CN106715581A - Epoxy resin composition, cured product, fiber-reinforced composite material, fiber-reinforced resin molded article, and method for producing fiber-reinforced resin molded article - Google Patents

Epoxy resin composition, cured product, fiber-reinforced composite material, fiber-reinforced resin molded article, and method for producing fiber-reinforced resin molded article Download PDF

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CN106715581A
CN106715581A CN201580051979.8A CN201580051979A CN106715581A CN 106715581 A CN106715581 A CN 106715581A CN 201580051979 A CN201580051979 A CN 201580051979A CN 106715581 A CN106715581 A CN 106715581A
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epoxy resin
fiber
composition
resin
reinforced
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CN106715581B (en
Inventor
小林厚子
松井茂树
谷井翔太
河崎显人
森永邦裕
木村真实
林弘司
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3227—Compounds containing acyclic nitrogen atoms
    • 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
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1535—Five-membered rings
    • C08K5/1539—Cyclic anhydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/06—Polysulfones; Polyethersulfones

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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)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)
  • Epoxy Resins (AREA)

Abstract

Provided are: an epoxy resin composition which has low viscosity and is still capable of providing a cured product that has excellent mechanical strength, heat resistance and wet heat resistance; a cured product which has the above-described properties; a fiber-reinforced composite material; a fiber-reinforced resin molded article; and a method for producing a fiber-reinforced resin molded article. Specifically provided are: an epoxy resin composition which is characterized by containing (a) an epoxy resin that is (a-1) an epoxy resin having an average number of functional groups of 2.3 or more or (a-2) an alicyclic epoxy resin, (b) an acid anhydride, (c) a polyol compound containing 2 or more alcoholic hydroxyl groups in each molecule and having a hydroxyl equivalent of from 30 g/eq to 650 g/eq, and (d) a curing accelerator.

Description

Composition epoxy resin, solidfied material, fibre reinforced composites, fiber-reinforced resin The manufacture method of formed products and fiber-reinforced resin formed products
Technical field
The present invention relates to for low viscosity and gained solidfied material can manifest excellent mechanical strength, heat resistance, humidity resistance Composition epoxy resin, the solidfied material with aforementioned properties, fibre reinforced composites, fiber-reinforced resin formed products and The manufacture method of fiber-reinforced resin formed products.
Background technology
The light weight and feature as mechanical strength of the fiber-reinforced resin formed products enhanced with reinforcing fiber are received To attracting attention, with automobile, the housing of aircraft or various components as representative, the utilization in various structure purposes expands.
Fiber-reinforced resin formed products can be to fibre reinforced composites application fiber winding method, compressing method, hand The manufacturing process such as work coating process, pultrusion method, RTM methods are manufactured.
Fibre reinforced composites are made comprising the composition of resin impregnated reinforcing fiber is made as fibre reinforced composites Resin, the generally durability of the stability under normal temperature is needed and solidfied material, intensity aspect are general more using hot Thermosetting resin.
It should be noted that when using thermosetting resin as the resin of fibre reinforced composites, fiber reinforcement is multiple The resin of condensation material needs that reinforcing fiber can be infiltrated in as previously described, therefore is low viscosity to thermosetting resin requirement.
And then, in the case where fiber-reinforced resin formed products are used for structure member, the material electric wire cores such as engine, in order that Fiber-reinforced resin formed products can be tolerated for a long time under excessively harsh use environment, to thermosetting resin requirement gained solidification Thing manifests excellent mechanical strength, heat resistance and moisture-proof thermal characteristics.
As the material that can be used in such purposes, for example, provide following composition epoxy resin：With (a) asphalt mixtures modified by epoxy resin Fat, (b) anionic polymerization initiator, (c) proton donor are inscape, and the compounding amount of (c) is relative to (a) 100 weight portion Be 1~30 weight portion, epoxy resin be liquid and relative to (b) and (c) epoxy resin uniform dissolution (for example, with reference to patent text Offer 1).However, the composition epoxy resin provided in aforementioned patent literature 1 has the viscosity higher than the viscosity of market demands, Difficulty is used as the resin of fibre reinforced composites.
In addition, as low viscous compositions of thermosetting resin, there is provided following drawing forming product epoxy composite Thing, it is characterised in that it is the drawing shaping epoxy resin comprising (a) epoxy resin, (b) acid anhydrides and (c) imdazole derivatives Composition, (a) epoxy resin is the viscosity at 25 DEG C comprising 60~100 weight portions in the weight portion of whole epoxy resin 100 It is the epoxy resin of 2 functional epoxy resins of below 3000mPas, (c) imdazole derivatives have substitution base to be included in 1 Imdazole derivatives imdazole derivatives (for example, with reference to patent document 2).But, the asphalt mixtures modified by epoxy resin provided in aforementioned patent literature 2 Oil/fat composition has that the heat resistance of gained solidfied material is not enough.
I.e., it is difficult to obtain as low viscosity and solidfied material can manifest excellent mechanical strength, heat resistance and moisture-proof thermal characteristics Thermosetting resin.
Prior art literature
Patent document
Patent document 1：International Publication No. 2002/081540
Patent document 2：Japanese Unexamined Patent Publication 2008-38082 publications
The content of the invention
Problems to be solved by the invention
Therefore, the problem to be solved by the present invention is that being provided as low viscosity and gained solidfied material can manifest excellent machinery Intensity, heat resistance, the composition epoxy resin of humidity resistance, the solidfied material with aforementioned properties, fibre reinforced composites, fibre The manufacture method of dimension reinforced resin formed products and fiber-reinforced resin formed products.
The scheme for solving problem
The present inventor etc. have made intensive studies to solve aforementioned problems, as a result find, by using with regulation The composition epoxy resin of epoxy resin, acid anhydrides, the polyol compound of regulation and curing accelerator, can solve the problem that foregoing class Topic, so as to complete the present invention.
That is, the present invention provides composition epoxy resin, its solidfied material and then using reinforcing fiber as the fiber of required composition Enhancing composite, fiber-reinforced resin formed products and its manufacture method, the composition epoxy resin are characterised by having Have：Average functional group number is more than 2.3 epoxy resin (a)；Acid anhydrides (b)；There is more than 2 alcohol hydroxyl groups and hydroxyl in the molecule Base equivalent is the polyol compound (c) of 30g/eq~650g/eq；With curing accelerator (d).
The effect of invention
In accordance with the invention it is possible to be provided as low viscosity and gained solidfied material can manifest excellent mechanical strength, heat resistance, The composition epoxy resin of humidity resistance, the solidfied material with aforementioned properties, fibre reinforced composites, fiber-reinforced resin into The manufacture method of shape product and fiber-reinforced resin formed products.
Specific embodiment
Composition epoxy resin of the invention is composition epoxy resin as described below, as epoxy resin (a), using flat Equal functional group number is more than 2.3 epoxy resin (a-1) or alicyclic epoxy resin (a-2), and the composition epoxy resin is also Have：Acid anhydrides (b)；There are more than 2 alcohol hydroxyl groups in molecule and hydroxyl equivalent is the polyol of 30g/eq~650g/eq Thing (c)；And curing accelerator (d).
Epoxy resin (a)
As aforementioned epoxy resins (a), as long as average functional group number is more than 2.3 epoxy resin (a-1) or alicyclic ring Formula epoxy resin (a-2) is just not particularly limited.As aforementioned epoxy resins (a-1), from from the viewpoint of workability, preferably put down Equal functional group number is more than 2.3 and less than 5 epoxy resin, and particularly preferably average functional group number is the ring of 2.3~4.0 scope Oxygen tree fat.When mixing various epoxy resin, used in the way of its average functional group number becomes more than 2.3 or using various Alicyclic epoxy resin (a-2) is preferred, it is also preferred that being applied in combination aforementioned epoxy resins (a-1) and alicyclic epoxy resin (a-2)。
As the epoxy resin (a-1) that foregoing average functional group number is more than 2.3, for example, can enumerate：Phenolic varnish type Epoxy resin, triphenylmethane type epoxy resin, Dicyclopentadiene-phenol addition reaction-type epoxy resin, phenol aralkyl type Epoxy resin, in the molecular structure epoxy resin, glycidyl amine type epoxy resin etc. with naphthalene skeleton, from for low viscosity and From the viewpoint of the heat resistance of gained solidfied material is further improved, triphenylmethane type epoxy resin, glycidol are preferably used Amine type epoxy resin.
As foregoing phenolic resin varnish type epoxy resin, for example, can enumerate：Phenol novolak type epoxy resin, cresols phenol Novolac type epoxy resin, phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, biphenyl phenolic resin varnish type epoxy resin etc..
As foregoing triphenylmethane type epoxy resin, for example, can enumerate：To phenols and the fragrance with phenolic hydroxyl group The condensation product of race's aldehyde carries out epoxy resin etc. obtained from epoxidation.
As the epoxy resin with naphthalene skeleton in previous molecular structure, for example, can enumerate：Naphthol novolac varnish type Epoxy resin, naphthols aralkyl-type epoxy resin, naphthols-phenol cocondensation phenolic resin varnish type epoxy resin, naphthols-cresols cocondensation Close double (the 2,7- diglycidyl ethers Oxy-1-naphthyl) alkane of phenolic resin varnish type epoxy resin, diglycidyl ether epoxide naphthalene, 1,1- Hydrocarbon etc..
As foregoing glycidyl amine type epoxy resin, it is not particularly limited, from the heat resistance and machinery of gained solidfied material From the viewpoint of intensity is improved, glycidyl amine type epoxy resins more than preferably 3 functions.
As glycidyl amine type epoxy resins more than 3 functions, for example, can enumerate the ring shown in following structural formula (1) Oxygen tree fat.
In formula, Q is-CO- ,-SO2-、-CH2-、-O-、-S-、-CH(CH3)-or-C (CH3)2-。
In these, used as glycidyl amine type epoxy resin, the heat resistance of and gained solidfied material good from workability enters one From the viewpoint of step is improved, workability and gained when fibre reinforced composites, fiber-reinforced resin formed products are manufactured Set out in terms of the heat resistance of solidfied material and the balancing good of mechanical strength, the diamino shown in particularly preferred following structural formula (2) Base diphenyl methane type epoxy resin.
As the commercially available product of such diaminodiphenyl-methane type epoxy resin, for example, can enumerate：SUMI-EPOXY ELM434 (Sumitomo Chemical Co's system), Araldite MY720, Araldite MY721, Araldite MY9512, Araldite MY9612, Araldite MY9634, Araldite MY9663 (above Huntsman Advanced Materials company systems), Epikote 604 (Japanese epoxy resin Co. Ltd. system) etc., can be directly commercially available using these Product.
As foregoing alicyclic epoxy resin (a-2), for example, can enumerate：With in ester ring type structure and 1 molecule have 2 The resin of individual above epoxy radicals, such as 3 ', 4 '-epoxycyclohexyl-methyl -3,4- epoxycyclohexyls formic acid esters, VCH Diepoxide, 6-caprolactone modified -3 ', 4 '-epoxycyclohexyl-methyl -3,4- epoxycyclohexyl formic acid esters etc..In these, from From the viewpoint of the heat resistance of gained solidfied material is further improved, 3 ', 4 '-epoxycyclohexyl-methyl -3,4- epoxies are preferably used Hexahydrobenzoid acid ester.
It should be noted that when aforementioned epoxy resins (a) are made up of a kind of epoxy resin, from the resistance to of workability and solidfied material From the viewpoint of hot, preferably it is made up of the anyone of glycidyl amine type epoxy resin, alicyclic epoxy resin.
In addition, as aforementioned epoxy resins (a), when being made up of various epoxy resin, from the infiltration to reinforcing fiber, The aspect that the heat resistance of workability and gained solidfied material is more excellent is set out, preferably by selected from phenol novolak type epoxy resin, More than at least one in triphenylmethane type epoxy resin epoxy resin and alicyclic epoxy resin are constituted, particularly preferably by Triphenylmethane type epoxy resin and alicyclic epoxy resin are constituted.
Acid anhydrides (b)
As long as the acid anhydrides (b) used in the present invention has anhydride group, can make the change of epoxy resin cure in the molecule Compound (so-called hardener for epoxy resin), is just not particularly limited.As such acid anhydrides (b), for example, can enumerate ring Unsaturated carboxylic acid anhydrides such as shape aliphatic anhydride, aromatic anhydride, maleic anhydride etc..As aforementioned cyclic aliphatic anhydride, can be with Enumerate tetrabydrophthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthaacid acid Acid anhydride, methyl ethano- tetrabydrophthalic anhydride, trialkyl tetrabydrophthalic anhydride, methyl norbornene dioic anhydride etc.. As aforementioned fragrance race acid anhydrides, phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride etc. can be enumerated.As foregoing insatiable hunger And carboxylic acid anhydrides, maleic anhydride etc. can be enumerated.In these, go out in terms of it can obtain the more excellent solidfied material of mechanical properties Hair, preferably uses annular aliphatic acid anhydrides.And then, the infiltration from composition epoxy resin to reinforcing fiber becomes excellent side Face is set out, and in aforementioned cyclic aliphatic anhydride, the viscosity at more preferably 25 DEG C is the compound of below 500mPas.
Polyol compound (c)
As the polyol compound (c) used in the present invention, as long as having more than 2 alcohol hydroxyl groups and hydroxyl in molecule Base equivalent is 30g/eq~650g/eq, is not particularly limited.For such polyol compound (c), for example, conduct Diatomic alcohol compounds, can enumerate ethylene glycol, propane diols, BDO, 1,3-BDO, 1,5-PD, 1,6- oneself two There is aromatic rings or cycloaliphatic ring and 2 compounds of alcohol hydroxyl group etc. in alcohol, 2- butyl -2- ethyls -1,3-PD, molecule, As trihydric alcohols, trimethylolpropane, glycerine etc. can be enumerated, as quaternary alcoholic compound, Ji Wusi can be enumerated Alcohol etc..
In these, become more from the heat resistance, humidity resistance that composition epoxy resin is more low viscosity and gained solidfied material From the viewpoint of excellent, diatomic alcohol compounds are preferably used, wherein, preferably using has aromatic rings or cycloaliphatic ring and 2 in molecule The compound of individual alcohol hydroxyl group.And then, wherein from the more excellent aspect of the mechanical strength of solidfied material, as foregoing polyols Compound (c), preferably using has aromatic rings or cycloaliphatic ring, polyalkylene oxide chain and 2 compounds of alcohol hydroxyl group in molecule.Make It is such compound, for example, can be represented with formula (3).
OH-B-A-B-OH (3)
Wherein, the A in formula (3) represents the divalent linking group containing aromatic rings or cycloaliphatic ring, and B is represented comprising polyalkylene oxide Divalent linking group, OH represents alcohol hydroxyl group.
As the A in aforementioned formula (3), if be as previously described the divalent linker containing aromatic rings or cycloaliphatic ring just It is not particularly limited, from the good aspect of the viewpoint and formability of the heat resistance of gained solidfied material, preferably following structural formula (A-1) divalent linker of~representation shown in (A-7).
Wherein, in structural formula (A-1)~(A-7), * B represent the bonding point with the B in structural formula (3).
And then, as the A in aforementioned formula (3), in the divalent linker shown in aforementioned structural formula (A-1)~(A-7), It is more low viscosity from gained composition epoxy resin and gained solidfied material can manifests the side of mechanical strength higher and heat resistance Face is set out, more preferably the divalent linker shown in aforementioned structural formula (A-4)~(A-7), wherein, particularly preferably (A-4) Shown divalent linker.
As the B in aforementioned formula (3), as long as being as previously described the just no spy of the divalent linker containing polyalkylene oxide Do not limit, from mechanical strength solidfied material aspect higher can be obtained, 2 polyalkylene oxide chains in preferably 1 molecule The average value of number of repeat unit is 1~9 scope, and more preferably average value is 1~3.Foregoing polyalkylene oxide chain have oxirane, The alkylene oxides such as expoxy propane, epoxy butane are used as repeat unit, even if being made up of the repeat unit of same structure, it is also possible to because of weight Multiple unit and it is different, or block polymerization form can also be used.
For the carbon number of the alkylene moiety in the repeat unit of foregoing polyalkylene oxide chain, it is not particularly limited, preferably carbon Number for 2~12, more preferably carbon number be 2~6, further preferred carbon number is 2~4, particularly preferred carbon number is 2~3 oxirane, Expoxy propane.
That is, as the B in aforementioned formula (3), particularly preferably comprising the divalence of the polyalkylene oxide chain shown in (B-1), (B-2) Linking group.
In previously described formula (B-1), (B-2), x, y are number of repeat unit, separately represent more than 1 integer, and its is average Value is preferably 1~9 scope.It should be noted that * A and the * OH in formula (B-1), (B-2) represent respectively with previously described formula (3) The bonding point of A, OH.
Accordingly, as foregoing polyols compound, particularly preferably with knot following structural formula (3-1)~(3-2) Suo Shi The compound of structure.
In structural formula (3-1)~(3-2), x1, x2, y1, y2 are each independently more than 1 integer, its average value be 1~ 9。
As the polyol compound with structure as previously described, for example, can enumerate double (the 4- polyoxyethylene-oxybenzene of 2,2- Base) propane, double (4- polyoxypropylenes-hydroxyphenyl) propane of 2,2- etc..It should be noted that in these, from the resistance to of gained solidfied material From the viewpoint of hot, humidity resistance is more excellent, double (4- polyoxypropylenes-hydroxyphenyl) propane of particularly preferred 2,2-.
The hydroxyl equivalent of the polyol compound (c) for being used in the present invention, from the working life for substantially ensuring that composition Viewpoint and obtain with the fracture toughness of gained solidfied material balance in terms of set out, it is necessary to be the model of 30g/eq~650g/eq Enclose, especially from further manifesting these performance aspects, the preferably scope of 30g/eq~450g/eq.
And then, boiling point under the preferred normal pressure of foregoing polyols compound is more than 100 DEG C, preferably more than 140 DEG C, it is more excellent Elect more than 180 DEG C as.When the boiling point of foregoing polyols compound is too low, when fiber-reinforced resin formed products are manufactured, to mould In tool during process, the epoxy resin composition of injection composition epoxy resin, the gasification of foregoing polyols compound, Sometimes space is produced in gained fiber-reinforced resin formed products.It should be noted that being compounded various foregoing polyols compounds When, preferably it is satisfied by foregoing condition.
Curing accelerator (d)
The curing accelerator (d) used in the present invention is that can improve contained foregoing acid anhydrides in composition epoxy resin etc. The compound of curing activity.As such curing accelerator, as long as promote epoxy radicals and acid anhydrides, the material of the reaction of carboxyl Just it is not particularly limited, for example, can enumerates urea derivative, imdazole derivatives, phosphorus series compound, tertiary amine, organic acid metal Salt, lewis acid, amine complex salt etc..Using the situation of foregoing curing accelerator, do not used with composition epoxy resin solid The situation for changing accelerator is compared, and with low temperature or rapidly carries out curing reaction.For example, can be at 150 DEG C~170 DEG C, with 2 points Clock~10 minute or so obtain solidfied material, and the heat resistance of the solidfied material is also improved sometimes.
Particularly, as curing accelerator (d) usually used in epoxy/acid acid anhydride curing system, imidazoles can be enumerated and is spread out It is biological.Can specifically enumerate：Imidazoles, 2-methylimidazole, 2- ethyls 4-methylimidazole, 2- phenylimidazoles, 2- phenyl -4- methyl miaows Azoles, DMIZ 1,2 dimethylimidazole, 1 benzyl 2 methyl imidazole, 1- cyano ethyls -2-methylimidazole, 1- cyano ethyl -2- phenyl miaows Azoles etc..In addition, in the case of the bin stability for needing height, it is also possible to use imidazolium compounds and phosphorous acid, Asia The mixture of the compound with hydroxyl such as phosphate monoester and diphosphite is potentiality catalyst.
Composition epoxy resin
As long as composition epoxy resin of the invention with foregoing epoxy resin (a), acid anhydrides (b), molecule have 2 with Upper alcohol hydroxyl group and hydroxyl equivalent are the polyol compound (c) and curing accelerator (d) of 30g/eq~650g/eq as must Need composition, be not particularly limited for other compositions, from can balance it is good have following aspect concurrently：Asphalt mixtures modified by epoxy resin Oil/fat composition is low viscosity, becomes good to the infiltration of reinforcing fiber；Curing reaction is carried out rapidly, productivity ratio becomes good, enters And the mechanical strength of gained solidfied material becomes more preferable, by aforementioned epoxy resins (a), foregoing acid anhydrides (b), foregoing polyols compound When the gross mass of () and said curing accelerator (d) is set to 100 mass parts c, preferably with the ratio of 0.1 mass parts~5.0 mass parts Example includes said curing accelerator (d).
And then, it is also more excellent from the heat resistance for low viscosity and gained solidfied material in composition epoxy resin of the invention From the viewpoint of, the gross mass of aforementioned epoxy resins (a), foregoing acid anhydrides (b), said curing accelerator (d) is set to 100 mass During part, foregoing glycols compound (c) are preferably included with the ratio of 1 mass parts~20 mass parts.
And then, in composition epoxy resin of the invention, as aforementioned epoxy resins (a), foregoing acid anhydrides (b), foregoing two Total functional equivalent of the mix ratio of alcoholic compound (c), aforementioned epoxy resins (a) and foregoing glycols compound and foregoing acid anhydrides The ratio between functional equivalent be preferably 1.0/0.7~1.0/1.0.
Other resins
The compound in addition to foregoing required composition can also be contained in composition epoxy resin of the invention.As this The compound of sample, can enumerate sour modified polybutadiene (e-1), polyethersulfone resin (e-2), polycarbonate resin, polyphenylene oxide tree Fat, phenolic resin etc..From from the viewpoint of heat resistance, the mechanical strength that can further improve gained solidfied material, particularly preferably It is applied in combination sour modified polybutadiene (e-1), polyethersulfone resin (e-2).Illustrated below for these compounds.
Sour modified polybutadiene (e-1)
Sour modified polybutadiene (e-1) due to the reactivity with epoxy resin, so being composition epoxy resin The compound included in its cross-linked network during curing reaction.Therefore, if being applied in combination sour modified polybutadiene (e-1), can Gained solidfied material is set to manifest excellent mechanical strength, heat resistance and humidity resistance.
As foregoing sour modified polybutadiene (e-1), can enumerate to have in butadiene skeletal and be derived from 1,3-butadiene, 2- Methyl isophthalic acid, the polybutadiene of 3- butadiene skeletals.As the material from 1,3-butadiene, can enumerate with 1,2- vinyl The material of arbitrary structures, the material with said structure of more than two kinds in the trans type of type, 1,4-, 1,4- cis types.As being derived from 2- methyl isophthalic acids, the material of 3- butadiene, can enumerate with 1,2- vinyl-types, 3,4- vinyl-types, Isosorbide-5-Nitrae-cis type, Isosorbide-5-Nitrae- The material of arbitrary structures, the material with two or more these structure in trans type.
As the sour altered contents of foregoing sour modified polybutadiene (e-1), it is not particularly limited, unsaturated carboxylic can be enumerated Acid.As unsaturated carboxylic acid, preferably acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, from anti- Set out in terms of answering property, preferably itaconic anhydride, maleic anhydride, further preferred maleic anhydride.
For the content of the unsaturated carboxylic acid in foregoing sour modified polybutadiene (e-1), from epoxy resin (a), polynary From the viewpoint of the reactivity of alcoholic compound (c), when sour modified polybutadiene is made up of the unit from 1,3-butadiene, its Acid number is preferably 5mgKOH/g~400mgKOH/g, more preferably 20mgKOH/g~300mgKOH/g, more preferably 50mgKOH/g~200mgKOH/g.
If acid number be more than 5mgKOH/g, it is reactive excellent with epoxy resin etc., the heat resistance of gained solidfied material and Humidity resistance is improved.On the other hand, if acid number is below 400mgKOH/g, reacted by with epoxy resin etc. is appropriate, institute The mechanical strengths such as the elongation characteristics of solidfied material are obtained to improve.
In addition, as long as unsaturated carboxylic acid composition is copolymerized in sour modified polybutadiene, its form is not limited.For example Can enumerate：Random copolymerization, block copolymerization, graft copolymerization (graft modification) etc..
When sour modified polybutadiene is made up of the material from 1,3-butadiene, sour modified polybutadiene (e-1) it is flat Equal molal weight is preferably 1000~8000, more preferably 2000~7000.Sour modified polybutadiene is by from 2- methyl isophthalic acids, 3- When the material of butadiene is constituted, preferably 1000~60000, more preferably 15000~40000.Average molar mass can make Determined with gel permeation chromatography (GPC).
Sour modified polybutadiene (e-1) can carry out unsaturated carboxylic acid-modified and obtain to polybutadiene, it is also possible to directly Use commercially available sour modified polybutadiene.As commercially available sour modified polybutadiene, for example, can use Evonik Degussa The maleic anhydride modified liquid polybutadiene of company system (polyvest MA75, Polyvest EP MA120 etc.), kuraray companies Production of maleic anhydride is modified polyisoprene (LIR-403, LIR-410) etc..
It should be noted that as foregoing sour modified polybutadiene (e-1), elongation, heat resistance from gained solidfied material, The aspect that humidity resistance becomes good is set out, by the epoxy resin (a) in composition epoxy resin, acid anhydrides (b), the modified poly- fourth of acid When the gross mass of diene (e-1) is set to 100 mass parts, preferably included with the ratio of 1 mass parts~40 mass parts, further preferably Foregoing sour modified polybutadiene (e-1) is included with the ratio of 3 mass parts~30 mass parts.
Polyethersulfone resin (e-2)
Polyethersulfone resin (e-2) is thermoplastic resin, in the curing reaction of epoxy resin, polyethers is free of in cross-linked network Sulphone resin (e-2), but by the excellent modifying agent effect with Tg high, gained solidfied material can be made to manifest more excellent machinery Intensity and heat resistance.
It should be noted that as foregoing polyethersulfone resin (e-2), becoming from the mechanical strength and heat resistance of gained solidfied material Good aspect is set out, by the epoxy resin (a) in composition epoxy resin, acid anhydrides (b), polyethersulfone resin (e-2) it is total When quality is set to 100 mass parts, preferably included with the ratio of 1 mass parts~30 mass parts, further preferably with 3 mass parts~20 The ratio of mass parts includes foregoing polyethersulfone resin (e-2).
Polycarbonate resin
As polycarbonate resin, for example, can enumerate：The phenol of binary or two functional-types and the condensation polymer of halo carbonyl or Resin obtained from making the phenol of binary or two functional-types be polymerized by ester-interchange method with carbonic diester.
Herein, for the raw material as polycarbonate resin binary or the phenol of two functional-types, for example, can enumerate：4, Double (4- hydroxy phenyls) ethane of 4 '-dihydroxybiphenyl, double (4- hydroxy phenyls) methane, 1,1-, double (the 4- hydroxy phenyls) third of 2,2- Double (3,5- dimethyl -4- hydroxy phenyls) propane of alkane, 2,2-bis(3-methyl-4-hydroxyphenyl) propane, 2,2-, the double (4- of 1,1- Hydroxy phenyl) hexamethylene, double (4- hydroxy phenyls) ethers, double (4- hydroxy phenyls) thioethers, double (4- hydroxy phenyls) sulfones, double (4- hydroxyls Base phenyl) sulfoxide, double (4- hydroxy phenyls) ketone, hydroquinones, resorcinol, catechols etc..It is preferably double in these dihydric phenols (hydroxy phenyl) alkanes, and then, particularly preferably with double (4- hydroxy phenyls) propane of 2,2- as main material.
On the other hand, as the halo carbonyl or carbonic diester with binary or the phenol reactant of two functional-types, for example can be with Enumerate：Phosgene；The dihalo formates of dihydric phenol, diphenyl carbonate, carboxylol ester, double (chlorphenyl) carbonic esters, The diaryl carbonates such as cresyl carbonate；Dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, dibutyl carbonate, carbonic acid Aliphatic carbonic acid ester compounds such as diamyl ester, carbonic acid dioctyl ester etc..
In addition, foregoing polycarbonates resin is in addition to the molecular structure of its polymer chain is for linear chain structure, in polymer There can also be branched structure on chain.The branched structure can by using 1,1,1- tri- (4- hydroxy phenyls) ethane, α, α ', α "-three (4- hydroxy phenyls) -1,3,5- triisopropylbenzenes, phloroglucin, trimellitic acid, istain double (orthoresols) etc. are used as former Expect composition and import.
Polyphenylene oxide resin
As polyphenylene oxide resin, for example, can enumerate poly- (2,6- dimethyl-Isosorbide-5-Nitrae-phenylene) ether, poly- (2- methyl -6- second Base -1,4- phenylenes) ether, poly- (2,6- diethyl -1,4- phenylenes) ether, poly- (2- ethyl -6- n-propyl -1,4- phenylenes) Ether, poly- (2,6- diη-propyl -1,4- phenylenes) ether, poly- (2- methyl -6- normal-butyl -1,4- phenylenes) ether, it is poly- (2- ethyls - 6- isopropyl -1,4- phenylenes) ether, poly- (2- methyl -6- hydroxyethyl -1,4- phenylenes) ether etc..
Wherein, preferably poly- (2,6- dimethyl-Isosorbide-5-Nitrae-phenylene) ether, or comprising 2- (dialkyl amido first Base) -6- methylphenylenes ether unit, 2- (N- alkyl-N- phenvlaminomethvls) -6- methylphenylene ether units etc. be used as part The polyphenylene oxide of structure.
For foregoing polyphenylene ether resin, can within the scope without prejudice to the object of the present invention use and lead in its resin structure Cross any means such as graft reaction, copolymerization and import carboxyl, epoxy radicals, amino, sulfydryl, silicyl, hydroxyl, dicarboxylic acids anhydride group The modified polyphenylene ether resin of isoreactivity functional group.
Phenolic resin
As phenolic resin, for example, can enumerate：Resol type phenol resin, novolak phenolics etc., phenol virtue Alkyl resin, polyvinylphenol resins, with melamine or benzoguanamine it is modified obtained from triazine modified phenol novolaks Resin etc..
Composition epoxy resin of the invention, can by containing foregoing polycarbonate resin, polyphenylene oxide resin Gained solidfied material is set to manifest more excellent mechanical strength, by the way that gained solidfied material containing foregoing phenolic resin, can be made Manifest more excellent anti-flammability.
Composition epoxy resin of the invention can contain fire retardant/fire-retardant in the scope for not damaging effect of the present invention to be helped Agent, filler, additive, organic solvent.As long as compounding order during manufacture composition epoxy resin can reach effect of the present invention The method of fruit is just not particularly limited.I.e., it is possible to be pre-mixed all the components to use, it is also possible to made with suitable order mixing With.In addition, method of compounding can for example use extruder, heating roller, kneader, roller mixer (roller mixer), class The kneading machines such as Berli banbury carry out mixing manufacture.Hereinafter, it is each for what may be contained in composition epoxy resin of the invention Component is planted to illustrate.
Fire retardant/flame retardant
In order to play anti-flammability, composition epoxy resin of the invention can contain the non-halogen for being substantially free of halogen atom Prime system fire retardant.
As foregoing non-halogen fire retardant, for example, can enumerate：Phosphorus flame retardant, nitrogenated flame retardant, silicon-series five-retardant, Inorganic flame retardant, organic metal salt flame retardant etc., do not have any limitation in their use, can be used alone, Can be using the fire retardant of various same ties, alternatively, it is also possible to be applied in combination the fire retardant of not homology.
As foregoing phosphorus flame retardant, it is also possible to use any one of inorganic system, organic system.As inorganic compound, The ammonium phosphate types such as red phosphorus, MAP, Diammonium phosphate (DAP), triammonium phosphate, ammonium polyphosphate, phosphoamide etc. can for example be enumerated inorganic It is nitrogenous phosphorus compound.
In addition, for foregoing red phosphorus, for the purpose for preventing hydrolysis etc., surface treatment is preferable to carry out, as surface treatment Method, for example, can enumerate：I () uses magnesium hydroxide, aluminium hydroxide, zinc hydroxide, titanium hydroxide, bismuth oxide, bismuth hydroxide, nitre The method that the inorganic compound such as sour bismuth or their mixture carries out covering treatment, (ii) uses magnesium hydroxide, aluminium hydroxide, hydrogen-oxygen Change the method that the mixture of the thermosetting resins such as inorganic compound and phenolic resin such as zinc, titanium hydroxide carries out covering treatment, (iii) with heat such as phenolic resin on the envelope of the inorganic compounds such as magnesium hydroxide, aluminium hydroxide, zinc hydroxide, titanium hydroxide Thermosetting resin carries out method of Double mulch treatment etc..
As foregoing organic phosphorus series compound, for example, can enumerate：Phosphate compound, phosphinic acid compounds, hypophosphorous acid General organic phosphorus series compound such as the nitrogenous phosphorus compound of compound, phosphine oxide compound, carboxy phosphinic acid compound, organic system and 9,10- Miscellaneous -10- phospho hetero phenanthrenes=10- the oxides of dihydro-9-oxy, 10- (2,5- dihydros phenyl) -10H-9- oxa- -10- phospho hetero phenanthrenes= The organic phosphatizations of ring-type such as 10- oxides, 10- (the hydroxy naphthyls of 2,7- bis-) -10H-9- oxa-s -10- phospho hetero phenanthrenes=10- oxides Compound.
In addition, in the case of using foregoing phosphorus flame retardant, hydrotalcite, hydrogen-oxygen can be applied in combination in the phosphorus flame retardant Change magnesium, boron compound, zirconium oxide, black dyes, calcium carbonate, zeolite, zinc molybdate, activated carbon etc..
As foregoing nitrogenated flame retardant, for example, can enumerate triaizine compounds, cyanurate compound, isocyanuric acid chemical combination Thing, phenthazine etc., preferably triaizine compounds, cyanurate compound, isocyanuric acid compound.
As foregoing triaizine compounds, for example, can enumerate：Melamine, methyl guanamines, benzoguanamine, cyanuramide (melon), melem (melem), adipoguanamine, ethylenebis melamine, melamine polyphosphate, three guanamines etc., remove Outside this, for example, can enumerate：The sulfuric acid amino triazine chemical combination such as sulfuric acid guanyl melamine, sulfuric acid melam, sulfuric acid melem Thing, the amino triazine phenol-formaldehyde resin modified and further the amino triazine is modified phenol with tung oil, isomerization Linseed oil etc. Urea formaldehyde be modified obtained from material.
As the concrete example of foregoing cyanurate compound, for example, can enumerate cyanurate, cyanurate melamine etc..
As the compounding amount of foregoing nitrogenated flame retardant, species, composition epoxy resin according to nitrogenated flame retardant other Composition, the degree of desired anti-flammability and suitably select, be for example compounded with epoxy resin, curing agent, non-halogen fire retardant And in the mass parts of composition epoxy resin 100 of all the components such as other fillers, additive, preferably with 0.05 mass parts~10 matter The scope compounding of part is measured, is particularly preferably compounded with the scope of 0.1 mass parts~5 mass parts.
In addition, during using foregoing nitrogenated flame retardant, metal hydroxides, molybdenum compound etc. can be applied in combination.
As foregoing silicon-series five-retardant, as long as the organic compound containing silicon atom is just not particularly limited, for example may be used To enumerate：Silicone oil, silicon rubber, organic siliconresin etc..
As the compounding amount of foregoing silicon-series five-retardant, species, composition epoxy resin according to silicon-series five-retardant other Composition, the degree of desired anti-flammability are suitably selected, for example be compounded with epoxy resin, curing agent, non-halogen fire retardant and In the mass parts of composition epoxy resin 100 of all the components such as other fillers, additive, preferably with 0.05 mass parts~20 mass The scope compounding of part.In addition, during using foregoing silicon-series five-retardant, molybdenum compound, aluminum oxide etc. can be applied in combination.
As aforementioned inorganic flame retardant, for example, can enumerate metal hydroxides, metal oxide, metal carbonate salinization Compound, metal powder, boron compound, low-melting glass etc..
As the concrete example of aforementioned metal hydroxide, for example, can enumerate aluminium hydroxide, magnesium hydroxide, dolomite, water Talcum, calcium hydroxide, barium hydroxide, zirconium hydroxide etc..
As the concrete example of aforementioned metal oxides, for example, can enumerate：Zinc molybdate, molybdenum trioxide, zinc stannate, oxidation Tin, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, oxidation Nickel, cupric oxide, tungsten oxide etc..
As the concrete example of aforementioned metal carbonate compound, for example, can enumerate zinc carbonate, magnesium carbonate, calcium carbonate, carbon Sour barium, basic magnesium carbonate, aluminium carbonate, ferric carbonate, cobalt carbonate, titanium carbonate etc..
As the concrete example of aforementioned metal powder, can for example enumerate aluminium, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, Nie, Copper, Tungsten, tin etc..
As the concrete example of foregoing boron compound, for example, can enumerate Firebrake ZB, zinc metaborate, barium metaborate, boric acid, boron Sand etc..
As the concrete example of foregoing low-melting glass, can for example enumerate CEEPREE (Bokusui Brown Co., Ltd.), hydrated glass SiO2-MgO-H2O、PbO-B2O3System, ZnO-P2O5- MgO systems, P2O5-B2O3- PbO-MgO systems, P-Sn-O- F systems, PbO-V2O5-TeO2System, Al2O3-H2The glassy compounds such as O systems, lead borosilicate system.
As the compounding amount of aforementioned inorganic flame retardant, species, composition epoxy resin according to inorganic flame retardant Other compositions, the degree of desired anti-flammability and suitably select, for example be compounded with epoxy resin, curing agent, non-halogen resistance Fire all the components such as agent and other fillers, additive the mass parts of composition epoxy resin 100 in, preferably with 0.05 mass parts~ The scope compounding of 20 mass parts, is particularly preferably compounded with the scope of 0.5 mass parts~15 mass parts.
As foregoing organic metal salt flame retardant, for example, can enumerate：Ferrocene, acetylacetone metal complex, have Machine metal carbonyl, organic cobalt salt compound, metal organic sulfonate, metallic atom and aromatic compound or jeterocyclic chemistry Compound carries out compound etc. obtained from ionic bonding or coordination bonding.
As the compounding amount of foregoing organic metal salt flame retardant, species, epoxy according to organic metal salt flame retardant The other compositions of resin combination, the degree of desired anti-flammability and suitably select, for example be compounded with epoxy resin, solidification In the mass parts of composition epoxy resin 100 of all the components such as agent, non-halogen fire retardant and other fillers, additive, preferably It is compounded with the scope of 0.005 mass parts~10 mass parts.
Filler
Composition epoxy resin of the invention can contain filler.When composition epoxy resin of the invention contains filler, Gained solidfied material can be made to manifest excellent mechanical property.
As filler, for example, can enumerate：Titanium oxide, bead, glass flake, glass fibre, calcium carbonate, barium carbonate, Calcium sulfate, barium sulfate, potassium titanate, aluminium borate, antifungin, fused silica, crystalline silica, aluminum oxide, silicon nitride, hydrogen The threadiness such as aluminum oxide, gombo hemp fiber, carbon fiber, alumina fibre, quartz fibre intensive, Non-fibrous intensive etc..It Can be used alone one kind, it is also possible to be applied in combination two or more.In addition, they can also be covered by organic matter, inorganic matter etc. Lid.
In addition, using glass fibre as filler when, the rove of long fibre type, chopped fiber type can be selected from and be chopped Precursor, milled fibre etc. are used.When using glass fibre in composition epoxy resin, preferably use and be surface-treated Fiber.By being compounded filler, the intensity of the non-ignitable layer (or carburization zone) generated during burning can be further improved.It is temporary during burning The non-ignitable layer (or carburization zone) of Shi Shengcheng not cracky, the heat insulation capacity that can be played stably, are obtained in that bigger fire-retardant effect Really.And then, it is also possible to assign high rigidity to material.
Additive
Composition epoxy resin of the invention can contain additive.Composition epoxy resin of the invention contains additive When, other characteristics raising such as rigidity, dimensional stability of gained solidfied material.As additive, for example, can add plasticizer, resist The stabilizers such as oxidant, ultra-violet absorber, light stabilizer, antistatic additive, conductivity-imparting agent, stress moderator, releasing agent, Crystallization promoter, hydrolysis inhibitor, lubricant, impact imparting agent, sliding modifying agent, bulking agent, nucleator, reinforcing agent, plus Strong agent, flowing regulator, dyestuff, sensitized material, colouring pigments, rubber polymer, thickener, sagging inhibitor, resist sagging Agent, defoamer, coupling agent, antirust agent, antibacterial mildew inhibitor, anti-fouling agent, electroconductive polymer etc..
Organic solvent
For composition epoxy resin of the invention, the feelings of fiber-reinforced resin formed products are being manufactured using fiber winding method Condition etc., can contain organic solvent.As the organic solvent that can be used herein, methyl ethyl ketone, acetone, diformazan can be enumerated Base formamide, methyl iso-butyl ketone (MIBK), methoxypropanol, cyclohexanone, methyl cellosolve, Ethylene glycol acetate, propylene glycol monomethyl Ether acetic acid ester etc..
The purposes ＞ of ＜ composition epoxy resins
Composition epoxy resin of the invention is low viscosity, and gained solidfied material can manifest excellent mechanical strength, resistance to Hot, humidity resistance, therefore can be used for fibre reinforced composites, fiber-reinforced resin formed products, solidfied material etc..Hereinafter, Manufacture method for them is illustrated.
1. fibre reinforced composites
Before fibre reinforced composites of the invention refer to the solidification after making composition epoxy resin be infiltrated in reinforcing fiber State material.Herein, reinforcing fiber can be any number of of twisted yarn, solution twist yarn or zero twisted yarn etc., multiple from fiber reinforcement Condensation material sets out in terms of having excellent formability, preferably solves twist yarn, zero twisted yarn.And then, the form of reinforcing fiber can make Fiber, the fabric closed up in one direction with machine direction.For fabric, can be from plain weave, satin weave etc. according to using Position, purposes and unrestricted choice.Specifically, from mechanical strength, excellent in te pins of durability aspect, can enumerate carbon fiber, Glass fibre, aramid fibre, boron fibre, alumina fibre, silicon carbide fibre etc., it is also possible to be applied in combination these fibers Two or more.Wherein, good aspect is become from the intensity of formed products, particularly preferred carbon fiber, the carbon fiber can be with Use the various materials such as polyacrylonitrile, asphalt series, artificial silk system.
Method as fibre reinforced composites are obtained by composition epoxy resin of the invention, is not particularly limited, Can for example enumerate：Each composition that composition epoxy resin will be constituted uniformly mixes and prepares varnish, then, reinforcing fiber is existed The unidirectional reinforcing fiber closed up on one direction impregnated in it is foregoing in the method for varnish that obtains (using pultrusion method, fiber State before the solidification of winding method)；Overlap the fabric of reinforcing fiber and be arranged at cavity plate, then with the closed rear injection tree of punch-pin Fat, carries out method (using the state before the solidification of RTM methods) of Pressure Infiltration etc..
For fibre reinforced composites of the invention, aforementioned epoxy resins composition is not necessarily required to infiltration to fibre bundle Inside, the form of the near surface in fiber can be locally lain in for composition epoxy resin.
And then, for fibre reinforced composites of the invention, reinforcing fiber is total relative to fibre reinforced composites The volume containing ratio of volume is preferably 40%~85%, from intensity aspect, more preferably 50%~70% model Enclose.When volume containing ratio is less than 40%, the content of aforementioned epoxy resins composition is excessive, there is following situation：Gained solidfied material Anti-flammability it is not enough or specific modulus and each characteristic required by the excellent fibre reinforced composites of specific strength cannot be met.Separately Outward, when volume containing ratio is more than 85%, reinforcing fiber is reduced with the cementability of resin combination sometimes.
2. fiber-reinforced resin formed products
Fiber-reinforced resin formed products of the invention refer to, the solidfied material with reinforcing fiber and composition epoxy resin Formed products, make fibre reinforced composites heat cure and obtain.As fiber-reinforced resin formed products of the invention, it is specific and Speech, the volume containing ratio of the reinforcing fiber in fiber reinforcement formed products is preferably 40%~85% scope, from the viewpoint of intensity Set out, particularly preferably 50%~70% scope.As such fiber-reinforced resin formed products, for example, can enumerate：Before Subframe, rear subframe, front pillar, center pillar, curb girder (side member), crossbeam (cross member), lower longeron (side sill), The automobile components such as roof side rail, power transmission shaft, the core component of electric wire, the tubing of offshore oil field, printing machine roller tube material, machine Device people fork material, the primary structure material of aircraft, secondary structure material etc..
Method as fiber reinforcement formed products are obtained by composition epoxy resin of the invention, is not particularly limited, excellent Choosing uses drawing forming method (pultrusion method), fiber winding method, RTM methods etc..Drawing forming method (pultrusion method) refer to as Lower method：Fibre reinforced composites are imported in mould, after being heating and curing, drawing is carried out using draw-off gear, thus will Fiber-reinforced resin formed products shape, and fiber winding method refers to following method：While making fibre reinforced composites (including unidirectional Fiber) rotated on aluminium insert, plastic bushing etc. while winding, then makes it be heating and curing, by fiber-reinforced resin formed products Shaping, RTM methods refer to the method using cavity plate and punch-pin both moulds, are to make fibre reinforced composites in foregoing mould The method for being heating and curing and shaping fiber-reinforced resin formed products.It should be noted that in molding large product, complicated shape Fiber-reinforced resin formed products when, preferably use RTM methods.
As the molding condition of fiber-reinforced resin formed products, preferably make fibre reinforced composites at 50 DEG C~250 DEG C Temperature range carry out heat cure, shaping, more preferably the temperature range at 70 DEG C~220 DEG C is formed.Because, it is described When forming temperature is too low, sufficient quick solidification cannot be obtained sometimes, when opposite too high, be sometimes prone to produce is caused by thermal strain Warpage.As other molding conditions, following method etc. can be enumerated：Fibre reinforced composites are made to enter at 50 DEG C~100 DEG C Row precuring, after being made inviscid solidfied material, and then is processed etc., with 2 ranks under 120 DEG C~200 DEG C of temperature conditionss Section solidifies it.
As the other method for obtaining by composition epoxy resin of the invention fiber reinforcement formed products, can enumerate： Fiber aggregate on mould middle berth, laminated multi-layer aforementioned resin, the manual coating process of fiber aggregate；Spray formation method；Make With formpiston/former any one, while varnish is infiltrated in the base material comprising reinforcing fiber and just being stacked and being shaped, cover energy Pressure is enough set to act on the flexible mold of molding, the vacuum bag to carrying out vacuum (decompression) shaping through gas-tight seal molding Method；The resin combination containing reinforcing fiber is made sheet in advance, SMC pressings being molded with dies compress etc..
3. solidfied material
Method as solidfied material is obtained by composition epoxy resin of the invention, as long as according to common epoxy resin group The curing of compound, such as heating temperature condition can be according to the appropriate selections such as species, purposes of curing agent of combination. For example, the method that composition epoxy resin is heated within the temperature range of room temperature~250 DEG C or so can be enumerated.Manufacturing process etc. Can also be using the usual way of composition epoxy resin, especially composition epoxy resin of the invention need not be distinctive Condition.
Embodiment
Then, the present invention is illustrated by embodiment, comparative example, below, as long as no especially record, then " part " and " % " is quality criteria.
Embodiment 1~10 and comparative example 1~2
According to the formula shown in table 1 below~2, epoxy resin, acid anhydrides, polyol compound, curing accelerator, acid are changed Property polybutadiene, polyethersulfone resin are put into kettle, are stirred and are homogenized, and thus obtain embodiment 1~10 and comparative example 1 ~2 composition epoxy resin.It should be noted that polyethersulfone resin is used in advance in acid anhydrides in heating for dissolving 5 at 110 DEG C Material obtained from being cooled down after hour.Then, make it is foregoing in the composition epoxy resin that obtains with as mutually being fitted with assessment item The mode of the thickness answered is flowed into the template by processing, and is shaped 10 minutes in 160 DEG C of conditions, obtains solidfied material.
Epoxy resin, acid anhydrides, polyol compound, curing accelerator and other groups used in embodiment and comparative example The compound that conjunction is used is as described below.
Epoxy resin (a)
·a-1-1：Triphenylmethane type epoxy resin EPICLON EXA-7250 (Dainippon Ink Chemicals's system, average functional group Number 3.5)
·a-2-1：Alicyclic epoxy resin CEL2021P (Daicel Chemical Industries, Ltd. system)
·a-1-2：Glycidyl amine type epoxy resin S-720 (SynasiaInk systems, average functional group number 4)
·a-1-3：Dicyclopentadiene type epoxy resin EPICLON HP-7200 (Dainippon Ink Chemicals's system, average functional group Number 2.3)
·a-1-4：Naphthalene type epoxy resin EPICLON HP-4710 (Dainippon Ink Chemicals's system, average functional group number 5)
Acid anhydrides (b)
·b-1：Tetrahydrochysene methyl nadic anhydride B-570H (Dainippon Ink Chemicals's system)
·b-2：(Hitachi is melted into strain formula meeting to methyl -3,6- endo-methylene group -1,2,3,6- tetrabydrophthalic anhydrides MHAC-P Society's system)
·b-3：3 or 4- methyl-hexahydrophthalic anhydride HN-5500E (Hitachi Chemical Co., Ltd.'s system)
·b-4：Hexahydrophthalic anhydride RIKACID HH (New Japan Chem Co., Ltd)
Polyol compound (c)
·c-1：Double (4- polyoxypropylenes hydroxyphenyl) propane BA-P13U Glycol (the Japanese emulsifying agent Co., Ltd. of 2,2- System, hydroxyl equivalent 468g/eq)
·c-2：Double (4- polyoxyethylene hydroxyphenyl) the propane BA-3U Glycol of 2,2- (Japanese emulsifying agent Co. Ltd. system, Hydroxyl equivalent 179g/eq)
·c-3：Double (4- polyoxyethylene hydroxyphenyl) propane BA-2Glycol (Japanese emulsifying agent Co. Ltd. system, the hydroxyls of 2,2- Base equivalent 165g/eq)
·c-4：Trimethylolpropane TMP (Mitsubishi Gas Chemical Co., Ltd's system, hydroxyl equivalent 45g/eq)
Curing accelerator (d)
·d-1：DMIZ 1,2 dimethylimidazole 1,2DMZ (Shikoku Chem's system)
·d-2：1- methylimidazoles 1MI (synthesis KCC of Japan)
·d-3：Amine system epoxy accelerator Fujicure 7000 (T. ＆ K. Inc. TOKA systems)
Sour modified polybutadiene (e-1)
·e-1-1：Maleic anhydride modified (the Evonik Degussa of liquid polybutadiene POLYVEST EP MA 120 Japan Co., Ltd. system)
·e-1-2：Maleic anhydride modified liquid polybutadiene POLYBESTMA75 (Evonik Degussa Japan Co., Ltd. systems)
Polyethersulfone resin (e-2)
·e-2-1：Polyethersulfone resin SUMIKAEXCEL PES5003PS (Sumitomo Chemical Co's system)
Unmodified polybutadiene：POLYBEST 110 (Evonik Degussa Japan Co., Ltd. system)
Aliphatic epoxy alkane：ADEKA Pluronic F-108 (Asahi Denka Co., Ltd.'s system, hydroxyl equivalent 8000g/eq
The measure ＞ of ＜ viscosity
Using viscosimeter (TOKI SANGYO CO.LTD.VISCOMETER TV-22) determine it is foregoing in the asphalt mixtures modified by epoxy resin that obtains Viscosity of the oil/fat composition at 25 DEG C.
The measure ＞ of ＜ humidity resistances
The solidfied material obtained in will be foregoing cuts out thick 2mm, width 10mm, the size of 80mm long, as test film 1.Connect , test film 1 is put into 24 hours during condition is set as 100 DEG C, 100% damp heat test machine, afterwards, be put into condition setting 24 hours in 180 DEG C of drying machine, aforesaid operations are repeated 5 times.After operation terminates, with the matter of percentage benchmark determination test piece 1 Amount is reduced.
The measure ＞ of ＜ mechanical strengths
According to JIS K6911, the bending strength of determination test piece 1.It should be noted that measure uses Shimano Inc Make made AUTOGRAPH AG-I.
The measure ＞ of ＜ heat resistances
With glass cutter will be foregoing in the solidfied material that obtains cut out thick 2mm, width 5mm, 50mm long, as test film 2.Connect , using determination of viscoelasticity device (SII NanoTechnology Inc. systems " DMS6100 ") determination test piece 2 based on two The dynamic viscoelastic of bending is held, the temperature that tan δ become maximum temperature (glass transition temperature) and the modulus reduction of value is determined (the initial temperature of storage modulus：E’).The results are shown in table 1.It should be noted that the condition determination of Measurement of Dynamic Viscoelasticity It is set to temperature range：Room temperature~260 DEG C, programming rate：3 DEG C/min, frequency：1Hz, strain amplitude：10μm.
[table 1]
[table 2]

Claims (21)

1. a kind of composition epoxy resin, it is characterised in that have：Epoxy resin (a), its be average functional group number for 2.3 with On epoxy resin (a-1) or alicyclic epoxy resin (a-2)；Acid anhydrides (b)；There is more than 2 alcohol hydroxyl groups and hydroxyl in molecule Equivalent is the polyol compound (c) of 30g/eq~650g/eq；And curing accelerator (d).
2. composition epoxy resin according to claim 1, wherein, the epoxy resin (a-1) is average functional group number It is more than 2.3 and less than 5 epoxy resin.
3. composition epoxy resin according to claim 1, wherein, the epoxy resin (a-1) is triphenyl methane type Epoxy resin or glycidyl amine type epoxy resin.
4. composition epoxy resin according to claim 3, wherein, as epoxy resin (a), it is applied in combination triphenyl first Alkane type epoxy resin and alicyclic epoxy resin (a-2).
5. composition epoxy resin according to claim 3, wherein, the glycidyl amine type epoxy resin is with following knots Structure formula (1) expression,
In structural formula (1), Q is-CO- ,-SO2-、-CH2-、-O-、-S-、-CH(CH3)-or-C (CH3)2-。
6. the composition epoxy resin according to any one of Claims 1 to 5, wherein, the polyol compound (c) is At least there is the compound of aromatic rings or cycloaliphatic ring in intramolecular.
7. composition epoxy resin according to claim 6, wherein, the polyol compound (c) be in intramolecular extremely There is the compound of polyalkylene oxide less.
8. composition epoxy resin according to claim 7, wherein, constitute the repetition list of the alkylene oxide of the polyalkylene oxide The average value of first number is 1~9.
9. the composition epoxy resin according to claim 7 or 8, wherein, the polyalkylene oxide is PEO or poly- Expoxy propane.
10. the composition epoxy resin according to any one of claim 1~9, it is also comprising sour modified polybutadiene (e- Or polyethersulfone resin (e-2) 1).
11. composition epoxy resins according to claim 10, wherein, the sour modified polybutadiene (e-1) is Malaysia Anhydride modified polybutadiene.
12. composition epoxy resin according to claim 10 or 11, wherein, by the epoxy resin (a), the acid anhydrides When the gross mass of () and the sour modified polybutadiene (e-1) is set to 100 mass parts b, with the ratio of 1 mass parts~40 mass parts Comprising the sour modified polybutadiene (e-1).
13. composition epoxy resins according to claim 10, wherein, by the epoxy resin (a), the acid anhydrides (b) When gross mass with the polyethersulfone resin (e-2) is set to 100 mass parts, institute is included with the ratio of 1 mass parts~30 mass parts State polyethersulfone resin (e-2).
A kind of 14. solidfied materials, it is to make the epoxy resin composition any one of claim 1~13.
A kind of 15. fibre reinforced composites, it is with the composition epoxy resin any one of claim 1~13 and increasing Strong fiber is used as required composition.
16. fibre reinforced composites according to claim 15, wherein, the volume containing ratio of the reinforcing fiber is In the range of 40%~85%.
A kind of 17. fiber-reinforced resin formed products, it is using the solidfied material and reinforcing fiber of claim 14 as required composition.
18. fiber-reinforced resin formed products according to claim 17, wherein, the volume containing ratio of the reinforcing fiber is In the range of 40%~85%.
The 19. fiber-reinforced resin formed products according to claim 17 or 18, it is the core component of electric wire.
A kind of 20. manufacture methods of fiber-reinforced resin formed products, wherein, answer the fiber reinforcement described in claim 15 or 16 Condensation material heat cure.
A kind of 21. manufacture methods of fiber-reinforced resin formed products, wherein, the fiber reinforcement described in claim 15 or 16 is answered Condensation material carries out drawing forming.
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