Composition of epoxy resin, pre-preg and fibre-reinforced composite material. RU patent 2513626.
 Composition of resin with chain mechanism of hardening and composite material re-enforced with fibres / 2511450Claimed invention relates to composition of resin with chain mechanism of hardening for composite material re-enforced with fibres. Described are versions of composition of resin with chain mechanism of hardening for obtaining composite material re-enforced with fibres, which contains: alicyclic epoxide compound (A), which contains two cyclohexene oxides in a molecule; and modified epoxy resin (B) of bisphenol type A, represented by formula (1) given below, where in modified epoxy resin (B) of bisphenol type A each R1 represents -CH(CH3)-, and R2 represents oxyalkylene group, and content of alicyclic epoxy compound (A) constitutes from 25 to 90 wt %, where total amount of component (A) and component (B) is taken as 100 wt %: [Chemical compound 1] |
| Semiconductor band with improved chemical resistance / 2510649 Invention relates to production of semiconductive materials used for corona shielding of high-voltage windings of electrical machines. The invention suggests semiconductive band containing fibrous substrate with semiconductive compound applied on it including (wt %): chlorosulphonated polyethylene (6.5-12.0), epoxy resin (0.5-3.0), curing agent (0.01-0.2), current-carrying filler (6.0-40.0) and organic solvent (remains). |
| Semiconductor band with improved elasticity / 2510648 Invention relates to production of semiconductive materials used for corona shielding of high-voltage windings of electrical machines. The invention suggests semiconductive band containing fibrous substrate with semiconductive compound applied on its top including current-conductive filler and polymer binding agent made of chlorosulphonated polyethylene mixed up with polyfucntional and multifunctional epoxy resins, anhydride and aerosil. |
 Composite reinforcements / 2509653Invention relates to reinforcements, particularly, to alternate-profile reinforcements for production of articles from concrete and aerated concrete by hot moulding at simultaneous effects of aggressive media. Composite reinforcements comprise bar with winding composed by fibrous filler impregnated with epoxy resin-based polymer binder and hardener. Proposed composition contains the following substances, in wt %: fibrous hardener - 60-80 and binder - 20-40 where binder comprises the following components in wt %: epoxy resin - 50-60, amine hardener - 40-50. Said resin comprises the following components, in wt %: diane epoxy resin - 47-80, modifier based on polyesters including glycidyl groups - 10-25, component produced by epoxidation of hydroxyphenylene oligomer from alkyl resorcinol - 10-28%. |
 Polymer composition / 2507227Invention relates to high-strength polymer compositions intended for making articles from composite materials, applying anticorrosive and decorative coatings with high resistance to weather and ultraviolet radiation. The polymer composition contains an adduct of amines with epoxy resins, an active diluent and a product of reacting di- or polyepoxy compounds with nitrogen-containing components, where the nitrogen-containing component used is a mixture consisting of a compound having in its structure one or more tertiary nitrogen atoms and simultaneously one or more functional groups -NCO, -OH, -CH2OH and a compound containing, along with a tertiary nitrogen atom, a primary or secondary amino group, and the reaction is carried out by mixing at temperature ranging from 40°C to 220°C in 10-150 minutes. |
 Method of producing epoxy resin curing agents / 2507226Invention relates to production of epoxy resin curing agents used to prepare epoxy compositions with improved processing properties and minimal toxicity, which enable to produce composite materials with high strength, thermophysical and dielectric properties. The method of producing epoxy resin curing agents involves reacting a liquid or molten aromatic, aliphatic, cycloaliphatic or alkylene aromatic di- or polyamine (B) with cycloaliphatic or aliphatic-cycloaliphatic dioxides (A) with excess amine, after which acrylate (V) and amino alcohol (G) are added to the obtained mixture and the reaction mixture is stirred for 20-180 minutes at T=30-180°C. |
 Polymer composition / 2506291Present invention relates to production of polymer compositions based on epoxy resins and modified amine curing agents, intended for producing high-strength composite materials with high resistance to thermal deformation. Described is a polymer composition based on epoxy resin, active epoxy diluents and nitrogen-containing curing agents intended for producing high-strength composite materials with high resistance to thermal deformation, characterised by that the curing agent is a product of reaction of an amine component with monocarboxylic acids, using as the amine component a mixture consisting of a primary aromatic amine or a mixture of aromatic amines (A), a secondary aliphatic amino alcohol (B) and a tertiary aliphatic amino alcohol (C) in weight ratio A:B:C from 98:0.2:1.8 to 80:5:15, and a monocarboxylic acid (D) is added in form of a 25-80% solution to the monoatomic aliphatic or aromatic alcohol, or ester thereof with a mono- or dicarboxylic acid, in ratio (A+B+C):D from 90:10 to 60:40 per 100% acid, followed by reaction by mixing in a reactor at temperature ranging from 50 to 130°C for 20 to 120 minutes and mixer speed of 100 to 3000 rpm, and additionally contains a thickener, a pigment or a dye, wherein the composition contains the following in pts.wt: epoxy resin - 100, active epoxy diluent - 5-130, curing agent - 15-110, thickener - 5-50, pigment and dye - 0.5-25. |
 Epoxy binder for reinforced plastic / 2505568Binder contains the following, pts.wt: 70-90 polyglycidyl derivative of low-molecular weight phenol-formaldehyde novolac, 10-30 epoxy-diane resin, 3-6 boron trifluoride and benzylamine complex, 60-80 2,2'-bis-(3,5-di-bromo-4-hydroxyphenyl)-propane, 1-3 bis-[3-(3,5-di-tert-butyl-4-oxyphenyl) propyl]phthalate and 90-160 alcohol-acetone mixture with weight ratio of alcohol to acetone of 1:1. |
| Press material for sealing integrated microcircuits / 2505567 Press material for sealing integrated microcircuits contains binder - o-cresol novolac epoxy resin with softening point of 50-65°C, a curing agent - cyan-acetic ester and diglycidyl ether of 1,4-butanediol, an accelerating atent - N1-(3,4-dichlorophenyl)-N,N-dimethylurea, filler - ground quartz, glycidyloxypropyltrimethoxy silane finishing agent, lubricant - oxidised polyethylene wax. |
| Method of making articles from composite / 2505403 Proposed method comprises preparing binder directly before impregnation of fibrous filler. Epoxy-novolac binder with number-average molecular weight of 300 a.u. and weight fraction of epoxy groups of 8-11 are produced by loading 10-28 wt % of product into reactor, said product being obtained by epoxidation of hydroxyphenyl oligomer from alkyl resorcinol, 47-80 wt % of diane epoxy resin and 10-25 wt % of modifier, and by boiling at 60-250°C for 30-180 minutes. Article is shaped by drawing fibrous filler impregnated with binder and hardener via replacement die and helical winding on reinforcing bundle core. |
| Epoxy binder for reinforced plastic / 2505568 Binder contains the following, pts.wt: 70-90 polyglycidyl derivative of low-molecular weight phenol-formaldehyde novolac, 10-30 epoxy-diane resin, 3-6 boron trifluoride and benzylamine complex, 60-80 2,2'-bis-(3,5-di-bromo-4-hydroxyphenyl)-propane, 1-3 bis-[3-(3,5-di-tert-butyl-4-oxyphenyl) propyl]phthalate and 90-160 alcohol-acetone mixture with weight ratio of alcohol to acetone of 1:1. |
 Epoxy resins and composite materials exhibiting improved combustion properties / 2494126Invention relates to epoxy resin-based composite materials. The epoxy resin-based composition contains: a) 50-70 wt % of a component which is an epoxy resin containing one or more epoxy resins; b) 15-35 wt % of a mixture of thermoplastic materials containing polyetherimide and polyamideimide, where the weight ratio of polyetherimide to polyamideimide ranges from 5:1 to 1:5; and c) 5-25 wt % of a component which is a curing agent, where the epoxy resin composition has sulphur dioxide release level below 100 ppm. Also disclosed is a method of preparing a composition, a component made from an uncured composite, a component made from the composite, where a matrix of the epoxy resin is cured, and a method of producing a prepreg. |
 Perfected prepreg / 2491167Invention relates to perfected prepregs and hardened laminates. Proposed prepreg comprises fiber matrix with multiple areas deposited thereat and lifted by, at least, five micrometers above said matrix. Lifted areas are formed by printing with deposition of materials by hardening by means of the process other than thermal treatment. |
 Improved epoxy systems for composite materials / 2487148Composition contains a system of epoxy resin which includes a reaction product of epoxy resin and a curing agent. The curing agent contains a first compound with an amino group of formula R1R2R3N, where R1 and R2 are independently an aliphatic or cyclic organic functional group and R3 is an alkyl group with 2-18 carbon atoms in the backbone chain; and a second compound with an amino group, with one or more primary or secondary amino groups, with stoichiometric ratio of -NH bonds of the second compound with an amino group to epoxy groups of the epoxy resin component of about 1:20-19:20. |
 Method of making prepreg / 2484956Invention relates to method of making prepreg used in production of multilayer polymer composites for aerospace engineering, car and ship building, etc, wherein heat protection materials with high heat resistance properties. Proposed method comprises placing workpiece into sealed container, evacuation of sealed container with workpiece, reiterated impregnation of workpiece in vacuum with polymer binder with subsequent reiterated drying. Pre-impregnation is performed before evacuation by dipping siliceous or siliceous-kapron workpiece in binder based on phenol-formaldehyde resin with content of solvent making 50-60 wt %. Note here that pre-impregnation and impregnation in vacuum are carried in fractions with total amount equal to design amount of binder while reiterated drying is performed at vacuum at P=0.08-0.1 MPa after every impregnation with exposure at t=25±10°C for 2-2.5 hours while final drying is performed at overpressure P=0.25-0.3 MPa with exposure at t=25±10°C for 12-13 h. |
 Laminar material / 2480339Invention relates to multilayer article. Proposed material comprises: at least, one metal plate and, at least, one composite to adhere to one surface of said metal plate. Composite comprises reinforcing material composed of woven or nonwoven material located on metal plate surface and resin compound for bonding reinforcing material with metal plate on hardening said resin compound. Reinforcing material may represent: nylon fiber, polyester fiber, nylon/polyester multicomponent fiber, nylon/viscose multicomponent rayon, polyester/viscose multicomponent rayon, armamide rayon, carbon fiber, glass finer and metal fiber, or mixes thereof. Resin may represent: epoxy resin, resin modified by butadiene and acrylonitrile copolymer with end carboxyl groups (CTBN/urethane/epoxy polyurethane, acryl and unsaturated polyester, or mixes thereof. |
| Cold curing epoxide composition / 2479601 Epoxide composition can be used as a saturating composition and an adhesive composition and for protective coatings of metal and concrete surfaces. The cold curing epoxide composition contains an epoxide base which includes an epoxy-diane resin having molecular weight of 340-540, an epoxy-urethane resin and a curing system which contains an aromatic amine and an imidazole-type heterocyclic compound. |
 Impregnation with hybrid resins / 2475506Invention relates to a hybrid resin which is particularly suitable for impregnating paper sheets. The hybrid resin contains: (i) melamine urea formaldehyde resin and (ii) unsaturated polyester resin and is used as an adhesive system or an impregnating resin. The invention also relates to use of the hybrid resin to impregnate materials in form of sheets made from fibrous material, to material impregnated with the hybrid resin and to a multilayer board which is coated on one side by a resin-soaked paper layer and on the opposite side by a resin-soaked stabilising layer, wherein the paper layer and/or stabilising layer is impregnated with the hybrid resin. |
| Epoxy binder, prepreg based thereon and article made therefrom / 2471829 Epoxide binder contains the following in pts.wt: epoxy-novolak resin 85-100, nitrogen-containing epoxy resin 85-100, a hardener, which is a product of reaction of 4,4'-diaminodiphenylsulpone and carboxylated nanotubes in weight ratio of 100:(1-10) 85-90, and a product of condensation of glycols with dimethyl terephthalate 5-20. The prepreg contains said epoxy binder and fibre filler - carbon bundles, tape and fabric, with the following ratio of components, wt %: said epoxy binder 30-50, said fibre filler 50-70. |
 Composition and method of producing binder, prepreg and cellular panel / 2460745Binder contains the following (pts.wt): low-molecular epoxydiane resin 10-20, high-molecular epoxy resin 3-6, bis(N,N'-dimethylcarbamide)diphenyl methane 3-5, epoxy-novolac resin 15-25, tetrabromodiane-based epoxy resin 16-24 and solvent - a mixture of aliphatic alcohol and acetone in ratio 1:2 0-50. The binder is obtained by dispersing bis(N,N'-dimethylcarbamide) in a portion of low-molecular epoxydiane resin. The high-molecular epoxy resin is then fused with the remaining portion of the low-molecular epoxydiane resin, the epoxy-novolac resin and the tetrabromodiane-based resin at 130-150°C, and then mixed at 50-70°C with the obtained dispersion with addition the required amount of solvent. Prepregs are obtained from the binder and a fibre filler. The prepreg is used to make lining in a three-layer panel. |
| Composition of resin with chain mechanism of hardening and composite material re-enforced with fibres / 2511450 Claimed invention relates to composition of resin with chain mechanism of hardening for composite material re-enforced with fibres. Described are versions of composition of resin with chain mechanism of hardening for obtaining composite material re-enforced with fibres, which contains: alicyclic epoxide compound (A), which contains two cyclohexene oxides in a molecule; and modified epoxy resin (B) of bisphenol type A, represented by formula (1) given below, where in modified epoxy resin (B) of bisphenol type A each R1 represents -CH(CH3)-, and R2 represents oxyalkylene group, and content of alicyclic epoxy compound (A) constitutes from 25 to 90 wt %, where total amount of component (A) and component (B) is taken as 100 wt %: [Chemical compound 1] |
FIELD: chemistry.
SUBSTANCE: invention relates to epoxy resin compositions and can be applied as matrix resin of fibre-reinforced composite material. Composition contains epoxy resin [A], amine-based hardening agent [B] and block-copolymer [C]. Epoxy resin [A] contains components [Aa] - epoxy resin of biphenyl type, which has biphenyl structure and [Ab]. Component [Ab] contains components [Ab1'] - diglycidyl aniline derivative, [Ab2] - liquid epoxy resin of bisphenol type and [Ab3] - solid epoxy resin of bisphenol type. Component [B] is dicyandiamide. Block-copolymer [C], at least, one block-copolymer, selected from group consisting of S-B-M, B-M and M-B-M. Block M represents block, consisting of polymethyl methacrylate homopolymer, or copolymer, containing, at least, 50 wt % of methyl methacrylate. Block B represents block, which does not mix with block M and has temperature of vitrifying 20°C or lower. Block S represents block, which does not mix with blocks B and M and has temperature of vitrifying higher than temperature of vitrifying of block B.
EFFECT: invention makes it possible to obtain composition of epoxy resin, from which after hardening hardened products with excellent t heat resistance, elasticity modulus and resilience are obtained.
8 cl, 7 tbl, 36 ex
THE TECHNICAL FIELD
The invention relates to compositions of epoxy resin used as a matrix resin fiber-reinforced composite material that is suitable for applications in sports, aerospace applications, and of industrial safety options application.
THE LEVEL OF TECHNOLOGY
In recent years, reinforced fiber composite materials, using a reinforcing fibres such as carbon fiber and aramid fiber, found application as structural materials in the aviation and automotive industries and for such applications in sports, like tennis rackets, Golf clubs and fishing rods, General industrial application forms, etc. due to their high specific strength and high specific modulus. Methods of production of reinforced fiber composite materials include the use of prepreg as an intermediate sheet material, which reinforcing fibres impregnated uncured matrix resin, layering multiple layers of prepreg and then heating for hardening; and the method of injection molding resins with pouring the liquid resin on reinforcing fibers are placed on the form, and then heating the resin to cure.
Of these means of production method using prepreg has the advantage that can be easily obtained fiber reinforced composite materials with high operational characteristics as the orientation of reinforcing fibers can strictly control and since the degree of freedom in designing the configuration of the laminate is high. As a matrix resins used in prepregs, predominantly use termootdelenija resin due to their thermal stability and productivity, and of them appropriately use of epoxy resin with regard to adhesion between resin and reinforcing fibers, dimensional stability and mechanical properties such as strength and stiffness of the obtained composite material.
Up to the present time as a way of increasing shock viscosity epoxy resin, for example, tested ways of mixing with rubber ingredient or thermoplastic resin, which are excellent from the point of view of impact strength, for the formation of structures with divided phase together with epoxy resin. However, these methods have problems such as a decrease in the elasticity modulus or heat resistance, decreased ability to recycle due to increased viscosity and quality deterioration in appearance due to the formation of voids, etc. For example, a method is proposed a significant increase in impact strength by the addition of large quantities of paroxysmal and polyethersulfone to induce phase separation (patent document 1). However, as the mixture of thermoplastic resin has a great impact on the increase of viscosity, the ability to process tends to deteriorate. Especially in the case where the composition of epoxy resin are used for the production of prepregs for the main construction materials of the plane, mix the number of thermoplastic resin should be lowered, in order to exclude negative impact on the ability to process, and there is a tendency inability to make epoxy resin strong enough.
On the contrary, in recent years, you can see ways to improve impact strength and impact resistance due to the use of deblocage or reblockage copolymer for structure formation with divided phase of nanoscale. For example, in patent documents 2-5 proposed ways to improve impact strength through the use of a styrene-butadiene copolymer, a styrene-butadiene-(methacrylic acid) or copolymer of butadiene-(methacrylic acid) in combination with certain epoxy resin. However, the cured resin, obtained by these methods is unsatisfactory from the point of view of heat resistance and elasticity modulus for use in the aviation industry.
To improve impact strength method of updating the components ratio of the composition of epoxy resin and control structure with divided phase block-copolymer, resulting improve impact strength (patent document 6). In addition, the strategy of using epoxy-amine type with a high degree of crosslinking in order to obtain the composition of epoxy resin with high elastic modulus, high heat resistance and high impact strength (patent document 7). These techniques are especially effective for such applications as Golf clubs, where as torsional strength and impact strength. On the other hand, for such applications as the bike frame and the bits that require a higher impact strength, impact strength composite materials tends to be insufficient. Moreover, difficult to use in case of aviation applications requiring high temperature resistance.
Patent document 1: JP 2007-314753A.
Patent document 2: WO 2006/077153.
Patent document 3: JP 2008-527718A.
Patent document 4: JP 2007-154160A.
Patent document 5: JP 2008-007682A.
Patent document 6: WO 2008/001705.
Patent document 7: WO 2008/143044.
DESCRIPTION OF INVENTION
THE GOALS OF THE INVENTION
The present invention consists in the elaboration of the composition of epoxy resin, which can be utverzhdena with the formation of the cured products, which are excellent from the point of view of impact strength, temperature resistance and elasticity modulus, due to the correction of defects of prior art, described above. Another aim is to develop fiber-reinforced composite material, which is excellent from the point of view of impact strength, temperature resistance and characteristics of static strength.
MEANS OF SOLVING PROBLEMS
The present invention has the following scheme for the solution of the above tasks. The composition of epoxy resin, containing as a component epoxy resin [And], hardening agents based on amine [B] and block-copolymer of [C], where epoxy resin [A] contains the following components [Aa] and [Ab], and the block-copolymer [C] is the following block-copolymer:
[Aa] epoxy resin, with at least one of the selected structure of condensed polycyclic structures, bifenilos patterns and oxazolidinones ring structure;
[Ab] epoxy selected from multifunctional epoxy-amine type [Ab1] and liquid epoxy resin befooling type [Ab2];
[C] at least one block-copolymer selected from the group consisting of S-B-B, M-M-M-M;
where the above-mentioned relevant blocks are linked by covalent bond or associated intermediate molecule that is connected with one unit one the covalent bond with another block other covalent bond; M unit is a unit consisting of polimetilmetakrilata of homopolymer, or copolymer, containing at least 50% of the mass. of methyl methacrylate; the block is a block-immiscible block M, and has a glass transition temperature of 20 C or below; and block S is a unit immiscible with blocks b and M, and has a glass transition temperature higher than the glass transition temperature of the unit Century
The preferred option of the present invention is the composition of epoxy resin, where condensed polycyclic structure component mentioned above [AA] represents at least one structure, selected from naphthalene patterns, fluorenone patterns and Dicyclopentadiene patterns, and the [] is diaminodiphenylmethane.
Other preferred option of the present invention is the composition epoxy resin, where the above-mentioned component [AA] is a epoxy resin bifenilos type with biphenylol structure; component [Ab] contains the following components [Ab1'], [Ab2] and [Ab3]; component [] represents a dicyandiamide:
[Ab1'] - derived glycidylazide presented the following General formula (I):
[Chemical formula 1]
where deputies R mean respectively and independently of each hydrogen atom, linear or branched alkyl from 1 to 5 carbon atoms or linear or branched alkoxy-group of 1 to 5 carbon atoms;
[Ab2] liquid epoxy resin befooling type;
[Abs] solid epoxy resin befooling type.
The present invention includes utverzhdennye epoxy resin, obtained by curing the above composition of epoxy resin, prepreg received by impregnation of reinforcing fibers above epoxy composition resin, fiber reinforced composite material obtained curing specified prepreg, and fiber reinforced composite material containing caulk products derived curing the above composition of epoxy resin and reinforcement fiber basis.
THE TECHNICAL RESULT OF THE INVENTION
In accordance with the present invention may be obtained composition of epoxy resin, which can be utverzhdena with the formation of the cured product, excellent from the point of view of impact strength, temperature resistance and elasticity modulus. In addition, if the United cured composition epoxy resins and fibres that can be obtained fiber reinforced composite material, excellent from the point of view of impact strength, temperature resistance and characteristics of static strength.
EMBODIMENTS OF THE INVENTION
In the present invention it is established that the composition of the resin with high toughness, high temperature resistance and high modulus can be obtained by combining epoxy resin in the form of a certain combination of two components [Aa] and [Ab] and the [C], which is described later. Detailed mechanism is not yet clear, but the reason believe that can be obtained structure with finely divided phases due to the influence of the difference between the polarity of the component [A]attributed to a specific ratio of mixture components [Aa] and [Ab], and polarity of the component [], or influence the difference between the value of SP component [A]attributed to a specific ratio of mixture components [Aa] and [Ab], and value SP component [].
In addition, fiber composite material, since the structure with divided phase is small enough degree of dispersion compared to the interval between reinforcing fibers, linearity of reinforcing fibres not broken, and can be obtained high static mechanical strength and high impact strength.
In case the composition of epoxy resin of the present invention is necessary to epoxy resin [A] contains one or more of epoxy resins with at least one of the selected structure of condensed polycyclic patterns, Besfamilny patterns and oxazolidinones ring structure [Aa]. Epoxy resin allow received utverjdenii the resin to be very high impact strength. If one or more of epoxy resins, selected from them, there can be reduced density knitting utverjdenii resin and improved impact strength while maintaining temperature resistance.
In the present description of condensed polycyclic structure refers to cyclic hydrocarbon, in which two or more single rings divide their hand, or to cyclic compound containing heteroatom. Single ring can be a ring containing saturated communication or may also be a ring with unsaturated bond. Unsaturated bond is a relationship selected from double carbon-carbon double bonds carbon-nitrogen and triple carbon-carbon. Specific examples of condensed polycyclic structures are naphthalene, fluorene, Dicyclopentadiene, anthracene, Xanten, pyrene, etc.
Commercially available products epoxy resin with the structure of naphthalene, include "Epiclon" (registered trademark) HP4032, HP4032D, HP4700 and HP4770 (respectively produced Dainippon Ink and Chemicals, Inc.); NC-7000 and NC-7300 (respectively produced by Nippon Kayaku Co., Ltd.); ESN-175 and 360 (respectively produced Tohto Kasei Co., Ltd.) etc.
Commercially available products epoxy resin with the structure of fluorine include "ONCOAT" (registered trademark) EX-1010, EX-1011, EX-1012, EX-1020, EX-1030, EX-1040, EX-1050 and EX-1051 (produced Nagase & Co., Ltd.) and other
Commercially available products epoxy resin Dicyclopentadiene type include "Epiclon" (registered trademark) NR, HP7200L and NRN (respectively produced Dainippon Ink and Chemicals, Inc.); Tactix558 (production Huntsman Advanced Materials), XD-1000-1L and XD-1000-2L (respectively produced by Nippon Kayaku Co., Ltd.); XD-1000-1L and XD-1000-2L (respectively produced by Nippon Kayaku Co., Ltd.) and other
Commercially available products epoxy resin with the structure of anthracene, include "jER" (registered trademark) YX8800 (produced by Japan Epoxy Resins Co., Ltd.) and other
Commercially available products epoxy resin with biphenylol structure, include "jER" (registered trademark) YX4000H, YX4000, YL6616, YL6121H, YL6640 and YL6677 (respectively produced Japan Epoxy Resins Co., Ltd.); NC3000 (produced by Nippon Kayaku Co., Ltd.) and other
Commercially available products epoxy resin with the structure oxazolidinones rings include AER4152 and HAS (respectively produced Asahi Kasei Epoxy Co., Ltd.) etc. In addition, epoxy resin containing structure oxazolidinones rings can also be obtained using the method described, for example, JP 2003-A and others; that is, the reaction of epoxy resin and isocyanate compounds in the presence of a catalyst. As epoxy resins are used as raw material, can be called epoxy befooling And type epoxy resin befooling F-type epoxy Novolac type, as well as epoxy getidletime type, aminoacridine resin, etc. In addition, as isocyanate connection can be called aromatic or aliphatic diisocyanate connection, polyisocyanate connection, etc. In this case polyisocyanate connection is a connection that has three or more isocyanate groups. For the display of high temperature resistance preferably aromatic diisocyanates connection or aromatic polyisocyanate. As the commercially available products aromatic diisocyanates connections can be called diphenylmethanediisocyanate, toluoldiisocyanates (respectively produced Tokyo Chemical Industry Co., Ltd.) and other As a commercial available aromatic polyisocyanate connections can be called "Millionate" (registered trademark) MR-100, MR-200, MR-300 and MR-400 (respectively produced by Nippon Polyurethane Industry Co., Ltd.). The catalyst used for the production of epoxy resin containing structure oxazolidinones rings, no special restrictions, if this catalyst is able to give structure oxazolidinones rings made of epoxy groups and isocyanate groups, but properly you can use Quaternary ammonium salts such as Tetramethylammonium, tetrabutylammonium etc.
In case the composition of epoxy resin of the present invention is necessary to epoxy resin [A] contains epoxy resin selected from multifunctional epoxy-amine type [Ab1] and liquid epoxy resin befooling type [Ab2].
Multifunctional epoxy-amine type [Ab1] refers to the epoxy resin containing molecule at least one or more amino groups of at least two glitzymimimimi groups associated with them. This structure gives sewn structure with a high degree of cross-linking in dry product, and, therefore, can be obtained such properties as high thermal resistance and high modulus of elasticity. If it is mixed with a block copolymer [C]may be higher modulus of elasticity of the cured product while maintaining temperature resistance and toughness.
As a multifunctional epoxy-amine type can be used, for example, tetrachlorodimethylmethane, tropicalrainfall, triglyceridemia, digitalronin, diglycidylether, tetrasotsiologii and products of replacement halogen, products of replacement of the alkyl, products of replacement of the aryl, products aryloxy-substitution products hydrogenation, etc. Of them may be preferable used tetrachlorodimethylmethane, tropicalrainfall, digitalronin and diglycerides, as can be obtained higher modulus of elasticity, the higher the plastic deformation, higher balance on both characteristics and a high impact strength.
As the commercially available products mentioned above tetrachlorodimethylmethane can be used "Sumiepoxy" (registered trademark) ELM434 (produced by Sumitomo Chemical Co., Ltd.), YH434L (produced Tohto Kasei Co., Ltd.), "jER" (registered trademark) 604 (produced by Japan Epoxy Resins Co., Ltd.), "Araldite" (registered trademark) MY720 and MY721 (produced Huntsman Advanced Materials), etc. As the commercially available products of tropicalrainfall or triglycineselenate can be used "Sumiepoxy" (registered trademark) ELM100 and ELM120 (produced by Sumitomo Chemical Co., Ltd.), "Araldite" (registered trademark) MY0510 and MY0600 (produced Huntsman Advanced Materials), "jER" (registered trademark) 630 (produced by Japan Epoxy Resins Co., Ltd.) etc. As the commercially available products digitalronin can be used GAN (produced by Nippon Kayaku Co., Ltd.) etc. as the commercially available products diglycidylethers can be used GOT (produced by Nippon Kayaku Co., Ltd.) etc. As the commercially available products of tetrametilmelamina and products of its hydrogenation can be used "TETRAD-X" (registered trademark) and "TETRAD-WITH" (a registered trademark) (produced by Mitsubishi Gas Chemical Co., Inc.) etc.
In addition, it is preferable that the composition of epoxy resin of the present invention contained liquid epoxy resin befooling type as a component [Ab2], as the impact strength of the cured product and technological properties of the composition of epoxy resin are great.
As a liquid epoxy resin befooling type a preferred epoxy befooling And type and epoxy resin befooling F type. For example, as epoxy befooling And type can be used "jER" (registered trademark) 825, 826, 827, 828, 828EL and HE (respectively produced Japan Epoxy Resins Co., Ltd.); "Epotohto" (registered trademark) YD-127, YD-128, YD-128G and YD-128S (respectively produced Tohto Kasei Co., Ltd.); "Epiclon" (registered trademark) 840, 840-S, 850, 850-S, 850-CRP and 850-LC (respectively produced Dainippon Ink and Chemicals, Inc.); "Sumiepoxy" (registered trademark) ELA128 (produced by Sumitomo Chemical Co., Ltd.); DER331 (produced by Dow Chemical) etc. In addition, as epoxy befooling F type can be used "jER" (registered trademark) 806, 806L and 807 (respectively production Japan Epoxy Resins Co., Ltd.); "Epotohto" (registered trademark) YDF-170 (production Tohto Kasei Co., Ltd.); "Epiclon" (registered trademark) 830, 830-S and 835 (respectively the production of Dainippon Ink and Chemicals, Inc.) etc.
In addition, the composition of epoxy resin of the present invention may be added to or improvements of technological properties by regulating viscosity, increases modulus of elasticity and heat resistance utverjdenii resin. Can be added one epoxy or a lot of epoxy resins in combination. In particular, can also be called a epoxy resin, phenol Novolac type epoxy resin kreselnaja Novolac type epoxy resin resorcinol type epoxy resin penalosaalcalde type epoxy resin triphenylmethanol type epoxy resin tetraphenylmethane type etc. As the commercially available products epoxy resins phenol Novolac type can be called "jER" (registered trademark) 152 and 154 (respectively produced Japan Epoxy Resins Co., Ltd.), "Epiclon" (registered trademark) N-740, N-770 and N-775 (respectively produced Dainippon Ink and Chemicals, Inc.) etc.
As the commercially available products epoxy resin kreselnaja Novolac type can be called "Epiclon" (registered trademark) N-660, N-665, N-670, N-and N 673-695 (respectively produced Dainippon Ink and Chemicals, Inc.); EOCN-1020, EOCN-102S and EOCN-104S (respectively produced by Nippon Kayaku Co., Ltd.) etc.
As the commercially available products epoxy resin triphenylmethanol type can be called "Tactix" 742 (registered trademark), EPPN-501H and EPPN-502H (respectively produced by Nippon Kayaku Co., Ltd.) etc. As epoxy tetraphenylmethane type can be called "jER" (registered trademark) 1031S (produced by Japan Epoxy Resins Co., Ltd.) etc.
Curing agent-based Amin as a component [B] the present invention is a component necessary for curing of epoxy resin. Curing agent-based Amin is a compound that contains molecules nitrogen atom and can respond with epoxy groups with the purpose of curing. As a curing agent, for example, can be called tetramethylguanidine, imidazole, their derivatives carboxylic acid hydrazides, tertiary amines, aromatic amines, aliphatic amines, dicyandiamide, its derivatives etc. As imidazole derivatives, for example, can be called 2-Mei, 1-benzyl-2-Mei, 2-ethyl-4-Mei, etc. as hydrazides of carboxylic acids can be called hydrazide adipic acid hydrazide naftalinovogo acid etc. As tertiary amines can be named N,N-dimethylaniline, N,N-dimethylbenzylamine, 2,4,6-Tris(dimethylaminomethyl)phenol, etc. As aromatic amines can be called 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, m-phenylenediamine, m-xylylenebis, diethyltoluamide etc. As aliphatic amines can be called Diethylenetriamine, Triethylenetetramine, ISOPHORONEDIAMINE, bis(aminomethyl)norbornene, bis(4-iminocyclohexa)methane, dimer of ester acid and polyethylenimine etc. In addition, this includes modified amines, obtained by the reaction of compounds, such as epoxysilane, Acrylonitrile, phenol and formaldehyde, or thiourea, with the amine that has an active hydrogen atom, such as aromatic or aliphatic amine Amin.
In addition, as the curing agent-based Amin [B] preferably also can be used latent hardening agents, as it makes perfect stability of the composition of the resin during storage. Latent hardening agent is a hardening agent that can be active due to a phase change or chemical change, etc. caused by specific stimulation, such as heat or light. As latent curing agent can be mentioned latent curing agent type amine adduct, latent hardening agents microcapsuling type, dicyandiamide, its derivatives etc. Latent curing agent type amine adduct is a product with high the molecular weight and is insoluble at temperature of storage, which is produced by the reaction of the active ingredient, such as the connection with the primary, secondary, or tertiary amine, or any connection from various derivative of imidazole, with connection capable of responding to such connections. Latent hardening agents microcapsuling type is a product obtained from the use of curing agent in the form of cores and application on the kernel shell, such as high-molecular substance, for example, epoxy, polyurethane resin, polystyrene connection or polyimide etc., or cyclodextrin etc. to reduce contact between epoxy resin and curing agent. Dicyandiamide derived get by combining dicyandiamide with any of various compounds, and may be called a product, obtained by reaction with epoxy resin, and the product obtained by the reaction of vinyl connection or acrylic connection, etc.
As the commercially available products latent curing agent type amine adduct can be called "Amicure" (registered trademark) PN-23, PN-H, PN-40, PN-50, PN-F MY-24 and MY-H (respectively produced Ajinomoto Fine-Techno Co., Inc.); "Adeka Hardener" (registered trademark) YONG-3292S, YONG-3615S and YONG-4070S (respectively produced Adeka Corporation), etc. As the commercially available products latent curing agent microcapsuling type can be called "Novacure" (registered trademark) HX-3721 and NC-3722 (respectively produced by Asahi Kasei Chemicals Corporation), etc. As the commercially available products dicyandiamide can be called DICY-7 and DICY-15 (respectively produced Japan Epoxy Resins Co., Ltd.) etc. Can be used any such hardening agents on the basis of Amin, or two or more of them can be used together.
Block-copolymer [C]at least one type selected from the group comprising the S-B-M,-M and-M-M (here and further reductions can also be used as a block-copolymer), in the present invention is an essential component to improve impact strength and impact strength when maintaining excellent heat resistance composition of epoxy resin.
The block is a block-immiscible block M, and has a glass transition temperature T article (hereinafter referred to simply T St ) 20 C or lower.
The glass transition temperature T St block can be measured using DMA using RSAII (production Rheometrics) even when using or composition of epoxy resin, or block-copolymer separately. That is, for measuring with the help of the method DMA to the plate model size 1 x 2,5 x 34 mm exert traction cycle of 1 Hz at temperature from -60 C to 250 C, and uses the value of tan δ as the glass transition temperature T article . In this case, the sample is prepared as follows. When used the composition of epoxy resin, plate cured product without voids are obespylivanie uncured composition of the resin in a vacuum and the subsequent drying in a set of molds with getting thickness of 1 mm using struts, with a thickness of 1 mm and made of "Teflon" (the trademark is registered) at a temperature of 130 C for 2 hours. When using a block-copolymer, plate without voids get similarly, using the double-screw extruder. Any of plates subject to cutting, to get the above dimensions, using a diamond cutter, and then throw the assessment.
Block S is immiscible with blocks b & M and has a glass transition temperature T article is higher than the glass transition temperature of the unit Century
In addition, in the case when the blockcopolymer is a S-B-M, it is preferable to any of the blocks S, B, and M was mixed with epoxy resin, and in case when a block-copolymer is an In-M or-M-M, it is preferable to any block In and M was mixed with epoxy resin, from the point of view of improving toughness.
It is preferable to mix the number of block copolymer [With] ranged from 1 to 10 of mass parts for 100 mass parts based on all of epoxy resin in the composition of epoxy resin from the point of view of mechanical properties and adaptability to the process of production of composite. Preferred interval is 2 to 7 of mass parts and more preferred interval is 3 to 6 mass parts. If you mix the number is less than 1 mass fraction, impact strength and plastic deformation of the cured product fall, and impact strength obtained fiber-reinforced composite material decreases. If you mix the number is more than 10 mass parts, the modulus of the cured product falls significantly, and the characteristics of static strength obtained fiber-reinforced composite material worse. In addition, the flow of resin at a temperature molding is insufficient, and the resulting fiber reinforced composite material has a tendency to formation of voids.
The introduction of a monomer that is different from methacrylate, in the above-mentioned unit M as co monomer can be carried out accordingly with regard Miscibility with epoxy resin and monitoring of the various properties of the cured product. Comonomer has no special restrictions and can be selected accordingly, but to get Miscibility with epoxy resin with high value of the SP, as appropriate, may be used monomer with the SP value is higher than the value of the SP methacrylate, especially water-soluble monomers. First of all, can be used acrylamide derivatives, especially accordingly can be used dimethylacrylamide. In addition, can also be applied reactive monomers.
In this case, the value of SP refers to the conventional solubility parameter, and that parameter is the index of solubility and Miscibility. There is a way to calculate the value of SP of physical properties, such as heat of vaporization, and the method of estimating the value of SP molecular structure. This paper will use the value of the SP, calculated from the molecular structure on the basis of method of Fedora (Fedors' method)described in the publication Polym. Eng. Sci., 14(2), 147-154 (1974), and used the unit is (cal/cm 3 ) 1/2 .
Furthermore, reactive monomer means monomer with functional group, capable to react with aksyanova group epoxy molecules or with functional group curing agent. For example, can be called monomers with reactive functional groups, such as aksyanova group, amino-group or carboxyl group, but reactive monomer is not limited. As a reactive monomers can also be used (meth)acrylic acid (in the present description of methacrylic acid and acrylic acid is usually described in terms of reduced "(meth)acrylic acid) or a monomer that can be hydrolyzed with the formation of (meth)acrylic acid. Preferably can be used reactive monomer, as Miscibility with epoxy resin and adhesion on interphase surface between epoxy and block copolymer can be improved.
As examples of other monomer that can form the block M, can be called getidelement and tert-butylmetacrylate. Preferably, the M-unit contains at least 60% syndiotactic PMMA (emission spectra obtained for pure, (polymethylmethacrylate)).
The glass transition temperature T St unit In equal 20 C or below, preferably 0 C or below, preferably -40 degrees or below. From the point of view of impact strength it is preferable that the glass transition temperature T article was lower, but if T article below -100 C, obtained fiber reinforced material may have problems in terms of their ability to recycle, such as the rough surface of the cut.
It is preferable that the block was In elastomeric block, and preferably monomer, used for the synthesis of such elastomeric unit, represented Dien selected from butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and 2-phenyl-1,3-butadiene. In particular, from the point of view of impact strength preferred choice of polybutadiene, polyisoprene, random copolymers and partially or fully hydrogenated of Polivanov. As polybutadiene can be called 1,2-polybutadiene (T article about 0 degrees Celsius) and others, but more preferably to use, for example, 1,4-polybutadiene with the low glass transition temperature T St (T article : approximately -90 degrees C). The reason is that the use of the unit with a low glass transition temperature T article is preferable from the point of view of impact resistance and toughness. The unit can also be Hidirova. Hydrogenation can be done in the usual way.
As a monomer, a constituent unit, also is preferred (meth)acrylate. As specific examples can be called a acrylate (-24 C), butyl acrylate (-54 C), 2-ethyl hexyl acrylate (-85 C), gidroxiatilkrahmal (-15 C) and 2-ethylhecsylocrylat (-10 C). In this case, enclosed in parentheses is the name of each acrylate refers to T St block, obtained using the corresponding acrylate. Of these (meth)acrylates preferably using butyl acrylate. Such acrylate monomers are mixed with acrylic block M, containing at least 50% of the mass. of methyl methacrylate.
Of them as a unit In the preferred block containing polymer selected from 1,4-polybutadiene, polymethylacrylate and poly(2-ethylhexyl acrylate).
In the case where trilogy copolymer S-B-M is used as a block-copolymer [C]S unit is immiscible with blocks b and M, and the glass transition temperature T St S unit is higher than the glass transition temperature of the unit Century Preferably, T article or melting point S unit was 23 degrees or higher and more preferably was 50 degrees or higher. As examples of block S can be called vinyl aromatic compounds, such as compounds derived from styrene, alpha-methylstyrene or vinyltoluene and compounds derived from Olkiluoto of ester Akilova acid and/or methacrylic acid, containing from 1 to 18 carbon atoms in the alkyl chain. Aromatic vinyl compound derived from Olkiluoto of ester Akilova acid and/or methacrylic acid, containing from 1 to 18 carbon atoms in the alkyl chain, is immiscible with block M, containing at least 50% of the mass. of methyl methacrylate.
When trilogy copolymer M-To-M is used as a block-copolymer [C]two blocks M a three block-copolymer-M-M may be the same or may be different from each other. In addition, the blocks received from a single monomer, but different molecular weight, can also be used.
When triblock copolymer M-To-M and diblock copolymer In-M is used together as a block-copolymer [C]M unit a three block-copolymer-M-M can be the same with the unit M or may differ from unit M diblock copolymer) In addition, the block of triblock M-To-M can be the same with the unit or may be different from the unit In diblock copolymer)
When triblock copolymer S-B-M and diblock copolymer In-M and/or triblock copolymer M-To-M is used together as a block-copolymer [C]M unit a three block-copolymer S-B-M, the appropriate blocks M a three block-copolymer M-To-M and M unit diblock copolymer-M may be the same or may be different from each other, and the corresponding units In the three block-copolymer S-In-M, a three block-copolymer M-To-M and diblock copolymer-M can also be the same or different from each other.
Block-copolymer [S] can be obtained via anionic polymerization, for example, described in the European patent № ER or at the European patent № HER.
As for specific examples of the three block-copolymer S-B-M, as copolymer, containing styrene butadiene methyl methacrylate, can be called Nanostrength 123, Nanostrength 250, Nanostrength 012, Nanostrength E20 and Nanostrength E40, respectively produced Arkema. As for specific examples of the three block-copolymer-M-M, as copolymer, containing methyl methacrylate-butyl acrylate-methacrylate, can be called Nanostrength M22 produced Arkema, and Nanostrength M22N received by copolymerization of monomer with high value SP, the above Nanostrength M22 produced Arkema, as the basis. Of them Nanostrength M22N received by copolymerization of monomer with high value SP may be used preferable, because it can be formed structure with finely divided phases and that can be obtained high impact strength.
As one of the preferred variants of the composition of epoxy resin of the present invention in the case where the curing agent-based Amin component [] represents diaminodiphenylmethane, preferably when condensed polycyclic structure in epoxy [Aa] represents at least one the structure selected from structure of naphthalene, patterns of fluorine and structure of Dicyclopentadiene. First of all, as epoxy resin [AA] epoxy resin with the structure oxazolidinones rings or structure of naphthalene, may be preferred as the ratio between the modulus of elasticity and impact resistance is good.
If diaminodiphenylmethane and epoxy resin with this structure, unite, can be obtained resin with high heat resistance and high modulus of elasticity and excellent from the point of view of impact strength. Mostly preferred epoxy resin with the structure oxazolidinones rings.
In the case where the curing agent-based Amin [In] is diaminodiphenylmethane, preferably when the contents of the component [AA] is from 30 to 80% of the mass. in calculation on 100% of the mass. component [And]. Preferred interval is from 30 to 70% of the mass. and even more preferred interval is 30 to 60% of the mass. If the content is less than 30% of the mass., temperature resistance utverjdenii resin can be increased to a lesser extent, and impact strength fiber-reinforced composite material falls, since the power-polymer [C] is roughly divided phase. If the content is more than 80% of the mass., the viscosity of the composition of epoxy resin becomes too high, and performance in the production of prepreg and formability in forming of prepreg may deteriorate depending on the circumstances.
In the case where amine curing agent [In] is diaminodiphenylmethane, preferably when the contents of the multifunctional epoxy-amine type [Ab1] is from 20 to 70% of the mass. in calculation on 100% of the mass. [A]. Is preferred interval from 25 to 50% of the mass., and even more preferable is the interval from 30 to 50% of the mass. If the content [Ab1] is less than 20% of the mass., the modulus of elasticity of the cured product falls, and characteristics of static strength fiber-reinforced composite material worse. If the content is more than 70% of the mass., plastic deformation is deteriorating, and impact strength of fiber-reinforced composite material is reduced, as the block-copolymer [C] is roughly divided phase.
In the case where the curing agent-based Amin [B] is diaminodiphenylmethane and where liquid epoxy resin befooling type [Ab2] also present, preferably from the point of view of the excellent toughness and technological properties, when there is 10 to 40% of the mass. liquid epoxy resin befooling type [Ab2] per 100% of the component [A]. The preferred interval is the interval from 15 to 35% of the mass., and still the preferred interval is an interval from 20 to 30% of the mass. If the content is less than 10% of the mass., block-copolymer [C] can be roughly divided phase, and impact strength fiber-reinforced composite material can fall depending on the circumstances. If the content is more than 40% of the mass., temperature resistant fiber-reinforced composite material may deteriorate depending on the circumstances.
Average epoxy equivalent component [AA] in the present invention has no special restrictions. However, in the case where the curing agent-based Amin [In] is diaminodiphenylmethane, preferably when epoxy equivalent is in the interval from 300 to 500, since the degree of cross-linking epoxy resin decreases, which gives the composition of the resin, which is excellent from the point of view of impact strength and impact strength. Epoxy equivalent can be determined by using a well-known test titration, but in the case where many epoxy resins with known epoxy equivalents used together, a rough estimate can be made as described below. Consider the case of use together three epoxy resins. For example, if epoxy resin X with epoxy equivalent Ex (g/EQ) are mixed in a number Wx % of the mass., epoxy resin Y with epoxy equivalent Ey (g/EQ) are mixed in a number Wy % of the mass. and epoxy resin Z with epoxy equivalent Ez (g/EQ) are mixed in a number of Wz % of the mass., the average epoxy equivalent can be obtained from the following formula:
Average epoxy equivalent=(Wx+Wy+Wz)/(Wx/Ex+Wy/Ey+Wz/Ez)
In the case where the composition of epoxy resin of the present invention is used especially as the markup for the main structural material of the aircraft, preferably when the cured product obtained by curing at 180 C for 2 hours, has the elastic modulus Flexural a 3.6 GPA or more and the glass transition temperature of 180 degrees or higher. If diaminodiphenylmethane used as curing agent-based Amin [B]high modulus Flexural and high glass transition temperature can be achieved simultaneously, and can be obtained high compressive strength when the through-hole in the conditions of tropical humidity.
The elastic modulus Flexural in the present invention is a value derived in accordance with standard JIS K 7171-1994, through preparation of the sample for testing width of 10 mm and a length of 60 mm from utverjdenii resin, the thickness of 2 mm and bending of the sample in three points with an amplitude of 32 mm The glass transition temperature in the present invention refers to the value obtained as the glass transition temperature T article , which corresponds to the midpoint of the interval vitrification, established by measuring the temperature interval from 30 to 350 C With a heating rate 10 C/min with the use of DSK.
For another preferred option composition of epoxy resin of the present invention, in the case where the dicyandiamide used as a curing agent-based Amin [B]preferably when the component [AA] is a epoxy resin type and bifenilos when the component [Ab] contains the following components [Ab1'], [Ab2] and [Ab3]:
[Ab1'] - derived digitalronin, presents the following General formula (I);
[Ab2] - liquid epoxy resin Besfamilnov type;
[Ab3] - solid epoxy resin befooling type;
[Chemical formula 2]
where Vice-R mean respectively and independently of each group, selected from the hydrogen atom, linear or branched alkyl groups from 1 to 5 carbon atoms and a linear or branched alkoxy groups from 1 to 5 carbon atoms.
In the case where the dicyandiamide used as a curing agent-based Amin [B]epoxy bifenilos type as a component [Aa] gives a high resistance due to the rigidity Besfamilny patterns. On the other hand, uvenilny structure is a highly linear, and in the case when you get cured product, plastic deformation is high, as is formed vysokopilya grid. In addition, when you get cured product epoxy resin bifenilos type is effective for obtaining the patterns with finely divided phases with a block copolymer [With].
As bifenilos patterns epoxy resin bifenilos type can also be used for product substitution of halogen, product substitution by alkyl or product hydrogenation, etc. as Well, especially taking into account technological properties, can be used the product methyl substitution.
Derived digitalronin [Ab1'] has low viscosity and reduces the viscosity of the composition of the resin in General, and, thus, is beautiful from the point of view of capacity for processing. In addition, when you get cured product, benzene rings are in cross stitched structure and, thus, free memory decreases with increase in the elasticity modulus. In addition, when you get cured product derived digitalronin is effective at getting patterns with finely divided phases with a block copolymer [C]. From derivatives digitalronin preferably can be used digitalronin or diglycidylether.
Derived digitalronin can be synthesized by the reaction of the corresponding derivative aniline and epichlorohydrin in the basic conditions and at removal of hydrogen chloride. As a derivative aniline as raw material you can use aniline, toluidine, 4-n-butylaniline, 4-tert-butylaniline, 2,6-diethylaniline, 2,4-dimethoxyaniline etc.
Component [Ab3] has no special restrictions, if he is a solid epoxy resin befooling type, and can be used epoxy befooling And type epoxy resin befooling F-type epoxy resin befooling S type or any of products and their replacement halogen, products of their alkyl substitution or products of their hydrogenation, etc. in Addition, not only monomer, but also the polymer can be used accordingly. From the point of view of impact strength and phase separation with a block copolymer [C] it is preferable to use the polymer.
As the commercially available products solid epoxy resin befooling And type can be called "jER" (registered trademark) 1001, 1002, 1003, 1004, 1004AF, 1005, 1006FS, 1007, 1009 and 1010 (respectively produced Japan Epoxy Resins Co., Ltd.), "Epotohto" (registered trademark) YD-011, YD-012, YD-013, YD-014, YD-017, YD-019 and YD-020G (respectively produced Tohto Kasei Co., Ltd.), "Epiclon" (registered trademark) 860, 1050, 1055, 3050, 4050 and 7050 (respectively produced Dainnippon Ink and Chemicals, Inc.) etc. As bronirovanii epoxy resin befooling And type can be called "jER" (registered trademark) V, V, 5050, T and 5051 (respectively production Japan Epoxy Resins Co., Ltd.), "Epiclon" (registered trademark) 152 and 153 (respectively produced Dainnippon Ink and Chemicals, Inc.) etc.
As the commercially available products solid epoxy resin befooling F type can be called "jER" (registered trademark) 806, 807, R, R, R and R (respectively produced Japan Epoxy Resins Co., Ltd.), "Epotohto" (registered trademark) YDF-2001 and YDF-2004 (respectively produced Tohto Kasei Co., Ltd.) etc.
As epoxy befooling S type can be called resin "Epiclon" (registered trademark) yekha-1514 (produced Dainnippon Ink and Chemicals, Inc.) etc.
In the case where the curing agent-based Amin [B] is dicyandiamide, preferably when the contents of the corresponding components is given below intervals. It is preferable that the component [AA] ranged from 20 to 50% of the mass. in calculation on 100% of the mass. component [] and the preferred interval is the interval from 25 to 40% of the mass. If the contents of the component [AA] is less than 20% of the mass. based on the number of the component [A]the glass transition temperature of the cured product is reduced, and temperature resistant fiber-reinforced composite material falls. If the contents of the component [AA] is more than 50% of the mass., the viscosity of the composition of epoxy resin becomes high, and problems may occur from the point of view of technological properties depending on the circumstances.
Preferably, when digitalronin as a component [Ab1'] is 5 to 20% of the mass. in calculation on 100% of the mass. component [A], and the preferred interval is the interval from 10 to 20% of the mass. If the contents of the component [Ab1'] is less than 5% of the mass. based on the number of the component [] viscosity of the composition of the resin becomes so high that it creates problems from the point of view of technological properties and make the structure with divided phase block-copolymer [C] rough and impact strength fiber-reinforced composite material can be reduced. In addition, if the contents of the component [Ab1'] is more than 20% of the mass., plastic deformation of the cured product is deteriorating, and impact strength of fiber-reinforced composite material can be reduced.
Preferably, liquid epoxy resin befooling type in as a component [Ab2] was present in such quantity, to ensure that the sum of the components [Ab1'] and [Ab2] is from 20 to 40% of the mass. in calculation on 100% of the mass. component [A], and the preferred interval is the interval from 25 to 40% of the mass. If the sum of the components [Ab1'] and [Ab2] is less than 20% of the mass., the viscosity of the composition of the resin becomes high, and problems may occur from the point of view of technological properties depending on the circumstances. If the sum of the components [Ab1'] and [Ab2] is more than 40% of the mass., impact strength of the cured product decreases, and impact strength fiber-reinforced composite material can be reduced. In addition, the structure with divided phase block-copolymer [C] becomes rough and mechanical properties and impact strength of fiber-reinforced composite material can be reduced.
In the case where the dicyandiamide used as a curing agent-based Amin [B]is preferable from the point of view of heat resistance and mechanical properties, when his mix ranges from 1 to 10 of mass parts for 100 mass parts of all epoxy resins in the composition of epoxy resin; and the preferred interval is an interval from 2 to 8 of mass parts. If you mix the number of dicyandiamide is less than 1 mass fraction, the plastic deformation of the cured product is deteriorating, and impact strength of fiber-reinforced composite material is reduced. If you mix the number of dicyandiamide is more than 10 mass parts, block-copolymer [C] forms a rough phase separation, and impact strength of fiber-reinforced composite material can be reduced depending on the circumstances. Preferably with resin mixed dicyandiamide in the form of powder with the stability during storage at room temperature and stability of viscosity in the preparation of pre-preg. In the case where the dicyandiamide in powder form mixed with resin, preferably when the average particle size is 10 microns or less, and is more preferable is 7 microns or less. If the average particle size is more than 10 microns for use as a prepreg, for example, it is possible that when the beams of reinforcing fibres impregnated with the composition of the resin by heat and pressure increase, dicyandiamide may not penetrate into bundles of reinforcing fibres and remain in the surface layers of fibre bundles, depending on the circumstances.
Dicyandiamide can be used separately or can be used in combination with catalyst for dicyandiamide or other hardening agent for epoxy resins. As a catalyst, which is used in combination with dicyandiamide, can be called urea, imidazoles, catalysts on the basis of Lewis acids etc. As a curing agent epoxy resin can be called aromatic amine curing agents, alicyclic amine curing agents, curing agents based on anhydrides, acid etc. As the commercially available products urea can be called DCMU99 (produced Hodogaya Chemical Co., Ltd.), Omicure24, Omicure52 and Omicure94 (respectively produced CVC Specialty Chemicals, Inc.) etc. As the commercially available products of imidazoles can be called 2MZ, 2PZ and 2E4MZ (respectively produced Shikoku Chemicals Corporation), etc. As catalysts on the basis of Lewis acids can be called complexes (boron halide)/base, such as complex (boron TRIFLUORIDE)/piperidine, complex (boron TRIFLUORIDE)/monoethylamine, complex (boron TRIFLUORIDE)/triethanolamine and complex (trichloride boron)/octylamine.
In the case where the dicyandiamide used as amine curing agent [B]preferably, when the average epoxy equivalent of all component epoxy resins [A] is from 200 to 400. The preferred interval is an interval of 200 to 300. If the average epoxy equivalent is less than 200, plastic deformation and fracture toughness utverjdenii resin may decrease. In addition, coarse phase separation block-copolymer [C] may reduce the impact resistance of a fiber-reinforced composite material. If the average epoxy equivalent is more than 400, temperature resistance utverjdenii resin is reduced, and the modulus of elasticity may deteriorate, reducing mechanical strength depending on the circumstances.
In addition, the composition of epoxy resin can contain other components, components than [A]-[C] to the extent that the effect of the present invention has not been lost. For example, to control the viscoelastic properties, improve stickiness and properties of formuemost with preliminary extraction of prepreg or for the increase of mechanical properties such as impact resistance fiber-reinforced composite material, and the solubility of thermoplastic resins epoxy resins can be blended with organic particles, such as rubber particles and particles thermoplastic resins, inorganic particles etc.
It is preferable to mixed thermoplastic resin, having the ability to communicate with hydrogen functional groups, such as alcohol-hydroxyl group, amide bond or sulfonylurea group, as thermoplastic resins, soluble in epoxy resins, as you can expect the effect of strengthening the adhesion between resin and reinforcing fibers. In particular, as thermoplastic resins having alcohol-hydroxyl group, can be called polivinilatsetatnye resins, such as polyvinylformamide and polyvinyl butyral, polyvinyl alcohol and paroxysmal. As thermoplastic resins having amide bond may be called polyamides, polyimides and polyvinylpyrrolidone. As thermoplastic resins containing sulfonylurea group, can be called polysulfones. Polyamides, polyimides and polysulfones can have in the main circuit of functional groups, such as ether linkages and carbonyl group. Polyamides can have group-deputies of nitrogen atoms amide groups. As for commercially available products thermoplastic resins having capable to form a relationship with hydrogen functional groups and soluble in epoxy resins, as polivinilatsetatnyj resins can be called "Denka Butyral and Denka Formal" (registered trademark) (produced Denki Depending Kogyo K.K.), "Vinylek" (registered trademark) (produced Chisso Corporation); as paroxysmal can be called "UCAR" (registered trademark), PKHP (Union Carbide produced); as polyamide resin can be called "Macromelt" (registered trademark) (produced by Henkel Hakusui Corporation), "Amilan" (registered trademark) SM (produced Toray Industries, Inc.); as polyimides can be called "Ultem" (registered trademark) (produced by General Electric) and "Matrimid" (registered trademark) 5218 (produced by Ciba); as can be polysulfones named "Victrex" (registered trademark) (produced Matsui Chemicals, Inc.) and "UDEL" (registered trademark) (produced by Union Carbide); and as polyvinylpyrrolidone can be called "Rubiscol" (registered trademark) (produced by BASF Japan).
In addition to the above-mentioned resins as thermoplastic resins, soluble in epoxy resins can be appropriately used acrylic resin with high Miscibility with epoxy resins and accountability viscoelastic properties. As the available products : acrylic resin can be called "Dianal" (registered trademark) BR series (produced by Mitsubishi Rayon Co., Ltd.) and "Matsumoto microsphere was (registered trademark) M, M100 and M500 (produced Matsumoto Yushi-Seiyaku Co., Ltd.) etc.
As the rubber particles preferably can be used particles cross stitched rubber and rubber particles by type of core-shell, with different polymer, grafted on the surfaces of particles custom made rubber, taking into account technological properties, etc.
As the commercially available products cross stitched rubber particles can be used sewn copolymer (modified carboxyla styrene/Acrylonitrile FX501P (produced by Japan Synthetic Rubber Co., Ltd.), fine particles acrylic rubber CX-MN (produced by Nippon Shokubai Co., Ltd.), series YR-500 (produced Tohto Kasei Co., Ltd.) etc.
As the commercially available products rubber particles by type of core-shell, for example, can be used copolymer of butadiene/altimetrie/Stirol "Paraloid" (registered trademark) EXL-2655 (produced by Kureha Chemical Industry Co., Ltd.), copolymer (ether of acrylic acid)/(methacrylic ester) "Staphyloid" (registered trademark) as-3355 and TR-2122 (produced by Takeda Chemical Industries, Ltd.), copolymer of the butyl acrylate/methacrylate "PARALOID" (registered trademark) EXL-2611 and EXL-3387 (produced by Rohm and Haas), "Kaneace" (registered trademark) MX series (produced Kaneka Corporation), etc.
As the particles of thermoplastic resins preferably can be used polyamide particles and polyimide particles. As the commercially available products of polyamide particles, you can use the SP-500 (produced Toray Industries, Inc.), "Orgasol" (registered trademark) (produced by Arkema) etc.
It is preferable from the point of view of the modulus of elasticity and toughness received utverjdenii resin to mix the number of organic particles, such as rubber particles or particles of thermoplastic resin, ranged from 0.1 to 30 mass parts per 100 mass component parts [A]. The preferred interval is the interval from 1 to 15 large parts.
In addition, especially in the case of prepreg for the main construction materials of the aircraft, preferably, when most of the low viscosity of the composition of epoxy resin of the present invention is from 0.05 to 20 PA·s, and the preferred interval is the interval from 0.1 to 10 PA·S. If the lowest viscosity is less than 0.05 PA·s, the ability to hold the shape of prepreg deteriorates, causing cracking depending on the circumstances, and, in addition, when the molding is a strong flow of resin, making the content reinforcing fibres unstable depending on the circumstances. If the lowest viscosity is more than 20 PA·s, from the composition of epoxy resin at the stage of formation of a film can form a thin places at the stage of saturation of reinforcing fibres can occur covered areas.
Viscosity in this case refers to a complex of viscoelastic module n * obtained using and by simply heating parallel plate with a diameter of 40 mm at a heating rate of 2 C/min, the measurement with frequency 0,5 Hz at 1 mm gap using the device for measurement viscoelastic properties (Rheometer RDA2, production Rheometrics).
In the composition of epoxy resin of the present invention block-copolymer [C] cause phase separation at a stage of hardening education structure with subtly distinct phases. More precisely, forms the structure with separate phases, as the unit of low Miscibility with epoxy resins set of blocks of block-copolymer [C] during curing undergoes a phase separation.
In this case, the degree of dispersion patterns separated phases is determined as follows. In fact, the structure with divided phase can be in the form or co-homogeneous structures or patterns with isolated areas, and related structures definitions are given.
In the case of structures with isolated areas the degree of dispersion patterns separated phases determined by the diameter of the particles in the phase with isolated areas. If the particle phase with isolated areas have the elliptic form, use the main axis of the ellipse, and if the particle phase with isolated areas are formless, use the limiting diameters of the circles. In addition, if each particle phase with isolated areas has the form of two or several concentric circles or ellipses, use the diameter of the most remote from the center of a circle or the main axis of the most remote from the center of the ellipse. Measure the main axis of all particles of a phase with isolated areas existing in selected areas, and srednedushevoe value measured value is used as the degree of dispersion patterns separated phases. Given areas is determined as follows based on the pictures in the microscope. In the case where the degree of dispersion patterns separated phases, as predicted, is of the order of 10 nm (from 10 to less than 100 nm), photography receive at increase of 20,000 times, and random pictures do they choose three square (4 mm) region (three square (200 nm) region on the sample). Similarly, in the case where the degree of dispersion patterns separated phases, as predicted, is about 100 nm (from 100 nm to less than 1000 nm), photography receive at increase in 2000 times, and on pictures randomly select three square (4 mm) region (three square (2 microns) field on the sample). In the case where the degree of dispersion patterns separated phases, as predicted, is about 1 micron (1 micron to less than 10 microns), photography receive at increase in 200 time, and pictures randomly select three square (4 mm) region (three square (20 microns) field on the sample). If the measured degree of dispersion patterns with divided phase is not consistent with the proposed procedure, the relevant area is measured again at increase corresponding to the appropriate order, and use the average value. However, when measured at pictures, particles of 0.1 mm or more is considered as particles of a phase with isolated areas.
In addition, in the case where the structure with divided phase is a co-homogeneous structure, degree of dispersion patterns with divided phase is determined by the wavelength of the concentration fluctuations. The wavelength of the concentration fluctuations is determined as follows. That is a photo in the microscope hold direct line with specified length and determine the points of intersection between each of straight lines and surface phases. Measure the distance between accordingly neighbouring points of intersection and use srednedushevoe value of measured values as the wavelength of the concentration fluctuations. The specified length set as follows on the basis of the pictures in the microscope. In the case where the wavelength of the concentration fluctuations, as predicted, is of the order of 10 nm (10 nm to less than 100 nm), photography receive at increase of 20,000 times, and pictures randomly select three straight lines length 20 mm (three straight lines with a length of 1000 nm for the sample). Similarly, in the case where the wavelength of the concentration fluctuations, as predicted, is about 100 nm (from 100 nm to less than 1000 nm), photography receive at increase in 2000 times, and pictures randomly select three straight lines length 20 mm (three straight lines length of 10 microns on the sample). In the case where the wavelength of the concentration fluctuations, as predicted, is about 1 micron (1 micron to less than 10 microns), photography receive at increase in 200 times, and pictures randomly select three straight lines length 20 mm (three straight lines with the length of 100 mm in the sample). In the case where the measured wavelength of the concentration fluctuations structure does not match the predicted order, again measured straight line corresponding length at increase corresponding to the appropriate order, and use the average value. However, when measured at pictures, wavelengths of the concentration fluctuations of 0,1 mm or more is considered the wavelengths of the concentration fluctuations with homogeneous structure.
As the pictures in the microscope can be photographed cross section utverjdenii resin using a scanning electron microscope or a transmission electron microscope. In accordance with the requirements for contrasting you can use the OS or other The contrast can be performed in the usual ways.
Preferably, the degree of dispersion patterns with divided phase was in the interval from 10 to 1,000 nm. The preferred interval is the interval from 10 to 200 nm. Especially in the case where the component [B] is dicyandiamide, preferably when the degree of dispersion patterns with divided phase is 50 nm or less. If the degree of dispersion patterns with divided phase is less than 10 nm, the cured product can be considered as being virtually uniform, and the effect of an increase in impact strength at the expense variance block-copolymer [C] not evident. In addition, if the degree of dispersion patterns with divided phase is over 1,000 nm, showing a rough phase separation, plastic deformation and fracture toughness of the cured product decreases, and impact strength fiber-reinforced composite material may decrease depending on the circumstances.
The effect of increasing the impact strength at the expense variance block-copolymer [C] appears when the cracks, reaching the dispersed phase, since (i) the concentrated load on the dispersed phase, causing cavitation, (ii) resin due to cavitation strain of the shift, (iii) the dispersed phase in itself deformed, absorbing energy, and (iv) distribution of cracks slowed down due to the dispersed phase. From above in paragraphs (i) and (ii) make the greatest contribution. In the case of a disperse phase, to cause cavitation, it is necessary that the degree of dispersion of the dispersed phase was less than the diameters of the spheres of plastic deformation on the thin ends of the cracks.
As reinforcing fibres used in the present invention may be called fiberglass, carbon fiber, carbon fiber, aramid fibres, boron fibers, alumina fiber, kremniyorganika fiber etc. Two or more types of reinforcing fibers can also be used in the mixture. To get the moldings, lighter in weight and more durable, it is preferable to use carbon fiber or graphite fiber.
All types of carbon fibers and carbon-fiber can be used for matching variants of application; but are preferred carbon fiber with modulus tensile from 150 to 900 HPa (measured in a tensile test strands in accordance with the method described in standard JIS R 7601), as can be obtained composite material, excellent from the point of view of impact resistance and high stiffness and mechanical strength. If you use such fibres, the effect of the present invention is most significant.
The wet method is a way of dissolution of the composition of epoxy resin in a solvent such as methyl ethyl ketone or methanol to reduce the viscosity, the immersion of reinforcing fibres in the solution composition of epoxy resin, then rough-and evaporation of solvent the use of furnaces, etc. How hot melt (dry method) is a method of impregnation of reinforcing fibers directly composition of epoxy resin, the viscosity is reduced by heat; or method, including a one-time application for packing paper or similar material composition of epoxy resin with the receipt of the film, the imposition of the above-mentioned film on both sides or one side of reinforcing fibres, heating and pressure increase for impregnation of reinforcing fibres composition of epoxy resin. How hot melt is the preferred method the present invention, as in the prepreg essentially not leave any solvent.
Fiber reinforced composite material of the present invention may be made by way of blending layers obtained prepreg and applying pressure to the laminate with heating and curing matrix resin, etc. In this case, as a way of supplying heat and pressure can be used a method of pressing, the way autoclave processing, method of forming the frame shape, the way we wrap tape and method of forming the internal pressure etc.
The way autoclave processing is a way of an overlay of prepreg on the instrumental plate with a given form, covering frame film and increase pressure and heat for curing at the outgassing of laminate. Can be obtained molded products with excellent mechanical properties and good quality appearance for the reasons that the orientation of fibers can accurately control and that voids formed a little.
How to wrap the ribbon is a way of winding around prepreg rod, such as the core, for example, for the formation of tubular element made from fiber-reinforced composite material, and this method is acceptable for the receipt of rod items such as Golf clubs and fishing rods. More specifically, this method of obtaining tubular element by winding a prepreg around the rod, and winding thermoplastic film as being wrapped tape around the external surface of prepreg for fixing, the pressure of prepreg, heating and curing of the resin in the furnace, and pull rod.
Furthermore, the method of moulding through internal pressure is a way of forming, including: installation into the mold blanks with prepreg wrapped around who are doing the internal pressure parts, such as a tube made of thermoplastic resins; introduction of high pressure gas in applied internal pressure item for applying pressure; and at the same time the heating of the mold. This method is preferred and can be used for forming tubular elements, such as frames, Golf clubs and bits, and, in addition, to form complex shapes, such as tennis rackets, badminton etc.
Fiber reinforced composite material of this the invention may also be obtained by the method including impregnation of reinforcing fibers directly composition epoxy resin without the use of prepreg; and then heating and drying; for example, by way of forming, such as the method of installation manually, the method of winding single thread, the way get uniaxially oriented fibers, fashion injection molding resins or the method of injection molding resins, etc. In these ways, it is preferable to prepare the composition of epoxy resin by mixing the two components, that is the main component containing epoxy resin and curing epoxy resin agent immediately before use.
Fiber reinforced composite material, which is used composition of epoxy resin of the present invention as a matrix resin can be appropriately used in sports options for use in the aviation industry and in variants General industrial use. More specifically, composite material can be used for aerospace applications, including use as a primary aviation construction material for the main wings, tail nodes, bottom floors etc.; as secondary structural material for flaps, ailerons, fairings, fairings, windshield, materials, interior decoration and so on; and in the case of the rocket engine and the underlying details of artificial satellites, etc. of such variants aerospace applications fiber reinforced composite material can be especially appropriate as the primary aviation construction material requiring impact strength and tensile strength at low temperatures as high altitude flights are accompanied by the influence of low temperatures, especially as the surface layers of the fuselage and surface layers of the main wings. In addition, in the case of sports applications such material is especially suitable for bicycles, Golf clubs, bits, fishing rods, tennis, badminton, squash, etc., Golf clubs, hockey, etc., ski sticks, etc. in Addition, in the case of General application such the material can be appropriately used as structural materials of moving objects, such as cars, ships and rolling stock, bearing shaft, leaf spring, the blades of the windmill, autoclaves, flywheels, paper rolls, engineering and architectural materials for construction, such as roofing materials, cable, bars and repair reinforcing materials, etc.
EXAMPLES
The composition of epoxy resin of the present invention is discussed in more detail below, with reference to examples. Below resins are used as raw materials for producing songs resins relevant working examples.
[AA] Epoxy resin
- Epoxy, having a structure oxazolidinones rings, HAS (production of Asahi Kasei Epoxy Co., Ltd.)
- Epoxy, having a structure oxazolidinones rings, AER4152 (production of Asahi Kasei Epoxy Co., Ltd.)
- Epoxy resin naphthalene type "Epiclon" (registered trademark) HP4032D (production Dainippon Ink and Chemicals, Inc.)
- Epoxy resin naphthalene type "Epiclon" (registered trademark) NR (production Dainippon Ink and Chemicals, Inc.)
- Epoxy resin naphthalene type "Epiclon" (registered trademark) NR (production Dainippon Ink and Chemicals, Inc.)
- Epoxy resin naphthalene type NC7300 (produced by Nippon Kayaku Co., Ltd.)
- Epoxy resin Dicyclopentadiene type "Epiclon" (registered trademark) NR (production Dainippon Ink and Chemicals, Inc.)
- Epoxy resin bifenilos type "jER" (registered trademark) YX4000H, YX4000 (produced by Japan Epoxy Resins Co., Ltd.)
- Epoxy resin fluorenone type "ONCOAT" (registered trademark) EX-1010 (production Nagase & Co., Ltd.)
[Ab1] Multifunctional epoxy-amine type
- Tetrachlorodimethylmethane, ELM434 (produced by Sumitomo Chemical Co., Ltd.)
- Tropicalrainfall, "Araldite" MY0500 (production Huntsman Advanced Materials)
- Tropicalrainfall, "Sumiepoxy" (registered trademark) ELM120 (produced by Sumitomo Chemical Co., Ltd.)
- Digitalronin, Diglycidylaniline (GAN) (produced by Nippon Kayaku Co., Ltd.)
- Diglycidylether, Diglycidyltoluidine (GOT) (produced by Nippon Kayaku Co., Ltd.)
[Ab2] Liquid epoxy resin befooling type
- Epoxy resin befooling And type "Epotohto" YD128 (production Tohto Kasei Co., Ltd.)
- Epoxy resin befooling F-type "Epiclon" (registered trademark) 830 (production Dainippon Ink and Chemicals, Inc.)
- Epoxy resin befooling And type "jER" (registered trademark) 828 (produced by Japan Epoxy Resins Co., Ltd.)
[Ab3] Solid epoxy resin befooling type
- Epoxy resin befooling And type "jER" (registered trademark) 1004AF (produced by Japan Epoxy Resins Co., Ltd.)
- Epoxy resin befooling And type "jER" (registered trademark) 1007 (produced by Japan Epoxy Resins Co., Ltd.)
- Epoxy resin befooling F-type "Epotohto" YDF2001 (production Tohto Kasei Co., Ltd.)
- Epoxy resin befooling F-type "jER" (registered trademark) 4004P (produced by Japan Epoxy Resins Co., Ltd.)
[Other epoxy]
- Epoxy Novolac type "jER" (registered trademark) 152 (produced by Japan Epoxy Resins Co., Ltd.)
- Epoxy resin triphenylmethanol type, EPPN-501H (produced by Nippon Kayaku Co., Ltd.)
[B] Curing agents for epoxy resins
- 4,4'-DDS (4,4'-diaminodiphenylmethane, hardening agents, production Sumitomo Chemical Co., Ltd.)
- 3,3'-DDS (3,3'-diaminodiphenylmethane, hardening agents, production Wakayama Seika Kogyo Co., Ltd.)
- Dicyandiamide (hardening agents, DICY7, production Japan Epoxy Resins Co., Ltd.)
[C] of Block copolymers
In the case where digitalronin or diglycidylether not used as a component [Ab1]specified number of ingredients, other than curing agent and accelerator of hardening add in kneading machine, and a mix heat up up to 160 C at hashing and stirred at 160 C for 1 hour with obtaining transparent viscous liquid. When mixing the liquid is cooled to 80 C and then add the specified number of curing agent and accelerator of hardening, and the mixture is additionally mix with obtaining the composition of epoxy resin. In addition, in the case where digitalronin or diglycidylether use as a component [Ab1]specified number of ingredients, other than digitalronin, curing agent and accelerator of hardening add in kneading machine, and a mix heat up up to 160 C at hashing and stirred at 160 C for 1 hour with obtaining transparent viscous liquid. Liquid at hashing is cooled to 80 C and adds the specified number digitalronin, curing agent and accelerator of hardening, the mixture is additionally mix with obtaining the composition of epoxy resin.
(2) Measurement of the viscosity of the composition of epoxy resin (working examples 25-36 and reference working examples 8-13)
The viscosity of the composition of epoxy resin determined by using and simply heating the parallel plate with a diameter of 40 mm at a heating rate of 2 C/min and measurement at a frequency of 0.5 Hz and with a gap of 1 mm using a device for measuring dynamic viscoelastic properties (ARES, the production of THE Instruments).
(3) the Modulus of elasticity at bending and deformation in bending utverjdenii resin
The composition of epoxy resin, obtained in paragraph (1), obespechivajut in vacuum and inject into the complete set of moulds, to to receive a thickness of 2 mm, using struts 2 mm thick "Teflon" (registered trademark). In the case where diaminodiphenylmethane used as a curing agent epoxy resin curing is carried out at a temperature of 180 C for 2 hours, and in the case where the curing agent epoxy use dicyandiamide, curing is carried out at a temperature of 130 C for 2 hours, get utverzhdennye resin with a thickness of 2 mm From the received plate utverjdenii resin cut out a test of a width of 10 mm and a length of 60 mm and conduct measurements by bending at three points with an amplitude of 32 mm in accordance with JIS K 7171-1994, get modulus of elasticity at bending and deformation in bending.
(4) thermal stability utverjdenii resin
From plate utverjdenii resin, obtained in the above section (3), select 7 mg utverjdenii resin and conduct measurements at a heating rate 10 C/min in the temperature interval from 30 to 350 degrees With using the device DSC2910 (type) (production TA Instruments); and the average temperature point, obtained on the basis of standard JIS K 7121-1987, used as the glass transition temperature T article for evaluation temperature resistance.
(5) Measurement of impact strength (1C ) utverjdenii resin
Uncured composition epoxy resin obespechivajut in vacuum and utverjdayut in the complete set of moulds, to get a 6 mm thick, with girth 6 mm "Teflon" (registered trademark) at the temperature 180 C for 2 hours when diaminodiphenylmethane used as epoxy curing agent, or at a temperature of 130 C for 2 hours when dicyandiamide used as epoxy curing agent, unless other conditions, receive utverzhdennye resin thickness of 6 mm Utverzhdennye resin cut to the size of 12.7 x 150 mm, get a sample for testing. Universal tensile machine Instron (production Instron) used for treatment and sample tests according to ASTM D5045 (1999). Initial preliminary crack introduce sample by inserting a razor blade, cooled to the temperature of liquid nitrogen, to a sample for testing and giving impetus to the razor with a hammer. Impact strength utverjdenii resin called strength at the critical load in warp mode 1 (open type).
(6) measure the degree of dispersion patterns with divided phase
Utverzhdennye resin, obtained above in section (5), contrast and get out of her thin slice. Using a transmission electron microscope (TEM) get the image in the EMP under the following conditions. As a contrast agent is used selectively OsO 4 RUO Li and 4 in response to the reaction of the composition of the resin to get enough contrast in morphology.
- The device: Transmission electron microscope H-7100 (production of Hitachi, Ltd.)
- Accelerating voltage: 100 sq
- Magnification: 10000-fold.
The image is used to monitor the wavelengths of the concentration fluctuations enriched component [And] phase and enriched component [C] phase. Structure with divided phase of the cured product is a co-uniform structure or structure with isolated areas depending on the type and ratio of components [A] and [C]. Relevant organizations estimate the following way.
In the case of homogeneous structures on pictures taken with the microscope, conduct direct line to the specified length and determine the points of intersection between each of straight lines and surface phases. Measure the distance between accordingly neighbouring points of intersection and use srednedushevoe the value of all measured distances as the wavelength of the concentration fluctuations. The specified length set, as described below, based on pictures taken with the microscope. When the wavelength of the concentration fluctuations, as predicted, is of the order of 0.01 microns (from 0.01 microns to less than 0.1 micron), photography receive at increase of 20,000 times, and pictures randomly select three straight lines length 20 mm (three of a segment of length 1 micron on the sample). Similarly, when the wavelength of the concentration fluctuations, as predicted, is of the order of 0.1 microns (from 0,1 microns up to less than 1 microns), photography receive at increase in 2000 times, and pictures randomly select three straight lines length 20 mm (three straight lines length of 10 microns the sample). When the wavelength of the concentration fluctuations, as predicted, is about 1 micron (1 micron to less than 10 microns), photography receive at increase in 200 times, and pictures randomly select three straight lines length 20 mm (three straight lines with the length of 100 mm in the sample). In the case where the measured wavelength concentration fluctuations does not match the intended order, again measured straight line corresponding length with the increase, the corresponding acceptable order, and use the average value.
In addition, in the case of structures with isolated areas measure the main axis of all particles of a phase with isolated areas existing in selected areas, and their srednedushevoe is used as the diameter of phase with isolated areas. In the case where the diameter of phase with isolated areas, as predicted, is less than 100 nm from the received image, photo, get with increasing 20,000 times, and pictures randomly select three square (4 mm) region (three square (1 micrometer) region on the sample). Similarly, in the case where the diameter of phase with isolated areas, as predicted, is of the order of 0.1 microns (from 0,1 microns up to less than 1 microns), photography receive at increase in 2000 times, and pictures randomly select three square (20 mm) region (three square (10 micron) region the sample). In the case where the diameter of phase with isolated areas, as predicted, is about 1 micron (1 micron to less than 10 microns), photography receive at increase in 200 times, and pictures randomly select three square (20 mm) region (three square (100 microns) field on the sample). In when the diameter of phase with isolated areas does not match predictable order, the relevant area is again measured at increase corresponding to acceptable order, and use the average value.
(7) compressive Strength after impact and compression strength when the through-hole in conditions of tropical humidity fiber-reinforced composite material
In working examples 1-24 and reference working examples 1-7 tests carried out in accordance with the following methods.
[Preparation prepara]
1. The composition of epoxy resin made above in section (1), put on paper cushioning using a knife devices for coating, get film resins. Then two such films resin impose on both sides of the carbon fiber "Torayca" (registered trademark) T800G-24K-31E (24000 fibres tensile strength tensile 5,9 HPa, the modulus tensile 290 HPa, elongation tensile 2,0%, production of Toray Industries, Inc.), posted like a painting in one direction; laminate heat up and exposed to increased pressure for impregnation of carbon fiber resin. Get a unidirectional prepreg with the mass of carbon fiber per unit area of 190 g/m 2 and with the mass content of matrix resin 35,5% of the mass.
[Preparation of fiber-reinforced composite material and compressive strength after a hit]
Twenty-four layer unidirectional prepreg, prepared in accordance with the method above, laminate in the configuration(+45°/0°/-45°/90°)×3 pseudoisochron, and molded in an autoclave at a heating rate of 1,5 OC/min at a pressure of 0.59 MPa and at the temperature of 180 C during 2 hours, get laminate. From laminate cut out the pattern length 150 mm and a width of 100 mm, and in accordance with the standard JIS K 7089-1996 put kick the falling mass of 6.7 j/mm to the Central part of the sample, get compressive strength after impact.
[Preparation of fiber-reinforced composite material and strength compression through the hole in the conditions of tropical humidity]
The composition of epoxy resin, obtained above in section (1), put on paper cushioning using a knife devices for coating, get film resins. Then two such films resin impose on both sides of the carbon fiber "Torayca" (registered trademark) T700SC-24K (24000 fibers, the modulus tensile 230 HPa, tensile strength tensile 500 kgs/mm 2 , the production of Toray Industries, Inc.), posted like a painting in one direction; laminate heat up and exposed to high pressure for impregnation of carbon fiber resin. Receive containing fibers of KZT700-SC unidirectional prepreg with the mass of carbon fiber per unit area 155 g/m 2 and with the mass content of matrix resin 72% of the mass.
In addition, prepare containing fibers M40SC unidirectional mass prepreg carbon fiber per unit area of 125 g/m 2 and with the mass content of matrix resin 75% of the mass. by the same method, except that as of reinforcing fibers use carbon fiber "Torayca" (registered trademark) M40SC-12K (production Toray Industries, Inc., the modulus tensile 380 HPa, tensile strength tensile 4900 MPa).
[Tubular elements made of composite material for the drop test in Sharpie]
Tubular elements made of composite material, with an inner diameter of 6.3 mm, prepared by overlying layers containing fibers of KZT700-SC, unidirectional prepreg so that the grain direction in each of the three layers could make 45 degree or 45C relative to the direction of the cylinder axis; and then by overlaying three layers containing fibers of KZT700-SC unidirectional prepreg so that the direction of fibres could be parallel to the direction of the cylinder axis in accordance with the following stages (a)-(e). As a core use a round rod of stainless steel with a diameter of 6.3 mm and a length of 1000 mm
(a) containing fibers of KZT700-SC unidirectional prepreg received in accordance with the method above, cut out two rectangular cloth with a length of 72 mm and a width of 650 mm (so that axial fiber could make 45 degrees to the direction of the long side). Two layers of prepreg stack so that the direction of fibres of two layers of prepreg could cross each other and to the layers of prepreg could be biased toward the short side at a distance of 10 mm (corresponding to half the circumference of the core).
(b) Core turn, to ensure that the long side of the rectangular layers of prepreg laid to processed with the possibility of freeing the core, could coincide with the direction of the axis of the core.
(C) a Rectangular blade length 85 mm and a width of 650 mm (so that the long side direction could be the axial direction fiber), cut from the above-mentioned containing fibers of KZT700-SC unidirectional prepreg, wound around the prepreg, covering the core, so that the direction of the fibers could coincide with axial direction of the core.
(d) Then wrap the tape (tape heat-resistant films) is wound around of prepreg, covering the core, and wrapped in a ribbon core is heated to form at 130 C for 90 minutes in the oven curing. Meanwhile, wrap the tape has a width of 15 mm and a wound in tension 3.0 kg and winding step (the length of the offset) 1,0 mm Tape is wound into two layers.
(e) Then the core pull out and wrap the tape off, get tubular elements made of composite material.
[The drop test in Sharpie tubular elements made of composite material]
Tubular elements made of composite material obtained by the method described above, cut to length 60 mm, get a sample for testing with an inner diameter of 6.3 mm and a length of 60 mm-Kick put on the side surface of the tubular element using mass of 300 kg·cm, to assess the impact strength on a Sharpie. The value of impact strength on a Sharpie refers to the value obtained by dividing the aggregate energy absorption in the cross-sectional area of the sample for testing.
Impact resistance in Sharpie (j/m 2 )=total energy absorption (j)/sectional Area of the sample for testing (m 2 )
In addition, to test the incision is not applied. The measurements are carried out 10 times, and for comparison is used the average value.
(9) Assessment G1c flat plate, made of composite material
In working examples 25-36 and reference working examples 8-13 tests carried out in accordance with the following methods.
[Flat plate, made of composite material, to test for impact strength of the open type (G1c)]
Flat plate prepared in accordance with the following stages (a)-(f) JIS K 7086.
(a) Twenty layers containing fibers T700SC unidirectional prepreg, prepared as described above, laminate so that the direction of the fibers remain parallel. However, in the Central division surface of the laminate (between 10-th and 11-th layer) fix 40-mm film at right angles to the direction of the fiber arrangement.
(b) Laminated prepreg cover nylon film, not allowing to form no light, heat and impact of the increased pressure at 135 C and With the internal pressure 588 kPa autoclave for 2 hours to happen curing education reinforced unidirectional fiber composite material.
(C) of unidirectional fibre-Reinforced composite material, received in paragraph (b), cut sizes, width 20 mm, length 195 mm Cutting is carried out so that the direction of fibres could be parallel the long side of the sample for testing.
(d) In accordance with the standard JIS K 7086 unit (length 25 mm made of aluminium) for a concentrated load connected to the end of the sample (on the side with the film's eye).
(e) Part with the inserted film opened with a sharp cutter, such as the knife to make an initial crack from 2 to 5 mm
(f) to facilitate the monitoring of the spread of crack, the test pieces are covered with white paint on both sides.
[Evaluation G1c flat plate, made of composite material]
In accordance with the standard JIS K 7086 (2006) to conduct tests using universal tensile machine Instron (production Instron). The movement speed of traverse is 0.5 mm/min up until the development of the crack reaches 20 mm and 1 mm/min after reaching 20 mm From the load shift and crack length expect G1c.
(10) the bend Test (90 degrees) flat plate made from composite material
In working example 25-36 and reference working examples 8-13 tests carried out in accordance with the following methods.
[Preparation of a flat plate, made of composite material, for bend test, 90 deg]
Flat plate is prepared in accordance with the following stages (a) and (b).
(a) Twenty layers containing fibers T700SC unidirectional prepara received in accordance with the method above, laminate (thickness 2 mm) so that the direction of fibers remained parallel. The resulting laminate utverjdayut under the same conditions as those described in paragraph (b) to assess G1c.
(b) unidirectional fibre-Reinforced composite material obtained in paragraph (a), cut the size of a width of 15 mm and a length of 60 mm In this case cutting conduct so that the direction of fibres could be parallel to the wide side of the sample.
[Bend test, 90 deg, flat plate composite material]
In accordance with the standard JIS K 7017 (1999) to measure the use of universal tensile machine Instron (production Instron) when speed of traverse 1.0 mm/min with an amplitude of 40 mm, indentor diameter 10 mm and diameter of the support prisms 4 mm, and expect bending strength at 90 degrees.
The ratio of mixture components in the relevant working examples and properties of the corresponding working examples and comparative examples, measured in accordance with the previously described methods, are presented in total in table 1-7.
(Reference example 1)
100 mass-part epoxy befooling F type (Epiclon 830) add 0,05 mass parts of tetrabutylammonium, and the mixture while stirring heated up to 175 degrees C. Then serves 20 mass parts toluoldiisocyanates that takes 3 hours, and mix again stirred at 175 degrees C for 4 hours, get the product modification by isocyanate epoxy resin befooling F type.
In addition, similar to using epoxy resin phenolic-Novolac type (jER152), toluoldiisocyanates as source materials, get the product modification by isocyanate epoxy Novolac type.
In addition, as source material using MR-100 as polyisocyanate connection and YD128 used as epoxy befooling And types for production of product modifications polyisocyanate epoxy resin befooling And type.
(Working example 1)
As shown in table 1, in case where GAS use as [AA], MY0500 as [Ab1], 4,4'-DDS as curing agent [In] and "Nanostrength" (registered trademark) E20F as [C] wave length of the concentration fluctuations in the structure with divided phase is pretty rough but mechanical properties of composite good.
(Working example 2)
The composition of epoxy resin prepared in the same way as in your example 1, except that as [C] use "Nanostength" (registered trademark) M22. The wavelength of the concentration fluctuations in the structure with divided phase is pretty rough, but the mechanical properties of a composite good.
(Working example 3)
The composition of epoxy resin receive the same way as in your example 1, except that as [C] use "Nanostength" (registered trademark) M22N. The degree of dispersion patterns with divided phase is fine. In the result of deformation in bending resin and impact strength resin improve, and properties of a composite is also improved.
(Working example 4)
The composition of epoxy resin prepared in the same way as in your example 3, except that mixed number [With] increase to 8 mass parts. The modulus of elasticity resin drops. As a result, the compressive strength when the through-hole as a property of the composite decreases, but remains at a level not calling them.
(Working example 6)
The composition of epoxy resin prepared in the same way as in your example 3, except that as [AA] use AER4152. As the physical properties of the resin and mechanical properties of the composite are good.
(Working example 7)
The composition of epoxy resin prepared in the same way as in your example 3, except that as [Ab1] use ELM434. The degree of dispersion patterns with divided phase is thin, and the physical properties of the resin and the composite properties are good.
(Working example 8)
The composition of epoxy resin prepared in the same way as in your example 7, except that mixed number [AA] reduce to 30 mass of parts and therefore slightly change blend number [Ab1] and [Ab2]. As the physical properties of the resin and the composite properties are good.
(Working example 9)
The composition of epoxy resin prepared in the same way as in your example 3, except that mixed number [Ab1] reduce to 20 mass of parts and therefore slightly change the mix number [Ab2]. As the elastic modulus Flexural resin and impact strength resins fall, and in the properties of the composite reduced, but remain at levels that do not cause problems.
(Working example 10)
The composition of epoxy resin prepared in the same way as in your example 3, except that mixed number [AA] reduce to 30 mass of parts and therefore slightly change the mix number [Ab1]. Structure with divided phase is pretty rough. However, the modulus of elasticity resin is improving, and the properties of the composite are at levels that do not cause problems.
(Working example 11)
The composition of epoxy resin prepared in the same way as in your example 3, except that mixed number [AA] reduce to 30 mass of parts and therefore slightly change the mix number [Ab2]. As the physical properties of the resin and the properties of the composite are at levels that do not cause problems.
(Working example 12)
The composition of epoxy resin prepared in the same way as in your example 3, except that mixed number [AA] increase to 70 mass of parts and therefore slightly change blend number [Ab1] and [Ab2]. The elastic modulus Flexural resin falls heavily, but as the physical properties of the resin and mechanical properties of the composite are at levels that do not cause problems.
(Working example 13)
The composition of epoxy resin prepared in the same way as in your example 3, except that as a [B] use 3,3'-DDS. Temperature resistance falls. However, the modulus of elasticity resin and impact strength resin sharply increased, and the mechanical properties of the composite are also good.
(Working example 14)
The composition of epoxy resin prepared in the same way as in your example 8, except that as a [B] use 3,3'-DDS. Temperature resistance falls. However, the modulus of elasticity resin and impact strength resin sharply increased, and the mechanical properties of the composite are also good.
(Working example 15)
The composition of epoxy resin prepared in the same way as in your example 13, except that as [AA] use the product modification by isocyanate epoxy Novolac type received in the reference case 1. Temperature resistance increases, and mechanical properties of the composite are also good.
(Working example 16)
The composition of epoxy resin prepared using the product modification of epoxy resin befooling F-type received in the reference case 1, and using HP4032D as [AA] and ELM120 as [Ab1]. The degree of dispersion patterns with divided phase is pretty rough, but as the physical properties of the resin and mechanical properties of the composite are good.
(Working example 17)
The composition of epoxy resin are prepared with NR as [AA] and Epiclon as [Ab2]. As the physical properties of the resin and mechanical properties of the composite are good.
(Working example 18)
The composition of epoxy resin are prepared with NR as [AA] and jER152 as other epoxy resin. As the physical properties of the resin and mechanical properties of the composite are good.
(Working example 19)
The composition of epoxy resin prepared in the same way as in your example 3, except that as [AA] use NC7300. As the physical properties of the resin and mechanical properties of the composite are good.
(Working example 20)
The composition of epoxy resin are prepared with YX4000H as [AA] and jER152 as another component epoxy. As the physical properties of the resin and mechanical properties of the composite are good.
(Working example 21)
The composition of epoxy resin are prepared with NR as [AA] and EPPN-N as another component epoxy resin. As the physical properties of the resin and mechanical properties of the composite are good.
(Working example 22)
The composition of epoxy resin prepared in the same way as in your example 3, except that as [AA] use of EX-1010. As the physical properties of the resin and mechanical properties of the composite are good.
(Working example 23)
The composition of epoxy resin are prepared with NR as [AA] and ELM434 and GOT as [Ab1]. Temperature resistant resin few drops. However, the elastic modulus Flexural resin increases, and the mechanical properties of the composite are also good.
(Working example 24)
The composition of epoxy resin prepared in the same way as in your example 13, except that as [AA] use the product modification polyisocyanate epoxy resin befooling And type received in the reference case 1. Temperature resistance increases, and the mechanical properties of the composite are also good.
(Working example 25)
The composition of epoxy resin are prepared with YX4000 as a component [AA], GAN as a component [Ab1'], YD128 as [Ab2], jER1004AF and jER1007 as a component [Ab3], dicyandiamide as a component [B] "Nanostrength" (registered trademark) M22N as a component []. The value of impact strength on a Sharpie tubular element of composite material and GIc flat plates made of composite material correspond to high values.
(Working example 26)
The composition of epoxy resin prepared in the same way as in your example 25, except that the entire jER1007 replace jER1004AF as a component [Ab3]. As the density of the cross-linkage increased thermal stability increases, but the impact strength is reduced. In addition, the structure with divided phase becomes quite rough, and the value of impact strength on a Sharpie tubular element of composite material and G1c flat plates made of composite material is somewhat reduced, but remain at levels that do not cause problems.
(Reference example 27)
The composition of epoxy resin prepared in the same way as in your example 25, except that the ratio YX4000 [Aa] and jER1004AF [Ab3] reduced and that the number jER1007 increase. The glass transition temperature does not fall, but the impact strength increases significantly, whereas the value of impact strength on a Sharpie tubular element of composite material and G1c flat plates made of composite material increase.
(Working example 28)
The composition of epoxy resin prepared in the same way as in your example 27, except that the number jER1007 as [Ab3] reduced and that the number YX4000 as [Aa] raise. The resistance is growing, but the impact strength falls. Structure with divided phase remains good, and the value of impact strength on a Sharpie is also good.
(Working example 29)
The composition of epoxy resin prepared in the same way as in your example 27, except that jER1004AF as [Ab3] replace Epiclon 830. Viscosity drops, and temperature resistance and elasticity modulus increase. Impact strength is high, the structure with divided phase becomes quite rude. The value of impact strength on a Sharpie and G1c are at levels that do not cause problems.
(Working example 30)
The composition of epoxy resin prepared in the same way as in your example 26, except that increase the number of block copolymer [C]. The modulus of elasticity decreases slightly, but the deformation and toughness slightly increase. Structure with divided phase remains equivalent. Due to the effects of improved extension (deformation) and the impact strength value of impact strength on a Sharpie and G1c grow.
(Working example 31)
The composition of epoxy resin prepared in the same way as in your example 27, except that the number YD128 as [Ab2] reduced and that the number GAN increase. Viscosity decreases, and the modulus increases a little. The value of impact strength on a Sharpie and G1c are good.
(Working example 32)
The composition of epoxy resin prepared in the same way as in your example 27, except that the number of GAN as [Ab1'] and reduce the number YD128 increase. Viscosity increases, and the modulus of elasticity falls. However, the deformation increases. Structure with divided phase becomes quite rough, and the value of impact strength on a Sharpie and G1c few fall but remain at levels that do not cause problems.
(Working example 33)
The composition of epoxy resin receive the same way as in your example 31, except that GAN as [Ab1'] replace GOT. The relevant properties do not change much, and the value of impact strength on a Sharpie and G1c are good.
(Working example 34)
Epoxy resin material receive the same way as in your example 27, except that jER1004AF as [Ab3] replace YDF2001. Viscosity decreases, and the modulus of elasticity and heat resistance increase. However, the impact strength decreases, and the structure with divided phase becomes quite rude. Accordingly, the values of impact strength on a Sharpie and G1c fall but remain at levels that do not cause problems.
(Working example 35)
The composition of epoxy resin receive the same way as in your example 27, except that E40 used as a block-copolymer [C]. Structure with divided phase becomes quite rough, and the value of impact strength on a Sharpie and G1c fall but remain at levels that do not cause problems.
The composition of epoxy resin prepared in the same way as in your example 34, except that the number YD128 as [Ab2] reduced and that the number YDF2001 and GAN increase. Moreover, increase the number of block copolymer [C]. The relevant properties are good, and structure with separate phases, as defined, is also fine. As a result, the value of impact strength on a Sharpie and G1c also increase.
(Reference for a working example 1)
Composition termootdelenija resin prepared in the same way as in your example 3, except that mix the number XAC4151 increase to 90 mass movements and that in this regard mix change the number MY0500. The viscosity of the resin is too high, and from the resin hard molded sheet.
(Reference for a working example 2)
Composition termootdelenija resin prepared in the same way as in your example 3, except that mix the number XAC4151 increase to 20 mass movements and that in this regard mix change the number YD128. The temperature drops, and impact strength resin also falls. As a result, the compression strength with a through hole as a property of the composite reduced.
(Reference for a working example 3)
Composition termootdelenija resin prepared in the same way as in your example 3, except that mix the number XAC4151 increase to 40 mass parts that mix the number MY0500 change to 10 mass movements and that mix change the number YD128. As the elastic modulus Flexural resin and impact strength resins fall. In the mechanical properties of the composite greatly deteriorate and become unsatisfactory.
(Reference for a working example 4)
Composition termootdelenija pitch receive the same way as in your example 3, except that mix the number XAC4151 change to 10 mass movements and that mix the number MY0500 change to 70 mass parts. The cured resin becomes quite rough at phase separation, and impact strength resin drops. As a result, the compressive strength after hitting as a property of the composite decreases.
(Reference for a working example 5)
Composition termootdelenija pitch receive the same way as in your example 3, except that instead of mixing ELM434 mix 50 mass parts YD128. As the elastic modulus Flexural resin and impact strength resins fall. In the mechanical properties of the composite greatly deteriorate and become unsatisfactory.
(Reference for a working example 6)
Composition termootdelenija pitch receive the same way as in your example 3, except that instead of mixing HAS mix 50 mass parts MY0500 and 50 mass parts YD128. Impact strength resin drops. As a result, the compressive strength after hitting as properties of the composite reduced.
(Reference for a working example 7)
Use the song, described in the patent document 4. Hardening agents, used as a component [B]is an 3,3'-diaminodiphenylmethane. As the elastic modulus Flexural and temperature resistant resin lower than in working examples 1-22.
(Reference for a working example 8)
Use the same composition of epoxy resin, as in the running example, 25, except that YX4000 as a component [Aa] replace epoxy resin befooling F type (YDF2001). Technological properties (viscosity) songs epoxy not very different from the technological properties of the working example 25. Resistant to slightly weakened in comparison with the temperature resistance of the working example 25. In addition, the structure with divided phase becomes rough, and accordingly G1c and impact resistance in Sharpie fiber-reinforced composite material greatly reduced.
(Reference for a working example 9)
Use the same composition of epoxy resin, as in the running example, 25, except that digitalronin (GAN) as a component [Ab1] and YD128 as a component [Ab2] replace Epiclon 830 as a component [Ab2]. Technological properties (viscosity) songs epoxy not very different from the technological properties of the working example 25. Resistant to slightly weakened in comparison with the temperature resistance of the working example 25. In addition, the structure with divided phase becomes rough, and accordingly the value G1c and impact strength on Sharpie fiber-reinforced composite material greatly reduced.
(Reference for a working example 10)
Use the same composition of epoxy resin, as in the running example, 25, except that jER1007 as a component [Ab3] replace YD128 as a component [Ab2]. The resistance is growing in comparison with the temperature resistance of the working example 25, but the structure with divided phase becomes rough. Values G1c and impact strength on Sharpie fiber-reinforced composite material greatly reduced.
(Reference for a working example 11)
Use the same composition, and in the running example, 25, except that a block-copolymer as a component of [C] do not add. Structure with separate phases do not receive, and the effect of an increase in impact strength using a block-copolymer is not available. Only low values could be obtained as values G1c and impact strength on Sharpie fiber-reinforced composite material.
(Reference for a working example 12)
Use the song, described in the patent document 7. Structure with divided phase regulate approximately 50 nm, but the G1c and impact strength on Sharpie fiber-reinforced composite material much fall.
(Reference for a working example 13)
Use the song, described in the patent document 5. Structure with divided phase becomes rough and values G1c and impact strength on Sharpie fiber-reinforced composite material much fall.
Table 1Composition epoxy resin (mass parts)
A working example 1
A working example 2
A working example 3
A working example 4
A working example 5
A working example 6
A working example 7
A working example 8
[Aa] HAS 50 50 50 50 50 50 30 AER4152 50 [Ab1] MY0500 30 30 30 30 30 30 ELM120 ELM434 30 40 [Ab2] YD128 20 20 20 20 20 20 20 30Epiclon 830
[B]4,4'-DDS
1 EQ. 1 EQ. 1 EQ. 1 EQ. 1 EQ. 1 EQ. 1 EQ. 1 EQ.3,3'-DDS
[C] E20 4 M22 4 M22N 4 1,5 8 4 4 4Resin properties
The glass transition temperature (OC)
195 197 198 198 187 195 205 199The elastic modulus Flexural (HPa)
3,8 3,8 3,8 4,0 3,6 3,9 3,8 3,8The bending deformation (mm)
10 10 12 9 14 13 11 10Impact strength (Cs)
1,1 1,1 1,4 1,1 1,5 1,3 1,4 1,2The degree of dispersion patterns with divided phase (nm)
800 550 50 30 70 40 25 110Properties composers that
Compressive strength after hitting (MPa)
348 341 367 352 373 365 369 355Compressive strength perforated sheet (MPa)
303 298 305 309 287 302 301 300 Table 2The composition of epoxy resin (mass parts)
A working example 9
A working example 10
A working example 11
A working example 12
A working example 13
A working example 14
A working example 15
A working example 16
[Aa] HAS 50 30 30 70 50 30Product modification by isocyanate Novolac resin
50Product modifications the isocyanate resin befooling F type
50 HP4032D 20 50 30 20 30 30 20 [Ab1] MY0500 ELM120 30 ELM434 40 [Ab2] YD128 30 20 40 10 20 30 20Epiclon 830
[B]4,4'-DDS
1 EQ. 1 EQ. 1 EQ. 1 EQ. 1 EQ.3,3'-DDS
1 EQ. 1 EQ. 1 EQ. [C] M22N 4 4 4 4 4 4 4 4Resin properties
The glass transition temperature (OC)
191 218 205 203 182 180 195 196The elastic modulus Flexural (HPa)
3,6 4,0 3,8 3,6 4,3 4,4 4,3 3,9The bending deformation (mm)
9 11 13 13 13 11 8 9Impact strength (Cs)
1,3 1 1,3 1,4 1,8 1,7 1,5 1,3The degree of dispersion patterns separated with phases (nm)
40 520 20 60 40 60 50 180Properties compo - Zita
Compressive strength after hitting (MPa)
358 354 368 360 378 375 364 358Compressive strength perforated sheet (MPa)
295 307 301 290 329 330 325 303 Table 3Composition epoxy resin (mass parts)
A working example 17
A working example 18
A working example 19
A working example 20
A working example 21
A working example 22
A working example 23
A working example 24
[Aa] NR 50 NR 40 NC7300 50 YX4000H 50 NR 50 30 EX-1010 50Product modifications polyisocyanate resin befooling And type
50 [Ab1] MY0500 30 30 30 30 30 30 ELM120 30 ELM434 40 GOT 30 [Ab2] YD128 20 20 20 20 20Epiclon 830
20Other aproximo crystals
jER152 10 20EPPN-501H
10 [B]4,4'-DDS
1 EQ. 1 EQ. 1 EQ. 1 EQ. 1 EQ. 0,9 EQ.3,3'-DDS
1 EQ. 1 EQ. [C] M22N 4 4 4 4 4 4 4 4moistva resin
The glass transition temperature (OC)
230 190 216 208 212 220 180 190The elastic modulus Flexural (HPa)
3,9 4,4 4,0 3,6 3,7 3,8 4,2 4,2The bending deformation (mm)
8 7 8 7 9 9 7 7Impact strength (Cs)
1,1 1,4 1,2 1,1 1,2 1,2 1,1 1,3The degree of dispersion patterns with divided phase (nm)
95 85 55 50 20 30 100 40The properties of the composite
Compressive strength after hitting (MPa)
345 370 345 337 350 353 347 360Compressive strength perforated sheet (MPa)
304 328 308 291 295 301 315 320 Table 4The composition of epoxy resin (mass parts)
A working example 25
A working example 26
A working example 27
A working example 28
A working example 29
A working example 30
[Aa] YX4000 35 35 30 35 30 35 [Ab1] GAN 15 15 15 15 15 15 GOT [Ab2] YD128 15 15 15 15 15 15Epiclon 830
10 [Ab3]jER1004AF
14 35 10 10 35 jER1007 21 30 25 30 YDF2001 [B]Dicyandiamide
3,97 4,08 3,71 3,95 4,17 4,08 [C] E40 M22N 4,4 4,4 4,4 4,4 4,4 5Accelerator of hardening
DCMU 1,7 1,7 1,7 1,7 1,7 1,7Resin properties
Viscosity (PA·s at 80 C)
27 19 44 37 16 29The glass transition temperature (OC)
127 130 120 125 128 129The module elasticity at bending (HPa)
3,4 3,44 3,39 3,39 3,48 3,3The bending deformation (mm)
10,5 9,9 13,3 12,2 12,9 10,6Impact strength (Cs)
1,7 1,62 1,92 1,75 1,8 1,7The degree of dispersion patterns with divided phase (nm)
10 20 10 10 30 20The properties of the composite
Impact resistance in Sharpie (tubular element, j/m 2 )
735 702 780 729 709 730G1c (j/m2 )
754 720 804 735 725 760Bending strength, 90 deg (MPa)
115 119 117 110 126 125 Table 5The composition of epoxy resin (mass parts)
A working example 31
A working example 32
A working example 33
A working example 34
A working example 35
A working example 36
[Aa] YX4000 30 30 30 30 30 30 [Ab1] GAN 20 10 15 15 20 GOT 20 [Ab2] YD128 10 20 10 15 15 5Epiclon 830
[Ab3]jER1004AF
10 10 10 10 jER1007 30 30 30 30 30 30 YDF2001 10 15 [B]Dicyandiamide
3,84 to 3.58 to 3.73 3,81 3,71 3,79 [C] E40 4,4 M22N 4,4 4,4 4,4 4,4 5Accelerator of hardening
DCMU 1,7 1,7 1,7 1,7 1,7 2Resin properties
Viscosity (PA·s at 80 C)
32 48 27 36 44 45The glass transition temperature (OC)
122 122 122 125 117 125The elastic modulus Flexural (HPa)
3,43 3,36 3,41 3,45 3,29 3,44Deformation bending (mm)
11,6 14,1 11,9 10,4 10,9 13,3Impact strength (Cs)
1,88 1,78 1,84 1,75 1,9 2,01The degree of dispersion patterns with divided phase (nm)
10 20 10 20 30 10The properties of the composite
Impact resistance in Sharpie (tubular element, j/m 2 )
774 744 769 714 710 811G1c (j/m2 )
796 752 793 736 733 849Bending strength, 90 deg (MPa)
111 109 112 121 115 122 Table 6The composition of epoxy resin (mass parts)
Ref. a working example 1
Ref. a working example 2
Ref. a working example 3
Ref. a working example 4
Ref. a working example 5
Ref. a working example 6
Ref. a working example 7
[Aa] HAS 90 20 40 10 50 YX4000H 50 [Ab1] MY0500 10 30 10 70 50 [Ab2] YD128 20 50 50 20 50 50Epiclon 830
50 [B]4,4'-DDS
1 EQ. 1 EQ. 1 EQ. 1 EQ. 1 EQ. 1 EQ.3,3'-DDS
1 EQ. [C] E40F M22 7,5 M22N 4 4 4 4 4 4Resin properties
The glass transition temperature (OC)
- 160 170 185 180 185 152The elastic modulus Flexural (HPa)
- 3,6 3,6 3,8 3,3 3,6 3,2The bending deformation (mm)
- 6 6 4 7 6 8,2Impact strength (Cs)
- 0,9 0,6 0,5 0,6 0,5 1,8The degree of dispersion patterns separated phases (nm)
- 40 70 1200 80 50 45The properties of the composite
Compressive strength after hitting (MPa)
- 335 284 257 276 241Compressive strength perforated sheet (MPa)
- 247 258 297 265 254 Table 7Composition epoxy resin (mass parts)
Ref. a working example 8
Ref. a working example 9
Ref. a working example 10
Ref. a working example 11
Ref. a working example 12
Ref. a working example 13
[Aa] YX4000 35 35 35 HP7200L 30 [Ab1] GAN 15 15 15 ELM100 30 [Ab2] YD128 15 36 15Epiclon 830
30 15 jER828 70 [Ab3]jER1004AF
14 14 14 14 10 jER1007 21 21 21 YDF2001 35 50jER4004P
10 [B]Dicyandiamide
2,87 3,75 4,93 3,97 3,9 5,5 [C] E40F 3 M22 4,4 4,4 4,4 4Accelerator of hardening
DCMU 1,7 1,7 1,7 1,7 2 3Other components
Vinylek K
3Resin properties
Viscosity (PA·s at 80 C)
41 54 7 18 36The glass transition temperature (OC)
102 118 133 127 120 135The degree of dispersion patterns with divided phase (nm)
200 >500 >500 - 50 >500The properties of the composite
Impact resistance in Sharpie (tubular element, j/m 2 )
587 574 529 471 601 520G1c (j/m2 )
614 630 547 422 633 539Bending strength, 90 deg (MPa)
107 109 115 116 119 106INDUSTRIAL APPLICABILITY
The composition of epoxy resin of the present invention can be recycled in utverjdenie products, having quite high toughness, high temperature resistance and high modulus of elasticity; therefore, the composition can be mixed with reinforcing fibres and can be obtained fiber reinforced composite material, which has the great impact strength, excellent thermal stability and beautiful characteristics of static strength. This allows you to use fiber with high modulus in the variants of use in areas in which the use of conventional products is difficult, and expect a further reduction in weight reinforced by fibers materials can contribute to progress in the relevant areas.
1. The composition of epoxy resin, containing as a component epoxy resin [And], hardening agents based on amine [In] and block-copolymer [I]where epoxy resin [A] contains the following components [AA] and [Ab]component [Ab] contains the following components [Ab1'], [Ab2] and [Ab3]component [] represents a dicyandiamide, and block-copolymer [I] represents the next block-copolymer: [AA] epoxy bifenilos type with biphenylol structure; [Ab1'] derived digitalronin, presents the following General formula (I): [Chemical formula 1]
where deputies and R, respectively, and independently from each other selected from the hydrogen atom, linear or branched alkyl from 1 to 5 carbon atoms and a linear or branched alkoxy groups from 1 to 5 carbon atoms; [Ab2] liquid epoxy resin befooling type; and [Ab3] solid epoxy resin befooling type; [C] at least one block-copolymer selected from the group consisting of S-B-M,-M, and M-B-M; where the above-mentioned relevant blocks are connected by covalent bond or connected intermediate molecule that is connected with one unit one the covalent bond with another block other covalent bond; M unit is a unit consisting of polimetilmetakrilata of homopolymer, or copolymer, containing at least 50% of the mass. of methyl methacrylate; the block is a block-immiscible block M, and has a glass transition temperature is 20 C or below; and block S is a unit immiscible with blocks b and M, and has a glass transition temperature higher than the glass transition temperature of the unit Century
2. The composition of epoxy resin according to claim 1, where a derivative digitalronin represented by the General formula (I), as a component [Ab1'] is digitalronin or diglycidylether.
3. The composition of epoxy resin according to claim 1, where the average epoxy equivalent of all component epoxy resins [And] is from 200 to 400.
4. The composition of epoxy resin according to claim 1, where component [A] contains 100% of the mass. component [And] from 20 to 50% of the mass. component [AA] and from 5 to 20% of the mass. component [Ab1'] and contains a component [Ab2]to ensure that the sum of the components [Ab1'] and [Ab2] is from 20 to 40% of the mass.; and contains a component [Ab3]to ensure that the sum of the components [AA] and [Ab3] is 60 to 80% of the mass.; component [] is 1 to 10 of mass parts for 100 mass the component parts of [A].
5. The composition of epoxy resin according to claim 1, where the unit In component [] consists of polymer selected from poly-1,4-butadiene, poly(butyl acrylate) and poly(2-ethylhexyl acrylate).
6. The composition of epoxy resin according to claim 1, where component [] is a block-copolymer, represented as M-B-M, and M unit as co monomer contains monomer with a value of SP higher than the value of SP of methyl methacrylate.
7. Prepreg containing fibres impregnated with the composition of epoxy on any one of claims 1 to 6.
8. Fiber reinforced composite material containing the cured product obtained by curing composition epoxy on any one of claims 1 to 6 and reinforcing fiber basis.