JP2017031275A - Method for curing thermosetting resin composition and thermosetting resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for curing a thermosetting resin composition capable of suppressing by-product when the thermosetting resin containing a cyanate ester compound is curing reacted.SOLUTION: There is provided a method for curing a thermosetting resin composition including containing at least one kind of curing accelerator selected from metal ion complex of crown ether and metal ion complex of cryptand in addition to a thermosetting resin containing a cyanate ester compound as included components of the thermosetting resin composition and heating and curing the same.SELECTED DRAWING: None

Description

  The present invention relates to a method for curing a thermosetting resin composition and a thermosetting resin composition.

  A cured product of a thermosetting resin composition containing a cyanate ester compound has a high glass transition point (Tg) and has excellent heat resistance characteristics. Therefore, it is used as a substrate material constituting an insulating layer such as a printed wiring board. Yes.

  Thermosetting resin compositions containing a cyanate ester compound are often used in combination with other resin components such as an epoxy resin, polyphenylene ether (PPE), and imide resin. It has been common to use metal soaps (organic acid metal salts) such as zinc octoate and copper naphthenate as the catalyst. (For example, Patent Documents 1 to 3).

JP 2011-246516 A Japanese Patent Laid-Open No. 11-21453 JP 2006-124494 A

  By the way, in the case of producing an insulating substrate for a printed wiring board using a thermosetting resin composition containing a cyanate ester compound, the inventor of the present application uses Tg or the like regardless of the same composition and the same thermoforming conditions. I noticed that the measurement results of heat resistance may be lower than expected. Then, the cause was examined and it was thought that the hardening inhibition was produced in the hardening reaction of a resin composition. In particular, we focused on the curing reaction of cyanate ester compounds. Cyanate ester compounds are known to self-polymerize and trimerize in a thermosetting reaction to form a triazine ring and cure, and this triazine ring structure is important for realizing high Tg and heat resistance characteristics. it is conceivable that. On the other hand, when water is present in the reaction system of the cyanate ester compound, hydrolysis of the cyanate group occurs as a side reaction of trimerization. As a result, a double product such as carbamate may be formed. This is presumed to be a cause of a decrease in Tg and heat resistance of the cyanate resin after curing.

  Therefore, removing water from the reaction system of the cyanate ester compound is thought to suppress side reactions that generate carbamate and the like, but in industrial production mass production scale, moisture is removed from the raw material and the resin composition that is a mixture thereof. It was virtually difficult to remove. For example, in the production of a printed wiring board or the like, the resin composition is generally used after being converted into a resin varnish with an organic solvent. However, it is very expensive to dehydrate the water contained in the organic solvent. Moreover, since polar solvents that easily absorb moisture are often used as the organic solvent, it has been extremely difficult to remove moisture from the resin varnish.

  This invention is made | formed in view of the said situation, and provides the hardening method of the thermosetting resin composition which can suppress the by-product at the time of carrying out hardening reaction of the thermosetting resin containing a cyanate ester compound. With the goal. It is another object of the present invention to provide a thermosetting resin composition capable of obtaining a cured product by the curing method and capable of preventing a decrease in Tg and heat resistance characteristics of the cured product.

  The inventor of the present application further studied to suppress side reactions that generate carbamate and the like in the reaction system of the cyanate ester compound even in the presence of moisture. As a result, it was found that this is possible by using a specific curing accelerator, and the present invention was completed by further study based on this finding.

  That is, according to one aspect of the present invention, a method for curing a thermosetting resin composition comprises a crown ether metal ion complex together with a thermosetting resin containing a cyanate ester compound as a component of the thermosetting resin composition. And a curing accelerator containing at least one selected from a metal ion complex of cryptand and heated to be cured.

  In the curing method, the central metal of the metal ion complex is preferably one selected from the group consisting of zinc, cobalt, iron, copper, manganese, and zirconium.

  Furthermore, it is preferable that the crown ether or the cryptant which is a ligand of the metal ion complex has 15 or more carbon atoms and 5 or more oxygen atoms.

  Moreover, in the said hardening method, it is preferable that the said cyanate ester compound has at least 2 or more cyanate groups in a molecule | numerator.

  It is preferable that content of the said hardening accelerator is 10 ppm-300 ppm by the metal concentration with respect to the whole resin composition containing the said thermosetting resin and the said hardening accelerator.

  Moreover, the thermosetting resin composition according to another aspect of the present invention comprises at least one selected from a thermosetting resin containing a cyanate ester compound, a metal ion complex of a crown ether, and a metal ion complex of a cryptand. And a curing accelerator containing.

  In the thermosetting resin composition, the central metal of the metal ion complex is preferably one selected from the group consisting of zinc, cobalt, iron, copper, manganese, and zirconium.

  Moreover, it is preferable that the crown ether or the cryptant which is a ligand of the metal ion complex has 15 or more carbon atoms and 5 or more oxygen atoms.

  Furthermore, the cyanate ester compound preferably has at least two or more cyanate groups in the molecule.

  Moreover, it is preferable that content of the said hardening accelerator is 10 ppm-300 ppm by the metal concentration with respect to the whole resin composition containing the said thermosetting resin and the said hardening accelerator.

  According to the present invention, even when water is present, hydrolysis during curing (reaction) of a resin composition containing a cyanate compound can be suppressed, and the curing reaction can be promoted.

  Hereinafter, although the embodiment concerning the present invention is described concretely, the present invention is not limited to these.

  The curing method of the thermosetting resin composition according to this embodiment includes a metal ion complex of crown ether and a metal ion complex of cryptand together with a thermosetting resin containing a cyanate ester compound as a component of the thermosetting resin composition. And a curing accelerator containing at least one selected from the group consisting of: and curing by heating.

  With such a configuration, even in an environment where water is present, it is considered that hydrolysis during curing (reaction) of a resin composition containing a cyanate compound can be suppressed and the curing reaction can be promoted. It is done. As a result, it is thought that it can contribute also to stabilization of the gel time of a resin varnish, without reducing Tg and heat resistance of the resin composition containing a cyanate compound after a curing reaction.

  This is considered to be because when a crown ether ring or cryptand is applied to the ligand of the metal catalyst, the catalytic activity is reduced and the hydrolysis reaction can be suppressed by reducing the Lewis acidity of the central metal. As a result, the trimerization reaction (generation of triazine ring) can be proceeded dominantly, and the generation of by-products such as carbamate can be suppressed.

  The cyanate compound in the present embodiment is a component that generally acts as a curing agent for various compounds for forming a resin and forms a rigid skeleton. For this reason, a high glass transition point (Tg) is given to the resin composition. Moreover, since the viscosity is low, the high fluidity of the resin varnish obtained can be maintained. Further, it has excellent dielectric properties such as dielectric constant and dielectric loss tangent.

  Cyanate ester compounds self-polymerize with each other due to the presence of a curing accelerator. Cyanate groups self-polymerize to form a triazine ring, and the formation of this triazine ring contributes to an improvement in heat resistance.

  The cyanate compound of this embodiment is preferably a cyanate compound having an average of two or more cyanate groups in one molecule.

  Specific examples thereof include, for example, bisphenol A type cyanate ester, 2,2-bis (4-cyanatophenyl) propane, bis (3,5-dimethyl-4-cyanatophenyl) methane, 2,2-bis ( And aromatic cyanate ester compounds such as 4-cyanatophenyl) ethane and derivatives thereof. These may be used alone or in combination of two or more.

  In the present embodiment, the thermosetting resin composition is not particularly limited as long as it is a resin composition containing the cyanate compound.

  For example, an epoxy resin, a phenol resin, an unsaturated imide resin, an amino resin, an unsaturated polyester resin, an aryl resin, a dicyclopentadiene resin, a silicone resin, a melamine resin, and the like can be given. Among these, an epoxy resin and a phenol resin are preferable as those that exhibit a good curing reaction in combination with a cyanate compound. One or more of these other thermosetting resins may be used in combination. In addition, the thermosetting compound contained as the thermosetting resin includes a cyanate compound and a compound that functions as a so-called curing agent (crosslinking material) for the resin component used in combination as the other main resin.

  When an epoxy resin is used in combination with a cyanate compound as the thermosetting resin, usable epoxy compounds are not particularly limited. For example, bisphenol type epoxy resin, novolac type epoxy resin, alicyclic epoxy resin, glycidyl ester , Glycidylamines, heterocyclic epoxy resins, brominated epoxy resins and the like. Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin. Examples of the novolak type epoxy resin include phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, dicyclopentadiene novolak type epoxy resin and the like. Examples of the alicyclic epoxy resin include 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate. 1-epoxyethyl-3,4-epoxycyclohexane and the like. Examples of the glycidyl esters include phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, and dimer acid glycidyl ester. Examples of the glycidylamines include tetraglycidyldiaminodiphenylmethane, triglycidyl P-aminophenol, N, N-diglycidylaniline, and the like. Examples of the heterocyclic epoxy resin include 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate. Examples of the brominated epoxy resin include tetrabromobisphenol A type epoxy resin, tetrabromobisphenol F type epoxy resin, brominated cresol novolak type epoxy resin, brominated phenol novolak type epoxy resin and the like. Of these epoxy resins, only one type may be used or two or more types may be used in combination.

  The curing accelerator used in the present embodiment contains at least one of a crown ether metal ion complex and / or a cryptand metal ion complex, and is characterized by comprising a crown ether metal ion complex and / or a cryptand metal. It may be at least one of the ionic complexes.

  In the present embodiment, the central metal of the metal ion complex is not particularly limited, but is preferably, for example, one selected from the group consisting of zinc, cobalt, iron, copper, manganese, and zirconium.

  The central metal is particularly preferably zinc, cobalt, or iron. These are from the viewpoint of being a central metal that is easily adapted to a crown ring having 15 to 18 carbon atoms and 5 to 6 oxygen atoms.

  In addition, the number of carbon atoms and the number of oxygen in the crown ether or cryptant which is a ligand of the metal ion complex, that is, the size of the ligand is not particularly limited, and the optimum size depends on the size of the metal atom. You can choose. The crown ether and / or cryptand includes those having a functional group representing a short-chain to long-chain alkyl group or an aryl group.

  Specifically, for example, the crown ether or the cryptant preferably has 15 or more carbon atoms and 5 or more oxygen atoms. This is because there is a merit that it is excellent in compatibility with a metal ion that effectively accelerates the reaction of a cyanate ester such as zinc, cobalt, and iron.

  In addition, although there is no upper limit in particular in the said carbon number and oxygen number, it is preferable that it is 21 or less about carbon number and 7 or less about oxygen number from the reason of compatibility with a center metal.

  More specifically, examples of the crown ether include 15-crown-5, 18-crown-6, dibenzo-15-crown-5, dibenzo-18-crown-6, and the like.

  As the cryptant, for example, cryptant [2,2,2] (IUPAC name: 1,10-diaza-4,7,13,16,24,24-hexaoxabicyclo [8.8.8] hexacosane) , Etc.

  Although the hardening accelerator used with the hardening method which concerns on this embodiment can be obtained using a well-known usual technique, a commercially available thing can be used. For example, it can be adjusted by mixing a crown ring as a ligand and a metal salt as a central metal in a reaction vessel.

  As said hardening accelerator, the compound for hardening acceleration other than the metal ion complex of a crown ether and / or the metal ion complex of a cryptand can also be included. The other curing accelerating compound is not particularly limited as long as it can accelerate the curing reaction of the thermosetting resin composition containing the cyanate compound. For example, an imidazole compound, an organic phosphine compound, And tertiary amine compounds. Among these curing accelerators, only one type may be used or two or more types may be used in combination.

  The thermosetting resin composition may further contain other components as necessary. Examples of other components include inorganic fillers, flame retardants, and additives.

  Various inorganic fillers including known ones can be used for the purpose of improving the heat resistance, flame retardancy, low expansion coefficient, thermal conductivity, etc. of the cured product of the thermosetting resin composition. Specific examples of the inorganic filler include silica, alumina, talc, aluminum hydroxide, magnesium hydroxide, titanium oxide, mica, aluminum borate, barium sulfate, and calcium carbonate. Of these inorganic fillers, only one type may be used or two or more types may be used in combination. Further, the inorganic filler may be used as it is, or may be used after being surface-treated with an epoxy silane type or aminosilane type silane coupling agent depending on the purpose.

  Examples of the flame retardant include a phosphorus flame retardant and a halogen flame retardant. Specific examples of phosphorus-based flame retardants include phosphoric acid esters such as condensed phosphate esters, cyclic phosphate esters, phosphazene compounds such as cyclic phosphazene compounds, and phosphinic acid metal salts such as aluminum dialkylphosphinates. Examples include flame retardants. Examples of the halogen flame retardant include bromine flame retardant. Moreover, a phosphorus flame retardant is preferably used from a halogen-free viewpoint. As a flame retardant, each illustrated flame retardant may be used independently and may be used in combination of 2 or more type.

  As additives, for example, antifoaming agents such as silicone antifoaming agents and acrylic ester antifoaming agents, heat stabilizers, antistatic agents, ultraviolet absorbers, dyes and pigments, lubricants, wetting and dispersing agents, etc. A dispersing agent etc. are mentioned. Of these additives, only one type may be used, or two or more types may be used in combination.

  The thermosetting resin composition of the present embodiment is prepared as follows, for example, by blending the above thermosetting resin, a curing accelerator, and other components as required.

  First, each component that can be dissolved in an organic solvent is introduced into the organic solvent and dissolved. At this time, heating may be performed as necessary. Thereafter, a component that is used as necessary and does not dissolve in an organic solvent, such as an inorganic filler, is added, and dispersed by using a ball mill, a bead mill, a roll mill, or the like until a predetermined dispersion state is obtained. A curable resin composition is prepared. The organic solvent used here is not particularly limited as long as it dissolves a benzoxazine compound or the like and does not inhibit the curing reaction. Specific examples include methyl ethyl ketone, acetone, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether acetate, 1-methoxy-2-propanol, and THF.

  The curing method of the present embodiment comprises at least one selected from a metal ion complex of a crown ether and a metal ion complex of a cryptand together with a thermosetting resin containing a cyanate ester compound as a component of the thermosetting resin composition. As long as the curing accelerator is contained and heated and cured, there are no particular limitations on other steps.

  Specifically, for example, the curing of the thermosetting resin composition according to the present embodiment can be performed by heating to a temperature at which the curing reaction of the cyanate compound substantially starts. As this heat curing, for example, it may be cured by heating to 190 ° C. or higher, and preferably cured in a range of 190 ° C. or higher and 210 ° C. or lower. In addition, the specific temperature conditions which harden the said thermosetting resin composition can be suitably set with the utilization use and the objective of a thermosetting resin composition, and are not restrict | limited in particular.

  In the curing method of this embodiment, the addition amount of the curing accelerator containing at least one selected from the metal ion complex of crown ether and the metal ion complex of cryptand is about 10 ppm to 300 ppm in terms of metal concentration relative to the entire resin composition. It is preferable that If it is less than 10 ppm, there is a risk of causing poor curing, and if it exceeds 300 ppm, there is a tendency to cause gelation of the varnish.

  The degree of progress of the curing reaction of the thermosetting resin composition in this embodiment can be measured by various methods, but it can be performed by measuring the component ratio of cyanate compound, triazine ring cured product, carbamate, etc. in the product. it can. In other words, by determining the ratio of triazine ring cured product / carbamate, the ratio between the positive reaction and the side reaction (the formation of carbamate) can be measured.

  Specifically, the ratio of each component in the product can be calculated by 13C-NMR analysis and 1H-NMR analysis.

  Next, the use application which can apply the said thermosetting resin composition is demonstrated. The application of the thermosetting resin composition is not particularly limited as long as the characteristics can be utilized, but it is particularly useful in the field of electronic materials, for example. Examples thereof include insulating materials in the field of metal-clad laminates and printed wiring boards, sealing materials used for sealing electronic parts such as semiconductor parts, and other molding materials for insulation or high heat resistance.

  As described above, the present specification discloses various modes of technology, of which the main technologies are summarized below.

  That is, according to one aspect of the present invention, a method for curing a thermosetting resin composition comprises a crown ether metal ion complex together with a thermosetting resin containing a cyanate ester compound as a component of the thermosetting resin composition. And a curing accelerator containing at least one selected from a metal ion complex of cryptand and heated to be cured.

  With such a configuration, even in an environment where water is present, it is considered that hydrolysis during the curing (reaction) of the resin composition containing a cyanate compound can be suppressed and the curing reaction can be promoted. It is done. As a result, it is thought that it can contribute also to stabilization of the gel time of a resin varnish, without reducing Tg and heat resistance of the resin composition containing a cyanate compound after a curing reaction.

  Moreover, in the said hardening method, it is preferable that the said cyanate ester compound has at least 2 or more cyanate groups in a molecule | numerator.

  It is preferable that content of the said hardening accelerator is 10 ppm-300 ppm by the metal concentration with respect to the whole resin composition containing the said thermosetting resin and the said hardening accelerator. Thereby, the cyanate ester compound can be cured.

  Hereinafter, the present invention will be described more specifically with reference to examples. In addition, this invention is not limited at all by the following Example.

(Examples 1-9 and Comparative Examples 1-6)
An epoxy resin (4-t-butylphenylglycidyl ether), a cyanate ester compound (phenylcyanate, manufactured by Tokyo Chemical Industry Co., Ltd.) and water are blended in the blending ratio (mmol) shown in Table 1, and the metal concentration is in the table. Each hardening accelerator shown in Table 1 was added so that it might become the density | concentration shown in (1). Specifically, each material was weighed in a container and heated to reflux for 3 hours. After the reaction, the component ratio (%) of the cured reaction product was calculated by 13C-NMR analysis and 1H-NMR analysis.

  Furthermore, the ratio of the positive reaction and the side reaction was calculated based on the ratio of the triazine ring and the carbamate using the obtained component ratio.

  The results are shown in Table 1.

  In the cured epoxy resin compositions obtained in Examples 1 to 9 according to the present invention, the curing reaction (positive reaction) sufficiently progressed, so that the triazine ring cured product was sufficiently generated. On the other hand, in Comparative Examples 1 to 6 using conventional curing accelerators, the positive reaction did not progress so much. In Comparative Example 1 in which water was not added, carbamate as a by-product was not generated, but in Comparative Examples 2 to 6 in which water was added, a large amount of carbamate was generated.

(Examples 10 to 18 and Comparative Examples 7 to 12)
Example 1 except that the curing accelerator was changed to the one shown in Table 2, the epoxy resin was changed to a bisphenol A type epoxy compound, and the cyanate ester compound was changed to a bisphenol A type cyanate ester ("Primase BADCy" manufactured by Lonza). In the same manner as above, an epoxy resin composition was obtained at the blending ratio (mmol) shown in Table 2. In the same manner as in Example 1, the product after the reaction and the positive reaction / side reaction were evaluated.

  The results are shown in Table 2.

  Even if the cyanate ester compound was changed, the cured epoxy resin compositions obtained in Examples 10 to 18 according to the present invention sufficiently proceeded with the curing reaction (positive reaction). It was generating enough. On the other hand, in Comparative Examples 7 to 12 using a conventional curing accelerator (curing catalyst), the positive reaction did not proceed so much. Further, in Comparative Example 7 in which no water was added, carbamate as a by-product was not generated, but in Comparative Examples 8 to 12 in which water was added, a large amount of carbamate was generated.

  From the above results, the curing method according to the present invention can favorably advance the curing reaction of the resin composition containing the cyanate ester compound, and even if water is present in the reaction system, it is a by-product. It was shown that the production of carbamate, which is a product, can also be suppressed.

Claims (10)

  As a component of the thermosetting resin composition, together with a thermosetting resin containing a cyanate ester compound, a curing accelerator containing at least one selected from a metal ion complex of crown ether and a metal ion complex of cryptand is contained, A method for curing a thermosetting resin composition, characterized by heating and curing.   The method for curing a thermosetting resin composition according to claim 1, wherein the central metal of the metal ion complex is one selected from the group consisting of zinc, cobalt, iron, copper, manganese, and zirconium.   The method for curing a thermosetting resin composition according to claim 1 or 2, wherein the crown ether or the cryptant which is a ligand of the metal ion complex has 15 or more carbon atoms and 5 or more oxygen atoms.   The method for curing a thermosetting resin composition according to claim 1, wherein the cyanate ester compound has at least two or more cyanate groups in a molecule.   The thermosetting according to any one of claims 1 to 4, wherein the content of the curing accelerator is 10 ppm to 300 ppm in terms of a metal concentration relative to the entire resin composition containing the thermosetting resin and the curing accelerator. Method for curing conductive resin composition.   A thermosetting resin composition comprising: a thermosetting resin containing a cyanate ester compound; and a curing accelerator containing at least one selected from a metal ion complex of a crown ether and a metal ion complex of a cryptand. object.   The thermosetting resin composition according to claim 6, wherein the central metal of the metal ion complex is one selected from the group consisting of zinc, cobalt, iron, copper, manganese, and zirconium.   The thermosetting resin composition according to claim 6 or 7, wherein the crown ether or the cryptant which is a ligand of the metal ion complex has 15 or more carbon atoms and 5 or more oxygen atoms.   The thermosetting resin composition according to any one of claims 6 to 8, wherein the cyanate ester compound has at least two or more cyanate groups in a molecule.   The thermosetting resin according to any one of 6 to 9, wherein the content of the curing accelerator is 10 ppm to 300 ppm in terms of metal concentration with respect to the entire resin composition containing the thermosetting resin and the curing accelerator. Composition.