WO2015076626A1 - Résine novolaque, agent de durcissement la contenant, et composition de résine époxy, et résine époxy novolaque, leur procédé de préparation, et composition de résine époxy contenant la résine époxy novolaque - Google Patents

Résine novolaque, agent de durcissement la contenant, et composition de résine époxy, et résine époxy novolaque, leur procédé de préparation, et composition de résine époxy contenant la résine époxy novolaque Download PDF

Info

Publication number
WO2015076626A1
WO2015076626A1 PCT/KR2014/011291 KR2014011291W WO2015076626A1 WO 2015076626 A1 WO2015076626 A1 WO 2015076626A1 KR 2014011291 W KR2014011291 W KR 2014011291W WO 2015076626 A1 WO2015076626 A1 WO 2015076626A1
Authority
WO
WIPO (PCT)
Prior art keywords
epoxy resin
formula
novolak
resin
novolac
Prior art date
Application number
PCT/KR2014/011291
Other languages
English (en)
Korean (ko)
Inventor
강현수
이상민
소영수
성상엽
Original Assignee
코오롱인더스트리 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020130143066A external-priority patent/KR101399258B1/ko
Priority claimed from KR1020130143056A external-priority patent/KR101472221B1/ko
Application filed by 코오롱인더스트리 주식회사 filed Critical 코오롱인더스트리 주식회사
Publication of WO2015076626A1 publication Critical patent/WO2015076626A1/fr

Links

Images

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
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • 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
    • C08G59/62—Alcohols or phenols

Definitions

  • the present invention relates to a novolak resin, a curing agent and an epoxy resin composition comprising the same, and more particularly, a novolak resin having a low viscosity while having excellent hygroscopic resistance and high thermal stability at high temperature, a novolak curing agent comprising the same And an epoxy resin composition.
  • the present invention relates to a novolak epoxy resin, a method for producing the same and an epoxy resin composition comprising a novolak epoxy resin, and more particularly, a furnace having a low viscosity and a high thermal stability and high moisture absorption resistance at high temperatures.
  • the present invention relates to a epoxy resin composition comprising a novolak epoxy resin, a method for producing the same, and the novolak epoxy resin.
  • Copper clad laminates (CCL) used for printed circuit boards are made by attaching copper foil to one or both sides of laminated insulating plates composed of various insulating materials and binders. As a result, requirements such as lead-free have been increased, and accordingly, the demand for copper-clad laminates requiring an insulating material having high glass transition temperature characteristics has recently increased considerably.
  • the novolak resin which is conventionally applied as a curing agent, contains a large amount of oligomer product having low polymerization degree in the polymerization process.
  • the component in which two monomers were polymerized has few reactors, and it reduces the hardening density of a final hardened
  • the curing is excessively accelerated, the surface is hardened before the solvent is sufficiently volatilized in the prepreg manufacturing process, so that a large amount of the solvent remains in the prepreg. The glass transition temperature is greatly reduced.
  • the main object of the present invention is to provide a novolak resin having low viscosity and remarkably improved high thermal stability and hygroscopic resistance at a high temperature of 280 ° C. or higher, and a method for producing the same.
  • the present invention also provides a novolak curing agent comprising a low viscosity novolak resin having excellent hygroscopic resistance and high thermal stability at high temperatures.
  • the present invention also provides an epoxy resin composition and a cured product of the epoxy resin composition capable of simultaneously improving hygroscopic resistance and thermal stability at high temperature by including the novolak resin as a curing agent.
  • the main object of the present invention is to provide a novolak epoxy resin and a method for producing the same, which has a low viscosity and remarkably improved high thermal stability and hygroscopicity at a high temperature of 280 ° C or higher.
  • the present invention also provides an epoxy resin composition comprising a novolak epoxy resin having low viscosity while having excellent hygroscopic resistance and high thermal stability at high temperature, and a cured product of the epoxy resin composition.
  • n is an integer of 0 to 5
  • X is -H, -Br, -C (CH 3 ) 2 C 6 H 4 OH or an alkyl group having 1 to 12 carbon atoms.
  • R is -CH 2-
  • X may be characterized in that -C (CH 3 ) 2 C 6 H 4 OH or -CH 3 .
  • a condensation reaction between the phenolic monomer and the formaldehyde-based monomer under an acid catalyst, the condensation water is removed to a furnace comprising a compound represented by an integer of n 0 to 5 in the formula Synthesizing a volac resin;
  • a heating step of heating and melting a novolak resin obtained from the synthesis step, wherein the novolak resin including a compound represented by an integer of n 0 to 5 in Formula 1 above a softening point;
  • n is an integer of 0 to 5
  • X is -H, -Br, -C (CH 3 ) 2 C 6 H 4 OH or an alkyl group having 1 to 12 carbon atoms.
  • the high vacuum distillation apparatus in step (c) may be characterized in that it is set to 200 to 280 °C under a pressure of 0.001 to 1.5 mbar.
  • Another embodiment of the present invention provides a novolak curing agent comprising the novolak resin.
  • the epoxy resin provides the epoxy resin composition and the cured product of the epoxy resin composition comprising the novolac curing agent.
  • n is an integer of 0 to 5
  • X is -H, -Br, -CF 3 , an alkyl group having 1 to 12 carbon atoms or to be.
  • R is -CH 2-
  • X is -H, Or -CH 3 .
  • the novolak epoxy resin may be characterized in that the PDI is 1.0 to 3.0.
  • the novolak epoxy resin may be characterized in that the melt viscosity at 160 °C 30 to 3,000cps.
  • the novolak epoxy resin may be characterized in that the softening point is 40 to 130 °C.
  • n is an integer of 0 to 5
  • X is -H, -Br, -CF 3 , an alkyl group having 1 to 12 carbon atoms or to be.
  • the high vacuum distillation apparatus in the step (c) may be characterized in that it is set to 200 to 280 °C under a pressure of 0.001 to 0.5 mbar.
  • Another embodiment of the present invention provides an epoxy resin composition comprising the novolac epoxy resin and a cured product of the epoxy resin composition.
  • a novolak resin and a novolak epoxy resin having low viscosity and high thermal stability and high hygroscopicity at high temperatures can be easily produced by a simple method, and novolak resin can be used without additional solvent. And it is possible to reduce the viscosity of the novolac epoxy resin can be useful economically, environmentally friendly.
  • Example 1 is a GPC graph of a bisphenol novolak resin obtained in Comparative Example 1-1 and a bisphenol novolak resin obtained in Example 1-1.
  • Example 3 is a GPC graph of a bisphenol novolac epoxy resin obtained in Example 4-1 of the present invention.
  • Example 4 is a GPC graph of a phenol novolac epoxy resin obtained in Example 6-1 of the present invention.
  • n is an integer of 0 to 5
  • X is -H, -Br, -C (CH 3 ) 2 C 6 H 4 OH or an alkyl group having 1 to 12 carbon atoms.
  • R is -CH 2-
  • X is -C (CH 3 ) 2 C 6 H 4 OH or -CH 3 It is in terms of hygroscopicity and heat resistance and workability desirable.
  • n 0 in which only two monomers are polymerized
  • the novolak resin of the present invention can achieve the improvement of the average number of functional groups in the molecule for improving the curing density required in the final cured product, and high heat resistance without including the polymer region, thereby copper clad laminate (Copper Clad It is possible to suppress the generation of micro-void generated during the manufacture of laminate (CCL) and to exhibit excellent hygroscopic resistance and high thermal stability at high temperature (above 280 ° C).
  • the compatibility of the resin and the wettability to the glass fiber can be improved.
  • the melt viscosity at 180 ° C is preferably 100 to 3,000 cps.
  • PDI is 1.0 to At the same time as 3.0
  • the softening point of 80 ° C or higher prevents the blocking of the resin, that is, the phenomenon of agglomeration in an environment with high temperature to high humidity, such as in summer, and excellent hygroscopicity and high temperature. High thermal stability can be ensured, and by making it 160 degrees C or less, melting of resin can be made easy and workability can be improved.
  • n is an integer of 0 to 5
  • X is -H, -Br, -C (CH 3 ) 2 C 6 H 4 OH or an alkyl group having 1 to 12 carbon atoms.
  • the method for producing a novolak resin according to the present invention synthesizes a novolak resin of a repeating unit represented by Chemical Formula 1 by condensation reaction between a phenolic monomer and a formaldehyde monomer under an acid catalyst and removal of the condensation water.
  • the synthesis of the novolak resin can be used without limitation, as long as it is a method capable of synthesizing the novolak resin, wherein the acid catalyst is generally not limited to use as long as it is a catalyst that can be used for the synthesis of novolak resin,
  • the reaction time can be carried out for 2 to 6 hours.
  • the temperature and pressure of the high vacuum distillation apparatus are 200 to 280 ° C. and 0.001 to 1.5 mbar, respectively.
  • the temperature of the high vacuum distillation unit is less than 200 ° C., only novolac resin of the appropriate molecular weight cannot be efficiently extracted, and the temperature is 280 ° C. If exceeded, it may cause thermal deformation or deterioration of the novolak resin due to high temperature.
  • the resin of the polymer region may also be separated together, and only novolac resins having an appropriate molecular weight may be taken out. Since only the resin having a molecular weight cannot be efficiently extracted, there is a problem in that separation efficiency is lowered.
  • Such a method for producing a novolak resin according to the present invention can be easily and conveniently produced through the polymerization degree and molecular weight control of the resin, while having excellent hygroscopic resistance and thermal stability, can be used as a low viscosity curing agent.
  • the present invention relates to a novolak curing agent containing the novolak resin.
  • Novolak resins prepared as described above may be particularly useful as novolak curing agents. When used as a novolac curing agent, it may be used alone or in combination with other curing agents.
  • One example of another curing agent is preferably a curing agent, and novolak, cresol novolak, and the like may also be possible. It is preferable to use at least 5% by weight or more of the total curing agent in combination with other curing agents in view of excellent hygroscopic resistance and thermal stability at high temperatures.
  • the epoxy resin In another aspect, the present invention, the epoxy resin; And an epoxy resin composition comprising the novolac curing agent and a cured product of the epoxy resin composition.
  • Epoxy resin composition according to the present invention by containing a novolak of the polymerization degree and molecular weight of the resin as a curing agent, while having a good solvent solubility compared to the conventional epoxy temporary composition, it is possible to balance the excellent hygroscopic resistance and thermal stability at high temperatures have.
  • the epoxy resin may be applied as long as it is a common epoxy resin, preferably an epoxy resin having two or more glycidyl groups and having an epoxy equivalent (EEW) of 150 to 300 g / eq.
  • the epoxy resin composition according to the present invention may include a novolak curing agent in an amount of 5 to 95 wt% based on the total weight of the composition in consideration of hygroscopic resistance, thermal stability, viscosity, and the like. If the novolac curing agent is added in an amount of less than 5% by weight based on the total weight of the composition, the effect is insignificant, and when added in excess of 95% by weight, the degree of curing may decrease.
  • the epoxy resin composition according to the present invention satisfies dimensional stability at high temperature, heat resistance, hygroscopicity, and the like, and is excellent in compatibility with other resins, and is used for sealing materials and moldings used for copper-clad laminates and electronic components used in printed circuit boards. It is possible to provide a cured product that can implement a balanced property suitable for the material, molding materials, adhesives, materials for electrical insulating paint, and the like.
  • n is an integer of 0 to 5
  • X is -H, -Br, -CF 3 , an alkyl group having 1 to 12 carbon atoms or to be.
  • Novolak epoxy resin of the present invention in the formula 2 R is -CH 2-
  • X is Or -CH 3 bisphenol novolac epoxy resin, which is preferable in view of workability and thermal properties in the production of copper-clad laminates.
  • n Compared to the conventional novolak epoxy resin having the same weight average molecular weight, by including the content of the compound of 0 to 2.8% by weight or less, or with no weight average molecular weight of 700 to 5,000 g / mol, It is possible to greatly improve the hygroscopic resistance, thermal stability and curing density.
  • an epoxy curing agent such as novolac, imidazole, amine, or the like
  • the novolac epoxy resin of the present invention can achieve the improvement of the average number of functional groups in the molecule for improving the curing density required in the final cured product and high heat resistance without including the polymer region, thereby copper foil laminated plate (Copper) It is possible to suppress the generation of micro-void generated during the production of clad laminate (CCL), and to exhibit excellent hygroscopic resistance and high thermal stability at high temperature (above 280 ° C).
  • PDI polydispersity index
  • the compatibility and wettability with respect to the glass fiber can be improved at the time of varnish blending of the resin.
  • a novolak-based polymer and epiclohydrin monomers under a basic catalyst in a poly / condensation reaction, and remove the condensation water and the salt formed by the integer of n 0 to 5 in the formula Synthesis step of synthesizing a novolac epoxy resin comprising a compound represented by;
  • a heating step of heating and melting a novolak epoxy resin obtained from the synthesis step, the compound represented by an integer of n 0 to 5 in Formula 2, above a softening point;
  • n is an integer of 0 to 5
  • X is -H, -Br, -CF 3 , an alkyl group having 1 to 12 carbon atoms or to be.
  • the method for producing an epoxy resin according to the present invention includes a compound of a repeating unit represented by the formula (2) by performing a poly / condensation reaction of a phenol novolak-based polymer and an epichlorohydrin monomer under a basic catalyst and removing the condensation water produced therein.
  • An epoxy resin is synthesized.
  • the step of synthesizing the epoxy resin can be used without limitation as long as it is a method capable of synthesizing the epoxy resin, and preferably, by the poly / condensation reaction of the phenol novolak-based polymer and the epichlorohydrin monomer under a basic catalyst. Can be done. At this time, the polycondensation reaction time may be performed for 2 to 6 hours.
  • Sodium hydroxide (NaOH) may be preferably used as the basic catalyst, and sodium hydroxide used as the catalyst is suitable for discoloration, minimization of by-product generation, and reaction rate of a resin prepared at a concentration of 30 to 60 wt%, and a phenol furnace. It is preferable to use the rockac polymer, the epichlorohydrin monomer and the basic catalyst in a molar ratio of 1: 3.5 to 5.5 mol: 0.9 to 1.5 mol.
  • the synthesized epoxy resin is heated and melted above the softening point so as to be easily introduced into a high vacuum distillation apparatus.
  • the softening point of the phenol epoxy resin is different depending on the epoxy resin, but is generally 40 to 80 °C. Softening points above or below were measured at a temperature rise rate of 2 / min. Using a FP90 instrument from METTLER TOLEDO.
  • the temperature and pressure of the main body of the high vacuum distillation apparatus can be set appropriately.
  • Such a method for producing a novolac epoxy resin according to the present invention can be easily and simply produced through the polymerization degree and molecular weight control of the produced resin, a low viscosity, excellent thermal stability and high moisture resistance at high temperatures.
  • This invention relates to the epoxy resin composition containing the said novolak epoxy resin, and the hardened
  • the epoxy resin composition according to the present invention includes a novolak epoxy resin having a controlled degree of polymerization and a molecular weight, thereby achieving a good solvent solubility compared to conventional epoxy temporary compositions, and achieving improved thermal stability and hygroscopic resistance at a higher temperature. .
  • the epoxy resin composition according to the present invention may include 5 to 95% by weight of novolak epoxy resin, based on the total weight of the composition in consideration of thermal stability, hygroscopicity, viscosity, and the like. If the novolac epoxy resin is added in an amount of less than 5% by weight based on the total weight of the composition, the effect is insignificant, and when it is added in excess of 95% by weight, adhesion characteristics may be lowered.
  • the epoxy resin composition according to the present invention satisfies dimensional stability at high temperature, heat resistance, hygroscopicity, and the like, and has excellent flowability of resin, sealing materials, molding materials, and molds used for copper-clad laminates and electronic components used in printed circuit boards. It is possible to provide a cured product capable of achieving a balance of properties suitable for materials, adhesives, materials for electrical insulating coating, and the like.
  • the bisphenol A novolac resin obtained in Comparative Example 1-1 was heated to 170 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 200 ° C. and a pressure of 1.7 mbar, 60 After operating for minutes, the low molecular weight component contained in the resin was removed to prepare a bisphenol A novolac resin.
  • VTA high vacuum distillation apparatus
  • the bisphenol A novolak resin obtained in Comparative Example 1-1 was heated to 170 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 245 ° C. and a pressure of 1.7 mbar, 60 After operating for minutes, the low molecular weight component contained in the resin was removed to prepare a bisphenol A novolac resin.
  • VTA high vacuum distillation apparatus
  • the bisphenol A novolak resin obtained in Comparative Example 1-1 was heated to 170 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 245 ° C. and a pressure of 1.7 mbar, 60 After operating for minutes, the low molecular weight component contained in the resin was removed to prepare a bisphenol A novolac resin.
  • VTA high vacuum distillation apparatus
  • the bisphenol A novolac resin obtained in Comparative Example 1-1 was heated to 180 ° C. to be in a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 255 ° C. and a pressure of 1.25 mbar. After operating for minutes, the low molecular weight component contained in the resin was removed to prepare a bisphenol A novolac resin.
  • VTA high vacuum distillation apparatus
  • the bisphenol A novolac resin obtained in Comparative Example 1-1 was heated to 180 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 260 ° C. and a pressure of 1.20 mbar, 60 After operating for minutes, the low molecular weight component contained in the resin was removed to prepare a bisphenol A novolac resin.
  • VTA high vacuum distillation apparatus
  • the phenol novolak resin obtained in Comparative Example 2-1 was heated to 160 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 240 ° C. and a pressure of 1.7 mbar, and then operated for 60 minutes. Then, the low molecular weight component contained in the resin was removed to prepare a phenol novolak resin.
  • VTA high vacuum distillation apparatus
  • the phenol novolak resin obtained in Comparative Example 2-1 was heated to 160 ° C. to be in a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 235 ° C. and a pressure of 1.55 mbar, and operated for 60 minutes. Then, the low molecular weight component contained in the resin was removed to prepare a phenol novolak resin.
  • VTA high vacuum distillation apparatus
  • the phenol novolak resin obtained in Comparative Example 2-1 was heated to 170 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 240 ° C. and a pressure of 1.50 mbar, and then operated for 60 minutes. Then, the low molecular weight component contained in the resin was removed to prepare a phenol novolak resin.
  • VTA high vacuum distillation apparatus
  • the phenol novolak resin obtained in Comparative Example 2-1 was heated to 170 ° C. to be in a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 240 ° C. and a pressure of 1.45 mbar, and operated for 60 minutes. Then, the low molecular weight component contained in the resin was removed to prepare a phenol novolak resin.
  • VTA high vacuum distillation apparatus
  • the phenol novolak resin obtained in Comparative Example 2-1 was heated to 170 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 240 ° C. and a pressure of 1.40 mbar, and then operated for 60 minutes. Then, the low molecular weight component contained in the resin was removed to prepare a phenol novolak resin.
  • VTA high vacuum distillation apparatus
  • the phenol novolak resin obtained in Comparative Example 3-1 was heated to 170 ° C. to be in a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 245 ° C. and a pressure of 1.70 mbar, and then operated for 60 minutes. Then, the low molecular weight component contained in the resin was removed to prepare a phenol novolak resin.
  • VTA high vacuum distillation apparatus
  • Phenolic obtained in Comparative Example 3-1 The novolak resin was heated to 170 ° C. to make it molten, and then put into a high vacuum distillation apparatus (VTA, Germany) at a temperature of 240 ° C. and a pressure of 1.60 mbar, and operated for 60 minutes.
  • the phenol novolak resin was prepared by removing the molecular weight component.
  • the phenol novolak resin obtained in Comparative Example 3-1 was heated to 180 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 250 ° C. and a pressure of 0.25 mbar, and then operated for 60 minutes. Then, the low molecular weight component contained in the resin was removed to prepare a phenol novolak resin.
  • VTA high vacuum distillation apparatus
  • the novolak resin obtained in Comparative Example 3-1 was heated to 180 ° C. to a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 250 ° C. and a pressure of 0.15 mbar, and operated for 60 minutes. Next, the low molecular weight component contained in the resin was removed to prepare a phenol novolak resin.
  • VTA high vacuum distillation apparatus
  • the bisphenol A novolac epoxy resin obtained in Comparative Example 6-1 was heated to 160 ° C. to a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 215 ° C. and a pressure of 1.51 mbar. After operating for minutes, the low molecular weight component contained in the resin was removed to prepare a bisphenol A novolac epoxy resin.
  • VTA high vacuum distillation apparatus
  • the bisphenol A novolac epoxy resin obtained in Comparative Example 6-1 was heated to 160 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 195 ° C. and a pressure of 0.51 mbar. After operating for minutes, the low molecular weight component contained in the resin was removed to prepare a bisphenol A novolac epoxy resin.
  • VTA high vacuum distillation apparatus
  • the bisphenol A novolac epoxy resin obtained in Comparative Example 6-1 was heated to 160 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 255 ° C. and a pressure of 0.50 mbar. After operating for minutes, the low molecular weight component contained in the resin was removed to prepare a bisphenol A novolac epoxy resin.
  • VTA high vacuum distillation apparatus
  • the bisphenol A novolac epoxy resin obtained in Comparative Example 6-1 was heated to 160 ° C. to a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 255 ° C. and a pressure of 0.15 mbar, 60 After operating for minutes, the low molecular weight component contained in the resin was removed to prepare a bisphenol A novolac epoxy resin.
  • VTA high vacuum distillation apparatus
  • the bisphenol A novolac epoxy resin obtained in Comparative Example 7-1 was heated to 160 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 250 ° C. and a pressure of 0.40 mbar, 60 After operating for minutes, the low molecular weight component contained in the resin was removed to prepare a bisphenol A novolac epoxy resin.
  • VTA high vacuum distillation apparatus
  • the bisphenol A novolac epoxy resin obtained in Comparative Example 7-1 was heated to 170 ° C. to a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 250 ° C. and a pressure of 0.30 mbar. After operating for minutes, the low molecular weight component contained in the resin was removed to prepare a bisphenol A novolac epoxy resin.
  • VTA high vacuum distillation apparatus
  • the bisphenol A novolac epoxy resin obtained in Comparative Example 7-1 was heated to 170 ° C. to a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 255 ° C. and a pressure of 0.15 mbar. After operating for minutes, the low molecular weight component contained in the resin was removed to prepare a bisphenol A novolac epoxy resin.
  • VTA high vacuum distillation apparatus
  • the phenol novolac epoxy resin obtained in Comparative Example 8-1 was heated to 150 ° C. to a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 190 ° C. and a pressure of 1.65 mbar, followed by 60 minutes. After the operation, the phenol novolac epoxy resin was prepared by removing the low molecular weight component contained in the resin.
  • VTA high vacuum distillation apparatus
  • the phenol novolac epoxy resin obtained in Comparative Example 8-1 was heated to 150 ° C. to a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 240 ° C. and a pressure of 1.75 mbar, followed by 60 minutes. After the operation, the phenol novolac epoxy resin was prepared by removing the low molecular weight component contained in the resin.
  • VTA high vacuum distillation apparatus
  • the phenol novolac epoxy resin obtained in Comparative Example 8-1 was heated to 150 ° C. to a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 250 ° C. and a pressure of 0.5 mbar, followed by 60 minutes. After the operation, the phenol novolac epoxy resin was prepared by removing the low molecular weight component contained in the resin.
  • VTA high vacuum distillation apparatus
  • the phenol novolac epoxy resin obtained in Comparative Example 8-1 was heated to 160 ° C. to a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 255 ° C. and a pressure of 0.45 mbar, followed by 60 minutes. After the operation, the phenol novolac epoxy resin was prepared by removing the low molecular weight component contained in the resin.
  • VTA high vacuum distillation apparatus
  • the phenol novolac epoxy resin obtained in Comparative Example 8-1 was heated to 160 ° C. to a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 260 ° C. and a pressure of 0.3 mbar, followed by 60 minutes. After the operation, the phenol novolac epoxy resin was prepared by removing the low molecular weight component contained in the resin.
  • VTA high vacuum distillation apparatus
  • the phenol novolac epoxy resin obtained in Comparative Example 8-1 was heated to 160 ° C. to a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 270 ° C. and a pressure of 0.15 mbar, followed by 60 minutes. After the operation, the phenol novolac epoxy resin was prepared by removing the low molecular weight component contained in the resin.
  • VTA high vacuum distillation apparatus
  • the novolac epoxy resin obtained in Comparative Example 9-1 was heated to 170 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 255 ° C. and a pressure of 1.75 mbar, followed by 60 minutes. After operation, a low molecular weight component contained in the resin was removed to prepare a cresol novolac epoxy resin.
  • VTA high vacuum distillation apparatus
  • the novolac epoxy resin obtained in Comparative Example 9-1 was heated to 170 ° C. to be in a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 195 ° C. and a pressure of 0.55 mbar, for 60 minutes. After operation, a low molecular weight component contained in the resin was removed to prepare a cresol novolac epoxy resin.
  • VTA high vacuum distillation apparatus
  • the novolak epoxy resin obtained in Comparative Example 9-1 was heated to 170 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 255 ° C. and a pressure of 0.51 mbar, followed by 60 minutes. After operation, a low molecular weight component contained in the resin was removed to prepare a cresol novolac epoxy resin.
  • VTA high vacuum distillation apparatus
  • the novolak epoxy resin obtained in Comparative Example 9-1 was heated to 170 ° C. to a molten state, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 255 ° C. and a pressure of 0.31 mbar, for 60 minutes. After operation, a low molecular weight component contained in the resin was removed to prepare a cresol novolac epoxy resin.
  • VTA high vacuum distillation apparatus
  • the novolak epoxy resin obtained in Comparative Example 9-1 was heated to 170 ° C. to be molten, and then charged into a high vacuum distillation apparatus (VTA, Germany) having a temperature of 260 ° C. and a pressure of 0.15 mbar for 60 minutes. After operation, a low molecular weight component contained in the resin was removed to prepare a cresol novolac epoxy resin.
  • VTA high vacuum distillation apparatus
  • Polystyrene reduced weight average molecular weight (Mw) and number average molecular weight (Mn) were determined by gel permeation chromatography (GPC) (Waters: Waters707).
  • the polymer to be measured was dissolved in tetrahydrofuran to a concentration of 4000 ppm, and 100 was injected into GPC.
  • the mobile phase of GPC used tetrahydrofuran and was introduced at a flow rate of 1.0 mL / min, and the analysis was performed at 35 ° C.
  • the column connected four Waters HR-05,1,2,4E in series.
  • the detector was measured at 35 ° C using RI and PAD Detecter.
  • PDI polydispersity index
  • GPC Gel permeation chromatography
  • the viscosity of the fully melted resin at 180 ° C. was measured using a Brookfield Viscometer (CAP 2000+).
  • Bisphenol A type Epoxy resin (KOLON INDUSTRY, KES-9361A75) having an epoxy equivalent weight (EEW) of 187 and a curing agent (the novolak resins of the Examples and Comparative Examples) were mixed in an equivalent ratio of 1: 1, and then used as a curing accelerator.
  • Laminates 400 mm x 400 mm x 0.75 mm
  • the varnish and prepreg (the semi-cured varnish in the prepreg) were shaken off. Gel time of making powder) was measured on a hot plate heated to 171 °C (use amount, varnish: 0.2cc, prepreg: 20mg).
  • the gel time of the varnish and the prepreg was measured on a hot plate heated to 171 °C (usage, varnish: 0.2cc, prepreg: 20 mg).
  • the copper-clad laminate obtained in (5) was cut to 6.35 mm ⁇ 6.35 mm ⁇ 0.75 mm (thickness), and the specimens were cut and dried in an oven at 105 ° C. for 2 hours to remove pollutants such as moisture, and then the Z-axis thermal expansion coefficient was measured by a thermal analyzer.
  • TMA TA Instrument Co., Q400
  • the copper-clad laminate obtained in (5) was cut into 50 mm ⁇ 05 mm ⁇ 0.75 mm (thickness) to obtain five specimens, which were then etched (etched) with FeCl 3 to completely peel the copper foil, followed by etching solution and residual water. Water was completely removed and dried in an oven at 105 ° C. for 2 hours to completely remove residual material. After removing the remaining material, put the specimens into a Pressure Cooker Test (PCT) chamber set at 121 ° C and 0.22 MPa, and hold them for 90 minutes. Then, the moisture on the specimens is removed, and the mass change rate before and after moisture absorption is calculated by the following equation. Calculated from 1.
  • PCT Pressure Cooker Test
  • the copper-clad laminate obtained in (5) was cut to 6.35 mm ⁇ 6.35 mm ⁇ 0/75 mm (thickness), and the specimens were cut and dried in an oven at 105 ° C. for 2 hours to remove pollutants such as moisture, and then a thermal analyzer (TMA, TA Instrument Q400) was used. In the measurement, the temperature was raised from 40 ° C. to 288 ° C. at 0 ° C./min, and then the time taken for specimen peeling while maintaining isothermal at 288 ° C. was measured.
  • TMA thermal analyzer
  • 'peeling' means not reversibly returning to its original size after rapid volume expansion, and if the measured value is 10 minutes or more, it is 'good', if it is within 5 minutes, 'normal', and if it is 1 minute or less, Marked as bad.
  • the novolak resin of the embodiment according to the present invention has a low viscosity characteristic compared to the novolak resin of the comparative example, and thermal stability such as low thermal expansion, high glass transition temperature, heat resistance at high temperature and the like. It was confirmed that the hygroscopicity was significantly increased.
  • the bisphenol novolak resins from which the low molecular weights of Examples 1-1 and 1-2 were removed were compared with the phenol novolak resins (Examples 2-1 to 2-3) in measuring glass transition temperature and gel time after curing. It was confirmed that the improvement.
  • n 0 content (% by weight) Mw (g / mol) PDI Melt viscosity (cps) Softening Point (°C) Gel time (sec.) Tg after curing (°C) Thermal stability (T288) CTE (%) Absorption rate (wt%) Comparative Example 6-1 18.56 2300 2.88 1678 65 126 225 Bad 2.58 0.35 Comparative Example 6-2 8.7 2990 2.72 1876 80 118 232 usually 2.57 0.33 Comparative Example 6-3 6.8 3010 2.68 2135 83 121 237 usually 2.58 0.32 Example 4-1 2.8 2945 2.32 2235 95 118 268 Good 2.23 0.23 Example 4-2 1.3 3068 2.28 2356 95 118 272 Good 2.22 0.21 Comparative Example 7-1 13.5 4163 4.04 2376 80.3 116 247 usually 2.76 0.34
  • Example 5-2 1.1 4757 2.87 2888 105 121 292 Good 2.20
  • the novolac epoxy resin of the embodiment has a low viscosity characteristics compared to the epoxy resin of the comparative example, thermal stability such as low thermal expansion, high glass transition temperature, heat resistance at high temperature and moisture absorption resistance This markedly increased.
  • the bisphenol A novolac epoxy resin from which the low molecular weights of Examples 4-1 to 5-3 were removed was added to the phenol novolac epoxy resin (Examples 6-1 to 6-4) and cresol novolac epoxy resin (Example 7). It was confirmed that the glass transition temperature and the gel time measurement after curing were improved from -1 and 7-2).
  • the present invention can easily produce a novolak resin and a novolak epoxy resin having a low viscosity and high thermal stability at high temperature (above 280 ° C.) and excellent hygroscopicity by a simple method, and can be produced without using a solvent. Since the viscosity of the volac epoxy resin can be reduced, it can be economically and environmentally friendly.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Epoxy Resins (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

La présente invention concerne une résine novolaque, un agent de durcissement la contenant, et une composition de résine époxy, et plus spécifiquement : une résine novolaque dont le degré de polymérisation et le poids moléculaire sont contrôlés pour se situer dans des plages spécifiques afin d'améliorer considérablement la stabilité thermique élevée à une température élevée et la résistance à l'humidité tout en ayant une faible viscosité; un agent de durcissement de novolaque la contenant; et une composition de résine époxy. De plus, la présente invention concerne une résine époxy novolaque, son procédé de préparation, et une composition de résine époxy contenant la résine époxy novolaque, et plus spécifiquement, fournit: une résine époxy novolaque dont le degré de polymérisation et le poids moléculaire sont contrôlés pour se situer dans des plages spécifiques afin d'améliorer considérablement la stabilité thermique élevée à une température élevée et la résistance à l'humidité tout en ayant une faible viscosité; son procédé de préparation; et une composition de résine époxy contenant la résine époxy novolaque.
PCT/KR2014/011291 2013-11-22 2014-11-21 Résine novolaque, agent de durcissement la contenant, et composition de résine époxy, et résine époxy novolaque, leur procédé de préparation, et composition de résine époxy contenant la résine époxy novolaque WO2015076626A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR1020130143066A KR101399258B1 (ko) 2013-11-22 2013-11-22 노볼락 에폭시 수지, 그 제조방법 및 노볼락 에폭시 수지를 포함하는 에폭시 수지 조성물
KR10-2013-0143066 2013-11-22
KR1020130143056A KR101472221B1 (ko) 2013-11-22 2013-11-22 노볼락 수지, 이를 포함하는 경화제 및 에폭시 수지 조성물
KR10-2013-0143056 2013-11-22

Publications (1)

Publication Number Publication Date
WO2015076626A1 true WO2015076626A1 (fr) 2015-05-28

Family

ID=53179819

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2014/011291 WO2015076626A1 (fr) 2013-11-22 2014-11-21 Résine novolaque, agent de durcissement la contenant, et composition de résine époxy, et résine époxy novolaque, leur procédé de préparation, et composition de résine époxy contenant la résine époxy novolaque

Country Status (2)

Country Link
TW (1) TW201520245A (fr)
WO (1) WO2015076626A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07316266A (ja) * 1994-05-26 1995-12-05 Matsushita Electric Works Ltd 封止用エポキシ樹脂成形材料及び半導体装置
JPH08165328A (ja) * 1994-12-14 1996-06-25 Toto Kasei Co Ltd 低誘電性エポキシ樹脂組成物
KR100444348B1 (ko) * 1996-02-09 2005-02-24 군에이 가가쿠 고교 가부시끼가이샤 에폭시수지,에폭시수지조성물및이의경화물
KR100697256B1 (ko) * 2005-07-06 2007-03-22 주식회사 두산 인쇄회로기판(ｐｃｂ)용 에폭시 수지 조성물, 이를이용하여 제조된 프리프레그 및 동박 적층판
JP2009096894A (ja) * 2007-10-17 2009-05-07 Showa Highpolymer Co Ltd 低分子量ノボラック樹脂、その製造方法およびそれを使用した熱硬化性樹脂組成物
KR100995678B1 (ko) * 2008-09-01 2010-11-22 주식회사 코오롱 페놀 노볼락 수지, 페놀 노볼락 에폭시 수지 및 에폭시 수지 조성물

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07316266A (ja) * 1994-05-26 1995-12-05 Matsushita Electric Works Ltd 封止用エポキシ樹脂成形材料及び半導体装置
JPH08165328A (ja) * 1994-12-14 1996-06-25 Toto Kasei Co Ltd 低誘電性エポキシ樹脂組成物
KR100444348B1 (ko) * 1996-02-09 2005-02-24 군에이 가가쿠 고교 가부시끼가이샤 에폭시수지,에폭시수지조성물및이의경화물
KR100697256B1 (ko) * 2005-07-06 2007-03-22 주식회사 두산 인쇄회로기판(ｐｃｂ)용 에폭시 수지 조성물, 이를이용하여 제조된 프리프레그 및 동박 적층판
JP2009096894A (ja) * 2007-10-17 2009-05-07 Showa Highpolymer Co Ltd 低分子量ノボラック樹脂、その製造方法およびそれを使用した熱硬化性樹脂組成物
KR100995678B1 (ko) * 2008-09-01 2010-11-22 주식회사 코오롱 페놀 노볼락 수지, 페놀 노볼락 에폭시 수지 및 에폭시 수지 조성물

Also Published As

Publication number Publication date
TW201520245A (zh) 2015-06-01

Similar Documents

Publication Publication Date Title
WO2017111300A1 (fr) Solution d'acide polyamique sur laquelle un monomère diamine ayant une nouvelle structure est appliqué, et film de polyimide comprenant la solution
WO2017047917A1 (fr) Polyimide modifié et composition de résine durcissable le contenant
WO2015194901A1 (fr) Charge inorganique, composition de résine époxy la contenant et élément électroluminescent comportant une couche isolante à base de cette composition
WO2018004273A1 (fr) Composition de résine thermodurcissable, et préimprégné et substrat l'utilisant
WO2017209414A1 (fr) Polyamidimide transparent à haute résistance et son procédé de préparation
WO2015046956A1 (fr) Poly(phénylène oxyde) modifié, et stratifié recouvert de cuivre utilisant celui-ci
WO2021054771A1 (fr) Résine contenant du phosphore à extrémité coiffée d'un groupe insaturé, son procédé de préparation et composition de résine comprenant une résine contenant du phosphore à extrémité coiffée d'un groupe insaturé
WO2019235712A1 (fr) Composé siloxane et composition précurseur de polyimide le comprenant
WO2022239955A1 (fr) Composition d'agent durcissant ignifuge pour époxy, et agent durcissant ignifuge pour époxy la comprenant
WO2015076626A1 (fr) Résine novolaque, agent de durcissement la contenant, et composition de résine époxy, et résine époxy novolaque, leur procédé de préparation, et composition de résine époxy contenant la résine époxy novolaque
WO2015046953A1 (fr) Stratifié cuivré utilisant un poly(oxyde de phénylène) modifié
WO2020130261A1 (fr) Composé d'agent de réticulation, composition photosensible le comprenant, et matériau photosensible l'utilisant
WO2019190289A1 (fr) Composition de copolymère séquencé
WO2022045737A1 (fr) Composition de résine photosensible positive
WO2020184972A1 (fr) Copolymère de polyimide, procédé de production de copolymère de polyimide, et composition de résine photosensible, film de résine photosensible et dispositif optique l'utilisant
WO2020213992A1 (fr) Résine époxyde, son procédé de préparation et composition de résine époxyde la comprenant
WO2016122144A1 (fr) Caoutchouc modifié d'isobutylène-isoprène, son procédé de production et son matériau durci
WO2023140644A1 (fr) Résine époxy modifiée pour encapsulation de dispositif à semi-conducteur, son procédé de fabrication, et composition de résine liquide pour encapsulation de dispositif à semi-conducteur présentant un faible gauchissement contenant celle-ci
WO2020209625A1 (fr) Copolymère séquencé de polyamide-imide, son procédé de préparation et film polyamide-imide le comprenant
WO2020060197A1 (fr) Composition de résine thermodurcissable servant à revêtir une couche mince métallique, couche mince métallique revêtue de résine au moyen de cette composition, et stratifié de feuille métallique associé
WO2020060262A1 (fr) Composition de résine durcissable comprenant des oligomères de phtalonitrile, et prépolymère de celle-ci
WO2020138644A1 (fr) Composition d'acide polyamique et film de polyimide transparent l'utilisant
WO2016052990A1 (fr) Résine époxy retardatrice de flammes, procédé pour sa préparation, et composition de résine époxy retardatrice de flammes la contenant
WO2022164171A1 (fr) Film adhésif thermodurcissable et film de revêtement le comprenant
WO2024010189A1 (fr) Résine à base de (méth)acrylate, et réserve de soudure de film sec la comprenant

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14864386

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14864386

Country of ref document: EP

Kind code of ref document: A1