CN104169364B - Thermoplastic elastomer resin composition and composite molded product - Google Patents
Thermoplastic elastomer resin composition and composite molded product Download PDFInfo
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- CN104169364B CN104169364B CN201380014375.7A CN201380014375A CN104169364B CN 104169364 B CN104169364 B CN 104169364B CN 201380014375 A CN201380014375 A CN 201380014375A CN 104169364 B CN104169364 B CN 104169364B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- 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
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
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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
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2274/00—Thermoplastic elastomer material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/302—Conductive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
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- 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)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
The present invention provides to be had shaping processability and engineering properties is excellent, thermal conductivity is high, the most favourable thermoplastic elastomer resin composition of high bonding force, injection molding forming etc. and is using this thermoplastic elastomer resin composition as the composite molded product of the grafting material of not same material in the joint of the not same material such as resin, metal, glass.The present invention relates to a kind of thermoplastic polyester elastomer resin combination, it is characterized in that, comprising polyester block copolymer composition (X) 30～85 volume % and conducting filler (D) 15～70 volume % that Shore D hardness is below 53D, described polyester block copolymer composition (X) is main composition composition with the hard segment (a1) being mainly made up of crystalline aromatic polyester unit and the soft chain segment (a2) being mainly made up of aliphatic poly ether unit and/or aliphatic poly ester units.
Description
Technical field
The present invention relates to there is in the joint of formed body the most of the same race high bonding force, be molded by injection into
The thermoplastic that the shaping processability of shape etc. is the most excellent, thermal conductivity is high, the most favourable
Property elastomer resin composition and by this thermoplastic elastomer resin composition in not same material
The composite molded product used as grafting material.
Background technology
In the joint of not same material, as the method obtaining resin and the complex of metal,
Propose and connect by injection molding forming on the parts after metal parts is implemented surface process
The method (for example, see patent documentation 1) of resin, but owing to metal parts is carried out specifically
Surface processes, and therefore operation becomes numerous and diverse, the most inefficent, and is difficult to obtain stable connecing
Close intensity.
It addition, propose following method: utilize laser to press from both sides between resin and non-same material
Hold elastomer and make elastomer melted and carry out the method (for example, see patent documentation 2,3) engaged；
Use and elastomer modified for molecular end portion is engaged, as laser cladding, the method sticking with glue agent
(for example, see patent documentation 3).But, there is following asking in the elastomer used in these methods
Topic: sufficient bond strength, particularly bond strength cannot be obtained and decline after long duration test.
It addition, in the case of using resin in electronic part material, this resin is not only in softness
Property aspect and all there is in terms of thermal diffusivity room for improvement.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2008-173967 publication (page 1～2)
Patent documentation 2: Japanese Unexamined Patent Publication 2008-7584 publication (page 1～2)
Patent documentation 3: Japanese Unexamined Patent Publication 2009-155402 publication (page 1～3)
Summary of the invention
Invent problem to be solved
The present invention reaches in the result carrying out studying to solve above-mentioned prior art problem,
Its object is to provide, in the joint of the not same material such as resin, metal, glass, there is height
Shaping processability and the engineering properties of engaging force, injection molding forming etc. are excellent, thermal conductivity is high,
The most favourable thermoplastic elastomer resin composition and this thermoplastic elastomehc of use
Gonosome resin combination is as the composite molded product of the grafting material of not same material.
For the method solving problem
The present inventor has been repeated further investigation to solve above-mentioned problem, it was found that
By coordinate the hard segment (a1) to be mainly made up of crystalline aromatic polyester unit and main by
The soft chain segment (a2) that aliphatic poly ether unit and/or aliphatic poly ester units are constituted is that main composition becomes
Point and polyester block copolymer composition (X) 30～85 volume that Shore D hardness is below 53D
% and conducting filler (D) 15～70 volume %, it is possible to solve above-mentioned problem at one stroke, based on
This opinion is studied further, thus completes the present invention.
That is, the present invention relates to invention below.
[1] a kind of thermoplastic polyester elastomer resin combination, it is characterised in that comprise Shore D
Hardness is polyester block copolymer composition (X) the 30～85 volume % of below 53D and heat conductivity is filled out
Material (D) 15～70 volume %, described polyester block copolymer composition (X) is with mainly by crystallinity virtue
Hard segment (a1) that fragrant adoption ester units is constituted and mainly by aliphatic poly ether unit and/or aliphatic
The soft chain segment (a2) that polyester unit is constituted is main composition composition.
[2] resin combination as described in above-mentioned [1], it is characterised in that described polyester block copolymerization
Compositions (X),
I () only by the hard segment (a1) to be mainly made up of crystalline aromatic polyester unit and mainly
The soft chain segment (a2) being made up of aliphatic poly ether unit and/or aliphatic poly ester units is main composition
The polyester block copolymer (A) of composition is constituted, or
(ii) hard segment (a1) to be mainly made up of and mainly is coordinated crystalline aromatic polyester unit
The soft chain segment (a2) being made up of aliphatic poly ether unit and/or aliphatic poly ester units is main composition
The polyester block copolymer (A) of composition, polyvinyl alcohol resin (B) and/or silane coupler (C) and
Become, and described polyester block copolymer composition (X) is set to 100 weight %, then coordinate poly-second
Enol system resin (B) 1～30 weight % and/or silane coupler (C) 0.01～5.0 weight % form.
[3] resin combination as described in above-mentioned [1] or [2], it is characterised in that conducting filler (D)
For insulating properties filler.
[4] resin combination as according to any one of described [1]～[3], it is characterised in that heat conduction
The Mohs' hardness of 60 more than volume % in property filler (D) 100 volume % is less than 4.
[5] resin combination as according to any one of described [1]～[4], it is characterised in that heat conduction
The true specific gravity of 60 more than volume % in property filler (D) 100 volume % is less than 3.
[6] resin combination as according to any one of described [1]～[5], it is characterised in that described
The hard segment (a1) of polyester block copolymer composition (X) comprises by p-phthalic acid and/or to benzene two
Polybutylene terephthalate (PBT) unit that formic acid dimethyl ester and 1,4-butanediol are derivative and by isophthalic
The poly-M-phthalic acid fourth two that dioctyl phthalate and/or dimethyl isophthalate derive with 1,4-butanediol
Alcohol ester units.
[7] resin combination as according to any one of described [1]～[6], it is characterised in that described
The hard segment (a1) of polyester block copolymer composition (X) comprises by p-phthalic acid and/or to benzene two
Formic acid dimethyl ester and M-phthalic acid and/or dimethyl isophthalate are with 1,4-butanediol derivative
Polybutylene terephthalate (PBT)/poly-M-phthalic acid butanediol ester unit.
[8] resin combination as according to any one of described [1]～[7], it is characterised in that described
The soft chain segment (a2) of polyester block copolymer composition (X) with poly-(tetramethylene ether) diol units is
Main composition composition.
[9] resin combination as according to any one of described [1]～[8], it is characterised in that poly-second
Enol system resin (B) is polyvinyl butyral resin and/or polyvinyl acetal resin.
[10] resin combination as according to any one of described [1]～[9], it is characterised in that described
Silane coupler (C) is epoxy silane coupler.
[11] resin combination as according to any one of described [1]～[10], it is characterised in that phase
For thermoplastic elastomer resin composition 100 volume %, it is combined with antioxidant (E) 0.01～5.0
Volume %.
[12] a kind of composite molded product, it is characterised in that use institute any one of described [1]～[11]
The thermoplastic elastomer resin composition stated being combined as the formed body being made up of not same material
Material.
[13] manufacture method of a kind of composite molded product, it is characterised in that have: by described [1]～[11]
According to any one of the work that connects with material hot melt the most of the same race of thermoplastic elastomer resin composition
Sequence.
Invention effect
According to the present invention, as explained below, can obtain with in the joint of not same material
Shaping processability and the engineering properties with high bonding force, injection molding forming etc. are excellent, heat conduction
The thermoplastic elastomer resin composition that rate is high.It addition, the thermoplastic elastomer resin of the present invention
Compositions can need the tables such as coating binder with metal fever welding unlike organic siliconresin
Face processes, therefore, it is possible to the most advantageously manufacture.
Detailed description of the invention
The present invention described further below.
The thermoplastic polyester elastomer resin combination of the present invention is characterised by, comprises Shore D
Hardness is polyester block copolymer composition (X) the 30～85 volume % of below 53D and heat conductivity is filled out
Material (D) 15～70 volume %, described polyester block copolymer composition (X) is with mainly by crystallinity virtue
Hard segment (a1) that fragrant adoption ester units is constituted and mainly by aliphatic poly ether unit and/or aliphatic
The soft chain segment (a2) that polyester unit is constituted is main composition composition.
The polyester block copolymer composition (X) used in the present invention, can only by with main by tying
The hard segment (a1) of crystalline substance aromatic polyester unit and main by aliphatic poly ether unit and/or fat
Polyester block copolymer (A) structure that soft chain segment (a2) is main composition composition that adoption ester units is constituted
Become, it is also possible on the basis of described polyester block copolymer (A), be combined with polyvinyl alcohol resin
And/or silane coupler (C) (B).
In view of the contact resistance etc. when engaging with electronic part material, described polyester block copolymerization
The Shore D hardness of compositions (X) is usually below 53D, preferably below 50D.If it is super
Cross 53D, then contact resistance increase etc. when engaging with electronic part material, from this side considerations
It is unpractical.By making the Shore D hardness of described polyester block copolymer composition (X) upper
In the range of stating, the injection molding forming etc. of obtained thermoplastic polyester elastomer resin combination
Shaping processability the most excellent.Here, above-mentioned Shore D hardness refers to, by material by injection
Mould-forming method or punching formation are configured to the lamellar of thickness 2mm, overlapping to thickness 6mm
Above, according to JIS K7215:2007, measure Durometer D hardness and the hardness that obtains, such as
ASKER CL-150 (macromolecule gauge company system) can be used to measure.
In the thermoplastic polyester elastomer resin combination of the present invention, described polyester block copolymerization
The use level of compositions (X) is usually 30～85 volume %, preferably 32～83 volume %, special
You Xuanwei 35～80 volume %.Use level at polyester block copolymer composition (X) is less than 30
With during more than 85 volume % during volume %, hardness, tensile break strength, stretching 10% deformation are answered
Any one in power, tension fracture elongation rate or all have the tendency of variation, thermal conductivity, various
Engaging force also reduces, the most preferred.
The polyester block copolymer (A) used in the present invention refers to, with main by crystalline aromatic
Hard segment (a1) that polyester unit is constituted and mainly by aliphatic poly ether unit and/or aliphatic polyester
The polyester block copolymer that soft chain segment (a2) is main composition composition that unit is constituted, hard segment (a1)
For mainly being derived with glycol or its ester formative by aromatic dicarboxylic acid or its ester formative derivant
The polyester that thing is formed.
As described aromatic dicarboxylic acid, can enumerate: p-phthalic acid, M-phthalic acid, neighbour
Phthalic acid, naphthalene-2,6-dicarboxylic acids, naphthalene-2,7-dicarboxylic acids, anthracene dicarboxylic acids, diphenyl-4,4 '-two
Carboxylic acid, diphenoxyethanedicarboxylic acid, 4,4 '-diphenyl ether dicarboxylic acids, 5-sulfoisophthalic acid,
With 3-sulfoisophthalic acid sodium etc..In the present invention, the described aromatic dicarboxylic acid of main use,
But a part for aromatic dicarboxylic acid can also be substituted by 1,4-cyclohexane dicarboxylic acid, Pentamethylene. two
The alicyclic dicarboxylic acids such as carboxylic acid, 4,4 '-dicyclohexyl dicarboxylic acids and adipic acid, succinic acid, oxalic acid,
The aliphatic dicarboxylic acids such as decanedioic acid, dodecane two keto acid, dimeric dibasic acid.Certainly, the ester of dicarboxylic acids
Formative derivant, such as lower alkyl esters, aryl ester, carbonic ester and etheride etc. are also
Can use comparably.
In the present invention, of more than two kinds above-mentioned acid composition is preferably used, include, for example: to benzene
Dioctyl phthalate and M-phthalic acid, p-phthalic acid and dodecane two keto acid, p-phthalic acid and two
The combination of polyacids etc..By using two or more acid composition, it is possible to reduce the crystallization of hard segment
Degree, additionally it is possible to give flexibility, and also improve with the hot glue viscosity of other thermoplastic resins.
Then, as the concrete example of glycol, the glycol of preferred molecular weight less than 400, such as:
1,4-butanediol, ethylene glycol, propylene glycol, pentamethylene glycol, hexamethylene glycol, new penta 2
The aliphatic diols such as alcohol, decamethylene glycol；1,1-CHDM, 1,4-bicyclohexane two
The alicyclic diol such as methanol, Tricyclodecane Dimethanol；With benzene dimethanol, double (to hydroxyl) biphenyl,
Double (to hydroxyl) diphenyl propane, 2,2 '-bis-[4-(2-hydroxyl-oxethyl) phenyl] propane, double [4-(2-
Hydroxyl-oxethyl) phenyl] sulfone, 1,1-double [4-(2-hydroxyl-oxethyl) phenyl] hexamethylene, 4,4 '-dihydroxy
Base para-terpheny, 4,4 '-dihydroxy is to aromatic diols such as quaterphenyls, and described glycol can also be with ester
The form of formative derivant, such as acetylate and alkali metal salt etc. uses.These dicarboxyls
Two or more kinds may be used for acid, its derivant, diol component and derivant thereof.
About the preference of described hard segment (a1), be preferably used comprise by p-phthalic acid and/or
Polybutylene terephthalate (PBT) unit that dimethyl terephthalate (DMT) and 1,4-butanediol are derivative and
The poly-isophthalic diformazan derivative with 1,4-butanediol by M-phthalic acid and/or dimethyl isophthalate
The material of acid butanediol ester unit, and the copolymer of both, particularly preferably use comprise by
P-phthalic acid and/or dimethyl terephthalate (DMT) and M-phthalic acid and/or M-phthalic acid two
Polybutylene terephthalate (PBT)/poly-M-phthalic acid butanediol that methyl ester is derivative with 1,4-butanediol
The material of ester units.
The soft chain segment (a2) of the polyester block copolymer (A) used in the present invention is aliphatic polyether list
Unit and/or aliphatic polyester.As aliphatic polyether, can enumerate: poly-(ethyleneether) glycol,
Poly-(propylidene ether) glycol, poly-(tetramethylene ether) glycol, poly-(hexa-methylene ether) glycol, epoxy
Ethane and the copolymer of expoxy propane, the oxirane addition polymers of poly-(propylidene ether) glycol, epoxy
Ethane and the copolymer diol etc. of oxolane.It addition, as the concrete example of aliphatic polyester,
Can enumerate: poly-(6-caprolactone), poly-heptalactone, poly-caprylolactone, poly adipate succinic acid ester, poly-
Ethylene glycol adipate etc..In these aliphatic poly ether units and/or aliphatic polyester, from gained
To the elastic characteristic of polyester block copolymer set out, the most poly-(tetramethylene ether) glycol, poly-(ring
Ethylene Oxide) the oxirane addition polymers of glycol, the copolymer diol of oxirane and oxolane,
Poly-(6-caprolactone), poly adipate succinic acid ester, 10PE27 etc., the most excellent
Select poly-(tetramethylene ether) glycol, the oxirane addition polymers of poly-(expoxy propane) glycol and epoxy
Ethane and the copolymer diol of oxolane.It addition, as the number-average molecular weight of these soft chain segments,
300～about 6000 it are preferably from about when copolymerization.
The copolymerization amount of the soft chain segment (a2) of the polyester block copolymer (A) used in the present invention is usually
20～95 weight %, preferably 25～90 weight %, can so set the copolymerization of (a1) and (a2)
Ratio.
The polyester block copolymer (A) used in the present invention can use known method manufacture, does not has
It is particularly limited to.As the concrete example of this manufacture method, such as, can be following either method:
The lower alcohol diester of dicarboxylic acids, the low molecular weight diols of excess is made to become with low melting point polymer segment
Divide and carry out ester exchange reaction in the presence of a catalyst, obtained reaction product is contracted
Poly-method；Make dicarboxylic acids and the glycol of excess and low melting point polymer chain segment components at catalyst
In the presence of carry out esterification, obtained reaction product is carried out the method etc. of polycondensation.
The polyester block copolymer (A) used in the present invention can use commercially available product.As commercially available product,
Can enumerate such as: Dong Li-Du Pont (strain) Ha processed イ ト レ Le 3046 (Shore D hardness: 27D), east
Beautiful-Du Pont (strain) Ha processed イ ト レ Le 4057N (Shore D hardness: 40D), Dong Li-Du Pont (strain) system
Ha イ ト レ Le 4767N (Shore D hardness: 47D) etc..
Described polyester block copolymer composition (X) is on the basis of described polyester block copolymer (A)
On when being also combined with polyvinyl alcohol resin (B) and/or silane coupler (C), if described polyester is embedding
Section copolymer compositions (X) be 100 weight %, usually 65～98.99 weight %, be preferably
69～96.95 weight %, particularly preferably 75～96.9 weight %.
As the polyvinyl alcohol resin (B) used in the present invention, it is not particularly limited, but preferably
Use polyvinyl butyral resin, polyvinyl acetal resin.Commercially available product can be used.
As polyvinyl alcohol resin (B) commercially available product, for instance that hydrops chemical industry (strain) エ processed ス Off
レ ッ Network ス BL-1, BX-L, BM-S, KS-3 etc., electrochemically industry (strain) 3000-1 processed,
3000-2,3000-4,4000-2 etc., and it is not limited to these.
If described polyester block copolymer composition (X) is 100 weight %, the polyethylene of the present invention
The use level of alcohol system resin (B) is usually 1～30 weight %, is preferably 3～20 weight %.If it is poly-
The use level of vinyl alcohol resin (B) is less than 1 weight %, then bond strength is low, if more than 30 weights
Amount %, then the mechanical strength of obtained thermoplastic elastomer resin composition is low, shaping processability
It is deteriorated, the most preferred.
As the silane coupler (C) used in the present invention, it is not particularly limited, but is preferably
1 molecule has amino, epoxy radicals, vinyl, pi-allyl, methylacryloyl, thioether group
Deng material, wherein, the silane coupler with epoxy radicals is preferably used.As silane coupled
The concrete example of agent (C), has: 3-TSL 8330,3-aminopropyl ethyoxyl silicon
Alkane, 3-(2-amino-ethyl) TSL 8330,3-(2-amino-ethyl) aminopropyl first
Base dimethoxysilane, 3-phenyl amino propyl trimethoxy silane, 3-glycidoxypropyl group three
Methoxy silane, 3-glycidoxypropyl group dimethoxysilane, 3-glycidoxypropyl group three second
TMOS, 3-glycidoxypropyl diethoxy silane, 2-(3,4-epoxycyclohexyl)
Ethyl trimethoxy silane, double (3-(triethoxysilyl) propyl group) disulfide, double (3-(three second
Epoxide silicyl) propyl group) four thioethers, vinyltriacetoxy silane, vinyl trimethoxy
Silane, VTES, acryloyl group trimethoxy silane, 3-methacryloxypropyl
Propyl trimethoxy silicane, 3-methacryloxypropyl methyl dimethoxysilane, 3-sulfydryl third
Base trimethoxy silane, 3-mercaptopropyi methyl dimethoxysilane etc., be preferably containing epoxy radicals
Compound, they can be used alone a kind, or are applied in combination two or more.
Described polyester block copolymer composition (X) is set to 100 weight %, the silane of the present invention
The use level of coupling agent (C) be usually 0.01～5.0 weight %, be preferably 0.05～3.0 weight %,
More preferably 0.1～1.5 weight %.If the use level of silane coupler (C) is less than 0.01 weight
Amount %, then bond strength, tension fracture elongation rate are low, if or more than 5 weight %, then occur
Emulsifying (Block Le ミ Application グ), or heat stability decline, the most preferred.By using silane
Coupling agent, it is possible to make the engineering propertiess such as tension fracture elongation rate improve further, it is possible to make with not
The engaging force of same material improves further.
Silane coupler (C) as the present invention, it is possible to use commercially available product.As commercially available product, can
Enumerate such as: Dong Li-DOW CORNING (strain) Z-6040, Z-6043 processed (are the chemical combination containing epoxy radicals
Thing) etc..
As the conducting filler (D) used in the present invention, can enumerate such as: zinc oxide, oxidation
Aluminum, magnesium oxide, magnesium silicate, boron nitride, aluminium nitride, silicon nitride, carborundum, oxidation calorize
Compound, calcium titanate etc..As alumina cpd, can enumerate: aluminium oxide, Kaolin, viscous
Soil, Muscovitum, Alborex M 12, Vermiculitum etc..Wherein, in the feelings of the purposes considering electronic part material
Under condition, particularly preferred insulating properties filler (such as magnesium silicate, magnesium oxide, alumina cpd etc.).
Conducting filler (D) can be used singly or in combination of two or more.
It addition, the aspect of the flexibility from obtained thermoplastic elastomer resin composition,
The Mohs' hardness of conducting filler (D) is not particularly limited, but preferably less than 4, more preferably
Less than 3, more preferably less than 2.Heat conductivity as the Mohs' hardness with described scope
Filler, specifically, can enumerate: boron nitride, magnesium silicate.Mohs' hardness can use known
Method measure.It addition, light-weighted from obtained thermoplastic elastomer resin composition
Aspect is set out, and the true specific gravity of thermal conductivity filler (D) is not particularly limited, but preferably less than 4,
More preferably less than 3.As the conducting filler of the true specific gravity with described scope, concrete and
Speech, can enumerate magnesium silicate.True specific gravity can use known Liquid displacement methods (pycnometric method) to measure.
It addition, and with conducting filler of more than two kinds in the case of, in order to obtain softness and
The resin combination of light weight, in whole conducting filler (D) 100 volume %, preferably comprises not
Family name's hardness is above-mentioned scope (preferably less than 4, more preferably less than 3, more preferably 2
Following) conducting filler 60 more than volume %, more preferably contain 80 more than volume %, enter one
Step preferably comprises 95 more than volume %.
The averaged particles footpath of conducting filler (D) is not particularly limited, typically about 0.5 μm～about
90 μm, from the viewpoint of thermal conductivity is excellent, preferably 1～80 μm, more preferably about
1 μm～about 60 μm.
As the conducting filler (D) used in the present invention, it is possible to use commercially available product.As commercially available
Product, can enumerate such as: RF-10C (trade name；Magnesium oxide；Space portion material (Ube Materials) (strain)
System), RF-30 (trade name；Magnesium oxide；Space portion material (strain) make), RF-50 (trade name；Oxidation
Magnesium；Space portion material (strain) make), RF-70C (trade name；Magnesium oxide；Space portion material (strain) makes), institute
Stating in the filler that space portion material (strain) makes, the numeral after " RF-" represents that space portion material (strain) announces
Mean diameter.Can enumerate: DAW-45 (trade name；Aluminium oxide；Electrochemically industry (strain)
System), DAW-05 (trade name；Aluminium oxide；Electrochemically industry (strain) system), described electrochemically
In the filler that industry (strain) is made, the numeral after " DAW-" represents that electrochemically industry (strain) is public
The mean diameter of cloth.Can enumerate: DAW-Network ラ ウ Application タ Le Network DR (trade name；Pine village industry
(strain) make), Network ラ ウ Application タ Le Network PP (trade name；Pine village's industry (strain) system) etc..
The use level of the conducting filler (D) of the present invention is usually 15～70 volume %, is preferably
20～68 volume %, particularly preferably 25～65 volume %.If the use level of conducting filler (D) is little
In 15 volume %, even if being then combined with polyester block copolymer composition (X), it is also possible to
Sufficient thermal conductivity cannot be obtained, if more than 70 volume %, then in forming process, use
Cannot spue during the melting mixing of extruder thus granule cannot be obtained, the most preferred.
It addition, the thermoplastic elastomer resin composition of the present invention can contain antioxygen as required
Agent (E).As the antioxidant (E) used in the present invention, can enumerate such as: aromatic amine system
Antioxidant, hindered phenol system antioxidant, sulfur system antioxidant, phosphorous antioxidant etc., its
In, aromatic amine system antioxidant is preferably used.They can be used alone a kind, or makes
Use two or more.
As the concrete example of aromatic amine system antioxidant, can enumerate: phenyl naphthyl amines, 4,4 '-
Dimethoxydiphenyl amine, 4,4 '-bis-(bis (alpha, alpha-dimethylbenzyl) base) diphenylamines and 4-isopropoxy
Diphenylamine etc., wherein, preferably diphenylamine based compound.
As the concrete example of hindered phenol system antioxidant, can enumerate: 2,4 '-dimethyl-6-tert-butyl group
Phenol, 2,6 di t butyl phenol, DBPC 2,6 ditertiary butyl p cresol, the tertiary fourth of hydroxymethyl-2,6-two
Base phenol, 2,6-di-t-butyl-alpha-alpha-dimethyl amino paracresol, 2,5-di-t-butyl-4-ethyl-phenol,
4,4 '-bis(2,6-di-butyl phenol), 2,2 '-methylene-bis--4-methyl-6-tert-butylphenols, 2,2 '-
Methylene-bis-(4-ethyl-6-tert-butyl phenol), 4,4 '-methylene-bis-(6-butyl o-cresol),
4,4 '-methylene-bis(2,6-di-butyl phenol), 2,2 '-methylene-bis-(4-methyl-6-cyclohexyl benzenes
Phenol), 4,4 '-butane-bis-(3 methy 6 tert butyl phenol), double (the 6-tert-butyl group-3 methyl of 4,4 '-sulfur
Phenol), double (3-methyl-4-hydroxyl-5-t-butylbenzyl) thioether, double (the 6-tert-butyl o first of 4,4 '-sulfur
Phenol), double (2 '-hydroxyl-the 3 '-tert-butyl group-the 5 '-first of 2,2 '-sulfur double (4-methyl-6-tert-butylphenol), 2,6-
Base benzyl)-4-methylphenol, 3,5-di-t-butyl-4-hydroxy benzenes sulfone acid diethyl ester, 2,2 '-two
Hydroxyl-3,3 '-two (Alpha-Methyl cyclohexyl)-5,5 '-dimethyl diphenyl methane, α-octadecyl-two
(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester, 6-(hydroxyl-3,5-di-tert-butyl amido)-2,4-
Double-(octyl group-sulfenyl)-1,3,5-triazine, hexamethylene glycol-bis-[β-(3,5-di-t-butyl-4-hydroxy benzenes
Phenol) propionic ester], N, N '-hexa-methylene-bis-(3,5-di-t-butyl-4-hydroxyhydrocinnamic acid amide),
2,2-sulfur [diethyl-bis--3 (3,5-di-tert-butyl-hydroxy phenyl) propionic ester], 3,5-di-t-butyl-4-
Two (octadecyl) ester of hydroxy benzenes sulfone acid, four [methylene-3-(3,5-di-tert-butyl-hydroxy phenyl)
Propionic ester] methane, 1,3,5-trimethyl-2,4,6-three (3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1,1,3-
Three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, three (3,5-di-tert-butyl-hydroxy phenyls) are different
Cyanurate, three [β-(3,5-di-tert-butyl-hydroxy phenyl) propiono-epoxide ethyl] isocyanuric acid
Ester etc..Wherein, particularly preferred four [methylene-3-(3,5-di-tert-butyl-hydroxy phenyl) propionic esters]
Methane equimolecular quantity is the material of more than 500.
As sulfur system antioxidant, can enumerate: thioether based compound, dithionate based compound,
Mercaptobenzimidazole based compound, thiocarbanilide based compound, thiodipropionate system chemical combination
The sulfur-containing compounds such as thing.Wherein, particularly preferred thiodipropionate system chemical combination.
As phosphorous antioxidant, can enumerate: phosphoric acid, phosphorous acid, ortho phosphorous acid derivant,
Phenyl-phosphonic acid, polyphosphonates, dialkyl group pentaerythritol diphosphites, dialkyl bisphenol A bis-
The phosphorus-containing compounds such as phosphite ester.Wherein, there is phosphorus atoms the most simultaneously and sulfur is former
The compound of son, there is the compound of more than 2 phosphorus atoms in the molecule.
In order to fully obtain the improved effect of resin combination, and obtain connecing with metal simultaneously
Prevent the effect of copper evil time tactile, emulsifying does not occur, do not make thermoplastic elastomer resin composition
Mechanical strength declines, and the total use level of these antioxidants is usually 0.01～5.0 volume %, excellent
Elect 0.05～3.0 volume %, more preferably 0.1～1.5 volume % as.
It addition, in the thermoplastic elastomer resin composition of the present invention, can be not being damaged this
Various additive is added in the range of bright purpose.As additive, can arbitrarily contain such as
The known shaping additive such as nucleating agent, lubrication prescription, UV absorbent, as hindered amine system
Coloring agent, the antistatic agents such as the photostabilizer of compound, hydrolysis modifying agent, pigment, dyestuff, lead
Electricity agent, fire retardant, reinforcing agent, filler, plasticizer, releasing agent etc..
The manufacture method of the thermoplastic elastomer resin composition of the present invention is not particularly limited, example
Polyester block copolymer composition (X), conducting filler (D) will be combined with as may be appropriately used
Raw material be supplied to screwe-type xtruder and carry out the method etc. of melting mixing.Described polyester block
Copolymer compositions (X) is coordinating polyester block copolymer (A), polyvinyl alcohol resin (B) and silicon
In the case of alkane coupling agent (C) forms, such as, may be appropriately used and will be combined with polyester block copolymerization
Thing (A), polyvinyl alcohol resin (B), silane coupler (C), conducting filler (D) and antioxidation
The raw material of agent (E) is supplied to screwe-type xtruder and carries out the method etc. of melting mixing.Melting mixing
Temperature be not particularly limited, be such as preferably heated to more than 200 DEG C.
The thermoplastic elastomer resin composition of the present invention can pass through injection molding forming, extrusion
The various methods such as shaping form processing.
Formed body in order to will be made up of not same material engages, the thermoplastic elastomer (TPE) of the present invention
Resin combination can use preferably as grafting material.As described not same material, can arrange
Lift metal, glass, pottery, resin (such as PPS etc.) etc., by by the thermoplastic elastomehc of the present invention
Gonosome resin combination connects with described various material hot melt the most of the same race, it is possible to produce combined shaping
Body.The surfaces such as coating binder are needed when engaging with not same material unlike silicones
Reason, the thermoplastic elastomer resin composition of the present invention can be various with described by thermal welding
Same material does not engages, from this aspect, the thermoplastic elastomer resin composition of the present invention
Favourable in industrial aspect with the manufacture of the composite molded product of not same material.Carry out thermal welding
Operation in heating-up temperature can be suitable in the range of the effect not damaging the present invention as required
Work as change.
As the joint method of formed body, as long as by the thermoplastic elastomer resin group of the present invention
The method of polymer melt, is not particularly limited, such as, can select: the method for irradiating laser,
Utilize method that hot plate carries out heating, use the method for high frequency, the formed bodies such as metal are added itself
Heat so that the melted method of thermoplastic elastomer resin composition, from injection machine, extrusion molding
Melted thermoplastic elastomer resin composition is spued and is connect by methods such as co-injections by machine
The method etc. closed.
As long as the effect of the present invention can be played, then the present invention wraps in the technical scope of the present invention
Include the various mode combined that above-mentioned composition carried out.
Embodiment
Then, enumerating embodiment and specifically describe the present invention further, the present invention is not limited to
These, can be by the people in the art with common knowledge in the technology of the present invention is conceived
Deform in a large number.
It addition, the hardness of thermoplastic elastomer resin composition in below example, stretching
Evaluating by following of the engaging force of fracture strength, tension fracture elongation rate and various material
Method is carried out.
[hardness]
Use injection machine (day essence Resin Industry NEX-1000), at dram temperature
210～240 DEG C (suitably changing according to the fusing point of the compositions used) becomes with mold temperature 50 DEG C
Under the conditions of shape, it is 120 × 75 × 2mm by the hot air drying shaping particles of more than 3 hours at 90 DEG C
Thickness side's plate, after overlapping 3 blocks of square plates, is measured according to the D type of JIS K7215:1986.
[tensile break strength, tension fracture elongation rate]
Use injection machine (day essence Resin Industry NEX-1000), at dram temperature
210～240 DEG C (suitably changing according to the fusing point of the compositions used) becomes with mold temperature 50 DEG C
Under the conditions of shape, it is JIS K71132 by the hot air drying shaping particles of more than 3 hours at 90 DEG C
Number dumb-bell test piece, is measured according to JIS K7113:1995.
[thermal conductivity]
Use injection machine (day essence Resin Industry NEX-1000), at dram temperature
210～240 DEG C (suitably changing according to the fusing point of the compositions used) becomes with mold temperature 50 DEG C
Under the conditions of shape, by the hot air drying shaping particles of more than 3 hours at 90 DEG C be 120 × 75 ×
2mm thickness side plate, cuts out flow direction 3mm and the flowing side of 10 blocks of resins from the party's plate
To the test film of vertical direction 20mm, with make height as 3mm, horizontal and indulge as 20mm
Flatbed manner tie up, and make test film.Use constant method thermal conductivity meter (ア Le バ ッ
Network science and engineering GH-1S), measure height 3mm direction by method based on ASTM E1530
Thermal conductivity.Highly 3mm direction is corresponding to the thermal conductivity of surface direction in injection moulded products.
[shaping engaging force with the co-injection of PBT resin]
To the PBT resin (east beautiful (strain) system " ト レ U Application " 1101G30) containing 30% glass
Use reciprocal (イ Application ラ イ Application) the screw type injection machine being set as dram temperature 250 DEG C, at 60 DEG C
Mold temperature (mold surface) in obtain the plate of length 65mm × wide 10mm × thickness 2.0mm
Shape formed body.The tabular formed body of the PBT resin containing 30% glass is placed in and is set as rotating cylinder
Temperature 210～240 DEG C (suitably changing according to the fusing point of the compositions used), mold temperature 50 DEG C
In the mold of forming machine, in the state of the length direction coincidence 10mm along tabular formed body
Lower by thermoplastic elastomer resin composition injection molding forming, obtain length 65mm × wide
The thermoplastic elastomer resin composition of 10mm × thickness 2.0mm and the PBT tree containing 30% glass
The formed body that fat engages with the area of 10mm × 10mm.Then, will be containing 30% glass
PBT resin formed body and the end of thermoplastic elastomer resin composition formed body sandwich and draw
Stretch the chuck of testing machine, stretch with the deformation velocity of 50mm/ minute, measure by engaging
The tensile shear in face and the power peeled off.Calculate the power peeled off by tensile shear divided by joint
Area 10mm2Obtained by be worth as engaging force.It addition, each conjugation test sheet is implemented durability
After the humid heat treatment of 80 DEG C × 95%RH × 120h of test, measure in the same way and cut based on stretching
The engaging force cut.
[making a concerted effort with the thermo-compressed of metal material]
Various metals using length 60mm × wide 10mm × thickness 1.5mm as not same material
Be configured at be set as 210～240 DEG C, downside (fusing point of compositions according to using suitably changes), on
The downside of the hot press that side is 60 DEG C, places 1 minute.Then, 10mm × thickness in length and breadth will be compressed to
The thermoplastic elastomer resin composition sheet of 0.2mm is configured on sheet metal, then with weight
The mode closing 10mm configures identical sheet metal.Then, increase the weight of 1MPa and suppress 30 seconds,
Make thermoplastic elastomer resin composition melt to engage with metal.Then, utilize by upside and under
Side is set as the press of 40 DEG C, and the conjugant comprising 2 sheet metals is suppressed 1MPa × 30 second,
Make thermoplastic elastomer resin composition solidify, thus obtain 2 sheet metals with 10mm2's
The tensile shear(ing) test sheet that area overlaps.Then, the two ends of tensile shear(ing) test sheet are sandwiched draw
Stretch the chuck of testing machine, measure drawing by stretching composition surface with the deformation velocity of 50mm/ minute
Stretch the power sheared and peel off.Calculate the power peeled off by tensile shear divided by bonding area
10mm2Obtained by be worth as engaging force.It addition, each conjugation test sheet is implemented endurancing
After the humid heat treatment of 80 DEG C × 95%RH × 120h, measure based on tensile shear in the same way
Engaging force.
The details using material is as described below.
[polyester block copolymer composition (X)]
Granule (is dried 5 little at 80 DEG C by X-1: Dong Li-Du Pont (strain) Ha processed イ ト レ Le 3046
Shi Hou, uses reciprocating screw type injection machine (the day essence Resin Industry system being set as 200 DEG C
NEX-1000), mold temperature (mold surface) the hemostasis mould-forming at 50 DEG C is vertical
The square plate formed products of 120mm × horizontal 70mm × thickness 2mm.By obtained formed products overlap 3
After block, the Shore D hardness measured according to JIS K7215:2007 is 27D)
Granule (is dried 5 at 80 DEG C by X-2: Dong Li-Du Pont (strain) Ha processed イ ト レ Le 4057N
After hour, use reciprocating screw type injection machine (the day essence Resin Industry system being set as 210 DEG C
NEX-1000), mold temperature (mold surface) the hemostasis mould-forming at 50 DEG C is vertical
The square plate formed products of 120mm × horizontal 70mm × thickness 2mm.By obtained formed products overlap 3
After block, the Shore D hardness measured according to JIS K7215:2007 is 40D)
Granule (is dried 5 little at 80 DEG C by X-3: Dong Li-Du Pont (strain) Ha processed イ ト レ Le 5557
Shi Hou, uses reciprocating screw type injection machine (the day essence Resin Industry system being set as 230 DEG C
NEX-1000), mold temperature (mold surface) the hemostasis mould-forming at 50 DEG C is vertical
The square plate formed products of 120mm × horizontal 70mm × thickness 2mm.By obtained formed products overlap 3
After block, the Shore D hardness measured according to JIS K7215:2007 is 55D)
X-4: by the Ha イ ト レ Le 4057N of 89.5 weight %, the エ ス レ ッ Network of 10 weight %
BL-1, the Z-6040 of 0.5 weight % are dry mixed, and use hasScrew rod 2 axles extrusion
Machine, 210 DEG C temperature set under by dry-blend melting mixing after granulate.By this granule
It is dried after 5 hours at 80 DEG C, uses reciprocating screw type injection machine (the day essence being set as 210 DEG C
Resin Industry NEX-1000), mold at the mold temperatures of 50 DEG C (mold surface) hemostasis
It is configured to the square plate formed products of vertical 120mm × horizontal 70mm × thickness 2mm.By obtained shaping
After overlapping 3 pieces of product, the Shore D hardness measured according to JIS K7215:2007 is 40D)
X-5: by the Ha イ ト レ Le 4057N of 84 weight %, the エ ス レ ッ Network of 15 weight %
BL-1, the Z-6040 of 1 weight % are dry mixed, and use has2 axle extruders of screw rod,
210 DEG C temperature set under by dry-blend melting mixing after granulate.This granule is existed
It is dried after 5 hours at 80 DEG C, uses reciprocating screw type injection machine (the day essence tree being set as 210 DEG C
Fat industry NEX-1000), it is molded as at the mold temperatures of 50 DEG C (mold surface) hemostasis
Shape is the square plate formed products of vertical 120mm × horizontal 70mm × thickness 2mm.By obtained formed products
After overlapping 3 pieces, the Shore D hardness measured according to JIS K7215:2007 is 39D)
X-6: by the エ ス レ ッ Network of Ha イ ト レ Le 5557,10 weight % of 89.5 weight %
BL-1, the Z-6040 of 0.5 weight % are dry mixed, and use hasScrew rod 2 axles extrusion
Machine, 230 DEG C temperature set under by dry-blend melting mixing after granulate.By this granule
It is dried after 5 hours at 80 DEG C, uses reciprocating screw type injection machine (the day essence being set as 230 DEG C
Resin Industry NEX-1000), mold at the mold temperatures of 50 DEG C (mold surface) hemostasis
It is configured to the square plate formed products of vertical 120mm × horizontal 70mm × thickness 2mm.By obtained shaping
After overlapping 3 pieces of product, the Shore D hardness measured according to JIS K7215:2007 is 54D)
[polyester block copolymer (A)]
A-1: Dong Li-Du Pont (strain) Ha processed イ ト レ Le 3046 (Shore D hardness: 27D)
A-2: Dong Li-Du Pont (strain) Ha processed イ ト レ Le 4057N (Shore D hardness: 40D)
A-3: Dong Li-Du Pont (strain) Ha processed イ ト レ Le 5557 (Shore D hardness: 55D)
[polyvinyl alcohol resin (B)]
B-1: hydrops chemical industry (strain) polyvinyl butyral resin processed エ ス レ ッ Network BL-1
[silane coupler (C)]
C-1: Dong Li-DOW CORNING (strain) Z-6040 processed (containing the compound of epoxy radicals)
[conducting filler (D)]
D-1: space portion material (strain) oxygenerating magnesium RF-50 Mohs' hardness 4, true specific gravity 3.65
D-2: space portion material (strain) oxygenerating magnesium RF-10C Mohs' hardness 4, true specific gravity 3.65
D-3: electrochemically industry (strain) oxygenerating aluminum DAW-45 Mohs' hardness 9, true specific gravity 3.9
D-4: electrochemically industry (strain) oxygenerating aluminum DAW-05 Mohs' hardness 9, true specific gravity 3.9
D-5: pine village industry (strain) magnesium silicate processed Network ラ ウ Application タ Le Network DR Mohs' hardness 1, very
Proportion 2.7
D-6: pine village industry (strain) magnesium silicate processed Network ラ ウ Application タ Le Network PP Mohs' hardness 1, very than
Weigh 2.7
[antioxidant (E)]
E-1: shiraishi calcium (strain) Na processed ウ ガ De 445 (aromatic amine system antioxidant)
[embodiment 1～9, comparative example 1～9]
By polyester block copolymer composition (X), conducting filler (D) and antioxidant (E) with table
1, the compounding ratio shown in table 2 is dry mixed, and use has2 axle extruders of screw rod,
220 DEG C temperature set under by dry-blend melting mixing after granulate.This granule is existed
After being dried 5 hours at 80 DEG C, carry out the determination test of various characteristic value.Measurement result such as table 1,
Shown in 2.
Table 1
Table 2
Knowable to the result of table 1,2, the thermoplastic elastomer resin composition of embodiment demonstrates
High thermal conductivity, hardness, tensile break strength, stretching 10% distortional stress, tension failure extend
Rate is excellent, and with the engaging force in the co-injection of PBT resin, various metal hot pressing in
Engaging force and respective 80 DEG C of 95%RH × 120h process after engaging force in also show that height
Value.It addition, employ in the embodiment 1,2,7,8 of magnesium silicate, proportion is the lowest, is inciting somebody to action
When the resin combination of the present invention uses as electronic part material etc., for the light weight of these parts
Change effectively.
On the other hand, the thermoplastic elastomer resin of the comparative example 1～9 not included in the present invention
Compositions, compared with the resin combination of the present invention, hardness, tensile break strength, stretching 10%
Distortional stress, any one of tension fracture elongation rate or be all deteriorated, or various engaging force fall
Low, in the compositions not containing polyvinyl alcohol resin, silane coupler, have on the whole
The tendency that engaging force after humid heat treatment is low.
It should be noted that the use level of heat filling (D) exceedes comparative example 9 nothing of prescribed limit
Method carries out spuing when using the melting mixing of 2 axle extruders thus cannot obtain granule.
Industrial applicability
The thermoplastic elastomer resin composition of the present invention is as it has been described above, when formed body
There is sufficient intensity and high thermal conductivity, shaping processability and engineering properties are excellent, with various
Same material does not has high engaging force, therefore can be suitable as setting with automobile component, motor
Grafting material in the joint of the not same material such as standby, industrial goods uses.It addition, as connecing
Conjunction method, can be logical in the case of the not same material not engaged hope is implemented to process especially
Cross and thermoplastic elastomer resin composition is melted and engages, the most extremely effective, thus
The most favourable.
Claims (8)
1. a thermoplastic polyester elastomer resin combination, it is characterised in that comprise Shore D
Hardness is polyester block copolymer composition (X) the 30～85 volume % of below 53D and heat conductivity is filled out
Material (D) 15～70 volume %, described polyester block copolymer composition (X) is with mainly by crystallinity virtue
Hard segment (a1) that fragrant adoption ester units is constituted and mainly by aliphatic poly ether unit and/or aliphatic
The soft chain segment (a2) that polyester unit is constituted is main composition composition, and conducting filler (D) contains silicic acid
Magnesium.
2. resin combination as claimed in claim 1, it is characterised in that described polyester block
Copolymer compositions (X),
I () only by the hard segment (a1) to be mainly made up of crystalline aromatic polyester unit and mainly
The soft chain segment (a2) being made up of aliphatic poly ether unit and/or aliphatic poly ester units is main composition
The polyester block copolymer (A) of composition is constituted, or
(ii) hard segment (a1) to be mainly made up of and mainly is coordinated crystalline aromatic polyester unit
The soft chain segment (a2) being made up of aliphatic poly ether unit and/or aliphatic poly ester units is main composition
The polyester block copolymer (A) of composition, polyvinyl alcohol resin (B) and/or silane coupler (C) and
Become, and described polyester block copolymer composition (X) is set to 100 weight %, then coordinate polyethylene
Alcohol system resin (B) 1～30 weight % and/or silane coupler (C) 0.01～5.0 weight % form.
3. resin combination as claimed in claim 1 or 2, it is characterised in that heat conductivity is filled out
The Mohs' hardness of 60 more than volume % in material (D) 100 volume % is less than 4.
4. resin combination as claimed in claim 1 or 2, it is characterised in that described polyester
The hard segment (a1) of block copolymer composition (X) comprises by p-phthalic acid and/or p-phthalic acid
Dimethyl ester and M-phthalic acid and/or poly-right derivative with 1,4-butanediol of dimethyl isophthalate
Benzene dicarboxylic acid butanediol ester/poly-M-phthalic acid butanediol ester unit.
5. resin combination as claimed in claim 1 or 2, it is characterised in that described polyester
The soft chain segment (a2) of block copolymer composition (X) is main with poly-(tetramethylene ether) diol units
Constituent.
6. resin combination as claimed in claim 2, it is characterised in that polyethenol series tree
Fat (B) is polyvinyl butyral resin and/or polyvinyl acetal resin.
7. a composite molded product, it is characterised in that use the heat described in claim 1 or 2
Plasticity polyester elastomer resin combination is as the composite wood of the formed body being made up of not same material
Material.
8. the manufacture method of a composite molded product, it is characterised in that have: by claim
The work that thermoplastic polyester elastomer resin combination described in 1 or 2 connects with material hot melt the most of the same race
Sequence.
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| PCT/JP2013/057117 WO2013137370A1 (en) | 2012-03-15 | 2013-03-14 | Thermoplastic elastomer resin composition and composite molded body |
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| CN107109036B (en) * | 2014-10-29 | 2019-10-25 | 住友精化株式会社 | The water-borne dispersions of polyester-based elastomer and its manufacturing method |
| WO2018159487A1 (en) | 2017-02-28 | 2018-09-07 | 東洋紡株式会社 | Polybutylene terephthalate resin composition for molded body for welding polyester elastomer, and composite molded body |
| CN107163508A (en) * | 2017-06-02 | 2017-09-15 | 叶剑明 | A kind of copolymerization polycarbonate composition of stress crack resistant and preparation method thereof |
| WO2019047832A1 (en) * | 2017-09-08 | 2019-03-14 | 东丽先端材料研究开发（中国）有限公司 | Bonded body of thermoplastic resin composition and metal and manufacturing method therefor |
| JP2019059204A (en) * | 2017-09-28 | 2019-04-18 | 東レ・デュポン株式会社 | Thermoplastic resin composite molding and method for producing thermoplastic resin composite molding |
| KR102483994B1 (en) * | 2018-09-28 | 2022-12-30 | 코오롱플라스틱 주식회사 | Thermoplastic elastic resin composition and product prepared by the same |
| JP7408010B2 (en) | 2021-03-10 | 2024-01-04 | 三菱電機株式会社 | Manufacturing method of dissimilar material joined body, and dissimilar material joined body |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63270865A (en) * | 1987-04-24 | 1988-11-08 | 東レ株式会社 | Production of yarn like far infrared ray emitting heat generator |
| EP0462525A2 (en) * | 1990-06-20 | 1991-12-27 | Cheil Synthetics Inc. | Copolyester elastomer composition containing a vinylbutyral copolymer having excellent adhesion properties |
| JP2000176050A (en) * | 1998-10-07 | 2000-06-27 | Bridgestone Sports Co Ltd | Golf ball material and golf ball |
| JP2003285873A (en) * | 2002-03-28 | 2003-10-07 | Mitsubishi Chemicals Corp | Easily unsealable container |
| JP2004206889A (en) * | 2002-12-20 | 2004-07-22 | Furukawa Electric Co Ltd:The | Fire-resistant cable |
| CN1536022A (en) * | 2003-04-07 | 2004-10-13 | 三菱化学株式会社 | Thermoplastic resin composition and multilayer laminated body |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100654529B1 (en) * | 2005-02-23 | 2006-12-05 | 제일모직주식회사 | Anisotropic conductive adhesive composition |
| JP4771371B2 (en) | 2006-06-28 | 2011-09-14 | 岡山県 | Dissimilar member joining method and dissimilar member joined product |
| JP5122116B2 (en) * | 2006-11-29 | 2013-01-16 | ポリプラスチックス株式会社 | Thermally conductive resin composition |
| JP2008173967A (en) | 2006-12-18 | 2008-07-31 | Taisei Plas Co Ltd | Composite of metal and resin, and its manufacturing method |
| JP5327937B2 (en) | 2007-12-25 | 2013-10-30 | 旭化成ケミカルズ株式会社 | Adhesive for laser welding |
-
2013
- 2013-03-14 CN CN201380014375.7A patent/CN104169364B/en active Active
- 2013-03-14 TW TW102108980A patent/TWI579328B/en active
- 2013-03-14 KR KR1020147022702A patent/KR102053787B1/en active IP Right Grant
- 2013-03-14 JP JP2014504986A patent/JP6009535B2/en active Active
- 2013-03-14 WO PCT/JP2013/057117 patent/WO2013137370A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63270865A (en) * | 1987-04-24 | 1988-11-08 | 東レ株式会社 | Production of yarn like far infrared ray emitting heat generator |
| EP0462525A2 (en) * | 1990-06-20 | 1991-12-27 | Cheil Synthetics Inc. | Copolyester elastomer composition containing a vinylbutyral copolymer having excellent adhesion properties |
| JP2000176050A (en) * | 1998-10-07 | 2000-06-27 | Bridgestone Sports Co Ltd | Golf ball material and golf ball |
| JP2003285873A (en) * | 2002-03-28 | 2003-10-07 | Mitsubishi Chemicals Corp | Easily unsealable container |
| JP2004206889A (en) * | 2002-12-20 | 2004-07-22 | Furukawa Electric Co Ltd:The | Fire-resistant cable |
| CN1536022A (en) * | 2003-04-07 | 2004-10-13 | 三菱化学株式会社 | Thermoplastic resin composition and multilayer laminated body |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2013137370A1 (en) | 2013-09-19 |
| JPWO2013137370A1 (en) | 2015-08-03 |
| JP6009535B2 (en) | 2016-10-19 |
| TW201343769A (en) | 2013-11-01 |
| KR20140135952A (en) | 2014-11-27 |
| TWI579328B (en) | 2017-04-21 |
| KR102053787B1 (en) | 2019-12-09 |
| CN104169364A (en) | 2014-11-26 |
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