CN110204859A - Heat-curable epoxy resin composition, fiber-reinforced thermosetting property composition epoxy resin and solidfied material - Google Patents
Heat-curable epoxy resin composition, fiber-reinforced thermosetting property composition epoxy resin and solidfied material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/046—Reinforcing macromolecular compounds with loose or coherent fibrous material with synthetic macromolecular fibrous material
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The present invention obtains heat resistance, excellent in te pins of durability, the excellent heat-curable epoxy resin composition of anti-drop and fiber-reinforced thermosetting property composition epoxy resin and its solidfied material when forming.A kind of heat-curable epoxy resin composition, containing epoxy resin and curing agent, viscosity is 200~4000mPas, and the glass transition temperature (Tg) of solidfied material is 195 DEG C~235 DEG C.
Description
Technical field
The present invention relates to a kind of heat-curable epoxy resin composition, fiber-reinforced thermosetting property composition epoxy resin,
And solidfied material.
Background technique
In the prior art, this characteristic of the mechanical strength of heat-curable epoxy resin is of concern, and is used for example
Such as using automobile, airplane skin, various components as representative various structural bodies on the way (for example, referring to patent document 1,
2).In addition, also proposed the fiber reinforced composite material by making the structure composition of epoxy resin impregnating reinforcing fiber in the prior art
Material, although can show mechanical strength, heat resistance, humidity resistance in obtained solidfied material for example, proposing is low viscosity
The fiber reinforced composite material of excellent characteristic, structure member, electricity of the formed products formed by the solidfied material for engine etc.
(for example, referring to patent document 3) in wire core material etc..
Existing technical literature
Patent document
Patent document 1:2016-84372 bulletin
Patent document 2:2016-89-78 bulletin
Patent document 3: No. 5954516 bulletins of Japanese Patent Publication No.
Summary of the invention
Problems to be solved by the invention
But in the technology disclosed in Patent Documents 1 to 3, it is assumed that by composition epoxy resin, fiber reinforced composite
Material especially as the core material of power line cable materials'use when, there are following problems: from can be substantially resistant to being transmitted electricity when
The heat resistance of fever, the angle of durability set out, can't say with sufficient characteristic；In addition, not from power line cable
Core material manufacture when the angle of anti-drop (liquid だ れ) set out and studied, from ensuring that the sufficient thickness as cable comes
It sees, characteristic is insufficient.
Therefore, the object of the present invention is to provide a kind of by limiting the viscous of heat-curable epoxy resin composition respectively
Degree with the Tg of its solidfied material within the limits prescribed, especially as the core material of power line cable materials'use when, can obtain
To can heat resistance substantially resistant to fever when being transmitted electricity, durability, and in the manufacture of the core material of cable, anti-drop is excellent, energy
Enough ensure the heat-curable epoxy resin composition of the sufficient thickness as cable.
The solution to the problem
The inventors of the present invention are conscientiously studied for above-mentioned the problems of the prior art point, as a result, it has been found that containing asphalt mixtures modified by epoxy resin
In the heat-curable epoxy resin composition of rouge and curing agent, by limiting viscosity and the heat-curable epoxy resin composition
Solidfied material glass transition temperature Tg within the limits prescribed, above-mentioned the problems of the prior art are able to solve, thus complete
At the present invention.That is, the present invention is as follows.
〔1〕
A kind of heat-curable epoxy resin composition, containing epoxy resin and curing agent, viscosity is 200~
4000mPas, the glass transition temperature Tg of solidfied material are 195 DEG C~235 DEG C.
〔2〕
According to heat-curable epoxy resin composition described in above-mentioned (1), wherein the epoxy resin contains ingredient (A-
1): being the epoxy resin and ingredient (A-2) of liquid at 25 DEG C: the epoxy resin that softening point is 50 DEG C or more.
〔3〕
According to heat-curable epoxy resin composition described in above-mentioned (1) or (2), wherein the curing agent contains acid anhydrides
And/or aminated compounds.
〔4〕
According to heat-curable epoxy resin composition described in above-mentioned (2) or (3), wherein the ingredient (A-1) contains rouge
Ring race epoxy.
〔5〕
According to described in any item heat-curable epoxy resin compositions of above-mentioned (2)~(4), wherein the ingredient (A-
2) containing the epoxy resin with structure shown in general formula (1).
In formula (1), R1And R2Indicate the linking group of singly-bound or divalent.
〔6〕
According to described in any item heat-curable epoxy resin compositions of above-mentioned (2)~(5), wherein relative to described
Total quality of ingredient (A-1) and the ingredient (A-2), the mass ratio of the ingredient (A-1) are 99~30 mass %.
〔7〕
A kind of fiber-reinforced thermosetting property composition epoxy resin, described in any item heat containing above-mentioned (1)~(6)
Curable epoxy resin composition and fibrous material, the fibrous material are selected from glass fibre, carbon fiber and aramid fiber group
At group at least either.
〔8〕
A kind of solidfied material of fiber-reinforced thermosetting property composition epoxy resin, any one containing above-mentioned (1)~(6)
The heat-curable epoxy resin composition and fibrous material, the fibrous material are selected from glass fibre, carbon fiber and virtue
At least either in the group of synthetic fibre fiber composition.
The effect of invention
In accordance with the invention it is possible to obtain heat resistance, excellent in te pins of durability, the excellent Thermocurable ring of anti-drop when forming
Epoxy resin composition.
Specific embodiment
Hereinafter, mode for carrying out the present invention (hreinafter referred to as " present embodiment ") is described in detail.Below
Present embodiment be only intended to illustrate example of the invention, the present invention and in being limited to following the description.The present invention can be
It does not depart from and carries out implementing after suitably deforming in its main scope.
(heat-curable epoxy resin composition)
The heat-curable epoxy resin composition of present embodiment is a kind of containing epoxy resin and curing agent, and viscosity is
200~4000mPas, the heat-curable epoxy resin group that the glass transition temperature (Tg) of solidfied material is 195 DEG C~235 DEG C
Close object.
(epoxy resin)
The heat-curable epoxy resin composition of present embodiment contains epoxy resin.The Thermocurable ring of present embodiment
The epoxy resin for including in epoxy resin composition refers to the high-molecular compound for the epoxy group for containing 2 or more by intramolecular
And its epoxy group ring-opening reaction and the synthetic resin that generates.Epoxy resin can suitably select various well known resins.It can be with
It enumerates but is not limited to hereinafter, for example, bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, second
Interior uride type epoxy resin, biphenyl type epoxy resin, cycloaliphatic epoxy resin, triphenylmethane type epoxy resin, phenol novolac
Type epoxy resin, cresol novolak type epoxy resin, naphthol novolac type epoxy resin, bisphenol A novolac type
Epoxy resin, bicyclopentadiene/phenol epoxy resin, cycloaliphatic amines epoxy resin, aliphatic epoxy resin, aliphatic amine epoxy
Resin etc..These can be used singly or in combination of two or more.
In the heat-curable epoxy resin composition of present embodiment, the epoxy resin is from the angle for ensuring suitable viscosity
Degree sets out, preferably comprise at 25 DEG C of (A-1) for the epoxy resin of liquid (hereinafter, be denoted as sometimes (A-1) epoxy resin, (A-1) at
Point) and (A-2) softening point be 50 DEG C or more of epoxy resin (hereinafter, being denoted as (A-2) epoxy resin, (A-2) ingredient sometimes).
If using (A-2) softening point is 50 DEG C or more of epoxy resin, due to drop before the B-staged (semi-solid preparation) after fiber impregnation
It is difficult to happen, therefore the fluctuation of quality will tail off.In addition, " being liquid at 25 DEG C " in (A-1) epoxy resin refers at 120 DEG C
After the above heating 2 hours, 25 DEG C are cooled to, it is viscous by E type in 2 hours after reaching 25 DEG C when being maintained at 25 DEG C later
The viscosity (viscosity at 25 DEG C) of degree meter measurement is 30000Pas or less.(A-2) in epoxy resin " softening point be 50 DEG C with
On " refer to that softening point when measuring by Mettler Toledo Inc.'s softening point measuring device (DP-60) is 50 DEG C or more.
In the heat-curable epoxy resin composition of present embodiment, from preferably immersion angle is ensured, (A-1) ingredient is excellent
It is selected in whole epoxy resin as 30~99 mass %, more preferably 40~99 mass %, further preferably 50~70 matter
Measure %.In addition, (A-2) ingredient is preferably in whole epoxies from the angle by improving heat resistance there are macromolecule component
It is 1~70 mass %, more preferably 1~60 mass %, further preferably 30~50 mass % in resin.
< (A-1) epoxy resin: being the epoxy resin > of liquid at 25 DEG C
(A-1) epoxy resin can be selected suitably using various well known epoxy resin.It can enumerate but unlimited
In hereinafter, for example, bisphenol A type epoxy resin, bisphenol f type epoxy resin, cycloaliphatic epoxy resin, aliphatic epoxy resin, two
Cyclopentadiene/phenol epoxy resin, aminobenzene phenol-type epoxy resin, cycloaliphatic amines epoxy resin, aliphatic amine epoxy resin etc..
These can be used singly or in combination of two or more.Especially from ensuring with high Tg's when acid anhydrides mixture
Angle is set out, as (A-1) epoxy resin, preferably cycloaliphatic epoxy resin.
Relative to total quality of (A-1) ingredient and (A-2) ingredient, the mass ratio of (A-1) epoxy resin is preferably 1~
70 mass %, more preferably 1~60 mass %, further preferably 30~50 mass %.Relative to (A-1) ingredient and (A-2)
Total quality of ingredient, the mass ratio of (A-1) ingredient are preferably 30~99 mass %, more preferably 40~99 mass %, into
One step is preferably 50~70 mass %.
< (A-2) epoxy resin: the epoxy resin > that softening point is 50 DEG C or more
(A-2) epoxy resin preferably has the epoxy resin of structure shown in the following general formula (1).It is heat-resisting after shaping as a result,
The physical property such as property, Strengthening and Toughening can be improved particularly.Also, due to being expected that the electrical characteristics of insulating resistance value variation etc. can improve, because
This is possibly realized as the long-time service of coating electric wire layer.
In the general formula (1), R1And R2Indicate the linking group of singly-bound or divalent.
R in general formula (1)1It is the linking group of singly-bound or divalent, as the linking group of divalent, can contains but be not limited to
Hereinafter, for example selected from biphenyl class, bisphenol-A class, Bisphenol F class, bisphenol AF class, bisphenol-A C class, bisphenol S class, phenol novolacs class
With the skeleton of one or more of the group of cresol novolak class composition, these skeletons also can have substituent group.
R in general formula (1)2It is the linking group of singly-bound or divalent, as the linking group of divalent, can enumerates but unlimited
In hereinafter, for example, can substituted alkylidene or can substituted arlydene etc..Herein, " alkylidene " is indicated from " alkyl "
The group for further removing 1 hydrogen atom of any position and derivative divalent, can enumerate but be not limited to hereinafter, for example, sub-
Methyl, ethylidene, methyl ethylidene, ethylethylene residue, 1,1- dimethylethylene, 1,2- dimethylethylene, trimethylene,
1- methyl trimethylene, 2- methyl trimethylene, tetramethylene etc. can preferably enumerate methylene, ethylidene, methyl Asia second
Base, 1,1- dimethylethylene, trimethylene etc..In addition, " arlydene ", which refers to, further removes any position from " aryl "
1 hydrogen atom and the group of derivative divalent.R2Shown in can substituted alkylidene and arlydene, in the position that can replace
It sets, can be replaced by 1 or 2 or more substituent group.As corresponding substituent group, can enumerate for example, halogen atom (such as
Fluorine atom, chlorine atom), the alkyl of carbon atom 1~6 (such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, sec-butyl,
Tert-butyl, amyl, hexyl), aryl (such as phenyl, naphthalene), aralkyl (such as benzyl, phenethyl), alkoxy (such as methoxy
Base, ethyoxyl) etc..
In present embodiment, the preferably described R2Selected from origin derived from isophorone, benzene, toluene, diphenyl methane and naphthalene
Linking group, hexa-methylene and the-(CH of the divalent of any one2-C6H4)n(there is polymethylene polyphenylene polyphenylene skeleton
Group) (wherein, n be 2~6 integer, in 1 molecule have it is multiple when, can respectively it is identical or different) composition group.
By having these groups, heat-resistant stability tends to further increase.
About the content of ingredient (A-2), relative to total quality of ingredient (A-1) and ingredient (A-2), ingredient (A-2)
Mass ratio is preferably 1~70 mass %, more preferably 1~60 mass %, further preferably 30~50 mass %.If ingredient
(A-2) mass ratio is 1 mass % or more, the solidification of the heat-curable epoxy resin composition containing the ingredient (A-2)
The heat resistance and mechanical properties of object can improve, thus preferably.But in order to be easy to get fracture toughness height and void-free forming
Product, preferably 70 mass % or less.
(curing agent)
As long as curing agent can make epoxy resin cure used in present embodiment, to its structure etc. without especially limit
It is fixed.As curing agent, it can enumerate but be not limited to hereinafter, for example, amine curing agent, phenol curing agent, anhydride solidify
Agent, latent curing agent etc..
As amine curing agent, it can enumerate but be not limited to hereinafter, for example, the amine of aliphatic amine, aromatic amine etc.
Compound.As aliphatic amine, it can enumerate but be not limited to hereinafter, for example, diethylenetriamines, trien, four
Five amine of ethylidene, m-xylene diamine, trimethylhexamethylenediamine, 2- methyl pentamethylene diamine, isophorone diamine, 1,
The bis- aminomethyl cyclohexanes of 3-, bis- (4- aminocyclohexyl) methane, norbornene diamines, 1,2- diaminocyclohexane, 1,8- bis-
Azabicyclo (5,4,0) hendecene -7 (DBU) etc..As aromatic amine, it can enumerate but be not limited to hereinafter, for example, diamino
Bis- (the 4-aminobenzoic acid of base diphenyl methane, m-phenylene diamine (MPD), diamino diphenyl sulfone, diethyl toluene diamine, trimethylene
Ester) ,-two P aminobenzoates of polytetrahydrofuran etc..
As phenol curing agent, it can enumerate but be not limited to hereinafter, for example, phenol resol resins, cresols phenol
Novolac resin, phenol aralkyl resin, cresols aralkyl resin, naphthols aralkyl resin, biphenyl modified phenolic resin, biphenyl
Modified phenol aralkyl resin, dicyclopentadiene-modified phenolic resin, amino triazine phenol-formaldehyde resin modified, naphthol novolac varnish-tree
Rouge, naphthols-phenol cocondensation novolac resin, naphthols-cresols cocondensation novolac resin, allyl acrylic acid phenolic aldehyde tree
Rouge etc..
As acid anhydride type curing agent, can enumerate but be not limited to hereinafter, for example, phthalic anhydride, trimellitic anhydride,
Pyromellitic dianhydride, maleic anhydride, tetrabydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylnadic anhydride, hexahydro
The acid anhydrides of phthalic anhydride, methylhexahydrophthalic anhydride etc..From the angle of viscosity, the asphalt mixtures modified by epoxy resin of present embodiment
Curing agent in oil/fat composition is preferably acid anhydrides (acid anhydride type curing agent).Further, at high temperature due to acid anhydride type curing agent
Reaction it is fast, therefore the shortening of manufacturing time is also possibly realized.
As latent curing agent, can enumerate but be not limited to hereinafter, for example, Imidazole Type Latent Curing Agent, by amine
The encapsulated substance etc. of adduct.Commercially available product also can be used in these latent curing agents, for example, can enumerate " PN23 ",
The Ajicure such as " PN40 ", " PN-H " (ア ミ キ ュ ア) series (aginomoto Fine-Techno society system), " HX-3088 ", " HX-
3941 ", the Novacure such as " HX-3742 " are serial (society, Asahi Chemical Industry system).
Above-mentioned curing agent can be used singly or in combination of two or more.When two or more is applied in combination, have
When a part can work as " curing agent ", remaining part is then used as " curing accelerator " to work.It is described herein
Curing agent refers to by heat, light, to react the substance for the function being crosslinked with epoxy resin, curing accelerator is main
Although referring to itself will not react with epoxy resin but have make epoxy resin and curing agent to react incidental function
Substance.
For the content of the curing agent in the heat-curable epoxy resin composition of present embodiment, it is not particularly limited, with
When adding up to 100 mass parts of epoxy resin ingredient, preferably 2~60 mass parts, more preferably 3~55 mass parts, further
Preferably 4~50 mass parts.When making in the content above range of curing agent, the reaction of heat-curable epoxy resin composition
Property, mechanical property, heat resistance etc. tend to further increase.
(other additives)
In the heat-curable epoxy resin composition of present embodiment, further, as arbitrary ingredient, it can also contain
1 kind in group be made of thermoplastic resin, thermoplastic elastomer (TPE) and the elastomer selected from triblock copolymer, in addition to this
Above additive (hereinafter referred to as " arbitrary additive ").These arbitrary additives not only have and make present embodiment
The viscoplasticity of heat-curable epoxy resin composition changes, optimization viscosity, store elastic modulus and thixotropic effect, moreover it is possible to mention
The fracture toughness of the solidfied material of the heat-curable epoxy resin composition of high present embodiment.
Thermoplastic resin, thermoplastic elastomer (TPE) and the elastomer that can be used as arbitrary additive can individually make
With a kind, two or more can also be applied in combination.In addition, the arbitrary additive can be dissolved in epoxy resin ingredient,
Present embodiment can be contained in the shape of particle, long fibre, staple fiber, fabric, non-woven fabrics, mesh, paper pulp etc.
In heat-curable epoxy resin composition.The arbitrary additive is with particle, long fibre, staple fiber, fabric, non-woven fabrics, net
The shape of shape object, paper pulp etc. by comprising when, by make present embodiment heat-curable epoxy resin composition impregnate undulation degree
When fiber-reinforced plastic is made in the compacting of prepreg made of material, it is able to suppress splitting, thus preferably.
Carbon-carbon bond, amido bond, imide bond, ester are selected from, it is preferable to use having on main chain as the thermoplastic resin
In the group that key, ehter bond, carbonic acid ester bond, urethane bond, urea bond, thioether bond, sulfone linkage, imidazoles key and carbonyl bond form at least
The thermoplastic resin of one key.More specifically, can enumerate for example, polyacrylate, polyamide, Nomex, polyester, poly-
Carbonic ester, polyphenylene sulfide, polybenzimidazoles, polyimides, polyetherimide, polysulfones and polyether sulfone etc. belong to the heat of engineering plastics
Plastic resin.Wherein, due to excellent heat resistance, particularly preferably using polyimides, polyetherimide, polysulfones and polyether sulfone etc..
In addition, environment resistant from the fracture toughness of the solidfied material for the heat-curable epoxy resin composition for improving present embodiment and maintenance
Angle set out, preferably these thermoplastic resins have reactive functional groups with epoxy resin.As having and epoxy resin
Preferred reactive functional group, carboxyl, amino and hydroxyl etc. can be enumerated.
(physical property of heat-curable epoxy resin composition)
(viscosity (Pas) of heat-curable epoxy resin composition)
The viscosity of the heat-curable epoxy resin composition of present embodiment is 200mPas~4000mPas, preferably
For 500mPas~3000mPas.From the angle for ensuring good drawing mouldability, be 200mPas~
4000mPas, preferably 200mPas~2000mPas, more preferably 300mPas~1500mPas.In addition, from
Ensure that good immersion angle is set out, be 500mPas~3000mPas, preferably 1400mPas~
3500mPas, more preferably 2000mPas~3000mPas.
The method of viscosity as adjustment heat-curable epoxy resin composition, can enumerate by adjusting epoxy resin
Deng molecular weight such as number-average molecular weight and weight average molecular weight etc. come the method that adjusts viscosity.In general, with the increase of molecular weight,
Viscosity can also rise.The method of adjustment of molecular weight as epoxy resin etc. can use well known method.
(glass transition temperature Tg of solidfied material)
For the heat-curable epoxy resin composition of present embodiment, the glass transition temperature (Tg) of solidfied material is
195 DEG C~235 DEG C, preferably 210~230 DEG C.
In present embodiment, as described above, by the way that specific range of viscosities and specific Tg range, Lai Shixian is applied in combination
The excellent resin combination of anti-drop when heat resistance, durability and molding.Although realizing such excellent resin combination
The mechanism details of object is unclear, even if but can deduce is due to the polymer chain with appropriate intermolecular interaction
Also there is appropriate transport properties of molecules, therefore not only before curing immersion excellent when solidifying, but also realizes relative to system
The good absorbability (elasticity modulus) of the various external force applied when at solidfied material formed body, be furthermore achieved be not easily broken,
The solidfied material formed body of excellent heat resistance.
(fiber-reinforced thermosetting property composition epoxy resin)
The heat-curable epoxy resin composition of present embodiment can be combined with fibrous material constitutes fibre strengthening thermosetting
The property changed composition epoxy resin.In addition, can be provided by solidifying the fiber-reinforced thermosetting property composition epoxy resin
Solidfied material, formed products.It is unlimited for the form of fibrous material used in present embodiment, it can enumerate for example, will
Tow, cloth and silk, chopped strand, continuous fiber are in one direction and the form of silk, the shape that continuous fiber longitude and latitude is woven into fabric
State, by tow in one direction and silk kept by weft auxiliary line form, by the sheet material of the unidirectional reinforcing fiber of multi-disc not
Equidirectional upper stacking is simultaneously sutured with auxiliary line and is fixed in the form of forming multi-shaft warp knitting knitted fabric and by reinforcing fiber system
At the form etc. of non-woven fabrics.Wherein, preferably continuous fiber longitude and latitude in one direction and the form of silk, is woven by continuous fiber
Multi-disc the form that keeps by weft auxiliary line of silk and is enhanced in one direction and unidirectionally fibre by tow by the form of fabric
The sheet material of dimension stacks in different directions and is sutured and fixed in the form of forming multi-shaft warp knitting knitted fabric with auxiliary line.From body
The angle of the intensity of existing solidfied material is set out, further preferably in one direction and the form of silk by continuous fiber.
Such as carbon fiber, graphite fibre, glass fibers can be used without limitation in material for constituting the fibrous material
Dimension, organic fiber, boron fibre, steel fibre etc..Especially glass fibre, carbon fiber, aramid fiber or their mixture for
Intensity, light-weighted contribution are big, thus preferably；Since the specific modulus of carbon fiber is good, thus more preferably.For using this implementation
The heat-curable epoxy resin composition of mode manufactures the method for fiber-reinforced thermosetting property composition epoxy resin also without limitation,
It can use but be not limited to hereinafter, such as autoclave method, vacuum bag method, fiber winding method, the drawing method of forming, resin transfer molding
(RTM) manufacturing process well known to method etc..In addition, for above-mentioned various parameters, as long as being not particularly limited, according to aftermentioned implementation
The measuring method of example is measured.
Embodiment
Hereinafter, the present invention is specifically described by embodiment, but the present invention is not limited to these Examples.Wherein, under
The content for stating the ingredient in table 1 is mass parts.In embodiment, comparative example, various characteristics are measured by following methods
's.
(measuring method)
((1) viscosity)
For the viscosity (mPas) of heat-curable epoxy resin composition, first by epoxy resin composition at 120 DEG C
After heating 2 hours, anhydride curing agent is added, uses non-deaeration kneading machine (rotation-revolution formula blender, THINKY society AR-
250), at stirring mode 3 minutes: rotation/revolution=800rpm/2000rpm, deaeration mode 2 minutes: rotation/revolution=
After mixing under conditions of 60rpm/2200rpm, the catalyst of acid anhydrides is further added, is stirred again by non-deaeration kneading machine
Afterwards, it is placed on the platform of rheometer (HAKKE MARS III Thermo SCIENTIFIC society system), is cooled to 40 DEG C, measurement
Viscosity after reaching 40 DEG C after ten minutes.
((2) glass transition temperature Tg, store elastic modulus)
The glass transition temperature (Tg) (DEG C) of the solidfied material of heat-curable epoxy resin composition is using Dynamic Viscoelastic
Property measurement device RSA-G2 (TA Instruments society system), by long 20mm × wide 10mm × thickness 2mm test film with 5 DEG C/minute
The speed of clock heats up, and measures store elastic modulus (MPa) and loss elastic modulus (MPa), finds out when its tan δ reaches maximum
Temperature.Store elastic modulus at this is 230 DEG C be 100MPa hereinafter, if be judged as impact resistance destructive height, such as defeated
The core material of electric wire can also obtain high durable in use, even if when transmission of electricity becomes high temperature, influenced to vibrate by wind and rain
Property.
Tg can be controlled by combining various epoxy resin.In order to obtain high heat resistance solidfied material, it is preferable to use
Polyfunctional epoxy resin as jER604, VG3101 or HP-4710, the AER4004 in the molecule with rigid backbone.
((3) damage difficulty)
The sample (long 30mm × wide 30mm × thickness 2mm) of the solidfied material of being thermally cured property composition epoxy resin is on hot plate
230 DEG C are heated to, drop weight test is carried out, is evaluated by following.
On surface occur cracking ×
Appearance recess zero is observed on surface
The substantially unchanged ◎ of appearance
(the immersion test of (4) to fibrous material)
Being thermally cured property composition epoxy resin at 40 DEG C dip coated in fibrous material: 2cm × 5cm (beautiful strain formula in east
Carbon fibre fabric " ト レ カ Network ロ ス CO-6363 " (registered trademark) (weight per unit area 198g/m of commercial firm2)), lift it
Afterwards, it is placed 3 minutes at 25 DEG C, the quality for measuring the heat-curable epoxy resin composition for being attached to fibrous material (is surveyed with n2
It is fixed, be averaged), it is evaluated according to following benchmark.The following institute of relationship between the quality (g) and evaluation result of resin combination
Show.
1.5g or more and less than 2.5g zero
Less than 1.5g ×
2.5g or more △
(material of heat-curable epoxy resin composition) (epoxy resin)
BE186EL (Conservancy Association's trade name): bisphenol A type epoxy resin
2021P (society, DAICEL Co., Ltd. trade name): cycloaliphatic epoxy resin
AER4004 (society, Asahi Kasei Corporation trade name): isocyanate modified epoxy resin
JER604 (society, Mitsubishi chemical Co., Ltd trade name): diaminodiphenyl-methane type epoxy resin
HP-4710 (society, Dainippon Ink Chemicals trade name): two naphthalene type epoxy resins
VG3101 (rintec society, P Co., Ltd. trade name): 3 functional epoxy resins of high heat resistance
(curing agent)
MHAC-P (society, Hitachi Chemical Co., Ltd. trade name): acid anhydrides
HN-5500 (society, Hitachi Chemical Co., Ltd. trade name): acid anhydrides
DBU (Wako Pure Chemical Industries, Ltd.'s trade name): diazabicyclo endecatylene
HX-3742 (society, Asahi Kasei Corporation trade name): Imidazole Type Latent Curing Agent
(embodiment), (comparative example)
According to composition described in table 1, heat-curable epoxy resin composition is manufactured, carries out the evaluation of (1), (4).Manufacture item
Part is as follows.The aluminium dish that joined resin is placed on 40 degree of hot plate.Resin quality is 10~20g or so.Thereto plus
Enter acid anhydrides, is stirred 2 minutes with bamboo stick.It after stirring, is added catalyst (DBU, HX-3742), is further stirred 2 minutes with bamboo stick.
Finally, being stirred using above-mentioned " rotation-revolution formula blender ".In addition, by Thermocurable asphalt mixtures modified by epoxy resin described in 100 mass parts tables 1
Oil/fat composition preheats 1 hour at 120 DEG C, and the formal solidification processing carried out at 180 DEG C 1 hour makes its solidification, makes thermosetting
The solidfied material of the property changed composition epoxy resin, carries out solidfied material evaluation ((2), (3)).
[table 1]
Industrial availability
Thermosetting epoxy resin composition of the invention can be suitable as automobile, electric/electronic device, building component
Etc. material for various purposes.Particularly, thermosetting epoxy resin composition of the invention can be suitable as the core material of power transmission line.
Claims (8)
1. a kind of heat-curable epoxy resin composition, containing epoxy resin and curing agent, viscosity is 200~4000mPa
S, the glass transition temperature Tg of solidfied material are 195 DEG C~235 DEG C.
2. heat-curable epoxy resin composition according to claim 1, wherein the epoxy resin contains ingredient (A-
1): being the epoxy resin and ingredient (A-2) of liquid at 25 DEG C: the epoxy resin that softening point is 50 DEG C or more.
3. heat-curable epoxy resin composition according to claim 1 or 2, wherein the curing agent contain acid anhydrides and/
Or amine compound.
4. heat-curable epoxy resin composition according to claim 2 or 3, wherein the ingredient (A-1) contains alicyclic ring
Race's epoxy.
5. according to described in any item heat-curable epoxy resin compositions of claim 2 to 4, wherein the ingredient (A-2)
Containing the epoxy resin with structure shown in general formula (1),
In formula (1), R1And R2Indicate the linking group of singly-bound or divalent.
6. according to described in any item heat-curable epoxy resin compositions of claim 2 to 5, wherein relative to it is described at
Divide total quality of (A-1) and the ingredient (A-2), the mass ratio of the ingredient (A-1) is 99~30 mass %.
7. a kind of fiber-reinforced thermosetting property composition epoxy resin, described in any item thermosettings containing claim 1 to 6
The property changed composition epoxy resin and fibrous material, the fibrous material are selected from glass fibre, carbon fiber and aramid fiber composition
Group at least either.
8. a kind of solidfied material of fiber-reinforced thermosetting property composition epoxy resin, any one institute containing claim 1 to 6
The heat-curable epoxy resin composition and fibrous material stated, the fibrous material are selected from glass fibre, carbon fiber and aramid fiber
At least either in the group of fiber composition.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810168318.9A CN110204859A (en) | 2018-02-28 | 2018-02-28 | Heat-curable epoxy resin composition, fiber-reinforced thermosetting property composition epoxy resin and solidfied material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810168318.9A CN110204859A (en) | 2018-02-28 | 2018-02-28 | Heat-curable epoxy resin composition, fiber-reinforced thermosetting property composition epoxy resin and solidfied material |
Publications (1)
| Publication Number | Publication Date |
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| CN110204859A true CN110204859A (en) | 2019-09-06 |
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ID=67778954
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|---|---|---|---|
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103249753A (en) * | 2011-01-27 | 2013-08-14 | 东丽株式会社 | Epoxy resin composition for resin transfer molding of fiber-einforced composite material, fiber-reinforced composite material, and method for producing same |
| CN104004320A (en) * | 2014-05-15 | 2014-08-27 | 江苏绿材谷新材料科技发展有限公司 | Flame-retardant high temperature-resistant epoxy resin composition capable of being used for pultrusion and preparation method thereof |
| CN104837921A (en) * | 2012-11-07 | 2015-08-12 | 陶氏环球技术有限公司 | A curable epoxy composition and a composite made therefrom |
| CN105219046A (en) * | 2015-09-06 | 2016-01-06 | 江苏恒神股份有限公司 | Intermediate temperature setting is wound around resin and preparation method thereof, gained is wound around one-way slabs |
-
2018
- 2018-02-28 CN CN201810168318.9A patent/CN110204859A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103249753A (en) * | 2011-01-27 | 2013-08-14 | 东丽株式会社 | Epoxy resin composition for resin transfer molding of fiber-einforced composite material, fiber-reinforced composite material, and method for producing same |
| CN104837921A (en) * | 2012-11-07 | 2015-08-12 | 陶氏环球技术有限公司 | A curable epoxy composition and a composite made therefrom |
| CN104004320A (en) * | 2014-05-15 | 2014-08-27 | 江苏绿材谷新材料科技发展有限公司 | Flame-retardant high temperature-resistant epoxy resin composition capable of being used for pultrusion and preparation method thereof |
| CN105219046A (en) * | 2015-09-06 | 2016-01-06 | 江苏恒神股份有限公司 | Intermediate temperature setting is wound around resin and preparation method thereof, gained is wound around one-way slabs |
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