TW201915081A - Epoxy resin composition, Cured product and Formulation for curing agent - Google Patents
Epoxy resin composition, Cured product and Formulation for curing agent Download PDFInfo
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- TW201915081A TW201915081A TW106133701A TW106133701A TW201915081A TW 201915081 A TW201915081 A TW 201915081A TW 106133701 A TW106133701 A TW 106133701A TW 106133701 A TW106133701 A TW 106133701A TW 201915081 A TW201915081 A TW 201915081A
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- epoxy resin
- curing agent
- based material
- acrylate
- resin composition
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 115
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 115
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 70
- 239000000203 mixture Substances 0.000 title claims abstract description 60
- 238000009472 formulation Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 51
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 36
- 229920000768 polyamine Polymers 0.000 claims abstract description 32
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 31
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 29
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims abstract description 27
- 125000004185 ester group Chemical group 0.000 claims abstract description 26
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001412 amines Chemical class 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 125000003700 epoxy group Chemical group 0.000 claims description 11
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- RXFCIXRFAJRBSG-UHFFFAOYSA-N 3,2,3-tetramine Chemical compound NCCCNCCNCCCN RXFCIXRFAJRBSG-UHFFFAOYSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 3
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 claims description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims 4
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims 2
- 125000005396 acrylic acid ester group Chemical group 0.000 claims 1
- 239000013078 crystal Substances 0.000 claims 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000011521 glass Substances 0.000 abstract description 2
- 239000010409 thin film Substances 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 69
- 239000000047 product Substances 0.000 description 26
- 239000000945 filler Substances 0.000 description 24
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 13
- 239000002023 wood Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 239000003292 glue Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 230000007547 defect Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920006295 polythiol Polymers 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000013035 low temperature curing Methods 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 229960004889 salicylic acid Drugs 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 1
- VNRLFQGYFLCRMU-UHFFFAOYSA-N 2-piperazin-1-ylethanamine Chemical compound NCCN1CCNCC1.NCCN1CCNCC1 VNRLFQGYFLCRMU-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- TXPIQGGVMGCSBG-UHFFFAOYSA-N NCCCNCCNCCCN.NCCCNCCN Chemical compound NCCCNCCNCCCN.NCCCNCCN TXPIQGGVMGCSBG-UHFFFAOYSA-N 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- KUDUQBURMYMBIJ-UHFFFAOYSA-N ethylene glycol diacrylate Substances C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4207—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
- C08G59/58—Amines together with other curing agents with polycarboxylic acids or with anhydrides, halides, or low-molecular-weight esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
Description
本發明是有關於一種黏合劑，特別是指一種環氧樹脂組成物。The invention relates to an adhesive, in particular to an epoxy resin composition.
供建築物或家具等設備用的木材在使用或加工的過程中，會產生裂縫或破損等的缺陷，而該缺陷的存在會使得該木材的機械強度變差，繼而影響該木材的應用性。因此，在木材存在有該缺陷的前提下，為提高木材的利用率並降低成本，木材缺陷的修補工序是一道必要執行的工序。目前該修補工序是以膠材修補該缺陷。此外，為使該建築物或該家具等設備具有適當的機械強度，往往會透過黏合數片木材的方式來改善，而黏合方式是透過膠材在該等木材間形成黏著層來進行。During the use or processing of wood for equipment such as buildings or furniture, defects such as cracks or breakage may occur, and the existence of the defects will cause the mechanical strength of the wood to deteriorate, and then affect the applicability of the wood. Therefore, under the premise of the existence of the wood defect, in order to improve the utilization rate of the wood and reduce the cost, the repair process of the wood defect is a necessary process. At present, the repairing process is to repair the defect with glue. In addition, in order to make the building or the furniture and other equipment have appropriate mechanical strength, it is often improved by bonding several pieces of wood, and the bonding method is performed by forming an adhesive layer between the woods through glue.
一般來說，木材需具有一定的含水率，以避免乾裂或翹曲等的問題產生，故使用膠材來修補缺陷或黏合的方式中，該膠材需具有在低溫(例如30℃以下)環境中能夠固化的特性，以避免木材中的水分喪失。該膠材基本上包含低溫固化劑及作為主劑的環氧樹脂，而該低溫固化劑大都為脂肪族多胺系材料，或聚硫醇系材料與胺類促進劑的組合。Generally speaking, wood needs to have a certain moisture content to avoid problems such as cracking or warping. Therefore, in the method of using glue to repair defects or adhesion, the glue must have a low temperature (for example, below 30 ° C) environment. The ability to cure in order to avoid the loss of moisture in the wood. The glue basically includes a low-temperature curing agent and an epoxy resin as a main agent, and the low-temperature curing agent is mostly an aliphatic polyamine-based material, or a combination of a polythiol-based material and an amine accelerator.
雖然使用該低溫固化劑，能夠使得該膠材在低溫環境中固化，然而，當使用脂肪族多胺系材料時，存在有膠材固化速度慢的問題，導致時間成本增加且產能也因此受到限制。而當使用聚硫醇系材料與胺類促進劑的組合時，該膠材的儲存的條件嚴苛，一旦不當的儲存，容易有黃變及結皮現象產生，導致該膠材的特性或操作性變差，此外，由該膠材所形成的固化物的玻璃轉移溫度低，導致該固化物的機械強度、耐熱性及耐衝擊強度不符合需求。Although the low-temperature curing agent can be used to cure the glue in a low-temperature environment, when an aliphatic polyamine-based material is used, there is a problem that the glue cures slowly, resulting in an increase in time cost and limited production capacity. . When a combination of a polythiol-based material and an amine accelerator is used, the storage conditions of the material are severe. Once improperly stored, yellowing and skinning are likely to occur, resulting in the characteristics or operation of the material. In addition, the properties of the cured product are deteriorated. In addition, the glass transition temperature of the cured product formed from the glue is low, resulting in that the mechanical strength, heat resistance, and impact resistance of the cured product do not meet requirements.
此外，當使用脂肪族多胺系材料作為固化劑時，為使該膠材在固化速度上能夠獲得改善，採用的改善方式之一是提高該脂肪族多胺系材料用量，然而，當修補的缺陷很狹窄或隨著該黏著層的減薄化(又稱薄型化)的需求增加時，該膠材的用量會受到限制，因此，透過提高該脂肪族多胺系材料用量來改善固化速度的方式，會使得該主劑的用量相對地被縮減，繼而導致該膠材固化後所需的機械強度降低，而無法滿足需求。有鑑於此，有必要開發一種具有薄膜快速固化效果且不會導致固化後機械強度降低的膠材，且在該膠材中，該主劑與該固化劑能夠相互地搭配滿足上述的訴求。In addition, when an aliphatic polyamine-based material is used as a curing agent, in order to improve the curing speed of the adhesive material, one of the improvement methods adopted is to increase the amount of the aliphatic polyamine-based material. When the defects are very narrow or the demand for the thinning (also known as thinning) of the adhesive layer increases, the amount of the adhesive will be limited. Therefore, the curing speed can be improved by increasing the amount of the aliphatic polyamine-based material. In this way, the amount of the main agent is relatively reduced, and the mechanical strength required after curing of the rubber material is reduced, which cannot meet the demand. In view of this, it is necessary to develop an adhesive material that has a rapid curing effect of the film and does not cause a decrease in mechanical strength after curing, and in the adhesive material, the main agent and the curing agent can be matched with each other to meet the aforementioned requirements.
因此，本發明的第一目的，即在提供一種具有薄膜快速固化的效果的環氧樹脂組成物。Therefore, a first object of the present invention is to provide an epoxy resin composition having an effect of rapidly curing a thin film.
於是，本發明環氧樹脂組成物，包含環氧樹脂組分及具有酯基及羥基的脂肪胺固化劑。該環氧樹脂組分包括結晶性環氧樹脂及丙烯酸酯系環氧樹脂。該具有酯基及羥基的脂肪胺固化劑由固化劑用配方經聚合反應後所形成，且該固化劑用配方包括脂肪族多胺系材料、丙烯酸酯系材料及液態環氧樹脂。Therefore, the epoxy resin composition of the present invention includes an epoxy resin component and an aliphatic amine curing agent having an ester group and a hydroxyl group. The epoxy resin component includes a crystalline epoxy resin and an acrylate-based epoxy resin. The fatty amine curing agent having an ester group and a hydroxyl group is formed by a polymerization reaction of a curing agent formulation, and the curing agent formulation includes an aliphatic polyamine-based material, an acrylate-based material, and a liquid epoxy resin.
本發明的第二目的，即在提供一種具有高的硬度及玻璃轉移溫度的固化物。A second object of the present invention is to provide a cured product having high hardness and glass transition temperature.
本發明固化物，是由環氧樹脂組成物經固化(curing)反應所形成，且該環氧樹脂組成物包含環氧樹脂組分及具有酯基及羥基的脂肪胺固化劑。該環氧樹脂組分包括結晶性環氧樹脂及丙烯酸酯系環氧樹脂。該具有酯基及羥基的脂肪胺固化劑由固化劑用配方經聚合反應後所形成，且該固化劑用配方包括脂肪族多胺系材料、丙烯酸酯系材料及液態環氧樹脂。The cured product of the present invention is formed by a curing reaction of an epoxy resin composition, and the epoxy resin composition includes an epoxy resin component and an aliphatic amine curing agent having an ester group and a hydroxyl group. The epoxy resin component includes a crystalline epoxy resin and an acrylate-based epoxy resin. The fatty amine curing agent having an ester group and a hydroxyl group is formed by a polymerization reaction of a curing agent formulation, and the curing agent formulation includes an aliphatic polyamine-based material, an acrylate-based material, and a liquid epoxy resin.
本發明的第三目的，即在提供一種固化劑用配方。A third object of the present invention is to provide a formulation for a curing agent.
於是，本發明固化劑用配方，包含脂肪族多胺系材料、丙烯酸酯系材料，及液態環氧樹脂。Therefore, the formulation for a curing agent of the present invention includes an aliphatic polyamine-based material, an acrylate-based material, and a liquid epoxy resin.
本發明的功效在於：透過該具有酯基及羥基的脂肪胺固化劑與該環氧樹脂組分的結晶性環氧樹脂及丙烯酸酯系環氧樹脂特定地相互搭配，使得該環氧樹脂組成物在30℃以下(特別是在0℃至5℃)的環境中使用具有薄膜(例如厚度為0.2cm至1cm)快速固化的優點，且由該環氧樹脂組成物所形成的固化物具有高的硬度及玻璃轉移溫度。The effect of the present invention is that the aliphatic amine curing agent having an ester group and a hydroxyl group and the crystalline epoxy resin and the acrylate epoxy resin of the epoxy resin component are specifically matched with each other, so that the epoxy resin composition Use in an environment below 30 ° C (especially 0 ° C to 5 ° C) has the advantage of rapid curing of a film (e.g., a thickness of 0.2cm to 1cm), and the cured product formed from the epoxy resin composition has a high Hardness and glass transition temperature.
以下將就本發明內容進行詳細說明。The content of the present invention will be described in detail below.
＜＜固化劑用配方＞＞＜＜ Formulation for curing agent ＞＞
＜脂肪族多胺系材料＞＜ aliphatic polyamine materials ＞
該脂肪族多胺系材料例如以往用在使環氧樹脂進行固化反應的低溫型脂肪族多胺。該脂肪族多胺可單獨一種使用或混合多種使用，且該脂肪族多胺例如但不限於乙二胺、二伸乙基三胺(diethylenetriamine)、三伸乙基四胺(triethylenetetramine)、四伸乙基五胺(tetraethylenepentamine)、1,6-己二胺(hexane-1,6-diamine)、3-(二乙胺基)丙胺[3-(diethylamino)-propylamine]、N,N'-二(3-胺基丙基)乙二胺[N,N'-bis(3-aminopropyl)ethylenediamine]，或N-(2-胺基乙基)哌嗪[N-(2-aminoethyl)piperazine]等。This aliphatic polyamine-based material is, for example, a low-temperature type aliphatic polyamine conventionally used for curing reaction of an epoxy resin. The aliphatic polyamines can be used singly or in combination. The aliphatic polyamines can be, for example, but not limited to, ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylene. Tetraethylenepentamine, hexane-1,6-diamine, 3- (diethylamino) -propylamine, N, N'-diamine (3-Aminopropyl) ethylenediamine [N, N'-bis (3-aminopropyl) ethylenediamine], or N- (2-aminoethyl) piperazine [N- (2-aminoethyl) piperazine], etc. .
＜液態環氧樹脂＞＜ Liquid epoxy resin ＞
該液態環氧樹脂指的是本身為液態且具有環氧基的環氧樹脂。該液態環氧樹脂中的環氧基能與該脂肪族多胺系材料中的胺基反應，使得該液態環氧樹脂能固定在該脂肪族多胺系材料上，而減少該脂肪族多胺系材料的揮發性，同時，上述反應會產生羥基，而利於並促進該環氧樹脂組成物的固化反應的固化速度，此外，透過該液態環氧樹脂，能夠使得該具有酯基及羥基的脂肪胺固化劑與該環氧樹脂組分中的各成分間有很好的相容性。The liquid epoxy resin refers to an epoxy resin that is liquid in nature and has an epoxy group. The epoxy group in the liquid epoxy resin can react with the amine group in the aliphatic polyamine-based material, so that the liquid epoxy resin can be fixed on the aliphatic polyamine-based material, and the aliphatic polyamine is reduced. At the same time, the above-mentioned reaction generates hydroxy groups, which is beneficial to and promotes the curing speed of the curing reaction of the epoxy resin composition. In addition, the liquid epoxy resin can make the fat having an ester group and a hydroxy group The amine curing agent has good compatibility with each component in the epoxy resin component.
該液態環氧樹脂例如但不限於雙酚A型環氧樹脂、雙酚F型環氧樹脂，或反應型環氧稀釋劑等。該反應型環氧稀釋劑例如但不限於單官能基稀釋劑或雙官能基稀釋劑等。該單官能基稀釋劑例如但不限於丁基縮水甘油醚(butyl glycidyl ether)或甲苯酚縮水甘油醚(cresol glycidyl ether)等。該多官能基稀釋劑例如但不限於1,6-己二醇二縮水甘油醚(1,6-hexanediol diglycidyl ether)。較佳地，該液態環氧樹脂的平均分子量範圍為100至400。該液態環氧樹脂的用量是依照選用的脂肪族多胺系材料及/或液態環氧樹脂的平均分子量進行調整，以使該具有酯基及羥基的脂肪胺固化劑中的胺基及羥基含量具有一定量，以利調整該環氧樹脂組成物的固化反應的固化速度以及該環氧樹脂組成物的交聯密度。在本發明的實施例中，以該脂肪族多胺系材料的總量為100重量份計，該液態環氧樹脂的用量範圍為20重量份至45.8重量份。The liquid epoxy resin is, for example, but not limited to, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or a reactive epoxy thinner. The reactive epoxy diluent is, for example, but not limited to, a monofunctional diluent or a difunctional diluent. The monofunctional diluent is, for example, but not limited to, butyl glycidyl ether or cresol glycidyl ether. The polyfunctional diluent is, for example, but not limited to, 1,6-hexanediol diglycidyl ether. Preferably, the average molecular weight of the liquid epoxy resin ranges from 100 to 400. The amount of the liquid epoxy resin is adjusted according to the selected aliphatic polyamine-based material and / or the average molecular weight of the liquid epoxy resin, so that the content of the amine group and the hydroxyl group in the fatty amine curing agent having an ester group and a hydroxyl group is adjusted. It has a certain amount to facilitate adjusting the curing speed of the curing reaction of the epoxy resin composition and the crosslinking density of the epoxy resin composition. In the embodiment of the present invention, based on the total amount of the aliphatic polyamine-based material being 100 parts by weight, the amount of the liquid epoxy resin used ranges from 20 parts by weight to 45.8 parts by weight.
＜丙烯酸酯系材料＞＜ Acrylic material ＞
該丙烯酸酯系材料中的雙鍵能與該脂肪族多胺系材料中的胺基反應，使得該丙烯酸酯系材料能夠固定在該脂肪族多胺系材料上，而減少該脂肪族多胺系材料的揮發性與毒性，並且透過該丙烯酸酯系材料，使得該具有酯基及羥基的脂肪胺固化劑的吸濕性降低而減少發泡問題的產生，此外，還可降低該環氧樹脂組成物的固化反應熱。該丙烯酸酯系材料例如但不限於單官能基丙烯酸酯或多官能基丙烯酸酯等。該單官能基丙烯酸酯例如但不限於丙烯酸-2-苯氧基乙酯(2-phenoxy ethyl acrylate)或2-(2-乙氧基乙氧基)乙基丙烯酸酯[2-(2-ethoxyethoxy) ethyl acrylate]等。該多官能基丙烯酸酯例如但不限於1,6-乙二醇二丙烯酸酯或三羥甲基丙烷三丙烯酸酯(trimethylolpropane triacrylate)等。以該脂肪族多胺系材料的總量為100重量份計，該丙烯酸酯系材料的用量範圍為4重量份至25重量份。該丙烯酸酯系材料與該液態環氧樹脂的重量比值範圍為0.09至1.2。The double bond in the acrylate-based material can react with the amine group in the aliphatic polyamine-based material, so that the acrylate-based material can be fixed on the aliphatic polyamine-based material, and the aliphatic polyamine-based material is reduced. The volatility and toxicity of the material, and through the acrylate-based material, the hygroscopicity of the fatty amine curing agent having an ester group and a hydroxyl group is reduced to reduce the occurrence of foaming problems. In addition, the composition of the epoxy resin can be reduced. The curing reaction is hot. The acrylate-based material is, for example, but not limited to, a monofunctional acrylate or a polyfunctional acrylate. The monofunctional acrylate is, for example, but not limited to, 2-phenoxy ethyl acrylate or 2- (2-ethoxyethoxy) ethyl acrylate [2- (2-ethoxyethoxy ) ethyl acrylate] and so on. The multifunctional acrylate is, for example, but not limited to, 1,6-ethylene glycol diacrylate, trimethylolpropane triacrylate, and the like. Based on the total amount of the aliphatic polyamine-based material being 100 parts by weight, the amount of the acrylate-based material used ranges from 4 to 25 parts by weight. The weight ratio of the acrylate-based material to the liquid epoxy resin ranges from 0.09 to 1.2.
該固化劑用配方還包含促進劑。The curing agent formulation further contains an accelerator.
＜促進劑＞＜ Accelerators ＞
該促進劑可單獨一種使用或混合多種使用，且該促進劑例如但不限於水楊酸、苯酚、苯甲醇，或三(二甲基胺基甲基)苯酚[tris(dimethylaminomethyl)phenol，簡稱DMP-30]等。The accelerator can be used singly or in combination, and the accelerator such as but not limited to salicylic acid, phenol, benzyl alcohol, or tris (dimethylaminomethyl) phenol (DMP for short) -30] and so on.
該固化劑用配方還包含功能試劑。The curing agent formulation also contains a functional agent.
＜功能試劑＞＜ Functional Reagents ＞
該功能試劑能夠用來提升由該環氧樹脂組成物所形成的固化物的特性，例如機械強度(例如硬度)或熱穩定性等。該功能試劑例如但不限於填料或經改質的填料等。The functional reagent can be used to improve the characteristics of the cured product formed from the epoxy resin composition, such as mechanical strength (such as hardness) or thermal stability. The functional reagent is, for example, but not limited to, a filler or a modified filler.
該填料可單獨一種使用或混合多種使用，且該填料例如但不限於碳酸鈣、三氧化二鋁、中空玻璃球，或氣相二氧化矽(fume silica)等。The filler may be used singly or in combination, and the filler is, for example, but not limited to, calcium carbonate, aluminum oxide, hollow glass sphere, or fumed silica.
該經改質的填料是由矽氧烷偶合劑與該填料進行反應所形成。該矽氧烷偶合劑可單獨一種使用或混合多種使用，且該矽氧烷偶合劑例如但不限於γ-縮水甘油氧丙基三甲氧基矽烷，或γ-胺丙基三甲氧基矽烷等。該填料如上所述，故不再贅述。相較於使用填料，該經改質的填料與該固化劑用配方中的各成分或該環氧樹脂組成物中的環氧樹脂組分間具有更佳的相容性，並能讓該環氧樹脂組成物具有儲存穩定性而不會有分層或沉澱等現象，且後續所製得的固化物也能具備更佳的特性。The modified filler is formed by a reaction between a siloxane coupling agent and the filler. The siloxane coupling agent may be used singly or in combination, and the siloxane coupling agent may be, for example, but not limited to, γ-glycidyloxypropyltrimethoxysilane, or γ-aminopropyltrimethoxysilane. The filler is as described above, so it will not be described again. Compared with the use of fillers, the modified fillers have better compatibility with the components in the formulation for the curing agent or the epoxy resin components in the epoxy resin composition, and can make the epoxy The resin composition has storage stability without delamination or precipitation, and the subsequent cured product can also have better characteristics.
＜＜環氧樹脂組成物＞＞＜＜ Epoxy resin composition ＞＞
＜環氧樹脂組分＞＜ Epoxy resin component ＞
[結晶性環氧樹脂][Crystalline epoxy resin]
該結晶性環氧樹脂指的是本身為固態或半固態的環氧樹脂。該結晶性環氧樹脂例如但不限於酚醛型環氧樹脂。該酚醛型環氧樹脂例如但不限於苯酚醛型環氧樹脂(phenol novolac epoxy resin)、甲酚醛型環氧樹脂(cresol novolac epoxy resin)、雙酚A酚醛型環氧樹脂(bisphenol A novolac type epoxy resin)，或具有三個以上官能基的酚醛型環氧樹脂等。The crystalline epoxy resin refers to an epoxy resin which is solid or semi-solid in itself. The crystalline epoxy resin is, for example, but not limited to, a phenolic epoxy resin. The phenolic epoxy resin is, for example, but not limited to, phenol novolac epoxy resin, cresol novolac epoxy resin, and bisphenol A novolac type epoxy resin), or a phenolic epoxy resin having three or more functional groups.
[丙烯酸酯系環氧樹脂][Acrylic epoxy resin]
該丙烯酸酯系環氧樹脂指的是具有丙烯酸酯基及環氧基的環氧樹脂。該丙烯酸酯系環氧樹脂中的丙烯酸酯基的雙鍵能快速地與該具有酯基及羥基的脂肪胺固化劑中的胺基反應，且反應所釋放出來的熱能能夠促使該環氧樹脂組分中的環氧基與該具有酯基及羥基的脂肪胺固化劑中的胺基反應。該丙烯酸酯系環氧樹脂與該結晶性環氧樹脂的重量比值範圍為0.3至2.25。The acrylate-based epoxy resin refers to an epoxy resin having an acrylate group and an epoxy group. The double bond of the acrylate group in the acrylate epoxy resin can quickly react with the amine group in the fatty amine curing agent having an ester group and a hydroxyl group, and the thermal energy released by the reaction can promote the epoxy resin group The epoxy group in the component reacts with the amine group in the fatty amine curing agent having an ester group and a hydroxyl group. The weight ratio of the acrylate-based epoxy resin to the crystalline epoxy resin ranges from 0.3 to 2.25.
該環氧樹脂組分還包含具有多個環氧基的液態環氧樹脂。The epoxy resin component further includes a liquid epoxy resin having a plurality of epoxy groups.
[具有多個環氧基的液態環氧樹脂][Liquid epoxy resin with multiple epoxy groups]
該具有多個環氧基的液態環氧樹脂用來調整該環氧樹脂組成物的黏度以及交聯密度。該具有多個環氧基的液態環氧樹脂例如但不限於雙酚A型環氧樹脂、雙酚F型環氧樹脂，或苯酚醛型環氧樹脂等。The liquid epoxy resin having a plurality of epoxy groups is used to adjust the viscosity and crosslinking density of the epoxy resin composition. The liquid epoxy resin having a plurality of epoxy groups is, for example, but not limited to, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or a phenol novolac type epoxy resin.
該環氧樹脂組分還包含功能試劑。The epoxy resin component also contains a functional agent.
[功能試劑][Functional reagent]
該功能試劑如該固化劑用配方中所述的功能試劑，故不再贅述。The functional reagent is the functional reagent described in the formula for the curing agent, so it will not be described again.
＜具有酯基及羥基的脂肪胺固化劑＞<A fatty amine curing agent having an ester group and a hydroxyl group>
該具有酯基及羥基的脂肪胺固化劑由上述的固化劑用配方經聚合反應後所形成。該固化劑用配方如上所述，故不再贅述。The fatty amine curing agent having an ester group and a hydroxyl group is formed by a polymerization reaction of the aforementioned curing agent formulation. The formulation for the curing agent is as described above, so it will not be described again.
本發明將就以下實施例來作進一步說明，但應瞭解的是，該等實施例僅為例示說明之用，而不應被解釋為本發明實施之限制。The present invention will be further described with reference to the following examples, but it should be understood that these examples are for illustrative purposes only and should not be construed as limiting the implementation of the present invention.
製備例1 具有酯基及羥基的脂肪胺固化劑Preparation example 1 fatty amine curing agent having ester group and hydroxyl group
步驟(a)，將14克的N,N'-二(3-胺基丙基)乙二胺及10克的二伸乙基三胺混合，接著，緩慢加入3克的1,6-乙二醇二丙烯酸酯及8克的雙酚A型環氧樹脂[廠牌：NanYa；型號：NPEL-128；環氧當量(EEW)：184至190；平均分子量：368至380(環氧當量×2)]，並攪拌60分鐘，且將溫度控制在40℃。In step (a), 14 g of N, N'-bis (3-aminopropyl) ethylenediamine and 10 g of diethylene triamine were mixed, and then 3 g of 1,6-ethyl Glycol diacrylate and 8 grams of bisphenol A epoxy resin [brand: NanYa; model: NPEL-128; epoxy equivalent (EEW): 184 to 190; average molecular weight: 368 to 380 (epoxy equivalent × 2)], and stirred for 60 minutes, and the temperature was controlled at 40 ° C.
步驟(b)，然後，加入10克的苯甲醇、2克的水楊酸及8克的苯酚，並升溫至90℃，且於該溫度下攪拌30分鐘。In step (b), 10 g of benzyl alcohol, 2 g of salicylic acid, and 8 g of phenol are added, the temperature is raised to 90 ° C., and the mixture is stirred at this temperature for 30 minutes.
步驟(c)，加入45克經改質的填料，並將溫度控制在60℃，且攪拌60分鐘，其中，該經改質的填料是由矽氧烷偶合劑[廠牌：Momentive；型號：A-1110；成分：一級胺基矽烷(primary amino silane)]進行8小時的水解反應後，加入表面具有羥基的填料，並攪拌反應3小時所形成。In step (c), 45 grams of the modified filler is added, and the temperature is controlled at 60 ° C., and stirred for 60 minutes, wherein the modified filler is a siloxane coupling agent [brand: Momentive; model: A-1110; Ingredients: Primary amino silane] After 8 hours of hydrolysis reaction, a filler having a hydroxyl group on the surface is added, and the reaction is formed by stirring for 3 hours.
步驟(d)，接著，於壓力為小於74cm-Hg的環境下，進行脫泡處理，並將溫度控制在60℃間且於該溫度下攪拌30分鐘。In step (d), a defoaming treatment is performed under an environment with a pressure of less than 74 cm-Hg, and the temperature is controlled between 60 ° C and the temperature is stirred for 30 minutes.
製備例2至6Preparation Examples 2 to 6
該製備例2至6是以與該製備例1相同步驟進行，不同主要在於：各成分的用量，且參閱表1。The preparations 2 to 6 were carried out in the same steps as the preparation 1, except that the amounts of the components were used, and see Table 1.
表1
實施例1 環氧樹脂組成物及固化物Example 1 epoxy resin composition and cured product
將100克的製備例1的具有酯基及羥基的脂肪胺固化劑與100克的環氧樹脂組分利用靜態混合管進行混合，並於0℃進行24小時的固化反應，而形成固化物。該環氧樹脂組分是將30克的結晶性環氧樹脂(廠牌：NanYa；型號：NPPN-442；成分：苯酚醛型環氧樹脂)、35克的丙烯酸酯系環氧樹脂(廠牌：EPON；型號：8111)，以及15克的具有多個環氧基的液態環氧樹脂(廠牌：NanYa；型號：NPPN-631；成分：苯酚醛型環氧樹脂)於60℃至70℃間進行混合並攪拌30分鐘。然後，加入20克經改質的填料，並將溫度控制在60℃至70℃間，且攪拌60分鐘，其中，該經改質的填料如製備例1中所述的經改質的填料。100 g of an aliphatic amine curing agent having an ester group and a hydroxyl group in Preparation Example 1 and 100 g of an epoxy resin component were mixed with a static mixing tube, and a curing reaction was performed at 0 ° C. for 24 hours to form a cured product. The epoxy resin component is 30 g of crystalline epoxy resin (brand: NanYa; model: NPPN-442; composition: phenolic epoxy resin), 35 g of acrylate epoxy resin (brand) : EPON; model: 8111), and 15 grams of liquid epoxy resin (brand: NanYa; model: NPPN-631; composition: phenolic epoxy resin) with multiple epoxy groups at 60 ° C to 70 ° C Mix and stir for 30 minutes. Then, 20 grams of the modified filler was added, and the temperature was controlled between 60 ° C. and 70 ° C., and stirred for 60 minutes, wherein the modified filler was the modified filler described in Preparation Example 1.
實施例2至10Examples 2 to 10
該實施例2至10是以與該實施例1相同步驟進行，不同主要在於：各成分的用量，參閱表2。The examples 2 to 10 are performed in the same steps as in the example 1, except that the amount of each component is shown in Table 2.
比較例1Comparative Example 1
將100克的液態聚硫醇固化劑(廠牌：Toray；型號：QE-340M)、10克的2,4,6-三(二甲基胺基甲基)苯酚，以及30克的碳酸鈣於25℃混合攪拌20分鐘，製成聚硫醇固化劑組分。將該聚硫醇固化劑組分與100克的雙酚A型環氧樹脂(廠牌：NanYa；型號：NPEL-128)利用靜態混合管進行混合，並於0℃進行24小時的固化反應，而形成固化物。100 grams of liquid polythiol curing agent (brand: Toray; model: QE-340M), 10 grams of 2,4,6-tris (dimethylaminomethyl) phenol, and 30 grams of calcium carbonate Mix and stir at 25 ° C for 20 minutes to make a polythiol curing agent component. The polythiol curing agent component was mixed with 100 g of a bisphenol A epoxy resin (brand: NanYa; model: NPEL-128) using a static mixing tube, and a curing reaction was performed at 0 ° C for 24 hours. A cured product is formed.
比較例2Comparative Example 2
將17克的作為脂肪多胺固化劑的N,N'-二(3-胺基丙基)乙二胺、3克的2,4,6-三(二甲基胺基甲基)苯酚，以及30克的碳酸鈣於25℃混合攪拌20分鐘，製成脂肪胺固化劑組分。將該脂肪胺固化劑組分與100克的雙酚A型環氧樹脂(廠牌：NanYa；型號：NPEL-128)利用靜態混合管進行混合，並於0℃進行24小時的固化反應，而形成固化物。17 grams of N, N'-bis (3-aminopropyl) ethylenediamine as a fatty polyamine curing agent, 3 grams of 2,4,6-tris (dimethylaminomethyl) phenol, And 30 grams of calcium carbonate were mixed and stirred at 25 ° C. for 20 minutes to prepare a fatty amine curing agent component. The fatty amine curing agent component was mixed with 100 g of a bisphenol A type epoxy resin (brand: NanYa; model: NPEL-128) using a static mixing tube, and a curing reaction was performed at 0 ° C for 24 hours, and A cured product was formed.
比較例3Comparative Example 3
將100克的製備例2的具有酯基及羥基的脂肪胺固化劑與100克的環氧樹脂組分利用靜態混合管進行混合，並於0℃進行24小時的固化反應，而形成固化物。該環氧樹脂組分包括80克的雙酚A型環氧樹脂(廠牌：NanYa；型號：NPEL-127E)與20克經改質的填料。該經改質的填料如製備例1中所述的經改質的填料。100 g of an aliphatic amine curing agent having an ester group and a hydroxyl group in Preparation Example 2 and 100 g of an epoxy resin component were mixed using a static mixing tube, and a curing reaction was performed at 0 ° C. for 24 hours to form a cured product. The epoxy resin component includes 80 grams of a bisphenol A epoxy resin (brand: NanYa; model: NPEL-127E) and 20 grams of modified filler. The modified filler is the modified filler described in Preparation Example 1.
比較例4Comparative Example 4
將100克的固化劑與100克的環氧樹脂組分利用靜態混合管進行混合，並於0℃進行24小時的固化反應，而形成固化物。該環氧樹脂組分包括30克的結晶性環氧樹脂(廠牌：NanYa；型號：NPPN-442；成分：苯酚醛型環氧樹脂)、35克的丙烯酸酯系環氧樹脂(廠牌：EPON；型號：8111)、15克的具有多個環氧基的液態環氧樹脂(廠牌：NanYa；型號：NPPN-631；成分：苯酚醛型環氧樹脂)，及20克的經改質的填料。該經改質的填料如製備例1中所述的經改質的填料。該固化劑是將25克的二伸乙基三胺、10克的苯甲醇、2克的水楊酸及8克的苯酚混合並升溫到90℃至100℃，且於該溫度下攪拌30分鐘，接著，加入55克的經改質的填料。該經改質的填料如製備例1中所述的經改質的填料。100 g of the curing agent and 100 g of the epoxy resin component were mixed using a static mixing tube, and a curing reaction was performed at 0 ° C. for 24 hours to form a cured product. The epoxy resin component includes 30 grams of crystalline epoxy resin (brand: NanYa; model: NPPN-442; composition: phenolic epoxy resin), 35 grams of acrylate epoxy resin (brand: EPON; model: 8111), 15 grams of liquid epoxy resin with multiple epoxy groups (brand: NanYa; model: NPPN-631; composition: phenolic epoxy resin), and 20 grams of modified Filler. The modified filler is the modified filler described in Preparation Example 1. The curing agent is a mixture of 25 g of diethylene triamine, 10 g of benzyl alcohol, 2 g of salicylic acid and 8 g of phenol, and the temperature is raised to 90 ° C to 100 ° C, and the mixture is stirred at this temperature for 30 minutes. Then, 55 grams of modified filler was added. The modified filler is the modified filler described in Preparation Example 1.
評價項目Evaluation item
玻璃轉移溫度(Tg，單位：℃)量測：為方便描述量測過程，以下以實施例1的固化物進行說明，其餘實施例及比較例則依照該方式進行量測。使用示差掃瞄熱量分析儀(differential scanning calorimeter，簡稱DSC；廠牌：TA Instruments；型號：Q30)對實施例1的固化物進行量測。參數條件為0℃升溫至150℃，且升溫速度為10℃/分鐘。Measurement of glass transition temperature (Tg, unit: ° C): In order to describe the measurement process conveniently, the cured product of Example 1 is used for description below, and the remaining examples and comparative examples are measured in this way. A differential scanning calorimeter (DSC; brand: TA Instruments; model: Q30) was used to measure the cured product of Example 1. The parameter condition is that the temperature rises from 0 ° C to 150 ° C, and the temperature rise rate is 10 ° C / min.
於30℃的環境中的可指觸時間及初固化時間量測：為方便描述量測過程，以下以實施例1進行說明，其餘實施例及比較例則依照該方式進行量測。將實施例1的具有酯基及羥基的脂肪胺固化劑與環氧樹脂組分分別放置於45℃的烘箱中1小時，並將一個具有厚度為0.5cm且直徑為5cm的裂縫的木板置於30℃的環境中1小時。接著，將該具有酯基及羥基的脂肪胺固化劑與該環氧樹脂組分混合並灌注於該木板的裂縫中，然後，開始記錄時間，且使用手指觸摸固化物的表面是否乾燥且不沾黏，並記錄達到乾燥且不沾黏的時間(t1)。Measurement of finger touch time and initial curing time in an environment of 30 ° C: To facilitate the description of the measurement process, the following description is made in Example 1, and the remaining examples and comparative examples are measured in this way. The fatty amine curing agent having the ester group and the hydroxyl group and the epoxy resin component of Example 1 were respectively placed in an oven at 45 ° C. for one hour, and a wooden board having cracks having a thickness of 0.5 cm and a diameter of 5 cm was placed in 1 hour at 30 ° C. Next, the fatty amine curing agent having an ester group and a hydroxyl group is mixed with the epoxy resin component and poured into cracks in the wood board, and then, the recording time is started, and the surface of the cured product is touched with a finger to check whether it is dry and non-sticking. Sticky, and record the time to dry and non-sticky (t1).
於0℃的環境中的可指觸時間及初固化時間量測：為方便描述量測過程，以下以實施例1進行說明，其餘實施例及比較例則依照該方式進行量測。將實施例1的具有酯基及羥基的脂肪胺固化劑與該環氧樹脂組分分別放置於45℃的烘箱中1小時。將一個具有厚度為0.5cm且直徑為5cm的裂縫的木板置於0℃的環境中1小時，接著，將該具有酯基及羥基的脂肪胺固化劑與該環氧樹脂組分混合並灌注於該木板的裂縫中，然後，開始記錄時間，且使用手指觸摸固化物的表面是否乾燥且不沾黏，並記錄達到乾燥且不沾黏的時間(t2)。Measurement of tactile time and initial curing time in an environment of 0 ° C .: To facilitate the description of the measurement process, the following description is made in Example 1, and the remaining examples and comparative examples are measured in this way. The fatty amine curing agent having an ester group and a hydroxyl group of Example 1 and the epoxy resin component were respectively placed in an oven at 45 ° C. for 1 hour. A wooden board having cracks having a thickness of 0.5 cm and a diameter of 5 cm was placed in an environment of 0 ° C. for 1 hour, and then the fatty amine curing agent having an ester group and a hydroxyl group was mixed with the epoxy resin component and poured into In the crack of the wooden board, then, the recording time is started, and the surface of the cured product is touched with a finger to check whether it is dry and non-sticky, and the time to dry and non-sticky is recorded (t2).
穩定性測試：為方便描述量測過程，以下以實施例1進行說明，其餘實施例及比較例則依照該方式進行量測。提供一個具有厚度為0.5cm且直徑為5cm的裂縫的木板。將實施例1的具有酯基及羥基的脂肪胺固化劑與該環氧樹脂組分混合並灌注於該木板的裂縫中，並使該環氧樹脂組分進行固化反應，形成固化物。然後，於1天後，利用一台研磨機將突出於該裂縫的固化物研磨掉，而使該木板表面呈現平整狀態。接著，將該木板置於溫度為45℃且相對溼度為90%的環境中72小時。然後，觀察該固化物是否有膨脹或收縮的現象。當該固化物存在膨脹或收縮現象，表示在高溫高濕下穩定性不佳。○：表示無膨脹及無收縮現象。×：表示有膨脹或有收縮現象。Stability test: In order to facilitate the description of the measurement process, the following description is made in Example 1, and the remaining examples and comparative examples are measured in this way. Provide a wooden board with cracks of 0.5 cm in thickness and 5 cm in diameter. The fatty amine curing agent having an ester group and a hydroxyl group in Example 1 is mixed with the epoxy resin component and poured into cracks in the wood board, and the epoxy resin component is subjected to a curing reaction to form a cured product. Then, after one day, the solidified product protruding from the crack was ground off with a grinder, so that the surface of the wood board was flat. Next, the board was left in an environment having a temperature of 45 ° C and a relative humidity of 90% for 72 hours. Then, it was observed whether the cured product was expanded or contracted. When the cured product has an expansion or contraction phenomenon, it indicates that the stability is not good under high temperature and high humidity. ○: indicates that there is no expansion or shrinkage. ×: indicates expansion or contraction.
硬度量測：為方便描述量測過程，以下以實施例1進行說明，其餘實施例及比較例則依照該方式進行量測。使用蕭氏(shore D)硬度計(廠牌：Teclock；型號：GS702N)對實施例1的固化物進行量測。Hardness measurement: In order to describe the measurement process conveniently, the following description is made in Example 1, and the remaining examples and comparative examples are measured in this way. A Shore D hardness tester (brand: Teclock; model: GS702N) was used to measure the cured product of Example 1.
表2
表3
由表2的實施例1至10及表3的比較例1至4的實驗數據可知，本發明環氧樹脂組成物透過該環氧樹脂組分中的結晶性環氧樹脂及丙烯酸酯系環氧樹脂與該具有酯基及羥基的脂肪胺固化劑特定地相互搭配在30℃以下(特別是在0℃)的環境中使用且灌注於厚度為0.5cm且直徑為5cm的裂縫具有於低溫下薄膜快速固化的優點，且本發明由該環氧樹脂組成物所形成的固化物具有較高的玻璃轉移溫度及硬度。From the experimental data of Examples 1 to 10 in Table 2 and Comparative Examples 1 to 4 in Table 3, it can be seen that the epoxy resin composition of the present invention permeates the crystalline epoxy resin and acrylate epoxy resin in the epoxy resin component. The resin and the fatty amine curing agent having an ester group and a hydroxyl group are specifically matched with each other. The resin is used in an environment of 30 ° C or less (especially 0 ° C) and is poured into a crack having a thickness of 0.5cm and a diameter of 5cm. The film has a film at low temperature. It has the advantages of fast curing, and the cured product formed by the epoxy resin composition has higher glass transition temperature and hardness.
此外，參閱表2的實施例7至10，當該丙烯酸酯系環氧樹脂與該結晶性環氧樹脂的重量比值範圍為0.3至0.86，使得該固化物在高溫高濕環境中不會有膨脹或收縮的現象，而具有不錯的穩定性。In addition, referring to Examples 7 to 10 in Table 2, when the weight ratio of the acrylate-based epoxy resin to the crystalline epoxy resin ranges from 0.3 to 0.86, the cured product does not swell in a high temperature and high humidity environment. Or shrinkage, and has good stability.
綜上所述，本發明透過該具有酯基及羥基的脂肪胺固化劑與該環氧樹脂組分的搭配，使得該環氧樹脂組成物在30℃以下(特別是在0℃)的環境中使用具有於低溫下薄膜快速固化的優點，且由該環氧樹脂組成物所形成的固化物具有高的硬度及玻璃轉移溫度，故確實能達成本發明的目的。In summary, in the present invention, the combination of the fatty amine curing agent having an ester group and a hydroxyl group with the epoxy resin component makes the epoxy resin composition in an environment of 30 ° C or less (especially 0 ° C). The use has the advantages of rapid curing of the film at low temperature, and the cured product formed from the epoxy resin composition has high hardness and glass transition temperature, so it can indeed achieve the purpose of the present invention.
惟以上所述者，僅為本發明的實施例而已，當不能以此限定本發明實施的範圍，凡是依本發明申請專利範圍及專利說明書內容所作的簡單的等效變化與修飾，皆仍屬本發明專利涵蓋的範圍內。However, the above are only examples of the present invention. When the scope of implementation of the present invention cannot be limited by this, any simple equivalent changes and modifications made according to the scope of the patent application and the contents of the patent specification of the present invention are still Within the scope of the invention patent.
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