JP4376648B2 - Cleaning resin composition - Google Patents

Description

  The present invention relates to a cleaning resin composition used for cleaning a processing molding machine used for molding various resins.

  Thermoplastic resins are widely used for injection molded products, extrusion molded products, films, and the like. Since these plastic molded products tend to be produced in a variety of products in small quantities, and the frequency of switching between products is increasing, cleaning in the molding machine at the time of product switching has become important for quality control. In the molding process of thermoplastic resins, the following methods are known as washing methods for molding machines at the time of product type switching.

  First, it is a method of washing with a resin to be used subsequently, that is, replacing a preceding product with a replacement resin without removing a screw. However, this method has a problem that a large amount of resin needs to be flowed for cleaning, and the loss is increased.

  Next, there is a method of disassembling and cleaning the processing molding machine, but this method has a problem that it takes too much time. For example, taking the case of color change in extrusion molding as an example, after the extruder is stopped, the screw is removed, the inside of the screw and cylinder is washed by a method such as brushing, and then complicated work such as re-installing the screw is performed. Necessary.

  Instead of these methods, a method of cleaning with various cleaning agents has been attempted since the amount of the replacement resin is small and the cleaning operation is simple. However, even in this cleaning method using a cleaning agent, the pre-residue remains after cleaning, causing burns and molding defects, and even if the pre-treatment agent can be completely discharged, the cleaning agent remains and moves to the next resin. There is a problem that a large amount of resin and a long time are required for the replacement of the resin.

Some cleaning agents have a surfactant added to the thermoplastic resin to improve the cleaning properties. However, adding a surfactant reduces friction with the screw of the molding machine or extruder, so it moves forward. There is a problem that it becomes difficult to send out the cleaning agent, and it takes time for cleaning or cannot be cleaned in some cases.
Japanese Patent Laid-Open No. 9-208992 JP 2000-119458 A JP 2000-119464 A JP 2002-1734 A

  In practical use, it is desired that the cleaning agent for a resin processing and molding machine satisfies the following requirements (i) and (ii) and, if necessary, the requirement (iii).

(I) Detergency when changing varieties: for extruding resin remaining in the processing molding machine;
(Ii) Self-discharge property of the cleaning agent: for preventing the cleaning agent itself from remaining in the processing machine;
(Iii) Foreign matter removability: For extruding foreign matters such as scorch (resin that the resin has deteriorated and stuck to the cylinder inner wall or screw due to heat applied during processing and molding) from the processing and molding machine.

  In order to satisfy the requirement (i), the viscosity of the cleaning agent may be increased by a resin, and in order to satisfy the requirement (ii), a surfactant may be added to increase the fluidity. However, both the requirements (i) and (ii) cannot be fully satisfied by merely blending the resin and the surfactant, and there is room for improvement.

  An object of the present invention is to provide a cleaning resin composition that satisfies the above two or three requirements, has a high cleaning power when applied to a processing molding machine, and can be easily replaced with a back agent. .

  As a result of research to satisfy both requirements (i) and (ii), the present inventor has determined that, in addition to viscosity and fluidity, the force that the cleaning agent presses the cylinder inner wall of the processing machine (as the reaction force) A force that presses the screw in the cylinder), i.e., elasticity, and using a swell ratio as a new indicator of elasticity, a cleaning agent satisfying a swell ratio in a predetermined range consisting of a combination of specific components is required (i The present invention has been completed by finding that both the requirements (ii) and (ii) as well as the requirement (iii) can be satisfied.

As a means for solving the problems, the present invention
(A) 100 parts by mass of base resin,
(B) 0.1-20 parts by mass of an anionic surfactant containing 50% by mass or more of alkanesulfonic acid or a salt thereof, and (C) 0.1-10 parts by mass of alkylene glycol fatty acid ester,
And a cleaning resin composition having a swell ratio of 1.2 or more.

Furthermore, the present invention provides other means for solving the problems,
(A) 100 parts by mass of base resin,
(B) 0.1-20 parts by mass of an anionic surfactant containing 50% by mass or more of alkanesulfonic acid or a salt thereof,
(C) A cleaning composition containing 0.2 to 10 parts by mass of an alkylene glycol fatty acid ester and (D) 0.1 to 20 parts by mass of an organophosphorus compound, and having a swell ratio of 1.2 or more. A resin composition is provided.

The “swell ratio” in the present invention is the ratio (d ₂ / d ₁ ) between the nozzle diameter (d ₁ ) and the strand diameter (d ₂ ) when the molten resin is extruded from the nozzle opening so as to form a strand. ). The “swell ratio” of the present invention is measured using a capillary rheometer (Toyo Seiki Co., Ltd., Capillograph 1B), resin processing temperature, shear rate 1 × 10 ² sec ⁻¹ , capillary length (20 mm), capillary diameter. It is a value measured under the condition of (1 mm).

  The cleaning resin composition of the present invention has an excellent cleaning effect with respect to an extruder, an injection molding machine, etc., and is very easy to replace with a back agent. Resin color can be changed.

  Examples of the base resin of the component (A) include styrene resins, olefin resins such as polypropylene, polymethacrylates, polyamide fibers, polyester resins, and the like. Among these, styrene resins are preferable.

  Styrene resins include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, or copolymers, as well as monomers copolymerizable with these styrene monomers, for example, vinyl resins such as acrylonitrile and methyl methacrylate. Mention may be made of copolymers with monomers.

  The styrene resin can be a rubber-modified styrene resin obtained by graft polymerization of the above styrene monomer and vinyl monomer on a diene rubber such as butadiene rubber, ethylene / propylene rubber, acrylic rubber, or the like. . Examples of such a styrenic resin include polystyrene, high impact polystyrene, AS resin, ABS resin, AAS resin, AES resin, MS resin, MBS resin, and the like.

  The styrene resin preferably has a weight average molecular weight in the range of 100,000 to 450,000, more preferably in the range of 100,000 to 300,000, and in the range of 150,000 to 250,000. More preferred.

  As described above, the swell ratio is a value measured at the processing temperature of the resin (processing temperature when a normal processing molding machine is used). In the case of the resins listed as the component (A) above, , Measured at 240 ° C.

  Component (B) is preferably an alkanesulfonic acid or a salt thereof represented by the following general formula (1). Since n in the general formula (1) is an average value, what is represented by the general formula (1) is a mixture having different carbon numbers. The component (B) contributes to the expression of self-discharging properties and thickens the composition (a composition in a molten state at the time of cleaning use) by forming a pseudo-crosslinked structure with the component (C). Is.

[Wherein, m is an average number of 5 to 30, n is 0 to 30, n ≦ m, and M is preferably H, Na, K, Mg, or Ca. ]
Examples of the anionic surfactant other than alkanesulfonic acid or a salt thereof include alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonate having 8 to 20 carbon atoms, alkyl or alkenyl. Examples thereof include one or more selected from ether carboxylates, α-sulfo fatty acid salts, α-sulfo fatty acid esters, and alkali metal salts of saturated or unsaturated fatty acids having 12 to 20 carbon atoms.

  (B) Content of alkanesulfonic acid or its salt in a component is 50 mass% or more, Preferably it is 90-100 mass%, More preferably, it is 99-100 mass%.

  (B) Content of a component is 0.5-20 mass parts with respect to 100 mass parts of (A) component, Preferably it is 1-10 mass parts, More preferably, it is 2-5 mass parts. When the content is 0.5 parts by mass or more, a sufficient cleaning effect can be imparted, and in particular, self-discharge is improved, and when it is 20 parts by mass or less, the self-discharge is good, and in the extruder or molding machine. Residual contamination is suppressed.

  (C) The alkylene glycol fatty acid ester of a component can mention ester compounds of alkylene glycol, such as ethylene glycol, propylene glycol, tetramethylene glycol, and hexamethylene glycol, and a C12-C22 fatty acid. The component (C) is for forming a pseudo-crosslinked structure with the component (B) and thickening the composition (a composition in a molten state at the time of cleaning use).

  As component (C), ethylene glycol monolaurate, ethylene glycol dilaurate, propylene glycol monolaurate, propylene glycol dilaurate, tetramethylene glycol monolaurate, tetramethylene glycol dilaurate, hexamethylene glycol monolaurate, hexamethylene glycol dilaurate , Ethylene glycol monomyristate, ethylene glycol dimyristate, propylene glycol monomyristate, propylene glycol dimyristate, tetramethylene glycol monomyristate, tetramethylene glycol dimyristate, hexamethylene glycol monomyristate, hexamethylene glycol dimyristate Myristate, ethylene glycol monopalmitate, ethylene glycol Cold dipalmitate, propylene glycol monopalmitate, propylene glycol dipalmitate, tetramethylene glycol monopalmitate, tetramethylene glycol dipalmitate, hexamethylene glycol monopalmitate, hexamethylene glycol dipalmitate, ethylene glycol monostearate , Ethylene glycol distearate, propylene glycol monostearate, propylene glycol distearate, tetramethylene glycol monostearate, tetramethylene glycol distearate, hexamethylene glycol monostearate, hexamethylene glycol distearate, ethylene glycol mono Oleate, ethylene glycol diolate, propylene glycol monooleate, Lopylene glycol dioleate, tetramethylene glycol monooleate, tetramethylene glycol dioleate, hexamethylene glycol monooleate, hexamethylene glycol dioleate, ethylene glycol monobehenate, ethylene glycol dibehenate, propylene glycol monobehenate, propylene glycol dibe Examples thereof include one or more selected from phenate, tetramethylene glycol monobehenate, tetramethylene glycol dibehenate, hexamethylene glycol monobehenate, hexamethylene glycol dibehenate, and the like.

  As the component (C), propylene glycol monobehenate is preferable, and a mixture of propylene glycol monobehenate represented by the following formulas (2) and (3) is more preferable.

The mass ratio [ (2) / (3) ] of the propylene glycol monobehenate of formula (2) and formula (3) is preferably 4: 1 to 1: 1, more preferably 3: 1 to 1: 1.

The content of the component (C) is 0.1 to 10 parts by mass, preferably 1 to 5 parts by mass, more preferably 1 to 3 parts by mass with respect to 100 parts by mass of the component (A). When the content is 0.1 parts by mass or more, a sufficient cleaning effect can be imparted, and in particular, the washability at the time of product change is improved, and when it is 10 parts by mass or less, the washability at the time of product change is good, Residual contamination in the extruder or molding machine is suppressed.

  The organic phosphorus compound as component (D) preferably has one or more ester oxygen atoms bonded to phosphorus atoms. Since the component (D) has a high dissolving power against scorching, it is a component that contributes to the expression of foreign matter removability.

  Component (D) is trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl). ) Phosphate, tris (o-phenylphenyl) phosphate, tris (p-phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phosphate , O-phenylphenyl dicresyl phosphate, dibutyl phosphate, monobutyl phosphate, di- 2-ethylhexyl) phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxymethyl phosphate, etc. One or more may be mentioned, and among these, triphenyl phosphate is preferred.

  The component (D) is composed of phosphites such as triphenyl phosphite, trisnonylphenyl phosphite, tristridecyl phosphite, dibutyl hydrogen phosphite and their condensates, triphenyl phosphine oxide, tricresyl phosphine oxide. 1 or 2 or more selected from diphenyl methanephosphonate, diethyl phenylphosphonate and the like can also be used.

  (D) Content of a component is 0.1-20 mass parts with respect to 100 mass parts of (A) component, Preferably it is 1-10 mass parts, More preferably, it is 2-5 mass parts. When the content is 0.1 parts by mass or more, a sufficient cleaning effect can be imparted, and in particular, the foreign matter removal property is improved. When the content is 20 parts by mass or less, the foreign matter removal property is good, and in the extruder or molding machine. Residual contamination is suppressed.

  In the composition of this invention, when solving the subject of this invention, it is preferable to link | relate content of (B) component and (C) component. As for the content ratio in the total amount of (B) component and (C) component, 55-99 mass% is preferable, as for (B) component, 60-90 mass% is more preferable, 70-80 mass% is still more preferable, ( Component C) is preferably 1 to 45% by mass, more preferably 10 to 40% by mass, and still more preferably 20 to 30% by mass.

  Moreover, 0.5-20 mass parts is preferable, as for total content of (B) and (C) component with respect to 100 mass parts of (A) component, 1-10 mass parts is more preferable, and 2-7 mass parts is further. preferable.

  In the composition of the present invention, it is preferable to relate the contents of the components (B), (C), and (D) in order to solve the problems of the present invention. The content ratios in the total amount of the components (B), (C), and (D) are as follows.

  (B) 20-90 mass% is preferable, 20-70 mass% is more preferable, 30-60 mass% is still more preferable.

  Component (C) is preferably 5 to 30% by mass, more preferably 5 to 20% by mass, and still more preferably 10 to 20% by mass.

  The component (D) is preferably 5 to 75% by mass, more preferably 25 to 70% by mass, and still more preferably 30 to 60% by mass.

  Moreover, 1-20 mass parts is preferable, as for total content of (B), (C), (D) component with respect to 100 mass parts of (A) component, 1-10 mass parts is more preferable, and 5-10 mass parts. Is more preferable.

  The composition of the present invention can contain other components within a range that can solve the problems of the present invention, and the components (E), (F), and (G) are particularly preferable.

The polyhydric alcohol as the component (E) is an acyclic or cyclic compound in which a plurality of hydroxyl groups are bonded. Examples of the component (E) include pentaerythritol, dipentaerythritol, tripentaerythritol, pentitols (such as adonitol and arabitol), hexitols (such as dulcitol and inositol), saccharides (such as amylose and xylan), and derivatives thereof. 1 or 2 or more selected from (N-methylglucamine etc.) etc. can be mentioned.

  (E) Content of a component is 0.5-20 mass parts with respect to 100 mass parts of (A) component, Preferably it is 5-10 mass parts. If the content is 0.5 parts by mass or more, a sufficient cleaning effect can be imparted, and if it is 20 parts by mass or less, it is suppressed from remaining in the extruder or the molding machine and contaminating.

  The metal soap as the component (F) is a salt of a fatty acid having 6 to 22 carbon atoms and a metal (Mg, Li, Zn, Ca, Al, Sn, etc.).

  As the component (F), magnesium caproate, lithium caproate, zinc caproate, calcium caproate, aluminum caproate, tin caproate, magnesium caprylate, lithium caprylate, zinc caprylate, calcium caprylate, aluminum caprylate , Tin caprylate, magnesium caprate, lithium caprate, zinc caprate, calcium caprate, aluminum caprate, tin caprate, magnesium laurate, lithium laurate, zinc laurate, calcium laurate, aluminum laurate, tin laurate , Magnesium myristate, lithium myristate, zinc myristate, calcium myristate, aluminum myristate, tin myristate, magnesium palmitate, palmitate Lithium acid, zinc palmitate, calcium palmitate, aluminum palmitate, tin palmitate, magnesium stearate, lithium stearate, zinc stearate, calcium stearate, aluminum stearate, tin stearate, magnesium oleate, lithium oleate, Name one or more selected from zinc oleate, calcium oleate, aluminum oleate, tin oleate, magnesium behenate, lithium behenate, zinc behenate, calcium behenate, aluminum behenate, tin behenate, etc. Can do.

  (F) Content of a component is 0.05-5 mass parts with respect to 100 mass parts of (A) component, Preferably it is 0.5-5 mass parts. When the content is 0.05 parts by mass or more, a sufficient cleaning effect can be imparted, and when it is 5 parts by mass or less, a metal salt (lithium, tin) having a low melting point melts even in a high temperature atmosphere of 200 ° C. or more, and extrusion. Residual contamination in the machine or molding machine is suppressed.

  (G) As a glass fiber which is a component, a thing with a fiber diameter of 5-16 micrometers and a fiber length of 0.5-12 mm is preferable. Further, since the cleaning effect is high and the residual in the molding machine is suppressed, it is more preferable that the surface is treated with a silane coupling agent and the sizing agent is treated with an acrylic resin sizing agent or the like. The degree of the bundling treatment at this time is not particularly limited, but the amount of attached organic matter (that is, equal to the amount of sizing agent used. The amount of attached organic matter means the amount of organic matter in the total amount of the glass fiber bundle and the sizing agent. ) Is preferably 0.3 to 1.5 mass%.

  (G) Content of a component is 5-30 mass parts with respect to 100 mass parts of (A) component, Preferably it is 10-30 mass parts. When the content is 5 parts by mass or more, the cleaning effect can be improved, and when the content is 30 parts by mass or less, it is suppressed that the resin remains in the molding machine or the molding machine is worn.

  The composition of the present invention is produced by premixing the above components with a mixer such as a Henschel mixer, a tumbler blender, or a kneader, and then kneading with an extruder, or melt-kneading with a heating roll or a Banbury mixer.

The composition of the present invention has a swell ratio of 1.2 or more, preferably 1.3 or more, which is a ratio (d ₂ / d ₁ ) of the nozzle diameter (d ₁ ) and the strand diameter (d ₂ ). More preferably, it is 1.4 or more.

The swell ratio is derived from the relationship between the nozzle diameter (d ₁ ) and the strand diameter (d ₂ ) as shown in FIG. 1, and the larger the swell ratio, the more the composition becomes the cylinder of the processing machine during cleaning. It means that the force that presses the inner wall (the force that presses the screw in the cylinder as the reaction force), that is, the elasticity is large. The greater the swell ratio (the greater the elasticity), the stronger the inner wall of the cylinder and the screw are pressed, so the dirt removal performance is enhanced.

  In addition, since the swell ratio leads to the removal performance of dirt, the lower limit value is important, and if it is equal to or higher than the lower limit value, it indicates that the cleaning performance of the molding machine is excellent, the upper limit value. There is no need to decide. The upper limit value is naturally determined by the specific content of the composition.

  The composition of the present invention is considered to satisfy the requirements (i) and (ii) by the following mechanism of action.

(A) component is a component which mainly exhibits the washing | cleaning property at the time of varieties change of requirement (i) by raising the viscosity of a composition, (B) component acts as surfactant, (i) It is a component that expresses detergency at the time of cultivar change and self-discharge of the composition of (ii). However, the addition of component (B) reduces the force with which the composition pushes the inner wall of the cylinder (evaluated by the swell ratio here) and reduces the cleaning ability. Therefore, only the components (A) and (B) are required. (I) and (ii) cannot be satisfied.

Therefore, as described in the present invention, when the component (C) is further contained in the combination of the components (A) and (B), when used (the composition is in a molten state), the alkanesulfonic acid of the component (B) Or the force which a composition presses a cylinder inner wall (here evaluated by a swell ratio) improves by the effect | action which arises by the combination with the salt and the alkylene glycol fatty acid ester of (C) component.

  As a result of such a change, the composition can achieve both the surface active force and the mechanical properties (here, the force by which the composition pushes the inner wall of the cylinder) that are important factors for the cleaning agent. Therefore, requirements (i) and (ii) are satisfied.

  Then, in addition to the components (A) to (C), the component (D) is further contained, whereby the requirement (iii) is satisfied together with the requirements (i) and (ii).

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further in detail, the scope of the present invention is not limited to these Examples. In addition, the detail of each component used by the Example and the comparative example is as follows.

(A) Component AS resin: “Cebian-N020” manufactured by Daicel Chemical Industries, Ltd.
(B) Component Sodium alkane sulfonate: Trade name Hostapur SAS93, manufactured by Clariant Co., Ltd. Sodium α-olefin sulfonate Product name Luporan PB-800 Made by Lion Corporation (C) Component Alkylene glycol fatty acid ester: Propylene glycol monobehenate, trade name Riquemar PB-100, manufactured by Riken Vitamin Co., Ltd. (D) Component Organic phosphorus compound: Triphenyl phosphate (Daihachi Chemical Industry Co., Ltd.)
Examples 1-3, Comparative Examples 1-4
After mixing each component of the composition shown in Table 1 with a tumbler blender, it was melt-kneaded with an extruder to obtain a pellet-shaped cleaning resin composition. Using these components, a washing test was conducted by the following method. The swell ratio is a measured value at 240 ° C., which is the resin processing temperature.

[Detergency evaluation A]
Black coloring of injection molding machine (Mitsubishi Heavy Industries'"Mitsubishi Injection Molding Machine 265 / 100MSII" (cylinder temperature 250 ° C) with PA / ABS with carbon fiber as a pre-used resin ("Novaloy AC5704" manufactured by Daicel Chemical Industries, Ltd.) The product (carbon black concentration 1%) was flowed 1 kg, and then the cleaning resin composition having the composition shown in Table 1 was flowed to evaluate the amount of the cleaning resin composition used until the black color disappeared. AS resin ("Sepian-N080" manufactured by Daicel Chemical Industries, Ltd.) is used as the resin for injection molding, and the amount of AS resin used until the residue of the cleaning resin composition disappears in the molded product and a good product is obtained. Was evaluated.

[Detergency evaluation B]
1 kg of halogen-based flame retardant ABS resin ("SER20" manufactured by Daicel Chemical Industries, Ltd.) is used as an advanced resin in an injection molding machine (Mitsubishi Heavy Industries "Mitsubishi Injection Molding Machine 265 / 100MSII" (cylinder temperature 250 ° C)). When the remaining 500 g of the resin used was discharged, the cleaning resin composition until the brown or black burnt lines disappeared after the cleaning resin composition shown in Table 1 was discharged. The amount of use was evaluated.

[Evaluation of slipperiness]
The resin composition for cleaning shown in Table 1 is put into an injection molding machine (Mitsubishi Heavy Industries “Mitsubishi Injection Molding Machine 265 / 100MSII” (cylinder temperature 250 ° C.) from the hopper, and the evaluation is based on the time when the screw position is measured from 0 to 100 mm. Went.

Explanatory drawing of a swell ratio.

Claims (3)

(A) 100 parts by mass of AS resin,
(B) 0.1-20 parts by mass of an alkanesulfonic acid represented by the following general formula (1) or a salt thereof,
(C) an alkylene glycol fatty acid ester, 0.2 to 10 parts by mass, and (D) a cleaning composition containing 0.1 to 20 parts by mass of an organic phosphorus compound,
(B) component, (C) component, and the content rate in the total amount of (D) component are (B) component 20-90 mass%, (C) component 5-30 mass%, and (D) component. Is 5 to 75% by mass, and the total content of (B), (C) and (D) components with respect to 100 parts by mass of component (A) is 1 to 20 parts by mass,
A cleaning resin composition having a swell ratio of 1.2 or more.

[Wherein, m is an average number of 5 to 30, n is 0 to 30, n ≦ m, M is H, alkali metal, or alkaline earth metal. ] (C) alkylene glycol fatty acid ester components, the cleaning resin composition of claim 1 wherein the propylene glycol monobehenate. The component (C) , propylene glycol monobehenate, is a mixture of the following formulas (2) and (3), and the mass ratio of the formulas (2) and (3) is 4: 1 to 1: 2. The cleaning resin composition according to claim 2 .

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