CN101275009B - Resin composition, resin compact, production method of resin compact and recycling method of resin compact - Google Patents
Resin composition, resin compact, production method of resin compact and recycling method of resin compact Download PDFInfo
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- CN101275009B CN101275009B CN2008100883678A CN200810088367A CN101275009B CN 101275009 B CN101275009 B CN 101275009B CN 2008100883678 A CN2008100883678 A CN 2008100883678A CN 200810088367 A CN200810088367 A CN 200810088367A CN 101275009 B CN101275009 B CN 101275009B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention provides a resin composition, a resin forming body, producing method and recycling method. The resin composition includes: an aliphatic polyester; a second polymer compound having a glass transition point higher than a glass transition point of the aliphatic polyester; and aluminum phosphate.
Description
Technical field
The present invention relates to the working method and the method for recycling thereof of resin combination, resin-formed body, resin-formed body.
Background technology
Consider from point of view of environment protection, cause concern in recent years as biological material such as Biodegradable resins such as aliphatic polyesters.
About using the resin-formed body of Biodegradable resin, known promising reinforcement flame retardant resistance and mixed the resin-formed body of fire retardant therein.Said fire retardant comprises for example broad varietys such as phosphorus type flame retardant, brominated flame retardant, chlorine based flame retardant, nitrogen compound based flame retardant and silicone fire retardant.In addition; Said phosphorus type flame retardant comprises; For example; Aluminate or phosphate, melamine phosphate, red phosphorus, SULPHOSUCCINIC ACID ESTER, condensed phosphoric acid esters, halogen-containing condensation organophosphate and melamine phosphate (referring to, for example the spy opens the 2004-027079 communique, the spy opens 2003-192929 communique and Te Kai 2004-190025 communique; Terminology used here " spy opens " meaning is " a still unexamined disclosed Japanese patent application ").
Summary of the invention
The working method and the method for recycling thereof that the purpose of this invention is to provide resin combination, resin-formed body and said resin-formed body are even said resin combination still can satisfy high-caliber physical strength and flame retardant resistance simultaneously containing under the situation of phosphorus type flame retardant.
(1) a kind of resin combination, said resin combination comprises:
Aliphatic polyester;
Second macromolecular compound, the second-order transition temperature of said second macromolecular compound is higher than the second-order transition temperature of said aliphatic polyester; With
Aluminate or phosphate.
(2) resin combination described in above-mentioned (1), wherein, the ratio A/B between the quality B of the quality A of said aliphatic polyester and said second macromolecular compound is 0.3～1.1.
(3) resin combination described in above-mentioned (1) or (2), said resin combination also comprises elastomerics.
(4) like each described resin combination in above-mentioned (1) to (3), said resin combination also comprises:
Elastomerics with nucleocapsid structure, said nuclear comprises divinyl, and said shell comprises acrylic acid or the like.
(5) like each described resin combination in above-mentioned (1) to (4), wherein, said aliphatic polyester is a POLYACTIC ACID.
(6) like each described resin combination in above-mentioned (1) to (5), wherein, said second macromolecular compound is a polycarbonate.
(7) a kind of resin-formed body, said resin-formed body comprise each described resin combination in above-mentioned (1) to (6).
(8) resin-formed body described in above-mentioned (7), said resin-formed body comprises fibrous aliphatic polyester phase.
(9) a kind of method of producing resin-formed body, said method comprises:
The temperature of each described resin combination is under the condition below 230 ℃ in making above-mentioned (1) to (6), with said resin combination injection molding.
(10) a kind of method for recycling of resin-formed body, said method comprises:
Pulverising step, said pulverising step are to pulverize the resin-formed body described in above-mentioned (7) or (8);
Heating steps, said heating steps are under the temperature of the fusing point that is lower than said aliphatic polyester, the crushed products that heating obtains in said pulverising step; With
Forming step, said forming step are to obtain resin-formed body with the crushed products moulding after the said heating.
(11) method described in above-mentioned (10),
Wherein, said pulverising step is with said resin-formed body freezing and pulverizing, and said forming step is to obtain resin-formed body with the crushed products injection molding behind the said heating steps.
The invention of above-mentioned (1) has following effect: even containing under the situation of phosphorus type flame retardant, compare with the resin combination that does not have this formation, said resin combination also can satisfy high-caliber physical strength and flame retardant resistance simultaneously.Especially, utilize the invention of above-mentioned (1) can obtain high-caliber physical strength, and consider when phosphorus type flame retardant can cause the aliphatic polyester hydrolysis thereby not necessarily be fit to the purposes of needs physical strength that this is very beyond thought effect.
The invention of above-mentioned (2) has the effect of the invention effect that can realize above-mentioned (1) effectively: even containing under the situation of phosphorus type flame retardant; Compare with the resin combination that does not have this formation; Said resin combination also can satisfy high-caliber physical strength and flame retardant resistance simultaneously, especially can make flame retardant resistance stronger.
The invention of above-mentioned (3) has the effect of the invention effect that can realize above-mentioned (1) or (2) effectively: even containing under the situation of phosphorus type flame retardant; Compare with the resin combination that does not have this formation; Said resin combination also can satisfy high-caliber physical strength and flame retardant resistance simultaneously, especially can make impact strength stronger.
The invention of above-mentioned (4) has the effect of the invention effect that can realize above-mentioned (1) effectively: even containing under the situation of phosphorus type flame retardant; Compare with the resin combination that does not have this formation; Said resin combination also can satisfy high-caliber physical strength and flame retardant resistance simultaneously, especially can make impact strength stronger.
The invention of above-mentioned (5) has the effect of the invention effect that can realize above-mentioned (1) effectively: even containing under the situation of phosphorus type flame retardant; Compare with the resin combination that does not have this formation, said resin combination also can satisfy high-caliber physical strength and flame retardant resistance simultaneously.
The invention of above-mentioned (6) has the effect of the invention effect that can realize above-mentioned (1) effectively: even containing under the situation of phosphorus type flame retardant; Compare with the resin combination that does not have this formation; Said resin combination also can satisfy high-caliber physical strength and flame retardant resistance simultaneously, especially can make impact strength stronger.
The invention of above-mentioned (7) has following effect: even containing under the situation of phosphorus type flame retardant, compare with the resin combination that does not have this formation, said resin combination also can satisfy high-caliber physical strength and flame retardant resistance simultaneously.Especially, utilize the invention of above-mentioned (7) can obtain high-caliber physical strength, and consider when phosphorus type flame retardant can cause the aliphatic polyester hydrolysis thereby not necessarily be fit to the purposes of needs physical strength that this is very beyond thought effect.
The invention of above-mentioned (8) has the effect of the invention effect that can realize above-mentioned (7) effectively: even containing under the situation of phosphorus type flame retardant; Compare with the resin combination that does not have this formation; Said resin combination also can satisfy high-caliber physical strength and flame retardant resistance simultaneously, especially can make flame retardant resistance stronger.
The invention of above-mentioned (9) has following effect: even containing under the situation of phosphorus type flame retardant, compare with the resin combination that does not have this formation, also can obtain to satisfy simultaneously the resin-formed body of high-caliber physical strength and flame retardant resistance effectively.
The invention of above-mentioned (10) has following effect: even containing under the situation of phosphorus type flame retardant; Compare with the resin combination that does not have this formation, also can make the resin-formed body that can satisfy high-caliber physical strength and flame retardant resistance simultaneously obtain recycling effectively.
The invention of above-mentioned (11) has the effect that can strengthen following effect more: even containing under the situation of phosphorus type flame retardant; Compare with the resin combination that does not have this formation, also can make the resin-formed body that can satisfy high-caliber physical strength and flame retardant resistance simultaneously obtain recycling effectively.
Description of drawings
To carry out detailed description to illustrative embodiments of the present invention based on following accompanying drawing, wherein:
Fig. 1 is the outward appearance skeleton view that comprises like the imaging device of a described housing of illustrative embodiments of resin-formed body of the present invention; With
Fig. 2 is for showing the Photomicrograph in the transverse section of the resin-formed body (ISO multi-usage test film) of gained among the embodiment 1.
Embodiment
Below, preferred illustrative embodiments of the present invention is described in detail, in case of necessity with reference will be made to the accompanying drawings.
(resin combination)
The resin combination of first illustrative embodiments of the present invention comprises second macromolecular compound and the aluminate or phosphate that aliphatic polyester, its second-order transition temperature are higher than the second-order transition temperature of said aliphatic polyester.
Said aliphatic polyester has no particular limits, but preferably has the aliphatic polyester of biological degradability, more preferably derived from the aliphatic polyester of plant.Its specific examples comprises POLYACTIC ACID, gathers (3-hydroxybutyric acid), poly-succinic fourth diester, gather hexanodioic acid fourth diester, poly-succinic second diester, gather hexanodioic acid second diester, the poly-succinic propylene diester, gather hexanodioic acid propylene diester, the own diester of poly-succinic and polyhexamethylene adipate.In these aliphatic polyesters, when considering the balance between flame retardant resistance and the physical strength (especially impact strength), preferred POLYACTIC ACID.Can use a kind of in these aliphatic polyesters or combination to use wherein two or more separately.Also can use the multipolymer of two or more formation in these aliphatic polyesters.
The weight-average molecular weight of said aliphatic polyester is preferably 5,000～200, and 000, more preferably 10,000～120,000.The number-average molecular weight of said aliphatic polyester is preferably 3,000～100, and 000, more preferably 5,000～70,000.If the weight-average molecular weight of said aliphatic polyester and number-average molecular weight all are lower than above-mentioned lower limit separately, impact strength trends towards deficiency, otherwise, if it surpasses the above-mentioned upper limit, cause formability not enough easily.
The content of said aliphatic polyester has no particular limits, but is based on the total amount of said resin combination, is preferably 20～80 quality %, more preferably 21～70 quality %.If the content of said aliphatic polyester is lower than above-mentioned lower limit, thereby recycling property has the trend of deterioration to cause carrying capacity of environment to increase, otherwise, if it surpasses the above-mentioned upper limit, then there is the insufficient tendency of physical strength or thermotolerance.
Said second macromolecular compound has no particular limits; As long as its second-order transition temperature is higher than the second-order transition temperature of said aliphatic polyester, its specific examples comprises that polycarbonate, polyarylester, aromatic polyester, polymeric amide, polyimide, polymethylmethacrylate, PS, polyoxymethylene, ppe and acrylonitrile-butadiene-styrene resin second-order transition temperatures such as (ABS resins) is higher than the material of the second-order transition temperature of said aliphatic polyester.In these materials, with regard to the better effect that obtains the enhancing impact strength, optimization polycarbonate and ABS resin, more preferably polycarbonate.Can use a kind of in these second macromolecular compounds separately, perhaps combination is used wherein two or more.Also can the multipolymer of two or more formation in these macromolecular compounds be used as said second macromolecular compound.
Subsidiary mentioning, the second-order transition temperature of the said aliphatic polyester or second macromolecular compound are the following second-order transition temperatures of measuring.Promptly; Utilize differential calorimeter (differential scanning calorimeter DSC-60; Make by Shimadzu Seisakusho Ltd.) under the intensification condition of 10 ℃/min, record thermography, will be through being defined as said second-order transition temperature from the midrange (Tgm) between two shoulder numerical value (shouldervalue) of the peak mensuration that glass transition produced with tangent method.
The second-order transition temperature of the said aliphatic polyester and second macromolecular compound has no particular limits; As long as the relation between this two the second-order transition temperature satisfies above-mentioned condition; But the second-order transition temperature of said aliphatic polyester is preferably-30～80 ℃; More preferably 0～70 ℃, the second-order transition temperature of said second macromolecular compound is preferably 0～300 ℃, more preferably 70～160 ℃.And the difference of the second-order transition temperature of the second-order transition temperature of said aliphatic polyester and said second macromolecular compound is preferably 5～250 ℃, more preferably 10～100 ℃.Especially; If this temperature difference is less than 5 ℃, the effect of enhancing thermotolerance, shock-resistance and the flame retardant resistance that should be provided by said second macromolecular material descends easily, otherwise; If this temperature difference surpasses 250 ℃, owing to causing being difficult to the molding temperature in that the difference of uniform temp current downflow property is excessive.
The weight-average molecular weight and the number-average molecular weight of said second macromolecular compound have no particular limits; As long as the second-order transition temperature of said second macromolecular compound is higher than the second-order transition temperature of said aliphatic polyester, but the weight-average molecular weight of said second macromolecular compound is preferably 5,000～100; 000; More preferably 10,000～80,000.The number-average molecular weight of said second macromolecular compound is preferably 2,500～40, and 000, more preferably 3,000～30,000.If the weight-average molecular weight of said second macromolecular compound and number-average molecular weight all are lower than above-mentioned lower limit separately, the insufficient trend of the impact strength of causing is arranged, otherwise, if it surpasses the above-mentioned upper limit, cause formability not enough easily.The aliphatic polyester in the said resin combination and second macromolecular compound weight-average molecular weight and number-average molecular weight separately is meant the said aliphatic polyester that records through GPC or the weight-average molecular weight and the number-average molecular weight of second macromolecular compound.About GPC, can use the HLC-8220GPC that makes by Tosoh Corp..In addition; During separately weight-average molecular weight and number-average molecular weight of the aliphatic polyester in measuring said resin combination and second macromolecular compound; With test sample be dissolved in the deuterochloroform to concentration be 0.1 quality %; And, can measure the weight-average molecular weight and the number-average molecular weight of the said aliphatic polyester or second macromolecular compound through GPC after separating from this solution.
Based on the total amount of said resin combination, the content of said second macromolecular compound is preferably 10～70 quality %, more preferably 35～65 quality %.If the content of said second macromolecular compound is lower than above-mentioned lower limit, thermotolerance reduces easily, otherwise if it surpasses the above-mentioned upper limit, mold temperature uprises, and the physical strength of gained resin-formed body is tended to reduce.
Phosphorus content in the said aluminate or phosphate is preferably more than the 20 quality %, more preferably more than the 27 quality %, further more preferably more than the 29 quality %.If the phosphorus content in the said aluminate or phosphate is lower than 20 quality %, then tend to be difficult to satisfy simultaneously flame retardant resistance and physical strength (especially impact strength).In addition, the phosphorus content in the said aluminate or phosphate is preferably below the 50 quality %, more preferably below the 40 quality %, further more preferably below the 30 quality %.If the phosphorus content in the said aluminate or phosphate surpasses 50 quality %, thereby the decomposition of the said aliphatic polyester or second macromolecular compound is quickened in the phosphoric acid volatilization when kneading or moulding, and this tends to cause physical strength to reduce.Here, the phosphorus content in the said aluminate or phosphate is meant phosphoric shared mass ratio in the quality of whole aluminate or phosphates.Can use method mensuration phosphorus contents such as fluorescent X-ray method.
The preferred content of selecting said aluminate or phosphate is so that the phosphorus content in the said resin combination is more than the 1 quality % based on the total amount of said resin combination.If the phosphorus content in the said resin combination is lower than 1 quality %, then tend to be difficult to satisfy simultaneously flame retardant resistance and physical strength (especially impact strength).The also preferred content of selecting said aluminate or phosphate is so that the phosphorus content in the said resin combination is below the 20 quality %.If the phosphorus content in the said resin combination surpasses 20 quality %, not only in forming step, can produce phosphorous gas, also can be like this when temperature rises in environment for use, and because this situation, said resin combination may excessively heat up.
The resin combination of this illustrative embodiments comprises following material as neccessary composition: aliphatic polyester, its second-order transition temperature are higher than second macromolecular compound and the aluminate or phosphate of the second-order transition temperature of said aliphatic polyester; Therefore can satisfy high-caliber physical strength and flame retardant resistance, heat-resisting enhance property in addition simultaneously.Here; The inventor thinks that the effect of strengthening flame retardant resistance ascribes the following fact to: the second-order transition temperature of said second macromolecular compound is higher than the second-order transition temperature of said aliphatic polyester; When mediating, have low flow and compare with said aliphatic polyester, thus can the dispersiveness of reinforced aluminum phosphoric acid salt in said resin combination in processes such as the kneading of said resin combination, moulding.More particularly, according to thinking that reason is following.Aliphatic polyester with high workability becomes liquid; And second macromolecular compound with low flow becomes solid or semisolid; Said aliphatic polyester flows and surrounds said second macromolecular compound; Thereby, in mediating product or resin-formed body, can form and contain aliphatic polyester mutually and second macromolecular compound incompatible zone mutually when the resin combination that is in this state uniaxial extension and take out or when carrying out moulding at high temperature.At this moment, said aliphatic polyester mutually with the second macromolecular compound thing be separately mutually fibrous, and along a plurality of incompatible zones of pre-determined direction (for example, draw direction) formation.On the other hand, aluminate or phosphate has optimum solvation in the character of said aliphatic polyester in mutually.Therefore; The fibrous aliphatic polyester that contains aluminate or phosphate can form in mediating product or resin-formed body mutually continuously; And the dispersiveness of aluminate or phosphate in said kneading product or resin-formed body obtained gratifying reinforcement, and the result can strengthen flame retardant resistance.
In addition, the quality of supposing said aliphatic polyester is A, and the quality of said second macromolecular compound is B, and the ratio A/B between these two kinds of compositions is preferably 0.3～1.1, more preferably 0.5～0.9.If A/B is less than 0.3; Above-mentioned contain fibrous aliphatic polyester mutually with second macromolecular compound incompatible zone mutually in; Aliphatic polyester almost can not form external phase mutually and become intermittently phase; This makes the dispersed not enough of the aluminate or phosphate that contained during aliphatic polyester mutually, and the result causes flame retardant resistance to trend towards weakening.And, thereby aluminate or phosphate aggegation in narrow zone causes in this narrow zone, forming the space defective easily, and physical strength reduces easily.On the other hand, if A/B surpasses 1.1, compare the second macromolecular compound phase; The area of aliphatic polyester phase becomes excessive; So that be difficult to form this and two be fibrous incompatible zone mutually, this makes the dispersed not enough of aluminate or phosphate, and the result causes flame retardant resistance to tend to weaken.In this case, the physical strength of aliphatic polyester is reflected on the physical strength of resin combination easily, and the physical strength of resin combination is tended to reduce.
The resin combination of this illustrative embodiments has aforesaid excellent properties, and is practical, and its reason is, when keeping high-caliber flame retardant resistance, can reduce the content of fire retardant.For example, in the resin combination that does not have above-mentioned formation, in order in the flame retardant resistance test, to reach UL-V2; In a large number (for example must contain; About 30 quality %) fire retardant, but according to this embodiment also can reach UL-V2 even the content of aluminate or phosphate is reduced to about 3 quality %.
The resin combination of this illustrative embodiments also can contain the fire retardant (hereinafter being referred to as " other fire retardants " for simplicity) except that said aluminate or phosphate, only otherwise can get final product by impact effect.The instance of said other fire retardants comprises phosphorus type flame retardant, brominated flame retardant, silicone fire retardant and the inorganic particle based flame retardant except that said aluminate or phosphate.In above-mentioned other fire retardants, consider the enhancing solvent resistance, be preferred by the compound with following formula (I) expression:
[wherein, Ar
1Expression has substituting group or does not have substituent arylidene, has substituting group or do not have substituent biphenylene, perhaps has substituting group or do not have substituent bisphenol type arylidene, Ar
2And Ar
3Expression independently of one another has substituting group or does not have substituent aryl, R
1And R
2Expression independently of one another contains having substituting group or not having substituent alkyl or have substituting group or do not have substituent aryl of 1～10 carbon atom.
Specific examples by the compound of formula (I) expression comprises by following structural formula (I-1) and the compound of (I-2) representing.In addition, commercially available prod (for example PX-200 (by Daihachi Chemical Industry Co., Ltd. make)) compound of also can be used as by following structural formula (I-1) expression uses.Similarly, commercially available prod (for example CR-741 (by Daihachi Chemical Industry Co., Ltd. make)) compound of also can be used as by following structural formula (I-2) expression uses.
See from the angle that satisfies flame retardant resistance and physical strength simultaneously; Based on the total amount of said resin combination, the content of said other fire retardants is preferably below the 10 quality %, more preferably below the 5 quality %; And; Based on described aluminate or phosphate, the content of said other fire retardants is preferably 5 quality %～50 quality %, more preferably 10 quality %～40 quality %.
The resin combination of this illustrative embodiments can only comprise aliphatic polyester, second macromolecular compound and aluminate or phosphate; But preferably also contain following elastomerics; For example have the nuclear and the core/shell structure of shell elastomerics, have the elastomerics of no shell structure and have the elastomerics (hereinafter being referred to as " elastomerics " sometimes simply) of the branched structure of being with side chain; This is because can satisfy the physical strength and the flame retardant resistance of higher level simultaneously; Especially, can further strengthen impact strength.Instance with elastomeric nuclear of core/shell structure comprises divinyl, vinylbenzene, TEB 3K, vinyl cyanide and vinyl-acetic ester.The instance of said shell comprises alkyl acrylate, alkyl methacrylate and ZGK 5.Can come suitably to select these materials according to the kind of the said aliphatic polyester or second macromolecular compound.Can modify the solution that perhaps in solvent, makes through the material dissolves that said nuclear is immersed by said shell and it is modified through graft polymerization to the nuclear in the said elastomerics with core/shell structure.Said elastomeric median size is preferably 0.5～50 μ m, more preferably 2～20 μ m.If said elastomeric median size is less than 0.5 μ m; The strengthening effect of impact strength tends to deficiency, otherwise, if it surpasses 50 μ m; Elastomerics dispersed in resin combination reduces easily, elastomerics introduced resin combination make the impact strength deterioration sometimes on the contrary.
The resin combination of this illustrative embodiments can also comprise such as additive and catalyzer such as filler, inhibitor, toughener, expanding material, weather resisting agent, toughner and hydrolysis agent in case of necessity.Based on the total amount of said resin-formed body, the content of these additives and catalyzer all is preferably below the 10 quality %.
Said filler preferably has the filler of 3～20 length-to-diameter ratio.Specifically, for example natural stuffing with length-to-diameter ratio of 3～20 such as mestha, bamboo fibers, mica, walnut shell and coffee shell is suitable.When this use has the filler of 3～20 length-to-diameter ratio, can when taking into account physical strength and flame retardant resistance, strengthen Rockwell hardness and surface impacts intensity.The inventor thinks; The reason that can obtain this effect is; When the weight-average molecular weight of second macromolecular compound during less than the weight-average molecular weight of aliphatic polyester; Filler with length-to-diameter ratio of 3～20 can make this aliphatic polyester crystallization, and second macromolecular compound will surround this needle crystal product.
Other preferred embodiments of said filler comprise at least a material that is selected from carbon nanotube and soccerballene (fullerene).When using carbon nanotube or soccerballene, can when taking into account physical strength and flame retardant resistance, strengthen hydrolytic resistance.The inventor thinks that the reason that can obtain this effect is that carbon nanotube or soccerballene can react with the end group of aliphatic polyester, second macromolecular compound and aluminate or phosphate.
Consider from the angle that satisfies high-caliber physical strength and flame retardant resistance simultaneously, particularly, consider that from the angle of further enhancing impact strength the resin combination of this embodiment preferably contains the hydrolysis agent.Said hydrolysis agent comprises that the active hydrogen in this resin combination is had reactive compound, its specific examples comprise carbodiimide, such as isocyanate compounds such as vulcabond and triisocyanate, such as multifunctional hydroxy compounds such as hydroxyl and dihydroxy compound, such as polyfunctional carboxylic acids such as dicarboxylicacid and tricarboxylic acid and ester derivative thereof, such as multi-functional amine compounds Yi such as diamines and triamines Ji the oxazoline compounds.Wherein, consider that from the angle that strengthens humidity resistance carbodiimide and isocyanate compound are preferred.In addition, carbodiimide can with such as resin melt kneading such as aliphatic polyesters, its favourable part is, can obtain the fully high hydrolysis effect that prevents through a small amount of interpolation.
The resin combination of this embodiment can advantageously provide has 2.5kJ/m
2The resin-formed body of above but shellfish impact strength.But shellfish impact strength used herein is meant the value that records through the described method of ISO-179 standard.When the resin-formed body of the housing that is formed for electronics, this embodiment resin combination because can guarantee 2.5kJ/m
2Above but shellfish impact strength is so be specially suitable.
(resin-formed body and working method thereof)
The resin-formed body of second illustrative embodiments of the present invention comprises the resin combination of first illustrative embodiments.Attach and mention that the constituent of the resin-formed body of second illustrative embodiments is identical with the constituent of the resin combination of first illustrative embodiments, omits its repeated description at this.
The working method of the resin-formed body of this illustrative embodiments has no particular limits, and the example comprises injection molding, injection compression molding, extrusion molding, blow molding, calendering formation, coating, cast and dip-coating.In these methods, with regard to the usage quantity that reduces solvent, preferred injection molding and injection compression molding.
In the working method of the resin-formed body of this illustrative embodiments, preferably before making said resin combination moulding with the resin combination thorough mixing.When producing said resin-formed body through injection molding; The resin combination of first illustrative embodiments or constituent can be used as ball shape compound packs in the injection moulding machine, perhaps said resin combination or constituent is mediated and the direct injection moulding.Condition of molding has no particular limits; As long as can obtain to use the effect of the resin combination of first illustrative embodiments; But, for example in injection molding situation, the preferred settings condition is so that the temperature of resin combination described in the injection moulding machine is below 230 ℃; More preferably 185～215 ℃, this is to contain fibrous aliphatic polyester phase and second macromolecular compound incompatible zone mutually because can form effectively.
The resin-formed body of second illustrative embodiments can be used for multiple use.The specific examples of the purposes of said resin-formed body comprises electrical equipment/electronic unit, its housing, automotive component, such as material of construction such as wallpaper and exterior material, tableware, sheet material, cushioning material and fiber.Wherein, preferred electron equipment unit and housing, this is because electronic equipment part and housing need have high impact strength, high flame retardant and excellent hydrolytic resistance, and usage quantity is big, can guarantee to reduce the good result of carrying capacity of environment.Here used housing is meant the housing of household electrical appliance, container, electronics etc.Especially, owing to need excellent weathering resistance therefore to be suitable for casting of electronic device.
When passing through to use the resin forming body structure housing of this illustrative embodiments; Resin-formed body with this illustrative embodiments can be constructed housing integral body, but need preferably use the resin forming body structure of this illustrative embodiments such as the part of performances such as surface impacts intensity.In this case, the part except that above-mentioned part can be used the resin forming body structure outside the resin-formed body of this illustrative embodiments.More particularly; Outside at stamping machine, duplicating machine, facsimile recorder etc.; The outside such as protecgulum, bonnet, paper feed pallet, paper delivery pallet, pleten, outlet parts, and the preferred resin forming body structure of the inner part etc. of outlet with this illustrative embodiments.On the other hand, inner cap, toner Cartridge, handle box etc. can be used resin-formed body or other resin forming body structures of this illustrative embodiments.
Fig. 1 is the figure that shows an illustrative examples of imaging device, and said imaging device comprises the housing with the resin forming body structure of this illustrative embodiments, and Fig. 1 is the outward appearance skeleton view when the front of said imaging device is seen.Among Fig. 1, imaging device 100 comprises and is positioned at agent set 110 forward protecgulum 120a and 120b.But protecgulum 120a and 120b are opening/closings, so that operator can operate the inside of this device.Because this structure, operator can replenish toning agent after toning agent consumption, change the handle box that uses up, and remove the paper that blocks when perhaps in device, paperboard occurring.Fig. 1 has shown the device when being in protecgulum 120a and 120b open mode.
Top at agent set 110; Setting operation panel 130; Operation through operator is such as paper size and various condition entries this operating panels relevant with graphicinformation such as number of pages, and the duplicating glass (copy glass) 132 that is placed with original copy to be read on it is set.Agent set 110 also comprises at an upper portion thereof can be with the original copy automatic transport to the master copy automatic conveying device 134 that duplicates on the glass 132.In addition, agent set 110 comprises image read-out, and said image read-out is used to scan the view data that is placed on the original image on the duplicating glass 132 and obtains to represent original image.View data through control part will utilize this image read-out to obtain is sent into image-generating unit.Image read-out and control part are contained in the housing 150 of a part that constitutes agent set 110.In addition, in housing 150, also be provided with detachable handle box 142 as image-generating unit.Can install or remove handle box 142 through rotating operation bar 144.
In the bottom of agent set 110, paper receiver 140a, 140b and 140c are set.In addition, in agent set 110, also arranged a plurality of transfer rollers, formed the drive access that can the paper in the paper receiver be sent to the image-generating unit that is positioned at this receiver top thus by the pair of rolls formation.Be utilized near the paper-fetching mechanism that disposes the drive access end and can the paper in each paper receiver be taken out and be transported to drive access page by page.Be provided with the paper feed pallet 136 that is used for manual paper feeding in the side of agent set 110, paper also can be sent into from this pallet.
Successively the paper that is formed with image through image-generating unit on it is transferred between two fixing rollers against each other and that supported by the housing 152 of a part that constitutes agent set 110 subsequently, discharges then outside the agent set 110.In agent set 110, at the opposition side of a side that is provided with paper feed pallet 136 a plurality of paper delivery pallets 138 are set, the paper after the imaging is drained in these pallets.
In imaging device 100, vibration when stress when protecgulum 120a and 120b often bear such as opening/closing and impact, imaging and the loads such as heat that in imaging device, produce.The loads such as heat that produce in vibration when the impact when handle box 142 often bears such as attaching/detaching, imaging and the imaging device.The loads such as heat that produce in vibration when housing 150 often bears such as imaging with housing 152 and the imaging device.Therefore, the resin-formed body of this illustrative embodiments is suitable as protecgulum 120a and the 120b of imaging device 100, outside, housing 150 and the housing 152 of handle box 142.
(method for recycling of resin-formed body)
The method for recycling of the resin-formed body of the 3rd illustrative embodiments of the present invention comprises the pulverising step of the resin-formed body of pulverizing second illustrative embodiments; At the heating steps that heats the crushed products that in said pulverising step, obtains under the temperature of the fusing point that is lower than said aliphatic polyester with the forming step of the crushed products moulding behind the heating steps with the acquisition resin-formed body.
In said pulverising step; The method that is used to pulverize said resin-formed body has no particular limits; But consider fully suppressing the above-mentioned ability of pulverizing in the damage in fibrous aliphatic polyester phase and second macromolecular compound incompatible zone mutually that contains, be fit to adopt freezing and pulverizing.The size of the resin-formed body after the pulverizing is preferably 0.5mm～7mm in median size.
In heating steps, as stated, the temperature the when crushed products that obtains in the pulverising step is heated is the temperature that is lower than the fusing point of said aliphatic polyester, is preferably below 180 ℃ more preferably 100～160 ℃.Owing to carried out heating steps under these conditions, the crystallization of aliphatic polyester phase is quickened, and with regard to the selfreparing of physical strength or keeping, this is preferred.And the crushed products behind the heating steps is easy to become spherical shape, can prevent it satisfactorily and bite screw rod or tusk in the machines such as injection moulding machine, and with regard to production efficiency, this also is preferred.
About the forming method in the forming step; Can be employed in illustrative various forming methods in the working method of resin-formed body of second illustrative embodiments, but forming step is preferably with the crushed products injection molding behind the heating steps to obtain the step of resin-formed body.
Condition of molding in the forming step has no particular limits; As long as the character as the resin-formed body of recycling raw material can fully be kept in the resin-formed body after regeneration; But, for example when injection molding, injection temperature is preferably 170～230 ℃; Die temperature is preferably 20～100 ℃, is preferably 5～120 seconds cooling time.
Embodiment
Will be through the present invention being described in more detail with reference to embodiment and comparative example, but the present invention is not limited to these embodiment.
Embodiment 1～22 and comparative example 1～3
In embodiment 1～22 and comparative example 1～3, the raw material shown in table 1～6 is packed in the twin screw kneader (TEM58SS is made by Toshiba Machine Co. Ltd) and when barrel temperature is 220 ℃, mediated to obtain resin combination (formulation).With Coinjection molding apparatus (NEX150E; By Nissei Plastic Industrial Co.; Ltd. make) barrel temperature be 220 ℃ when being 30 ℃ with die temperature with the resin combination injection molding that is obtained; Obtained ISO multi-usage test film thus and (met the requirement of ISO527 tension test and ISO178 flexure test, the thickness of part of detecting: 4mm, width: 10mm) with UL94V test film (thickness is two kinds of test films of 0.8mm and 1.6mm).In embodiment 20～22, to make ISO multi-usage test film and UL94V test film with embodiment 1～3 identical mode, the barrel temperature when difference is these test film injection moldings becomes 230 ℃, and die temperature becomes 30 ℃.Subsidiary mentioning; Aliphatic polyester as the compsn that is used for embodiment; The weight-average molecular weight of LACEA H-100 (being made by Mitsui Chemical Inc.) is 45000, and the weight-average molecular weight of Terramac TE4000 (being made by Unitika Ltd.) is 60000.
Subsequently, preparation ISO multi-usage dumb bell specimen, and measure respectively based on but shellfish (Charpy) impact strength of ISO179 with based on the heat-drawn wire of ISO75.When measuring heat-drawn wire, the two kind conditions of loading of using have been set as 0.45MPa and 1.80MPa.In addition, use the UL94V test film to carry out the UL-V test according to the method for UL-94.The gained result lists in table 1～6.
Observe the fracture xsect of the ISO multi-usage test film that obtains among the embodiment 1 with 7,500 times ratio of enlargement through tunnel type electron microscope (TEM) (H-7500 is made by Hitachi, Ltd).Fig. 2 has shown the Photomicrograph that is obtained.As can beappreciated from fig. 2; Contain fibrous aliphatic polyester phase (POLYACTIC ACID phase; The white portion that is present in the regional A of Fig. 2) with second macromolecular compound mutually the formation in the incompatible zone of (the polycarbonate phase is present in the black part of the area B of Fig. 2) obtained affirmation.
Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
Embodiment 23～43 and comparative example 4～6
In embodiment 23～43 and comparative example 4～6; At Coinjection molding apparatus (NEX150E; By Nissei Plastic Industrial Co., Ltd. makes) in, with the corresponding relation of the resin combination of embodiment 23 corresponding embodiment 1 and the resin combination of embodiment 24 corresponding embodiment 2 etc.; Use the resin combination of embodiment 1～22 and comparative example 1～3 to carry out injection molding respectively, to produce outlet inner part and outlet outside parts as the internal part of colored compounding machine.When producing the outlet inner part, condition of molding is set to 220 ℃ of barrel temperatures and 40 ℃ of die temperatures, and when producing outlet outside portion part, condition of molding is set to 210 ℃ of barrel temperatures and 30 ℃ of die temperatures.In all cases, the shape and size of said outlet inner part and outlet outside parts all with by the outlet inner part of the color copy machine Apeos 450 of Fuji-Xerox's manufactured with export outside the shape and size of parts identical.
About the outlet inner part, measure the number of the short formed body (formed body during resin combination underfilling mould) in 100 continuously shaped unit.And, with the ISO178 method outlet inner part is carried out otch and handle, and mensuration has welding portion and do not have welding portion but shellfish impact strength separately.In addition, carry out the UV-V test and estimate the flame retardant resistance that exports inner part with the UL94 method.
In addition, use the grinding and cutting machine will export the inner part freezing and pulverizing, after 100 ℃ of these crushed products of heating 4 hours, with as above identical condition under carry out injection molding and export inner part to produce.Said pulverizing, heating and moulding repeat 5 times, and the but shellfish impact strength of measuring the outlet inner part then in the same manner as described above is to estimate recycling property.
Whether about outlet outside parts, detecting by an unaided eye exists outer the contraction (cooling during owing to moulding causes resin combination to shrink and produces the state that part caves in; Sometimes produce pattern from the teeth outwards).In addition; Top being positioned over the outlet outside parts on the platform vertically disposes the long right cylinder of 1.3m; Through being that 50mm, quality are that the steel ball of 500g drops into from said cylindrical top it is fallen to these outlet outside parts with diameter, estimating whether to exist in the parts outside the outlet after impacting with steel ball and break.The gained result lists in table 7～12.Subsidiary mentioning; In this test, to through above-mentioned moulding and before test, do not carry out pretreated outlet outside parts (referring to " not thermal treatment " hurdle in table 7～12) and outside 4 hours outlet of 100 ℃ of thermal treatment parts (in referring to table 7～12 " thermal treatment " hurdle) estimate.
Table 7
Table 8
Table 9
Table 10
Table 11
Table 12
Embodiment 44
To obtain ISO multi-usage test film and UL-94V test film with embodiment 1 identical mode; Difference is; When preparation resin combination (formulation); The condensed phosphoric acid esters (PX200, by Daihachi Chemical Industry Co., Ltd. makes) of 2.0 mass parts is further joined in the raw material.
Subsequently, respectively the test film that obtains among embodiment 1 and the embodiment 44 is carried out the evaluation of relevant solvent resistance or oil-proofness.Particularly; Solvent shown in the following table 13 or oil are coated on the ISO multi-usage test film; And in the environment of 25 ℃ and 55% humidity; Simultaneously, through to exerting pressure, the central part of test film is applied 0.5% strain with the surface of the surface opposite that is coated with solvent with the two ends fixed of test film.After 20 hours, estimate and whether break.The result lists in table 13.
Table 13
Embodiment 1 embodiment 44
Whether water is denied
Virahol takes place not
The benzene that breaks takes place not
(KF8009 is taken place not by Shin-Etsu amino modified oil
Silicone makes)
(Tellus 68, taken place not by Showa Shell for MO
Sekiyu K.K. makes)
(SUNPRESS S304 is taken place not by Sugimura press oil
Chemical Industrial Co., Ltd. makes)
It is in order to explain and purpose of description that above description to illustrative embodiments of the present invention is provided.Its intention does not lie in precise forms that exhaustive the present invention discloses or the present invention is limited to the precise forms that is disclosed.Obviously, many improvement and variation are conspicuous to those skilled in the art.Selecting and describing these illustrative embodiments is of the present invention various embodiments and the various improvement projects that are applicable to desired specific end use in order to explain principle of the present invention and practical use thereof to greatest extent, to make others skilled in the art to understand thus.Scope of the present invention is limited claim and equivalent thereof.
Claims (10)
1. resin combination, said resin combination comprises:
Aliphatic polyester;
Second macromolecular compound, the second-order transition temperature of said second macromolecular compound is higher than the second-order transition temperature of said aliphatic polyester; With
Aluminate or phosphate,
Wherein, the ratio A/B between the quality B of the quality A of said aliphatic polyester and said second macromolecular compound is 0.3～1.1.
2. resin combination as claimed in claim 1, said resin combination also comprises elastomerics.
3. resin combination as claimed in claim 1, said resin combination also comprises:
Elastomerics with nucleocapsid structure, said nuclear comprises divinyl, and said shell comprises acrylic acid or the like.
4. resin combination as claimed in claim 1, wherein, said aliphatic polyester is a POLYACTIC ACID.
5. resin combination as claimed in claim 1, wherein, said second macromolecular compound is a polycarbonate.
6. resin-formed body, said resin-formed body comprises the described resin combination of claim 1.
7. resin-formed body as claimed in claim 6, said resin-formed body comprise fibrous aliphatic polyester phase.
8. method of producing resin-formed body, said method comprises:
Be under the condition below 230 ℃ in the temperature that makes the described resin combination of claim 1, with said resin combination injection molding.
9. the method for recycling of a resin-formed body, said method comprises:
Pulverising step, said pulverising step are to pulverize the described resin-formed body of claim 6;
Heating steps, said heating steps are the crushed products that in said pulverising step, obtains in heating under the temperature of the fusing point that is lower than said aliphatic polyester; With
Forming step, said forming step are to obtain resin-formed body with the crushed products moulding behind the said heating steps.
10. method as claimed in claim 9, wherein, said pulverising step is with said resin-formed body freezing and pulverizing, said forming step is to obtain resin-formed body with the crushed products injection molding behind the said heating steps.
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| JP2007092711 | 2007-03-30 | ||
| JP2007-092711 | 2007-03-30 | ||
| JP2007-321186 | 2007-12-12 | ||
| JP2007321186A JP2008274222A (en) | 2007-03-30 | 2007-12-12 | Resin composition, resin-molded article, production method and recycling method for resin-molded article |
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| KR101225948B1 (en) | 2008-12-19 | 2013-01-24 | 제일모직주식회사 | Polylactic acid/polycarbonate resin composition |
| KR101277718B1 (en) | 2008-12-19 | 2013-06-24 | 제일모직주식회사 | Polylactic acid/polycarbonate resin composition |
| JP2011021928A (en) * | 2009-07-14 | 2011-02-03 | Fuji Electric Holdings Co Ltd | Method for selecting halogen-based flame retardant-containing resin for mold forming |
| JP5893848B2 (en) * | 2011-05-13 | 2016-03-23 | 帝人株式会社 | Aromatic polycarbonate resin composition and molded article thereof |
| EP2828323A4 (en) * | 2012-03-20 | 2015-09-09 | Rhodia Operations | Flame retardant polymer compositions |
| JP6446707B2 (en) * | 2015-03-13 | 2019-01-09 | 三菱ケミカル株式会社 | Filament for three-dimensional printer molding and method for producing resin molded body |
| CN108431131B (en) * | 2015-12-22 | 2021-06-01 | 出光兴产株式会社 | Polycarbonate resin composition and molded article thereof |
| JP7178671B2 (en) * | 2020-12-17 | 2022-11-28 | 群馬県 | Manufacturing method for recycled plastic pellets |
| US20230081057A1 (en) * | 2021-08-30 | 2023-03-16 | Western Digital Technologies, Inc. | Housings for electronic devices and memory devices |
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| US6833075B2 (en) * | 2002-04-17 | 2004-12-21 | Watervisions International, Inc. | Process for preparing reactive compositions for fluid treatment |
| CN1886465A (en) * | 2003-12-02 | 2006-12-27 | 伊斯曼化学公司 | Compositions for the preparation of void-containing articles |
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| US6833075B2 (en) * | 2002-04-17 | 2004-12-21 | Watervisions International, Inc. | Process for preparing reactive compositions for fluid treatment |
| CN1886465A (en) * | 2003-12-02 | 2006-12-27 | 伊斯曼化学公司 | Compositions for the preparation of void-containing articles |
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