JP6812750B2 - Cleaning agent for resin molding machines - Google Patents

Description

The present invention relates to a cleaning agent for a resin molding machine. More specifically, it has excellent detergency against stains caused by colorants such as dyes and pigments and stains remaining in the resin molding machine such as filler residue, and reduces the burden of color change to the next process. Regarding cleaning agents for resin molding machines that can be used.

Resin molding machines such as extrusion molding machines and injection molding machines are used for coloring, kneading, or molding resins. When molding is performed using these resin molding machines, raw materials such as resins, colorants such as pigments and dyes, and additives such as antioxidants and antistatic agents adhere to the cavities, cylinders, and screws of the molding machines. In addition, problems such as deterioration of these raw materials in the molding machine and formation of carbides and the like may occur. Further, this raw material and its deteriorated product may be mixed in the molded product in a later process and cause defects such as poor appearance and deterioration of mechanical properties. Therefore, it is desired to completely remove the residue from the inside of the resin molding machine at the end of the process.

As a method of completely removing the resin from the resin molding machine, there is a manual disassembly and cleaning of the inside of the molding machine. However, disassembly and cleaning requires a great deal of time because it needs to be disassembled and assembled once. In addition, the cavity, cylinder, and screw are worn by the brush used for cleaning. Furthermore, there are places where it is difficult to manually clean due to the structure of the molding machine, such as inside the cylinder. In order to solve these problems, it is required to develop a method for removing the residue from the inside of the molding machine without disassembling and cleaning the resin molding machine.

As a method of removing the residue in the molding machine without disassembling and cleaning, a method of filling the molding machine with a material to be molded next and removing the residue (hereinafter, referred to as "purge") can be mentioned. However, purging has a problem that not only it takes time to replace the colorant or resin used in the previous step, but also a considerable amount of waste is generated. In addition, it is difficult to completely remove the deteriorated material remaining in the molding machine, and troubles such as poor appearance are likely to occur in the subsequent process.

In order to solve these problems, a cleaning agent in which an inorganic filler or a liquid substance is mixed with a thermoplastic resin is known. For example, Patent Documents 1 to 3 are mentioned as a cleaning agent in which an inorganic filler is mixed with a thermoplastic resin. Patent Document 1 proposes a cleaning agent in which an inorganic porous substance and a lubricant are mixed with a thermoplastic resin having a specific melt mass flow rate (hereinafter referred to as MFR, also referred to as melt viscosity). Patent Document 2 proposes a cleaning agent in which a nonionic surfactant, a metal soap, and an inorganic filler are mixed with a polyolefin resin. Patent Document 3 proposes a cleaning agent in which a thermoplastic resin is mixed with bishydroxyalkyl terephthalate or the like. However, these methods have poor affinity with colorants such as pigments and dyes, and it is difficult to perform sufficient cleaning.

Japanese Unexamined Patent Publication No. 5-269755 Japanese Unexamined Patent Publication No. 58-149998 International Publication WO2008 / 146822

The problem to be solved by the present invention is excellent detergency for colorants such as dyes and pigments, excellent permeability in a resin molding machine, and cleaning by a simple method that does not require disassembly and cleaning of the resin molding machine. It is an object of the present invention to provide a cleaning agent which can be used.

The present inventor has completed the present invention as a result of diligent studies to solve the above problems. That is, the present invention is a cleaning agent for a resin molding machine, which comprises a polyolefin resin (A), an inorganic filler (B), a surfactant (C), a polar functional group-containing polyolefin wax (D) and a fatty acid metal salt (E). Regarding. However, the polyolefin resin (A) excludes the polyolefin wax (D).

The present invention also relates to the cleaning agent for a resin molding machine in which the acid value of the polar functional group-containing polyolefin wax (D) is 0.1 to 60 mgKOH / g.

The present invention also relates to a cleaning agent for a resin molding machine, which has a melting point of the fatty acid metal salt (E) of 100 to 230 ° C. and contains 0.1 to 70 parts by mass with respect to 100 parts by mass of the polyolefin resin.

The present invention also relates to the cleaning agent for a resin molding machine, wherein the surfactant (C) contains a nonionic surfactant.

The present invention also relates to the resin molding machine cleaning agent having a melt mass flow rate of 10 to 35 g / 10 minutes.

Further, in the present invention, the polyolefin resin (A) 25 to 40% by mass, the inorganic filler (B) 35 to 65% by mass, and the surfactant (C) 0.1 to 10 in 100% by mass of the cleaning agent for a resin molding machine. The present invention relates to the above-mentioned cleaning agent for a resin molding machine, which contains 0.1 to 10% by mass of a polyolefin wax (D) containing a polar functional group and 4 to 15% by mass of a metal fatty acid salt (E).

Further, in the present invention, a mixture containing a polyolefin resin (A), an inorganic filler (B), a surfactant (C), a polar functional group-containing polyolefin wax (D) and a fatty acid metal salt (E) is melt-kneaded. The present invention relates to a method for producing a characteristic cleaning agent for a resin molding machine. However, the polyolefin resin (A) excludes the polyolefin wax (D).

According to the present invention, stains due to high-concentration colorants, which were difficult to remove with conventional cleaning agents, and stains such as mold joints, which had to be removed by disassembling and cleaning the resin molding machine, can be easily removed. Can be removed.

Hereinafter, the present invention will be described in detail. In this specification, "cleaning agent for resin molding machine" may be abbreviated as "cleaning agent".

<Polyolefin resin (A)>
The polyolefin resin (A) preferably contains a single heavy body such as ethylene, propylene, butene, or pentene, or a copolymer as a main component. Specifically, for example, polyethylene-based resin, polypropylene-based resin, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, propylene-vinyl acetate. Copolymer, propylene-methylacrylate copolymer, propylene-methylmethacrylate copolymer, propylene-ethylacrylate copolymer, polybutene, poly-3-methyl-1-butene copolymer, poly-4-methyl-1 -Pentene copolymers and ethylene-based ionomer resins can be mentioned. These can be used alone or in combination of two or more. Among these, as the polyolefin resin, polypropylene-based resin and polyethylene-based resin, which are inexpensive and have excellent workability and are widely used in various industrial parts and home appliances, are preferable.

Polypropylene-based resins include, for example, homopolypropylene, block propylene copolymer, random propylene copolymer, ethylene propylene copolymer rubber, polypropylene obtained by using a metallocene compound as a polymerization catalyst, and maleic anhydride-modified polypropylene. Examples thereof include modified polypropylene resins such as glycidyl (meth) acrylate-modified polypropylene and 2-hydroxyethyl (meth) acrylate-modified polypropylene.

Polyethylene-based resins include, for example, high-density polyethylene, low-density polyethylene, ultra-low-density polyethylene, linear low-density polyethylene, ultra-high-molecular-weight polyethylene, polyethylene obtained by using a metallocene compound as a polymerization catalyst, cyclic polyethylene, and anhydrous. Examples thereof include modified polyethylene resins such as maleic acid-modified polyethylene, glycidyl (meth) acrylate-modified polyethylene, and 2-hydroxyethyl (meth) acrylate-modified polyethylene. High-density polyethylene is mentioned as a preferable polyethylene-based resin.

The polyolefin resin (A) has an MFR of 0.01 to 40 g / 10 minutes, preferably 0.01 to 30 g / 10 minutes in JIS (Japanese Industrial Standards) K7210: 1999 (ISO1133: 1997).

Specific examples of the polyolefin resin (A) include SunTech HD B870 (Asahi Kasei Chemicals, MFR 0.3 g / 10 minutes, HDPE), SunAllomer PM580X (SunAllomer, MFR 5.0 g / 10 minutes, PP), Examples thereof include Novatec PPBC03C (manufactured by Japan Polypropylene Corporation, MFR 30 g / 10 minutes, PP).

<Inorganic filler (B)>
The inorganic filler (B) is a carbonate such as calcium carbonate, a sulfate such as barium sulfate, a silicate such as talc, mica, wallastonite, a hydroxide such as calcium hydroxide, a hydroxide such as silica. It is an oxide. It is preferably carbonate, more preferably calcium carbonate.

The average particle size of the inorganic filler (B) is preferably 0.01 to 30 μm, more preferably 0.1 to 7.0 μm, and even more preferably 0.1 to 4.0 μm. The specific surface area of the inorganic filler (B) is preferably 1000 to 100,000 cm ² / g. Further, the DOP refueling amount of the inorganic filler (B) is preferably 1 to 50 mL / 100 g. The average particle size is the average value of the major axis length and the minor axis length of 50 inorganic filler particles observed with a scanning electron microscope (Hitachi, Ltd., field emission scanning electron microscope S-4300). And said. The specific surface area is a value based on the air permeation method, and the DOP refueling amount is a value based on JIS K5101.

Specific examples of the inorganic filler (B) include Shiraishi SB Blue (manufactured by Shiraishi Calcium Co., Ltd., calcium bicarbonate), BF-200 (manufactured by Shiraishi Calcium Co., Ltd., calcium bicarbonate), MICRO ACE K-1 (manufactured by Japan Talc), Fine powder talc) and the like.

<Surfactant (C)>
The surfactant (C) is an ionic surfactant or a nonionic surfactant, and is preferably a nonionic surfactant.

Examples of the nonionic surfactant (C) include polyoxyethylene cetyl ether and polyoxyethylene alkyl ether such as polyoxyethylene stearyl ether; polyoxyethylene phenyl ether such as polyoxyethylene nonylphenyl ether; and sorbitan monostearate. Such as sorbitan fatty acid ester; polyoxyethylene sorbitan fatty acid ester such as polyoxyethylene sorbitan monolaurate; glycerin fatty acid ester such as stearate monoglyceride; and polyethylene glycol monolaurate, and polyoxyethylene-polyoxypropylene block polymer and the like. Polyoxyethylene fatty acid ester and the like.

Specific examples of the nonionic surfactant (C) include Emargen 108 (manufactured by Kao, nonionic surfactant, polyoxyethylene lauryl ether) and Emargen A-500 (manufactured by Kao, nonionic surfactant). , Polyoxyethylene distyrene phenyl ether), PL-330 (manufactured by Kao, nonionic surfactant, polyoxyethylene; polyoxypropylene block copolymer, diisodecyl adipate) and the like, and these nonionic surfactants It is preferable to contain at least one type of activator.

<Polyolefin wax containing polar functional group (D)>
The polar functional group-containing polyolefin wax (D) is a polyolefin wax having a polar functional group selected from a carbonyl group, a carboxyl group, a maleic anhydride group and the like, and preferably has an acid value of 0.1 to 60 mgKOH / g. More preferably, it is 10 to 30 mgKOH / g. Here, the acid value is a value measured under the conditions according to JIS K0070.

Specific examples of the polar functional group-containing polyolefin wax include high wax NP50605A (manufactured by Mitsui Chemicals, acid value 11 mgKOH / g, containing anhydrous carboxylic acid group), AC polyethylene 316A (manufactured by Honeywell, acid value 16 mgKOH / g, carbonyl group). Included), Umex 1010 (manufactured by Sanyo Kasei Co., Ltd., acid value 52 mgKOH / g, containing maleic anhydride group).

<Fatty acid metal salt (E)>
The fatty acid metal salt (E) refers to a fatty acid metal salt, excluding the above-mentioned surfactant (C). The fatty acid metal salt (E) is preferably a metal salt of a linear aliphatic monocarboxylic acid. The fatty acid metal salt preferably has 10 to 30 carbon atoms, more preferably 12 to 18 carbon atoms. One type or two or more types of fatty acid metal salt (E) can be used.

Examples of the linear aliphatic monocarboxylic acid having 12 to 18 carbon atoms include lauric acid, palmitic acid, stearic acid, oleic acid, and ricinoleic acid, and examples of the metal salt thereof include calcium salt, zinc salt, and magnesium salt. , Barium salt, aluminum salt and the like, of which calcium salt, zinc salt and magnesium salt are preferable, and zinc salt and magnesium salt are more preferable. Preferred fatty acid metal salts (E) include zinc stearate and magnesium stearate. The fatty acid metal salt (E) preferably has a melting point of 100 to 230 ° C., more preferably 110 ° C. to 180 ° C. More preferably, it is 110 ° C to 140 ° C.

The cleaning agent in the present invention has an MFR of 0.01 to 50 g / 10 minutes, preferably 10 to 35 g / 10 minutes, and more preferably 10 to 35 g / 10 minutes in JIS (Japanese Industrial Standards) K7210: 1999 (ISO1133: 1997). 18 to 25 g / 10 minutes.

In the cleaning agent for a resin molding machine of the present invention, one or more kinds of additives may be appropriately blended as long as the productivity and cleaning property of the cleaning agent are not affected. The additives used are not particularly limited, and are, for example, various commonly used leveling agents, pigment dispersants, ultraviolet absorbers, antioxidants, viscosity modifiers, light-resistant stabilizers, metal deactivators, and emulsifiers. Oxide decomposition agents, fillers, reinforcing agents, plasticizers, lubricants, anticorrosive agents, rust preventives, emulsifiers, mold decolorizers, fluorescent whitening agents, organic flameproofing agents, inorganic flameproofing agents, dripping inhibitors, Examples thereof include melt flow modifiers and antistatic agents.

In the cleaning agent for a resin molding machine of the present invention, a polyolefin resin (A), an inorganic filler (B), a surfactant (C), a polyolefin wax (D) having a polar functional group, and a fatty acid metal salt (E) are added. If necessary, add additives, etc., mix with a Henschel mixer, tumbler, extruder, etc., and further mix with a kneader, roll mill, super mixer, Henschel mixer, sugar mixer, vertical granulator, high speed mixer, fur matrix, ball mill, etc. Mixing with a batch kneader such as a steel mill, sand mill, vibration mill, attritor or Banbury mixer, twin-screw extruder, single-screw extruder, rotor-type twin-screw kneader, etc. A resin composition in the form of powder, granules, beads, or the like can be obtained.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to Examples. In the examples, parts and% represent parts by mass and% by mass, respectively, unless otherwise specified. The raw materials used in the examples are shown below. In addition, the compounding ratio of each of the above components is shown in Table 1.

<Polyolefin resin (A)>
(A-1): Suntech HD B870 (Asahi Kasei Chemicals, MFR 0.3 g / 10 minutes, HDPE), (A-2): Prime Polypro J704UG (Prime Polymer, MFR 5 g / 10 minutes, b-PP) ), (A-3) Novatec LL UJ370 (manufactured by Japan Polyethylene Corporation, MFR 16g / 10 minutes, LLDPE)

<Inorganic filler (B)>
(B-1): Shiraishi SB Blue (manufactured by Shiraishi Calcium, carbonate, average particle size = 2.4 μm, specific surface area = 10000 cm ² / g, DOP refueling amount = 26 mL / 100 g), (B-2): BF-200 (manufactured by Shiraishi Calcium, carbonate, average particle size = 5.3 μm, specific surface area = 4000 cm ² / g, DOP refueling amount = 26 mL / 100 g), (B-3): MICRO ACE K-1 (Japan) Made by Tark, silicate, average particle size = 8.5 μm, specific surface area = 70000 cm ² / g, DOP refueling amount = 35 mL / 100 g)
<Surfactant (C)>
(C-1): PL-330 (Kao Corporation, nonionic surfactant, polyoxyethylene and diisodecyl adipate), (C-2): Electro stripper EA (Kao Corporation, nonionic surfactant, Alkyldiethanolamine) (C-3): Emar 10G (Kao Corporation, anionic surfactant, sodium lauryl sulfate)

<Polyolefin wax containing polar functional group (D)>
(D-1): High wax NP50605A (manufactured by Mitsui Chemicals, acid value 11 mgKOH / g, containing maleic anhydride group), (D-2): AC polyethylene 316A (manufactured by Honeywell, acid value 16 mgKOH / g, carbonyl group) (Contains), (D-3): Umex 1010 (manufactured by Sanyo Kasei Co., Ltd., acid value 52 mgKOH / g, containing maleic anhydride group)
<Non-polar polyolefin wax>
(D-4): NL500 (manufactured by Mitsui Chemicals, no acid value, non-polar polyolefin wax)

<Fatty acid metal salt (E)>
(E-1); Tannan Wax FZ (manufactured by Tannan Chemical Industry Co., Ltd., melting point 117 to 122 ° C.), (E-2): Daiwax M (manufactured by Dainichi Chemical Industry Co., Ltd., magnesium stearate, melting point 133 to 141) ° C.) (E-3): Dywax C (manufactured by Dainichi Chemical Industry Co., Ltd., calcium stearate, melting point 140 to 160 ° C.)

(Example 1)
<Manufacturing of cleaning agent>
34 parts of (A-1) as the polyolefin resin (A), 50 parts of (B-1) as the inorganic filler, 5 parts of (C-1) as the surfactant (C), and a polyolefin wax having a polar functional group. 1 part of (D-1) as (D) and 10 parts of (E-1) as a fatty acid metal salt (E) are mixed and put into a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) at a set temperature of 220 ° C. A cleaning agent for a resin molding machine was obtained by melt-kneading.

(Examples 2 to 19, Comparative Examples 1 to 6)
Cleaning agents for resin molding machines were obtained in the same manner as in Example 1 except that the materials and formulations shown in Table 1 were changed. The blanks in Table 1 indicate that they are not blended.
However, Examples 8, 10, 17 to 19 are reference examples.

<Evaluation of detergency of cleaning agent>
LDPE (Suntech LD-F2270 manufactured by Asahi Kasei Chemicals Co., Ltd.) was molded at a temperature of 220 ° C. using a single-layer T-die film molding machine to form a film having a width of 12 cm and a thickness of 100 μm (film A). Subsequently, 10 parts of phthalocyanine pigment (Lionol Blue FG7330 manufactured by Toyo Color Co., Ltd.), 10 parts of polyethylene wax (manufactured by Mitsui Chemicals Co., Ltd., high wax NL500), and 80 parts of LDPE (manufactured by Asahi Kasei Chemicals Co., Ltd. After extruding 500 parts of the colorant obtained by melt-kneading in (Asahi Kasei Chemicals Co., Ltd., Suntech LD-F2270), 500 parts of the mixture was extruded. After that, a film (film B) having the same shape as the film A was molded again using LDPE (Suntech LD-F2270 manufactured by Asahi Kasei Chemicals Co., Ltd.). The haze of film A and film B (HA and HB, respectively) were measured and evaluated as follows.
| HA-HB | ≤25: Especially good "A"
25 << | HA-HB | ≤30: Good "B"
| HA-HB | is a value other than "A" and "B": defective "C"
However, the haze is a value measured by using Haze Guard Plus (manufactured by Gardner) and based on ISO13468 and ISO14782.

<Evaluation of permeability of cleaning agent>
Permeability was evaluated by the cleaning agent MFR. The MFR of the obtained cleaning agent in JIS (Japanese Industrial Standards) K7210: 1999 (ISO1133: 1997) was measured and evaluated as follows.
18 ≤ MFR (g / 10 minutes) ≤ 25: Especially good "A"
10 ≤ MFR (g / 10 minutes) <18 or 25 <MFR (g / 10 minutes) ≤ 35: Good "B"
MFR is out of the above range: defective "C"
The above evaluation of MFR corresponds to the result of disassembling the head portion of the single-layer T-die film molding machine whose detergency was evaluated and visually evaluating the colorant stains accumulated between the parts. That is, it was particularly good when colorant stains could not be confirmed between the parts of the single-layer T-die film molding machine, good when slight colorant stains could be confirmed, and defective when colorant stains could be clearly confirmed.

The cleaning agent for a resin molding machine of the present invention had good detergency and permeability (Examples 1 to 19). On the other hand, the cleaning agents of Comparative Examples 1 to 6 had poor detergency or permeability.

Claims (6)

Polyolefin resin (A), the inorganic filler (B), surfactant (C), a polar functional group-containing polyolefin wax (D) and the fatty acid metal salt (E) seen including,
The polyolefin resin (A) has a melt mass flow rate of 0.01 to 5 g / 10 minutes.
The inorganic filler (B) is a carbonate having an average particle size of 0.01 to 7.0 μm.
The fatty acid metal salt (E) is at least one selected from the group consisting of zinc stearate, magnesium stearate, and calcium stearate.
25-40% by mass of the polyolefin resin (A), 35-65% by mass of the inorganic filler (B), 0.1-10% by mass of the surfactant (C) in 100% by mass of the cleaning agent for a resin molding machine. , 0.1 to 10% by mass of the polar functional group-containing polyolefin wax (D) and 4 to 15% by mass of the fatty acid metal salt (E).
Cleaning agent for resin molding machines.
However, the polyolefin resin (A) excludes the polyolefin wax (D). The cleaning agent for a resin molding machine according to claim 1, wherein the polar functional group-containing polyolefin wax (D) has an acid value of 0.1 to 60 mgKOH / g. The cleaning agent for a resin molding machine according to claim 1 or 2, wherein the fatty acid metal salt (E) has a melting point of 100 to 230 ° C. and contains 0.1 to 70 parts by mass with respect to 100 parts by mass of the polyolefin resin. The cleaning agent for a resin molding machine according to any one of claims 1 to 3, wherein the surfactant (C) contains a nonionic surfactant. The cleaning agent for a resin molding machine according to any one of claims 1 to 4, wherein the melt mass flow rate of the cleaning agent for a resin molding machine is 10 to 35 g / 10 minutes. Polyolefin resin (A), the inorganic filler (B), surfactant (C), a polar functional group-containing polyolefin wax (D) and the fatty acid metal salt (E) seen including,
The polyolefin resin (A) has a melt mass flow rate of 0.01 to 5 g / 10 minutes.
The inorganic filler (B) is a carbonate having an average particle size of 0.01 to 7.0 μm.
The fatty acid metal salt (E) is at least one selected from the group consisting of zinc stearate, magnesium stearate, and calcium stearate.
25-40% by mass of the polyolefin resin (A), 35-65% by mass of the inorganic filler (B), 0.1-10% by mass of the surfactant (C) in 100% by mass of the cleaning agent for a resin molding machine. Cleaning for a resin molding machine, which comprises melt-kneading a mixture containing 0.1 to 10% by mass of the polar functional group-containing polyolefin wax (D) and 4 to 15% by mass of the fatty acid metal salt (E). Method of manufacturing the agent.
However, the polyolefin resin (A) excludes the polyolefin wax (D).