CN103122140B - Resin composition and molded article comprising the same - Google Patents
Resin composition and molded article comprising the same Download PDFInfo
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- CN103122140B CN103122140B CN201310050893.6A CN201310050893A CN103122140B CN 103122140 B CN103122140 B CN 103122140B CN 201310050893 A CN201310050893 A CN 201310050893A CN 103122140 B CN103122140 B CN 103122140B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- 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
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- 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
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- 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
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
- C08L77/08—Polyamides derived from polyamines and polycarboxylic acids from polyamines and polymerised unsaturated fatty acids
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Abstract
Provided is a resin composition comprising a thermoplastic resin (A), a filler (B), and a predetermined amount of a melt viscosity reducing agent (C). The melt viscosity reducing agent (C) used in a predetermined amount is either the following (a) or (b): (a) The melt viscosity reducing agent (C) is a polyfunctional allyl compound (C1), and the content of polyfunctional allyl compound (C1) with respect to a total of 100 parts by mass of the thermoplastic resin (A) and filler (B) is 3 to 20 parts by mass, or (b) the melt viscosity reducing agent (C) is a dimer acid-based thermoplastic resin (C2), and the content of the dimer acid-based thermoplastic resin (C2) with respect to a total of 100 parts by volume of the thermoplastic resin (A) and filler (B) is 10 to 45 parts by volume.
Description
The divisional application (denomination of invention of original application is " resin combination and the formed body formed by it ", and the applying date of original application is on January 19th, 2010) of the application's to be Chinese application number be application for a patent for invention of 2010800031090.
Technical field
The formed body that the present invention relates to resin combination and formed by it, the resin combination particularly relating to melt fluidity when possessing shaping and the formed body formed by it.
Background technology
As the known thermoplastic resin being used as shaping raw material, polypropylene (PP), ABS, polymeric amide (PA6, PA66 etc.), polyester (PET, PBT etc.), polycarbonate (PC), liquid crystal polyester (LCP), polyphenylene sulfide (PPS) etc. can be enumerated.These resins are widely used in the fields such as various e-machine, electronic unit, mechanical part.These thermoplastic resins improve intensity, thermotolerance by being combined with the strengthening packing material of talcum, glass fibre etc., or also by being combined with the packing material with specific function and imparting various function.
In the framework of the portable electronic device of PDA, mobile telephone, PC etc., use the noncrystal thermoplastic resin of the polycarbonate resin, ABS resin etc. of the appearance of products formed, low warpage properties excellence.In recent years, along with e-machine miniaturization, lighting, framework also requires it is thin molded article.For this reason, in above-mentioned polycarbonate resin, ABS resin, talcum, glass fibre etc. has been coordinated to be used as strengthening material.But in these reinforced resin compositions, the use level along with this strengthening material increases, although the intensity of framework etc. improves, the mobility of resin reduces.Therefore, be especially difficult to make this thin-walled of framework and the formed product of complicated shape.
On the other hand, for recent e-machine, along with its high performance, miniaturization and lighting, the hot countermeasure heat produced by various electronic unit externally spread efficiently has become very important problem.Therefore, require that improvement is more and more higher as the cry of the thermal diffusivity of the resin molding material of this e-machine constituent material.As the known method of the thermal diffusivity for modified resin formed material, the method for the packing material (boron nitride, aluminium nitride, silicon nitride, aluminum oxide, magnesium oxide, zinc oxide, silicon carbide, graphite etc.) that known cooperation thermal conductivity is high.Such as, describe in JP62-131033A respectively and powdered graphite is filled in thermally conductive resin products formed obtained in thermoplastic resin, describe magnesium oxide, alumina filled resin-made heating panel obtained in polyphenylene sulfide in JP2001-151905A.But, in order to obtain highly thermal-conductive resin composition, packing material must be added in large quantities.Like this, therefore there is molding processibility and reduce significantly, limit the problem that the purposes of resin combination is such.
As this method being added with the processibility of the resin combination of packing material in large quantities of improvement, the method for known interpolation softening agent.But, if add softening agent, then exists and not only make the intensity of resin combination reduce significantly, and softening agent volatilizees such problem when melting mixing.Also there is the problem that plasticizer exudation is such.
Summary of the invention
Therefore, the resin combination adding the melt fluidity excellence in man-hour when problem of the present invention is to provide injection molding etc. and the formed body formed by it.
Main idea of the present invention is as described below.
(1) a kind of resin combination, it is characterized in that, melt viscosity depressant (C) containing thermoplastic resin (A), packing material (B) and specified amount, the melt viscosity depressant (C) of described specified amount is following (a) and any one in (b):
A () melt viscosity depressant (C) is multi-functional allylic cpd (C1), relative to total amount 100 mass parts of thermoplastic resin (A) with packing material (B), the content of multi-functional allylic cpd (C1) is 3 ~ 20 mass parts.
B () melt viscosity depressant (C) is dimeracid base thermoplastic resin (C2), relative to thermoplastic resin (A) total amount 100 capacity part with packing material (B), the content of dimeracid base thermoplastic resin (C2) is 10 ~ 45 capacity parts.
(2) resin combination Gen Ju (1), is characterized in that, multi-functional allylic cpd (C1) is compound skeleton with isocyanuric acid ester.
(3) resin combination Gen Ju (1), it is characterized in that, multi-functional allylic cpd (C1) is the primary amine (D) that represented by following formula (i) and have the reaction of multi-functional compounds (E) of allyl group and glycidyl and the allylic cpd that obtains
R-(NH
2)
n(i)
Here, n=1 ~ 4, R represents 1 ~ 4 replacement residue of fragrant family or fatty family.
(4) resin combination Gen Ju (3), is characterized in that, the multi-functional compounds (E) with allyl group and glycidyl is compound skeleton with isocyanuric acid ester.
(5) according to (2) or the resin combination described in (4), it is characterized in that, compound skeleton with isocyanuric acid ester is single glycidyl diallyl isocyanuric acid ester.
(6) resin combination Gen Ju (1), is characterized in that, dimeracid base thermoplastic resin (C2) is polyamide resin and/or vibrin.
(7) according to the resin combination described in any one in (1) ~ (6), it is characterized in that, packing material (B) is the thermal conductivity packing material (B1) of the thermal conductivity with more than 10W/ (mK).
(8) resin combination Gen Ju (7), is characterized in that, thermoplastic resin (A) is 20/80 ~ 95/5 with the volume ratio (A/B1) of thermal conductivity packing material (B1).
(9) according to (7) or the resin combination described in (8), it is characterized in that, thermal conductivity packing material (B1) is the flaky graphite from median size 1 ~ 300 μm, the graphitized carbon fibre of 1 ~ 30 μm, average fiber footpath, average fiber length 1 ~ 20mm, there is the flakey boron nitride of the median size 1 ~ 200 μm of hexagonal crystal structure, the aluminum oxide that median size is 0.5 ~ 150 μm, the magnesium oxide that median size is 0.5 ~ 150 μm, at least one selected in the zinc oxide of the magnesiumcarbonate that median size is 0.5 ~ 150 μm and median size 0.5 ~ 150 μm.
(10) according to the resin combination described in any one of (1) ~ (9), it is characterized in that, thermoplastic resin (A) is polyamide resin.
(11) formed body, is characterized in that, is to make the resin combination according to any one of (1) ~ (10) shaping and obtained.
(12) formed body, is characterized in that, is make the shaping rear irradiation radioactive rays of the resin combination according to any one of (1) ~ (10) and obtained.
According to the present invention, can provide due to the melt viscosity depressant (C) containing specified amount, the resin combination therefore adding the melt fluidity excellence in man-hour and the formed body obtained by it.
Especially when melt viscosity depressant (C) is for multi-functional allylic cpd (C1), because multi-functional allylic cpd (C1) has multiple allyl group in 1 molecule, so can by making resin and allyl group be cross-linked and strengthen the mechanical characteristics of products formed by known method, therefore, it is possible to obtain mechanical characteristics excellence and the resin combination adding the melt fluidity excellence in man-hour and the formed body formed by it.
Embodiment
Below the present invention is described in detail.
As may be used for thermoplastic resin of the present invention (A), there is no particular limitation, polyethylene can be enumerated, polypropylene, the ethene-alpha-olefin copolymer of ethylene-propylene copolymer etc., polymethylpentene, polyvinyl chloride, polyvinylidene dichloride, polyvinyl acetate, vinyl-vinyl acetate copolymer, polyvinyl alcohol, polyvinyl acetal, fluoro-resin (poly(vinylidene fluoride), tetrafluoroethylene etc.), polyethylene terephthalate, polybutylene terephthalate, PEN, poly(lactic acid), polystyrene, polyacrylonitrile, styrene-acrylonitrile copolymer, ABS resin, polyphenylene oxide (PPE), MODIFIED PP E, polymeric amide, polyimide, polyamidoimide, polyetherimide, the polymethacrylate of polymethylmethacrylate etc., polyacrylic, polycarbonate, polyarylate, polyphenylene sulfide, polysulfones, polyethersulfone, polyethers nitrile, polyetherketone, polyketone, liquid crystalline polymers etc.Wherein, from the view point of formability, reagent resistance, economy, preferred polyamide, in addition, from the view point of formability, thermotolerance, physical strength, also preferred liquid crystalline polymers.
As polyamide resin used in the present invention, the mixture of obtained homopolyamide and copolyamide and these resins by lactan or the polycondensation of amino acid whose polymerization or diamines and carboxylic acid can be enumerated.
As the preference of polyamide resin, polycaprolactam (nylon 6) can be enumerated, nylon 46 (nylon 46), polyhexamethylene adipamide (nylon66 fiber), polycaprolactam/polyhexamethylene adipamide multipolymer (nylon 6/66), poly-11 lactan (nylon 11), polycaprolactam/poly-11 lactan multipolymers (nylon 6/11), nylon 12 (nylon 12), polycaprolactam/nylon 12 multipolymer (nylon 6/12), polyhexamethylene sebacamide (NYLON610), nylon 612 (nylon 612), poly hexamethylene adipamide 11 methylene diamine (nylon 11 6), poly-6I hexamethylene isoterephalamide (nylon 6I), poly-hexamethylene terephthalamide (nylon 6T), poly-hexamethylene terephthalamide/poly-6I hexamethylene isoterephalamide multipolymer (nylon 6T/6I), polycaprolactam/poly-hexamethylene terephthalamide multipolymer (nylon 6/6T), polycaprolactam/poly-6I hexamethylene isoterephalamide multipolymer (nylon 6/6I), polyhexamethylene adipamide/poly-hexamethylene terephthalamide multipolymer (nylon66 fiber/6T), polyhexamethylene adipamide/poly-6I hexamethylene isoterephalamide multipolymer (nylon66 fiber/6I), poly-paraphenylene terephthalamide's trimethylhexane diamine (nylon TMDT), poly-two (4-aminocyclohexyl) methanedodecanoamide (nylon PACM12), poly-two (3-methyl-4-aminocyclohexyl) methanedodecanoamide (nylon dimethyl PACM12), poly-m-phenylene adipamide (nylon MXD 6), poly-paraphenylene terephthalamide 11 methylene diamine (nylon 11 T), and the mixture of these polyamide resins or multipolymer etc.Wherein, from the view point of formability, economy, preferred nylon 6, nylon66 fiber.
May be used for liquid crystalline polymers of the present invention and refer to the melt processable polymkeric substance with the character that can form optical anisotropy melting behaviors.This liquid crystalline polymers has the character of the parallel sequence by being subject to shear-stress and polymer molecular chain formation rule in the molten state.Generally speaking this polymer molecule is elongated, partially flat; Along the major axis of molecule, its rigid phase is when high; Usually there are the multiple chain lengthening keys that there is any one coaxial or parallel relation.Such as, the polyester of all aromatic system or semiaromatic family, polyester-imide, polyesteramide or their mixture etc. can be enumerated.
As the preference of liquid crystalline polymers, liquid crystal polyester, liquid crystal polyesteramide, liquid crystal polyester carbonic ether, liquid crystal polyester elastomerics etc. can be enumerated.Wherein, from the view point of formability, preferred liquid crystal polyester.
As liquid crystal polyester, the polyester forming anisotropy melting behaviors be made up of the structural unit being selected from aromatic hydroxyl carbonyl unit, aromatic series dihydroxyl unit, aromatic series dicarbonyl unit, ethene dihydroxyl unit etc. can be enumerated.
Resin combination of the present invention contains packing material (B).As the packing material used in the present invention (B), there is no particular limitation, can enumerate to improve the packing material used for the purpose of mechanical properties, thermal properties etc., the packing material used for the purpose of the function of giving electroconductibility, thermal conductivity, magnetic, piezoelectricity, absorption of electromagnetic wave, flame retardant resistance, ultraviolet radiation absorption etc. as representative examples.As the form of packing material (B), spherical, powdery, threadiness, needle-like, squamous, flakey, crystal whisker-shaped, micro-coiled type, nanotube-shaped etc. can be enumerated.
As the concrete example of packing material (B), acetylene black can be enumerated, Ketjen black, carbon nanotube, carbon nanofiber, metal powder (silver, copper, aluminium, titanium, nickel, tin, iron, stainless steel etc.), electroconductive zinc oxide, stannic oxide, Indium sesquioxide, various ferrite, martial ethiops, aluminum oxide, magnesium oxide, zinc oxide, magnesiumcarbonate, silicon carbide, aluminium nitride, boron nitride, silicon nitride, carbon, graphite, barium titanate, Pb-based lanthanumdoped zirconate titanates, potassium titanate, xonotlite, mica, talcum, montmorillonite, hydrotalcite, calcium carbonate, zinc carbonate, wollastonite, barium sulfate, molybdenumdisulphide, vinyl fluoride (such as Teflon (registered trademark)) powder, silicon-dioxide, granulated glass sphere, glass sphere, titanium oxide, aluminium hydroxide, magnesium hydroxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, boric acid, zinc borate, cerium oxide, calcium oxide, silica gel, sepiolite, activated carbon, zeolite, tungsten, zirconium white, cellulose fine particle, wood powder, bean dregs, rice husk, glass fibre, carbon fiber, graphitized carbon fibre, aromatic polyamide fibre, steel fiber, Stainless Steel Fibre, silica fiber, silica alumina fiber, Zirconium oxide fibre, silicon nitride fiber, boron fibre, potassium titanate fiber, the natural fiber etc. of mestha and hemp etc.
In resin combination of the present invention, thermoplastic resin (A) is preferably 20/80 ~ 95/5 with the volume ratio (A/B) of packing material (B) [comprising thermal conductivity packing material (B1) described later], be more preferably 30/70 ~ 90/10, be particularly preferably 30/70 ~ 60/40.When the use level of packing material (B) is less than 5 capacity %, there is the situation that cannot obtain the effect having coordinated packing material fully; If use level is more than 80 capacity %, then mobility reduces significantly, and therefore, load when there is forming process becomes too high, the situation that operability reduces.
In the present invention, in order to give thermal conductivity to resin combination, the thermal conductivity packing material (B1) of the thermal conductivity with more than 10W/ (mK) can be used as packing material (B).As thermal conductivity packing material (B1), any one in conductive filler materials, insulativity packing material can be used.The thermal conductivity of thermal conductivity packing material (B1) can use its sinter to measure.As the concrete example (what record in parantheses is the typical value [unit: W/ (mK)] of thermal conductivity) of thermal conductivity packing material (B1), aluminum oxide (36) can be enumerated, magnesium oxide (60), zinc oxide (25), magnesiumcarbonate (15), silicon carbide (160), aluminium nitride (170), boron nitride (210), silicon nitride (40), carbon (10 ~ hundreds of), the inorganic system packing material of graphite (10 ~ hundreds of) etc., silver (427), copper (398), aluminium (237), titanium (22), nickel (90), tin (68), iron (84), the metal system packing material etc. of stainless steel (15) etc.These thermal conductivity packing materials can use one, in addition, also may be two kinds or more.
Except specific packing material described later, the median size of thermal conductivity packing material (B1) is preferably 0.5 ~ 300 μm, is more preferably 1 ~ 150 μm.When median size is less than 0.5 μm, be easy to due to poor dispersion produce cohesion block, cannot obtain uniform products formed, mechanical properties reduces, or produces deviation in thermal conductivity, therefore not preferred.If median size is more than 300 μm, then exists and be difficult to fill at resin middle and high concentration, or products formed surface becomes coarse situation, therefore not preferred.
For the present invention, in above-mentioned illustrative packing material, as thermal conductivity packing material (B1), heat transfer efficiency during owing to coordinating to thermoplastic resin (A) is high, therefore preferably uses graphite, boron nitride.In addition, from the view point of economy, preferably use aluminum oxide, magnesium oxide, magnesiumcarbonate, zinc oxide.
As the form of the graphite system packing material that can use in the present invention, spherical, powdery, threadiness, needle-like, flakey, crystal whisker-shaped, micro-coiled type, nanotube-shaped etc. can be enumerated.Wherein, flaky graphite, graphitized carbon fibre can make heat transfer efficiency improve when coordinating with thermoplastic resin (A), therefore particularly preferably.
The median size of flaky graphite is preferably 1 ~ 300 μm, is more preferably 5 ~ 150 μm.When median size is less than 1 μm, because poor dispersion is easy to generate cohesion block, therefore, existence cannot obtain uniform products formed, and mechanical properties declines, or in thermal conductivity, produce the situation of deviation.If median size is more than 300 μm, then exists and be difficult to fill at resin combination middle and high concentration, and the situation of products formed surface roughen.
As graphitized carbon fibre, the carbon fiber of preferred asphalt series, this is on the books in such as JP2003-49327A, wherein, preferably by taking mesophase pitch as raw material, it being calcined under the high temperature of 1000 ~ 3000 DEG C and has carried out graphited pitch-based carbon fiber fully.There is no particular limitation for graphited degree, but along with close to graphite fibre, the thermal conductivity of length direction increases.In the present invention, the thermal conductivity of the length direction of graphitized carbon fibre is generally more than 100W/ (mK), is preferably 500W/ (mK).
The average fiber footpath of graphitized carbon fibre is preferably 1 ~ 30 μm, more preferably 5 ~ 20 μm.When average fiber footpath is less than 1 μm, enough thermal conductivitys cannot be obtained, if average fiber footpath is more than 30 μm, then there is the situation that formability etc. reduces.
The average fiber length of graphitized carbon fibre is preferably 1 ~ 20mm, more preferably 3 ~ 15mm.When average fiber length is less than 1mm, enough thermal conductivitys cannot be obtained.Average fiber length is longer, and not only thermal conductivity is higher, and flexural strength, bending elastic modulus are also larger.But if average fiber length is more than 20mm, then the decline of mobility becomes large, from aspects such as formabilities, not preferably.
As the commercially available product of graphitized carbon fibre, such as, can enumerate the trade(brand)name " GRANOC " of Japanese graphite fibre Inc., the trade(brand)name " DIALEAD " etc. of Chan Zi Inc. of Mitsubishi Chemical.
As the form of the boron nitride that can use in the present invention, spherical, powdery, threadiness, needle-like, flakey, crystal whisker-shaped, micro-coiled type, nanotube-shaped etc. can be enumerated.Owing to being easy to orientation on direction, face when forming formed body, consequently thermal conductivity can be improved, therefore preferred flakey.By containing boron nitride, can, when not making the insulativity of resin combination decline, thermal conductivity be improved.
The median size of boron nitride element is preferably 1 ~ 200 μm, more preferably 5 ~ 100 μm.When median size is less than 1 μm, be easy to due to poor dispersion generate cohesion block, therefore, existence cannot obtain uniform products formed, and mechanical properties declines, or in thermal conductivity, produce the situation of deviation.If median size is more than 200 μm, then exists and be difficult to fill at resin combination middle and high concentration, and the situation of products formed surface roughen.
There is no particular limitation for the crystallographic system of boron nitride.Even if be the boron nitride of hexagonal system, isometric system, other any one crystalline structure, also can be suitable for.Wherein, there is the boron nitride of hexagonal crystal structure because thermal conductivity is large preferably.
As the form of the aluminum oxide that can use in the present invention, magnesium oxide, magnesiumcarbonate, zinc oxide, spherical, fibrous, fusiform, bar-shaped, needle-like, tubular, column etc. can be enumerated.Due to the reduction of the Resin Flow when coordinating with thermoplastic resin (A) can be suppressed, so preferably spherical.By containing aluminum oxide, magnesium oxide, magnesiumcarbonate, can, when not making the insulativity of resin combination decline, thermal conductivity be improved.
The median size of aluminum oxide, magnesium oxide, magnesiumcarbonate, zinc oxide is preferably 0.5 ~ 150 μm, more preferably 1 ~ 100 μm.When median size is less than 0.5 μm, be easy to due to poor dispersion produce cohesion block, therefore exist and cannot obtain uniform products formed, mechanical properties reduces, or in thermal conductivity, produce the situation of deviation.If median size is more than 150 μm, then exists and be difficult to carry out at resin combination middle and high concentration, and the situation of products formed surface roughen.
Improving with the adaptation of thermoplastic resin (A) to be used in packing material of the present invention (B), surface treatment can be implemented with coupler.As the example of coupler, silane system coupler can be enumerated, titanium system coupler etc., such as can enumerate gamma-amino propyl trimethoxy silicane, N-β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane, the amino silicone methane series coupler of N-β-(amino-ethyl)-gamma-amino dimethylamine oxygen butyldimethylsilyl etc., γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyl group Ethoxysilane, β-(3, 4-epoxycyclohexyl) the epoxy silane system coupler of ethyl trimethoxy silane etc., sec.-propyl three stearyl-titanic acid ester, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester, the titanium system coupler etc. of tetra isopropyl two (the sub-phosphorus acyloxy of dioctyl) titanic acid ester etc.These couplers can be used individually, also can be used together.
Resin combination of the present invention contains the fluidity amendment (C) of specified amount.The fluidity amendment (C) used in the present invention is any one in multi-functional allylic cpd (C1) and dimeracid base thermoplastic resin (C2).
There is no particular limitation for multi-functional allylic cpd (C1), but be necessary for liquid state under the melt processing temperature of resin combination.In addition, multi-functional allylic cpd (C1) reduces, so also can be effective as softening agent and play a role owing to can make the melt viscosity of interpolation resin.
As the concrete example of multi-functional allylic cpd (C1), triallyl isocyanuric acid ester can be enumerated, single glycidyl diallyl isocyanuric acid ester, diglycidyl monoallyl isocyanuric acid ester, trimethyl allyl isocyanuric acid ester, single glycidyl dimethyl allyl group isocyanuric acid ester, diglycidyl monomethyl allyl group isocyanuric acid ester, triallyl cyanurate, single glycidyl diallyl cyanurate, diglycidyl monoallyl cyanurate, trimethyl allyl cyanurate, single glycidyl dimethyl allyl group cyanurate, diglycidyl monomethyl allyl group cyanurate, allyl glycidol amine, diallyl list glycidyl amine, monoallyl 2-glycidyl amine, single glycidyl dimethyl allylamine, diglycidyl monomethyl allylamine, glycidyl acryl chlorendic acid ester, allyl glycidyl adipic acid ester, allyl glycidyl carbonic ether, allyl glycidyl alkyl dimethyl ammonium chloride, allyl glycidyl fumaric acid esters, allyl glycidyl isophthalic acid ester, allyl glycidyl malonic ester, allyl glycidyl barkite, allyl glycidyl phthalic ester, allyl glycidyl propyl group isocyanuric acid ester, allyl glycidyl sebate, allyl glycidyl succinate, allyl glycidyl terephthalate, allyl glycidyl tartrate, glycidyl methacrylic phthalic ester etc.In these compounds, preferably there is on skeleton the compound of isocyanuric acid ester, particularly from operability, economy aspect, preferred triallyl isocyanuric acid ester, single glycidyl diallyl isocyanuric acid ester.
In addition, as multi-functional allylic cpd (C1), except above-claimed cpd, the primary amine (D) that represented by following formula (i) can be used and there is the reaction of multi-functional compounds (E) of allyl group and glycidyl and the allylic cpd that obtains.
R-(NH
2)n (i)
Here, n=1 ~ 4, R represent that 1 ~ 4 of fragrant family or fatty family replaces residue.
The Diamines of the preferred n=2 of the primary amine (D) that formula (i) represents.As the concrete example of the Diamines of n=2, quadrol can be enumerated, hexanediamine, Isosorbide-5-Nitrae-diamino-cyclohexane, 1,3-diamino-cyclohexane, 4，4′-diaminodicyclohexylmethane, two (amino methyl) hexanaphthene of 1,3-, Isosorbide-5-Nitrae-bis-(amino methyl) hexanaphthene, 4,4 '-diaminocyclohexyl propane, two (4-aminocyclohexyl) sulfone, 4,4 '-diamino two hexamethylene ether, 2,2 '-dimethyl-4,4 '-diamino bicyclohexane, 2,2 '-bis-(trifluoromethyl)-4,4 '-diamino bicyclohexane, 2,2 '-bis-(trichloromethyl)-4,4 '-diamino bicyclohexane, 2,2 '-bis-(trisbromomethyl)-4,4 '-diamino bicyclohexane, 2,2 '-two fluoro-4,4 '-diamino bicyclohexane, 2,2 '-two chloro-4,4 '-diamino bicyclohexane, 2,2 '-two bromo-4,4 '-diamino bicyclohexane, 4,4 '-diamino bicyclohexane, 2,2-two (4-aminocyclohexyl)-1,1,1,3,3,3-HFC-236fa, 2,3-diamino bicyclic [2.2.1] heptane, 2,5-diamino bicyclic [2.2.1] heptane, 2,6-diamino bicyclic [2.2.1] heptane, 2,7-diamino bicyclic [2.2.1] heptane, two (amino methyl)-dicyclo [2.2.1] heptane of 2,5-, two (amino methyl)-dicyclo [2.2.1] heptane of 2,6-, two (amino methyl)-dicyclo [2.2.1] heptane of 2,3-, diethylenetriamine, dipropylenetriamine, Triethylenetetramine (TETA), two (amino methyl) benzene of 1,2-, two (amino methyl) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(amino methyl) benzene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, 2,2 '-bis-(trichloromethyl)-4,4 '-benzidine, 2,2 '-bis-(trisbromomethyl)-4,4 '-benzidine, 2,2 '-two fluoro-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-benzidine, 2,2 '-two bromo-4,4 '-benzidine, 4,4 '-benzidine, 4,4 '-diamino-benzophenone, two (4-aminophenyl) fluorenes of 9,9-, two (4-amino-2-fluorophenyl) fluorenes of 9,9-, two (4-amino-2-bromophenyl) fluorenes of 9,9-, two (4-amino-2-chloro-phenyl-) fluorenes of 9,9-, two (4-amino-3-fluorophenyl) fluorenes of 9,9-, two (4-amino-3-bromophenyl) fluorenes of 9,9-, two (4-amino-3-chloro-phenyl-) fluorenes of 9,9-, two (4-amino-2-trifluoromethyl) fluorenes of 9,9-, two (4-amino-3-trifluoromethyl) fluorenes of 9,9-, two (4-aminophenyl) sulfone, Isosorbide-5-Nitrae-diaminobenzene, 1,3-diaminobenzene, 4,4 '-diamino-diphenyl ether, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl propane, 2,2-two (4-aminophenyl)-1,1,1,3,3,3-HFC-236fa, 3,4 '-diamino-diphenyl ether etc.
In the primary amine (D) that formula (i) represents, as the concrete example of the monoamine of n=1, methylamine can be enumerated, dimethylamine, ethamine, diethylamine, Tri N-Propyl Amine, di-n-propylamine, Isopropylamine, n-Butyl Amine 99, isobutylamine, sec-butylamine, TERTIARY BUTYL AMINE, Di-n-Butyl Amine, monoamylamine, diamylamine, ethyl butyl amine, normal hexyl Amine, two normal hexyl Amines, hexahydroaniline, amino dodecane, cetylamine, stearylamine, aniline, Ortho Toluidine, meta-aminotoluene, para-totuidine, 23 dimethyl aniline, 2,6-xylidine, 3,4-xylidine, 3,5-xylidine, Ortho-Chloro aniline, m-chloro aniline, p-Chlorobenzoic acid amide, o-bromoaniline, m-bromoaniline, para-bromoaniline, o-Nitraniline, m-nitraniline, p-Nitroaniline, Ortho-Aminophenol, Metha Amino Phenon, p-aminophenol, ORTHO ANISIDINE, m-anisidine, P-nethoxyaniline, O-ethoxyl amine, m-oxethyl aniline, p-ethoxyaniline, o-Aminobenzaldehyde, NSC 36957, p-Aminobenzaldehyde, Gas chromatography, m-aminophenyl nitrile, p-aminophenyl nitrile, 2-phenylaniline, 3-phenylaniline, 4-phenylaniline, 2-aminophenylphenyl ether, 3-aminophenylphenyl ether, 4-aminophenylphenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-aminobenzophenone, 2-aminophenylphenyl thioether, 3-aminophenylphenyl thioether, 4-aminophenylphenyl thioether, 2-aminophenylphenyl sulfone, 3-aminophenylphenyl sulfone, 4-aminophenylphenyl sulfone, alpha-naphthylamine, beta-naphthylamine, 1-amino-beta naphthal, 2-amino-1-naphthols, 4-amino-1-naphthols, 5-amino-1-naphthols, 5-amino-beta naphthal, 7-amino-beta naphthal, 8-amino-1-naphthols, 8-amino-beta naphthal, 1-amino anthracene, 2-amino anthracene, 9-amino anthracene etc.
In the primary amine (D) that formula (i) represents, as the concrete example of n=3, can 1 be enumerated, 3,5-triaminobenzene, three (3-aminophenyl) amine, three (4-aminophenyl) amine, three (3-aminophenyl) benzene, three (4-aminophenyl) benzene, 1,3,5-tri-(3-amino-benzene oxygen) benzene, 1,3,5-tri-(4-amino-benzene oxygen) benzene, 1,3,5-tri-(4-amino-benzene oxygen) three azines etc.
In the primary amine (D) that formula (i) represents, as the concrete example of the tetraamine of n=4, can 1 be enumerated, 2,4,5-tetramino benzene, 3,3 ', 4,4 '-tetra-amino-biphenyl, 3,3 ', 4,4 '-tetramino sulfobenzide, 3,3 ', 4,4 '-tetramino diphenyl sulfide, 2,3,6,7-tetramino naphthalene, 1,2,5,6-tetramino naphthalene etc.
For the object of the various characteristics of adjustment etc., also can be used together the multiple amine in these primary amines (D).
As the multi-functional compounds (E) with allyl group and glycidyl reacted with above-mentioned primary amine (D), if having the monosomy compound of allyl group and glycidyl, then there is no particular limitation.If illustrate, single glycidyl diallyl isocyanuric acid ester can be enumerated, diglycidyl monoallyl isocyanuric acid ester, single glycidyl dimethyl allyl group isocyanuric acid ester, diglycidyl monomethyl allyl group isocyanuric acid ester, single glycidyl diallyl cyanurate, diglycidyl monoallyl cyanurate, single glycidyl dimethyl allyl group cyanurate, diglycidyl monomethyl allyl group cyanurate, allyl glycidol amine, diallyl list glycidyl amine, monoallyl 2-glycidyl amine, single glycidyl dimethyl allylamine, diglycidyl monomethyl allylamine, glycidyl acryl chlorendic acid ester, allyl glycidyl adipic acid ester, allyl glycidyl carbonic ether, allyl acyl group glycidyl dimethyl ammonium chloride, allyl glycidyl fumaric acid esters, allyl glycidyl isophthalic acid ester, allyl glycidyl malonic ester, allyl glycidyl barkite, allyl glycidyl phthalic ester, allyl glycidyl propyl group isocyanuric acid ester, allyl glycidyl sebate, allyl glycidyl succinate, allyl glycidyl terephthalate, allyl glycidyl tartrate, glycidyl methacrylic phthalic ester etc.
In these compounds, as multi-functional compounds (E), preferred skeleton has the compound of isocyanuric acid ester, particularly preferred single glycidyl diallyl isocyanuric acid ester.
By primary amine as above (D) is mixed with the multi-functional compounds (E) with allyl group and glycidyl, the addition reaction utilizing the heat based on amine and glycidyl to carry out, obtains in 1 molecule, have multiple allylic compound.During reaction, primary amine (D) with the proportioning of multi-functional compounds (E) is: relative to primary amine (D) 1 equivalent, glycidyl is 1 ~ 2 equivalent.When primary amine (D) is for fatty family, the nucleophilicity of amine is strong, therefore, relative to 1 amine, 2 glycidyls can be made to carry out addition reaction.That is, such as can think relative to aliphatie diamine 1 mole, Racemic glycidol radical reaction 4 molar weight.When primary amine (D) is fragrant family, the nucleophilicity of amine is more weak, exists and 2 glycidyls cannot be made to carry out the situation of addition reaction.That is, such as can think relative to aromatic diamines 1 mole, Racemic glycidol radical reaction roughly 2 molar weight.
There is no particular limitation for the method making primary amine (D) and multi-functional compounds (E) carry out reacting, such as, as mentioned above, can by primary amine (D) being mixed with multi-functional compounds (E) with specified amount, and make its heating and melting, thus carry out above-mentioned reaction easily.Now, also suitable reaction solvent can be used as required.Heating temperature for reacting can set the scope of 80 ~ 200 DEG C usually.There is no particular limitation for atmosphere during reaction, can react in atmosphere.But, when the problem of oxidation that existence causes due to oxygen, can replace atmosphere with rare gas elementes such as nitrogen.
The boiling point of reaction product obtained is like this high, therefore, not volatile when melt-processed, also effectively can be used as crosslinking coagent, end-capping reagent etc.In addition, owing to there is multiple allyl group in 1 molecule, so allyl group and resin can be made to be cross-linked by known method, can strengthen resin expeditiously.
In resin combination of the present invention, relative to total amount 100 mass parts of thermoplastic resin (A) with packing material (B), the addition of multi-functional allylic cpd (C1) is necessary for 3 ~ 20 mass parts, is preferably 4 ~ 15 mass parts.When addition is less than 3 mass parts, there is the situation that cannot obtain enough melt fluiditys.On the contrary, when more than 20 mass parts, there is melt viscosity and excessively to reduce and cannot granular situation when melting mixing, or the situation that the physical property that there is the formed body obtained reduces significantly.
Multi-functional allylic cpd (C1) owing to having multiple allyl group in 1 molecule, so according to known method, by with linking agent and use, or with the radiation exposure process of electron beam, gamma-rays etc. and use, thermoplastic resin (A) can be made to be cross-linked.Wherein, process this respect can be carried out with the short period of time from after being shaped to required shape, be cross-linked preferably by electron beam, gamma-rays.Gamma-rays is compared with electron beam, and transmissivity is strong, therefore, owing to irradiating evenly, uses gamma-ray being cross-linked so be more preferably.Electron beam irradiation can use known rumbatron etc., and gamma-ray irradiation can use the known irradiating unit utilizing Co 60 gamma ray source etc.The radiation dose of electron beam is preferably 1 ~ 300kGy, is more preferably 50 ~ 100kGy.When for gammairradiation, radiation dose is preferably 10 ~ 100kGy, is more preferably 20 ~ 40kGy.If the radiation dose of radioactive rays exceedes above-mentioned higher limit, then intensity is made to reduce due to the decomposition of resin, therefore not preferred.In addition, when being less than above-mentioned lower value, can not play based on crosslinked effect, therefore not preferred.Irradiating atmosphere usually can in the presence of the air, but as required can under nitrogen atmosphere, irradiate in vacuum.
Dimeracid base thermoplastic resin (C2) is described.In the present invention, so-called dimeracid base thermoplastic resin (C2), be main sour composition with dimeracid or dicarboxylic acid, the obtained thermoplastic resin by these sour compositions and the polycondensation of the composition such as diamines, ethylene glycol, wherein said dimeracid is the dimer of the lipid acid such as soybean oil, tung oil, Yatall MA, and described dicarboxylic acid comprises the derivative that the derivative that can generate its acid amides maybe can generate its ester.The principal constituent of dimeracid is dimer, but in addition, also can contain monomer, tripolymer etc.In addition, the dimer of lipid acid and dimeracid or the derivative that comprises the acid amides that can generate it maybe can generate the dicarboxylic acid of the derivative of its ester can be hydride.
Dimeracid base thermoplastic resin (C2) melt viscosity compared with thermoplastic resin (A) is low, the melt viscosity of resin can be made to reduce, so be effective as softening agent and play a role by adding dimeracid base thermoplastic resin (C2).Further, dimeracid base thermoplastic resin (C2) is resin, and its decomposition temperature is high, non-volatile when melt-processed, therefore, effectively can use as softening agent.And then even if add dimeracid base thermoplastic resin (C2), the reduction of physical strength is also little, and then, be effective not oozing out this respect.
As dimeracid base thermoplastic resin (C2), there is no particular limitation.Polymeric amide, polyester etc. can be enumerated.Wherein, preferred polyamide in operability, economy.
As dimeracid basis polymeric amide, there is no particular limitation, can enumerate by dimeracid or comprise the polyamide resin etc. that the dicarboxylic acid component of the derivative that can generate its acid amides and diamines formed.Such as can enumerate the reaction product of the dimer of the lipid acid such as soybean oil, tung oil, Yatall MA and dimeracid and the such alkyl polyamine class of such as quadrol, diethylenetriamine etc.
As dimeracid base polyester, there is no particular limitation, can enumerate by dimeracid or comprise the vibrin etc. that the dicarboxylic acid component of the derivative that can generate its ester and glycol formed.Such as can enumerate the reaction product of the dimer of the lipid acid such as soybean oil, tung oil, Yatall MA and dimeracid and the such diol component of such as ethylene glycol, BDO and terephthalic acid, m-phthalic acid etc.
May be used alone dimeracid basis polymeric amide and dimeracid base polyester, also both can be mixed and use.
In resin combination of the present invention, relative to thermoplastic resin (A) total amount 100 capacity part with packing material (B), the addition of dimeracid base thermoplastic resin (C2) is necessary for 10 ~ 45 capacity parts, is preferably 10 ~ 25 capacity parts.When the use level of dimeracid base thermoplastic resin (C2) is less than 10 capacity part, existence cannot obtain the situation of the effect being combined with dimeracid base thermoplastic resin (C2) fully.On the contrary, if use level is more than 45 capacity parts, then there is mechanical properties and reduce significantly, or cannot granular situation be carried out when melting mixing.
In resin combination of the present invention, as long as there is no large infringement to its characteristic, pigment, thermo-stabilizer, antioxidant, weather agent, fire retardant, lubricant, releasing agent, static inhibitor, nucleator, compatilizer etc. just can be added.As thermo-stabilizer, antioxidant, such as, can enumerate Hinered phenols, phosphorus compound, hindered amine, sulphur compound, copper compound, alkali-metal halogenide etc.As fire retardant, hydrated metal compound (aluminium hydroxide, magnesium hydroxide etc.) can be enumerated, containing nitrogen compound (melamine series, guanidine system), phosphorus flame retardant, halogen-system fire retardant, inorganic flame retardant etc.As nucleator, the metal-salt of glucitol compounds, phenylformic acid and compound thereof, phosphate metal salt, rosin compound etc. can be enumerated.As compatilizer, ionomer system compatilizer, oxazoline system compatilizer, elastic system compatilizer, reactive compatibilizers, copolymerization system compatilizer etc. can be enumerated.1 kind in these additives can be used, or be two kinds or more.In resin combination of the present invention, mix the method for these additives, there is no particular limitation.
Resin combination of the present invention is can by with general forcing machine, such as single axle extruding machine, biaxial extruder, roll-type mixing roll, Brabender mixing roll etc., to thermoplastic resin (A), packing material (B), multi-functional allylic cpd (C1) or dimeracid base thermoplastic resin (C2), further as required and the various additives added carry out melting mixing to manufacture.Now, and be also effective with static mixer, dynamic mixer.Mixing in good condition in order to make, preferably use biaxial extruder.For packing material (B), multi-functional allylic cpd (C1) or dimeracid base thermoplastic resin (C2), there is no particular limitation, can add from hopper in an extruder, or use side feeder to add.
By the known melt molding method such as use injection molding, compressed moulding, extrusion moulding, transfer mould, sheet shaping, resin combination of the present invention can be shaped to the shape of needs, thus make formed body.On the basis of shape resin combination being shaped to needs, irradiate radioactive rays by mode as above, resin can be made to be cross-linked.
In the present invention, as by concrete example that is shaping for the resin combination of the thermal conductivity packing material (B1) being combined with the thermal conductivity with more than 10W/ (mK) and the formed body obtained, electric, the electronic unit of the sealing material, junctor, socket, relay1 block, winder, optical pick-up, vibrator, computer association parts etc. for semiconductor element, resistance etc. can be enumerated; The domestic electrical product component such as VTR, televisor, flatiron, air-conditioning, stereophonic sound system, suction cleaner, refrigerator, cooker, lighting fixtures; The radiating component for the heat from electronic unit is externally spread such as radiating seat, radiator element, fan; The lighting fixtures parts such as lamp socket, lamp reflector, lampshade; The acoustic product parts such as compact disk, CD, loud speaker; The communicating machine parts such as optical fiber lasso, portable telephone, fixed telephone, fax, modulator-demodulator unit; Duplicating machine, the printing press associated members such as disengaging pawl, well heater retainer; The mechanical part of impeller, fan gear, gear, bearing, motor part and fuselage etc.; The trolley parts such as automobile mechanism part, engine parts, engine room inner part, electrical equipment component, internal unit parts; The utensil for cooking such as microwave oven, oven-to-table ware; Aircraft, spaceship, space machine parts; Sensor class parts etc.
Embodiment
Below, based on embodiment, the present invention is specifically described.But the present invention is not limited to these embodiments.
In following embodiment and comparative example, the test method of various physics value is as described below.
[1] MFR (melting index):
For the particle of thermoplastic resin composite, landing-type flow assay instrument (Toyo Seiki manufacturing company system) is used to measure its MFR value under given load, specified temperature.Now pore mould is the pore mould using diameter 1mm × long 10mm.
[2] flexural strength, bending elastic modulus:
With method described in ASTM specification D-790 for benchmark measures.
[3] shock strength:
With method described in ASTM specification D-256 for benchmark, the test film of band recess is used to measure Izod impact strength.
[4] thermal conductivity:
Thermal conductivity λ method of calculation are as follows: utilize following method to obtain thermal diffusivity α, density p, specific heat Cp, and calculate its product with following formula, as thermal conductivity λ.
λ=αρCp
λ: thermal conductivity (W/ (mK))
α: thermal diffusivity (m
2/ sec)
ρ: density (g/m
3)
Cp: specific heat (J/gK)
Thermal diffusivity α uses laser pulse method thermal constant determinator TC-7000 (ULVAC-RIKO.Inc system), measures the resin flows direction according to the pliability test sheet made by [2] with laser pulse method.Density p uses electronic hydrometer ED-120T (MIRAGE trading company system) to measure.Specific heat Cp uses differential scanning calorimeter DSC-7 (PerkinElmer Co., Ltd system), carries out measuring under the condition of heat-up rate 10 DEG C/minute.
[5] formability
Will for after examination resin combination fully drying, using injection moulding machine (Toshiba Machine Co. Ltd's system: EC-100 type), is the strip sample of wide 13mm, long 130mm, thick 0.8mm by its injection molding.For the state of the matrix band of gained, carried out the evaluation of 3 grades by following shown standard.
Good: no problem in appearance, and the size of regulation can be shaped to
Slightly poor: the size that can be shaped to regulation, but the smoothness on matrix band surface is poor
Difference: poor fluidity, cannot be shaped to the size of regulation
The raw material used in embodiment and comparative example is as follows.
(1) thermoplastic resin (A)
PA6A: polyamide 6 (relative viscosity 2.6, the density 1.13g/cm obtained by the polymerization of lactan
3)
PA6B: polyamide 6 (relative viscosity 1.9, the density 1.13cm obtained by the polymerization of lactan
3)
PA66: by hexanediamine with being polymerized of hexanodioic acid and obtained polyamide 66 (relative viscosity 2.8, density 1.14cm
3)
LCP: liquid crystal polyester (Unitika Corp RODRUN LC-5000, density 1.41g/cm
3)
PA12: polymeric amide 12 (Arkema Rilsan AMN, relative viscosity 2.3, density 1.01g/cm
3)
PP: polypropylene (Japan Polypropylene Corporation MA1B, density 0.9g/cm
3)
PLA: poly(lactic acid) (NatureWorks Inc., weight-average molecular weight (MW)=190,000, density 1.25g/cm
3)
(2) packing material (B)
GrA: flaky graphite (Japanese graphite industrial system, median size 40 μm, thermal conductivity 100W/ (mK), density 2.25g/cm
3)
GrB: flaky graphite (Japanese graphite industrial system, median size 130 μm, thermal conductivity 100W/ (mK), density 2.25g/cm
3)
GrCF: graphitized carbon fibre (Nippon Graphite Fiber Inc., 9 μm, average fiber footpath, average fiber length 3mm, density 2.2g/cm
3)
BN: hexagonal system flakey boron nitride (Denki Kagaku Kogyo kabushiki's system, median size 15 μm, density 2.26g/cm
3)
ALOA: aluminum oxide (Denki Kagaku Kogyo kabushiki's system, median size 10 μm, thermal conductivity 38W/mK, density 3.97g/cm
3)
ALOB: aluminum oxide (Denki Kagaku Kogyo kabushiki's system, median size 50 μm, thermal conductivity 38W/ (mK), density 3.97g/cm
3)
TC: talcum (Japanese talcum Inc. K-1, median size 8 μm, density 2.7g/cm
3)
MgO: magnesium oxide (Shen Dao chemical company system, median size 5 μm, thermal conductivity 50W/ (mK), density 3.58g/cm
3)
MgCO: magnesiumcarbonate (Shen Dao chemical company system, median size 10 μm, thermal conductivity 15W/ (mK), density 3.05g/cm
3)
ZnO: zinc oxide (Sakai Chemical Industry Inc., median size 10 μm, thermal conductivity 25W/ (mK), density 5.78g/cm
3)
AF: polyparaphenylene-3,4 '-hydroxyl diphenylene terephthalamide fiber (Teijin TechnoProducts Inc., 12 μm, average fiber footpath, average fiber length 3mm, density 1.39g/cm altogether
3)
GF: glass fibre (Owens Corning Japan Inc., 10 μm, average fiber footpath, average fiber length 3mm, density 2.50g/cm
3)
(3) multi-functional allylic cpd (C1)
TAIC: triallyl isocyanuric acid ester (Japan changes into Inc. TAIC, liquid state, boiling point 150 DEG C)
DAMGIC: single glycidyl diallyl isocyanuric acid ester (four countries change into Inc. DA-MGIC, solid-state, fusing point 40 DEG C, 5% weight that utilizes TGA to measure reduce temperature be 178 DEG C)
·C11
Use 1, two (amino methyl) benzene (MXDA) of 3-is as primary amine (D), use single glycidyl isocyanuric acid ester (DAMGIC) as multi-functional compounds (E), relative to MXDA1 equivalent, measure DAMGIC2 equivalent, they added in round-bottomed flask, limit is stirred, while heat 30 minutes at 80 DEG C.Heat 30 minutes at 180 DEG C further, obtain water white fraction.The liquid object obtained is progressively cooled to room temperature, the solid matter now generated is pulverized, obtains the white powder of multi-functional allylic cpd (C11).
Use TGA device (Perkin-Elmer Inc. TGA-7), in nitrogen displacement atmosphere, with the speed of heat-up rate 20 DEG C/minute, make the sample of 5mg from room temperature, be warmed up to till 600 DEG C, measure the quality change of sample.5% Mass lost temperature of the gained powder utilizing TGA to measure is 375 DEG C.The 5% Mass lost temperature of the MXDA utilizing TGA to measure is 52 DEG C.The fusing point of gained powder is the scope of 55 ~ 70 DEG C.
·C12:
Relative to MXDA1 equivalent, DAMGIC is 1 equivalent.In addition, identical with the situation of C11, synthesize, obtain water white liquid object.The liquid object that obtains of gained is slowly cooled to room temperature, the solid matter that have cured is pulverized, obtains the white powder of multi-functional allylic cpd (C12).
5% Mass lost temperature of the gained powder utilizing TGA to measure is 335 DEG C.The fusing point of gained powder is the scope of 50 ~ 60 DEG C.
·C13:
Use hexanediamine (HMDA) as primary amine (D).In addition, identical with the situation of C11, synthesize, obtain water white liquid object.By the liquid object of gained cool to room temperature lentamente, now, the solid matter generated is pulverized, obtains the white powder of multi-functional allylic cpd (C13).
5% Mass lost temperature of the gained powder utilizing TGA to measure is 356 DEG C.The 5% Mass lost temperature of the HMDA utilizing TGA to measure is 76 DEG C.The fusing point of gained powder is the scope of 35 ~ 45 DEG C.
(4) dimeracid base thermoplastic resin (C2)
Production Example 1 (C21)
The raw material of two for dimeracid (build food picked from the fields product industrial system, do not add hydrogen)/1,3-(amino methyl) benzene=46.5/53.5 (mol ratio) ratio is charged in reactive tank, at 240 DEG C, makes it react 2 hours.After reaction terminates, taken out, cut off, obtained dimeracid basis polyamide resin particle.
Gained particle 230 DEG C, 21.18N time melting index (MFR) be 1800g/min.
Production Example 2 (C22)
The raw material of the ratio of dimeracid (build food picked from the fields product industrial system, do not add hydrogen)/65.3% hexanediamine aqueous solution/hexanolactam=10.3/7.3/82.4 (mol ratio) is charged in reactive tank, at 250 DEG C, makes it react 2 hours.After reaction terminates, taken out, cut off, obtained dimeracid basis polyamide resin particle.Gained particle 230 DEG C, 21.18N time melting index (MFR) be 1300g/min.
Production Example 3 (C23)
By dimeracid (build food picked from the fields product industrial system, do not add hydrogen)/terephthalic acid/1, the raw material of 4 butyleneglycols=13.2/26.8/60 (mol ratio) ratio is charged in reactive tank, esterification is carried out at 240 DEG C, utilize universal method below, add titanium catalyst, at 240 DEG C, carry out polycondensation in 3 hours.After reaction terminates, taken out, cut off, obtained dimeracid base polyester resin particle.Gained particle 200 DEG C, 21.18N time melting index (MFR) be 800g/min.
(5) softening agent
HB: alkyl paraben (KAO. Corp. SA EXCEPARL HD-PB, liquid state, the 5% Mass lost temperature 285 DEG C utilizing TGA to measure)
(embodiment 1)
To main hopper supply polyamide 6 (PA6A) 30 mass parts and multi-functional allylic cpd (C12) 5 mass parts of biaxial extruder (Toshiba Machine Co. Ltd's system: TEM26SS, screw diameter 26mm), by its melting at 260 DEG C.Halfway, supply glass fibre (GF) 70 mass parts by side feeder, carry out melting mixing fully.Then, extruded as wire, after cooling curing, cut into particulate state, obtain resin combination.
After this resin combination fully drying, use injection moulding machine (Toshiba Machine Co. Ltd's system: EC-100 type), under the condition of barrel temperature 270 DEG C, die temperature 100 DEG C, 20 seconds injection molding time, 10 seconds cooling times, injection molding becomes above-mentioned strip sample.
Its evaluation result is as shown in table 1.When carrying out mixing and injection molding operation, do not observe the generation of volatilization gas.
(comparative example 1)
Compared with embodiment 1, be transformed to and do not add multi-functional allylic cpd (C1).In addition, carry out the operation identical with embodiment 1, obtain resin combination, by its injection molding, carry out the evaluation of formability.Its evaluation result is as shown in table 1.When mixing and injection molding operation, do not observe the generation of volatilization gas.
(embodiment 2 ~ 8, comparative example 2 ~ 7)
Compared with embodiment 1, thermoplastic resin (A), packing material (B), multi-functional allylic cpd (C1) are transformed to the kind shown in table 1 and quantity respectively.In addition, carry out the operation identical with embodiment 1, obtain resin combination.Further, by its injection molding, the evaluation of formability is carried out.Fibrous filler utilizes side feeder from midway supply, and packing material is in addition supplied by main hopper, and liquid triallyl cyanurate (TAIC) uses infusion to enter in mixing roll midway and implements melting mixing.
Its evaluation result is summarized, as shown in table 1.In addition, for embodiment 4 and 6, in mixing and injection molding operate, produce a large amount of volatilization gas, on the surface of the formed body obtained, triallyl cyanurate oozes out.
[table 1]
As known from Table 1, in embodiment 1 ~ 8, multi-functional allylic cpd (C1) plays a role as softening agent, therefore good forming ability, on the other hand, in comparative example 1 ~ 7.Do not coordinate softening agent, or use level is very few, therefore, under identical mold temperature, does not obtain matrix band attractive in appearance.
(embodiment 9)
To supplying polyamide 6 (PA6B) 41 mass parts with the main hopper of identical biaxial extruder used in embodiment 1, as flaky graphite (GrA) 59 mass parts of thermal conductivity packing material (B1) and single glycidyl isocyanuric acid ester (DAMGIC) 4 mass parts, melting mixing at 250 DEG C.And, extruded as wire, after cooling curing, be cut to particulate state, obtain resin combination.
After the resin combination that obtains fully drying, 250 DEG C, measure its MFR under the condition of load 100kg, result is 100g/10min.
Then, with identical injection moulding machine used in embodiment 1, under the condition of barrel temperature 260 DEG C, die temperature 100 DEG C, 20 seconds injection molding time, 10 seconds cooling times, by this resin combination injection molding, obtain evaluate formed body.In addition, in mixing and injection molding operate, the generation of volatilization gas is not observed.
Its evaluation result is as shown in table 2.
(embodiment 10 ~ 27, comparative example 8 ~ 18)
Compared with embodiment 9, thermoplastic resin (A), thermal conductivity packing material (B1), multi-functional allylic cpd (C1), other packing materials, other softening agent are transformed to the kind shown in table 2 and quantity respectively.In addition, carry out the operation identical with embodiment 1, obtain resin combination.By this resin combination injection molding, measure various physical property.Now, fibrous filling agent is supplied from midway by side feeder, and packing material is in addition supplied by main hopper.Liquid triallyl cyanurate (TAIC) uses pump to be injected in mixing roll midway and implements melting mixing.
For embodiment 16 and 21, when mixing and injection molding time create volatilization gas in large quantities.For embodiment 16, on the surface of the formed body of gained, triallyl cyanurate oozes out.
To in embodiment 10,12,14,16,17,19, the formed body obtained in comparative example 8,11,14 irradiate with Co 60 be source of radiation gamma-rays 30kGy after, carry out strength detection, the physical property of carrying out before and after gammairradiation compares.
The evaluation result of embodiment 9 ~ 27, comparative example 8 ~ 18 is summarized, as shown in table 2.
Multi-functional allylic cpd (C1) in embodiment 9 ~ 27 plays a role as softening agent, and therefore, MFR value is large, and formability is excellent.On the other hand, do not coordinate in comparative example 8 ~ 13 and comparative example 15 ~ 17 as softening agent multi-functional allylic cpd (C1) or coordinate very few, therefore with suitably employ the use level of multi-functional allylic cpd (C1) and compared with each embodiment that have employed other identical condition, MFR value is little, insufficient formability.
Although especially embodiment 21 ~ 26 and comparative example 15 ~ 17 are combined with packing material (B) in large quantities, but compared with comparative example 15 ~ 17, embodiment 21 ~ 26 can make mold temperature reduce by coordinating the multi-functional allylic cpd (C1) of specified amount.Comparative example 14 is combined with commercially available softening agent, although result MFR value is high, formability is excellent, compared with embodiment, and the bad mechanical property of formed body.The use level of the multi-functional allylic cpd (C1) of comparative example 18 is too much, and therefore, melt viscosity is too low, cannot extrude as wire and carry out cooling curing, cannot make injection molding particle when melting mixing.
Embodiment 10,12,14,16,17,19 is combined with multi-functional allylic cpd (C1), and therefore, by gammairradiation, polyamide resin is cross-linked, and improves flexural strength.On the other hand, comparative example 8,11,14 do not coordinate multi-functional allylic cpd, therefore, do not find the raising of the intensity produced by gammairradiation.
(embodiment 28)
Supply polyamide 6 (PA6A) 35 capacity % and dimeracid base thermoplastic resin (C21) 15 capacity % to the main hopper of identical biaxial extruder used in embodiment 1, at 260 DEG C, carry out melting., supply glass fibre (GF) 50 capacity % by side feeder halfway, on the basis of carrying out sufficient melting mixing, melting mixing thing is extruded into wire, cooling curing.Then, be cut to particulate state, obtained resin combination.
After this resin combination fully drying, use and identical injection moulding machine used in embodiment 1, under the same conditions as example 1, its injection molding is become above-mentioned strip sample.
Its evaluation result is as shown in table 3.When mixing and injection molding operation, do not observe the generation of volatilization gas.
(comparative example 19)
Compared with embodiment 28, do not add dimeracid base thermoplastic resin (C2).In addition, carry out the operation identical with embodiment 28, obtain resin combination.By the resin combination injection molding of gained, carry out the evaluation of formability.Its evaluation result is as shown in table 3.When mixing and injection molding operation, do not observe the generation of volatilization gas.
(embodiment 29 ~ 37, comparative example 20 ~ 26)
Compared with embodiment 28, thermoplastic resin (A), packing material (B), dimeracid base thermoplastic resin (C2) are transformed to kind as shown in table 3 and quantity respectively.In addition, carry out operation similarly to Example 28, obtain resin combination.Now, fibrous filling agent is by side feeder in midway supply, and packing material is in addition supplied by main hopper and implements melting mixing.By the resin combination injection molding obtained, carry out the evaluation of formability.Evaluation result is summarized, as shown in table 3.
[table 3]
As known from Table 3, embodiment 28 ~ 37 is combined with dimeracid base thermoplastic resin (C2), therefore good forming ability.On the other hand, comparative example 19 ~ 26 does not coordinate dimeracid base thermoplastic resin (C2), or use level is very few, under the condition of molding identical with embodiment 28 ~ 37, the smoothness on its matrix band surface is poor, or cannot obtain the matrix band of the size specified.
(embodiment 38)
To supplying polyamide 6 (PA6A) 50 capacity % with the main hopper of identical biaxial extruder used in embodiment 1, as flaky graphite (GrA) the 40 capacity % of thermal conductivity packing material (B1) and dimeracid basis polymeric amide (C21) 10 capacity %, carrying out melting mixing at 260 DEG C.And extruded by melting mixing thing as wire, cooling curing, is cut to particulate state, obtains resin combination.
After the resin combination that will obtain fully drying, 270 DEG C, under the condition of load 100kg, measure its MFR, result is 158g/10min.
Use and identical injection moulding machine used in embodiment 1, barrel temperature 270 DEG C, die temperature 80 DEG C, injecting forming temperature 20 seconds, under 10 seconds cooling times by this resin combination injection molding, its injection molding is become above-mentioned strip sample.
Its evaluation result is as shown in table 4.The generation of volatilization gas is not observed in mixing and injection molding operate.
(embodiment 39 ~ 56, comparative example 27 ~ 40)
Compared with embodiment 38, thermoplastic resin (A), thermal conductivity packing material (B1), dimeracid base thermoplastic resin (C2), other packing material, other softening agent are transformed to kind as shown in table 4 and quantity respectively.In addition, carry out the operation identical with embodiment 38, obtain resin combination.By this resin combination injection molding, measure various physical property.Now, fibrous filling agent is by side feeder from midway supply, and packing material is in addition supplied by main hopper and implements melting mixing.
The evaluation result of embodiment 38 ~ 46, comparative example 27 ~ 34 is as shown in table 4, and the evaluation result of embodiment 47 ~ 56, comparative example 35 ~ 40 is as shown in table 5.
[table 4]
[table 5]
Dimeracid base thermoplastic resin (C2) in embodiment 38 ~ 56 plays a role as softening agent, and therefore MFR value is large, and formability is excellent.On the other hand, comparative example 27 ~ 30 and comparative example 32 ~ 40 do not coordinate dimeracid base thermoplastic resin (C2), therefore, with suitably employ the use level of dimeracid base thermoplastic resin (C2) and compared with each embodiment that have employed other identical conditions, MFR value is little, insufficient formability.Especially embodiment 44 ~ 46 and comparative example 32 ~ 34, although be combined with packing material (B) in large quantities, but compared with comparative example 32 ~ 34, embodiment 44 ~ 46, by coordinating the dimeracid base thermoplastic resin (C2) of specified amount, can make mold temperature reduce.Comparative example 31 is combined with commercially available softening agent.In this case, although MFR value is high, formability is excellent, and when melting mixing, softening agent volatilizees, in addition, compared with the resinous polymer of embodiment, and the bad mechanical property of formed body.
Claims (5)
1. a resin combination, it is characterized in that, containing thermoplastic resin (A), the melt viscosity depressant (C) of packing material (B) and specified amount, the melt viscosity depressant (C) of described specified amount is the dimeracid basis polyamide resin as dimeracid base thermoplastic resin (C2), relative to total amount 100 parts by volume of thermoplastic resin (A) with packing material (B), the content of dimeracid base thermoplastic resin (C2) is 25 ~ 45 parts by volume, thermoplastic resin (A) is 30/70 ~ 60/40 with the volume ratio A/B of packing material (B).
2. resin combination according to claim 1, is characterized in that, packing material (B) is the thermal conductivity packing material (B1) of the thermal conductivity with more than 10W/ (mK).
3. resin combination according to claim 2, it is characterized in that, thermal conductivity packing material (B1) is the flaky graphite from median size 1 ~ 300 μm, the graphitized carbon fibre of 1 ~ 30 μm, average fiber footpath, average fiber length 1 ~ 20mm, there is the flakey boron nitride of the median size 1 ~ 200 μm of hexagonal crystal structure, the aluminum oxide that median size is 0.5 ~ 150 μm, the magnesium oxide that median size is 0.5 ~ 150 μm, at least one selected in the zinc oxide of the magnesiumcarbonate that median size is 0.5 ~ 150 μm and median size 0.5 ~ 150 μm.
4. resin combination according to claim 1, is characterized in that, thermoplastic resin (A) is polyamide resin.
5. a formed body, is characterized in that, is to make the resin combination according to any one of Claims 1 to 4 shaping and obtained.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
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| JP2009009912 | 2009-01-20 | ||
| JP2009-009912 | 2009-01-20 | ||
| JP2009-248342 | 2009-10-29 | ||
| JP2009248342 | 2009-10-29 | ||
| CN201080003109.0A CN102203191B (en) | 2009-01-20 | 2010-01-19 | Resin composition and molded article comprising the same |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201080003109.0A Division CN102203191B (en) | 2009-01-20 | 2010-01-19 | Resin composition and molded article comprising the same |
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| CN103122140A CN103122140A (en) | 2013-05-29 |
| CN103122140B true CN103122140B (en) | 2015-07-22 |
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| CN201310050893.6A Expired - Fee Related CN103122140B (en) | 2009-01-20 | 2010-01-19 | Resin composition and molded article comprising the same |
| CN201080003109.0A Expired - Fee Related CN102203191B (en) | 2009-01-20 | 2010-01-19 | Resin composition and molded article comprising the same |
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| CN (2) | CN103122140B (en) |
| TW (1) | TWI468453B (en) |
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| CN103140552B (en) | 2010-09-30 | 2015-04-29 | 宇部兴产株式会社 | Polyamide resin composition and molded article comprising the same |
| TWI588194B (en) * | 2011-12-23 | 2017-06-21 | 奇美實業股份有限公司 | Resin composite |
| TWI478974B (en) * | 2011-12-23 | 2015-04-01 | Chi Mei Corp | Resin composite |
| KR101457016B1 (en) * | 2011-12-30 | 2014-11-03 | 제일모직주식회사 | Thermal conductive thermoplastic resin composition having excellent water-resistance and article using the same |
| JP5908739B2 (en) * | 2012-02-01 | 2016-04-26 | ユニチカ株式会社 | Resin composition and molded body comprising the same |
| CN102661222A (en) * | 2012-06-04 | 2012-09-12 | 韩金红 | External horizontal-type fuel pump oil outlet tray, manufacturing process and impeller matched with oil outlet tray |
| JP6007610B2 (en) * | 2012-06-20 | 2016-10-12 | 東洋紡株式会社 | Thermally conductive resin composition |
| CN103205044A (en) * | 2013-03-27 | 2013-07-17 | 江苏金聚合金材料有限公司 | Silane grafted polyethylene thermally conductive composite material and preparation method and application thereof |
| JP6526939B2 (en) * | 2013-06-14 | 2019-06-05 | スターライト工業株式会社 | Thermal conductive resin molding |
| JP2015023099A (en) * | 2013-07-17 | 2015-02-02 | 大日本印刷株式会社 | Method of manufacturing semiconductor light-emitting device, method of manufacturing molded body, electron beam curable resin composition, resin frame for reflector, and reflector |
| JP6094412B2 (en) * | 2013-07-17 | 2017-03-15 | 大日本印刷株式会社 | Semiconductor light emitting device manufacturing method, molded body manufacturing method, electron beam curable resin composition, reflector resin frame, and reflector |
| CN103589149B (en) * | 2013-11-20 | 2016-06-29 | 湖南映宏新材料股份有限公司 | Composite for supporting roller bearing seat and preparation method thereof |
| JP6436915B2 (en) * | 2013-12-26 | 2018-12-12 | ユニチカ株式会社 | Flame retardant polyamide resin composition and molded article comprising the same |
| WO2015129100A1 (en) * | 2014-02-25 | 2015-09-03 | 住友電気工業株式会社 | Transparent polyamide resin composition, transparent polyamide resin crosslinked molded article |
| JP2017509762A (en) * | 2014-04-01 | 2017-04-06 | ディーエスエム アイピー アセッツ ビー．ブイ． | Thermally conductive composition |
| CN103937177B (en) * | 2014-04-19 | 2016-03-16 | 中山市永威新材料有限公司 | A kind of high heat conduction modified plastics and preparation method thereof |
| JP6841588B2 (en) * | 2014-10-31 | 2021-03-10 | 花王株式会社 | Polyamide resin composition for damping material |
| CN104460903B (en) * | 2014-12-03 | 2018-08-14 | 吉首大学 | Notebook PC radiator |
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| US20180230352A1 (en) * | 2015-08-26 | 2018-08-16 | Denka Company Limited | Thermally conductive resin composition |
| CN105385013A (en) * | 2015-12-04 | 2016-03-09 | 太仓陶氏电气有限公司 | Nonmetal radiator |
| US11352480B2 (en) | 2016-03-18 | 2022-06-07 | Ticona Llc | Polyaryletherketone composition |
| JP6259142B2 (en) * | 2016-04-27 | 2018-01-10 | 花王株式会社 | fan |
| KR101736667B1 (en) * | 2016-05-16 | 2017-05-17 | 주식회사 소룩스 | Lighting apparatus having heat dissipation plastic plate for insulation |
| KR101736668B1 (en) * | 2016-05-30 | 2017-05-17 | 주식회사 소룩스 | LED Lighting Apparatus For Radiation Area |
| WO2018216836A1 (en) * | 2017-05-26 | 2018-11-29 | 주식회사 하이씨엔티 | Thermally conductive insulation composition and heat sink made therefrom |
| TWI660991B (en) * | 2017-12-28 | 2019-06-01 | 邦泰複合材料股份有限公司 | Plating high density plastic |
| US11118053B2 (en) | 2018-03-09 | 2021-09-14 | Ticona Llc | Polyaryletherketone/polyarylene sulfide composition |
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| CN117916319A (en) * | 2021-09-01 | 2024-04-19 | Ｕｂｅ株式会社 | Polyamide resin composition |
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- 2010-01-19 CN CN201310050893.6A patent/CN103122140B/en not_active Expired - Fee Related
- 2010-01-19 JP JP2010547480A patent/JP5686605B2/en not_active Expired - Fee Related
- 2010-01-19 CN CN201080003109.0A patent/CN102203191B/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| CN102203191B (en) | 2014-07-09 |
| TW201035204A (en) | 2010-10-01 |
| JP5686605B2 (en) | 2015-03-18 |
| JPWO2010084845A1 (en) | 2012-07-19 |
| WO2010084845A1 (en) | 2010-07-29 |
| CN102203191A (en) | 2011-09-28 |
| CN103122140A (en) | 2013-05-29 |
| TWI468453B (en) | 2015-01-11 |
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