CN106554616B - Amilan polyamide resin composition and its formed body - Google Patents
Amilan polyamide resin composition and its formed body Download PDFInfo
- Publication number
- CN106554616B CN106554616B CN201610696561.9A CN201610696561A CN106554616B CN 106554616 B CN106554616 B CN 106554616B CN 201610696561 A CN201610696561 A CN 201610696561A CN 106554616 B CN106554616 B CN 106554616B
- Authority
- CN
- China
- Prior art keywords
- ingredient
- resin composition
- polyamide resin
- amilan polyamide
- polyamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides the Amilan polyamide resin composition and formed body for improving the variation of anti-flammability, hinge characteristic, hinge characteristic.A kind of Amilan polyamide resin composition, it includes (A) polyamide 66/6 copolymers and/or polyamide 66 resins, (B) polyamide 6 and (C) cyanurate melamine based flame retardant, wherein, relative to (A) ingredient, (B) total 100 mass parts of ingredient, the Amilan polyamide resin composition includes 4~8 mass parts (C) ingredient, polyamide 66 unit/polyamide 6 unit quality ratio in Amilan polyamide resin composition is 88/12~73/27, 98% relative sulfuric acid viscosity η r (according to JIS K6920) of Amilan polyamide resin composition is 2.50~2.83, the average grain diameter of (C) ingredient in Amilan polyamide resin composition is 1.0 μm or less.
Description
Technical field
The present invention relates to Amilan polyamide resin compositions, specifically, are related to the polyamide resin of anti-flammability, hinge characteristic good
Oil/fat composition and its formed body.
Background technique
Polyamide using mechanical property as representative in terms of have excellent characteristic, therefore always with
To be widely used in the various parts such as automobile component, electronic and electric components, industrial machinery part.Especially because good-toughness, because
And it is used for the product that connector, clip etc. have hinge part.In most cases, anti-flammability is required for these products.Especially
It is from the viewpoint of environment, it is expected that using the fire retardant of Halogen.
It as the typical example of such fire-resistant polyamide resin, can enumerate: using the fire-retardant of cyanurate melamine
Property polyamide material, such as connector, clip for electric and electronic field etc. (referring to patent document 1 with 2).In patent document
In 3 and 4, following method: the highly concentrated masterbatch of pre-production cyanurate melamine is proposed, and make it using molding machine etc.
It mixes and forms with polyamide.In addition, proposing following method in patent document 5: in polyamide and cyanurate
The stage of melamine mixing cooperates specific dispersing agent.
Existing technical literature
Patent document 1: Japanese Unexamined Patent Application 53-125459 bulletin
Patent document 2: Japanese Unexamined Patent Application 53-031759 bulletin
Patent document 3: Japanese Unexamined Patent Publication 08-245875 bulletin
Patent document 4: Japanese Unexamined Patent Publication 11-302533 bulletin
Patent document 5: Japanese Unexamined Patent Publication 2003-301104 bulletin
Summary of the invention
Problem to be solved by the invention
For the above-mentioned fire-resistant polyamide resin for using cyanurate melamine, cyanurate melamine is in polyamide
It is not fully compatible in resin, is filled in the composition in the shape dispersed as inorganic filler.Therefore, it has been filled with cyanogen urea
For the Amilan polyamide resin composition of sour melamine, toughness has reduced tendency.In production masterbatch or utilize dispersion
Agent dispersed as in the prior art, it is difficult to take into account the anti-flammability and hinge characteristic (ヒ ソ ジ characteristic) as opposite performance
Balance.
The present invention has been made in view of the above-described circumstances, and an object thereof is to provide one kind, not only anti-flammability and hinge characteristic are excellent
It is good, and improve the Amilan polyamide resin composition of the variation of hinge characteristic.
The means used to solve the problem
The present inventor has made intensive studies to solve the above-mentioned problems, as a result, it has been found that, by that will include polyamide resin
The resin combination of rouge and cyanurate melamine is set as particular range, and by 98% sulfuric acid phase of Amilan polyamide resin composition
Prescribed limit is set as to the average grain diameter of the cyanurate melamine in viscosities il r, Amilan polyamide resin composition, can be obtained excellent
Good anti-flammability and hinge characteristic, so as to complete the present invention.
That is, Amilan polyamide resin composition of the invention include (A) polyamide 66/6 copolymers and/or polyamide 66 resin,
(B) polyamide 6 and (C) cyanurate melamine based flame retardant；Wherein, relative to the total of (A) ingredient and (B) ingredient
100 mass parts, the Amilan polyamide resin composition includes 4~8 mass parts of (C) ingredient fire retardant, in Amilan polyamide resin composition
Polyamide 66 unit/polyamide 6 unit quality ratio be 88/12~73/27, the 98% of the Amilan polyamide resin composition
Relative sulfuric acid viscosity η r (according to JIS K6920) is 2.50~2.83, the average grain of (C) ingredient in Amilan polyamide resin composition
Diameter is 1.0 μm or less.
Preferably, total 100 mass parts relative to (A) ingredient and (B) ingredient, the Amilan polyamide resin composition also wrap
(D) containing 0.1~1.0 mass parts includes the surfactant of the aliphatic ester of at least one polyalkylene polyol.
Preferably, the polyamide 66 of (A) ingredient/6 copolymers include the polyamide 66 unit of 50~95 mass %, 5~50
The polyamide 6 unit of quality %.
Preferably, the 98% relative sulfuric acid viscosity η r (according to JIS K6920) of (A) ingredient is 2.3~2.9.
Preferably, the 98% relative sulfuric acid viscosity η r (according to JIS K6920) of (B) ingredient is 2.1~2.7.
Preferably, 98% relative sulfuric acid viscosity η r (according to JIS K6920) of Amilan polyamide resin composition be 2.50~
2.70。
Preferably, (D) ingredient is selected from by polyethylene glycol oxide monolaurate, polyoxyethylene monostearate ester, polyoxy
Change ethylene distearate, polyethylene glycol oxide monoleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene
Alkene sorbitan monosterate, polyoxyethylene sorbitan tristearate, polyethylene glycol oxide Sorbitan
At least one of the group of Sorbitane monooleate and polyoxyethylene sorbitan trioleate composition.
Formed body of the invention is obtained by by Amilan polyamide resin composition molding of the invention.
Formed body can be the connector component with hinge part.
Formed body can be clip.
Invention effect
Amilan polyamide resin composition of the invention includes (A) polyamide 66/6 copolymers and/or polyamide 66 resin, (B)
Polyamide 6 and (C) cyanurate melamine based flame retardant, relative to total 100 mass parts of (A) ingredient and (B) ingredient,
The Amilan polyamide resin composition includes 4~8 mass parts of (C) ingredient, the polyamide 66 unit in Amilan polyamide resin composition/poly-
The quality ratio of amide Unit 6 is 88/12~73/27,98% relative sulfuric acid viscosity η r of Amilan polyamide resin composition (according to
JIS K6920) it is 2.50~2.83, the average grain diameter of (C) ingredient in Amilan polyamide resin composition is 1.0 μm hereinafter, therefore
Mechanical property, chemical-resistant, the good mouldability, electrical spy of Amilan polyamide resin composition inherently can not damaged
Property etc. in the case where, improve anti-flammability, hinge characteristic, can be used suitable for appliances parts, electronic component, automobile component etc.
On the way.
Detailed description of the invention
Fig. 1 is the top view of the molded product of the test for hinge characteristic.
Fig. 2 is the side view of the molded product of the test for hinge characteristic.
Appended drawing reference
1 hinge formed body
22 hinge parts
Specific embodiment
Hereinafter, being described in detail for the present invention.
[Amilan polyamide resin composition]
Amilan polyamide resin composition of the invention includes (A) polyamide 66/6 copolymers and/or polyamide 66 resin, (B)
The Amilan polyamide resin composition of polyamide 6 and (C) cyanurate melamine based flame retardant, wherein relative to (A) ingredient and
(B) total 100 mass parts of ingredient, the Amilan polyamide resin composition include 4~8 mass parts of (C) ingredient, polyamide group
Closing polyamide 66 unit/polyamide 6 unit quality ratio in object is 88/12~73/27, Amilan polyamide resin composition
98% relative sulfuric acid viscosity η r (according to JIS K6920) is 2.50~2.83, and (C) ingredient in Amilan polyamide resin composition is put down
Equal partial size is 1.0 μm or less.
Hereinafter, each ingredient is described in detail.
[(A) ingredient: polyamide 66/6 copolymers and/or polyamide 66 resin]
Polyamide 66 resin, which refers to, to be had amido bond (- NHCO-) in main chain and includes hexa-methylene unit and adipic acid
The polymer of unit.Be not particularly limited, can be enumerated for example as polyamide 66 resin: by hexamethylene diamine and oneself two
Polymer obtained from sour polycondensation, by polymer obtained from 6-aminocapronitrile and adipic acid polycondensation, by hexamethylene diamine and
Polymer obtained from Adipoyl Chloride polycondensation, by polymer obtained from 6-aminocapronitrile and Adipoyl Chloride polycondensation etc..Wherein, from
The accessibility of raw material is set out, preferably preferably by polymer obtained from hexamethylene diamine and adipic acid polycondensation.
Polyamide 66/6 copolymers refer to the copolymer of polyamide 66 unit and polyamide 6 unit, preferably comprising 50~
The polyamide 66 unit of 95 mass %, 5~50 mass % polyamide 6 unit polyamide 66/6 copolymers, more preferably wrap
Polyamide 66/6 copolymers of the polyamide 6 unit of polyamide 66 unit, 10~20 mass % containing 80~90 mass %.
By using such polyamide, the fire-retardant of Amilan polyamide resin composition of the invention can be further increased
Property, hinge characteristic.In addition, being also preferred from the viewpoint of with the compatibility of aftermentioned (B) polyamide 6.
(A) relative viscosity measured at 1%, 25 DEG C of concentration in 98% sulfuric acid according to JIS K6920 of ingredient is preferably
2.3~2.9 range, more preferably 2.3~2.8 range.By the way that the relative viscosity of (A) ingredient is set as 2.3 or more, energy
Enough further increase toughness, the mechanical strength of formed body.In addition, by the way that relative viscosity is set as 2.9 hereinafter, can make fire-retardant
Property, the processing and forming of formed body are more easier, and can obtain good appearance.
For (A) ingredient, ingredient is preferably used as containing copper acetate, cuprous iodide (potassium iodide can be used together) by addition
Copper compound or steady containing organic heat such as Hinered phenols heat stabilizer, hindered amines heat stabilizer and phosphorous heat stabilizer
Agent etc. is determined, to obtain thermostabilization formula.Thus, it is possible to further increase the thermostabilization of Amilan polyamide resin composition of the invention
Property.
Above-mentioned thermostabilization formula can be implemented according to arbitrary manufacturing process.For example, acetic acid can be added in monomer
Copper, cuprous iodide and organic heat stabilizers, are then polymerize, and can also used after obtaining polymer by polymerization
It is added in the polyamide of molten condition in the manufacturing procedure of extruder, molding machine etc..Alternatively, it is also possible to directly with polymerize
Object pellet mixing, then for processing and forming process.
[(B) ingredient: polyamide 6]
(B) polyamide 6 that Amilan polyamide resin composition of the invention is included is for showing polyamide group
The high hinge characteristic for closing object is necessary.(B) amount of ingredient is not particularly limited, and from hinge characteristic and inhibits hinge characteristic
Polyamide 66 unit/polyamide 6 unit from the perspective of the viewpoint and mechanical property of variation, in Amilan polyamide resin composition
Quality ratio is 88/12~73/27, preferably 88/12~75/25, more preferably 86/14~75/25.By by polyamide 6
Quality ratio be set as 12 or more, hinge characteristic can be further increased, by the way that the quality ratio of polyamide 6 is set as 27
Hereinafter, there can be sufficient compatibility with (A) ingredient, the effect for inhibiting the variation of hinge characteristic can be improved.
(B) relative viscosity measured at 1%, 25 DEG C of concentration in 98% sulfuric acid according to JIS K6920 of ingredient is preferably
2.1~2.7 range, more preferably 2.4~2.6 range.By the way that the relative viscosity of (B) ingredient is set as 2.1 or more, energy
Enough further increase hinge characteristic, toughness, mechanical strength, the anti-flammability of formed body.By the way that the relative viscosity of (B) ingredient is set
For 2.7 hereinafter, the anti-flammability of formed body can be further increased, and good appearance can be obtained.
[(C) ingredient: cyanurate melamine based flame retardant]
(C) ingredient that Amilan polyamide resin composition of the invention is included be melamine or derivatives thereof and cyanurate or
The reaction product of its derivative is not particularly limited as long as the reaction product.(C) ingredient for example can be by cyanurate
Or derivatives thereof aqueous solution in add melamine or derivatives thereof, be stirred at about 90 DEG C~about 100 DEG C, to as anti-
The sediment for answering product to obtain is filtered drying, is then crushed and micro mist is made, thus manufactured.
As preferred (C) ingredient, can enumerate: the cyanogen urea as melamine and the reaction with same mole product of cyanurate
Sour melamine.Cyanurate melamine may include 0.001 mass % or more wherein and 0.30 mass % is not below anti-
The melamine answered, cyanurate.Such cyanurate melamine is commercially available, in the present invention it is possible to appropriate to use industry
On the commercially available cyanurate melamine that can obtain.
(C) ingredient is in the dispersity dispersed in (A) ingredient and (B) ingredient.Therefore in Amilan polyamide resin composition
(C) scanning electron microscope (SEM) observation resin combination section can be used in the average grain diameter of ingredient.More specifically, it cuts
Amilan polyamide resin composition is cut, and observes the cut surface using scanning electron microscope (SEM).For direction of observation,
In the case where object is observed as cylindrical pellets shape, it is cut into the section basically perpendicular to pellet long side and is observed.?
In the case where object is observed as matrix band, observed at the section perpendicular to flow direction.It is not in the particle of (C) ingredient
In the case where spherical shape, the diameter of the center of gravity by particle is measured with every 2 °, is averaged to it, obtained value is made
For the partial size of the particle.And average grain diameter is the flat of the dispersed particle measured by image analysis apparatus (image analysis software)
Mean value.
The average grain diameter of (C) ingredient in Amilan polyamide resin composition is 1.0 μm or less.By combining polyamide
The average grain diameter of (C) ingredient in object be set as 1.0 μm hereinafter, can obtain the tensile elongation of good resin combination,
Hinge characteristic, low temperature hinge characteristic etc..
It is any as long as it can be 1.0 μm or less by the control of the average grain diameter of (C) ingredient in Amilan polyamide resin composition
Method preferably by (A) ingredient, (B) ingredient together melting mixing and utilize mechanical shear but from the viewpoint of economy
The method for cutting into row crushing.
The median particle diameter (D50) of (C) ingredient before mixing (A) ingredient and (B) ingredient is not particularly limited, from (C) at
Preferably 1 μm~5 μm, more preferably 1.5 μm~4 μm from the perspective of the dispersibility divided.Median particle diameter by (C) ingredient is
1 μm or more, processing becomes easy, and the aggregation for being able to suppress (C) ingredient is deteriorated.By the median particle diameter of (C) ingredient be 5 μm with
Under, the balance of dispersibility and processing in Amilan polyamide resin composition is excellent.
Herein, so-called median particle diameter (D50) is as defined in JIS Z8901, to be greater than in the particle diameter distribution of particle
The quality of the particle of a certain partial size accounts for partial size when the 50% of the quality of all particles, is surveyed by laser diffraction scattering method
It is fixed.Specifically, it is by laser diffraction scattering method, be that the longitudinal axis is mapped as horizontal axis, with frequency (quality) using partial size, by its frequency
The obtained value of particle size determination when the summation of several mass accumulations is set as 100%, when reaching 50% as mass accumulation.
From the viewpoint of anti-flammability and toughness, the content of (C) ingredient in Amilan polyamide resin composition relative to (A) at
Divide and total 100 mass parts of (B) ingredient are 4~8 mass parts, preferably 4~7 mass parts, more preferably 4~6 mass parts are special
It You Xuanwei not 4~5.5 mass parts.
[(D) ingredient: surfactant]
Amilan polyamide resin composition of the invention preferably comprises the aliphatic ester comprising at least one polyalkylene polyol
Surfactant.
As the aliphatic ester of polyalkylene polyol, can enumerate for example: polyethylene glycol, polypropylene glycol, polytetramethylene glycol
Equal polyalkylene polyols and capric acid, lauric acid, myristic acid, palmitinic acid, stearic acid, behenic acid, cerinic acid, montanic acid, melissa
Esters of aliphatic carboxylic acids such as acid, oleic acid, erucic acid or derivatives thereof, they are industrially easy to get.From the dispersibility of (C) ingredient
From the perspective of, the preferably aliphatic ester of polyethylene glycol, the more preferably higher fatty acids (carbon atom number 12 of polyethylene glycol
More than a) ester or derivatives thereof.
It as the high-grade aliphatic ester of preferred polyethylene glycol, can enumerate: polyethylene glycol oxide monolaurate, polyoxygenated
Ethylene monostearate, polyethylene glycol oxide distearate, polyethylene glycol oxide monoleate, particularly preferred polyethylene glycol oxide Dan Yue
Cinnamic acid ester, polyoxyethylene monostearate ester, polyethylene glycol oxide monoleate.
In addition, the higher fatty acids ester derivant as preferred polyethylene glycol, can enumerate: polyethylene glycol oxide dehydration mountain
Pears sugar alcohol monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan three are hard
Resin acid ester, polyoxyethylene sorbitan monoleate, polyoxyethylene sorbitan trioleate.
Total 100 mass of the content of (D) ingredient in Amilan polyamide resin composition relative to (A) ingredient and (B) ingredient
Part is preferably 0.1~1.0 mass parts.By being set as the content, the dispersion of (C) ingredient in Amilan polyamide resin composition is good
It is good, the Amilan polyamide resin composition that hinge characteristic and anti-flammability further increase can be made.In addition, by will (C) ingredient with
(D) ingredient is set as above-mentioned content range, when formed body is made, it is thus identified that further effect: obtaining generating material dirt (メ
ャ ニ) the case where few better quality formed body.The mechanism for obtaining the effect there is no final conclusion, be because of (D) ingredient by inference
Plasticizer as polyamide ((A) ingredient and (B) ingredient) works (but, it's not limited to that for function and effect).
98% relative sulfuric acid viscosity η r (according to JIS K6920) of Amilan polyamide resin composition of the invention be 2.50~
2.83, more preferably 2.50~2.70, more preferably 2.55~2.70.It, can by the way that relative viscosity is set as 2.50 or more
The hinge characteristic for improving formed body, by being set as 2.83 hereinafter, anti-flammability can be further increased.
For Amilan polyamide resin composition of the invention, in the test to the position with thickness 0.4mm, width 5mm
Piece carries out in the hinge test of 180 degree bending, until the number (breaks) of fracture is 4000 times or more, preferably 5000 times
More than, more preferably 5500 times or more.Breaks can be measured by the method recorded in aftermentioned embodiment.
(other resins)
It as needed can be in the range of not damaging the purpose of the present invention in Amilan polyamide resin composition of the invention
Add other resins.As other resins, can enumerate for example: nylon 46 (polyamide 46), polycyclic adipyl oneself
Diamines (polyamide 6 C), polyhexamethylene sebacamide (polyamide 610), poly- dodecanoamide (polyamide 612), acyl in poly- 11
Amine (polyamide 11), nylon 12 (polyamide 12), poly-6I hexamethylene isoterephalamide (polyamide 6 I), poly- paraphenylene terephthalamide
Hexamethylene diamine (polyamide 6 T), poly-paraphenylene terephthalamide's nonamethylene diamine (polyamide 9T), ten dimethylene diamines (polyamides of poly- paraphenylene terephthalamide
Amine 12T), poly-meta-xylylene adipamide (polyamide MXD6) and comprising the different polyamide of at least two in them formed at
Polyamide copolymer and their mixture, various elastomers for dividing etc..
[other ingredients]
It as needed can be in the range of not damaging the purpose of the present invention in Amilan polyamide resin composition of the invention
Add the inorfils such as usual filler such as glass fibre, carbon fiber, mica, talcum, clay mineral, aluminium oxide, dioxy
The inorganic fillers such as SiClx and apatite, aluminium hydroxide, magnesium hydroxide, zinc borate, zinc stannate, zinc hydroxyl stannate, ammonium polyphosphate,
The fire retardants such as ethylenebis guanamines, polyphosphoric acid melamine, sulfuric acid melamine, phthalic acid melamine and aluminum phosphate,
The pigment such as titanium white and carbon black, the phosphorous acid metal salt such as colorant, sodium hypophosphite, using hindered phenol and hindered amine as the thermostabilization of representative
Agent, the lubricants such as higher fatty acid metal salt, higher fatty acid amides, high-grade aliphatic ester, various plasticizer and antistatic
The various additives such as agent.
[manufacturing method of Amilan polyamide resin composition]
The manufacturing method of Amilan polyamide resin composition of the invention is not particularly limited, can by (A) ingredient, (B) at
Divide, (C) ingredient ((D) ingredient as needed, be illustrated below for the case where including (D) ingredient) is all once melted
Melt mixing, it, can also be to remaining complete from the viewpoint of the dispersibility of the cyanurate melamine based flame retardant of (C) ingredient
Portion's ingredient is added a part of (C) ingredient after carrying out melting mixing and carries out melting mixing again.Furthermore it is also possible to prepare packet in advance
The masterbatch of the ingredient containing (A)~(D), and melting mixing is carried out using the masterbatch.
(A) ingredient, (B) ingredient the shape of polyamide be not particularly limited, preferably partical.At this point, from
From the perspective of simplifying equipment, (D) Ingredients Surfactant can be made in (A) ingredient, the polyamide resin pellet of (B) ingredient
Surface spreading simultaneously adheres to and (opens up), then, then (C) ingredient cyanurate melamine based flame retardant is made to sprawl and adhere to, to make
At blend, melting mixing is then carried out.When forming this composition, from the viewpoint of dispersibility, (C) ingredient can also be made
A part is added after carrying out melting mixing to remaining whole components and melts again in the case where not sprawling and adhering to
It is kneaded.
In the manufacturing method of Amilan polyamide resin composition of the invention, the method for melting mixing is not particularly limited,
It is preferred that in mixing (A) ingredient, (B) ingredient, (C) ingredient and (D) ingredient, using an at least raw material feed device to extruder
The method for supplying and carrying out melting mixing.Supply of each ingredient to extruder can use different raw material feed devices respectively,
Also same raw material feed device can be used.
It as extruder, is not particularly limited, preferably double screw extruder.As double screw extruder, it is specific and
Speech, can enumerate: section again grand corporation ZSK series, Toshiba Machinery Co., Ltd. TEM series, Nippon Steel Works strain formula
TEX series of commercial firm etc., the L/D (screw rod effective length/outer screw diameter) of double screw extruder be preferably 20 or more and 60 with
Under range, preferably 30 or more and 50 or less.
The method for supplying source materials to double screw extruder is not particularly limited.There is no especially limits for raw material feed device
It is fixed, single screw rod feeder, twin-screw feeder, plate feeder, rotary table feeder, liquid supply pump etc. can be used.Wherein
The variable error of the raw material supply of the screw feeder of weight-loss type is few, therefore preferably.In addition, plurality of raw materials is put into one
When raw material feed device, at least two raw materials mixer, the taper blender etc. in raw material to be put into can be mixed
It is put into after conjunction.
From the viewpoint of productivity and inhibiting heat deterioration, it is high by 5 to be kneaded fusing point of temperature when melting preferably than (A) ingredient
DEG C~30 DEG C of temperature, more preferably 5 DEG C higher than the fusing point of (A) ingredient~20 DEG C of temperature.
[formed body]
Formed body obtained from Amilan polyamide resin composition of the invention is formed has high flame retardant, hinge characteristic, suppression
The feature of the variation of hinge characteristic processed, therefore it is suitable as the electrical and electronic parts such as socket, switch, shell, lid, automobile interior exterior portion
Component, automobile electric component etc. and the pellet of the moulding material of injection molded article, these injection molded articles used.It is especially suitable
Together in connector component, clip with hinge part.Especially the high flame retardant of thin-walled, the variation of hinge characteristic are small, Neng Gouyou
Help the requirement being thinning etc. of formed body in recent years, the variation of hinge characteristic is small, can aid in the defect rate of formed body
Reduce etc., therefore industrial meaning is very big.
Embodiment
Using embodiment and comparative example, the present invention is described in more detail.
(raw material evaluation of physical property method)
The evaluation of physical property recorded in embodiment below, comparative example carries out in the following way.
<relative sulfuric acid viscosity η r>
(A) relative sulfuric acid viscosity η r (25 DEG C, 1g/100ml) basis of ingredient, (B) ingredient and Amilan polyamide resin composition
JIS K6920 is measured.
<fusing point>
(A) fusing point of ingredient shows differential thermal amount determining device DSC-7 using Perkinelmer Inc.'s system to measure.For rising
Temperature, cooling conditions are carried out respectively with 20 DEG C/min.Sample about 10mg is started to warm up from room temperature, observes endotherm peak temperature
(Tm1), then than 20 DEG C~50 DEG C of Tm1 high at a temperature of keep 3 minutes.Then sample is cooled to room temperature, then again
It heats up and observes endothermic peak.Using temperature shown in the summit as fusing point.
<median particle diameter>
(C) median particle diameter of ingredient uses Shimadzu Corporation's laser diffraction granularity distribution measurement device
SALD-7000 is measured.It is dispersed in sample in pure water, in this, as measurement sample, is measured using flow cell.With partial size
It is longitudinal axis mapping for horizontal axis, with frequency (quality), mass accumulation reaches when the summation of the mass accumulation of the frequency is set as 100%
Partial size when 50% is as median particle diameter (D50).
(preparation of each ingredient)
[(A) ingredient: polyamide 66/6 resins, polyamide 66 resin]
(a-1) ingredient: polyamide 66/6 resins
It will include corresponding to the 90 mass % of bonding units of polyamide 66, corresponding to the bonding list of polyamide 6 for manufacturing
AH salt (the adipic acid of monomer solution required for the copolyamide 66/618.8kg of 10 mass % of member and 50 mass %
With the equimolar salt of hexamethylene diamine) aqueous solution 39.2kg and epsilon-caprolactams 1.9kg are put into 80 liters of autoclave, and are filled
Divide stirring.After being sufficiently displaced from nitrogen, by temperature from room temperature to 220 DEG C.At this point, the pressure in autoclave is calculated as with gauge pressure
1.8MPa is continuoused heating 1 hour on one side water is expelled to outside system while, so that pressure is not up to 1.8MPa or more.Then,
At the time of internal temperature reaches 270 DEG C, used while water is expelled to outside system 60 minutes by pressure reduction to atmospheric pressure,
Then stop heating, polymer is discharged from lower nozzle with strands shape, is cut into diameter 3mm φ × 3mm with cutting machine after water cooling
Long cylindrical pellets, thus obtain 66/6 resin of copolyamide coccoid (mass ratio 66: 6=90 of copolymer composition:
10,245 DEG C of η r:2.63, fusing point).
(a-2) ingredient: polyamide 66/6 resins
In addition to being pressed while water is expelled to outside system by the time of the internal temperature of autoclave reaches 270 DEG C
Power is reduced to the time of atmospheric pressure to be set as other than 45 minutes, implements (the quality of copolymerizable ingredient in a manner of same as (a-1)
Than 245 DEG C of 66: 6=90: 10, η r:2.2, fusing point).
(a-3) ingredient: polyamide 66/6 resins
In addition to being pressed while water is expelled to outside system by the time of the internal temperature of autoclave reaches 270 DEG C
Power is reduced to the time of atmospheric pressure to be set as other than 75 minutes, implements (the quality of copolymerizable ingredient in a manner of same as (a-1)
Than 245 DEG C of 66: 6=90: 10, η r:2.9, fusing point).
(a-4) ingredient: polyamide 66 resin
Preparation contains the aqueous solution of the 50 mass % of monomer mixture comprising equimolar hexamethylene diamine and adipic acid
15kg.Then, with agitating device and in the autoclave that lower part has the 40L volume of discharge nozzle, above-mentioned list is put into
Monomer solution is sufficiently stirred at 50 DEG C in body aqueous solution.After being sufficiently displaced from autoclave with nitrogen, monomer water is stirred on one side
Temperature in autoclave is warming up to about 270 DEG C from 50 DEG C on one side and polymerize by solution.At this point, the pressure in autoclave is with table
Pressure is calculated as about 1.8MPa, water is expelled to outside system at any time, so that being not up to 1.8MPa or more in the pressure.In addition, adjusting
Polymerization time is so that the relative sulfuric acid viscosity of polyamide 66 resin reaches about 2.73.
After polymerization in autoclave, polyamide 66 resin is discharged from lower nozzle with strands shape, by water cooling and cuts
It cuts, to obtain the polyamide 66 resin (η r:2.73) of partical.
[(B) ingredient: polyamide 6]
(b-1): polyamide 6 space portion is emerging to produce SF1013A relative sulfuric acid viscosity 2.6 processed
(b-2): polyamide 6 space portion is emerging to produce 1010X1 relative sulfuric acid viscosity 2.0 processed
(b-3): polyamide 6 space portion is emerging to produce 1030B relative sulfuric acid viscosity 4.4 processed
[(C) ingredient: cyanurate melamine based flame retardant]
(c-1): cyanurate melamine median particle diameter (D50): 2.6 μm
(c-2): cyanurate melamine median particle diameter (D50): 6.5 μm
[(D) ingredient: surfactant]
(d-1) PEM: polyethylene glycol oxide monolaurate Kao Corp EMANON (registered trademark) 1112
[embodiment 1]
Use (a-1) polyamide 66/6 copolymers, (b-1) polyamide 6, (c-1) cyanurate melamine, weight-loss type
Feeder (K-TRON corporation LWF-D5), supply to double screw extruder (Toshiba Machinery Co., Ltd. TEM35BS, double spiral shells
The equidirectional screw rod of bar is rotary-type, L/D=47.6) the first supply mouth.In 260 DEG C of barrel temperature, discharge rate 30kg/ hours, spiral shell
It is squeezed out under conditions of bar revolving speed 150rpm.Two mixing areas are arranged in the screw rod of extruder.From extruder front end nozzle with line
Expect that polymer is discharged in shape, and carry out water cooling, cutting, to obtain Amilan polyamide resin composition pellet.
[embodiment 2~9, comparative example 1~7]
Other than the composition of each ingredient to be set as in table 1 documented, in a manner of similarly to Example 1, production
The Amilan polyamide resin composition pellet of embodiment 2~9 and comparative example 1~7.It should be noted that expecting for embodiment 9
Cylinder temperature is to implement at 270 DEG C.
(evaluation of Amilan polyamide resin composition)
The Amilan polyamide resin composition pellet of each embodiment and comparative example is evaluated.By each assessment item and its knot
Fruit is shown in table 1.Each assessment item evaluation method is as follows shown.
<relative sulfuric acid viscosity measurement>
The resin combination 1.00g for cutting out the Amilan polyamide resin composition pellet manufactured from each embodiment and comparative example
It is dissolved in 98% concentrated sulfuric acid 100g, is measured at 25 DEG C according to JIS K6920.
<polyamide 66 unit/polyamide 6 unit quality ratio in resin combination>
Make pellet dissolution in deuterated formic acid, and measures13C-NMR.At this point, according to from polyamide 66 and polyamide 6
The peak area ratio of carbon calculates the molar ratio of polyamide 66 and polyamide 6, is then converted into mass ratio multiplied by molecular weight, thus
Find out quality ratio.
<average grain diameter of (C) ingredient>
Using the face vertical with the long side of the cylindrical pellets of resin combination obtained in embodiment and comparative example as cut
The section is observed in face using scanning electron microscope with 3000 times of multiple.Use image analysis software (Media
Cybernetics corporation Image-Pro Plus5.0J) measurement average grain diameter.
<tensile elongation>
Amilan polyamide resin composition pellet will expected using injection (mo(u)lding) machine (day essence resin Co. Ltd. system PS40E)
It is infused under the conditions of cylinder temperature is set as 270 DEG C, mold temperature set is 80 DEG C and injection 25 seconds, injection moulding in cooling 10 seconds
Molding is penetrated, to obtain the ISO test film of 4mm thickness.Using obtained ISO test film, stretch according to ISO527-1
The measurement of long rate.
<hinge characteristic hinge characteristic standard deviation low temperature hinge characteristic>
For the Amilan polyamide resin composition pellet manufactured in each embodiment and comparative example, using injection (mo(u)lding) machine, (day is smart
Industrial Co., Ltd's system: 270 DEG C of PS40E barrel temperature, 80 DEG C of mold temperature), it is shaped to Fig. 1 and hinge shown in Fig. 2 molding
Body 1.Fig. 1 is the top view of hinge molded product 1, and Fig. 2 is the side view of hinge molded product 1.Hinge molded product 1 has hinge part
22.For the hinge molded product 1 of made each example, under 23 DEG C, 50%RH atmosphere, hinge testing machine is repeated using automatic,
By 22 bending of hinge part to almost 180 °, the dynamic of the position for returning back to original position (0 °) is repeated with 33 beats/min of speed
Make, measurement fractures in the stage of bending several times.For hinge test, 15 are measured, and using 15 average value as hinge
Chain characteristic value, using standard deviation as change index.For hinge characteristic value, it is believed that in 4000 also unbroken situations
It is qualified.In addition, according to benchmark evaluation standard deviation below.
A: 2000 are less than
B:2000 or more~be less than 4000
C:4000 or more
In addition, after hinge formed body 1 is stood 2 hours under 0 DEG C of environment, being used test film as low temperature hinge characteristic
Curved 180 ° of record book in accordion form, the test film number being broken in 20 is counted, evaluation is proceeded as follows.
A: number of fracture 0~5
B: number of fracture 6~10
C: number of fracture 11 or more
<anti-flammability>
Use the pellet of the resin combination manufactured in embodiment and comparative example, supply to the coaxial-type for being set as 270 DEG C
Screw of injection molding machine is injection moulded out UL-94 testing vertical flammability measurement testing piece under conditions of 80 DEG C of mold temperature
(thickness: 0.35mm and 0.71mm).Each 5 using the different test film of thus molding thickness, tried according to UL-94 vertical combustion
It tests, evaluates anti-flammability, implement the judgement of anti-flammability V-0, V-1, V-2, HB.
As shown in table 1, according to the present invention, anti-flammability, hinge characteristic good, and the variation of hinge characteristic can be improved,
Industrial applicability
Amilan polyamide resin composition of the invention is due to high flame retardant, thus as various mechanical industry components, electricity
The industries such as pneumoelectric subassembly, especially connector, clip are useful with material.
Claims (10)
1. a kind of Amilan polyamide resin composition, it includes (A) polyamide 66/6 copolymers and/or polyamide 66 resins, (B) polyamides
6 resin of amine and (C) cyanurate melamine based flame retardant, wherein
Relative to total 100 mass parts of (A) ingredient and (B) ingredient, the Amilan polyamide resin composition includes 4~
8 mass parts (C) ingredient,
Polyamide 66 unit/polyamide 6 unit quality ratio in the Amilan polyamide resin composition is 88/12~73/27,
The 98% relative sulfuric acid viscosity η r according to JIS K6920 of the Amilan polyamide resin composition is 2.50~2.83,
The average grain diameter of (C) ingredient in the Amilan polyamide resin composition is 1.0 μm or less.
2. Amilan polyamide resin composition as described in claim 1, wherein relative to (A) ingredient and (B) ingredient
Total 100 mass parts, the Amilan polyamide resin composition also include that (D) of 0.1~1.0 mass parts includes at least one poly- alkylene
The surfactant of the aliphatic ester of polylol.
3. Amilan polyamide resin composition as claimed in claim 1 or 2, wherein polyamide 66/6 copolymers of (A) ingredient
The polyamide 6 unit of polyamide 66 unit comprising 50~95 mass %, 5~50 mass %.
4. Amilan polyamide resin composition as claimed in claim 1 or 2, wherein (A) ingredient according to JIS K6920's
98% relative sulfuric acid viscosity η r is 2.3~2.9.
5. Amilan polyamide resin composition as claimed in claim 1 or 2, wherein (B) ingredient according to JIS K6920's
98% relative sulfuric acid viscosity η r is 2.1~2.7.
6. Amilan polyamide resin composition as claimed in claim 1 or 2, wherein the Amilan polyamide resin composition according to JIS
The 98% relative sulfuric acid viscosity η r of K6920 is 2.50~2.70.
7. Amilan polyamide resin composition as claimed in claim 2, wherein (D) ingredient is selected from by polyethylene glycol oxide list
Laurate, polyoxyethylene monostearate ester, polyethylene glycol oxide distearate, polyethylene glycol oxide monoleate, polyoxygenated
Ethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyethylene glycol oxide dehydration mountain
Three oleic acid of pears sugar alcohol tristearate, polyoxyethylene sorbitan monoleate and polyoxyethylene sorbitan
At least one of the group of ester composition.
8. a kind of formed body is obtained and forming Amilan polyamide resin composition according to any one of claims 1 to 7
It arrives.
9. formed body as claimed in claim 8 is the connector component with hinge part.
10. formed body as claimed in claim 8 is clip.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-188331 | 2015-09-25 | ||
| JP2015188331 | 2015-09-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106554616A CN106554616A (en) | 2017-04-05 |
| CN106554616B true CN106554616B (en) | 2019-03-15 |
Family
ID=58418358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610696561.9A Active CN106554616B (en) | 2015-09-25 | 2016-08-19 | Amilan polyamide resin composition and its formed body |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6800652B2 (en) |
| CN (1) | CN106554616B (en) |
| TW (1) | TWI607056B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108424639A (en) * | 2018-03-13 | 2018-08-21 | 苏州银禧科技有限公司 | Dedicated modified nylon 6 material of a kind of automobile halogen-free flameproof thermostabilization bellows and preparation method thereof |
| US20190322805A1 (en) * | 2018-04-18 | 2019-10-24 | Invista North America S.A R.L. | Flame-retardant polyamide composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101679743A (en) * | 2007-06-05 | 2010-03-24 | 旭化成化学株式会社 | Polyamide resin composition |
| CN101712758A (en) * | 2004-05-21 | 2010-05-26 | 三菱化学株式会社 | Polyamide resin and hinged molded articles |
| WO2013099522A1 (en) * | 2011-12-27 | 2013-07-04 | 東レ株式会社 | Flame-retardant polyamide resin composition and molded article formed from same |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1268411A (en) * | 1969-06-12 | 1972-03-29 | Hallam Sleigh & Cheston Ltd | Means for locking two relatively angularly-movable members in angularly-adjusted positions |
| JPH1126060A (en) * | 1997-06-30 | 1999-01-29 | Mitsubishi Eng Plast Kk | Connector with polyamide resin hinge |
| JPH11228818A (en) * | 1998-02-18 | 1999-08-24 | Unitika Ltd | Flame-retarded polyamide resin composition |
| JPH11349809A (en) * | 1998-06-08 | 1999-12-21 | Showa Denko Kk | Flame-retarded polyamide resin composition |
| JP2003049000A (en) * | 2001-08-03 | 2003-02-21 | Mitsubishi Engineering Plastics Corp | Flame retardant polyamide tube |
| JP2003105650A (en) * | 2001-09-27 | 2003-04-09 | Mitsubishi Engineering Plastics Corp | Flame-retardant polyamide mesh sheet |
| JP4030301B2 (en) * | 2001-12-12 | 2008-01-09 | ユニチカ株式会社 | Flame retardant polyamide resin composition |
| JP5887100B2 (en) * | 2011-10-19 | 2016-03-16 | 旭化成ケミカルズ株式会社 | Polyamide resin composition |
| CN103408926B (en) * | 2013-06-26 | 2016-04-20 | 深圳市亚太兴实业有限公司 | A kind of polyamide compoiste material and preparation method thereof |
-
2016
- 2016-08-12 JP JP2016158622A patent/JP6800652B2/en active Active
- 2016-08-19 CN CN201610696561.9A patent/CN106554616B/en active Active
- 2016-08-19 TW TW105126553A patent/TWI607056B/en active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712758A (en) * | 2004-05-21 | 2010-05-26 | 三菱化学株式会社 | Polyamide resin and hinged molded articles |
| CN101679743A (en) * | 2007-06-05 | 2010-03-24 | 旭化成化学株式会社 | Polyamide resin composition |
| WO2013099522A1 (en) * | 2011-12-27 | 2013-07-04 | 東レ株式会社 | Flame-retardant polyamide resin composition and molded article formed from same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106554616A (en) | 2017-04-05 |
| JP2017061674A (en) | 2017-03-30 |
| TWI607056B (en) | 2017-12-01 |
| TW201714963A (en) | 2017-05-01 |
| JP6800652B2 (en) | 2020-12-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101161594B1 (en) | Polyamide resin composition | |
| CN105524453B (en) | The manufacturing method of Amilan polyamide resin composition and its formed body and Amilan polyamide resin composition | |
| US11492489B2 (en) | High heat resistance polyamide molding compound | |
| CN106554616B (en) | Amilan polyamide resin composition and its formed body | |
| JP5400456B2 (en) | Polyamide resin composition and molded body comprising the same | |
| JP5854564B2 (en) | Polyamide resin composition and molded product | |
| JP5013764B2 (en) | Flame retardant polyamide resin composition and production method | |
| CN106366648B (en) | Amilan polyamide resin composition and formed body | |
| JP6436534B2 (en) | Polyamide masterbatch pellet, polyamide resin composition and molded body using the same | |
| JP2005162821A (en) | Polyamide resin composition | |
| CN106366647B (en) | Amilan polyamide resin composition and formed body | |
| JP6195766B2 (en) | Polyamide resin composition and molded product | |
| JP5247611B2 (en) | Method for producing polyamide resin | |
| JP5636278B2 (en) | Polyamide resin composition | |
| JP6867782B2 (en) | Polyamide resin composition and its molded product | |
| JP2018035221A (en) | Electric wiring protective member for vehicles | |
| JP2017025166A (en) | Plastic hook molded body | |
| JP2004307589A (en) | Flame-retardant polyamide resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |