JP6254902B2 - Triazine compound, method for synthesizing the compound, and epoxy resin composition - Google Patents

Description

  The present invention relates to a novel triazine compound, a method for synthesizing the compound, and an epoxy resin composition.

Polymers such as epoxy resins, phenol resins, and polyester resins are thermosetting and excellent in corrosion resistance and electrical insulation, so in the fields of electronic components and printed circuit boards, adhesives, conductive pastes, It is widely used as a raw material for resist inks, sealing materials, insulating materials, substrate matrix materials, and the like.
However, such a polymer has a function to suppress migration, that is, a function to suppress a phenomenon that a metal constituting a wiring (circuit) or an electrode on an insulating material moves on the insulating material due to a potential difference in a high humidity environment. Therefore, there is a problem that it causes an insulation failure of electronic parts and printed circuit boards.
In addition, further improvement in adhesion between these polymers and metal materials such as copper, silver, iron, aluminum, palladium and nickel and inorganic materials such as glass substrates has been demanded.

Various substances are used as additives for solving such problems, but substances having a triazine skeleton are effective in suppressing the migration and improving the adhesion to various metals. It is said that.
For example, a method using 2,4-diamino-6-vinyl-1,3,5-triazine or an analog thereof has been proposed by Kamagata et al. (Non-patent Document 1, Patent Documents 1 to 3).
However, since these substances have high crystallinity, there is a problem that they are poorly compatible with polymers and organic solvents used for polymer dilution.

IEICE Transactions C, Vol.J69-C, No.1, 126-130 (1986)

Japanese Examined Patent Publication No. 62-53531 Japanese Patent Publication No. 63-54300 Japanese Patent Publication No. 1-19344

  An object of this invention is to provide the triazine compound excellent in compatibility with a polymer or an organic solvent, the synthesis | combining method of this compound, and the epoxy resin composition containing this compound.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the intended purpose can be achieved by using a triazine compound having a sulfide (thioether) bond. It has come to be completed.
That is, the first invention is a triazine compound represented by chemical formula (I) or chemical formula (II).

（式中、Ｒ^１およびＲ^２は同一または異なっていてもよく、水素原子、炭素数１〜４のアルキル基、ヒドロキシ基またはメトキシ基を表す。Ｒ^３およびＲ^４は水素原子または炭素数１〜１６のアルキル基を表す。但し、Ｒ^１が１分子中に複数ある場合、複数のＲ^１は互いに独立して同一または異なっていてもよく、Ｒ^２が１分子中に複数ある場合、複数のＲ^２は互いに独立して同一または異なっていてもよい。ｎは１〜２０の整数を表す。）

(In the formula, R ¹ and R ² may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxy group or a methoxy group. R ³ and R ⁴ represent a hydrogen atom or 1 carbon atom. represents a ~ 16 alkyl group. However, when R ¹ are a plurality in one molecule, a plurality of R ¹ may be the same or different and independently of one another, when R ² are a plurality in one molecule, a plurality And R ^{2 s} may be the same or different independently from each other, and n represents an integer of 1 to 20.)

（式中、Ｒ^１およびＲ^２は前記と同様である。Ｒ^５はメチレン基、酸素原子または硫黄原子を表す。但し、Ｒ^５が１分子中に複数ある場合、複数のＲ^５は互いに独立して同一または異なっていてもよい。ｐおよびｑは０〜２０の整数を表し、ｒは１〜１６の整数を表す。）

(Wherein, .R ⁵ R ¹ and R ² are as defined above represents a methylene group, an oxygen atom or a sulfur atom. However, if R ⁵ there are a plurality in one molecule, a plurality of R ⁵ are each independently And p and q represent an integer of 0 to 20, and r represents an integer of 1 to 16.)

  According to a second aspect of the present invention, the 2,4-diamino-6-vinyl-1,3,5-triazine represented by the chemical formula (III) is reacted with the thiol compound represented by the chemical formula (IV). This is a method for synthesizing a triazine compound represented by chemical formula (I).

（式中、Ｒ^１〜Ｒ^４およびｎは、前記と同様である。）

(Wherein R ^{1 to} R ⁴ and n are the same as described above.)

  The third invention is characterized in that 2,4-diamino-6-vinyl-1,3,5-triazine represented by the chemical formula (III) is reacted with a thiol compound represented by the chemical formula (V). This is a method for synthesizing the triazine compound represented by the chemical formula (II).

（式中、Ｒ^１、Ｒ^２およびＲ^５と、ｐ、ｑおよびｒは、前記と同様である。）

(In the formula, R ¹ , R ² and R ⁵ and p, q and r are the same as described above.)

  A fourth invention is an epoxy resin composition comprising the triazine compound of the first invention or the triazine compound synthesized by the synthesis method of the second invention or the third invention.

  5th invention contains the triazine compound of 1st invention or the triazine compound synthesize | combined by the synthesis | combining method of 2nd invention or 3rd invention, The adhesive agent for semiconductor sealing agents characterized by the above-mentioned Or it is an epoxy resin composition for sealing agents.

  When the triazine compound of the present invention is used as an additive for a polymer such as an epoxy resin, a phenol resin, a polyester resin, an acrylic resin, or a polystyrene resin, the triazine compound is dissolved or uniformly dispersed in the polymer, and It is expected to exhibit the effect of preventing the migration of components and printed boards, and improving the adhesion between the metal materials and inorganic materials constituting the electronic components and printed boards and the polymer.

Hereinafter, the present invention will be described in detail.
The present invention is a triazine compound represented by the chemical formula (I) or (II), and has a sulfide (thioether) bond in the molecule.

As an example of the triazine compound represented by the chemical formula (I),
2,4-diamino-6- [2- (aminomethylthio) ethyl] -1,3,5-triazine,
2,4-diamino-6- [2- (2-aminoethylthio) ethyl] -1,3,5-triazi,
2,4-diamino-6- [2- (3-aminopropylthio) ethyl] -1,3,5-triazine,
2,4-diamino-6- [2- (4-aminobutylthio) ethyl] -1,3,5-triazine,
2,4-diamino-6- [2- (5-aminopentylthio) ethyl] -1,3,5-triazine,
2,4-diamino-6- [2- (6-aminohexylthio) ethyl] -1,3,5-triazine,
2,4-diamino-6- [2- (8-aminooctylthio) ethyl] -1,3,5-triazine,
2,4-diamino-6- [2- (10-aminodecylthio) ethyl] -1,3,5-triazine,
2,4-diamino-6- [2- (18-aminooctadecylthio) ethyl] -1,3,5-triazine,
2,4-diamino-6- [2- (N, N-dimethylaminomethylthio) ethyl] -1,3,5-triazine,
2,4-diamino-6- {2- [2- (N, N-dimethylamino) ethylthio] ethyl} -1,3,5-triazine,
2,4-diamino-6- {2- [3- (N, N-dimethylamino) propylthio] ethyl} -1,3,5-triazine,
2,4-diamino-6- {2- [4- (N, N-dimethylamino) butylthio] ethyl} -1,3,5-triazine,
2,4-diamino-6- {2- [5- (N, N-dimethylamino) pentylthio] ethyl} -1,3,5-triazine,
2,4-diamino-6- {2- [6- (N, N-dimethylamino) hexylthio] ethyl} -1,3,5-triazine,
2,4-diamino-6- {2- [8- (N, N-dimethylamino) octylthio] ethyl} -1,3,5-triazine,
2,4-diamino-6- {2- [10- (N, N-dimethylamino) decylthio] ethyl} -1,3,5-triazine,
Examples include 2,4-diamino-6- {2- [18- (N, N-dimethylamino) octadecylthio] ethyl} -1,3,5-triazine.

As an example of the triazine compound represented by the chemical formula (II),
2,4-diamino-6- [2- (mercaptomethylthio) ethyl] -1,3,5-triazine,
2,4-diamino-6- [2- (2-mercaptoethylthio) ethyl] -1,3,5-triazine,
2,4-diamino-6- [2- (3-mercaptopropylthio) ethyl] -1,3,5-triazine,
2,4-diamino-6- [2- (4-mercaptobutylthio) ethyl] -1,3,5-triazine,
2,4-diamino-6- [2- (5-mercaptopentylthio) ethyl] -1,3,5-triazine,
2,4-diamino-6- [2- (6-mercaptohexylthio) ethyl] -1,3,5-triazine,
2,4-diamino-6- [2- (8-mercaptooctylthio) ethyl] -1,3,5-triazine,
2,4-diamino-6- [2- (10-mercaptodecylthio) ethyl] -1,3,5-triazine,
2,4-diamino-6- [2- (18-mercaptooctadecylthio) ethyl] -1,3,5-triazine,
2,4-diamino-6- {2- [2- (2-mercaptoethoxy) ethylthio] ethyl} -1,3,5-triazine,
2,4-diamino-6- (2- {2- [2- (2-mercaptoethoxy) ethoxy] ethylthio} ethyl) -1,3,5-triazine,
Examples include 2,4-diamino-6- {2- [2- (2-mercaptoethylthio) ethylthio] ethyl} -1,3,5-triazine.

  These triazine compounds include 2,4-diamino-6-vinyl-1,3,5-triazine represented by the chemical formula (III) and a thiol compound represented by the chemical formula (IV) or the chemical formula (V). Can be synthesized at an appropriate reaction temperature and reaction time in an appropriate amount of reaction solvent.

As an example of the thiol compound represented by the chemical formula (IV),
Mercaptomethylamine,
2-mercaptoethylamine,
3-mercaptopropylamine,
4-mercaptobutylamine,
5-mercaptopentylamine,
6-mercaptohexylamine,
8-mercaptooctylamine,
10-mercaptodecylamine,
18-mercaptooctadecylamine,
N, N-dimethylmercaptomethylamine,
N, N-dimethyl-2-mercaptoethylamine,
N, N-dimethyl-3-mercaptopropylamine,
N, N-dimethyl-4-mercaptobutylamine,
N, N-dimethyl-5-mercaptopentylamine,
N, N-dimethyl-6-mercaptohexylamine,
N, N-dimethyl-8-mercaptooctylamine,
N, N-dimethyl-10-mercaptodecylamine,
N, N-dimethyl-18-mercaptooctadecylamine and the like can be mentioned.

Moreover, as an example of the thiol compound represented by the chemical formula (V),
Methanedithiol,
1,2-ethanedithiol,
1,3-propanedithiol,
1,4-butanedithiol,
1,5-pentanedithiol,
1,6-hexanedithiol,
1,8-octanedithiol,
1,10-decanedithiol,
1,18-octadecanedithiol,
Bis (2-mercaptoethyl) ether,
1,2-bis (2-mercaptoethoxy) ethane,
Examples thereof include bis (2-mercaptoethyl) sulfide.

  Examples of the reaction solvent include alcohol solvents such as methanol and ethanol, halogen solvents such as chloroform and dichloromethane, hydrocarbon solvents such as toluene and hexane, and ether solvents such as tetrahydrofuran and 1,4-dioxane. Is mentioned.

  About the said reaction temperature, it can set suitably in the range of room temperature-100 degreeC. The reaction time is determined according to the set reaction temperature, but is preferably 0.5 to 24 hours, and more preferably 1 to 6 hours.

The triazine compound of the present invention can be blended with an epoxy compound together with a curing agent and, if necessary, a curing agent and a curing accelerator (curing catalyst) to form an epoxy resin composition.
The epoxy compound may have at least two epoxy groups in the molecule, but is a mixture of a substance having at least two epoxy groups in the molecule and a substance having one epoxy group in the molecule. May be.

In this case, the amount of the triazine compound of the present invention is preferably 0.01 to 150 parts by weight, more preferably 0.1 to 50 parts by weight, based on 100 parts by weight of the epoxy compound. More preferred.
And it is preferable to set it as the ratio of 0.01-300 weight part with respect to 100 weight part of epoxy compounds, and, as for the compounding quantity of a hardening | curing agent, it is more preferable to set it as the ratio of 0.1-200 weight part.
Moreover, it is preferable to make the compounding quantity of a hardening accelerator into the ratio of 0.01-2.0 weight part with respect to 100 weight part of epoxy compounds, and to set it as the ratio of 0.1-0.5 weight part. More preferred.

As an example of the epoxy compound,
Bisphenol A type epoxy resin,
Bisphenol F type epoxy resin,
Novolac epoxy resins such as phenol novolac epoxy resins and cresol novolac epoxy resins,
Alicyclic epoxy resin,
Cyclic alicyclic epoxy resins such as 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate;
1,3,4,6-tetraglycidylglycoluril, 1,3,4,6-tetraglycidyl-3a, 6a-dimethylglycoluril, 1,3,4,6-tetraglycidyl-3a, 6a-diphenylglycoluril Nitrogen-containing cyclic epoxy resins such as triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl monoglycidyl isocyanurate and hydantoin type epoxy resin,
Hydrogenated bisphenol A type epoxy resin,
Aliphatic epoxy resin,
Glycidyl ether type epoxy resin,
Bisphenol S type epoxy resin,
Biphenyl type epoxy resin,
Dicyclo ring type epoxy resin,
In addition to naphthalene type epoxy resins and halogenated epoxy resins,
Epoxy-modified organopolysiloxane compounds obtained by a hydrosilylation addition reaction between an organic compound having a carbon-carbon double bond and a glycidyl group and a silicon compound having a SiH group (for example, JP 2004-99751 A and JP Epoxy-modified organopolysiloxane compounds disclosed in Japanese Patent Application Publication No. 2006-282898.
In addition, the epoxy resin here refers to the epoxy compound before hardening.

As an example of the curing agent,
A compound having a phenolic hydroxyl group,
In addition to acid anhydrides and amines,
Mercaptan compounds such as mercaptopropionic acid esters and epoxy resin-terminated mercapto compounds,
Organic phosphine compounds such as triphenylphosphine, diphenylnaphthylphosphine, diphenylethylphosphine,
Aromatic phosphonium salts,
Aromatic diazonium salts,
Aromatic iodonium salt,
Aromatic selenium salts and the like can be mentioned.

Examples of the compound having a phenolic hydroxyl group include
Bisphenol A,
Bisphenol F,
Bisphenol S,
Tetramethylbisphenol A,
Tetramethylbisphenol F,
Tetramethylbisphenol S,
Tetrachlorobisphenol A,
Tetrabromobisphenol A,
Dihydroxynaphthalene,
Phenol novolac,
Cresol novolac,
Bisphenol A novolak,
Brominated phenol novolac,
Resorcinol and the like can be mentioned.

Examples of the acid anhydride include
Methyltetrahydrophthalic anhydride,
Methyl hexahydrophthalic anhydride,
Hexahydrophthalic anhydride,
5-norbornene-2,3-dicarboxylic anhydride,
Trimellitic anhydride,
Nadic acid anhydride,
Highmic anhydride,
Methyl nadic anhydride,
Methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride,
Bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride,
And methylnorbornane-2,3-dicarboxylic acid anhydride.

Examples of the amines include
Diethylenetriamine,
Triethylenetetramine,
Hexamethylenediamine,
Dimer acid-modified ethylenediamine,
4,4'-diaminodiphenyl sulfone,
4,4'-diaminodiphenyl ether,
1,8-diazabicyclo [5.4.0] -7-undecene, etc.
Examples thereof include imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole.

Examples of the curing accelerator include
Amine compounds such as 1,8-diazabicyclo [5.4.0] -7-undecene, diethylenetriamine, triethylenetetramine, N, N-dimethylbenzylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol ,
Imidazole compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole,
Organic phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine,
Phosphonium compounds such as tetrabutylphosphonium bromide, tetrabutylphosphonium diethyl phosphorodithioate,
Tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazolium tetraphenylborate, 1,5-diazabicyclo [4,3,0] nonene-5-tetraphenylborate,
Examples thereof include aliphatic carboxylic acid metal salts such as lead acetate, tin octylate, and cobalt hexanoate.
Some of these substances are also used as the aforementioned curing agent.

The epoxy resin composition of the present invention includes an inorganic filler such as amorphous silica, crystalline silica, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, and titanium oxide as necessary. , Fiber filler such as glass fiber, boron fiber, carbon fiber, carbon black, graphite, carbon nanotube, fullerene, iron oxide, gold, silver, aluminum powder, iron powder, nickel, copper, zinc, chromium, solder, nano Size metal crystals, conductive fillers such as intermetallic compounds, phenol resin, polyester resin, acrylic resin, polystyrene resin, polyurethane resin, polyether resin, melamine resin, acrylic modified epoxy resin, urethane modified epoxy resin, rubber modified epoxy Various types of resin, alkyd-modified epoxy resin, etc. Other mers,
Aliphatic polyols such as ethylene glycol and propylene glycol, aliphatic or aromatic carboxylic acid compounds, carbon dioxide generation inhibitors such as phenol compounds, flexibility imparting agents such as polyalkylene glycols, antioxidants, plasticizers, lubricants, Silane coupling agents, inorganic filler surface treatment agents, flame retardants, antistatic agents, colorants, antistatic agents, leveling agents, ion trapping agents, slidability improvers, various rubbers, impact resistance improvements Add additives such as agents, thixotropic agents, surfactants, surface tension reducing agents, antifoaming agents, anti-settling agents, light diffusing agents, ultraviolet absorbers, antioxidants, mold release agents, fluorescent agents, etc. Can do.

  The epoxy resin composition of the present invention includes an organic solvent such as toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and butyl acetate for solvent (solution) and viscosity adjustment of the epoxy resin composition, Reactive diluents such as butyl glycidyl ether, N, N′-glycidyl-o-toluidine, phenyl glycidyl ether, styrene oxide, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, Non-reactive diluents such as dioctyl phthalate, dibutyl phthalate, dioctyl adipate and petroleum solvents can be blended.

  The epoxy resin composition of the present invention is not particularly limited in its preparation method, and is prepared by measuring a predetermined amount of each of the aforementioned components and stirring and mixing them. For example, it can be prepared by mixing or melt-kneading using a roll kneader, a kneader, an extruder or the like after preliminary mixing.

  The epoxy resin composition of the present invention is not particularly limited in its curing method, and a conventionally known curing device such as a closed curing furnace or a tunnel furnace capable of continuous curing can be used. The heating source is not particularly limited, and conventionally known methods such as hot air circulation, infrared heating, and high frequency heating can be employed. The curing temperature and the curing time may be set as appropriate.

  There is no particular limitation on the use of the epoxy resin composition of the present invention, and it can be applied to various fields and products in which resin materials are used. Electrical / electronic materials use, building use, civil engineering use, It can be widely used for automobiles and medical materials.

  For example, examples of applications in electrical / electronic materials include adhesives, sealing materials, sealing materials, insulating materials, thermally conductive materials, hot melt materials, paints, potting agents, etc. Sealing materials and layer forming materials for electronic components such as printed wiring boards, interlayer insulating films, wiring coating films, color filters, flexible display films, resist materials, forming materials for display devices such as alignment films, resist materials, buffers Examples thereof include a material for forming a semiconductor device such as a coating film, and a material for forming an optical component such as a hologram, an optical waveguide, an optical circuit, an optical circuit component, and an antireflection film.

  Examples of materials used in building applications include seals used for joints between exterior materials such as various metal panels and exterior materials such as siding boards, coating materials and primers, and exterior materials, base materials, ceiling materials, and interior materials. Materials, adhesives, injection materials, damping materials, soundproofing materials, conductive materials for shielding electromagnetic waves, putty materials, etc., adhesives for tiles and stone materials to outer wall materials and base materials, wood flooring materials for various floors Polymer material floor sheets, adhesives for floor tile adhesion, adhesives, cracking injection materials for various exterior materials and interior materials, etc. Examples of materials in civil engineering applications include roads, bridges, tunnels -Seals for breakwaters and various concrete products, coating materials, primers, paints, injection materials, putty materials, molding materials, spray materials, etc. Examples of materials in automotive applications include automobile bodies Sealing materials, coating materials, cushioning materials, damping materials, soundproofing materials, spraying materials, etc., automotive interior adhesives, adhesive materials, coating materials, foamed materials, etc., automotive parts sealing materials, adhesives, etc. Examples include sealing materials for various steel plate joints such as baths, adhesives, and coating materials. Examples of medical materials include medical rubber materials, medical adhesives, and medical device sealing materials.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In addition, the main raw materials used for the synthesis test of an Example are as follows.

[Main ingredients]
・ 2,4-Diamino-6-vinyl-1,3,5-triazine: Shikoku Kasei Kogyo Co., Ltd. 2-Mercaptoethylamine: Tokyo Kasei Kogyo Co., Ltd. 1,2-bis (2-mercaptoethoxy) ethane: Same as above Bis (2-mercaptoethyl) sulfide: Same as above

[Example 1]
<Synthesis of 2,4-diamino-6- [2- (2-aminoethylthio) ethyl] -1,3,5-triazine>
In a 100 mL flask equipped with a thermometer, 6.86 g (50.0 mmol) of 2,4-diamino-6-vinyl-1,3,5-triazine, 3.86 g (50.0 mmol) of 2-mercaptoethylamine and 50 mL of methanol Was added to prepare a reaction solution.
While stirring this reaction solution, reaction was performed at 65 ° C. for 1 hour, and then the reaction solution was concentrated under reduced pressure to obtain 10.70 g of white crystals (yield 100%).

The melting point and ¹ H-NMR spectrum data of the obtained crystal were as follows.
Melting point: 126-128 ° C
・¹ H-NMR (d ₆ -DMSO) δ: 6.63 (br, 4H), 2.80 (t, 2H), 2.67 (t, 2H), 2.58 (t, 2H), 2.50 (t, 2H), 1.61 ( br, 2H).
The IR spectrum data of this crystal was as shown in the chart shown in FIG.
From these spectral data, the obtained crystal was identified as the title triazine compound represented by the chemical formula (I-1).

[Example 2]
<Synthesis of 2,4-diamino-6- (2- {2- [2- (2-mercaptoethoxy) ethoxy] ethylthio} ethyl) -1,3,5-triazine>
In a 100 mL flask equipped with a thermometer, 6.86 g (20.0 mmol) of 2,4-diamino-6-vinyl-1,3,5-triazine, 22.6 g of 1,2-bis (2-mercaptoethoxy) ethane. (100.0 mmol) and 20 mL of methanol were added to prepare a reaction solution.
While stirring this reaction solution, the reaction was carried out at 65 ° C. for 1 hour. Subsequently, the reaction solution was concentrated under reduced pressure, and then 50 mL of toluene was added thereto, followed by stirring at room temperature for 30 minutes. The lower layer was extracted by a liquid separation operation and concentrated under reduced pressure to obtain 6.07 g (yield 95%) of a transparent liquid.

The ¹ H-NMR spectrum data of the obtained liquid was as follows.
・¹ H-NMR (d ₆ -DMSO) δ: 6.60 (br, 4H), 3.47-3.56 (m, 8H), 2.82 (t, 2H), 2.58-2.66 (m, 6H), 2.30 (s, 1H ).
Further, the IR spectrum data of this liquid was as shown in the chart of FIG.
From these spectral data, the obtained liquid was identified as the title triazine compound represented by the chemical formula (II-1).

Example 3
<Synthesis of 2,4-diamino-6- {2- [2- (2-mercaptoethylthio) ethylthio] ethyl} -1,3,5-triazine>
Example 2 except that 13.7 g (100.0 mmol) of bis (2-mercaptoethyl) sulfide was used instead of 22.6 g (100.0 mmol) of 1,2-bis (2-mercaptoethoxy) ethane. The same operation was performed to obtain 5.65 g (yield 97%) of a transparent liquid.

The obtained liquid ¹ H-NMR spectrum data was as follows.
・¹ H-NMR (d ₆ -DMSO) δ: 6.59 (br, 4H), 2.86 (t, 2H), 2.68-2.75 (m, 8H), 2.59 (t, 2H), 2.48-2.52 (m, 1H ).
Further, the IR spectrum data of this liquid was as shown in the chart of FIG.
From these spectral data, the obtained liquid was identified as the title triazine compound represented by the chemical formula (II-2).

Example 4
<Evaluation test of solubility in organic solvents>
About the triazine compound of the present invention (Examples 1 to 3) and 2,4-diamino-6-vinyl-1,3,5-triazine which is a precursor of the triazine compound, the solubility in various organic solvents was evaluated. (Test Nos. 1-4).
The operation procedure of the evaluation test is as follows.
At room temperature, 100 mg of the triazine compound and 2 mL of the organic solvent were put into a test tube and stirred, and the solubility of the triazine compound in the organic solvent was visually observed.
When the triazine compound is completely dissolved at room temperature, it is determined as ◯. When the triazine compound is not completely dissolved at room temperature but is completely dissolved at 70 ° C., it is determined as Δ. did.
In addition, methanol, acetone, methyl ethyl ketone (MEK), and ethyl acetate were used as the organic solvent.
The test results obtained were as shown in Table 1.

According to these results, the triazine compound of the present invention is recognized as having excellent solubility in organic solvents as compared with the precursor 2,4-diamino-6-vinyl-1,3,5-triazine. .
Therefore, the triazine compound of the present invention is expected to be excellent in compatibility with polymers such as epoxy resins, phenol resins, and polyester resins.

Example 5
<Preparation of epoxy resin composition (compositions 1-4) and evaluation test for adhesion>
As an epoxy compound, 100 parts by weight of a bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name: jER828), and as a curing agent, 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: 2E4MZ) 5 parts by weight, 4 parts by weight of silica (Evonik, product name: Aerosil 300) and 5 parts by weight of the triazine compound shown in Table 2 were weighed as fillers, and a revolving mixer (trade name: Awatori) The mixture was stirred and mixed for 5 minutes and defoamed for 1 minute to prepare epoxy resin compositions (Compositions 1 to 3).
An epoxy resin composition was prepared in the same manner as described above except that the triazine compound was not used (Composition 4).
Each of these compositions was uniformly applied to a steel sheet, heated under conditions of 60 ° C./4 hours, and subsequently heat-cured under conditions of 150 ° C./4 hours, and then measured for tensile shear adhesive strength. (JIS K6850) and the adhesion (adhesion) to the steel sheet was evaluated.
The test results obtained were as shown in Table 2.

According to these results, it can be recognized that the cured products of Compositions 1 to 3 have superior adhesion performance to the steel plate as compared to the cured product of Composition 4.
Therefore, when the epoxy resin composition containing the triazine compound of the present invention is used as an adhesive, a semiconductor sealant or a sealant, it is expected to exhibit excellent adhesion to metal materials and inorganic materials. The

2 is an IR spectrum chart of the crystal obtained in Example 1. FIG. 4 is an IR spectrum chart of the liquid obtained in Example 2. 4 is an IR spectrum chart of the liquid obtained in Example 3.

When the triazine compound of the present invention is used as an additive for a polymer such as an epoxy resin, a phenol resin, a polyester resin, an acrylic resin, or a polystyrene resin, the triazine compound is dissolved or uniformly dispersed in the polymer, and Suppresses migration of parts and printed circuit boards, and improves adhesion between polymers and various inorganic materials such as copper, silver, iron, aluminum, palladium, and nickel that make up electronic parts and printed circuit boards. Since the effect is expected, the industrial utility of the present invention is great.

Claims (5)

Triazine compound represented by chemical formula (I) or chemical formula (II)

(In the formula, R ¹ and R ² may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxy group or a methoxy group. R ³ and R ⁴ represent a hydrogen atom or 1 carbon atom. represents a ~ 16 alkyl group. However, when R ¹ are a plurality in one molecule, a plurality of R ¹ may be the same or different and independently of one another, when R ² are a plurality in one molecule, a plurality And R ^{2 s} may be the same or different independently from each other, and n represents an integer of 1 to 20.)

(Wherein, .R ⁵ R ¹ and R ² are as defined above represents a methylene group, an oxygen atom or a sulfur atom. However, if R ⁵ there are a plurality in one molecule, a plurality of R ⁵ are each independently And p and q represent an integer of 0 to 20, and r represents an integer of 1 to 16.) Formula and 2,4-diamino-6-vinyl-1,3,5-triazine represented by (III), formula (IV) with a thiol compound is reacted features and to that chemical formula represented (I) A method for synthesizing a triazine compound represented by the formula:

(In the formula, R ¹ and R ² may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxy group or a methoxy group. R ³ and R ⁴ represent a hydrogen atom or 1 carbon atom. represents a ~ 16 alkyl group. However, when R ¹ are a plurality in one molecule, a plurality of R ¹ may be the same or different and independently of one another, when R ² are a plurality in one molecule, a plurality And R ^{2 s} may be the same or different independently from each other, and n represents an integer of 1 to 20.)

(Wherein R ^{1 to} R ⁴ and n are the same as described above.) Structural Formula (III) and 2,4-diamino-6-vinyl-1,3,5-triazine represented by the formula (V) with a thiol compound is reacted features and to that chemical formula shown ( A method for synthesizing the triazine compound represented by II).

(In the formula, R ¹ and R ² may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxy group or a methoxy group. R ⁵ represents a methylene group, an oxygen atom or a sulfur atom. represented. However, when R ¹ are a plurality in one molecule, a plurality of R ¹ may be the same or different and independently of one another, if R ⁵ there are a plurality in one molecule, a plurality of R ⁵ are each independently And p and q represent an integer of 0 to 20, and r represents an integer of 1 to 16.)

(In the formula, R ¹ , R ² and R ⁵ and p, q and r are the same as described above.)   An epoxy resin composition comprising the triazine compound according to claim 1 or the triazine compound synthesized by the synthesis method according to claim 2 or claim 3. An epoxy resin composition for an adhesive, a semiconductor encapsulant or a sealant, comprising the triazine compound according to claim 1 or the triazine compound synthesized by the synthesis method according to claim 2 or claim 3. object.

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