JP5080163B2 - Cleaning resin composition - Google Patents

Description

  The present invention relates to a cleaning resin composition used for cleaning a molding machine used for molding various resins and ceramic materials, and a method of cleaning a molding machine using the same.

  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, a method of cleaning with a cleaning agent is known as a method of cleaning a molding machine at the time of product type switching.

  In the case of this cleaning method, the pre-resin remains after cleaning, causing burns and molding defects, and even if the pre-agent can be completely discharged, the cleaning agent remains and is replaced with the next resin. Has a problem of requiring a large amount of resin and a long time.

  Moreover, in order to improve cleaning property, what mix | blended glass fiber and a metal fiber is used widely as a cleaning agent, but in this case, a residue will be generated when the cleaning agent after cleaning is incinerated. There's a problem.

  Patent Document 1 describes blending inorganic fibers and / or inorganic powders, organic fibers and / or organic powders, metal fibers and / or metal powders as components of the cleaning material. Although the cellulose fiber is illustrated as an organic fiber, there is no specific description about a cellulose fiber, and what is used in the Example is only glass fiber.

Patent Document 2 describes blending cellulose materials such as wood flour, rice husk, pulp, cork and the like as components of the cleaning agent, but only wood flour is used in the examples. .
Japanese Patent No. 3050774 JP 2000-34499 A

  Conventionally, it has been described that cellulose fibers can be blended as a component of a cleaning agent, but there has been no concrete effect.

  The present invention has high detergency and can prevent combustion residue when incinerated after use, and can also be used for washing ceramic molding molding machines. It is an object of the present invention to provide a resin composition and a cleaning method for a molding machine using the resin composition.

  As a means for solving the problems, the invention of claim 1 provides a cleaning resin composition containing (A) a thermoplastic resin and (B) cellulose fibers in which the cellulose fiber aggregate is defibrated.

  In the invention of claim 2, as a means for solving the problem, the cellulose fiber in which the cellulose fiber aggregate of the component (B) is fibrillated is obtained by integrating the cellulose fiber and the thermoplastic resin. The resin composition for washing | cleaning of description is provided.

  Invention of Claim 3 is for washing | cleaning of the shaping | molding processing machine for melt-kneading and shape | molding a thermoplastic resin as a solution means of a subject, The inorganic compound or the metal may be contained, Claim 1 or The cleaning resin composition according to 2, is provided.

  Invention of Claim 4 is for washing | cleaning of the shaping | molding processing machine for knead | mixing and shape | molding ceramic powder and binder resin as a solution means of a subject, and does not contain an inorganic compound and a metal substantially. The cleaning resin composition according to 1 or 2 is provided.

  The invention of claim 5 is a method for cleaning a molding machine using the cleaning resin composition according to any one of claims 1 to 4 as a means for solving another problem, and a cylinder of the molding machine. Provided is a cleaning method in which the cleaning resin composition is used at a temperature set to 200 ° C. or lower.

  The cleaning resin composition of the present invention has good cleaning performance of a molding machine and can prevent combustion residues from being generated when the used composition is incinerated. Further, the cleaning resin composition of the present invention can be used for cleaning a molding machine for forming ceramics.

<(A) component>
As the thermoplastic resin of component (A), styrene resin, polycarbonate resin, olefin resin such as polypropylene, polyphenylene sulfide resin, polymethacrylate, polyamide resin, polyester resin, polysulfone resin (PSF), polyacetal , Polyetheretherketone (PEEK), polyetherimide (PEI), polyethersulfone (PES), polyamideimide (PAI), polyimide (PI) and the like. Among these, those selected from styrene resins, olefin resins, polyamide resins, polymethacrylates, and polyacetals 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 monomers 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. Particularly preferred are polystyrene and AS resin.

  The styrene resin preferably has a weight average molecular weight in the range of 100,000 to 600,000, more preferably in the range of 100,000 to 500,000, and in the range of 150,000 to 450,000. More preferred.

  As the olefin resin, single weight of α-olefin such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 3-methylbutene-1,4-methylpentene-1, etc. Or a copolymer of these α-olefins, such as random or block, or a copolymer containing these α-olefins as a main component (preferably 50% by mass or more) and copolymerized with other monomers. Can be mentioned.

  Other monomers include butadiene, isoprene, dicyclopentadiene, 1,4-hexadiene, 4-ethylidene-2-norbornene, dicyclopentadiene and other dienes, acrylic acid, methacrylic acid, maleic acid, vinyl acetate, methacrylic acid. Examples thereof include unsaturated acids such as acid methyl and maleic imide or derivatives thereof, and aromatic alkenyl compounds such as styrene and α-methylstyrene.

  As the olefin resin, one or more selected from high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and polypropylene (PP) are preferable. Further, as the (A) component polyolefin resin, an acid obtained by copolymerizing an unsaturated acid such as acrylic acid, methacrylic acid, maleic acid, vinyl acetate, methyl methacrylate, maleic imide, or a derivative thereof together with the above-described one. A small amount of a modified polyolefin resin can be contained.

  Polyamide resins include polyamide resins formed from diamines and dicarboxylic acids and their copolymers, specifically nylon 66, polyhexamethylene sebacamide (nylon 6 · 10), polyhexamethylene dodecanamide (nylon). 6/12), polydodecamethylene dodecanamide (nylon 1212), polymetaxylylene adipamide (nylon MXD6), polytetramethylene adipamide (nylon 46) and mixtures and copolymers thereof; nylon 6/66 Nylon 66 / 6T (6T: polyhexamethylene terephthalamide) in which 6T component is 50 mol% or less, Nylon 66 / 6I (6I: polyhexamethyleneisophthalamide) in which 6I component is 50 mol% or less, nylon Copolymers such as 6T / 6I / 66, nylon 6T / 6I / 610; poly Xamethylene terephthalamide (nylon 6T), polyhexamethylene isophthalamide (nylon 6I), poly (2-methylpentamethylene) terephthalamide (nylon M5T), poly (2-methylpentamethylene) isophthalamide (nylon M5I), nylon Examples thereof include copolymers such as 6T / 6I and nylon 6T / M5T. In addition, copolymer nylon such as amorphous nylon may be used, and examples of amorphous nylon include polycondensates of terephthalic acid and trimethylhexamethylenediamine. .

  Examples of the polymethacrylate include known homopolymers of alkyl esters of methacrylic acid or copolymers with other monomers. Examples of the polyacetal include a homopolymer obtained by polymerizing only known formaldehyde, a copolymer containing paraformaldehyde and an oxyethylene unit, and the like.

  30-95 mass% is preferable, as for content of (A) component in the cleaning agent resin composition of this invention, 40-90 mass% is more preferable, and 40-80 mass% is still more preferable.

<(B) component>
(B) a cellulose fiber component of cellulose fiber aggregate is disintegrated is an essential component for improving the cleaning property, the mechanical means, those cellulose fiber aggregate is disintegrated, For example, a large number of fibrillated cellulose fibers are entangled to form a lump as a whole.

  Cellulose fiber aggregates are a combination of many cellulose fibers combined, and may be natural products (for example, plants themselves, thinly processed plants) or industrial products (for example, paper pulp), hemp Aggregates such as fiber, bamboo fiber, cotton fiber, wood fiber, kenaf fiber, hemp fiber, jute fiber, banana fiber, and coconut fiber can be used.

  The cellulose fiber preferably has a high α-cellulose content from the viewpoint of high thermal stability, more preferably 80% by mass or more, still more preferably 85% by mass or more, and particularly preferably 90% by mass or more.

  As the cellulose fiber aggregate, a pulp sheet or a cut product thereof is preferable. The thickness, shape, and size of the pulp sheet or its cut product are not particularly limited, and can be selected so that the defibrating work can be performed smoothly.

  When the cellulose fiber aggregate is a sheet, for example, a sheet having a thickness of 0.1 to 5 mm, preferably 1 to 3 mm, a width of 1 to 50 cm, and a length of about 3 to 100 cm can be used.

  When the cellulose fiber aggregate is a cut product of a sheet, for example, a strip having a thickness of 0.1 to 5 mm, preferably 1 to 3 mm, a width of 2 mm to 1 cm, and a length of about 3 mm to 3 cm, or A rectangular shape having a side of about 2 mm to 1 cm is preferable.

The moisture content of the cellulose fiber aggregate is preferably 20% by mass or less, more preferably 17% by mass or less, and still more preferably 15% by mass or less. A water content of 20% by mass or less is preferable because the temperature rise due to generation of frictional heat is facilitated in the next step, and the cellulose fiber aggregate is easily defibrated and no aggregate remains. The water content is determined by the moisture measurement due Karufu I Fischer method.

  If necessary, organic fibers other than cellulose fibers can be used. In the total amount of cellulose fibers and organic fibers, the ratio of cellulose fibers is preferably 50% by mass or more, more preferably. It is 55 mass% or more. Examples of organic fibers other than cellulose fibers include nylon fibers, polyester fibers, and acrylic fibers.

  Further, the component (B) is obtained by integrating and integrating the same thermoplastic resin as the component (A) to the fibrillated cellulose fiber aggregate in order to improve kneadability with the component (A) (for example, in the form of pellets) Can also be used.

  The method for defibrating the cellulose fiber aggregate is not particularly limited. For example, the following first to third defibrating methods can be applied.

(1) First defibrating method (the method described in JP 2007-84713 A)
[First step]
In the first step, the cellulose fiber aggregate is put into a mixer having rotating blades as stirring means, and the cellulose fiber aggregate is defibrated by stirring at high speed.

  The mixer only needs to have rotating blades as stirring means, and preferably has heating means. For example, a Henschel mixer manufactured by Mitsui Mining Co., Ltd., FM20C / I (capacity 20 L), ( Kawata Supermixer SMV-20 (capacity 20 L) can be used.

  The rotating blades are usually composed of two upper blades and lower blades, or three upper blades, intermediate blades, and lower blades, but the number is not limited. The shape of the blade is not limited, but for example, the kneading type is used for the upper blade, the high circulation / high load is used for the lower blade, and the melt is used when the intermediate blade is used.

  In the first step, it is preferable to stir in the range of the average peripheral speed of the rotating blades during stirring in the range of 10 to 100 m / second, more preferably the average peripheral speed is 10 to 90 m / second, and still more preferably the average peripheral speed is 10 Stir at ~ 80 m / sec.

  The treatment in the first step is not limited as long as the cellulose fiber aggregate can be sufficiently defibrated. For example, the point in time when the cellulose fiber aggregate has been visually confirmed to be cottony can be confirmed. The end of Since the average peripheral speed and stirring time of the rotating blades change depending on the type, shape, size, input amount, and the like of the cellulose fiber aggregate, the time point when it changes to cotton as described above may be used as a reference. Is preferred.

The cellulose fiber defibrated by applying the treatment method of the first step can be used as it is as the component (B) of the present invention, but the following steps can also be carried out.
[Second step]
In the second step, a mixture in which the thermoplastic resin is adhered to the fibrillated cellulose fibers by melting the thermoplastic resin by the generated frictional heat by stirring the thermoplastic resin in the mixer. Get. The 1st process and the 2nd process can be made into one continuous process, without stopping stirring of a mixer.

  The thermoplastic resin used in this step can be the same as the component (A) described above. When the same component as the component (A) is used during the production of the component (B), the content of the component (A) in the composition includes the amount of the thermoplastic resin included in the component (B). It will be.

  In the first step, since the cellulose fiber aggregate is defibrated in the mixer, a required amount of thermoplastic resin is added thereto and stirred at a high speed. This high-speed stirring generates frictional heat and raises the temperature in the mixer, so that the thermoplastic resin melts and adheres to the fibrillated cellulose fibers, and a mixture of cellulose fibers and the thermoplastic resin is obtained.

  In the second step, a small amount of an oxidizing agent can be added together with the thermoplastic resin. When the cleaning resin composition of the present invention is applied for cleaning a molding machine for kneading and molding ceramic powder and a binder resin, the fibrillated cellulose fibers remain in the molding machine after cleaning. there's a possibility that. If cellulose fibers remain in this way, when ceramic powder and a binder resin are put into a molding machine, there is a possibility that the cellulose fibers are mixed therein.

  In the case of oxide-based ceramics, the mixed cellulose fibers are also burned and removed because they are heated in an oxygen atmosphere in the sintering step after molding. However, in the case of nitride-based or carbide-based ceramics, Since it is heated in a non-oxygen atmosphere, it may remain in the molded body without being removed by combustion. Therefore, in the second step, an oxidizing agent is added together with the thermoplastic resin, and the cellulose fiber, the thermoplastic resin, and the cleaning composition containing the component (B) in which the oxidizing agent is integrated into the cellulose fiber in the molding machine. By leaving the oxidizing agent in the attached state, the cellulose fibers can be burned and removed even when heated in a non-oxygen atmosphere.

  In the second step, it is preferable to stir in the range of the average peripheral speed of the rotating blades during stirring in the range of 10 to 100 m / second, more preferably the average peripheral speed is 10 to 90 m / second, and still more preferably the average peripheral speed is 10 Stir at ~ 80 m / sec. If stirring is continued, the temperature in the mixer will continue to rise, and the power of the motor will increase. It is preferable to reduce the rotational speed by gradually or decelerating the stirring speed in accordance with the increase in power and the temperature in the mixer so that the average peripheral speed falls within the above range.

  When stirring is continued in this state, the power increases again, so the mixture is discharged to the cooling mixer used in the next third step to be connected. At this time, in this mixture, the fibrillated cellulose fibers are adhered almost uniformly in the thermoplastic resin.

  In the second step, the mixer can be heated by a heating means in order to assist the temperature increase in the mixer and facilitate the production of the mixture of cellulose fibers and thermoplastic resin. The temperature at this time is preferably about 120 to 140 ° C.

  The total amount of cellulose fiber and thermoplastic resin is set according to the volume of the mixer and the like. As for the ratio of a cellulose fiber and a thermoplastic resin, 5-500 mass parts of cellulose fibers are preferable with respect to 100 mass parts of thermoplastic resins, More preferably, it is 7-450 mass parts, More preferably, it is 10-400 mass parts.

  In particular, when increasing the blending ratio of cellulose fibers, for example, when blending more than 67 parts by mass of cellulose fibers with respect to 100 parts by mass of resin, it is desirable to use a thermoplastic resin having a low viscosity.

  For example, when polypropylene is used, the melt flow rate is preferably 20 to 200 g / 10 min under the conditions of a temperature of 230 ° C. and a load of 21 and 6 N. When polyethylene is used, the melt flow rate is 190 ° C. The load is preferably 10 to 200 g / 10 min under the conditions of load 21 and 6N.

  For example, when an ABS resin is used, the melt flow rate is preferably 10 to 200 g / 10 minutes under the condition of a temperature of 220 ° C. and a load of 100 N, and when polystyrene is used, the condition of a temperature of 200 ° C. and a load of 50 N is used. The thing of 5-100 g / 10min is preferable.

[Third step]
In the third step, the mixture obtained in the second step is stirred at a low speed while being cooled. By the treatment in this step, the mixture is solidified (granulated by solidification). In the third step, in order to increase the cooling efficiency of the mixer, it is preferable to use a mixer (preferably having a cooling means) different from the mixer used in the first step and the second step.

  In the third step, it is preferable to stir in the range of 1 to 30 m / sec of the average peripheral speed of the rotating blades during stirring, more preferably 2 to 25 m / sec, more preferably 3 to 3. Stir at ~ 25 m / sec. The stirring speed in the third step is smaller than the stirring speed in the first step and the second step.

  In the treatment in the third step, the point in time when the mixture of the cellulose fiber and the thermoplastic resin is solidified to such an extent that it can be handled as a molding material can be terminated. In addition, since the thermoplastic resin once solidified will melt again if the temperature in the mixer rises too much due to generation of frictional heat, it is preferable to manage the temperature in the mixer also in the third step.

  By such a treatment, a solidified product (granulated product) containing cellulose fibers and a thermoplastic resin is obtained, and this can be used as the component (B).

(2) Second defibrating method [first step]
In the first step, the cellulose fiber aggregate is defibrated by a defibrator to obtain cotton-like cellulose fibers.

  The defibrating machine can be uncoiled by acting mechanically on the cellulosic fiber aggregate to form a flocculent cellulosic fiber (which is intertwined with a large number of cellulosic fibers). Anything is acceptable. The defibrator is preferably one that employs a dry defibrating method, and examples thereof include those used for defibrating commercially available waste paper. As such a defibrating machine, a defibrating machine (Model FF-270, FF-280, FF-290) manufactured by Ruikou Co., Ltd., a recycling breaker RB-100 manufactured by Ikegami Machinery Co., Ltd. Examples include a waste paper defibrator manufactured by the association, a small dry defibrator “Fiber Riser” manufactured by West Japan Technology Development Co., Ltd., and a turbo mill manufactured by Turbo Industry Co., Ltd.

  The treatment in the first step is not limited as long as the cellulose fiber aggregate can be sufficiently defibrated. For example, the point in time when the cellulose fiber aggregate has been visually confirmed to be cottony can be confirmed. The end of Since the average peripheral speed and stirring time of the rotating blades change depending on the type, shape, size, input amount, and the like of the cellulose fiber aggregate, the time point when it changes to cotton as described above may be used as a reference. Is preferred.

  The cellulose fiber defibrated by applying the treatment method of the first step can be used as it is as the component (B) of the present invention, but the following steps can also be carried out.

  Subsequent to the first step, the second and third steps of the first defibrating method described above are performed to obtain a solidified product (granulated product) containing cellulose fibers and a thermoplastic resin. Can be used as component (B).

(3) Third defibrating method [first step]
In the first step, the cellulose fiber aggregate is put into a mixer having rotating blades as stirring means, and the cellulose fiber aggregate is defibrated by stirring at high speed.

The cellulose fiber aggregate used in the present invention is a rod-shaped pulp sheet. The “bar shape” means an elongated shape having a strength higher than that of a single sheet. As a rod-shaped pulp sheet, for example,
(I) A pulp sheet wound once or twice or more (preferably 2-5 turns) and rolled into a cylindrical shape,
(II) One or two or more rolls of a pulp sheet rolled into a cylindrical shape, and then crushed in the radial direction into an elongated plate shape,
(III) The pulp sheet is folded into one or more times (preferably 2 to 10 times) so as to be in different directions, and is formed into an elongated plate shape,
(IV) A pulp sheet folded in the same direction once or a plurality of times (preferably 2 to 10 times) into a long and narrow plate shape,
(V) A pulp sheet that is folded in a random direction once or a plurality of times (preferably 2 to 10 times) into an elongated plate shape, or the like can be used.

  The shape of the pulp sheet is not particularly limited, and may be any shape as long as it can be formed in the above-mentioned forms (I) to (V), such as a rectangle, a square, a circle, a sector, a triangle, a pentagon or more polygon. Can be used.

  For example, a pulp sheet having a thickness of 0.1 to 5 mm, preferably 1 to 3 mm, a width of 10 to 50 cm, and a length of about 60 to 100 cm can be used.

The pulp sheet preferably has a burst strength measured by the method described in JIS P8112 and P8131 (using a Murren burst strength tester) in the range of 0.5 to 10.0 kPam ² / g. If it is within this range, the above-described methods (I) to (V) can be applied to obtain a rod-like pulp sheet. Even if the tensile strength is less than the lower limit, the number of windings and the number of foldings may be increased.

  The cylindrical form (I) is, for example, wound in a cylindrical form as shown in FIGS. 1 (a) and 1 (b). FIG. 1 shows a state where the pulp sheet is wound twice and a half. The crushed one becomes the plate-like form (II).

  The plate-like form of (III) is, for example, as shown in FIGS. 2 (a) and 2 (b), in which a pulp sheet is alternately folded into different directions to form an elongated plate (ie, Folded in a bellows shape). FIG.2 (c) has shown what was folded in the same direction corresponding to the plate-shaped form of (IV).

  As long as the rod-shaped pulp sheet has the same degree of strength as the cylindrical or plate-like pulp sheet of (I) to (V) above, it is simply one sheet without being rolled or folded. It may be just cut the sheet.

  In consideration of workability, the rod-like pulp sheet preferably has a ratio of length / width (diameter) of 3 or more.

  The mixer only needs to have rotating blades as stirring means, and preferably has heating means. For example, a Henschel mixer manufactured by Mitsui Mining Co., Ltd., FM20C / I (capacity 20 L), ( Kawata Supermixer SMV-20 (capacity 20 L) can be used.

  The rotating blades are usually composed of two upper blades and lower blades, or three upper blades, intermediate blades, and lower blades, but the number is not limited. The shape of the blade is not limited, but for example, the kneading type is used for the upper blade, the high circulation / high load is used for the lower blade, and the melt is used when the intermediate blade is used.

  In the first step, it is preferable to stir in the range of the average peripheral speed of the rotating blades during stirring in the range of 10 to 100 m / second, more preferably the average peripheral speed is 10 to 90 m / second, and still more preferably the average peripheral speed is 10 Stir at ~ 80 m / sec.

  In the first step, as shown in FIG. 3, the fiber sheet is defibrated so that the angle between the rod-shaped pulp sheet and the blades of the mixer falls within a predetermined range. FIG. 3 is for explaining the contact state between the rod-shaped pulp sheet and the blades of the mixer, and is not for explaining the structure of the mixer.

  In the first step, the angle α formed by the center line of the rod-shaped pulp sheet 1 shown in FIG. 3 and the center line of the blades 11 of the mixer 10 (or the surface of the circular rotating surface generated by the rotating blades 11) is 45. It is -90 degrees, Preferably it is 60-90 degrees, More preferably, it is 75-90 degrees, and it is still more preferable that it is 90 degrees or the angle approximated to it. In addition, as described above, when the mixer has a two-blade configuration of the upper blade and the lower blade, or a three-blade configuration of the upper blade, the intermediate blade, and the lower blade, the angle α formed with at least the first upper blade in contact is within the above range. As long as

  In the first step, the end of the rod-like pulp sheet 1 (the end far from the blade 11) is mechanically or artificially fixed in the state shown in FIG. The rod-shaped pulp sheet 1 is pushed in toward the rotating blades 11 while maintaining the predetermined angle α. Then, when the fixed end of the rod-shaped pulp sheet 1 approaches the rotating blade 11, the fixed state is released. When defibrating in this manner, the defibrating portion (contact portion) at the tip of the rod-shaped pulp sheet 1 also vibrates due to the rotational pressure of the blades 11, and thus the angle α may vary somewhat. The variation range of the angle α may be a range of about ± 10 ° from the initial set angle α.

  The treatment in the first step is not limited as long as the cellulose fiber aggregate can be sufficiently defibrated. For example, the point in time when the cellulose fiber aggregate has been visually confirmed to be cottony can be confirmed. The end of Since the average peripheral speed and stirring time of the rotating blades change depending on the type, shape, size, input amount, and the like of the cellulose fiber aggregate, the time point when it changes to cotton as described above may be used as a reference. Is preferred.

  By applying such a defibrating method in the first step, for example, as in the invention of Japanese Patent Application Laid-Open No. 2007-84713, the defibrated state is further improved as compared with the case where the pulp sheet is defibrated as it is with a mixer. In addition, dispersibility when mixed with a thermoplastic resin is also improved.

  The cellulose fiber defibrated by applying the treatment method of the first step can be used as it is as the component (B) of the present invention, but the following steps can also be carried out.

  Subsequent to the first step, the second and third steps of the first defibrating method described above are performed to obtain a solidified product (granulated product) containing cellulose fibers and a thermoplastic resin. Can be used as component (B).

  The content of the component (B) in the cleaning agent resin composition of the present invention (the content of only the fibrillated cellulose fibers) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and 20 to 20%. 60 mass% is still more preferable.

<(C) component>
The cleaning resin composition of the present invention can contain an anionic surfactant as the component (C) as necessary.

  The component (C), an anionic surfactant, is a component for improving detergency and discharge properties, and is an alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, having 8 to 20 carbon atoms. From α-olefin sulfonates, alkane sulfonates, alkyl or alkenyl ether carboxylates, α-sulfo fatty acid salts, α-sulfo fatty acid esters, alkali metal salts of saturated or unsaturated fatty acids having 12 to 20 carbon atoms, etc. One or more selected may be mentioned.

  As the anionic surfactant, an anionic surfactant containing 50% by mass or more of alkanesulfonic acid or a salt thereof is particularly preferable.

  The alkanesulfonic acid or a salt thereof is preferably one 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 alkanesulfonic acid or salt thereof used as the component (C) contributes to the expression of self-excretion.

[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, alkali metal salts of saturated or unsaturated fatty acids having 12 to 20 carbon atoms, and the like.

  (C) 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%.

  As for content of the anionic surfactant of (C) component, 0.1-20 mass parts is preferable with respect to a total of 100 mass parts of (A) component and (B) component, More preferably, it is 0.1-0.1 mass part. It is 10 mass parts, More preferably, it is 0.1-5 mass parts. If the blending amount exceeds 20 parts by weight, it will not be mixed with the polyolefin resin of component (A), and the detergency and discharge effects of less than 0.1 part by weight will be reduced.

<Other ingredients>
The cleaning resin composition of the present invention further contains a component selected from (D) an alkylene glycol fatty acid ester, (E) an organic phosphorus compound, (F) a polyhydric alcohol, and (G) a metal soap as necessary. be able to.

  Examples of the (D) component alkylene glycol fatty acid ester include ester compounds of alkylene glycol such as ethylene glycol, propylene glycol, tetramethylene glycol, and hexamethylene glycol and fatty acids having 12 to 22 carbon atoms.

  As the organic phosphorus compound of component (E), those having at least one ester oxygen atom bonded to a phosphorus atom are preferable. Since the component (E) has a high dissolving power against scorching, it is a component that contributes to the expression of foreign matter removability.

  The polyhydric alcohol as component (F) is an acyclic or cyclic compound having a plurality of hydroxyl groups bonded thereto. Examples of the component (F) 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.

  (G) As a metal soap of a component, the salt of a C6-C22 fatty acid and metals (Mg, Li, Zn, Ca, Al, Sn, etc.) is preferable.

  The cleaning resin composition of the present invention is used for washing a molding machine for melting and kneading a thermoplastic resin and molding, and for washing a molding machine for kneading and molding a ceramic powder and a binder resin. can do.

  In the case of applying the cleaning resin composition of the present invention for cleaning of a molding machine for melting and kneading a thermoplastic resin, the glass fiber, artificial mineral fiber, metal, and the like are further added to improve the cleaning performance. Fiber and wollastonite can be included.

  When the cleaning resin composition of the present invention is applied for cleaning a molding processing machine for kneading and molding ceramic powder and a binder resin, it does not substantially contain a component that becomes an impurity of the ceramic material. Desirably, for example, it does not contain components such as glass fiber, artificial mineral fiber, metal fiber and wollastonite, and it does not contain other inorganic compounds or metals. The term “substantially not containing” means that the content of the inorganic compound or metal in the composition is 1% by mass or less, and the content is preferably 0.5% by mass or less. Preferably it is 0.1 mass%, and it is especially preferable that it is 0 mass%.

  The cleaning resin composition of the present invention is prepared 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. To manufacture.

  When cleaning a molding machine (for example, an injection molding machine or an extrusion molding machine) using the cleaning resin composition of the present invention, the cleaning resin composition is set with the cylinder temperature of the molding machine set to 200 ° C. or lower. Feed and wash.

  After washing the molding machine for kneading and forming the ceramic powder and the binder resin using the cleaning resin composition of the present invention, the nitride or carbide ceramic powder and the binder resin are kneaded and molded. In some cases, an oxidant can be blended together with ceramic powder and a binder resin and kneaded. Nitride-based or carbide-based ceramics are sintered in a non-oxygen atmosphere (nitrogen atmosphere, etc.), but the cellulose fibers contained in the cleaning resin composition remain in the molding machine and are mixed into the molded body. In that case, it will remain without being burned. However, by mixing an oxidizing agent in the raw material, the remaining cellulose fibers can be burned and removed even when sintered in a non-oxygen atmosphere.

Production Example 1 [Production of Component (B-1)]
[First step]
Heat the heater mixer (upper blade: kneading type, lower blade: high circulation / high load, with heater and thermometer, capacity 20L, Henschel mixer FM20C / I, manufactured by Mitsui Mining Co., Ltd.) to 140 ° C. Various cellulose fiber products shown in Table 1 were charged and stirred at an average peripheral speed of 50 m / sec.

  After about 2 minutes, the cellulose fiber product changed to cotton. In Comparative Examples 1 and 2, the next second step was performed immediately after completion of the cellulose fiber charging.

[Second step]
Subsequently, after introducing polypropylene into the heater mixer, stirring was continued at an average peripheral speed of 50 m / sec. The power of the motor at this time was 2.5 kW. When the mixer temperature reached 120 ° C., MPP was added and stirring was continued.

  At about 10 minutes, power started to increase. One minute later, the power increased to 4 kW, so the peripheral speed was reduced to a low speed of 25 m / sec. Furthermore, the power started to increase again due to the continued low speed stirring. After 1 minute and 30 lines from the start of low speed rotation, the current value reached 5 kW, so the outlet of the mixer was opened and discharged to the connected cooling mixer.

[Third step]
Cooling mixer [Rotating blade: Standard blade for cooling, with water cooling means (20 ° C) and thermometer, capacity 45L, product name cooler mixer FD20C / K, manufactured by Mitsui Mining Co., Ltd.) Start stirring at an average peripheral speed of 10m / sec. The stirring was terminated when the temperature in the mixer reached 80 ° C. By the treatment in the third step, the mixture of cellulose fibers and polypropylene was solidified, and a granulated product having a diameter of about several mm to 2 cm was obtained.

Production Example 2 [Production of Component (B-2)]
[First step]
Various cellulose fiber products shown in Table 1 were put into a defibrating machine (Turbo Industry Co., Ltd .; Turbo Mill T-250) and defibrated. Visually, it was confirmed that the fiber was completely defibrated. Operating conditions are 8300rpm. The processing capacity was about 20 kg / h.

[Second step]
Subsequently, after introducing polypropylene into the heater mixer, stirring was continued at an average peripheral speed of 50 m / sec. The power of the motor at this time was 2.5 kW. When the mixer temperature reached 120 ° C., MPP was added and stirring was continued.

  At about 10 minutes, power started to increase. One minute later, the power increased to 4 kW, so the peripheral speed was reduced to a low speed of 25 m / sec. Furthermore, the power started to increase again due to the continued low speed stirring. After 1 minute and 30 lines from the start of low speed rotation, the current value reached 5 kW, so the outlet of the mixer was opened and discharged to the connected cooling mixer.

[Third step]
Cooling mixer [Rotating blade: Standard blade for cooling, with water cooling means (20 ° C) and thermometer, capacity 45L, product name cooler mixer FD20C / K, manufactured by Mitsui Mining Co., Ltd.) Start stirring at an average peripheral speed of 10m / sec. The stirring was terminated when the temperature in the mixer reached 80 ° C. By the treatment in the third step, the mixture of cellulose fibers and polypropylene was solidified, and a granulated product having a diameter of about several mm to 2 cm was obtained.

  Using the obtained granulated product, extrusion molding was performed using a twin screw extruder to obtain a resin molded body of the present invention. The cylinder temperature was 190 ° C. Formability (kneading property, extrudability) using a twin screw extruder was good.

Production Example 3 [Production of (B-3) Component]
[First step]
Heat the heater mixer (upper blade: kneading type, lower blade: for high circulation / high load, with heater and thermometer, capacity 200L) to 140 ° C, and make the rod-shaped pulp sheet shown in Table 1 at a predetermined angle α. The mixture was put into a mixer (see FIG. 3) and stirred at an average peripheral speed of 50 m / sec. At about 3 minutes, the rod-like pulp sheet changed to cotton.

[Second step]
Subsequently, after introducing polypropylene into the heater mixer, stirring was continued at an average peripheral speed of 50 m / sec. The current value of the motor at this time was 30A. When the mixer temperature reached 120 ° C., MPP was added and stirring was continued.

  At about 10 minutes, power started to increase. After another minute, the current value increased to 50 A, so the peripheral speed was reduced to a low speed of 25 m / sec. Furthermore, the power started to increase again due to the continued low speed stirring. Since the current value reached 60 A after 1 minute and 30 lines from the start of low-speed rotation, the mixer was opened and discharged to the connected cooling mixer.

[Third step]
Cooling mixer [Rotating blade: Standard blade for cooling, with water cooling means (20 ° C) and thermometer, capacity 500L) Stirring was started at an average peripheral speed of 10m / sec and stirred when the temperature in the mixer reached 80 ° C. Ended. By the treatment in the third step, the mixture of cellulose fibers and polypropylene was solidified, and a granulated product having a diameter of about several mm to 2 cm was obtained.

  Using the obtained granulated product, extrusion molding was performed using a twin screw extruder to obtain a resin molded body of the present invention. The cylinder temperature was 190 ° C. Formability (kneading property, extrudability) using a twin screw extruder was good.

Reference Example 1, Examples 1 to 3 , Comparative Examples 1 to 2
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 used components, materials, and measurement methods in Examples and Comparative Examples are as follows.

(A) Component Polypropylene (J139, manufactured by Prime Polymer)
Acid-modified polypropylene (manufactured by Sanyo Chemical Industries, Yumex 1010)
(B) Component The component manufactured in Production Example 3 above.

Component (C) Sodium α-olefin sulfonate (trade name Luporan PB-800, manufactured by Lion Corporation)
Component (D) Propylene glycol monobehenate (trade name Riquemar PB-100, manufactured by Riken Vitamin Co., Ltd.)
(E) Component Triphenyl phosphate (Daihachi Chemical Industry Co., Ltd.)
Glass fiber: ECS-03-T-120 from Nippon Electric Glass Co., Ltd.
(1) Evaluation of detergency Using an injection molding machine ("Mitsubishi Injection Molding Machine 265 / 100MSII" manufactured by Mitsubishi Heavy Industries), 1 kg of the following leading resin was poured at a molding temperature of 175 ° C. Then, each composition of Table 1 was poured, and the detergency was evaluated by the amount used (kg) until the black color disappeared.

(Preceding resin)
What added carbon black so that it might become a 1 mass% density | concentration with respect to polypropylene (J139, prime polymer company make) was used.

(2) Presence or absence of combustion residue TG / DTA measurement of the composition after use for cleaning was performed to evaluate the amount of combustion residue.
Measurement conditions Apparatus: TG / DTA6200 manufactured by SII Nano Technology Co., Ltd.
Measurement atmosphere: Air 200ml / min
Measurement temperature: 30-580 ° C
Temperature increase rate: 20 ° C / min
Sample amount: 13-15mg

(A) is a perspective view of the cylindrical pulp sheet used at the 1st process of the fibrillation (3rd fibrillation method) of a cellulose fiber aggregate, (b) is a top view of (a). (A) is a perspective view of another form of a plate-like pulp sheet used in the first step of defibrating the cellulose fiber aggregate (third defibrating method), (b) is a plan view of (a), (C) is a top view of the plate-shaped pulp sheet of another form. The figure for demonstrating the fibrillation method of the 1st process of the fibrillation (3rd fibrillation method) of a cellulose fiber aggregate.

Claims (5)

A cleaning resin composition comprising (A) a thermoplastic resin , (B) cellulose fibers from which the cellulose fiber aggregate has been defibrated, and (C) an anionic surfactant .   The cellulose fiber in which the cellulose fiber aggregate of component (B) is defibrated is one in which the cellulose fiber and the thermoplastic resin are integrated, and the component (B) is mixed with the thermoplastic resin of component (A). The resin composition for washing | cleaning of Claim 1 which is what is done.   The cleaning resin composition according to claim 1 or 2, which is used for cleaning a molding machine for melt-kneading and molding a thermoplastic resin and may contain an inorganic compound or a metal.   The cleaning resin composition according to claim 1 or 2, which is used for cleaning a molding machine for kneading and forming ceramic powder and a binder resin, and does not substantially contain an inorganic compound and a metal.   It is a washing | cleaning method of the molding machine using the resin composition for washing | cleaning of any one of Claims 1-4, The cylinder temperature of a molding machine is set to 200 degrees C or less, The said resin composition for washing | cleaning Use a cleaning method.

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