JP2011190365A - Resin composition and resin molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition and a resin molded article improved in mechanical strength compared to a resin composition comprising a kneaded material prepared by melt-mixing an ion complex of an anionic flame retardant and a polymer compound containing a cationic component with a matrix resin. <P>SOLUTION: The resin composition comprises a second kneaded material prepared by melt-mixing a first kneaded material which is prepared by melt-mixing an anionic flame retardant and a matrix resin, and a polymer compound containing a cationic component. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a resin composition and a resin molded body.

  Cited Document 1 proposes a flame retardant biodegradable resin composition containing, in a biodegradable resin, at least one chemical substance selected from urea, ammonium phosphate, ammonium polyphosphate, and a guanidine-based compound. Has been.

  Citation 2 proposes a composition containing a biodegradable organic polymer compound, a flame retardant additive, and a biodegradable polymer compound hydrolysis inhibitor.

  In Cited Document 3, at least two kinds selected from polylactic acid resin, bromine-based flame retardant, chlorine-based flame retardant, phosphorus-based flame retardant, nitrogen compound-based flame retardant, silicone-based flame retardant, and other inorganic flame retardants A resin composition containing a flame retardant is proposed.

  Cited Document 4 proposes filling high-strength fibers as a filler in order to compensate for the insufficient strength of the biodegradable resin.

Japanese Patent Laid-Open No. 2004-27079 JP 2003-192929 A JP 2004-190025 A Japanese Patent No. 2979158

  The present invention is a resin having improved mechanical strength as compared with a resin composition containing a kneaded product obtained by melt-mixing an ion complex of an anionic flame retardant and a polymer compound containing a cation component and a matrix resin. It is an object to provide a composition and a resin molded body.

  The invention according to claim 1 includes a second kneaded material obtained by melt-mixing a first kneaded material obtained by melt-mixing an anionic flame retardant and a matrix resin and a polymer compound containing a cationic component. It is a resin composition.

  The invention according to claim 2 is a resin molded body including the resin composition according to claim 1.

  According to the invention of claim 1, compared with a resin composition including a kneaded material obtained by melt-mixing an ion complex of an anionic flame retardant and a polymer compound containing a cationic component, and a matrix resin. There is an effect that a resin composition with improved strength is provided.

  According to the invention which concerns on Claim 2, compared with the resin composition containing the kneaded material which melt-mixes the ion complex of the anionic flame retardant and the high molecular compound containing a cation component, and a matrix resin, it is a machine. There is an effect that a resin molded body with improved strength is provided.

It is the schematic which shows an example of the image forming apparatus provided with the housing | casing comprised using the resin molding which concerns on this Embodiment, and office equipment components.

  Hereinafter, an embodiment of the present invention will be described in detail.

-Resin composition-
The resin composition of the present embodiment includes a second mixture obtained by mixing and melting a first kneaded product obtained by melt-mixing an anionic flame retardant and a matrix resin and a polymer compound containing a cationic component. Contains.

  Since the resin composition of the present embodiment has the above-described configuration, it is considered that excellent mechanical strength can be obtained while maintaining flame retardancy.

  The reason for the above effect is not clear, but is presumed as follows. However, the present invention is not limited by the following estimation.

The second kneaded product contained in the resin composition of the present embodiment is obtained by adding a polymer compound containing a cation component to the first kneaded product obtained by melting and mixing an anionic flame retardant in a matrix resin. Further, it is mixed and melted. For this reason, it is considered that a polymer compound containing a cation component forms an ionic complex by forming an ionic bond with an anionic flame retardant dispersed in a matrix resin.
Thus, the anionic flame retardant dispersed in the matrix resin and the polymer compound containing the cation component form an ionic bond to form an ionic complex, so that the ionic complex aggregates in the matrix resin. It is thought that the formation of aggregates is suppressed. And since formation of the aggregate of this ion complex is suppressed, it is thought that mechanical strength improves in the resin composition containing this 2nd kneaded material, and the resin molding containing a resin composition.
In addition, since an anionic flame retardant that uses a flame retardant that easily plasticizes the matrix resin, even when the amount of the anionic flame retardant added is suppressed, the anionic flame retardant dispersed in the matrix resin is used. Since the flame retardant and the polymer compound containing a cation component form an ionic bond, it is considered that good mechanical strength can be obtained while maintaining flame retardancy.

  On the other hand, when an ion complex obtained by forming an ionic bond between an anionic flame retardant and a polymer compound containing a cation component (hereinafter referred to as a comparative ion complex) is dispersed in a matrix resin and melt-mixed It is considered that the comparative ion complex is difficult to melt in the matrix resin, and therefore, the aggregate of the comparative ion complex is easily formed in the matrix resin. For this reason, in the matrix resin, the area | region of the aggregate by a comparison ion complex will be in a harder state than another area | region, and it is thought that it is inferior to mechanical strength compared with the resin composition of this Embodiment as a result.

  Hereinafter, details of each component will be described.

-First kneaded product-
(Anionic flame retardant)
The anionic flame retardant used in the present embodiment is a flame retardant having an anionic component. Specific examples of the anionic flame retardant include a phosphorus flame retardant and a sulfonic acid flame retardant.

  Of the anionic flame retardants listed above, in particular, phosphorus flame retardants such as phosphate esters and condensed phosphate esters are considered to plasticize the matrix resin as the amount added to the matrix resin increases. However, since the resin composition of the present embodiment is configured as described above, even if the amount of the flame retardant added is suppressed in order to suppress the plasticization of the matrix resin, the resin composition is difficult. It is thought that the mechanical strength can be improved while maintaining the flame retardant.

  Although it does not specifically limit as a phosphorus flame retardant, Low molecular phosphate ester, such as a trimethyl phosphate and a triphenyl phosphate, Tris phosphate (2,6-dimethylphenyl), Tris phosphate (2,6-diethylphenyl) ), Tris phosphate (2,6-di-n-propylphenyl), tris phosphate (2,6-diisopropylphenyl), tris phosphate (2,6-di-n-butylphenyl), tris phosphate ( 2,6-di-sec-butylphenyl), phosphate tris (2,6-di-tert-butylphenyl), phosphate tris [(2,3,6-, 2,4,6-) trimethylphenyl] Tris phosphate [(2,3,6-, 2,4,6-) triethylphenyl] and Tris phosphate [(2,3,6-, 2,4,6-) tri-n-propylphenyl] And resorcin bis [bis (2,6-dimethylphenyl) phosphate], resorcin bis [2,6-dimethylphenyl cresyl phosphate], and resorcin bis [phosphorus, which are condensates of these phosphate monomers. Acid (2,6-dimethylphenyl) phenyl], hydroquinone bis [phosphate bis (2,6-dimethylphenyl)], hydroquinone bis [phosphate (2,6-dimethylphenyl) cresyl], hydroquinone bis [bisphosphate] (2,6-dimethylphenyl) phenyl], bisphenol A bis [bis (2,6-dimethylphenyl) phosphate], bisphenol A bis [phosphate (2,6-dimethylphenyl) cresyl], bisphenol A bis [phosphorus Acid (2,6-dimethylphenyl) phenyl], bisphenol S bis [phosphate bis (2,6 Dimethylphenyl)], bisphenol S bis [phosphate (2,6-dimethylphenyl) cresyl], bisphenol S bis [phosphate (2,6-dimethylphenyl) phenyl], biphenol bis [bis (2,6-phosphate) Dimethylphenyl)], biphenol bis [phosphate (2,6-dimethylphenyl) cresyl] and biphenol bis [phosphate (2,6-dimethylphenyl) phenyl] and the like.

In addition, in this Embodiment, a "flame retardant" means what improves the flame retardance prescribed | regulated by UL-94 of the resin composition obtained by adding to resin compared with the case of resin alone. .
In addition, flame retardance (UL standard) is UNDERWRITERS LABORATORIES INC. In the United States. It is a safety standard for electrical equipment that has been established and approved by the company, and is a standard defined by a vertical combustion test using the UL combustion test method. There are V-0, V-1, and V-2 depending on the degree of flame retardancy, and the closer to V-0, the higher the flame retardant material. When there is no melt falling while burning within 10 seconds to 30 seconds, the level is V-0 or more and V-1 or less, and V-2 when there is a melt falling while burning.

(Matrix resin)
The matrix resin is not particularly limited as long as it is a polymer compound. Specifically, biodegradable resin, ABS resin, ACS resin, alkyd resin, amino resin, ASA resin, bismaleimide triazine resin, L Roll plastic resin, chlorinated polyether, chlorinated polyethylene, allyl resin, epoxy resin, ethylene-propylene copolymer, ethylene-vinyl acetate-vinyl chloride copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer Polymer resin, FRP, ionomer, methacrylate ester-styrene copolymer, nitrile resin, polyester, olefin vinyl alcohol copolymer, petroleum resin, phenol resin, polyacetal, polyacrylate, polyallyl sulfone, polybenzimidazole, polybutadiene, Ribylene, polybutylene terephthalate, polycarbonate (PC), polyether ether ketone, polyether ketone, polyether nitrile, polyether sulfone, polyethylene, polyethylene terephthalate, polyketone, methacrylic resin, polymethylpentene, polypropylene, polyphenylene ether (PPE), Polyphenylene sulfide, polysulfone, polystyrene (PS), SAN resin, butadiene-styrene resin, polyurethane, polyvinyl acetal, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, fluorine resin, silicone resin, polyvinyl acetate, xylene resin, thermoplastic Elastomer, EPDM, CR, BR, Nitrile rubber, Natural rubber, Acrylonitrile butadiene rubber, Fluoro rubber Butyl rubber, and the like. These can be used individually by 1 type or in combination of 2 or more types.

  Among these, in particular, when an anionic flame retardant is added to a biodegradable resin, polycarbonate, or the like, depending on the type and amount of the anionic flame retardant, these matrix resins may be plasticized and mechanical strength may be significantly reduced. However, according to the resin composition of the present embodiment, since it is configured as described above, it is considered that the mechanical strength can be improved while achieving flame retardancy.

(First kneaded product)
The first kneaded product is obtained by mixing and melting the anionic flame retardant and the matrix resin. The anionic flame retardant is desirably mixed in a range of 0.1 parts by mass or more and 100 parts by mass or less, and mixed in a range of 0.5 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the matrix resin. It is desirable.
When the content of the anionic flame retardant in the first kneaded product is within the above range, sufficient flame retardancy is obtained and the kneading and moldability are not adversely affected.

  Mixing and melting of the anionic flame retardant and the matrix resin is performed using a kneader. The kneader is not particularly limited, and examples thereof include a single screw extruder, a twin screw extruder, a Henschel mixer, a Banbury mixer, a single screw extruder, a multi-screw extruder, and a kneader.

  The melting temperature at the time of mixing and melting may be a temperature at which the matrix resin melts, and varies depending on the type of the matrix resin, the mixing amount (addition amount) of the anionic flame retardant, and the like. The range below ℃ is mentioned.

  Since the first kneaded material is obtained by mixing and melting the anionic flame retardant and the matrix resin, the anionic flame retardant contained in the first kneaded material is dispersed in the matrix resin. It will be in the state.

-Second kneaded product-
The second kneaded product is obtained by adding a polymer compound containing a cation component to the first kneaded product in which an anionic flame retardant is dispersed in a matrix resin, and mixing and melting it.

(Polymer compound containing cationic component)
The polymer compound containing a cation component may be a polymer compound containing an anion component of an anionic flame retardant contained in the first kneaded material to be mixed and melted and a cation component that forms an ionic bond.

  Examples of the polymer compound containing a cation component that forms an ionic bond with the anion component of the anionic flame retardant include a polymer compound containing a nitrogen atom. Among these, a polymer compound having a nitrogen atom in the main skeleton, a polymer compound having a substituent containing nitrogen, and the like can be given. And as this substituent (cationic group), a primary-tertiary amino group, a quaternary ammonium base, etc. are mentioned.

  By using a polymer compound containing a nitrogen atom as the polymer compound containing a cation component, the affinity for the matrix resin is improved, so that it is considered that the mechanical strength of the resin composition can be further improved.

  Specific examples of the polymer compound containing a nitrogen atom include polyalkyleneimines such as polyethyleneimine and polypropyleneimine; methylenediamine, ethylenediamine, propylenediamine, 1,2-diaminopropane, 1,3-diaminopentane, and hexamethylene. Aliphatic polyamines such as diamine, diaminoheptane, diaminododecane, diethylenetriamine, diethylaminopropylamine, N-aminoethylpiperazine, triethylenetetramine; alicyclic amines such as diaminocyclohexane, bis- (4-aminocyclohexyl) methane; diaminotoluene , Aromatic polyamines such as diaminoxylene, tetramethylxylylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone; It is below. Moreover, the high molecular compound containing monomers, such as allylamine which has an amino group, N, N- dimethylamino ethyl acrylate, N, N- dimethylaminopropyl acrylamide, is mentioned.

(Second kneaded product)
As described above, the second kneaded material is obtained by adding a polymer compound containing a cationic component to the first kneaded material in which an anionic flame retardant is dispersed in a matrix resin, and mixing and melting the mixture.
The polymer compound containing a cation component is desirably added in a range of 50 parts by mass or more and 150 parts by mass or less, and added in a range of 80 parts by mass or more and 120 parts by mass or less with respect to 100 parts by mass of the anionic flame retardant. It is desirable that
If the addition amount of the polymer compound containing the cationic component in the second kneaded product is within the above range, it is considered that the flame retardancy is sufficient and good mechanical strength can be obtained.

  Mixing and melting of the first kneaded product and the polymer compound containing a cation component are performed using a kneader. Examples of the kneader include the above-described kneader.

  The melting temperature at the time of mixing and melting the first kneaded material and the cation component may be a temperature at which the polymer compound containing the first kneaded material and the cation component is melted. Although it varies depending on the content rate, the content rate of the anionic flame retardant, the type of the polymer compound containing the cation component, the content rate of the polymer compound containing the cation component, and the like, specifically, a range of 150 ° C. or more and 300 ° C. or less Is mentioned.

―Other ingredients―
In addition to the components described above, additives such as antioxidants, reinforcing agents, compatibilizers, weathering agents, and hydrolysis inhibitors, catalysts, etc., as necessary, may be added to the resin composition of the present embodiment. May be further added. In addition, as for content of these additives and a catalyst, it is desirable that it is each 5 mass% or less on the basis of the total amount of the total solid of a resin composition.

-Resin molding-
The resin molding which concerns on this embodiment is comprised including the resin composition which concerns on the above-mentioned this embodiment.
That is, the resin molded body according to the present embodiment is obtained by molding the resin composition according to the present embodiment. For example, the resin composition according to the present embodiment is molded by a molding method such as injection molding, extrusion molding, blow molding, heat press molding, calendar molding, coating molding, cast molding, dipping molding, vacuum molding, transfer molding, etc. The resin molding which concerns on embodiment is obtained.

The injection molding is performed using, for example, a commercially available apparatus such as NEX150 manufactured by Nissei Plastic Industry, NEX70000 manufactured by Nissei Plastic Industry, SE50D manufactured by Toshiba Machine.
In this case, the cylinder temperature is preferably 220 ° C. or higher and 280 ° C. or lower, and more preferably 230 ° C. or higher and 270 ° C. or lower. The mold temperature is preferably 40 ° C. or higher and 80 ° C. or lower, and more preferably 50 ° C. or higher and 70 ° C. or lower.

  The resin molded body according to the present embodiment is suitably used for applications such as electronic / electrical equipment, home appliances, containers, automobile interior materials, and the like. More specifically, housings such as home appliances and electronic / electrical equipment, various parts, wrapping films, storage cases such as CD-ROMs and DVDs, tableware, food trays, beverage bottles, chemical wrap materials, etc. Especially, it is suitable for parts of electronic / electric equipment.

FIG. 1 is an external perspective view of an image forming apparatus, which is an example of a part of an electronic / electric device provided with a molded body according to the present embodiment, as viewed from the front side.
The image forming apparatus 100 in FIG. 1 includes front covers 120 a and 120 b on the front surface of the main body device 110. These front covers 120a and 120b can be freely opened and closed so that an operator can operate the inside of the apparatus. Thus, the operator replenishes the toner when the toner is exhausted, replaces the exhausted process cartridge, or removes the jammed paper when a paper jam occurs in the apparatus. FIG. 1 shows the apparatus with the front covers 120a and 120b opened.

  On the upper surface of the main unit 110, an operation panel 130 on which various conditions relating to image formation such as a paper size and the number of copies are input by an operation of an operator, and a copy glass 132 on which a document to be read is arranged are provided. Yes. In addition, the main body device 110 includes an automatic document conveying device 134 that conveys a document on the copy glass 132 at the top thereof. Further, main device 110 includes an image reading device that scans a document image placed on copy glass 132 and obtains image data representing the document image. Image data obtained by the image reading apparatus is sent to the image forming unit via the control unit. Note that the image reading device and the control unit are housed in a housing 150 that forms part of the main body device 110. The image forming unit is provided in the housing 150 as a detachable process cartridge 142. The process cartridge 142 is attached and detached by turning the operation lever 144.

  A toner container 146 is attached to the casing 150 of the main body device 110, and toner is replenished from the toner supply port 148. The toner stored in the toner storage unit 146 is supplied to the developing device.

  On the other hand, sheet storage cassettes 140a, 140b, and 140c are provided at the lower portion of the main unit 110. In addition, the main body apparatus 110 has a plurality of conveying rollers formed of a pair of rollers arranged in the apparatus, thereby forming a conveying path through which the sheets of the sheet storage cassette are conveyed to the upper image forming unit. ing. The paper in each paper storage cassette is taken out one by one by a paper take-out mechanism disposed near the end of the transport path and sent out to the transport path. Further, a manual paper supply unit 136 is provided on a side surface of the main apparatus 110, and paper is supplied from here.

  The paper on which the image is formed by the image forming unit is sequentially transferred between two fixing rolls that are supported by a casing 152 that forms part of the main body device 110 and is in contact with each other. Paper is discharged to the outside. The main body device 110 is provided with a plurality of paper discharge sections 138 on the side opposite to the side where the paper supply section 136 is provided, and the paper after image formation is discharged to these paper discharge sections.

  In the image forming apparatus 100, for example, the resin molded body according to the present embodiment is used for the front covers 120a and 120b, the exterior of the process cartridge 142, the casing 150, and the casing 152.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following, “part” and “%” are based on mass unless otherwise specified.

<Example 1>
-Adjustment of the first kneaded material-
As an anionic flame retardant, 20 parts by mass of a phosphorus flame retardant (trade name: CR741, manufactured by Daihachi Chemical Co., Ltd.) is added to 100 parts by mass of ethyl cellulose as a matrix resin, and a twin screw extruder (Toshiba Machine Co., Ltd., TEM35). ) For 8 minutes at 200 ° C. to prepare a first kneaded product.

  Next, 10 parts by mass of polyethyleneimine with a cationic component as a polymer compound is added to the first kneaded product, and again melted at 200 ° C. for 8 minutes using a twin screw extruder (manufactured by Toshiba Machine Co., Ltd., TEM35). The mixture was mixed to prepare a second kneaded product (resin composition A1).

  The following evaluation was performed using the adjusted resin composition A1. The evaluation results are shown in Table 1.

<Strength evaluation>
(Evaluation of mechanical strength (Flatwise Charpy test (Charpy test without notch)))
About the test piece for burning tests (width 13mm, length 125mm, thickness 2.0mm), the Charpy impact strength was measured by installing a test piece flat according to JISK7111-1.

―Mechanical strength evaluation criteria―
G1: When the Charpy impact strength measurement result is 40% or more of the measurement result of the matrix resin.
G2: When the Charpy impact strength measurement result is 25% or more and less than 40% of the measurement result of the matrix resin.
G3: When the Charpy impact strength measurement result is less than 25% of the measurement result of the matrix resin.

(Charpy test with notch)
According to JIS K7111-1, the notch Charpy impact strength was measured by fixing both ends of the test piece and hitting from the back side with the notch.

―Mechanical strength evaluation criteria―
G1: When the notched Charpy impact strength measurement result is 40% or more of the measurement result of the matrix resin.
G2: When the measurement result of notched Charpy impact strength is 25% or more and less than 40% of the measurement result of the matrix resin.
G3: When the Charpy impact strength measurement result with notch is less than 25% of the measurement result of the matrix resin.

<Evaluation of flame retardancy>
Using the test piece for the combustion test, a vertical combustion test of UL-94 is performed, and determined according to UL-94 standard judgment criteria in five ranks of HB, V-0, V-1, V-2 and fire spread. did. The results are shown in Table 1.

<Evaluation of heat resistance>
Using the test piece for combustion test, a weighted deflection temperature based on JIS K 7191-2 at a plate thickness of 4 mm was measured, and heat resistance was evaluated according to the following criteria. The evaluation results are shown in Table 1.
・ G1: Deflection temperature of matrix resin -30 ℃ or higher ・ G2: Deflection temperature of matrix resin -30 ℃ or less

<Dispersibility evaluation>
The dispersibility of the flame retardant in the adjusted resin composition A1 was evaluated.
As a method for evaluating dispersibility, the prepared resin composition was pressed at 200 ° C. to prepare a film having a thickness of 500 μm, and observed with an electron microscope. The evaluation results are shown in Table 1.

-Evaluation criteria for dispersibility-
G1: The flame retardant is uniformly dispersed and the dispersibility is good.
G2: The flame retardant is not confirmed to be agglomerated, but the flame retardant can be confirmed in the form of particles and dispersed unevenly.
-G3: Many agglomerated portions of the flame retardant were confirmed and dispersed unevenly, resulting in poor dispersibility.

<Bleed evaluation>
The adjusted resin composition A1 was melt-molded by a press at 200 ° C. to prepare a resin molded body (UL-94 test piece for combustion test: width 13 mm, length 125 mm, thickness 2.0 mm).

The produced test specimen for combustion test was allowed to stand for 400 hours at a temperature of 60 ° C. and a relative humidity of 85%, and bleed was evaluated according to the following criteria. The results are shown in Table 1.
G1: No alteration or discoloration is observed on the specimen surface.
G2: Alteration, discoloration, etc. were observed visually on the surface of the test piece.
G3: The state in which the flame retardant oozed out from the inside of the sticky specimen surface (bleeded) was visually observed.

<Example 2 to Example 8>
A resin composition and a resin molded body were prepared in the same manner as in Example 1 except that the composition of the resin composition prepared in Example 1 was changed to the composition shown in Table 1. Evaluation was performed in the same manner as in Example 1. went. The evaluation results are shown in Table 1.

<Comparative Examples 1 to 7>
A comparative resin composition and a comparative resin molded body were produced in the same manner as in Example 1 except that the composition of the resin composition prepared in Example 1 was changed to the composition shown in Table 2, and the same as in Example 1. Evaluation was performed. The evaluation results are shown in Table 2.

  As is clear from the results in Tables 1 and 2, in the examples, the mechanical strength was improved as compared with the comparative examples. Good results were also obtained for flame retardancy. On the other hand, in the comparative example, the mechanical strength was inferior compared with the Example.

DESCRIPTION OF SYMBOLS 100 Image forming apparatus 110 Main body apparatus 120a, 120b Front cover 136 Paper supply part 138 Paper discharge part 142 Process cartridge 150, 152 Case

Claims (2)

  A resin composition comprising a second kneaded material obtained by melt-mixing a first kneaded material obtained by melt-mixing an anionic flame retardant and a matrix resin and a polymer compound containing a cationic component.   The resin molding containing the resin composition of Claim 1.

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