid, petroselinic acid,
Oleic acid, elaidic acid, asclepic acid, vaccenic acid, linoleic acid, α-eleostearic acid, β-eleostearic acid, punicic acid, linolenic acid, γ-linolenic acid,
Moloctic acid, stearidonic acid, stearolic acid, arachidic acid, gadoleic acid, gondoinic acid, arachidonic acid, behenic acid, cetoleic acid, erucic acid, brassic acid, iwasic acid, lignoceric acid, ceracoleic acid, nisinic acid, serotic acid, ximene. Acid, montanic acid, melissic acid, lumecic acid, dodecanoyl lactic acid, tetradecanoyl lactic acid,
Hexadecanoyl lactic acid, lithium, sodium, potassium, magnesium, calcium, zinc or aluminum salts of fatty acids such as octadecanoyl lactic acid, aliphatic hydroxy acid metal salts (eg glycolic acid, lactic acid, hydroacrylic acid, α-oxybutyric acid, Tartronic acid, glyceric acid, malic acid, tartaric acid, meso-tartaric acid, gulonic acid,
Citric acid, 2-hydroxytetradecanoic acid, iprolic acid, 2-hydroxyhexadecanoic acid, yarapinolic acid, uniperic acid, ambretoleic acid, aleuritic acid,
Lithium, sodium of 2-hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid, 18-hydroxyoctadecanoic acid, 9,10-dihydroxyoctadecanoic acid, ricinoleic acid, camlorenic acid, licanoic acid, ferric acid, cerebronic acid , Potassium, magnesium, calcium, zinc or aluminum salts),

Aliphatic metal phosphates (eg (mono, dimixed) methyl phosphate, (mono, dimixed) ethyl phosphate, (mono, dimixed) propyl phosphate,
(Mono, dimixed) butyl phosphoric acid, (mono, dimixed) pentyl phosphoric acid, (mono, dimixed) hexyl phosphoric acid, (mono, dimixed) octyl phosphoric acid,
(Mono, dimixed) 2-ethylhexyl phosphoric acid, (mono, dimixed) decyl phosphoric acid, (mono, dimixed) lauryl phosphoric acid, (mono, dimixed) myristyl phosphoric acid, (mono, dimixed) palmityl phosphoric acid,
(Mono, dimixed) stearyl phosphate, (mono, dimixed) oleyl phosphate, (mono, dimixed)
Linole phosphoric acid, (mono, dimixed) linoleyl phosphoric acid, (mono, dimixed) docosyl phosphoric acid, (mono,
Lithium, sodium, potassium, magnesium, calcium, zinc or aluminum of aliphatic phosphoric acid such as (dimixed) erucylphosphate, (mono, dimixed) tetracosylphosphate, (mono, dimixed) hexacosylphosphate, (mono, dimixed) octacosylphosphate Examples of the metal salt selected from the above include not only normal salts but also various types of acidic salts or basic salts. Especially magnesium oxide,
Preferred are calcium oxide, magnesium hydroxide, calcium hydroxide, sodium carbonate, magnesium carbonate, calcium carbonate, sodium phosphate, calcium phosphate, sodium silicate, sodium acetate, sodium lactate or calcium lactate. These compounds B can be used alone, or two or more compounds B can be used in combination. The compounding ratio of the compound B is not particularly limited with respect to the thermoplastic polymer, but is preferably 0.01 to 50% by weight, more preferably 0.01 to 10% by weight.

In the composition of the present invention, various additives usually added to the thermoplastic polymer, such as phenol-based, thioether-based, phosphorus-based antioxidants and heat stabilizers (provided that compound B is ), Light stabilizers, heavy metal deactivators (copper damage inhibitors), clarifying agents, nucleating agents, lubricants (excluding compound B), antistatic agents (excluding compound A). ), Anti-fogging agent (excluding compound A), plasticizer, anti-blocking agent, non-dripping agent, radical generating agent such as peroxide, flame retardant (providing compound B)
except for. ), Flame retardant aid, pigment, halogen scavenger (excluding compound B), dispersant (excluding compound B), neutralizing agent (excluding compound B), organic type or Inorganic antibacterial agents, inorganic fillers (eg mica, clay, zeolite, kaolin, bentonite, perlite, diatomaceous earth, asbestos, silicon dioxide, titanium dioxide, zinc sulfide, barium sulfate, magnesium sulfate, calcium silicate, aluminum silicate) , Glass fiber, potassium titanate, carbon fiber, carbon black, graphite and metal fiber), coupling agents (for example, silane-based, titanate-based, boron-based, aluminate-based,
The above-mentioned inorganic filler or organic filler (for example, wood flour, pulp, waste paper, synthetic fiber, natural fiber, etc.) surface-treated with a surface treatment agent such as zircoaluminate type is used within a range not impairing the object of the present invention. Can be used together. Particularly, when an inorganic filler is used in combination, the cleaning effect of the composition of the present invention is synergistically improved, and therefore it is preferable to use it together.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The composition of the present invention is a thermoplastic polymer such as powder, beads, flakes, pellets and the like used in the present invention, wherein the above-mentioned compounds A and B and the usual thermoplastic polymer are used. A predetermined amount of each of the above-mentioned various additives to be added to the above is mixed by using an ordinary mixing device such as a Henschel mixer (trade name), a super mixer, a ribbon blender, a Banbury mixer, etc., and an ordinary single-screw extruder or multi-screw extruder is used. It can be obtained by melt-kneading pelletizing at a melt-kneading temperature of 50 ° C. to 400 ° C., preferably 100 ° C. to 350 ° C. with an extruder, a pressure kneader, a Brabender or a roll. The strand cutting for pelletizing may be either underwater cutting or air cutting. The obtained composition is used as it is or diluted with another thermoplastic polymer as a masterbatch, and then used for washing a molding machine of various thermoplastic polymers such as an injection molding machine, an extrusion molding machine and a blow molding machine. To be done.

[0018]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The evaluation methods used in Examples and Comparative Examples were as follows. Washing test: Using a 35 ton injection molding machine, 300 g of the colored preceding polymer is supplied and injected. Next, 100 g of the cleaning thermoplastic polymer composition is supplied, and further the replacement polymer is supplied and injection molding is repeated until the color of the replacement polymer disappears.
The amount of the displacing polymer consumed (required amount of the displacing polymer), and the time from the start of supplying the cleaning thermoplastic polymer composition to the time when the displacing polymer contaminated by the preceding polymer disappears Color required time) is measured. The one having a good cleaning effect is one having a small amount of the replacement polymer and a short time required for the decoloring.

Examples 1 to 16 and Comparative Examples 1 to 6 As a thermoplastic polymer, polyethylene (melt index (JIS K7210: 190 ° C., load 21.18N; hereinafter abbreviated as MI)) high density polyethylene of 1.5 g / 10 min. Homopolymer), as compound A, an ester complex of glyceryl monostearate and boric acid, an ester complex of pentaerythritol monolaurate and boric acid, an ester complex of pentaerythritol dibehenate and boric acid, or sorbitan. Ester type complex of monooleate and boric acid, as compound B magnesium oxide, magnesium hydroxide, lithium carbonate, lithium phosphate, lithium silicate, hydrotalcite, basic aluminum lithium hydroxy carbonate hydrate, Lithium acetate, lithium glycolate or (mono , Dimixed) Lithium methyl phosphate and other additives were put in a Henschel mixer (trade name) in the mixing ratios shown in Tables 1 and 2 below, and the mixture was stirred and mixed at a rotation speed of 500 rpm for 3 minutes, and then the caliber was used. A 65 mm twin-screw extruder melt-kneads the cylinder temperature of 230 ° C and the die temperature of 220 ° C to extrude the strands, cools them in a water tank, cuts them with a pelletizer, pelletizes them, and gives them a milky white pellet-like thermoplasticity. A polymer composition was obtained. Further, as Comparative Examples 2 to 6, polyethylene (a high-density polyethylene homopolymer having a MI of 1.5 g / 10 min) was mixed with predetermined amounts of the additives shown in Table 2 below, and melted in accordance with Examples 1 to 16. The mixture was kneaded to obtain a pellet-shaped thermoplastic polymer composition.

Using the thus obtained thermoplastic polymer composition as a detergent, a cleaning test was conducted on an injection molding machine contaminated with an ABS resin containing 1% by weight of carbon black as a preceding polymer. After supplying and washing the thermoplastic polymer composition at a cylinder temperature of an injection molding machine of 230 ° C., polypropylene (melt flow rate (JI
SK7210: 230 ° C, load 21.18N; hereinafter abbreviated as MFR. ) 5.0 g / 10 min polypropylene homopolymer) and the cleaning test was evaluated by the above test method.
However, in Comparative Example 1, the cleaning test was performed only with the replacement polymer without using the thermoplastic polymer composition. The results are shown in Tables 1 and 2.

Examples 17 to 32, Comparative Examples 7 to 12 Polypropylene (MFR 5.0 g / 10
Polypropylene homopolymer), an ester type complex of glyceryl monostearate and boric acid as compound A, an ester type complex of pentaerythritol monolaurate and boric acid, an ester type complex of pentaerythritol dibehenate and boric acid. Complex or ester-type complex of sorbitan monooleate and boric acid, as compound B calcium oxide, calcium hydroxide, sodium carbonate, disodium hydrogen phosphate, sodium silicate, hydrotalcite, basic aluminum-lithium-hydroxy- Predetermined amounts of carbonate hydrate, sodium acetate, sodium lactate or sodium (mono, dimixed) ethyl phosphate and other additives are shown in Tables 3 and 4 below.
Put in a Henschel mixer (trade name) in the mixing ratio described in, stir and mix at a rotation speed of 500 rpm for 3 minutes, and then calibrate a diameter of 65.
mm twin screw extruder, cylinder temperature 220 ℃, die temperature 210
The strand was extruded by melt-kneading under the condition of ° C, cooled in a water tank, cut with a pelletizer and pelletized to obtain a milky white pellet-shaped thermoplastic polymer composition.
Further, as Comparative Examples 8 to 12, polypropylene (MFR 5.0 g /
(10 minutes polypropylene homopolymer) was blended with a predetermined amount of each of the additives shown in Table 4 below, and melt-kneaded according to Examples 17 to 32 to obtain a pellet-shaped thermoplastic polymer composition. It was

Using the thus obtained thermoplastic polymer composition as a cleaning agent, a cleaning test was conducted on an injection molding machine contaminated with an ABS resin containing 1% by weight of carbon black as a preceding polymer. After supplying and washing the thermoplastic polymer composition at a cylinder temperature of the injection molding machine of 230 ° C., the polymer was replaced with polypropylene (polypropylene homopolymer of MFR 5.0 g / 10 min) as a replacement polymer, and the above test method was used. The cleaning test was evaluated. However, in Comparative Example 7, the cleaning test was performed only with the replacement polymer without using the thermoplastic polymer composition. The results are shown in Tables 3 and 4.

Examples 33 to 48, Comparative Examples 13 to 18 Polystyrene as a thermoplastic polymer (Asahi Kasei Kogyo Co., Ltd.)
Manufactured by Styron 600) under the trade name of compound A, ester-type complex of glyceryl monostearate and boric acid, ester-type complex of pentaerythritol monolaurate and boric acid, ester of pentaerythritol dibehenate and boric acid. Complex or ester complex of sorbitan monooleate and boric acid, as compound B zinc oxide, zinc hydroxide, sodium hydrogen carbonate, potassium phosphate, potassium silicate, hydrotalcite, basic aluminum-lithium-hydroxy- A predetermined amount of carbonate hydrate, potassium 2-ethylhexanoate, potassium citrate or potassium (mono-, di-mixed) propyl phosphate and other additives at the blending ratios shown in Tables 5 and 6 below are used in the Henschel mixer ( Put in the product name) and stir for 3 minutes at 500 rpm After combining, the twin-screw extruder with a diameter of 65 mm melt-kneads the cylinder temperature 220 ° C and the die temperature 220 ° C to extrude the strands, cools them in a water tank, cuts them with a pelletizer and pelletizes them into a milky white color. A thermoplastic polymer composition in the form of pellets was obtained. Further, as Comparative Examples 14 to 18, polystyrene (Asahi Kasei Co., Ltd., trade name Stylon 600) was compounded with a predetermined amount of each of the additives described in Table 6 below, and melt-kneading treatment was performed in accordance with Examples 33 to 48. Then, a pellet-shaped thermoplastic polymer composition was obtained.

Using the obtained thermoplastic polymer composition as a cleaning agent, a cleaning test was performed on an injection molding machine contaminated with an ABS resin containing 1% by weight of carbon black as a preceding polymer. After supplying and washing the thermoplastic polymer composition at a cylinder temperature of the injection molding machine of 230 ° C, the polymer was replaced with polystyrene (Asahi Kasei Co., Ltd., trade name Stylon 600) as a replacement polymer, and the above test method was used. The cleaning test was evaluated. However, in Comparative Example 13, a cleaning test was performed using only the replacement polymer without using the thermoplastic polymer composition. The results are shown in Tables 5 and 6.

Examples 49 to 64, Comparative Examples 19 to 24 Polyvinyl chloride (average degree of polymerization 80
0) as the compound A, an ester complex of glyceryl monostearate and boric acid, an ester complex of pentaerythritol monolaurate and boric acid, an ester complex of pentaerythritol dibehenate and boric acid, or sorbitan mono. Ester type complex of oleate and boric acid, as compound B aluminum oxide, aluminum hydroxide, potassium carbonate, magnesium phosphate, magnesium silicate, hydrotalcite, basic aluminum.
Lithium hydroxy carbonate hydrate,
Magnesium laurate, basic magnesium 12-hydroxyoctadecanoate or magnesium (mono-, di-mixed) butyl phosphate and other additives were added to Henschel Mixer (trade name) in the respective proportions shown in Tables 7 and 8 below. After putting in and stirring and mixing at a rotation speed of 500 rpm for 3 minutes, the cylinder temperature was 180 with a twin-screw extruder with a diameter of 65 mm.
C. and a die temperature of 170.degree. C. were melt-kneaded to extrude the strands, cooled in a water tank, cut with a pelletizer and pelletized to obtain a milky white pellet-shaped thermoplastic polymer composition. Further, as Comparative Examples 20 to 24, polyvinyl chloride (average degree of polymerization of 800) was blended with predetermined amounts of the additives shown in Table 8 below, and melt-kneaded in accordance with Examples 49 to 64 to form pellets. A thermoplastic polymer composition of was obtained.

Using the obtained thermoplastic polymer composition as a cleaning agent, a cleaning test was conducted on an injection molding machine contaminated with a polyvinyl chloride compound containing 1% by weight of carbon black as a preceding polymer. After supplying and cleaning the thermoplastic polymer composition at a cylinder temperature of 180 ° C. of the injection molding machine, it was replaced with an ethylene-vinyl acetate copolymer (Tosoh Corp., trade name Ultrasen 631) as a replacement polymer. Then, the cleaning test was evaluated by the above test method.
However, in Comparative Example 19, the cleaning test was performed only with the replacement polymer without using the thermoplastic polymer composition. The results are shown in Tables 7 and 8.

Examples 65 to 80, Comparative Examples 25 to 30 Ethylene-vinyl acetate copolymer (trade name: Ultracene 631 manufactured by Tosoh Corp.) as a thermoplastic polymer and glyceryl monostearate and boron as compound A Ester complex with acid, pentaerythritol monolaurate with boric acid, ester complex with pentaerythritol dibehenate with boric acid, or ester complex with sorbitan monooleate with boric acid, Compound B As magnesium oxide, magnesium hydroxide, basic magnesium carbonate, calcium phosphate, talc, hydrotalcite, basic aluminum lithium hydroxycarbonate hydrate, calcium stearate, calcium lactate or (mono, dimixed) 2-ethylhexyl calcium phosphate and other Each predetermined amount of the additive was put into a Henschel mixer (trade name) at a blending ratio shown in Tables 9 and 10 below, stirred and mixed at a rotation speed of 500 rpm for 3 minutes, and then a twin screw extruder having a diameter of 65 mm and a cylinder temperature of 190. The mixture was melt-kneaded at a temperature of 60 ° C. and a die temperature of 180 ° C., the strands were extruded, cooled in a water tank, cut with a pelletizer and pelletized to obtain a milky white pellet-shaped thermoplastic polymer composition. Further, as Comparative Examples 26 to 30, ethylene-vinyl acetate copolymer (manufactured by Tosoh Corporation, trade name Ultrasen 631) was blended with predetermined amounts of the additives shown in Table 10 below, and Examples 65 to 80 were prepared. Melt-kneading treatment was carried out in accordance with to obtain a pellet-like thermoplastic polymer composition.

Using the resulting thermoplastic polymer composition as a cleaning agent, a cleaning test was performed on an injection molding machine contaminated with a polyvinyl chloride compound containing 1% by weight of carbon black as a preceding polymer. After supplying and cleaning the thermoplastic polymer composition at a cylinder temperature of 180 ° C. of the injection molding machine, it was replaced with an ethylene-vinyl acetate copolymer (Tosoh Corp., trade name Ultrasen 631) as a replacement polymer. Then, the cleaning test was evaluated by the above test method.
However, in Comparative Example 25, the washing test was conducted only with the replacement polymer without using the thermoplastic polymer composition. The results are shown in Tables 9 and 10.

Examples 81-96, Comparative Examples 31-36 ABS resins (Asahi Kasei Co., Ltd.) as thermoplastic polymers
Manufactured by Stylak 200) under the trade name of Compound A, an ester-type complex of glyceryl monostearate and boric acid,
Ester-type complex of pentaerythritol monolaurate and boric acid, ester-type complex of pentaerythritol dibehenate and boric acid, or ester-type complex of sorbitan monooleate and boric acid, calcium oxide and calcium hydroxide as compound B , Calcium carbonate, zinc phosphate, sodium silicate, hydrotalcite, basic aluminum lithium hydroxycarbonate hydrate, zinc octadecanoyl lactate, zinc tartrate or zinc (mono, dimixed) stearyl phosphate and other Add a predetermined amount of each additive to the Henschel mixer (trade name) at the blending ratios shown in Tables 11 and 12 below,
After stirring and mixing at a rotation speed of 500 rpm for 3 minutes, a twin-screw extruder with a diameter of 65 mm melts and kneads the mixture at a cylinder temperature of 230 ° C and a die temperature of 220 ° C to extrude the strands, cool them in a water tank, and cut with a pelletizer. Then, the mixture was pelletized to obtain a milky white pellet-shaped thermoplastic polymer composition. Further, as Comparative Examples 32 to 36, ABS resins (manufactured by Asahi Kasei Kogyo Co., Ltd., trade name Stylac 200) were blended with predetermined amounts of the additives shown in Table 12 below, and the results were obtained in accordance with Examples 81 to 96. Melt-kneading treatment was performed to obtain a pellet-shaped thermoplastic polymer composition.

Using the obtained thermoplastic polymer composition as a cleaning agent, a cleaning test was conducted on an injection molding machine contaminated with an ABS resin containing 1% by weight of carbon black as a preceding polymer. After supplying and washing the thermoplastic polymer composition at a cylinder temperature of the injection molding machine of 230 ° C, the polymer was replaced with polystyrene (Asahi Kasei Co., Ltd., trade name Stylon 600) as a replacement polymer, and the above test method was used. The cleaning test was evaluated. However, in Comparative Example 31, the cleaning test was performed only with the replacement polymer without using the thermoplastic polymer composition. The results are shown in Tables 11 and 12.

Examples 97 to 112, Comparative Examples 37 to 42 Amorphous ethylene-propylene random copolymer (EPM: propylene content 25% by weight; Mooney viscosity ML1 + 4 (100 ° C.) 30) as a thermoplastic polymer, As the compound A, an ester form complex of glyceryl monostearate and boric acid, an ester form complex of pentaerythritol monolaurate and boric acid, an ester form complex of pentaerythritol dibehenate and boric acid, or sorbitan monooleate and borate. Ester-type complex with acid, zinc oxide, aluminum hydroxide, zinc carbonate, disodium hydrogen phosphate, talc, hydrotalcite, basic aluminum / lithium / hydroxy / carbonate hydrate, aluminum montanate, citrate as compound B Aluminum acid or (mono, dimixed) octaco Table 1 each below a predetermined amount Berlin aluminum and other additives
Put in a Henschel mixer (trade name) in the mixing ratios described in 3, 14 and stir-mix at a rotation speed of 500 rpm for 3 minutes, then use a twin screw extruder with a diameter of 65 mm at a cylinder temperature of 230 ° C and a die temperature of 220 ° C. The strands were melt-kneaded, extruded, cooled in a water tank, cut with a pelletizer and pelletized to obtain a milky white pellet-shaped thermoplastic polymer composition. Further, as Comparative Examples 38 to 42, amorphous ethylene-
A propylene random copolymer (EPM: propylene content 25% by weight; Mooney viscosity ML1 + 4 (100 ° C.) 30) was blended with respective predetermined amounts of the additives shown in Table 14 below,
Melt-kneading was carried out in accordance with Examples 97 to 112 to obtain pellet-shaped thermoplastic polymer compositions.

Using the thus obtained thermoplastic polymer composition as a cleaning agent, a cleaning test was conducted on an injection molding machine contaminated with an ABS resin containing 1% by weight of carbon black as a preceding polymer. After supplying and washing the thermoplastic polymer composition at a cylinder temperature of the injection molding machine of 230 ° C., the polymer was replaced with polypropylene (polypropylene homopolymer of MFR 5.0 g / 10 min) as a replacement polymer, and the above test method was used. The cleaning test was evaluated. However, in Comparative Example 37, the washing test was performed only with the replacement polymer without using the thermoplastic polymer composition. The results are shown in Tables 13 and 14.

The compounds and additives relating to the present invention shown in Tables 1 to 14 are as follows. Compound A [1]: Ester complex of glyceryl monostearate and boric acid Compound A [2]: Ester complex of pentaerythritol monolaurate and boric acid Compound A [3]: Pentaerythritol dibehenate and bor Ester complex with acid Compound A [4]: Ester complex with sorbitan monooleate and boric acid Compound B [1]: Magnesium oxide Compound B [2]: Calcium oxide Compound B [3]: Zinc oxide Compound B [4]: Aluminum oxide Compound B [5]: Magnesium hydroxide Compound B [6]: Calcium hydroxide Compound B [7]: Zinc hydroxide Compound B [8]: Aluminum hydroxide Compound B [9]: Lithium carbonate Compound B [10]: Sodium Carbonate Compound B [11]: Sodium Bicarbonate Compound B [12]: Potassium Carbonate Compound B [ 13]: basic magnesium carbonate compound B [14]: calcium carbonate compound B [15]: zinc carbonate compound B [16]: lithium phosphate compound B [17]: disodium hydrogen phosphate compound B [18]: phosphorus Potassium acid compound B [19]: Magnesium phosphate compound B [20]: Calcium phosphate compound B [21]: Zinc phosphate compound B [22]: Lithium silicate compound B [23]: Sodium silicate compound B [24] : Potassium silicate Compound B [25]: Magnesium silicate Compound B [26]: Talc Compound B [27]: Hydrotalcite (basic magnesium aluminum aluminum hydroxy carbonate hydrate: Mg4.5Al2 (OH) 13CO3・ 3.5H2O)
[Kyowa Chemical Industry Co., Ltd., trade name DHT-4A] Compound B [28]: basic aluminum lithium hydroxycarbonate hydrate (Al4Li2 (O
H) 12CO3 ・ 1.6H2O) [Mizuka Chemical Co., Ltd., trade name MIZUKALAC]

Compound B [29]: Lithium acetate Compound B [30]: Sodium acetate Compound B [31]: Potassium 2-ethylhexanoate Compound B [32]: Magnesium laurate Compound B [33]: Calcium stearate Compound B [34]: Zinc octadecanoyl lactate Compound B [35]: Aluminum montanate Compound B [36]: Lithium glycolate Compound B [37]: Sodium lactate Compound B [38]: Potassium citrate Compound B [39]: Basic magnesium 12-hydroxyoctadecanoate (0.44MgO ・ (C17H34 (OH) COO)
2Mg) Compound B [40]: Calcium lactate Compound B [41]: Zinc tartrate Compound B [42]: Aluminum citrate Compound B [43]: (Mono, dimixed) lithium methylphosphate Compound B [44]: (Mono, Dimixed) Sodium Ethyl Phosphate Compound B [45]: (Mono, Dimixed) Potassium Phosphate Compound B [46]: (Mono, Dimixed) Magnesium Butyl Phosphate Compound B [47]: (Mono, Dimixed) 2-Ethylhexyl Calcium Phosphate Compound B [48]: (mono, dimixed) zinc stearyl phosphate Compound B [49]: (mono, dimixed) aluminum octacosyl phosphate Phenolic antioxidant: tetrakis [methylene-3-
(3 ', 5'-Di-t-butyl-4'-hydroxyphenyl) propionate] methanephosphorus antioxidant: bis (2,4-di-t-butylphenyl)-
Pentaerythritol-diphosphite H-St: stearic acid PEWAX: polyethylene wax (number average molecular weight 1,50
0) TPCB: tris (2-phenylcyclohexyl) borate

[0035]

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GMSB: triester of glyceryl monostearate and boric acid

[0037]

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CBC: an ester-type complex of catechol and boric acid

[0039]

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[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

[Table 4]

[0044]

[Table 5]

[0045]

[Table 6]

[0046]

[Table 7]

[0047]

[Table 8]

[0048]

[Table 9]

[0049]

[Table 10]

[0050]

[Table 11]

[0051]

[Table 12]

[0052]

[Table 13]

[0053]

[Table 14]

The examples and comparative examples shown in Tables 1 and 2 are the cases where polyethylene was used as the thermoplastic polymer.
As can be seen from Tables 1 and 2, Examples 1 to 16 were prepared by compounding the compound A and the compound B according to the present invention, and Examples 1 to 16 and Comparative Example 1 (thermoplastic weight in Examples 1 to 16) were used. It is understood that Examples 1 to 16 are remarkably excellent in cleaning effect, when compared with those in which a cleaning test was performed only with the replacement polymer without using the coalescing composition. Comparing Comparative Example 2 and Examples 1 to 16 in which the compound A is blended alone, the cleaning effect of Comparative Example 2 is improved to some extent but is not yet sufficiently satisfactory, and Examples 1 to 16 are remarkably excellent. You can see that In addition, comparing Comparative Example 3 in which Compound B was blended alone with Examples 1 to 16, the cleaning effect of Comparative Example 3 was improved as compared with Comparative Example 1, but Examples 1 to 16 were significantly superior. You can see that further,
Comparative Examples 4 to 6 in which the compound A in Examples 1 to 16 was replaced with a boric acid triester of cyclohexanols, a triester of a fatty acid partial ester of a polyol and boric acid, or an ester type complex of catechol and boric acid, respectively. Comparing Examples 1 to 16, the cleaning effects of Comparative Examples 4 to 6 are improved as compared with Comparative Example 1, but are not yet sufficiently satisfactory, and Examples 1 to 16 are remarkably excellent. .

Therefore, each comparative example which does not simultaneously satisfy the combination of the two components of the compound A and the compound B according to the present invention,
It is clear that the effect of the present invention is not exerted. That is, it can be said that the cleaning effect obtained in the present invention is a unique effect that can be seen only when the compound A and the compound B are used in combination in the present invention.

Tables 3 to 14 use polypropylene, polystyrene, polyvinyl chloride, ethylene-vinyl acetate copolymer, ABS resin or amorphous ethylene-propylene random copolymer, respectively, as the thermoplastic polymer. However, the same effects as those described above were also confirmed.

[0057]

By using the thermoplastic polymer composition provided by the present invention, a very effective method for cleaning a molding machine at the time of grade switching in thermoplastic polymer processing has been realized. That is, by using a small amount of the composition of the present invention, it is possible to significantly reduce the consumption amount as compared with the case where the molding machine is cleaned only by the replacement with the polymer supplied later. Taking an injection molding machine as an example, the required amount of the replacement polymer can be reduced to 1/8 or less by using the composition of the present invention in combination with the subsequent color change using only the replacement polymer. Also, the color change time is 1
It can be shortened to / 6 or less.

Claims (2)

[Claims] 1. A thermoplastic polymer composition comprising a thermoplastic polymer and an ester type complex of a higher fatty acid partial ester of a polyol and boric acid, and one or more metal compounds selected from the following: Stuff. Metal oxide (however, metal is magnesium, calcium, zinc or aluminum.) Metal hydroxide (however, metal is magnesium, calcium, zinc or aluminum) Carbonate metal salt (however, metal is lithium or sodium) ,
Indicates potassium, magnesium, calcium or zinc. ) Phosphoric acid metal salt (provided that metal represents lithium, sodium, potassium, magnesium, calcium or zinc) Silicic acid metal salt (provided that metal represents lithium, sodium, potassium or magnesium) Hydrotalcites or Lithium aluminum complex hydroxide salt Fatty acid metal salt (provided that the metal is lithium, sodium, potassium, magnesium, calcium, zinc or aluminum.) Aliphatic hydroxy acid metal salt (provided that the metal is lithium, sodium, potassium, magnesium) , Shows calcium, zinc, or aluminum.) Aliphatic metal phosphate (provided that the metal shows lithium, sodium, potassium, magnesium, calcium, zinc, or aluminum) 2. A thermoplastic polymer, 1 to 90% by weight of an ester type complex of a higher fatty acid partial ester of a polyol and boric acid with respect to the composition, and a metal compound with respect to the composition.
The thermoplastic polymer composition according to claim 1, which is blended in an amount of 0.01 to 50% by weight.