CN106916341A - The manufacture method of acetate fiber promotor composition - Google Patents
The manufacture method of acetate fiber promotor composition Download PDFInfo
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- CN106916341A CN106916341A CN201610865255.3A CN201610865255A CN106916341A CN 106916341 A CN106916341 A CN 106916341A CN 201610865255 A CN201610865255 A CN 201610865255A CN 106916341 A CN106916341 A CN 106916341A
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- 239000000203 mixture Substances 0.000 title claims abstract description 115
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 17
- 229920006221 acetate fiber Polymers 0.000 title abstract 4
- 229920002301 cellulose acetate Polymers 0.000 claims abstract description 60
- 238000002156 mixing Methods 0.000 claims abstract description 43
- 239000004014 plasticizer Substances 0.000 claims abstract description 19
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 claims description 40
- 238000001816 cooling Methods 0.000 claims description 29
- 239000001087 glyceryl triacetate Substances 0.000 claims description 20
- 235000013773 glyceryl triacetate Nutrition 0.000 claims description 20
- 229960002622 triacetin Drugs 0.000 claims description 20
- 238000001125 extrusion Methods 0.000 claims description 17
- 238000000465 moulding Methods 0.000 claims description 5
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 claims description 3
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 claims description 3
- 239000001069 triethyl citrate Substances 0.000 claims description 3
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000013769 triethyl citrate Nutrition 0.000 claims description 3
- 238000007792 addition Methods 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 8
- 238000003756 stirring Methods 0.000 description 20
- 239000003381 stabilizer Substances 0.000 description 18
- 239000008188 pellet Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004898 kneading Methods 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000012760 heat stabilizer Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 101000837308 Homo sapiens Testis-expressed protein 30 Proteins 0.000 description 2
- 102100028631 Testis-expressed protein 30 Human genes 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- -1 etc.) Substances 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- WQNHWIYLCRZRLR-UHFFFAOYSA-N 2-(3-hydroxy-2,5-dioxooxolan-3-yl)acetic acid Chemical compound OC(=O)CC1(O)CC(=O)OC1=O WQNHWIYLCRZRLR-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to the manufacture method of acetate fiber promotor composition, problem of the invention is the manufacture method of the acetate fiber promotor composition for providing the manufacture material for turning into the products formed that flexibility is high and impact resistance is good.Therefore, the manufacture method of acetate fiber promotor composition of the invention includes：Relative to the mass parts of (A) cellulose acetate 100, do not include more than aromatic ring and the mass parts of plasticizer 20 of 200~450g/mol of molecular weight and mixed in addition (B) molecule, wherein, the total capacity of (A) composition and (B) composition is more than 10L, and relative to (A) composition, whole additions of (B) composition are added mixing several times by described in.
Description
Technical Field
The present invention relates to a method for producing a cellulose acetate composition which is a material for producing a molded article having flexibility and high impact resistance, and a method for producing the molded article.
Background
Cellulose acetate is generally used in the form of a composition comprising a plasticizer because of insufficient thermoplasticity.
In british patent No. 2489491, it is described that a water-soluble plasticizer can be added to a cellulose acetate composition up to 30 mass%, and 25 mass% or 20 mass% can be preferably added (page 10). In the examples, 10 mass% or 20 mass% of a plasticizer was added, but the actual amount used (total mass or total volume of cellulose acetate and triacetin) was not described in detail.
Examples 1 to 2 of jp 2002-a-060545 disclose that cellulose acetate 70 wt% and triacetin 30 wt% are fed to a twin-screw extruder and pelletized at 220 ℃, and examples 7 to 9 thereof disclose that cellulose acetate and triacetin are stirred in a henschel mixer at the ratio shown in table 3 and then a film is formed by the single-screw extruder. However, the actual amount used (total mass or total volume of cellulose acetate and triacetin) is not specified.
Disclosure of Invention
The present invention addresses the problem of providing a method for producing a cellulose acetate composition which is a material for producing a molded article having flexibility and high impact resistance, and a method for producing the molded article.
The present invention provides a method for producing a cellulose acetate composition and a method for producing a molded article, the method for producing a cellulose acetate composition comprising: 20 parts by mass or more of a plasticizer (B) having a molecular weight of 200 to 450g/mol and containing no aromatic ring in the molecule is added to 100 parts by mass of the cellulose acetate (A) and mixed, wherein the total volume of the component (A) and the component (B) is 10L or more, and the total amount of the component (B) to the component (A) is added and mixed in a plurality of portions.
The present invention also provides a method for producing a cellulose acetate composition and a method for producing a molded article, the method for producing a cellulose acetate composition comprising: the method for producing a cellulose acetate film, which comprises adding and mixing 20 parts by mass or more of a plasticizer (B) having a molecular weight of 200-450 g/mol and containing no aromatic ring in the molecule thereof, to 100 parts by mass of the cellulose acetate (A), wherein the total volume of the component (A) and the component (B) is 10L or more, comprises a1 st step of adding and mixing the entire amount of the component (B) to the component (A) in a mixer in a plurality of portions, and a2 nd step of supplying the composition obtained in the 1 st step to an extruder and performing extrusion molding, wherein in the 1 st step, a cooling step is provided between the plurality of addition and mixing steps.
Further, the present invention provides a method for producing a cellulose acetate composition and a method for producing a molded article, the method for producing a cellulose acetate composition comprising: the method for producing a cellulose acetate fiber comprises adding and mixing 20 parts by mass or more of a plasticizer (B) having a molecular weight of 200 to 450g/mol and not containing an aromatic ring in the molecule thereof with 100 parts by mass of the cellulose acetate (A), wherein the total volume of the component (A) and the component (B) is 10L or more, a first step of adding and mixing a part of the entire amount of the component (B) to the component (A) in a mixer 1 time or a plurality of times, and a second step of supplying the composition obtained in the first step to an extruder and performing extrusion molding, wherein the first step comprises a cooling step between the plurality of addition and mixing steps, and the second step comprises supplying the remaining amount of the component (B) to the extruder.
According to the production method of the present invention, even when the amount of the plasticizer to be added is increased, a composition having high fluidity and obtained by uniformly kneading cellulose acetate and the plasticizer can be obtained, and therefore, the molding workability of the composition by an extruder can be improved.
In addition, the physical properties of the composition molded by the extruder can be improved when the composition is injection molded.
Detailed Description
< method for producing cellulose acetate composition >
The cellulose acetate of the component (a) used in the production method of the present invention is a known cellulose acetate, and in the present invention, a cellulose acetate having a degree of substitution (degree of substitution of acetyl group) of 2.7 or less is preferable, and a cellulose acetate having a degree of substitution of 2 to 2.7 is more preferable.
The plasticizer having a molecular weight of 200 to 450g/mol, which does not contain an aromatic ring in the molecule of the component (B) used in the production method of the present invention, is preferably a component selected from triacetin (triacetin) (molecular weight 218g/mol), triethyl citrate (molecular weight 276g/mol), and acetyl tributyl citrate (molecular weight 402 g/mol).
In the production method of the present invention, the entire amount of the component (B) to be added is added and mixed in a plurality of times to the component (a).
In the production method of the present invention, the cellulose acetate composition can be produced by the 1 st production method and the 2 nd production method.
(1) Production method 1
The first production method is as follows:
it has the following components:
a1 st step of adding and mixing the entire amount of the component (B) to the component (A) in a mixer in a plurality of portions; and
a2 nd step of supplying the composition (intermediate composition) obtained in the 1 st step to an extruder and extruding the composition,
in the step 1, a cooling step is provided between the plurality of addition mixing steps.
In the step 1, the entire amount of the component (B) to be added is added to and mixed with the component (a) in a mixer in a plurality of portions.
When the addition and mixing are carried out in a plurality of times, the addition and mixing are preferably carried out 2 to 4 times, more preferably 2 times or 3 times.
When the component (B) is added in a plurality of times, the amount added in 1 time is preferably less than 20 parts by mass, more preferably 18 parts by mass or less, and still more preferably 15 parts by mass or less, relative to 100 parts by mass of the component (a).
(B) When the number of times of addition of the component (B) is n, the amount is preferably about 1/n per time. When the number of addition is 2, the addition is preferably carried out in 2 portions and about 1/2 amounts are added each time, and when the number of addition is 3, the addition is preferably carried out in 3 portions and about 1/3 amounts are added each time, but the amounts of addition may be different from one another.
The mixer is not particularly limited, and a drum mixer, a henschel mixer, a ribbon mixer, a kneader, or the like can be used.
The mixer is preferably a high-speed mixer capable of stirring and mixing at a rotational speed of 200r/min or more, preferably 400r/min or more, and more preferably 500r/min or more.
In the step 1, after the whole amount of the component (a) and a part amount of the component (B) are added to and mixed in the mixer, cooling is performed between the addition and mixing of the component (a) and the component (B) to be subsequently performed.
When the component (B) was added to the component (A) in 2 portions, cooling was performed 1 time, and when the component (B) was added to the component (A) in 3 portions, cooling was performed 2 times.
The cooling method can adopt the following steps: natural cooling (for example, leaving the mixer at a room temperature of 20 to 30 ℃), air-blowing cooling, or cooling by placing a condenser tube in contact with the periphery of the mixer and flowing water through the condenser tube.
When the natural cooling method is adopted as the cooling method, the mixing is stopped after the mixing is performed for 1 to 10 minutes, and the mixture is left for 20 to 50 minutes to cool.
The proportion of the component (B) to be added to the component (a) in the production method of the present invention is 20 parts by mass or more, preferably 25 to 45 parts by mass, more preferably 28 to 40 parts by mass, and still more preferably 30 to 40 parts by mass, based on 100 parts by mass of the component (a).
The total capacity of the component (a) and the component (B) used in the production method of the present invention is 10L or more, preferably 50L or more, and more preferably 100L or more.
Even if the ratio of the component (B) to the component (A) is in the above range, when the total volume of the components (A) and (B) is small (for example, 1L or less), the total amount is small, and therefore the production method of the present invention is not necessarily adopted, and a method of kneading directly with an extruder as in examples 1 and 2 of Japanese patent application laid-open No. 2002-060545, or a method of kneading with an extruder after mixing with a Henschel mixer as in examples 7 to 9 of the same document can be adopted.
However, if the total volume of the components (A) and (B) is 10L or more, it is difficult to produce a composition containing the components (A) and (B) in the above-mentioned addition ratio by the method described in the examples of Japanese patent application laid-open No. 2002-060545, as shown in comparative examples 1 to 3 of the present invention.
In the 2 nd step, the composition (intermediate composition) of the component (a) and the component (B) obtained in the 1 st step is supplied to an extruder and extrusion-molded.
In the 2 nd step, pellets may be formed by extrusion molding, or may be extrusion molded into a desired shape such as a film, a sheet, or a tube.
In the 1 st step or the 2 nd step, a known resin additive may be added as necessary within a range in which the problem of the present invention can be solved.
Known resin additives include: fillers, flame retardants, flame retardant aids, stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, light stabilizers, etc.), colorants, antistatic agents, lubricants, antiblocking agents, dispersants, antibacterial agents, and the like.
(2) No. 2 manufacturing method
The production method of the 2 nd embodiment is a method of:
it has the following components:
a1 st step of adding and mixing a part of the total amount of the component (B) to the component (A) in a mixer 1 time or a plurality of times; and
a2 nd step of supplying the composition (intermediate composition) obtained in the 1 st step to an extruder, kneading the composition and extruding the composition,
in the step 1, a cooling step is provided between the plurality of addition mixing steps,
in the 2 nd step, the remaining component (B) is supplied to the extruder.
In the step 1, a part of the total amount of the component (B) to be added is added to and mixed with the component (a) in a mixer 1 time or a plurality of times.
In the step 1, the component (B) is preferably added in an amount of 30 to 60% of the total amount of the component (B), more preferably 35 to 50%.
The total amount of component (B) added in step 1 is preferably less than 20 parts by mass, more preferably 18 parts by mass or less, and still more preferably 15 parts by mass or less, per 100 parts by mass of component (a).
When the mixture is added in a plurality of portions, the amount of 1/2 is preferably 2 times, and each portion is preferably added.
The mixer is not particularly limited, and a drum mixer, a henschel mixer, a ribbon mixer, a kneader, or the like can be used.
The mixer is preferably a high-speed mixer capable of stirring and mixing at a rotational speed of 200r/min or more, preferably 400r/min or more, and more preferably 500r/min or more.
In the 1 st step, the entire amount of the component (a) and a part of the component (B) are added to and mixed in a mixer.
When the component (B) was added and mixed to the component (A) in 2 portions, cooling was performed 1 time therebetween.
The cooling method can adopt the following steps: natural cooling (for example, leaving the mixer at a room temperature of 20 to 30 ℃), air-blowing cooling, or cooling by placing a condenser tube in contact with the periphery of the mixer and flowing water through the condenser tube.
When the natural cooling method is adopted as the cooling method, the mixing is stopped after the mixing is performed for 1 to 10 minutes, and the mixture is left for 20 to 50 minutes to cool.
The proportion of the component (B) to be added to the component (a) in the production method of the present invention is 20 parts by mass or more, preferably 25 to 45 parts by mass, more preferably 28 to 40 parts by mass, and still more preferably 30 to 40 parts by mass, based on 100 parts by mass of the component (a).
The total capacity of the component (a) and the component (B) used in the production method of the present invention is 10L or more, preferably 50L or more, and more preferably 100L or more.
Even if the ratio of the component (B) to the component (A) is in the above range, when the total volume of the components (A) and (B) is small (for example, 1L or less), the total amount is small, and therefore the production method of the present invention is not necessarily adopted, and a method of kneading directly with an extruder as in examples 1 and 2 of Japanese patent application laid-open No. 2002-060545, or a method of kneading with an extruder after mixing with a Henschel mixer as in examples 7 to 9 of the same document can be adopted.
However, if the total volume of the components (A) and (B) is 10L or more, it is difficult to produce a composition containing the components (A) and (B) in the above-mentioned addition ratio by the method described in the examples of Japanese patent application laid-open No. 2002-060545, as shown in comparative examples 1 to 3 of the present invention.
In the 2 nd step, the composition of the component (a) and the component (B) (intermediate composition) obtained in the 1 st step and the remaining amount of the component (B) are supplied to an extruder and extrusion-molded.
(B) The balance of the components may be supplied to the extruder together with the composition (intermediate composition) of the components (a) and (B) obtained in the step 1, but is preferably added from the middle of the extruder (near the middle position).
In the 2 nd step, pellets may be formed by extrusion molding, or may be extrusion molded into a desired shape such as a film, a sheet, or a tube.
In the 1 st step or the 2 nd step, a known resin additive may be added as necessary within a range in which the problem of the present invention can be solved.
Known resin additives include: fillers, flame retardants, flame retardant aids, stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, light stabilizers, etc.), colorants, antistatic agents, lubricants, antiblocking agents, dispersants, antibacterial agents, and the like.
(method of producing molded article)
The method for producing a molded article of the present invention is a method for producing a desired molded article from the cellulose acetate composition by a known resin molding method such as injection molding or press molding after producing the composition by the above-described production method 1 or 2.
The molded article obtained by the production method of the present invention is, for example, a molded article selected from the group consisting of a sheet, a film, a plate, a tube and a rod.
The molded article obtained by the production method of the present invention has high impact resistance, and therefore can be used as a part or a cover in the fields of OA/home electric appliances, electric/electronic appliances, communications equipment, sanitary, transportation vehicles such as automobiles, housing-related fields such as furniture and building materials, and miscellaneous goods.
Further, the molded article obtained by the production method of the present invention is also high in flexibility, and therefore, is suitable for use in applications where it is in direct contact with a human.
Preferred embodiments of the present invention are described below.
<1>
A method of making a cellulose acetate composition comprising:
adding and mixing 20 parts by mass or more of (B) a plasticizer having a molecular weight of 200 to 450g/mol and containing no aromatic ring to 100 parts by mass of (A) cellulose acetate,
the total volume of the component (A) and the component (B) is 10L or more,
the whole amount of the component (B) is added to the component (A) in a plurality of portions.
<2>
A method of making a cellulose acetate composition comprising:
adding and mixing 20 parts by mass or more of (B) a plasticizer having a molecular weight of 200 to 450g/mol and containing no aromatic ring to 100 parts by mass of (A) cellulose acetate,
the total volume of the component (A) and the component (B) is 10L or more,
the manufacturing method comprises: a1 st step of adding and mixing the entire amount of the component (B) to the component (a) in a mixer in a plurality of portions; and a2 nd step of supplying the composition obtained in the 1 st step to an extruder and performing extrusion molding,
in the step 1, a cooling step is provided between the plurality of addition mixing steps.
<3>
The production method of the above <1> or <2>, wherein the plurality of times is 2 to 4 times, preferably 2 or 3 times.
<4>
The production method according to any one of the above <1> to <3>, wherein the amount of the component (B) added per 1 time is less than 20 parts by mass, preferably 18 parts by mass or less, and more preferably 15 parts by mass or less with respect to 100 parts by mass of the component (A) in the plurality of times, and the amount of the component added may be different from one time to another.
<5>
The production method according to any one of <1> to <4>, wherein the plurality of times is n times, and the amount of the component (B) added for each 1 time is about 1/n.
<6>
A method of making a cellulose acetate composition comprising:
adding and mixing 20 parts by mass or more of (B) a plasticizer having a molecular weight of 200 to 450g/mol and containing no aromatic ring to 100 parts by mass of (A) cellulose acetate,
the total volume of the component (A) and the component (B) is 10L or more,
the manufacturing method comprises: a1 st step of adding and mixing a part of the total amount of the component (B) to the component (a) 1 time or a plurality of times in a mixer; and a2 nd step of supplying the composition obtained in the 1 st step to an extruder and performing extrusion molding,
in the above step 1, when the addition mixing step is carried out a plurality of times, a cooling step is provided between the plurality of times,
in the step 2, the remaining amount of the component (B) is supplied to an extruder.
<7>
The production method of the above <6>, wherein in the step 1, the component (B) is added in an amount of 30 to 60%, preferably 35 to 50%, of the total amount of the component (B).
<8>
The production method of the above <6> or <7>, wherein the total amount of the component (B) added in the 1 st step is less than 20 parts by mass, preferably 18 parts by mass or less, and more preferably 15 parts by mass or less, relative to 100 parts by mass of the component (A).
<9>
The production methods of <6> to <8> wherein the component (B) in the step 1 is added and mixed 2 times.
<10>
The production methods of the above <6> to <9>, wherein in the 2 nd step, the remaining amount of the component (B) is supplied to the extruder together with the composition (intermediate composition) of the component (a) and the component (B) obtained in the 1 st step, or is added from the middle of the extruder (near the intermediate position).
<11>
The production method according to any one of the above <1> to <10>, wherein the cooling method is a natural cooling method in which the mixer is left in a gas atmosphere at a temperature of 20 to 30 ℃ at room temperature, a forced air cooling method, or a method in which a condenser pipe is disposed in contact with the periphery of the mixer and water is passed through the condenser pipe to cool the mixer.
<12>
The production method of the above <11>, wherein the natural cooling method is a cooling method in which mixing is stopped after 1 to 10 minutes of mixing, and the mixture is left standing for 20 to 50 minutes.
<13>
The production method according to any one of <1> to <12>, wherein the ratio of the component (B) to the component (A) is: the amount of the component (B) is preferably 25 to 45 parts by mass, more preferably 28 to 40 parts by mass, and still more preferably 30 to 40 parts by mass, based on 100 parts by mass of the component (A).
<14>
The production method according to any one of the above <1> to <13>, wherein a total volume of the component (A) and the component (B) is preferably 50L or more, more preferably 100L or more.
<15>
The production process according to any one of the above <1> to <14>, wherein in the 1 st step or the 2 nd step, if necessary, a resin additive such as a filler, a flame retardant aid, a stabilizer (an antioxidant, an ultraviolet absorber, a heat stabilizer, a light resistance agent, or the like), a colorant, an antistatic agent, a lubricant, an antiblocking agent, a dispersant, or an antibacterial agent is added.
<16>
The production method according to any one of <1> to <15>, wherein the mixer is a high-speed mixer capable of stirring and mixing at a rotation speed of 200r/min or more, preferably 400r/min or more, and more preferably 500r/min or more.
<17>
The production method according to any one of the above <1> to <16>, wherein the component (B) is selected from triacetin, triethyl citrate, and acetyl tributyl citrate.
<18>
A method for producing a molded article, comprising: a process for producing a cellulose acetate composition by the production method according to any one of <1> to <17>, and
and a step of molding the cellulose acetate composition.
<19>
The method for producing a molded article according to the above <18>, wherein the molded article is selected from the group consisting of a sheet, a film, a plate, a cylinder and a rod.
Examples
< ingredients used >
(A) Cellulose acetate
L-50, degree of substitution 2.5, degree of viscosity-average polymerization 180, manufactured by Daicel
(B) Plasticizer
Trade name "Triacetin DRA 150" (liquid), molecular weight 218, (manufactured by Daicel corporation)
(others)
Stabilizer 1: trade name "Irgafos 168", manufactured by BASF Japan (strain)
Stabilizer 2: trade name "Adekacizer O-130P" manufactured by ADEKA
Stabilizer 3: citric acid anhydride, manufactured by Kishida Chemical Co., Ltd
Titanium oxide: "Ti-Pure R-103", manufactured by DuPont
Example 1
Cellulose acetate compositions shown in table 1 were produced.
(step 1: step a 1)
Cellulose acetate of the component (A) shown in Table 1, stabilizer 1 and stabilizer 3 were added to a high-speed mixer (super mixer "SWV-50" manufactured by Kawata, capacity of stirring tank 50L), and stirring was performed at 510r/min for 1 minute.
Thereafter, while stirring with a high-speed mixer, a partial amount (15 parts by mass) of triacetin of the component (B) and the stabilizer 2 were supplied for 5 minutes by using a shower head. The triacetin as the component (B) and the stabilizer 2 are used as a material obtained by mixing them in advance.
Thereafter, the stirring was stopped, and the mixture was left at room temperature (20 to 25 ℃) for about 30 minutes. As a result, the temperature inside the mixture reached 40 ℃ to 35 ℃ or lower.
Thereafter, stirring was performed for 15 seconds.
(step 1: step a 2)
Then, the remaining amount (15 parts by mass) of triacetin of the component (B) was added by using a shower head while stirring with a high-speed mixer.
(B) After the addition of the triacetin as the component (a), the mixture was further stirred for 15 seconds to obtain a composition (intermediate composition). The composition (intermediate composition) is a dry powdery substance and can be easily taken out from the high-speed mixer.
The total volume of the components (A) and (B) was 15L (about 6 kg).
(step 2)
Next, the composition taken out of the high-speed mixer was supplied to a main feeder of an extruder, extruded into a strand-like shape, and then cooled and cut to produce pellets (pellets of a cellulose acetate composition).
(extrusion Molding conditions)
An extruder: TEX30 α (L/D ═ 42) (total 12 barrels)
Discharge amount (Q): 15kg/h
Rotational speed (Ns): 200r/min
Barrel temperature: 200 ℃ and 180 DEG C
Die temperature: 250 deg.C
Examples 2 and 3
Cellulose acetate compositions shown in table 1 were produced.
(step 1: step a 1)
Cellulose acetate of the component (A) shown in Table 1, stabilizer 1 and stabilizer 3 were added to a high-speed mixer (super mixer "SWV-50" manufactured by Kawata, capacity of stirring tank 50L), and stirring was performed at 510r/min for 1 minute.
Thereafter, while stirring with a high-speed mixer, a partial amount of triacetin of the component (B) (15 parts by mass in each of examples 2 and 3) and the stabilizer 2 were supplied for 5 minutes by using a shower head. The triacetin as the component (B) and the stabilizer 2 are used as a material obtained by mixing them in advance.
Thereafter, the stirring was stopped, and the mixture was left at room temperature (20 to 25 ℃) for about 30 minutes. As a result, the temperature inside the mixture reached 40 ℃ to 35 ℃ or lower.
Thereafter, stirring was performed for 15 seconds.
(step 1: step a 2)
Thereafter, while stirring with a high-speed mixer, the remaining amount of triacetin of the component (B) was added for 5 minutes by using a shower head (10 parts by mass in example 2 and 15 parts by mass in example 3).
(step 1: step a 3)
Thereafter, the remaining amount of triacetin of the component (B) was added by using a shower head for 5 minutes while stirring with a high-speed mixer (10 parts by mass in each of examples 2 and 3).
(B) After the addition of the triacetin as the component (a), the mixture was further stirred for 15 seconds to obtain a composition (intermediate composition). The composition (intermediate composition) is a dry powdery substance and can be easily taken out from the high-speed mixer.
(step 2)
Next, the composition taken out of the high-speed mixer was supplied to a hopper of an extruder in the same manner as in example 1, extruded into a strand-like shape, and then cooled and cut to produce pellets (pellets of a cellulose acetate composition).
Comparative examples 1 and 2
Cellulose acetate compositions shown in table 1 were produced.
(step 1: step a 1)
Cellulose acetate of the component (A) shown in Table 1, stabilizer 1 and stabilizer 3 were added to a high-speed mixer (super mixer manufactured by Kawata, "SWV-50" 50L), and the mixture was stirred at 510r/min for 1 minute.
Thereafter, the entire amount of triacetin of the component (B) and the stabilizer 2 were supplied for 5 minutes by using a shower head while stirring with a high-speed mixer. The triacetin as the component (B) and the stabilizer 2 are used as a material obtained by mixing them in advance.
Thereafter, the stirring was stopped, and the mixture was left at room temperature (20 to 25 ℃) for about 30 minutes. As a result, the temperature inside the mixture reached 40 ℃ to 35 ℃ or lower.
Thereafter, stirring was carried out for 15 seconds to obtain a composition for comparison (intermediate composition). The above-mentioned composition (intermediate composition) was formed into a block as a whole.
In addition, in the same manner as in examples 1 to 3, the composition taken out of the high-speed mixer was supplied to the hopper (main feeder) of the extruder, but the solid matter in the form of a block was caught in the hopper of the extruder and could not be fed into the extruder.
(defective fraction)
In examples 1 to 3 and comparative examples 1 and 2, the intermediate composition obtained by stirring with a high-speed mixer was added to a sieve having a mesh size of 4mm, and vibration was applied to the sieve by hand for 5 minutes. The percentage (% by mass) of the remaining intermediate composition which did not pass through the sieve until the end was determined as the fraction defective.
[ Table 1]
The intermediate compositions of examples 1 to 3 were in a dry powdery state, and therefore, the subsequent extrusion molding by an extruder was also easy.
The intermediate compositions of comparative examples 1 and 2 were in the form of a block, and therefore, in order to perform extrusion molding by an extruder, a pulverization operation by a pulverizer was required. Further, after the pulverization, a mixture of various large lumps was obtained, and a part of the mixture was pulverized.
Examples 4 to 7
(step 1: step a 1)
The first step (step a 1) was carried out in the same manner as in examples 1 to 3 using the components shown in Table 2 to obtain a composition (intermediate composition).
In the step 1, only the amount of the component (B) which is half or less of the total amount added is added, and therefore the composition (intermediate composition) is a dry powdery substance and the operation of taking out the composition from the high-speed mixer is easy.
(step 2)
The composition obtained in step 1 was supplied to a main feeder of an extruder, extruded into a strand-like shape, and then cooled and cut to produce pellets (pellets of a cellulose acetate composition). In the 2 nd step, the remaining amount of the component (B) was added from the 6 th cylinder.
(extrusion Molding conditions)
An extruder: TEX30 α (L/D ═ 42) (total 12 barrels)
Discharge amount (Q): 15kg/h
Rotational speed (Ns): 200r/min
Barrel temperature: 200 ℃ and 180 DEG C
Die temperature: 250 deg.C
Comparative example 3
Extrusion molding was attempted by supplying all the components shown in Table 2 from a hopper (main feeder) of a direct extruder, but cellulose acetate and a plasticizer were not uniformly mixed, and the thermoplastic property was insufficient to form a block. Therefore, it was not extruded from the extruder.
Pellets of the compositions of examples 4 to 7 were supplied to an injection molding machine, and after injection molding of the ISO multipurpose test pieces, the pellets were used for evaluation tests.
(conditions of injection Molding)
Temperature of the cylinder: 220 deg.C
Temperature of the die: 50 deg.C
(tensile nominal strain)
The tensile nominal strain of the test piece was measured at a speed of 50mm/min based on ISO527 (tensile strength unit: MPa, tensile nominal strain unit:%).
(flexural modulus of elasticity)
The measurement was carried out based on ISO178 (unit: MPa).
(Charpy impact strength)
Charpy impact strength (kJ/m) was determined on the basis of ISO179/1eA2) (unit: KJ/m)2)。
[ Table 2]
The intermediate compositions of examples 4 to 7 were in a dry powdery state, and therefore, the subsequent extrusion molding by an extruder was also easy. Comparative example 3 could not be extrusion molded.
Further, the injection-molded article is also excellent in mechanical properties and also high in flexibility because the amount of the plasticizer is increased, and for example, when a material molded into a tubular shape is touched with a finger, the material feels soft and comfortable.
Industrial applicability
The composition obtained by the method for producing a cellulose acetate composition of the present invention can give a molded article having high flexibility and good impact resistance.
Therefore, the composition can be used not only as parts and covers in the fields of OA/home electric appliances, electric/electronic fields, communication equipment, sanitary fields, transportation vehicles such as automobiles, housing-related fields such as furniture and building materials, and miscellaneous goods fields, but also in applications where the composition is directly in contact with humans.
Claims (8)
1. A method of making a cellulose acetate composition comprising:
adding and mixing 20 parts by mass or more of (B) a plasticizer having a molecular weight of 200 to 450g/mol and containing no aromatic ring to 100 parts by mass of (A) cellulose acetate,
wherein,
the total volume of the component (A) and the component (B) is 10L or more,
the whole amount of the component (B) is added to the component (A) in a plurality of portions.
2. A method of making a cellulose acetate composition comprising:
adding and mixing 20 parts by mass or more of (B) a plasticizer having a molecular weight of 200 to 450g/mol and containing no aromatic ring to 100 parts by mass of (A) cellulose acetate,
wherein,
the total volume of the component (A) and the component (B) is 10L or more,
the manufacturing method comprises:
a1 st step of adding and mixing the whole amount of the component (B) to the component (A) in a mixer in a plurality of portions, and
a2 nd step of supplying the composition obtained in the 1 st step to an extruder and performing extrusion molding,
in the step 1, a cooling step is provided between the plurality of addition mixing steps.
3. A method of making a cellulose acetate composition comprising:
adding and mixing 20 parts by mass or more of (B) a plasticizer having a molecular weight of 200 to 450g/mol and containing no aromatic ring to 100 parts by mass of (A) cellulose acetate,
wherein,
the total volume of the component (A) and the component (B) is 10L or more,
the manufacturing method comprises:
a1 st step of adding and mixing a part of the total amount of the component (B) to the component (A) 1 time or a plurality of times in a mixer, and
a2 nd step of supplying the composition obtained in the 1 st step to an extruder and performing extrusion molding,
in the step 1, a cooling step is provided between the plurality of addition mixing steps,
in the step 2, the remaining amount of the component (B) is supplied to an extruder.
4. The method for producing a cellulose acetate composition according to claim 2 or 3, wherein the mixer is a high-speed mixer capable of mixing at a rotation speed of 200r/min or more.
5. The method for producing a cellulose acetate composition according to any one of claims 1 to 4, wherein the component (B) is selected from the group consisting of: triacetin, triethyl citrate, acetyl tributyl citrate.
6. The method for producing a cellulose acetate composition according to any one of claims 1 to 5, wherein the amount of the component (B) added is 25 to 45 parts by mass with respect to 100 parts by mass of the component (A).
7. A method for producing a molded article, comprising:
a process for producing a cellulose acetate composition by the production method according to any one of claims 1 to 6, and
and a step of molding the cellulose acetate composition.
8. The method for producing a molded article according to claim 7, wherein the molded article is selected from the group consisting of: sheet, film, plate, cartridge, rod.
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| CN111116997A (en) * | 2019-12-30 | 2020-05-08 | 南通醋酸纤维有限公司 | Biodegradable pipe and preparation method and application thereof |
| CN111134357A (en) * | 2019-12-30 | 2020-05-12 | 南通醋酸纤维有限公司 | A high-density hollow nozzle rod and its composite nozzle rod |
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| CN111546740A (en) * | 2019-12-30 | 2020-08-18 | 南通醋酸纤维有限公司 | Biodegradable paper-plastic composite structure and preparation method thereof |
| CN112424277A (en) * | 2018-08-09 | 2021-02-26 | 株式会社大赛璐 | Cellulose acetate composition and molded article |
| CN112795055A (en) * | 2020-12-30 | 2021-05-14 | 南通醋酸纤维有限公司 | Degradable pipe and preparation method and application thereof |
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| JP7162366B1 (en) | 2021-07-26 | 2022-10-28 | 株式会社 ネクアス | Cellulose acetate composition and method for producing the same |
| JP7162367B1 (en) * | 2021-07-26 | 2022-10-28 | 株式会社 ネクアス | Cellulose acetate composition production method and its production system |
| JP2023131404A (en) * | 2022-03-09 | 2023-09-22 | 株式会社 ネクアス | Cellulose acetate composition and method for producing the same |
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| CN111546740B (en) * | 2019-12-30 | 2023-12-19 | 南通醋酸纤维有限公司 | Biodegradable paper-plastic composite structure and preparation method thereof |
| CN112795055A (en) * | 2020-12-30 | 2021-05-14 | 南通醋酸纤维有限公司 | Degradable pipe and preparation method and application thereof |
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