WO2007097305A1 - 熱硬化性樹脂の製造方法、熱硬化性樹脂、それを含む熱硬化性組成物、成形体、硬化体、並びにそれらを含む電子機器 - Google Patents
熱硬化性樹脂の製造方法、熱硬化性樹脂、それを含む熱硬化性組成物、成形体、硬化体、並びにそれらを含む電子機器 Download PDFInfo
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- WO2007097305A1 WO2007097305A1 PCT/JP2007/053044 JP2007053044W WO2007097305A1 WO 2007097305 A1 WO2007097305 A1 WO 2007097305A1 JP 2007053044 W JP2007053044 W JP 2007053044W WO 2007097305 A1 WO2007097305 A1 WO 2007097305A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
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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
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/18—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or their halogen derivatives only
Definitions
- thermosetting resin thermosetting resin
- thermosetting composition containing the same, molded product, cured product, and electronic device including them
- the present invention relates to a method for producing a thermosetting resin having excellent heat resistance, good electrical properties, and greatly improved brittleness, a thermosetting resin obtained thereby, and the thermosetting resin.
- the present invention relates to a composition containing the same, a molded body thereof, a cured body, and an electronic device including them.
- thermosetting resins such as phenol resin, melamine resin, epoxy resin, unsaturated polyester resin, bismaleimide resin, and the like are based on their thermosetting properties. It is used in a wide range of industrial fields due to its excellent chemical properties, heat resistance, mechanical strength, and reliability.
- benzoxazine compounds undergoes ring-opening polymerization reaction and thermosetting without generation of volatile matter causing problems (
- benzoxazine compounds may be abbreviated).
- benzoxazine compounds In addition to the basic characteristics of thermosetting resin as described above, benzoxazine compounds have excellent storage stability, a relatively low viscosity when melted, and a wide range of molecular design freedom. It is a rosin with advantages.
- Such a benzoxazine compound is disclosed, for example, in JP-A-49-47378 (Patent Document 1).
- thermosetting resin having such excellent dielectric properties
- Dihydrobenzoxazine compounds represented by (1) and formula (2) are known (for example, non-specific (See Permissible Literature 1 and 2)
- the resin obtained by ring-opening polymerization of the benzoxazine ring of the powerful dihydrobenzoxazine compound is not accompanied by the generation of volatile components during thermal curing, and is also excellent in flame retardancy and water resistance. It is.
- the above-mentioned conventional dihydrobenzoxazine compound has excellent dielectric properties among the thermosetting resins as described above, it has responded to the recent increase in performance of electronic devices * parts. Accordingly, higher dielectric properties are desired.
- the dielectric constant is 3.5 or less as a characteristic at 100 MHz and 1 GHz at an ambient temperature of 23 ° C, and The dielectric loss under the same conditions is required to be not more than 0.015 in terms of the dielectric loss tangent value.
- the dielectric loss usually tends to be proportional to the frequency and the dielectric loss tangent of the material, while the frequency used in electronic equipment and components tends to be higher. The demand is getting higher.
- Japanese Patent Laid-Open No. 2005-239827 proposes a technique for dealing with fine processing ( Patent publication 2).
- this technology is disadvantageous in terms of hygroscopicity and electrical properties due to the presence of free OH groups.
- JP 2003-64180 A discloses a thermosetting resin having a benzoxazine structure in the main chain and excellent in heat resistance and mechanical properties, in which a bifunctional phenolic part is disclosed. Are bonded with a siloxane group (Patent Document 3).
- Non-Patent Document 3 and Patent Document 4 also disclose a benzoxazine compound having a specific structure having a benzoxazine structure in the main chain.
- Non-Patent Document 3 discloses only compounds, and does not describe characteristics evaluation.
- Patent Document 4 does not disclose guidelines for improving heat resistance or imparting flexibility and composite materials.
- Non-Patent Document 4 discloses a decomposition mechanism of a cured product of a benzoxazine compound. The phosphorus and monofunctional talesols described in this document have volatility at low temperatures.
- Patent Document 5 discloses a method for producing a benzoxazine compound in which both diamine and monoamine are essential as amines. However, the use of monoamine is disadvantageous from the viewpoint of heat resistance.
- Patent Document 1 JP-A-49-47378
- Patent Document 2 Japanese Patent Laid-Open No. 2005-239827
- Patent Document 3 Japanese Patent Laid-Open No. 2003-64180
- Patent Document 4 Japanese Patent Laid-Open No. 2002-338648
- Patent Document 5 Japanese Patent No. 3550814
- Non-Patent Document 1 Konishi Chemical Industry Co., Ltd. website [Searched on November 24, 2005], Internet ' ⁇ Not ⁇ ⁇ URL: nttp: //www.konishi-chem.co.jp/cgi-data/ / pdf / pdf_2.pdf>
- Non-Patent Document 2 Shikoku Kasei Kogyo Co., Ltd. website [Searched 24 November 2005], Internet URL: nttp: / 1 www.shikoku.co.jp/ products /benzo.html>
- Non-Special Reference 3 Benzoxazine Monomers and Polymers: New Phenolic Resins by Ring
- Non-Patent Document 4 H.Y ⁇ ow and H.Ishida, Polymer, 40, 4365 (1999)
- an object of the present invention is to provide a method for producing a thermosetting resin having excellent heat resistance, excellent electrical characteristics, and greatly improved brittleness, and a thermosetting resin obtained thereby. That's true.
- Another object of the present invention is to provide a composition containing the above thermosetting resin, a molded product thereof, a cured product, and an electronic device containing them.
- the present inventor does not use an aliphatic amine or an aromatic monoamine, but uses a specific aromatic diamine and a specific phenol compound, and is heat-cured.
- the knowledge that the manufacturing method of a characteristic rosin can achieve the said objective was acquired.
- the present invention is based on such knowledge. That is, the configuration of the present invention is as follows.
- benzoxazine resin refers to a resin having the dihydrobenzoxazine ring structure.
- thermosetting resin having a dihydrobenzoxazine ring structure characterized by the above.
- X is an organic group having 6 or more carbon atoms including an aromatic ring, and may have N, 0, F as a hetero atom. However, the benzene rings on both sides of X are bonded to different atoms in X. ]
- ⁇ is an organic group having 5 or more carbon atoms, and may have N, 0, or F as a hetero atom. However, the benzene rings on both sides of Y are bonded to different atoms in Y. ]
- thermosetting resin according to 1 above wherein X in the general formula (I) has a structure shown below.
- n an integer of 0 to 10.
- thermosetting resin according to 1 above wherein X in the general formula (I) has a structure shown below.
- n an integer of 0 to 10.
- thermosetting resin according to 1 above wherein X in the general formula (I) has a structure shown below.
- n an integer of 0 to 10.
- X is an organic group having 6 or more carbon atoms including an aromatic ring, and may have N, 0, F as a hetero atom. However, the benzene rings on both sides of X are bonded to different atoms in X. ]
- ⁇ is an organic group having 5 or more carbon atoms, and may have N, 0, or F as a hetero atom. However, the benzene rings on both sides of Y are bonded to different atoms in Y. ]
- Z is an organic group having 4 or more carbon atoms and has N, 0, F as heteroatoms.
- thermosetting resin according to 1 above wherein the Y force in the general formula (II) is a group represented by the following formula.
- thermosetting resin according to 1 above comprising one benzene ring.
- Y in the general formula (II) is one or more groups selected from the group of the following formulas, and Y is bonded to the meta or para position with respect to the NH groups of the benzene rings on both sides thereof.
- thermosetting resin A method for producing a thermosetting resin according to 10.
- thermosetting resin according to 1 above comprising at least two benzene rings.
- Y in the general formula (II) is one or more groups selected from the group of the following formulas;
- thermosetting resin A method for producing the thermosetting resin as described.
- thermosetting resin characterized by being a thermosetting resin having a dihydrobenzoxazine structure represented by the following general formula (IV).
- X is an organic group having 6 or more carbon atoms including an aromatic ring, and may have N, 0, F as a hetero atom. However, the benzene rings on both sides of X are bonded to different atoms in X.
- Y is an organic group having 5 or more carbon atoms, and may have N, 0, or F as a hetero atom. However, the benzene rings on both sides of Y are bonded to different atoms in Y. m represents an integer of 1 to 50. ]
- X in the general formula (IV) has any structure of the following group of X :, and Y in the general formula (IV) is any of the following groups of Y: 15.
- thermosetting composition comprising at least the thermosetting resin according to 14.
- thermosetting composition obtained by semi-curing or not curing the thermosetting composition according to 16 above.
- thermosetting resin obtained from the thermosetting resin according to 14 above.
- thermosetting composition obtained from the thermosetting composition according to 16 above.
- thermosetting resin manufactured by the manufacturing method described in 1 above.
- thermosetting composition comprising at least the thermosetting resin according to 21 above.
- thermosetting composition according to 22 above A molded article obtained by semi-curing or not curing the thermosetting composition according to 22 above.
- thermosetting resin having excellent heat resistance, good electrical properties, and greatly improved brittleness
- thermosetting cake obtained by the production method. Fats, compositions containing the greaves, molded articles, cured bodies, and electronic devices containing them are provided.
- thermosetting resin (Method for producing thermosetting resin]
- thermosetting resin includes: a) a polyfunctional phenol compound represented by the following general formula (I); b) a diamine compound represented by the following general formula (II); and c). An aldehyde compound is heated and reacted. And the thermosetting rosin which has a dihydrobenzoxazine ring structure can be obtained with the manufacturing method of this invention.
- the resulting thermosetting resin has excellent heat resistance, good electrical properties, and greatly improved brittleness.
- X is an organic group having 6 or more carbon atoms including an aromatic ring, and may have N, 0, F as a hetero atom. However, the benzene rings on both sides of X are bonded to different atoms in X. ]
- Y is an organic group having 5 or more carbon atoms, and may have N, 0, or F as a hetero atom. However, the benzene rings on both sides of Y are bonded to different atoms in Y. ]
- the polyfunctional phenolic compound represented by the general formula (I) is used as the component a).
- the strong polyfunctional phenol compound is not particularly limited as long as it is a bifunctional or higher polyfunctional phenol.
- these bifunctional or higher polyfunctional phenols are used alone or in combination of two or more.
- the polyfunctional phenolic compound of component a) used in the present invention has an X force X in the general formula (I) of 6 or more carbon atoms including an aromatic ring, preferably 8 or more carbon atoms, Preferably 12 to 12 carbon atoms
- X may have N, 0, or F as a hetero atom.
- X is bonded to the OH group of the benzene ring on both sides in the para position, particularly in terms of reactivity during synthesis of thermosetting resin, heat resistance of the cured product, mechanical properties, and electrical properties.
- the structure of X is any one or any of the following.
- X preferably has the structure shown below in terms of reactivity during synthesis of thermosetting resin, heat resistance of the cured product, mechanical properties, and electrical properties.
- n represents an integer of 0 to 10, preferably 0 to 5.
- X preferably has the structure shown below in terms of reactivity during synthesis of thermosetting resin, heat resistance of the cured product, mechanical properties, and electrical properties.
- n represents an integer of 0 to 10, preferably 0 to 5.
- X preferably has the structure shown below in terms of reactivity during synthesis of thermosetting resin, heat resistance of the cured product, mechanical properties, and electrical properties.
- n an integer of 0 to 10.
- polyfunctional phenolic compounds of component a) include 4, 4 '[1, 4 phenol-lenbis (1-methylethylidene)] bisphenol (Mitsui Chemicals). Manufactured by: Bisphenol P), 4, 4 '[1, 3 Phenolenbis (1-methylethylidene)] bisphenol (Mitsui Chemicals Co., Ltd .: Bisphenol M), Biphenol-Novolac type phenol resin (Maywa Kasei: MEH7851), xylylene novolac-type phenol resin (Maywa Kasei: MEH7800), and the like. These polyfunctional phenol compounds are used singly or in combination.
- the diamine compound represented by the general formula (II) is used as the component b).
- Powerful jaminy compounds are essential, especially in terms of improving flexibility.
- the diamine compound of component b) used in the present invention is a long-chain aromatic diamine compound, and Y in the general formula (II) has 5 or more carbon atoms, preferably 5 to 5 carbon atoms. 20, more preferably 5 to 15 organic groups. If Y has N, 0, or F as a heteroatom, the electrical characteristics can be improved. In addition, the benzene rings on both sides of Y are not bonded to the same atom in Y.
- Y is preferably a group represented by the following formula, particularly in terms of solubility during synthesis of thermosetting resin, mechanical properties of the cured product, and electrical properties.
- Y preferably contains one benzene ring from the viewpoints of heat resistance, mechanical properties, and electrical properties of the cured product.
- ⁇ containing one benzene ring are selected from the group of the following formulas-and the ⁇ is a meta-position or
- the cocoon has these groups because the cured product is excellent in heat resistance, mechanical properties, and electrical properties.
- the bifunctional group is composed of benzoxazine rosin in a straight line and is less susceptible to gelation and has a poor synthesis.
- soot has a small amount of benzene ring, particularly in terms of heat resistance, mechanical properties, and electrical properties of the cured product. It is preferable to include at least two.
- Y contains at least two benzene rings are selected from the group of the following formulas:-or more groups, and meta-positions or NH groups on the benzene rings on both sides of Y.
- Examples include those that bind to the position.
- Y has these groups, it is particularly preferable because the cured product is excellent in heat resistance, mechanical properties, and electrical properties.
- diamine compound of component b) examples include 1,3 bis (3 aminophenoxy) benzene, 1,3 bis (4 aminophenoxy) benzene, 1,4 bis (3 aminophenoxy).
- the aldehyde compound of component c) used in the present invention is not particularly limited, but formaldehyde is preferred.
- formaldehyde examples include paraformaldehyde, which is a polymer thereof, and an aqueous solution. Can be used in the form of formalin Noh. The reaction progresses more slowly when using norformaldehyde.
- acetoaldehyde, propionaldehyde, butyl aldehyde and the like can be used as other aldehyde compounds.
- a monofunctional phenolic compound represented by the following general formula (III) is further used as the component d) together with the components a) to c) described above. It is possible to provide a method to do this.
- processability such as solubility can be secured.
- Z is an organic group having 4 or more carbon atoms and has N, 0, F as heteroatoms.
- the monofunctional phenolic compound as component d) has a large side chain molecular weight, and Z in the general formula (III) has 4 or more carbon atoms, preferably 6 or more carbon atoms, more preferably 8 to 20 organic groups. As the number of carbon atoms increases, the free volume increases and the dielectric constant may decrease. Z may have N, 0, or F as a hetero atom.
- the substituent Z is bonded to the OH group in the para position, and the substituent Z is a group represented by the following formula: It is preferable that
- Z is preferably a group substituted in the para position with respect to the OH group and represented by the following formula.
- Z is mainly a para-position with respect to the OH group in the benzene ring in the general formula (III) in terms of dielectric properties such as non-volatility at high temperature, dielectric constant and dielectric loss tangent. And a group represented by the following formula is preferred.
- the substituent Z of the monofunctional phenol compound represented by the general formula (III) is the above general formula in terms of dielectric properties such as non-volatility, dielectric constant and dielectric loss tangent at high temperatures.
- the benzene ring in (III) is preferably bonded to the OH group in the para position, and the substituent Z is a group represented by the following formula:
- monofunctional phenolic compound of component d) examples include 2-cyclohexylphenol, 4-cyclohexylphenol, 2-phenolphenol, 4-phenolphenol.
- These monofunctional phenol compounds are used singly or in combination.
- the a), b) and c) components can be reacted by heating in a suitable solvent.
- a monofunctional phenolic compound or a polyfunctional phenolic compound may be further added.
- Examples of monofunctional phenolic compounds that can be additionally added here include monofunctional phenols as described above, and examples of polyfunctional phenolic compounds include polyfunctional phenols as described above, and 4 , 4'-biphenol, 2, 2, -biphenol, 4, 4'-dihydroxydiphenyl ether, 2, 2, -dihydroxydiphenyl ether, 4, 4'-dihydroxydiphenyl methane, 2, 2, 1-dihydroxydiphenylmethane 2, 2 bis (4 hydroxyphenyl) bread, 4, 4, 1-dihydroxybenzophenone, 1, 1-bis (4 hydroxyphenyl) ethane, 1, 1-bis (4 hydroxyphenol) ) Propane, 1,1-bis (4-hydroxyphenol) butane, 2,2-bis (4-hydroxyphenol) butane, 1,1-bis (4-hydroxyphenol) but-2-methylpropane, 1, 1—Bis (4 Hydroxyphenol) cyclohexane, 1,1 bis (4 hydroxyphenol) cyclopentane, 1,1 bis (4 hydroxyphenol)
- the solvent used in the production method of the present invention is not particularly limited, but the one having a good solubility of the raw material phenolic compound is a diamine compound and the product polymer is good. However, it is easy to obtain a polymer having a high degree of polymerization.
- solvents include aromatic solvents such as toluene and xylene, halogen solvents such as chloroform, dichloromethane, and THF. And ether solvents such as dioxane.
- the reaction temperature and reaction time are not particularly limited, but the reaction may usually be carried out at a temperature of room temperature to about 120 ° C for about 10 minutes to 24 hours. In the present invention, it is particularly preferable to react at 30 to 110 ° C. for 20 minutes to 9 hours because the reaction proceeds to a polymer capable of expressing the function as the thermosetting resin according to the present invention. . At high temperatures and for long-term reactions, the potential for gelling due to the formation of higher molecular weight resins or three-dimensional cross-linked polymers is the desired low temperature. However, it is desirable to increase the reaction time or the reaction temperature at a point where the molecular weight is sufficiently high for coating and the resin cannot be synthesized in a short reaction.
- removing water generated during the reaction out of the system is also an effective technique for promoting the reaction.
- a polymer can be precipitated by adding a large amount of a poor solvent such as methanol to the solution after the reaction, and the desired polymer can be obtained by separating and drying the polymer.
- monofunctional amine compounds, trifunctional amine compounds, and other diamine compounds may be used as long as the properties of the thermosetting resin of the present invention are not impaired.
- a monofunctional amine is used, the degree of polymerization can be adjusted, and when a trifunctional amine is used, a branched polymer is obtained.
- the physical properties can be adjusted by using other diamine compounds in combination. These can be used at the same time as the diamine compound essential to the present invention. In consideration of the order of the force reaction, they can be added to the reaction system and reacted later.
- thermosetting resin of the present invention includes a structure represented by the following general formula (IV).
- thermosetting resin of the present invention can also be obtained by the above-described method for producing a thermosetting resin.
- X is an organic group having 6 or more carbon atoms including an aromatic ring, and may have N, 0, F as a hetero atom. However, the benzene rings on both sides of X are bonded to different atoms in X.
- Y is an organic group having 5 or more carbon atoms, and may have N, 0, or F as a hetero atom. However, the benzene rings on both sides of Y are bonded to different atoms in Y.
- m represents an integer of 1 to 50.
- the structure can be identified by IR, NMR, GC-MS and other techniques.
- X When m is 2 or more, X may be different in the synthesized thermosetting resin, which need not all be the same. Similarly, when m is 2 or more, Y may be different in the synthesized thermosetting resin, and in the general formula (IV), X may be the following: It is preferable that X has a structure of any of the groups of X: and Y preferably has a structure of any of the following groups of Y :.
- thermosetting resin of the present invention has particularly excellent heat resistance, good electrical properties, and greatly improved brittleness.
- thermosetting composition of the present invention contains at least the thermosetting resin described above.
- the thermosetting composition according to the present invention preferably contains the thermosetting resin as a main component, for example, the thermosetting resin as a main component, and other components as other components. What contains a thermosetting resin is mentioned.
- thermosetting resins as subcomponents include, for example, epoxy resins, thermosetting modified polyphenylene ether resins, thermosetting polyimide resins, key resin resins, and melamine resins.
- examples thereof include fats, urea resins, aryl resins, phenol resins, unsaturated polyester resins, bismaleimide resins, alkyd resins, furan resins, polyurethane resins, and alin resins.
- epoxy resin, phenol resin, and thermosetting polyimide resin are more preferable from the viewpoint of further improving the heat resistance of the molded article formed with this composition strength.
- These other thermosetting resins may be used alone or in combination of two or more.
- thermosetting composition it is preferable to use a compound having at least one, preferably two dihydrobenzoxazine rings in the molecule described in the known literature as an accessory component.
- a compound having at least one dihydrobenzoxazine ring in the molecule only one kind may be used or two or more kinds may be used in combination.
- thermosetting composition according to the present invention includes a flame retardant, a nucleating agent, an anti-oxidation agent (anti-aging agent), a heat stabilizer, a light stabilizer, and an ultraviolet absorber as necessary.
- Various additives such as an agent, a lubricant, a flame retardant aid, an antistatic agent, an antifogging agent, a filler, a softener, a plasticizer, and a colorant may be contained. These may be used alone or in combination of two or more.
- a reactive or non-reactive solvent can also be used.
- thermosetting resin composition according to the present invention may be formed into a film by dissolving the thermosetting resin composition in an organic solvent, casting it, and drying the solvent.
- thermosetting resin or thermosetting resin composition that is useful for the present invention has a higher solubility in an organic solvent such as toluene. This is a cast in solution When forming a film, the amount of solvent can be reduced, and if the solvent content is low, the energy for solvent evaporation is small, the drying time is short, and there is no blistering due to rapid drying. This is because there is an effective advantage.
- the molded body according to the present invention is obtained by semi-curing or not curing the thermosetting resin described above or a thermosetting composition containing the same.
- thermosetting resin is to stop the curing of the thermosetting resin at an intermediate stage, and to a state where the curing can proceed further.
- Semi-cured thermosetting resin is sometimes referred to as a stage. (The following description is also synonymous)
- thermosetting resin described above has moldability even before curing, and therefore the dimensions and shape thereof are not particularly limited.
- a sheet (plate), a block, And other parts for example, an adhesive layer
- the sheet-like material may be formed on a support film.
- the cured body according to the present invention is obtained by curing the thermosetting resin having thermosetting property, the base composition having thermosetting property, and the molded body having thermosetting property by heating.
- the curing method any conventionally known curing method can be used. In general, heating may be performed at about 120 to 300 ° C. for several hours, but the heating temperature may be lower or the heating time may be increased. If insufficient, in some cases, curing may be insufficient and mechanical strength may be insufficient. Also, if the heating temperature is too high or the heating time is too long, in some cases, side reactions such as decomposition may occur and the mechanical strength may be disadvantageously reduced. Therefore, it is desirable to select appropriate conditions according to the characteristics of the thermosetting compound to be used.
- an appropriate curing accelerator may be added.
- the curing accelerator any curing accelerator generally used in ring-opening polymerization of dihydrobenzoxazine compounds can be used.
- polyfunctional phenols such as catechol and bisphenol A can be used.
- Sulfonic acids such as ⁇ -toluenesulfonic acid, p-phenolsulfonic acid, carboxylic acids such as benzoic acid, salicylic acid, oxalic acid, adipic acid, cobalt (II) acetyl cetate, aluminum (III) acetyl Setonate, Zirconium (IV) Acetylacetate Metal complexes such as nates, metal oxides such as calcium oxide, cobalt oxide, magnesium oxide and iron oxide, calcium hydroxide, imidazole and its derivatives, tertiary amines such as diazabicyclodecene, diazabicyclononene and their salts And phosphorous compounds such as triphenylphosphine, triphenylphosphine'benzoquinone derivative, triphenylphosphine'triphenylboron salt, tetraphenylphosphonium'tetraphenylporate, and derivatives thereof.
- the addition amount of the curing accelerator is not particularly limited. However, if the addition amount is excessive, the dielectric constant of the molded article increases, the dielectric loss tangent is increased, and the mechanical properties are adversely affected. In general, therefore, it is desirable to use a curing accelerator at a ratio of preferably 5 parts by weight or less, more preferably 3 parts by weight or less, with respect to 100 parts by weight of the thermosetting resin.
- thermosetting resin or the thermosetting composition thus obtained as described above has a benzoxazine structure in the polymer structure, thereby realizing excellent dielectric properties. can do.
- the cured body of the present invention is excellent in reliability, flame retardancy, moldability and the like based on the thermosetting properties of the thermosetting resin or the thermosetting composition.
- the glass transition temperature (Tg) is high, it can be applied to parts where stress is applied or moving parts, and volatile by-products are not generated during polymerization. Volatile by-products do not remain in the molded body, which is preferable for hygiene management.
- the cured product of the present invention is preferably used for applications such as electronic components and electronic devices and materials thereof, multilayer boards, copper-clad laminates, sealants, adhesives, and the like that particularly require excellent dielectric properties. Can do.
- the electronic component includes a substrate or an IC element, a resistor, a capacitor, a coil, a substrate having an electrical conductor layer on the surface of the cured body of the present invention, and a terminal for electrical connection such as a flexible substrate. Refers to the board on which is mounted.
- Example 1 Typical examples of the present invention are shown below, but the present invention is not limited thereto.
- Example 1
- Example 1 The polymer obtained in Example 1 was held at 180 ° C for 1 hour by a hot press method to obtain a 0.5 mmt sheet-like cured body.
- the obtained cured product was transparent, brown and uniform, and had excellent flexibility.
- the obtained sheet was cut into fine pieces and 5% weight reduction temperature (10% CZmin) in an air atmosphere by the TGA method using the product name “DTG-60” manufactured by Shimadzu Corporation. Td 5) was evaluated.
- the cured product of Example 2 showed a good value of Td5 of 415 ° C.
- Example 1 In Example 1, 21.21 g (0.06 mol) of bisphenol M (Mitsui Chemicals) was used in place of 1,4,4-diisopropylbenzene. A thermosetting resin was synthesized in the same manner as in Example 1 except that. The yield was 40.56g. The weight average molecular weight of the obtained rosin was 10,600 as measured by GPC.
- Example 4
- Example 3 In the same manner as in Example 2, the grease of Example 3 was evaluated. The results are summarized in Table 2. The thermosetting resin of Example 3 showed good results in both electrical characteristics and heat resistance.
- Example 3 In the same manner as in Example 2, the grease of Example 5 was evaluated. The results are summarized in Table 3. The thermosetting resin of Example 3 showed good results in both electrical characteristics and heat resistance.
- biphenyl novolac type phenol resin (Maywa Chemical Co., Ltd. ⁇ 7851 SS ”, OH S204) 30.00 g, ⁇ , ⁇ '-bis (4-aminophenol) — 1, 4-diisopropyl pentbenzene (Tokyo Kasei) 98%) 21.08g (0.061mol), paraformaldehyde ( (Wako Pure Chemicals, 94%) 8.13 g (0.25 mol) was added and reacted for 6 hours under reflux while removing the generated water. The solution after the reaction was poured into a large amount of methanol to precipitate the product. Thereafter, the product was separated by filtration and washed with methanol. The washed product was dried under reduced pressure to obtain 45.52 g of thermosetting resin having a benzoxazine structure.
- Example 7 instead of ⁇ 1, ⁇ , monobis (4-aminophenol) 1,4-diisopropylbenzene (Tokyo Kasei, 98%), 2, 2bis [4 mono (4 aminophenoxy) [Fuel] propane (manufactured by Wakayama Seika Co., Ltd., 99.9%)
- a thermosetting resin having a benzoxazine structure was synthesized in the same manner as in Example 7, except that the amount was changed to 24.90 g (0.061 mol). The yield was 45.80g.
- thermosetting resin of Examples 9 and 10 showed good results in both electrical characteristics and heat resistance.
- thermosetting resin containing a benzoxazine compound having the following structure as a main component 31.21 g.
- the weight average molecular weight was 16,600.
- thermosetting resin of Example 11 showed good results in both electrical characteristics and heat resistance.
- Example 13 In the same manner as in Example 2, the resin of Example 13 was evaluated. The results are summarized in Table 6. The thermosetting resin of Example 13 showed good electrical properties.
- thermosetting resin mainly composed of a benzoxazine compound having the following structure.
- thermosetting resin of Example 15 showed good results in both electrical characteristics and heat resistance.
- Example 17 In the same manner as in Example 2, the resin of Example 17 was evaluated. The results are summarized in Table 8. The thermosetting resin of Example 17 showed good results in both electrical characteristics and heat resistance.
- thermosetting resin of Comparative Example 1 was inferior in both electrical properties and heat resistance.
- thermosetting resin of Comparative Example 3 was inferior in electrical characteristics and heat resistance, and the film was whitened when bent.
- a, a —bis (4-hydroxyphenyl) -1,4-diisopropylbenzene (Tokyo Kasei, 98%) 22. 98 g (0.065 mol), Bisalin P (Tokyo) Kasei Chemical, 98%) 22.85 g (0.065 mol), Norahonoremua / Redehide (Turoko Mitsuru Pure Chemical, 94%) 8.72 g (0.273 mol) were added under reflux while removing the generated water. The reaction was performed for 6 hours. The solution after the reaction was poured into a large amount of methanol to precipitate the product. Thereafter, the product was separated by filtration and washed with methanol.
- thermosetting resin containing a benzoxazine compound having the following structure was obtained.
- the obtained polymer was insoluble in general-purpose solvents such as toluene and DMF. Also, Even if hot pressing was performed, the film could not be formed due to infusibility.
- the benzoxazine succinate synthesized in each example so as to be 20%, 30, 30, 40, 50, and 60% by weight was added, and stirred for 24 hours at room temperature to dissolve. I confirmed that.
- bent M-form having a substituent at the meta position such as bisphenol M or bis-line M, improves the solubility even at a high molecular weight.
- Sample films were prepared so that the composites of Examples 1, 3, 5, 7, 8, 11, 13, 15, 17 and Comparative Examples 1 and 3 had a width of 10 mm and a thickness of 75.
- a 50% by weight solution was prepared with toluene having the same weight as that of each resin, and the sample was drawn by an applicator and then removed by drying in an oven to prepare a sample.
- a bending test was performed on the produced film. In the bending test, the sample film is folded in half and pressed from both sides with a force of 3 kgf, and then the film is spread. Transparent only with creases: ⁇ , the film turns white: ⁇ , the film breaks : X was evaluated. Implementation ⁇ rows 1, 3, 5, 7, 8, 11, 13, 15, 17! / Evaluation results ⁇ or ⁇ ! The deviation is also ⁇ , in Comparative Example 1 X, in Comparative Example 3 It was an evaluation result.
- the present invention relates to a method for producing a thermosetting resin having excellent heat resistance, good electrical properties, and greatly improved brittleness, a thermosetting resin obtained thereby, and a composition containing the thermosetting resin It has industrial applicability as a molded body, a cured body, and an electronic device including them.
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
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JP2007550621A JP4248592B2 (ja) | 2006-02-20 | 2007-02-20 | 熱硬化性樹脂の製造方法、熱硬化性樹脂、それを含む熱硬化性組成物、成形体、硬化体、並びにそれらを含む電子機器 |
US12/280,029 US20090054614A1 (en) | 2006-02-20 | 2007-02-20 | Method for producing thermosetting resin, thermosetting resin, thermosetting composition containing same, molded body, cured body, and electronic device containing those |
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JP2010053324A (ja) * | 2008-08-29 | 2010-03-11 | Sekisui Chem Co Ltd | ベンゾオキサジン環を有する熱硬化性樹脂を含有する樹脂組成物 |
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JP2016113581A (ja) * | 2014-12-17 | 2016-06-23 | Dic株式会社 | ベンゾオキサジン化合物、ベンゾオキサジン樹脂、ベンゾオキサジン樹脂の製造方法、硬化性樹脂組成物、その硬化物、frp材料、半導体封止材料、ワニス、回路基板、プリプレグ、及びビルドアップフィルム |
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TWI339665B (ja) | 2011-04-01 |
JPWO2007097305A1 (ja) | 2009-07-16 |
KR20080094071A (ko) | 2008-10-22 |
JP4248592B2 (ja) | 2009-04-02 |
US20090054614A1 (en) | 2009-02-26 |
TW200804444A (en) | 2008-01-16 |
KR100977927B1 (ko) | 2010-08-24 |
CN101421324A (zh) | 2009-04-29 |
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