JP4895487B2 - Thermosetting resin composition, method for producing the same, and method for producing molded product - Google Patents

Description

  The present invention relates to a thermosetting resin composition containing a polyamine borate, and further relates to a method for producing such a thermosetting resin composition and a method for producing a molded product using the thermosetting resin composition.

Reaction products of amine compounds such as monoamine and diamine and boric acid have been studied for a long time (see, for example, Patent Document 1). In these documents, an aqueous solution obtained by reacting an amine compound and boric acid is used as it is as a latex coagulant or a catalyst for producing α-alkylacrolein. Recently, an example of using it as a component of a cement composition has been reported (see, for example, Patent Document 2).
On the other hand, demands for heat resistance are becoming increasingly severe for thermosetting resins such as epoxy resins and novolak phenolic resins used in various industrial fields. One of the effective means for improving the heat resistance is to select a curing agent. As the curing agent for epoxy resin and novolak phenol resin, amine compounds are most widely used. However, the glass transition temperature (T _g ) of a resin cured product using an amine curing agent is about 150 ° C. at the highest, and the heat resistance is not sufficient. In addition, many amine compounds have an irritating odor and have a safety problem in handling.
When an amine compound is used as a curing agent for an epoxy resin, it is known that boric acid is used as an additive such as a curing inhibitor (see, for example, Patent Document 3). In this case, there is a problem that the amine compound is toxic, and depending on the type, the odor is strong and the handling is troublesome. Further, when the amount of boric acid to be added is small, the heat resistance of the obtained cured product is not sufficient, and when the amount of boric acid is increased, the storage stability is inferior or the obtained cured product has a low temperature T _g. For example, a sub peak of tan δ is observed at 107 ° C., which adversely affects the properties of the cured product.
In addition, a method for producing a laminate using a composition in which an epoxy resin is combined with a curing agent of an organic phosphorus compound and monoamine borate as a curing accelerator has been reported (for example, see Patent Document 4). However, since the monoamine borate used does not act as a curing agent, the heat resistance of the resulting cured product has not been greatly improved.
Furthermore, a sealant for a tape carrier package containing a phenol novolak resin as a curing agent and 2-ethyl-4-methylimidazole tetraphenylborate as a curing accelerator in an epoxy resin is known (see, for example, Patent Document 5). . The 2-ethyl-4-methylimidazole tetraphenylborate used here is a compound in which tetraphenylborate is bonded to a boron atom and a phenyl group without interposing an oxygen atom, It does not contribute to the improvement of heat resistance.
JP-A-4-338355 Special table 2003-504294 gazette JP-A-4-227924 US Pat. No. 3,738,862 Japanese Patent Laid-Open No. 11-343392

The objective of this invention is providing the polyamine borate containing thermosetting resin composition which can make boron content high with respect to a thermosetting resin.
That is, an object of the present invention is to add a polyamine borate to a thermosetting resin such as an epoxy resin or a novolak phenol resin, thereby providing a resin composition capable of providing a heat-resistant cured product having a high glass transition temperature. And a manufacturing method thereof.

As a result of intensive studies to achieve the above object, the present inventor has used polyamine borate obtained by reacting a polyamine compound and inexpensive boric acid as a curing agent for a thermosetting resin. In order to complete the present invention, boric acid groups are introduced into thermosetting resins such as epoxy resins and novolak phenolic resins at the molecular level to obtain a cured product having high heat resistance, that is, a high glass transition temperature. It came.
That is, the present invention is a thermosetting resin, and as its curing agent, a polyamine compound and a general formula (1)
B (OR) n (OH) 3-n (1)
(Wherein n is an integer from 0 to 3, R is an alkyl group of C _m H _{2m + 1} , and m is an integer from 1 to 10). The present invention relates to a thermosetting resin composition containing polyamine borate as an essential component, a method for producing the thermosetting resin composition, and a method for producing a molded product using the thermosetting composition.

The present invention has almost no amine-stimulated odor and has a property of being well soluble in methanol. By adding polyamine borate used as a curing agent for thermosetting resins to thermosetting resins, amine curing can be achieved as in the past. The boron content can be increased as compared with the case where a boric acid-based compound is added as an agent and a curing property adjusting agent. Moreover, the cured product of the resulting thermosetting resin composition has a very high glass transition temperature.
Moreover, the powdery thermosetting epoxy resin composition using the polyamine borate of the present invention has not only a high glass transition temperature but also excellent storage stability and flowability.

In the present invention, the polyamine borate used as the curing agent for the thermosetting resin includes a polyamine compound and a general formula (1) B (OR) n (OH) 3-n (1)
(Wherein n is an integer from 0 to 3, R is an alkyl group of C _m H _{2m + 1} , and m is an integer from 1 to 10). It is.
For example, polyamine borate removes a solvent from a reaction product obtained by reacting a polyamine compound and a boric acid compound in a solvent or water, and in some cases, separates and purifies the amine to stimulate the amine. It can be obtained as powdered polyamine borate without odor.

  As the polyamine compound used in the present invention, a polyamine compound capable of curing a thermosetting resin is used. In the case of an epoxy resin, a polyamine having at least one of an amino group and an imino group in the molecule is particularly preferably used. Such polyamine compounds are preferably aliphatic polyamines, aromatic polyamines and alicyclic polyamines, and may have a nitrilo group in the molecule.

A general formula of a typical polyamine compound used is shown in the following formula.

R ₁ , R ₂ and R ₃ in the general formula (2) represent hydrogen, an alkyl group having 1 to 20 carbon atoms, and an alkanol group having 1 to 20 carbon atoms. X represents any of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkanol group having 1 to 20 carbon atoms, or an oxyalkylene group having 2 to 50 carbon atoms. However, at least one of R1, R2, R3 and X is hydrogen. Y represents a phenyl group, an alkylene or alkylene ether group having 2 to 50 carbon atoms, and n represents an integer of 1 to 5.

  Moreover, the imidazole compound shown by General formula (3) is also mentioned as a polyamine type compound.

In the general formula (3), R ₄ represents methyl, ethyl, isopropyl, alkyl having 11 carbon atoms, alkyl having 17 carbon atoms, phenyl or the like, and R ₅ represents hydrogen, methyl or the like.

Specific examples of the polyamine compound include the following.
(1) Aliphatic polyamine:
Ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, propylenediamine, dipropylenetriamine, cyclohexanediamine, hexamethylenediamine, triethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, bis ( Hexamethylene) triamine.
(2) Alicyclic polyamine:
Metacenediamine, isophoronediamine, N-aminoethylpiperazine, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane, 1,3,5-tris (aminomethyl) benzene.
(3) Aromatic polyamine:
m-phenylenediamine, metaxylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone.
(4) Polyamidoamine:
Polyamidoamines produced by the reaction of aliphatic polyamines with polymerized fatty acids and benzoic acid, such as lacqueramide TD-984 and Epicron B-053 (both manufactured by Dainippon Ink and Chemicals, Inc.).
(5) Secondary amine compound:
N-methylpiperazine, hydroxyethylpiperazine.
(6) Imidazole compounds:
2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole.
(7) Dicyandiamide
(8) Hexamine

As the boric acid compound in the present invention, the general formula (1)
B (OR) n (OH) 3-n (1)
(Wherein, n an integer from 0 to 3, R is an alkyl group C _m H _{2m + 1, m} represents. An integer of 1 to 10) boric acid and boric acid esters represented by the boric acid Partial polycondensates of esters are used. Specific examples of boric acid include, for example, orthoboric acid, metaboric acid, tetraboric acid, and mixtures thereof. Specific examples of boric acid esters include, for example, trimethyl borate, triethyl borate, Examples include tripropyl borate and tributyl borate. These boric acid and boric acid ester can be used individually or in combination of 2 or more types. Moreover, those partial hydrolysates and partial polycondensates can also be used. Of these, boric acid is most preferably used.
The partial polycondensate can be obtained by a method in which the borate ester represented by the general formula (1) is mixed and stirred with water, a solvent, and, if necessary, an acid or base catalyst.

Specific examples of the polyamine borate obtained by the reaction of the polyamine compound represented by the above general formula and the boric acid compound include ethylenediamine borate, diethylenetriamine borate, triethylenetetramineborate, tetraethylene. Aliphatic polyamine borates such as pentamine borates. In the case of small molecules of ethylenediamine and diethylenetriamine, crystalline and amorphous polyamine borates can be produced separately, and both are used as polyamine borates effective in the present invention. For example, when a solvent such as N, N-dimethylformamide is used as a synthesis solvent, a crystalline polyamine borate can be obtained. On the other hand, when water is used as the synthesis solvent, an amorphous polyamine borate is obtained. In this non-crystalline polyamine borate, the ¹¹ B-NMR signal shifts to a lower magnetic field side than the crystalline polyamine borate and the absorption of BO bond stretching vibration in FT-IR is crystalline polyamine borate. A shift to a lower wave number than the salt was observed, suggesting that the chemical structure of borate groups is different. In addition, both the crystalline and non-crystalline polyamine borates have a measured boron content higher than the calculated boron content of the mononuclear borate. Was estimated to be a polynuclear condensed borate. On the other hand, as a result of X-ray structural analysis of a single crystal obtained by dissolving crystalline ethylenediamine borate in methanol and then cooling overnight, it agrees with the structure of the mononuclear borate represented by the following formula (4) I found out that This mononuclear borate is considered to be obtained by esterification of the mononuclear borate represented by the formula (5), and the mononuclear borate represented by the formula (5) is included in the crystalline ethylenediamine borate. It was concluded that nuclear borate was also included.

  On the other hand, when a large molecule of triethylenetetramine or tetraethylenepentamine is used, only an amorphous polyamine borate can be obtained even if the synthesis solvent is a solvent such as N, N-dimethylformamide. Moreover, from the measured boron content and amine content, it was concluded that the main component of the obtained polyamine borate was a polynuclear condensed borate.

Another specific example of the polyamine borate of the present invention is polyamidoamine borate. When polyamidoamine is used, crystalline and non-crystalline polyamidoamine borate can be made differently depending on the molar ratio of amine to boric acid. For example, when 1 mol or more of boric acid is charged with respect to 1 mol of an amino group and an imino group in an amine, a crystalline polyamidoamine borate is obtained. On the other hand, when the amount of boric acid charged is less than 0.6 mol relative to 1 mol of the amino group or imino group, an amorphous polyamidoamine borate is obtained. Further, from the measurement of the boron content, it was found that the main component of the crystalline polyamidoamine borate is a polynuclear condensed borate.
As another specific example of the polyamine borate of the present invention, a tertiary polyamine hexamine borate can be exemplified. In this case, a crystalline polyamine borate is obtained. Moreover, since the measured value of boron content was higher than the calculated value of the boron content of mononuclear borate, it was concluded that the main component of the obtained hexamine borate was a polynuclear condensed borate.

  Specific examples of imidazole borate include 2-ethyl-4-methylimidazole borate. From the X-ray diffraction pattern and the measured boron content, it was found that crystalline imidazole condensed borate was obtained.

  The synthesis of the polyamine borate in the present invention can be performed, for example, as follows. That is, the polyamine compound solution is dropped while stirring or dissolving boric acid in a solvent or water. In some cases, the boric acid solution may be dropped while stirring the solvent solution or aqueous solution of the polyamine compound with the addition order reversed. Subsequently, the reaction is carried out at room temperature or under heating for a fixed time. As a result, polyamine borate precipitates and the precipitate (polyamine borate) is recovered by suction filtration. On the other hand, the reaction product may be dissolved in the reaction solvent. In that case, the solvent is distilled off by an evaporator to recover the polyamine borate. The reaction product obtained as described above is washed several times with N, N-dimethylformamide, acetone or the like and then vacuum dried to obtain a white powdered amine borate.

  As a synthetic solvent for polyamine borate in the present invention, a solvent capable of dissolving at least one of boric acid compounds or polyamine compounds is required. Specific examples include lower alcohols such as methanol, ethanol and isopropanol, acetone, methyl ethyl ketone, tetrahydrofuran, N, N-dimethylformamide, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, water and the like. These can be used alone or in a mixture of two or more. Among them, it is particularly preferable to use N, N-dimethylformamide or water. The amount of the solvent used is preferably such that the solvent is 300 to 1500 parts by mass with respect to 100 parts by mass in total of the boric acid compound and the polyamine compound.

  As a synthesis condition of the polyamine borate in the present invention, the molar ratio between the nitrogen-containing group in the polyamine compound and the boron in the borate compound is important. When the ratio of the boric acid compound is increased, a polynuclear condensed borate is easily formed, and a polyamine borate having a high boron content can be obtained. On the other hand, when the ratio of the polyamine compound is increased, a polyamine borate having a lower boron content can be obtained. Generally, the amount of boron is preferably 0.25 to 10 mol, more preferably 0.5 to 8 mol, relative to a total of 1 mol of the nitrogen-containing group in the polyamine compound, that is, the amino group, imino group and nitrilo group. , Particularly preferably 1 to 6 mol. When the amount is less than 0.25 mol or exceeds 10 mol, the yield of polyamine borate is low, which is not preferable because it is economically disadvantageous. Moreover, although it changes with kinds of polyamine type compound to be used about reaction temperature, generally 15 to 150 degreeC is preferable, More preferably, it is 20 to 120 degreeC, Especially preferably, it is 25 to 100 degreeC. The reaction time depends on the reaction temperature, but usually 1 to 15 hours is preferably used.

The polyamine borate used in the present invention is a solid powder having almost no irritating odor peculiar to amines, has a property of being well soluble in water or a lower alcohol such as methanol, and is thermosetting such as an epoxy resin or a novolak phenol resin. It is suitably used as a curing agent for the conductive resin.
Examples of the thermosetting resin in the present invention include an epoxy resin, a novolac phenol resin, and a polyurethane resin.

The epoxy resin is a conventional epoxy resin having an average of two or more epoxy groups in one molecule, and the kind thereof is not particularly limited. For example, the following various epoxy resins can be used alone or in combination of two or more.
(1) Phenolic glycidyl ether type epoxy resin:
Phenolic glycidyl ether type epoxy resin obtained by reaction of phenolic compounds such as bisphenol-A, bisphenol-F, tetrabromobisphenol-A, tetraphenylolethane, phenyl novolak, cresol novolak, and epichlorohydrin.
(2) Alcohol-based glycidyl ether type epoxy resin:
(a) a polyol obtained by an addition reaction between a phenol compound such as bisphenol-A, bisphenol-F, tetrabromobisphenol-A, tetraphenylolethane and alkylene oxide, or a polyol such as hydrogenated bisphenol A, and (b) Alcohol glycidyl ether type epoxy resin obtained by reaction with epichlorohydrin.
(3) Glycidyl ester type epoxy resin:
Diglycidyl ester type epoxy resins such as hexahydrophthalic acid diglycidyl ester and dimer acid glycidyl ester.
(4) Glycidylamine type epoxy resin:
Glycidyl amine type epoxy resins such as 1,3-diglycidyl hydantoin, triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane, triglycidyl loop paraaminophenol and the like.
(5) Mixed epoxy resin:
Mixed epoxy resins such as epoxy resins obtained by reaction of aminophenol or oxybenzoic acid and epichlorohydrin, cycloaliphatic epoxy resins having a cyclopetadiene or dicyclopentadiene skeleton, and brominated epoxy resins.

  In the present invention, in order for the cured product of the epoxy resin composition to obtain a sufficiently high glass transition temperature and excellent mechanical properties, the epoxy group equivalent of the epoxy resin is preferably 100 to 1000, more preferably 110. It is -800, Most preferably, it is 120-500.

As the curing agent for the epoxy resin in the present invention, among the polyamine borates described above, polyamines such as ethylenediamine borate, diethylenetriamine borate, triethylenetetramine borate, tetraethylenepentamine borate, etc. Preferable examples include borate, polyamidoamine borate obtained from lacqueramide TD-984, Epicron B-053, and the like, and imidazole borate such as 2-ethyl-4-methylimidazole borate. These polyamine borates are crystalline, non-crystalline, mononuclear borates, polynuclear condensed borates, and any effective epoxy in the present invention. Used as a curing agent for resins.

The amount of each polyamine borate used as the epoxy resin curing agent in the present invention can be determined based on the amount of the amine compound contained therein that is usually used as the epoxy resin curing agent, but the resulting cured product In order to obtain sufficient heat resistance, the amount of use can be greatly exceeded. Generally, it is preferable to add 4 to 120 parts by weight, that is, 4 to 120 phr with respect to 100 parts by weight of the epoxy resin. As a specific example, when an aliphatic polyamine borate is used, 5 to 50 phr, more preferably 10 to 40 phr, and particularly preferably 15 to 30 phr are used with respect to the epoxy resin. When polyamidoamine borate is used, 10 to 120 phr, more preferably 15 to 80 phr, and particularly preferably 20 to 60 phr is used with respect to the epoxy resin. When 2-ethyl-4-methylimidazole borate is used, 4-35 phr, more preferably 6-30 phr, and particularly preferably 8-25 phr is used for the epoxy resin.
In addition, the polyamine borate has a boron content of 0.2 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin from the viewpoint of preferable heat resistance, strength and other physical properties of the cured epoxy resin. It is preferable to add so that it becomes.
In the present invention, it is essential to use the polyamine borate as a curing agent for the epoxy resin. On the other hand, the monoamine borate that has been used as a curing accelerator for conventional epoxy resins, for example, dipropylamine borate is insufficient in curability even if it is added to the epoxy resin and cured, Strength and heat resistance are not enough.
Moreover, even if polyamine as a curing agent and boric acid or boric acid ester as curing inhibitors are individually added to the epoxy resin and cured, if the amount of boric acid is small, the heat resistance of the cured product is inferior. When a considerably large amount is added, only a cured product having a reduced strength due to a loss of curability can be obtained.

  As a solvent for the epoxy resin composition that can be used in the present invention, a solvent that can uniformly dissolve the epoxy resin and polyamine borate or a solvent that does not dissolve the polyamine borate but dissolves the epoxy resin is used. The As the solvent capable of dissolving the epoxy resin and the polyamine borate, those containing a lower alcohol are usually used. For example, a solvent such as acetone, methyl ethyl ketone, tetrahydrofuran, N, N-dimethylformamide, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, methyl ethyl cellosolve, and about 1 to 6 carbon atoms such as methanol, ethanol, isopropanol And a mixture of solvents to which a lower alcohol is added. Moreover, when aiming at an epoxy resin composition having excellent storage stability, it is preferable to use a solvent that dissolves the epoxy resin without dissolving the polyamine borate as the solvent. For example, acetone, methyl ethyl ketone, tetrahydrofuran, N, N-dimethylformamide, N-methylpyrrolidone, N, N-dimethylacetamide, methyl ethyl cellosolve and the like can be mentioned, and these can be used alone or in a mixture of two or more.

In the method for producing an epoxy resin composition in the present invention, it is extremely important to perform a heat treatment in a solution state in which an epoxy resin and a polyamine borate are uniformly dissolved in a solvent in order to obtain a uniform transparent epoxy resin composition. It is. The heat treatment in a solution state refers to heating in a closed system without substantially removing the solvent, so that the solution does not gel. By performing such heat treatment, the epoxy resin and the polyamine borate react or interact with each other, and the polyamine borate is uniformly compatible at the molecular level in the epoxy resin solution. The composition obtained by removing the solvent from the resulting solution is uniformly transparent without aggregation of polyamine borate. On the other hand, when there is no heat treatment in a solution state, polyamine borate precipitates together with solvent removal, and the resulting cured product becomes an opaque and brittle material.
The conditions of the heat treatment in the solution state vary depending on the ease of reaction or interaction between the polyamine borate used and the epoxy resin. Basically, as the lower limit and upper limit of the heat treatment, it is important to perform the heat treatment in a range where the polyamine borate is not precipitated by subsequent solvent removal (lower limit) and in a range where the solution does not gel (upper limit). is there. When the heat treatment is excessively performed, the composition thickens or gels, which is not preferable from the viewpoint of practicality.
Specifically, the heat treatment temperature in the solution state is 25 to 100 ° C., more preferably 30 to 90 ° C., particularly preferably 40 when aliphatic polyamine borate and polyamidoamine borate are used as the curing agent. Can be performed at -80 ° C. Although heat processing time changes with heat processing temperature, 0.1 to 40 hours are preferable, More preferably, it is 0.2 to 30 hours, Especially preferably, it is 0.3 to 20 hours.
When imidazole borate is used, the heat treatment temperature in the solution state is preferably 30 to 150 ° C, more preferably 40 to 130 ° C, and particularly preferably 50 to 110 ° C. Although heat processing time changes with heat processing temperature, 0.3-50 hours are preferable, More preferably, it is 0.5-40 hours, Most preferably, it is 1-25 hours.

  In the method for producing an epoxy resin composition having storage stability of the present invention, an epoxy resin composition having excellent storage stability is obtained by performing a fine dispersion treatment without dissolving polyamine borate in the epoxy resin. It is done. As a method for finely dispersing polyamine borate, (1) a method in which polyamine borate is added to an epoxy resin and kneaded using a mixer or a roll, (2) polyamine borate and a solvent are mixed with an epoxy resin. And (3) a method of adding polyamine borate, a solvent and glass beads to an epoxy resin, and mixing and dispersing using a shaker or the like. By performing these treatment methods, the polyamine borate is finely dispersed in the epoxy resin on the order of microns or less, and becomes a latent curing agent that does not react with the epoxy resin at room temperature. The obtained composition does not aggregate or settle polyamine borate and becomes a uniform material.

  By removing the solvent from the epoxy resin composition obtained in the present invention without proceeding the curing reaction, a solventless epoxy resin composition can be produced. Although the solvent removal temperature varies depending on the curing agent used, it is preferably 100 ° C. or less, more preferably 80 ° C. or less, and particularly preferably 60 ° C. or less.

The solution-like thermosetting epoxy resin composition produced by the above-described method can be used as a heat-resistant paint for substrates such as metals, ceramics, and heat-resistant plastics, and also as a heat-resistant impregnating agent for glass fibers. be able to.
As one application example of the solution-like thermosetting epoxy resin composition of the present invention, an uncured coating layer of the solution-like thermosetting epoxy resin composition is formed on the surface of the heat-resistant substrate sheet. Heat resistance by, for example, superposing another heat-resistant substrate sheet on the uncured coating layer and curing the uncured coating layer by thermocompression bonding the two heat-resistant substrate sheets. Mention may be made of laminated sheets.
As heat-resistant base sheet, inorganic materials such as copper, aluminum, titanium and ceramic, organic materials such as heat-resistant polyester, polyamide and polyimide, organic and inorganic such as glass fiber reinforced polyester and glass fiber reinforced epoxy resin Examples thereof include a sheet made of a heat resistant material selected from composite materials.
For example, the epoxy resin composition is applied or impregnated on a heat-resistant substrate, and then dried to obtain a prepreg. A copper-clad laminate can be produced by overlaying a copper foil on this prepreg and heating and compressing.
Moreover, after apply | coating the said epoxy resin composition directly to copper foil and drying, it superimposes it with an epoxy resin glass cloth board, and can also manufacture a copper clad laminated board by heat-compressing.
The copper-clad laminate produced by the method described above is excellent in heat resistance and moisture and solder resistance, and is suitably used as an electronic component.

When obtaining a powdery thermosetting epoxy resin in the present invention, the epoxy resin and polyamine borate are uniformly dissolved in a solvent containing a lower alcohol, the solution is heated, and then the solvent is removed. It can manufacture by grind | pulverizing the solid thermosetting epoxy resin composition obtained.
The solvent in the solution-like thermosetting epoxy resin composition can be removed by a conventional method using a hot air dryer, freeze dryer, vacuum dryer, or the like. It is preferable to remove the solvent by heating the resin composition in a temperature range of 25 ° C. to 120 ° C. in an air atmosphere under heating gas flow or reduced pressure. The solvent removal temperature varies depending on the type of solvent and the type of polyamine borate to be used, but it is, for example, 30 ° C to 100 ° C. The pulverization can be carried out by a known and commonly used method, preferably pulverizing to an average particle size of 300 μm or less, and further drying the obtained powder at a temperature of 30 to 100 ° C. under reduced pressure.

  The powdery thermosetting epoxy resin composition produced by the above-described method is compression-molded under heating, and optionally cured by further heat treatment to obtain a heat-resistant cured product. The molding temperature at that time varies depending on the epoxy resin and polyamine borate used, and is not particularly limited, but is usually 90 ° C to 200 ° C.

  As the novolak phenol resin in the present invention, a normal novolac type phenol resin obtained by a reaction between a phenol compound and an aldehyde compound is used. Specifically, monovalent phenolic compounds such as phenol, naphthol and bisphenol A, divalent phenolic compounds such as resorcin and xylenol, or trivalent phenolic compounds such as pyrogallol and hydroxyhydroquinone, and these phenols A phenolic compound consisting of a derivative of an alkyl compound, alkyl, carboxyl, halogen, amine or the like, or a mixture of two or more of them, and an aliphatic aldehyde such as formaldehyde or acetaldehyde, or an aldehyde compound of an aromatic aldehyde such as benzaldehyde or furfural. It is a known novolak-type phenol resin obtained by reacting under an acidic catalyst such as hydrochloric acid, sulfuric acid, succinic acid, phosphoric acid and the like.

In the present invention, hexamine condensed borate is suitably used as the curing agent for the novolak phenol resin. The amount used varies depending on the amine content of the hexamine condensed borate, but is generally preferably 8 to 80 parts by weight, more preferably 10 to 60 parts by weight, particularly preferably 100 parts by weight of the novolak phenol resin. Is 15 to 45 parts by weight.
As the organic solvent of the novolak phenol resin composition in the present invention, an organic solvent capable of uniformly dissolving the novolak phenol resin and the hexamine condensed borate is used. As the organic solvent capable of dissolving the novolak phenol resin and the hexamine condensed borate, those containing a lower alcohol are usually used. For example, a mixture of an organic solvent in which a lower alcohol having about 1 to 6 carbon atoms such as methanol is added to an organic solvent such as acetone, methyl ethyl ketone, cyclohexanone, chloroform, benzene, toluene, and xylene can be used.

In the present invention, a powdery thermosetting novolak is obtained by removing the organic solvent from a solution in which the novolak phenol resin and the hexamine condensed borate are uniformly dissolved in an organic solvent containing a lower alcohol, and pulverizing the resulting solid. A phenol resin composition can be produced.
The organic solvent in the solution-like thermosetting novolak phenol resin composition can be removed by a conventional method using a hot air dryer, a freeze dryer, a vacuum dryer, etc. It is preferable to remove the organic solvent by heating the curable novolak phenol resin composition in a temperature range of 25 ° C. to 80 ° C. under reduced pressure. The pulverization can be carried out by a known and commonly used method. Preferably, the pulverization is performed to an average particle size of 300 μm or less, and the obtained powder is further dried at a temperature of 25 to 80 ° C. under reduced pressure.

  The above-mentioned powdery thermosetting novolak phenol resin composition is compression-molded under heating, and is optionally cured by further heat treatment to obtain a heat-resistant cured product. The molding temperature varies depending on the novolak phenol resin used and is not particularly limited, but is usually 80 ° C to 200 ° C.

  The thermosetting novolak phenol resin composition of the present invention provides a cured product having a glass transition temperature higher by 150 ° C. or more than a cured product of novolak phenol resin using a normal hexamine curing agent. Taking advantage of this excellent heat resistance, it is used in a wide range of fields such as molding materials, heat insulating materials, paints, sliding materials, and laminated materials.

Thus, the following merits can be manifested in the present invention.
The polyamine borate obtained by reacting the polyamine compound and the inorganic boric acid compound of the present invention has almost no amine-stimulated odor and has a property of being well soluble in methanol or an organic solvent containing methanol, such as an epoxy resin or a novolak. Used as a curing agent for thermosetting resins such as phenol resins.
In the present invention, the thermosetting epoxy resin composition obtained by using the above polyamine borate as a curing agent and uniformly dissolving or finely dispersing it in an epoxy resin gives a cured product having an extremely high glass transition temperature.
The powdery thermosetting epoxy resin composition using the above polyamine borate of the present invention not only has a high glass transition temperature, but also has excellent storage stability and flowability. That is, the powdery thermosetting epoxy resin composition of the present invention has good heat compression moldability after storage at room temperature for 3 months, and is suitable for long-term storage and distribution transfer.
The thermosetting epoxy resin composition using the polyamine borate according to the present invention has not only a high glass transition temperature as an intermediate layer of the heat-resistant laminated sheet but also excellent moisture and solder resistance. That is, after the heat-resistant laminated sheet prepared with the thermosetting epoxy resin composition of the present invention was treated in boiling water at 121 ° C. for 2 hours and immersed in a solder bath at 260 ° C. for 30 seconds, swelling, bubbles, cracks, etc. Did not occur.
In addition, the thermosetting novolac phenol resin composition obtained by uniformly dissolving in a novolak phenol resin using hexamine borate as a curing agent in the present invention gives a cured product having an extremely high glass transition temperature.

Next, the present invention will be specifically described with reference to synthesis examples and examples.
In the following synthesis examples, nuclear magnetic resonance spectrum (NMR) was measured using Lambda300 manufactured by JEOL. ¹¹ B-NMR spectrum was based on boric acid peak in heavy water.
Fourier transform infrared absorption spectrum (FT-IR) is used JASCO Corp. FT / IR-550, was measured in a range of 4000cm ^-1 ~400cm ^-1.
The X-ray diffraction apparatus RINT ULTIMA ⁺ manufactured by Rigaku Corporation was used for the measurement of powder X-ray diffraction.
Mass spectrometry was performed by the EI / MS measurement method with direct introduction of the sample using a mass spectrometer GCMS9100-MK manufactured by Shimadzu Corporation.
The boron content was measured by ICP using an Optima 3300DV manufactured by Perkn Elmer, and quantified by a calibration curve prepared in advance using boric acid.
The amine was quantified by an internal standard method of ¹ H-NMR. That is, a certain amount of benzene or chloroform was added to the sample as an internal standard, and the amount was quantified by the area ratio between the peak and a specific amount of amine of the certain amount of polyamine borate.
The following reagents were used for the synthesis examples of the present invention.
Polyamine compound Ethylenediamine (EDA): Wako Pure Chemical Industries, Ltd., reagent special grade Diethylenetriamine (DETA): Wako Pure Chemical Industries, Ltd., reagent special grade Triethylenetetramine (TETA): Wako Pure Chemical Industries, Ltd., reagent special grade Tetraethylenepentamine (TEPA): manufactured by Wako Pure Chemical Industries, Ltd., reagent-grade polyamidoamine Epicron B-053: manufactured by Dainippon Ink & Chemicals, Inc., active hydrogen equivalent 77g / eq
Polyamidoamine racamide TD-984: Dainippon Ink & Chemicals, Inc., active hydrogen equivalent 97g / eq
Hexamine: Wako Pure Chemical Industries, Ltd., reagent grade
2-Ethyl-4-methylimidazole (2E4MZ): Wako Pure Chemical Industries, Ltd., reagent grade
(2) Boric acid: Wako Pure Chemical Industries, Ltd., reagent grade
(3) Solvent
N, N-dimethylformamide (DMF): Wako Pure Chemical Industries, Ltd., reagent grade Methyl ethyl ketone (MEK): Wako Pure Chemical Industries, reagent grade Acetone: Wako Pure Chemical Industries, reagent grade 1 tetrahydrofuran ( THF): manufactured by Wako Pure Chemical Industries, Ltd., reagent grade hexane: manufactured by Wako Pure Chemical Industries, Ltd., reagent 1 grade chloroform: manufactured by Wako Pure Chemical Industries, Ltd., reagent grade Methanol: manufactured by Wako Pure Chemical Industries, Ltd., reagent grade

(Synthesis Example 1) [Synthesis of ethylenediamine condensed borate]
While stirring a solution of 10 g (0.162 mol) of boric acid in 70 g of DMF, 4.86 g (0.081 mol) of ethylenediamine EDA was added dropwise. A white precipitate immediately precipitated. The mixture was stirred at room temperature for 2 hours, and the precipitate was collected by suction filtration. Subsequently, the obtained precipitate was washed in the order of DMF and acetone, and vacuum dried at 50 ° C. for 2 hours to obtain 6.34 g of white powder 1a. Further, DMF was distilled off from the filtrate with an evaporator, and the obtained white solid was washed with acetone. By vacuum drying at 50 ° C. for 2 hours, 4.58 g of a white powder of the same compound as 1a was obtained. The yield of the reaction product with respect to the raw material was 73.5%. The analysis results are shown in Tables 1, 3 and 5.

(Synthesis Example 2) [Synthesis of ethylenediamine condensed borate]
While stirring a solution of 40 g (0.647 mol) of boric acid in 250 g of DMF, 9.72 g (0.162 mol) of ethylenediamine EDA was added dropwise. A white precipitate immediately precipitated. The mixture was stirred at room temperature for 4 hours, and the precipitate was collected by suction filtration. Subsequently, the obtained precipitate was washed with DMF and acetone in this order and dried in vacuo at 50 ° C. for 15 hours to obtain 35.4 g of white powder 2a as a reaction product in a yield of 71.2% with respect to the raw material. The NMR spectrum was the same as that of 1a, but other analysis results are shown in Tables 3 and 5.

(Synthesis Example 3) [Synthesis of ethylenediamine condensed borate]
While stirring a solution of 30 g (0.485 mol) boric acid in 250 g DMF, 29.2 g (0.485 mol) ethylenediamine EDA was added dropwise. A white precipitate immediately precipitated. The mixture was stirred at room temperature for 15 hours, and the precipitate was collected by suction filtration. Subsequently, the obtained precipitate was washed with DMF and acetone in this order and dried in vacuo at 50 ° C. for 15 hours to obtain 28.1 g of white powder 3a as a reaction product in a yield of 47.4% with respect to the raw material. The NMR spectrum was the same as that of 1a, but other analysis results are shown in Tables 3 and 5.

(Synthesis Example 4) [Synthesis of ethylenediamine condensed borate]
While stirring a solution prepared by dissolving 30 g (0.485 mol) of boric acid in 120 g of distilled water H2O, 14.6 g (0.243 mol) of ethylenediamine EDA was added dropwise. The reaction was performed at room temperature for 2 hours. Then, water was distilled off with an evaporator, followed by vacuum drying at 60 ° C. for 5 hours to obtain 34.2 g of white powder 4a as a reaction product in a yield of 77% with respect to the raw material. The NMR spectrum was the same as that of 1a, but other analysis results are shown in Tables 3 and 5.

(Synthesis Example 5) [Synthesis of diethylenetriamine condensed borate]
While stirring a solution of 60 g (0.971 mol) boric acid in 500 g DMF, 33.4 g (0.324 mol) diethylenetriamine DETA was added dropwise. A white precipitate immediately precipitated. The mixture was stirred at room temperature for 5 hours, and the precipitate was collected by suction filtration. Subsequently, the obtained precipitate was washed with DMF, acetone and hexane in this order, and vacuum dried at 50 ° C. for 15 hours to obtain 64.8 g of white powder 1b as a reaction product in a yield of 69.4% based on the raw material. The analysis results are shown in Tables 1, 3 and 5.

(Synthesis Example 6) [Synthesis of diethylenetriamine condensed borate]
While stirring a solution of 60 g (0.971 mol) boric acid in 500 g DMF, 11.1 g (0.108 mol) diethylenetriamine DETA was added dropwise. A white precipitate immediately precipitated. The mixture was stirred at room temperature for 13 hours, and the precipitate was collected by suction filtration. Subsequently, the obtained precipitate was washed in the order of DMF and acetone, and vacuum dried at 50 ° C. for 12 hours to obtain 48.3 g of a white powder 2b of the reaction product with a yield of 67.9% based on the raw material. The NMR spectrum was the same as that of 1b, but other analysis results are shown in Tables 3 and 5.

(Synthesis Example 7) [Synthesis of diethylenetriamine condensed borate]
While a solution obtained by diluting 33.4 g (0.324 mol) of diethylenetriamine DETA in 250 g of DMF was stirred, a solution of 30 g (0.485 mol) of boric acid in 150 g of DMF was added dropwise. A white precipitate immediately precipitated. The mixture was stirred at room temperature for 14 hours, and the precipitate was collected by suction filtration. Subsequently, the obtained precipitate was washed in the order of DMF and acetone, and vacuum dried at 50 ° C. for 5 hours to obtain 28.5 g of white powder 3b as a reaction product in a yield of 45% with respect to the raw material. The NMR spectrum was the same as that of 1b, but other analysis results are shown in Tables 3 and 5.

(Synthesis Example 8) [Synthesis of diethylenetriamine condensed borate]
While stirring a solution of 20 g (0.324 mol) of boric acid in 160 g of distilled water H2O, 11.2 g (0.108 mol) of diethylenetriamine DETA was added. The reaction was performed at room temperature for 12 hours. Then, water was distilled off with an evaporator, followed by vacuum drying at 60 ° C. for 17 hours to obtain 25 g of white powder 4b as a reaction product in a yield of 80% with respect to the raw material. The NMR spectrum was the same as that of 1b, but other analysis results are shown in Tables 3 and 5.

(Synthesis Example 9) [Synthesis of diethylenetriamine condensed borate]
While stirring a solution of 20 g (0.324 mol) of boric acid in 200 g of distilled water H2O, 22.4 g (0.216 mol) of diethylenetriamine DETA was added. The reaction was carried out at room temperature for 13 hours. Then, after distilling off water with an evaporator, acetone was added and washed. The obtained white powder was vacuum-dried at 50 ° C. for 4 hours to obtain 26.8 g of a reaction product 5b in a yield of 63.2% based on the raw material. The NMR and FT-IR spectra were similar to 4b, but the other analysis results are shown in Table 5.

(Synthesis Example 10) [Synthesis of triethylenetetramineborate]
While stirring a solution obtained by dissolving 60 g (0.971 mol) of boric acid in 600 g of DMF, 35.5 g (0.243 mol) of triethylenetetramine TETA was added dropwise. A white precipitate immediately precipitated. The mixture was stirred at room temperature for 12 hours, and the precipitate was collected by suction filtration. Subsequently, the obtained precipitate was washed with DMF, acetone and hexane in this order, and vacuum dried at 50 ° C. for 15 hours to obtain 69.9 g of a white powder 1c as a reaction product in a yield of 73.2% based on the raw material. The analysis results are shown in Tables 1, 3 and 5.

(Synthesis Example 11) [Synthesis of triethylenetetramineborate]
While stirring a solution of 20 g (0.324 mol) of boric acid in 160 g of distilled water H2O, 11.85 g (0.081 mol) of triethylenetetramine TETA was added. The reaction was performed at room temperature for 15 hours. Then, water was distilled off with an evaporator, followed by vacuum drying at 60 ° C. for 5 hours to obtain 26.9 g of a white powder 2c as a reaction product in a yield of 84.3% based on the raw material. The NMR and FT-IR spectra were similar to 1c, but the other analysis results are shown in Table 5.

(Synthesis Example 12) [Synthesis of tetraethylenepentamine borate]
While stirring a solution of 60 g (0.971 mol) boric acid in 600 g DMF, 36.8 g (0.194 mol) tetraethylenepentamine TEPA was added dropwise. A white precipitate immediately precipitated. The mixture was stirred at room temperature for 13 hours, and the precipitate was collected by suction filtration. Subsequently, the obtained precipitate was washed with DMF, acetone and hexane in this order, and vacuum dried at 50 ° C. for 9 hours to obtain 70.7 g of a white powder 1d of the reaction product at a yield of 73% based on the raw material. The analysis results are shown in Tables 1, 3 and 5.

Synthesis Example 13 Synthesis of tetraethylenepentamine borate
While stirring a solution of 20 g (0.324 mol) of boric acid in 160 g of distilled water H 2 O, 12.27 g (0.065 mol) of tetraethylenepentamine TEPA was added. The reaction was performed at room temperature for 15 hours. Then, water was distilled off with an evaporator, followed by vacuum drying at 60 ° C. for 2 hours to obtain 28 g of white powder 2d as a reaction product in a yield of 86.6% with respect to the raw material. The NMR and FT-IR spectra were similar to 1d, but the other analysis results are shown in Table 5.

(Synthesis Example 14) [Synthesis of Epicron B-053 condensed borate]
While stirring a solution in which 30 g (0.485 mol) of boric acid was suspended in 200 g of MEK, 37.4 g of Epicron B-053 was added dropwise. The mixture was stirred at room temperature for 24 hours, and a white precipitate was collected by suction filtration. Subsequently, the obtained precipitate was washed with DMF, acetone, and hexane in this order, and vacuum-dried at 50 ° C. for 15 hours to obtain 20.9 g of an ocherous powder 1e as a reaction product at a yield of 31% based on the raw material. The analysis results are shown in Tables 4 and 6.

(Synthesis Example 15) [Synthesis of Epicron B-053 borate]
While stirring a solution obtained by dissolving 45 g (0.728 mol) of boric acid in 500 g of DMF, 112.1 g of Epicron B-053 was added dropwise. A white precipitate immediately precipitated. The mixture was stirred at room temperature for 7 hours, and the precipitate was collected by suction filtration. Subsequently, the obtained precipitate was washed with acetone and hexane in this order, and vacuum-dried at 50 ° C. for 15 hours to obtain 50.1 g of a light ocher powder 2e as a reaction product with a yield of 31.8% based on the raw material. The analysis results are shown in Tables 4 and 6.

(Synthesis Example 16) [Synthesis of TD-984 borate]
While stirring a solution prepared by dissolving 30 g (0.485 mol) of boric acid in 500 g of DMF, 94.1 g of racamide TD-984 was poured. A precipitate immediately precipitated. The mixture was stirred at room temperature for 13 hours, and the precipitate was collected by suction filtration. Subsequently, the obtained precipitate was washed in the order of DMF and acetone, and vacuum dried at 50 ° C. for 4 hours to obtain 46 g of light ocher powder 1f as a reaction product in a yield of 37.1% with respect to the raw material. The analysis results are shown in Tables 4 and 6.

(Synthesis Example 17) [Synthesis of hexamine condensed borate]
To a solution of 30 g (0.485 mol) boric acid dissolved in 200 g distilled water H2O, 17 g (0.121 mol) hexamine was added and dissolved by stirring. The reaction was performed at 100 ° C. for 8 hours. And water was distilled off with the evaporator and the obtained white solid was wash | cleaned in order of acetone, chloroform, and hexane. Furthermore, by vacuum drying at 50 ° C. for 15 hours, 32.9 g of white powder 1j of the reaction product was obtained with a yield of 63.8% based on the raw material. The analysis results are shown in Tables 2, 4 and 6.

(Synthesis Example 18) [Synthesis of hexamine condensed borate]
To a solution obtained by dissolving 60 g (0.971 mol) of boric acid in 300 g of distilled water H2O, 17 g (0.121 mol) of hexamine was added and dissolved by stirring. The reaction was performed at 100 ° C. for 4 hours. Subsequently, water was distilled off with an evaporator, and DMF was added to the concentrated solution to precipitate a precipitate. The white solid recovered by filtration was washed with acetone, and then vacuum dried at 50 ° C. for 2 hours to obtain 40.6 g of a white powder 2j of the reaction product in a yield of 52.7% based on the raw material. The NMR spectrum was the same as that of 1j, but other analysis results are shown in Tables 4 and 6.

(Synthesis Example 19) [Synthesis of hexamine condensed borate]
To a solution of 30 g (0.485 mol) of boric acid dissolved in 300 g of distilled water H2O, 34 g (0.242 mol) of hexamine was added and dissolved by stirring. The reaction was performed at 100 ° C. for 4 hours. And water was distilled off by the evaporator and the obtained white solid was wash | cleaned in order of DMF, chloroform, and acetone. Furthermore, by vacuum drying at 50 ° C. for 2 hours, 24.2 g of white powder 3j as a reaction product was obtained with a yield of 37.8% based on the raw material. The NMR and FT-IR spectra were similar to 2j, but the other analysis results are shown in Table 6.

(Synthesis Example 20) [Synthesis of 2-ethyl-4-methylimidazole condensed borate]
While stirring a solution of 20 g (0.324 mol) of boric acid in 80 g of DMF, a solution of 17.8 g (0.162 mol) of 2-ethyl-4-methylimidazole 2E4MZ in 40 g of DMF was added dropwise. A white precipitate immediately precipitated. The mixture was stirred at room temperature for 13 hours, and the precipitate was collected by suction filtration. Subsequently, the obtained precipitate was washed in the order of DMF and acetone, and vacuum dried at 50 ° C. for 4 hours to obtain 12.9 g of white powder 1k as a reaction product with a yield of 34.1% based on the raw material. The analysis results are shown in Tables 2, 4 and 6. In mass spectrometry, a peak having a mass number of 110 corresponding to 2-ethyl-4-methylimidazole was detected.
(Synthesis Example 21) [Synthesis of dipropylamine condensed borate]
While stirring a solution obtained by dissolving 15.3 g (0.25 mol) of boric acid in 80 g of DMF, 25 g (0.25 mol) of dipropylamine was added dropwise. The reaction was carried out at room temperature for 19 hours. Then, DMF was distilled off with an evaporator, and the obtained solid was washed with acetone three times. Furthermore, when vacuum-dried at 70 ° C. for 3 hours, 15 g of white powder of dipropylamine borate was obtained in a yield of 37.5% based on the raw material. The analysis results are shown in Table 6.

In the following examples and comparative examples, the light transmittance was measured by measuring the parallel transmittance of a 300 μm thick film using NDH-300A manufactured by Nippon Denshoku Industries Co., Ltd. The glass transition temperature and the storage elastic modulus (E ′) were measured using a solid dynamic viscoelasticity measuring device (DMA-200 manufactured by Seiko Denshi Kogyo Co., Ltd.) at a measurement frequency of 1 Hz and a heating rate of 2 ° C./min. The glass transition temperature (T _g ) was tan δ peak temperature (tan δ max). In addition, the water absorption was calculated from the initial weight and the weight increase after being left in an atmosphere of 100% humidity for 70 hours, and the ratio was calculated.

(Example 1 and Comparative Example 1)
MEK was added dropwise while stirring a solution of 24.4 g of ethylenediamine condensed borate 1a in 80 g of methanol. After adding 100g of bisphenol A type epoxy resin Epicron 850 (Dainippon Ink Chemical Co., Ltd., epoxy equivalent 190g / eq) to the clear solution, stirring and mixing, heat treatment in solution state at 50 ° C for 1.5 hours And an epoxy resin composition solution was obtained. Subsequently, the solution was applied onto a clean aluminum foil, subjected to solvent casting for 12 hours, dried at 50 ° C., 60 ° C., 70 ° C., 80 ° C., 90 ° C. for 1 hour each, Heat treatment was performed at 180 ° C. for 2 hours each to obtain a cured product of the epoxy resin composition. When the obtained cured product was baked at 1000 ° C. for 2 hours in an air atmosphere, 11.5 g of black ash was obtained.
The cured product was excellent in transparency, and the light transmittance in the visible light region was 93% (100 μm thickness conversion). Moreover, there were no cracks, wrinkles, bubbles, etc., and a good surface morphology was shown. Table 7 shows the evaluation results of the obtained cured product.
Using the 300 μm thick cured film obtained in Example 1, dynamic viscoelasticity measurement (frequency: 1 Hz) was performed. The relationship between the obtained storage elastic modulus (E ′), tan δ, and temperature is shown in FIG. The vertical axis in FIG. 1 is the storage elastic modulus (E ′), and the horizontal axis is the temperature (° C.). FIG. 1 also shows the results of Comparative Example 1 which is a cured product having the same epoxy resin composition except that ethylenediamine is used instead of ethylenediamine condensed borate. In Comparative Example 1, the peak temperature (T _g ) of tan δ was 54.3 ° C, whereas the cured epoxy resin of Example 1 was 288.4 ° C. It is clear that the heat resistance of the cured epoxy resin using polyamine borate as a curing agent is greatly improved.

(Example 2)
Example 2 is an example except that Loebrombisphenol A type epoxy resin Epicron EXA-9101 (Dainippon Ink Chemical Co., Ltd., epoxy equivalent 368 g / eq, solid content 80.5%), ethylenediamine condensed borate 1a was used. In the same manner as in 1, an epoxy resin composition and a cured product thereof were prepared. The evaluation results of the obtained cured product are shown in Table 7 as in Example 1.

(Examples 3 and 4 and Comparative Example 2)
Example 3 uses diethylenetriamine condensed borate 1b, Example 4 uses Loebrombisphenol A type epoxy resin Epicron 1121N-80M (Dainippon Ink Chemical Co., Ltd., epoxy equivalent 493 g / eq, solid content 80 %) And diethylenetriamine condensed borate 1b, otherwise a transparent solution of epoxy resin and polyamine borate was prepared in the same manner as in Example 1, and further heated at 80 ° C. for 30 minutes. Processed. Using the resulting epoxy resin composition solution, a cured product was prepared in the same manner as in Example 1. Further, a cured product of Comparative Example 2, which was an epoxy resin composition having the same composition as Example 3, except that diethylenetriamine was used instead of polyamine borate, was also prepared. Compared with the T _g of the cured product of the epoxy resin composition of Comparative Example 2 using a normal amine curing agent, the cured product of the epoxy resin composition obtained in Examples 3 and 4 using polyamine borate was extremely It showed a high T _g. Table 8 shows the evaluation results of the obtained cured product.

(Example 5 and Comparative Examples 3 to 4)
Example 5 prepared a transparent solution of an epoxy resin and a polyamine borate in the same manner as in Example 1 except that tetraethylenepentamine condensed borate 1d was used, and was further in a solution state at 80 ° C. for 30 minutes. Heat treatment was performed at Using the resulting epoxy resin composition solution, a cured product was prepared in the same manner as in Example 1. When the dynamic viscoelasticity of the obtained cured product was measured, T _g was 289 ° C.
On the other hand, in the cured product of Comparative Example 3 using dipropylamine condensed borate of monoamine borate as a curing accelerator and dicyandiamide (DICY) as an amine curing agent, T _{g is} only 144 ° C., No improvement in heat resistance was observed. For the cured product obtained by mixing with epoxy resin using boric acid and TEPA curing agent instead of polyamine borate, in the case of Comparative Example 4 where the amount of boric acid added is small, the T _{g is} only 143 ° C. There was no improvement in heat resistance. On the other hand, if you increase to correspond boric acid amount in Example 5, sub peak of tanδ was observed at 107 ° C., it showed that T _g of the partially cured resin was low. These results are summarized in Table 9.

(Examples 6 to 8)
Example 6 uses triethylenetetramine condensed borate 1c, Example 7 uses epiclone 1121N-80M and triethylenetetramine condensed borate 1c, Example 8 uses epiclone 1121N-80M and tetraclone A transparent solution of an epoxy resin and a polyamine borate was prepared in the same manner as in Example 1 except that ethylene pentamine condensed borate 1d was used, and further heated in a solution state under the conditions shown in Table 10. Processed. Using the resulting epoxy resin composition solution, a cured product was prepared in the same manner as in Example 1. All of the obtained cured products exhibited excellent transparency and a high glass transition temperature (T _g ). Also, despite having a high T _g, also showed a relatively low water absorption. The evaluation results of the obtained cured product are shown in Table 10.

(Examples 9 to 11 and Comparative Example 5)
Example 9 uses B-053-condensed borate 1e, Example 10 uses B-053-borate 2e, Example 11 uses epiclone 1121N-80M and B-053-boron A transparent solution of an epoxy resin and a polyamine borate was prepared in the same manner as in Example 1 except that the acid salt 2e was used, and further a heat treatment in a solution state was performed under the conditions shown in Table 11. Using the resulting epoxy resin composition solution, a cured product was prepared in the same manner as in Example 1. Further, a cured product of Comparative Example 5, which was an epoxy resin composition having almost the same composition as Example 9, except that B-053 was used instead of polyamine borate, was also prepared. Compared to the T _g of the cured product of the epoxy resin composition of Comparative Example 5 using a normal polyamidoamine curing agent, the cured product of the epoxy resin composition obtained in Examples 9 to 11 using polyamine borate. T _g is greatly improved. The evaluation results of the obtained cured product are shown in Table 11.

(Examples 12 and 13)
Example 12 uses TD-984-borate 1f, Example 13 uses epiclone 1121N-80M and TD-984-borate 1f, and otherwise the same as in Example 1 A transparent solution of resin and polyamine borate was prepared, and heat treatment was performed in the solution state under the conditions shown in Table 12. Using the resulting epoxy resin composition solution, a cured product was prepared in the same manner as in Example 1. The results are shown in Table 12.

(実施例14と15及び比較例6)
実施例14は、2-エチル-4-メチルイミダゾール縮合ホウ酸塩1kを用いること、実施例15は、エピクロンEXA-9101及び2-エチル-4-メチルイミダゾール縮合ホウ酸塩1kを用いること、それ以外は実施例1と同様にしてエポキシ樹脂とポリアミンホウ酸塩との透明溶液を調製し、更に表13に示した条件で溶液状態での加熱処理を行った。得られたエポキシ樹脂組成物溶液を用いて実施例1と同様にしてその硬化物を作成した。また、ポリアミンホウ酸塩の変わりに2-エチル-4-メチルイミダゾールを用いた以外は実施例14とほぼ同一の組成のエポキシ樹脂組成物である比較例6の硬化物も作成した。2-エチル-4-メチルイミダゾールを用いた比較例6のエポキシ樹脂組成物の硬化物のT_gに比べ、ポリアミンホウ酸塩を使用した実施例14と15で得られたエポキシ樹脂組成物の硬化物のT_gが極めて高いことがわかる。尚、得られた硬化物の評価結果を表13に示す。

(Examples 14 and 15 and Comparative Example 6)
Example 14 uses 2-ethyl-4-methylimidazole condensed borate 1k, Example 15 uses epiclone EXA-9101 and 2-ethyl-4-methylimidazole condensed borate 1k, A transparent solution of an epoxy resin and a polyamine borate was prepared in the same manner as in Example 1, except that heat treatment was performed in a solution state under the conditions shown in Table 13. Using the resulting epoxy resin composition solution, a cured product was prepared in the same manner as in Example 1. Further, a cured product of Comparative Example 6, which was an epoxy resin composition having almost the same composition as Example 14, except that 2-ethyl-4-methylimidazole was used instead of polyamine borate, was also prepared. Curing of the epoxy resin compositions obtained in Examples 14 and 15 using polyamine borate compared to the T _g of the cured product of the epoxy resin composition of Comparative Example 6 using 2-ethyl-4-methylimidazole It can be seen that the _{Tg of the} object is extremely high. The evaluation results of the obtained cured product are shown in Table 13.

(Examples 16 and 17)
Example 16 was prepared by mixing 100 g of epiclone 850, 24 g of diethylenetriamine condensed borate 1b, and 47 g of diluent MEK, placing them in a container together with glass beads, and shaking them for 15 hours using a shaker. The salt was uniformly dispersed in the epoxy resin. When the obtained composition was allowed to stand at 50 ° C. for two months or more, the solution did not thicken and there was no aggregation or sedimentation of polyamine borate, and excellent storage stability was exhibited. A cured product of the epoxy resin composition was produced in the same manner as in Example 1 except that this composition was heat-treated at 180 ° C. for 5 hours. Cured product obtained showed very high T _g.
In addition, in Example 17, a storage-stable epoxy resin composition and a cured product thereof were prepared in the same manner as in Example 16 except that epiclone EXA-9101 and tetraethylenepentamine borate 1d were used. The evaluation results are shown in Table 14.

(Example 18)
While stirring a solution of 21.3 g of tetraethylenepentamine condensed borate 1d in 80 g of methanol, 80 g of MEK was added dropwise. After adding 100 g of epiclone 850 to the obtained transparent solution and stirring and mixing, heat treatment was performed in a solution state at 80 ° C. for 50 minutes to obtain an epoxy resin composition solution. Next, the solution was cast on a tray, cast in a solvent at room temperature for 12 hours, dried in a hot air dryer at 50 ° C. and 60 ° C. for 1 hour, and further at 70 ° C. for 1 hour. Was vacuum dried. The obtained sample was frozen with liquid nitrogen and pulverized to a size of 300 μm or less. Subsequently, the obtained powder was dried at 60 ° C. under vacuum for 2 hours to obtain a powdery thermosetting epoxy resin composition.
Next, the obtained powdery thermosetting epoxy resin composition was hot-pressed at 150 ° C. to produce a 1 mm thick plate-like epoxy resin molded piece. 2 hours subsequently 0.99 ° C. The press molding pieces, further cured product obtained by heat treatment for 4 hours at 180 ° C. is excellent in heat resistance, glass transition temperature by measuring the dynamic viscoelasticity met 243 ° C. . Further, it was excellent in transparency, and the light transmittance in the visible light region of the above-mentioned molded piece was 80%. Furthermore, after holding this powdery thermosetting epoxy resin composition at room temperature for 3 months, the physical properties of the hot press and the cured product were measured, and the same results were obtained and the storage stability was excellent. confirmed.

(Example 19)
While stirring a solution of 14.5 g of tetraethylenepentamine condensed borate 1d in 33 g of methanol, 33 g of MEK was added dropwise. 125 g of epiclone 1121N-80M was added to the obtained transparent solution, mixed with stirring, and then heat-treated in a solution state at 80 ° C. for 30 minutes to obtain a uniform transparent epoxy resin composition solution. The glass transition temperature of the cured film produced using the composition solution was 268 ° C. by dynamic viscoelasticity measurement. Subsequently, the above composition solution was applied to a copper foil (32 micron thickness) using a 0.25 mm applicator, and solvent casting was performed in the atmosphere for 2 hours. Subsequently, vacuum drying was performed at 25 ° C. for 13 hours to obtain a copper foil provided with an uncured layer of a curable epoxy resin composition. The thickness of the uncured coating film layer was about 60 μm. The coated copper foil was overlapped with a glass cloth resin molded plate and hot-pressed at 150 ° C. and 100 MPa to prepare a copper-clad laminate. The obtained copper-clad laminate was treated in water vapor at 121 ° C. for 2 hours and then subjected to a moisture resistance solder resistance test in which it was immersed in a solder bath at 260 ° C. for 30 seconds. As a result, it showed good moisture and solder resistance with no occurrence of blisters, bubbles or cracks.

FIG. 3 is a graph showing storage elastic modulus (E ′) and temperature dispersion of tan δ of the cured epoxy resin obtained in Example 1 and Comparative Example 1.

Claims (9)

Thermosetting resin and its curing agent, polyamine compound and general formula (1)
B (OR) _n (OH) _3-n (1)
(Wherein n is an integer from 0 to 3, R is an alkyl group of C _m H _{2m + 1} , and m is an integer from 1 to 10). Containing polyamine borate as an essential component,
The thermosetting resin is an epoxy resins having two or more epoxy groups in a molecule,
The content of the previous SL polyamine borate, Ri 4 to 120 parts by mass der per 100 parts by weight of the epoxy resin, and boron content of the polyamine borate, relative to the epoxy resin 100 parts by weight 1.2 to 10 parts by mass,
The thermosetting resin composition characterized by the above-mentioned. The thermosetting resin according to claim 1, wherein the polyamine compound is an aliphatic polyamine, an aromatic polyamine, or an alicyclic polyamine, and has one or more of an amino group and an imino group in the molecule. Composition. The thermosetting resin composition according to claim 1 or 2, wherein the content ratio of the nitrogen-containing group of the polyamine compound and the boron of the boric acid compound (B) is 1: 1 to 1: 6. . The thermosetting resin composition according to any one of claims 1 to 3, wherein the thermosetting resin and the polyamine borate are dissolved in an organic solvent containing a lower alcohol. Polyamine compounds and the following general formula (1)
B (OR) _n (OH) _3-n (1)
(Wherein n is an integer from 0 to 3, R is an alkyl group of C _m H _{2m + 1} , and m is an integer from 1 to 10). To produce polyamine borate,
Then, a method for producing a thermosetting resin composition comprising a step of mixing the polyamine borate and a thermosetting resin in an organic solvent,
The thermosetting resin is an epoxy resins having two or more epoxy groups in a molecule,
The amount of pre-Symbol polyamine borate, Ri 4 to 120 parts by mass der per 100 parts by weight of the epoxy resin, and boron content of the polyamine borate, relative to the epoxy resin 100 parts by weight 1.2 to 10 parts by mass,
The manufacturing method of the thermosetting resin composition characterized by the above-mentioned. The method for producing a thermosetting resin composition according to claim 5 , wherein the organic solvent is removed after the step of mixing the polyamine borate and the thermosetting resin in an organic solvent. A method for producing a molded product obtained by curing a thermosetting resin composition,
Polyamine compounds and the following general formula (1)
B (OR) _n (OH) _3-n (1)
(Wherein n is an integer from 0 to 3, R is an alkyl group of C _m H _{2m + 1} , and m is an integer from 1 to 10). To produce polyamine borate,
Thereafter, the polyamine borate and the thermosetting resin are mixed in an organic solvent,
Furthermore, a thermosetting resin composition from which the organic solvent has been removed is manufactured,
Compression-molding the thermosetting resin composition under heating and curing,
The thermosetting resin is an epoxy resins having two or more epoxy groups in a molecule,
The amount of pre-Symbol polyamine borate, Ri 4 to 120 parts by mass der per 100 parts by weight of the epoxy resin, and boron content of the polyamine borate, relative to the epoxy resin 100 parts by weight 1.2 to 10 parts by mass,
The manufacturing method of the molding characterized by the above-mentioned. An uncured coating layer of the thermosetting resin composition according to claim 1 is provided on the surface of the heat-resistant substrate sheet, and another heat-resistant substrate sheet is superimposed on the uncured coating layer, A method for producing a heat-resistant laminate sheet, comprising: heat-pressing both the heat-resistant substrate sheets and then curing the uncured coating film layer. The method for producing a heat-resistant laminate sheet according to claim 8 , wherein the heat-resistant laminate sheet is a copper-clad laminate.

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