WO2005014699A1 - Procede de preparation d’objets a base de resines thermodures - Google Patents
Procede de preparation d’objets a base de resines thermodures Download PDFInfo
- Publication number
- WO2005014699A1 WO2005014699A1 PCT/FR2003/002048 FR0302048W WO2005014699A1 WO 2005014699 A1 WO2005014699 A1 WO 2005014699A1 FR 0302048 W FR0302048 W FR 0302048W WO 2005014699 A1 WO2005014699 A1 WO 2005014699A1
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- WO
- WIPO (PCT)
- Prior art keywords
- block
- formulation
- mol
- block copolymers
- blocks
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Definitions
- the present invention relates to the field of thermosetting resins, particularly to a formulation based on thermosetting compounds having a thermoplastic behavior and which can be both implemented by the usual techniques of transformation of thermoplastic materials and having the ability to react to form a thermoset material.
- the invention also relates to the process for obtaining this formulation and to the finished articles prepared from it.
- thermoset material is defined as being formed of polymer chains of variable length linked together by covalent bonds so as to form a three-dimensional network.
- Thermosetting materials can be obtained, for example, by reacting a thermosetting resin such as an epoxy with an amine type hardener.
- Thermoset materials have many interesting properties which make them used as structural adhesives or as a matrix for composite materials or in applications for the protection of electronic components.
- Epoxy materials have a density. high crosslinking, which gives them a high glass transition temperature, Tg, which gives the material excellent thermomechanical properties.
- Tg glass transition temperature
- their implementation remains very delicate because they are liquids before reaction, which does not allow their handling.
- the formulations of the invention comprise a thermosetting resin and a block copolymer having at least one block consisting mainly of methyl methacrylate units, used as a rheology control agent. These materials can be made by dissolving the copolymer in the thermosetting resin followed by the addition of the hardener and cross-linking when hot.
- the invention allows the manufacture of complex objects based on thermoset materials without the use of solvent.
- the first object of the invention is a process for the preparation of materials and of objects of thermals based on. the. techniques for using thermoplastic materials.
- This process can be described by the following stages: a- preparation of a formulation based on thermosetting materials, by conventional techniques such as extrusion, calendering, kneading or dissolution in a reactor b- recovery and possible storage of the formulation prepared in a c- Preparation of finished objects by the transformation of the product obtained in b according to the transformation techniques usually reserved for thermoplastic materials that the skilled person knows well.
- the formulation of the invention comprises:
- a rheology regulating agent comprising at least one block copolymer chosen from block copolymers S-B-M, B-M and M-B-M in which:
- each block is linked to the other by means of a covalent bond or to an intermediate molecule linked to one of the blocks by a covalent bond and to the other block by another covalent bond,
- M is a homopolymer PMMA or a copolymer comprising at least 50% by weight of methyl methacrylate
- thermosetting resin (II) from 20 to 99% by weight of the total weight of the formulation of at least one thermosetting resin (II)
- the formulation may contain without departing from the scope of the invention the various organic and inorganic fillers known to those skilled in the art such as fibers, pigments, fillers, UV absorbers, fillers allowing an improvement in fire resistance.
- thermoset material exhibits a thermoplastic behavior and can be implemented by the usual techniques for transforming thermoplastic materials but having the ability to react to form a thermoset material. This formulation may during the reaction be in a perfectly liquid or rubbery state.
- thermoset material it is defined as being formed of polymer chains of variable length linked together by covalent bonds so as to form a three-dimensional network.
- cyanoacrylates bismaleimides and epoxy resins crosslinked by a hardener or crosslinked by anionic or cationic polymerization.
- thermoset formulations of bismaleimide type are for example: methylenedianiline + benzophenone dianhydride + nadic imide methylenedianiiine + benzophenone dianhydride + pentylacetylene methylenedianiline + maleic anhydride + maleimide.
- thermoset material advantageously comes from the reaction of a thermosetting epoxy resin and a hardener. It is also defined as any product of the reaction of an oligomer carrying oxirane functions and a hardener. Due to the reactions involved in the reaction of these epoxy resins, a crosslinked material is obtained corresponding to a more or less dense three-dimensional network depending on the basic characteristics of the resins and hardeners used.
- epoxy resin designated below by. E, any organic compound having at least two functions of the oxirane type, polymerizable by ring opening.
- epoxy resins designates all the usual epoxy resins which are liquid at room temperature (23 ° C.) or at a higher temperature. These epoxy resins can be monomeric or polymeric on the one hand, aliphatic, cycloaliphatic, heterocyclic or aromatic on the other hand.
- epoxy resins examples include the diglycidyl ether of resorcinol, the diglycidyl ether of bisphenol A, the triglycidyl p-amino phenol, the diglycidyl ether of bromo-bisphenol F, the triglycidyl ether of m- amino phenol, tetraglycidyl methylene dianiline, triglycidyl ether of (trihydroxyphenyl) methane, polyglycidyl ethers of phenol-formaldehyde novolac, polyglycidyl ethers of orthocresol novolac and tetraglycidyl ethers of tetraphenyl ethane. Mixtures of at least two of these resins can also be used.
- epoxy resins having at least 1.5 oxirane functions per molecule and more particularly epoxy resins containing between 2 and 4 oxirane functions per molecule. Also preferred are epoxy resins having at least one aromatic ring such as the diglycidyl ethers of bisphenol A.
- hardeners are used epoxy resins which react at room temperature or at temperatures above room temperature.
- Acid anhydrides among which succinic anhydride,
- Aromatic or aliphatic polyamines including diamino diphenyl sulphone (DDS) or methylene dianiline or also 4,4'-Methylenebis- (3-chloro-2,6-diethylaniline) (MCDEA), • - La dicyandiamide and its derivatives.
- DDS diamino diphenyl sulphone
- MCDEA 4,4'-Methylenebis- (3-chloro-2,6-diethylaniline)
- La dicyandiamide • - La dicyandiamide and its derivatives.
- the block copolymer SBM M consists of methyl methacrylate monomers or contains at least 50% by mass of methyl methacrylate, preferably at least 75% by mass of methyl methacrylate.
- the other monomers constituting the block M can be acrylic monomers or not, be reactive or not.
- reactive monomer is meant: a chemical group capable of reacting with the oxirane functions of the epoxy molecules or with the chemical groups of the hardener.
- reactive functions mention may be made of: oxirane functions, functions amines, carboxy functions.
- the reactive monomer can be (meth) acrylic acid or any other hydrolyzable monomer leading to these acids.
- glycidyl methacrylate tert-butyl methacrylate.
- Advantageously M consists of at least 60% syndiotactic PMMA.
- the Tg of B is less than 0 ° C and preferably less than - 40 ° C.
- the monomer used to synthesize the elastomeric block B can be any monomer used to synthesize the elastomeric block B.
- B is advantageously chosen from poly (dienes), in particular poly (butadiene), poly (isoprene) and their random copolymers, or alternatively from poly (dienes) partially or completely hydrogenated.
- polybutadienes advantageously those with the lowest Tg are used, for example polybutadiene-1, 4 of Tg (around -90 ° C.) lower than that of polybutadiene-1, 2. (around 0 ° C).
- B blocks can also be hydrogenated. This hydrogenation is carried out according to the usual techniques.
- the monomer used to synthesize the elastomeric block B can also be an aikyl (meth) acrylate, the following Tg are obtained in brackets according to the name of the acrylate: ethyl acrylate (-24 ° C.) , butyl acrylate, (-54 ° C), 2-ethylhexyl acrylate (-85 ° G), hydroxyethyl acrylate (-15 ° C) and 2-ethylhexyl methacrylate (-10 ° C).
- the acrylates are different from those of block M to respect the condition of incompatible B and M.
- the blocks B consist mainly of polybutadiene-1, 4.
- the Tg or Tf of S is advantageously greater than 23 ° C and of
- blocks S that may be mentioned are those which derive from vinyl aromatic compounds such as styrene, ⁇ -methyl styrene, vinyltoluene, and those which derive from alkyl esters of acrylic and / or methacrylic acids having from 1 to 18 carbon atoms in the alkyl chain. In the latter case, the acrylates are different from those of block M to respect the condition of incompatible S and M.
- the SBM triblock has a number-average molar mass which can be between 10,000 g / mol and 500,000 g / mol, preferably between 20,000 and 200,000 g / mol.
- the SBM triblock advantageously has the following composition expressed as a mass fraction, the total being 100%: M: between 10 and 80% and preferably between 15 and 70%. B: between 2 and 80% and preferably between 5 and 70%. S: between 10 and 88% and preferably between 15 and 85%.
- the block copolymers used in the materials of the present invention can be produced by anionic polymerization, for example according to the methods described in patent applications EP 524,054 and EP 749,987.
- the proportion of impact modifier is from 10 to 60% for respectively 90 to 40% of thermoset resin.
- the S and B blocks are incompatible and they. are constituted. same, monomers. and__ possibly comonomers as blocks S and blocks B of the triblock S-B-M. Blocks
- the diblock S-B can be identical or different from the other blocks S and B present in the other block copolymers of the impact modifier in the thermoset material.
- the diblock S-B has a number-average molar mass which can be between 10,000 g / mol and 500,000 g / mol, preferably between 20,000 and 200,000 g / mol.
- the S-B diblock advantageously consists of a mass fraction of B between
- the rheology regulating agent comprises at least one SBM block copolymer and at least one block copolymer SB. It advantageously comprises between 5 and 80% of SB diblock for respectively from 95 to 20% of SBM triblock.
- compositions are generally prepared from S-B and the reaction often leads to a mixture of S-B and S-B-M which is then separated to have S-B-M.
- part of the S-B-M can be replaced by an S-B diblock.
- This part can be up to 70% by weight of the S-B-M.
- the S-B-M triblock can be replaced with an M-S-B-S-M or M-B-S-B-M pentabloc.
- They can be prepared by anionic polymerization like the di or triblocks mentioned above but using a difunctional initiator.
- the number-average molar mass of these pentablocs is in the same intervals as that of the S-B-M triblocks.
- the proportion of the two blocks M together, of the two blocks B or S together is in the same intervals as the proportions of S, B and M in the triblock S-B-M.
- the formulations of the invention can be prepared by mixing the thermosetting resin not yet crosslinked using a conventional mixing device.
- the product obtained can be in the form of granules, sheet or film.
- the material thus obtained unreacted or partially reacted may thus be in the form of a manipulable rubber material.
- This implementation will be done at a temperature where the reaction kinetics of the thermosetting material is slow.
- step [c] during implementation in the form of a finished object and by simply increasing the temperature, the thermosetting resin will be transformed into thermoset material.
- the rubber material during the reaction may, depending on the nature of the resin (II) and of the agent (l) used, return to the liquid state or remain in the rubber state.
- this invention can be applied to a reactive liquid resin which can form, after reaction, a linear or branched polymer having a thermoplastic behavior.
- This approach can be successfully applied for example to acrylic resin without departing from the scope of the invention.
- the finished articles of the invention can be used in various industries.
- this resin may also be in the form of films with a thickness of less than 100 ⁇ m or sheet having been prepared by sheath extrusion, by cast extrusion or by calendering. This extrusion will be done at a temperature that prevents advancement of the reaction. important then, these .films originallyouieuiJjes_p . will have to be L attached to a substrate and finally crosslinked by increasing the temperature or simply stored at a temperature where the reaction kinetics are slow, for example 0 ° C.
- thermoplastics such as polyethersulfones, polysulfones, polyetherimides, polyphenylene ethers
- thermoplastics such as polyethersulfones, polysulfones, polyetherimides, polyphenylene ethers
- DGEBA digisycid ether of Bisphenol A
- Hardener it is an amine hardener which is an aromatic diamine, 4,4'-Methylenebis- (3-chloro-2,6-diethylaniline) sold by the company Lonza under the commercial reference
- SBM1 it is a triblock copolymer S-B-M in which S is polystyrene, B is polybutadiene and M is PMMA containing 22% by mass fraction of Polystyrene, 9% by mass fraction of
- SBM2 it is a triblock copolymer S-B-M in which S is polystyrene, B is polybutadiene and M is PMMA containing 12% in
- the core-shell particles are dispersed in the DGEBA using a calender.
- the cycles are 10 minutes of mixing followed by 10 minutes of rest.
- the mixture is then brought to 100 ° C. (above the amine melting temperature) and the diamine is dispersed for 10 minutes
- the mixtures are cooked for 2 hours at 220 ° C.
- Tg The measurement of Tg was carried out by dynamic mechanical analysis on the post-cooked samples using a device - heometrics (Rheometrics-Solid-. Analyze J- ⁇ SAII).
- the parallelepipedal samples (1 * 2.5 * 34mm 3 ) are subjected to a temperature sweep between 50 and 250 ° C at a pulling frequency of 1 Hz.
- the glass transition temperature is taken at most tan d.
- a parallelepipedic sample of dimension 20x20x1 mm is placed in a 100ml beaker filled with toluene for a period of 15 days.
- the beaker is kept hermetically sealed at room temperature. After 15 days of immersion, the sample is taken and its mass checked.
- the percentage of swelling is obtained by the following equation:
- Example 1 40 gr of SBM of composition 203050 and of average molar mass in number of the PS block 7000 gr / mole are introduced into a roller mixer as well as 60 gr of DGEBA DER332® epoxy mixture from the company DOW Chemicals of molar mass 348.5 gr / mole and of amine MDEA from the company Lonza. DGEBA as well as MDEA are introduced into the stoichiometric mixture, namely 41, 53 g of DGEBA and 18.47 g of MDEA. The mixing is carried out at 150 ° C. This mixture is first pressed in the form of a transparent plate 1 mm thick, its elongation at break in tension is 650% and its glass transition temperature is 0 ° C. This mixture is then cooked at 220 ° C for 2 h. this mixture has a liquefaction temperature of 150 ° C. The glass transition temperature of the plate obtained is 154 ° C. and no swelling in toluene is observable.
- Example 3 (according to the invention) 30 g of SBM of composition 203050 and of average molar mass in number of the PS block 7000 gr / mole, 10 gr of PPO® Blendex 803 from the company i Electrique are introduced into a roller mixer. than 60 gr of DGEBA DER332® epoxy mixture from the company DOW Chemicals with a molar mass of 348.5 gr / mol and of amine MDEA. DGEBA as well as MDEA are introduced into the stoichiometric mixture, namely 41, 53 g of DGEBA and 18.47 g of MDEA. The mixing is carried out at 150 ° C.
- This mixture is first of all pressed in the form of a transparent plate 1 mm thick, its elongation at break in tension is 620% and its glass transition temperature is 0 ° C. This mixture is then cooked at 220 ° C for 2 h. this mixture has a liquefaction temperature of 230 ° C. The glass transition temperature of the plate obtained is 158 ° C. and no swelling in toluene is observable.
- Example 5 40 g of paraloid KM355® type core shell are introduced into a roller mixer.
- This core-shell bark has a core consisting mainly of butyl acrylate and a core of polymethyl methacrylate and 60 gr epoxy mixture DGEBA DER332® from the company DOW Chemicals with a molar mass of 348.5 gr / mole and an amine MDEA.
- DGEBA as well as MDEA are introduced into the stoichiometric mixture, namely 41, 53 g of DGEBA and 18.47 g of MDEA.
- the mixture obtained during cooling is translucent and has no cohesion.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005507540A JP2007514795A (ja) | 2003-07-02 | 2003-07-02 | 熱硬化性樹脂から物品を製造する方法 |
CA002531039A CA2531039A1 (fr) | 2003-07-02 | 2003-07-02 | Procede de preparation d'objets a base de resines thermodures |
EP03817959A EP1664160A1 (fr) | 2003-07-02 | 2003-07-02 | Procede de preparation d'objets a base de resines thermodures |
CNA03827020XA CN1826372A (zh) | 2003-07-02 | 2003-07-02 | 用热固性树脂生产目标物的方法 |
PCT/FR2003/002048 WO2005014699A1 (fr) | 2003-07-02 | 2003-07-02 | Procede de preparation d’objets a base de resines thermodures |
US10/562,549 US20090008826A1 (en) | 2003-07-02 | 2003-07-02 | Method For Production Of Objects From Thermosetting Resins |
AU2003264680A AU2003264680A1 (en) | 2003-07-02 | 2003-07-02 | Method for production of objects from thermosetting resins |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/FR2003/002048 WO2005014699A1 (fr) | 2003-07-02 | 2003-07-02 | Procede de preparation d’objets a base de resines thermodures |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005014699A1 true WO2005014699A1 (fr) | 2005-02-17 |
Family
ID=34130576
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2003/002048 WO2005014699A1 (fr) | 2003-07-02 | 2003-07-02 | Procede de preparation d’objets a base de resines thermodures |
Country Status (7)
Country | Link |
---|---|
US (1) | US20090008826A1 (fr) |
EP (1) | EP1664160A1 (fr) |
JP (1) | JP2007514795A (fr) |
CN (1) | CN1826372A (fr) |
AU (1) | AU2003264680A1 (fr) |
CA (1) | CA2531039A1 (fr) |
WO (1) | WO2005014699A1 (fr) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008051373A2 (fr) * | 2006-10-19 | 2008-05-02 | Dow Global Technologies Inc. | Compositions de résine époxy durcissables ayant une meilleure adhérence sur les substrats métalliques et leurs procédés de fabrication et d'utilisation |
EP2031000A1 (fr) | 2007-08-29 | 2009-03-04 | Essilor International (Compagnie Générale D'Optique) | Procédé de préparation d'un materiau transparent de type alliage de polymère thermodurcissable / polymère thermoplastique et son application dans l'optique pour la fabrication de verres organiques |
EP2030998A1 (fr) | 2007-08-29 | 2009-03-04 | Essilor International (Compagnie Générale D'Optique) | Procédé de préparation d'un article moulé transparent à base d'un alliage de polymer thermoplastique et de polymère thermodurcissable |
US7670683B2 (en) * | 2005-12-22 | 2010-03-02 | 3M Innovative Properties Company | Damage-resistant epoxy compound |
US9676899B2 (en) | 2006-05-01 | 2017-06-13 | Dsm Ip Assets B.V. | Radiation curable resin composition and rapid three dimensional imaging process using the same |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2883880B1 (fr) * | 2005-03-31 | 2007-05-11 | Essilor Int | Formulation poly(thio)urethane thermodurcissable comprenant au moins un copolymere a blocs et son application dans l'optique pour la fabrication de verres organiques a tenacite amelioree |
FR2896506B1 (fr) * | 2006-01-20 | 2008-04-04 | Essilor Int | Composition polymerisable a base de polyurethane-uree et de copolymeres a blocs et materiau transparent obtenu a partir de celle-ci |
FR2896507B1 (fr) * | 2006-01-20 | 2008-04-04 | Essilor Int | Composition polymerisable a base de polyurethane et de copolymeres a blocs et materiau transparent obtenu a partir de celle-ci. |
US9168429B2 (en) * | 2013-03-14 | 2015-10-27 | Karsten Manufacturing Corporation | Golf club heads with optimized characteristics and related methods |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3536654A (en) * | 1966-12-27 | 1970-10-27 | Shell Oil Co | Heat-curable solution coating compositions of an epoxy-amine adduct and an imidazole,their preparation and use |
GB1453516A (en) * | 1974-01-18 | 1976-10-27 | Dainippon Toryo Kk | Method for continuous extrusion moulding of thermosetting resins |
GB2046270A (en) * | 1979-04-12 | 1980-11-12 | Nippon Soda Co | Curable polybutadiene modified epoxy resin |
EP0870790A1 (fr) * | 1995-08-04 | 1998-10-14 | Asahi Denka Kogyo Kabushiki Kaisha | Composition solidifiable de resine epoxy |
FR2809741A1 (fr) * | 2000-05-31 | 2001-12-07 | Atofina | Materiaux thermodurs a tenue au choc amelioree |
EP1279688A1 (fr) * | 2001-07-13 | 2003-01-29 | Toray Composites (America), Inc. | Résine époxy a durcissement rapide renforcée par fibres de carbone |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6352782B2 (en) * | 1999-12-01 | 2002-03-05 | General Electric Company | Poly(phenylene ether)-polyvinyl thermosetting resin |
-
2003
- 2003-07-02 CN CNA03827020XA patent/CN1826372A/zh active Pending
- 2003-07-02 AU AU2003264680A patent/AU2003264680A1/en not_active Abandoned
- 2003-07-02 CA CA002531039A patent/CA2531039A1/fr not_active Abandoned
- 2003-07-02 US US10/562,549 patent/US20090008826A1/en not_active Abandoned
- 2003-07-02 EP EP03817959A patent/EP1664160A1/fr not_active Withdrawn
- 2003-07-02 JP JP2005507540A patent/JP2007514795A/ja active Pending
- 2003-07-02 WO PCT/FR2003/002048 patent/WO2005014699A1/fr active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3536654A (en) * | 1966-12-27 | 1970-10-27 | Shell Oil Co | Heat-curable solution coating compositions of an epoxy-amine adduct and an imidazole,their preparation and use |
GB1453516A (en) * | 1974-01-18 | 1976-10-27 | Dainippon Toryo Kk | Method for continuous extrusion moulding of thermosetting resins |
GB2046270A (en) * | 1979-04-12 | 1980-11-12 | Nippon Soda Co | Curable polybutadiene modified epoxy resin |
EP0870790A1 (fr) * | 1995-08-04 | 1998-10-14 | Asahi Denka Kogyo Kabushiki Kaisha | Composition solidifiable de resine epoxy |
FR2809741A1 (fr) * | 2000-05-31 | 2001-12-07 | Atofina | Materiaux thermodurs a tenue au choc amelioree |
EP1279688A1 (fr) * | 2001-07-13 | 2003-01-29 | Toray Composites (America), Inc. | Résine époxy a durcissement rapide renforcée par fibres de carbone |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7670683B2 (en) * | 2005-12-22 | 2010-03-02 | 3M Innovative Properties Company | Damage-resistant epoxy compound |
CN101341213B (zh) * | 2005-12-22 | 2011-11-23 | 3M创新有限公司 | 抗损伤性环氧复合物 |
US9676899B2 (en) | 2006-05-01 | 2017-06-13 | Dsm Ip Assets B.V. | Radiation curable resin composition and rapid three dimensional imaging process using the same |
WO2008051373A2 (fr) * | 2006-10-19 | 2008-05-02 | Dow Global Technologies Inc. | Compositions de résine époxy durcissables ayant une meilleure adhérence sur les substrats métalliques et leurs procédés de fabrication et d'utilisation |
WO2008051373A3 (fr) * | 2006-10-19 | 2008-06-19 | Dow Global Technologies Inc | Compositions de résine époxy durcissables ayant une meilleure adhérence sur les substrats métalliques et leurs procédés de fabrication et d'utilisation |
US20100068958A1 (en) * | 2006-10-19 | 2010-03-18 | Dow Global Technologies Inc. | Curable epoxy resin compositions having improved adhesion to metal substrates and processes for making and using the same |
US8877866B2 (en) | 2006-10-19 | 2014-11-04 | Dow Global Technologies Llc | Curable epoxy resin compositions having improved adhesion to metal substrates and processes for making and using the same |
EP2031000A1 (fr) | 2007-08-29 | 2009-03-04 | Essilor International (Compagnie Générale D'Optique) | Procédé de préparation d'un materiau transparent de type alliage de polymère thermodurcissable / polymère thermoplastique et son application dans l'optique pour la fabrication de verres organiques |
EP2030998A1 (fr) | 2007-08-29 | 2009-03-04 | Essilor International (Compagnie Générale D'Optique) | Procédé de préparation d'un article moulé transparent à base d'un alliage de polymer thermoplastique et de polymère thermodurcissable |
Also Published As
Publication number | Publication date |
---|---|
EP1664160A1 (fr) | 2006-06-07 |
JP2007514795A (ja) | 2007-06-07 |
US20090008826A1 (en) | 2009-01-08 |
CN1826372A (zh) | 2006-08-30 |
AU2003264680A1 (en) | 2005-02-25 |
CA2531039A1 (fr) | 2005-02-17 |
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