JP6300608B2 - Novel compound and epoxy resin composition containing the same - Google Patents

Description

  The present invention relates to a novel compound and an epoxy resin composition containing the same, and more specifically, a specific thiocyanate salt, and a one-component heat excellent in storage stability and curability formed by blending the specific thiocyanate salt. The present invention relates to a curable epoxy resin composition.

  Epoxy resins have excellent adhesion to various substrates, and cured products obtained by curing epoxy resins with curing agents have relatively good heat resistance, chemical resistance, electrical properties, mechanical properties, etc. Therefore, it is used in a wide range of applications such as paints, adhesives, and various molding materials.

  Conventionally, epoxy resin compositions have been mainly two-component systems in which a curing agent or a curing accelerator is added immediately before use. The two-component system has the characteristics that it can be cured at room temperature or low temperature, but on the other hand, it must be weighed and mixed immediately before use, and the pot life is short, so it can be applied to automatic machines. It has a drawback that its use conditions are limited such as difficulty. In order to eliminate such drawbacks, a one-component curable epoxy resin composition is desired.

  In order to obtain such a one-component curable resin composition, a curing agent that does not react at room temperature but has a property of starting and curing by heating, a so-called latent curing agent is required. As the latent curing agent, for example, dicyandiamide, dibasic acid dihydrazide, boron trifluoride amine complex salt, guanamines, melamine, imidazoles and the like have been proposed. However, for example, a mixture of dicyandiamide, melamine, and guanamines with an epoxy resin is excellent in storage stability, but has a drawback of requiring high temperature of 150 ° C. or more and long curing conditions. . Moreover, although these and a hardening accelerator are used together and shortening hardening time is also performed widely, the fault that storage stability will be impaired remarkably will arise. On the other hand, dibasic acid dihydrazide and imidazoles cure at a relatively low temperature, but have poor storage stability. Boron trifluoride amine complex salt has the advantages of excellent storage stability and short curing time, but has disadvantages such as poor water resistance and corrosiveness to metals.

  For example, Patent Document 1 proposes to use an ionic liquid composed of a combination of an ammonium cation or a phosphonium cation, a carboxylic acid anion, or the like as a curing agent for an epoxy resin. Absent.

International Publication No. 2009/014270

  An object of the present invention is to provide an epoxy resin composition having excellent storage stability and excellent curability.

  As a result of intensive studies to solve the above problems, the present inventors have found that a specific thiocyanate salt exhibits an excellent effect as an epoxy resin curing agent and can achieve the above-mentioned object, and has reached the present invention. .

  That is, the present invention provides a compound represented by the following general formula (I).

（式中、Ｒ１は、窒素原子を含むことのできる炭化水素基であって、置換基を有することのできる環状構造を形成し得るものであり、Ｒ２は水素原子、アルキル基又はアリール基を表すか、Ｒ１と一緒になって不飽和結合を形成することができ、Ｒ３は水素原子、アルキル基、又はアリール基を表す。）

(In the formula, R1 is a hydrocarbon group that can contain a nitrogen atom, and can form a cyclic structure that can have a substituent, and R2 represents a hydrogen atom, an alkyl group, or an aryl group. R3 can form an unsaturated bond together with R1, and R3 represents a hydrogen atom, an alkyl group, or an aryl group.)

  The present invention also provides an epoxy resin composition comprising (A) an epoxy resin and (B) at least one or two or more compounds represented by the following general formula (I). It is.

（式中、Ｒ１は、窒素原子を含むことのできる炭化水素基であって、置換基を有することのできる環状構造を形成し得るものであり、Ｒ２は水素原子、アルキル基又はアリール基を表すか、Ｒ１と一緒になって不飽和結合を形成することができ、Ｒ３は水素原子、アルキル基、又はアリール基を表す。）

(In the formula, R1 is a hydrocarbon group that can contain a nitrogen atom, and can form a cyclic structure that can have a substituent, and R2 represents a hydrogen atom, an alkyl group, or an aryl group. R3 can form an unsaturated bond together with R1, and R3 represents a hydrogen atom, an alkyl group, or an aryl group.)

  According to the present invention, a practical epoxy resin composition having an easily available raw material as a constituent element and having a balance between appropriate curing characteristics and storage stability can be obtained. In particular, by using a one-pack type epoxy resin composition that does not contain a curable resin component that is solid at room temperature, it is possible to provide a one-pack type epoxy resin composition that is excellent in workability and suitable for narrow space adhesion and impregnation adhesion. Became.

1 is a chart of ¹ H-NMR spectrum of curing agent B (Compound No. 2) produced in Example 2. FIG. 2 is a chart of ¹³ C-NMR spectrum of curing agent B (Compound No. 2) produced in Example 2.

  Hereinafter, the present invention will be described in detail based on preferred embodiments. First, the novel compound represented by the above general formula (I) of the present invention will be described.

R1 in the general formula (I) is a hydrocarbon group that forms a cyclic structure together with two nitrogen atoms or two nitrogen atoms and R2 in the formula, and the hydrocarbon group includes a nitrogen atom. And may contain an unsaturated bond. Further, the number and position of nitrogen atoms and the number and position of unsaturated bonds are not limited.
Specific ring structures include five-membered nitrogen-containing heterocycles such as imidazole ring, imidazoline ring, and triazole ring, six-membered nitrogen-containing heterocycles such as pyrimidine ring and triazine ring, benzimidazole ring, and benzotriazole ring. , A nitrogen-containing heterocycle formed by condensing the above heterocycle such as a purine ring, pteridine ring, quinazoline ring and the like with another ring.
These ring structures may have a substituent. Specific examples of the substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, an amyl group, C 1-10 alkyl groups such as isoamyl group, tertiary amyl group, hexyl group, isohexyl group, octyl group, 2-ethylhexyl group, tertiary octyl group, nonyl group, decyl group, phenyl group, naphthyl group, etc. Examples thereof include aryl groups having 6 to 12 carbon atoms, halogen atoms such as fluorine, chlorine, bromine and iodine, cyano groups, sulfo groups, hydroxyl groups and nitro groups.
Examples of the alkyl group represented by R2 and R3 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tertiary butyl group, amyl group, isoamyl group, tertiary amyl group, hexyl group, and isohexyl. Groups, octyl groups, 2-ethylhexyl groups, tertiary octyl groups, nonyl groups, decyl groups and other alkyl groups having 1 to 10 carbon atoms,
Examples of the aryl group represented by R2 and R3 include aryl groups having 6 to 12 carbon atoms such as a phenyl group and a naphthyl group.

  Preferred examples of the compound represented by the general formula (I) include compounds represented by the following general formulas (I-1) to (I-5).

（式中、Ｒ２'及びＲ３〜Ｒ１５はそれぞれ独立して水素原子、アルキル基又はアリール基を表す。）

(In the formula, R2 ′ and R3 to R15 each independently represent a hydrogen atom, an alkyl group or an aryl group.)

In the general formulas (I-1) to (I-5), R2 ′ and R3 to R15 Examples of the alkyl group represented by: methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tertiary butyl group, amyl group, isoamyl group, tertiary amyl group, hexyl group, isohexyl group, octyl Group, 2-ethylhexyl group, tertiary octyl group, nonyl group, decyl group and other alkyl groups having 1 to 10 carbon atoms, and the aryl group represented by R2 ′ and R3 to R15 is a phenyl group. And aryl groups having 6 to 12 carbon atoms such as a naphthyl group.

As a method for producing the compound represented by the general formula (I) of the present invention, for example, as shown in the following [Chemical Formula 4], an acidic substance such as hydrochloric acid is added to a nitrogen-containing heterocyclic compound corresponding to the cation structure. In addition, the intermediate (I) can be produced by reacting with thiocyanate salt such as sodium thiocyanate in the presence of alcohol (alcohol) or water (H ₂ O). Is not limited.

  As the compound represented by the general formula (I) of the present invention, the following compound No. 1-No. 5 and the like, but are not limited thereto.

  The compound represented by the general formula (I) of the present invention described above has a balance between moderate curing characteristics and storage stability because it is composed of readily available raw materials, and is therefore a thermosetting latent curing agent. Can be added to the epoxy resin and used for various applications described later.

  Next, the epoxy resin composition of the present invention will be described in detail.

  Examples of the epoxy resin that is the component (A) used in the present invention include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; dihydroxynaphthalene, biphenol, methylene Bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as alcohol, sulfonyl bisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, terpene phenol; ethylene glycol, propylene glycol , Butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, polyglycidyl ethers of polyhydric alcohols such as bisphenol A-ethylene oxide adduct; maleic acid, fumaric acid, itaconic acid , Succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid Aliphatic, aromatic or alicyclic such as dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid Homopolymers or copolymers of glycidyl esters of polybasic acids and glycidyl methacrylate; N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane, diglycidyl orthotoluidine Epoxy compounds having a glycidylamino group such as vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexyl Epoxidation products of cyclic olefin compounds such as methyl-6-methylcyclohexanecarboxylate and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; Epoxidation conjugates such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymer Examples thereof include heterocyclic compounds such as diene polymers and triglycidyl isocyanurate. In addition, these epoxy resins may be those internally crosslinked by a prepolymer of a terminal isocyanate or those having a high molecular weight with a polyvalent active hydrogen compound (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphate ester, etc.). .

(A) As an epoxy resin, the polyglycidyl ether of a polyhydric polyhydric phenol compound is preferable from the viewpoint of the workability | operativity and sclerosis | hardenability, and bisphenol F and bisphenol A are more preferable.
The polyepoxy compound preferably has an epoxy equivalent of 70 to 3000, more preferably 90 to 2000. If the epoxy equivalent is less than 70, the physical properties of the cured product may be lowered, and if it is greater than 3000, sufficient curability may not be obtained.

  (B) component used for the epoxy resin composition of this invention is a compound represented by general formula (I) of this invention mentioned above, and the compound demonstrated above is mentioned. (B) As a compound represented by general formula (I), the compound represented by the general formula (I-1)-(I-5) mentioned above can be mentioned preferably.

  In the epoxy resin composition of the present invention, the content of the compound represented by (B) the general formula (I) is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the (A) epoxy resin. More preferably, it is 1-20 mass parts. (B) If the content of the compound represented by the general formula (I) is less than 0.1 parts by mass, it may cause poor curing. If it exceeds 50 parts by mass, the storage stability may be remarkably deteriorated. There is sex.

  If necessary, other curing agents other than the compound represented by the general formula (I); curing catalyst; reactive or non-reactive such as monoglycidyl ethers, dioctyl phthalate, dibutyl phthalate, benzyl alcohol, coal tar, etc. Diluent (plasticizer); glass fiber, carbon fiber, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, silica, fine powder silica, titanium dioxide, carbon black, graphite, iron oxide, Fillers or pigments such as bituminous materials; γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -N′-β- (amino Ethyl) -γ-aminopropyltriethoxysilane, γ-anilinopropyltriethoxysila , Γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, vinyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltriethoxy Silane coupling agents such as silane, γ-methacryloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane; candelilla wax, carnauba wax, wood wax, ibotarou, beeswax, lanolin, Lubricants such as whale wax, montan wax, petroleum wax, fatty acid wax, fatty acid ester, fatty acid ether, aromatic ester, aromatic ether; thickener; thixotropic agent; antioxidant; light stabilizer; Flame retardant; Antifoam agent; Rust preventive agent; Idarushirika, may contain additives customary for such colloidal alumina, further xylene resins, it may be used in combination tacky resin such as petroleum resin.

  The resin composition of the present invention is, for example, a paint or adhesive for concrete, cement mortar, various metals, leather, glass, rubber, plastic, wood, cloth, paper, etc .; adhesive tape for packaging, adhesive label, frozen food label, Removable label, POS label, adhesive wallpaper, adhesive for adhesive flooring; art paper, lightweight coated paper, cast coated paper, coated paperboard, carbonless copying machine, impregnated paper, etc .; natural fiber, synthetic fiber, glass Fiber treatment agents such as fibers, carbon fibers, metal fibers, etc., fraying prevention agents, processing agents, etc .; building materials such as sealing materials, cement admixtures, waterproofing materials; a wide range of sealing agents for electronic and electrical equipment, etc. Can be used for applications.

  Next, the present invention will be described in more detail with reference to production examples and examples, but the present invention is not limited to these production examples and examples.

Production Example 1 [Production of Intermediate A]
1.6 g (20 mmol) of sodium thiocyanate was dissolved in 40 ml of water, and 200 g (20 mmol) of 0.1M aqueous silver nitrate solution was added dropwise while stirring at 25 ° C., and the reaction was carried out for 2 hours. Thereafter, the precipitate was filtered and dried to obtain 2.3 g of light yellow powdery intermediate A (Ag ⁺ (SCN) ⁻ ).

Production Example 2 [Production of Intermediate B]
In 55 ml of methanol, 4.5 g (55 mmol) of 1-methylimidazole was dissolved, and 5.8 g (55 mmol) of 35% hydrochloric acid aqueous solution was added dropwise while stirring at 25 ° C. to react for 1 hour. Thereafter, the solvent was removed with an evaporator and dried under reduced pressure to obtain 6.6 g of a light brown solid intermediate B (compound represented by the following [Chemical Formula 10]).

Production Example 3 [Production of Intermediate C]
In 43 ml of methanol, 4.7 g (43 mmol) of 2-ethyl-4-methylimidazole was dissolved, and while stirring at 25 ° C., 4.5 g (43 mmol) of 35% hydrochloric acid aqueous solution was added dropwise and reacted for 1 hour. Thereafter, the solvent was removed with an evaporator and dried under reduced pressure to obtain 5.9 g of a light yellow powdery intermediate C (compound represented by the following [Chemical Formula 11]).

Production Example 4 [Production of Intermediate D]
2.6 g (26 mmol) of 1-metyl-1,4,5,6-tetrahydropyrimidine was dissolved in 26 ml of methanol, and 2.7 g (26 mmol) of 35% aqueous hydrochloric acid solution was added dropwise while stirring at 25 ° C. for 1 hour. Thereafter, the solvent was removed with an evaporator and dried under reduced pressure to obtain 3.7 g of a light yellow powdery intermediate D (compound represented by the following [Chemical Formula 12]).

Example 1 [Production of curing agent A]
Intermediate B (1.0 g, 8.5 mmol) was dissolved in 17 ml of water, and Intermediate A was added in 1.0 g (8.5 mmol) portions while stirring at 25 ° C., followed by reaction for 24 hours. Thereafter, the solvent was removed with an evaporator and dried under reduced pressure to obtain 1.1 g of a light yellow liquid curing agent A.

Example 2 [Production of curing agent B]
Intermediate C 1.5 g (10.0 mmol) was dissolved in 20 ml of water, and Intermediate A was added in 1.2 g (10.0 mmol) portions while stirring at 25 ° C., followed by reaction for 24 hours. Thereafter, the solvent was removed with an evaporator and dried under reduced pressure to obtain 1.6 g of a light yellow powdery curing agent B. The identification results of the obtained curing agent B by ¹ H-NMR and ¹³ C-NMR are shown below. FIG. 1 shows a ¹ H-NMR chart, and FIG. 2 shows a ¹³ C-NMR chart.
<Identification results>
¹ H-NMR (400 MHz, CD ₃ OD) d: 1.36 (3H, t, J = 7.8 Hz), 2.30 (3H, d, J = 1.2 Hz), 2.93 (2H, q, J = 7.6 Hz), 7.07 (1H, d, J = 1.2 Hz)
¹³ C-NMR (100 MHz, CD ₃ OD) d: 8.5, 10.3, 19.0, 114.8, 129.0, 132.4, 148.3

Example 3 [Production of Curing Agent C]
Intermediate D (1.2 g, 9.2 mmol) was dissolved in 40 ml of water, and Intermediate A was added in 1.1 g (9.2 mmol) portions while stirring at 25 ° C., followed by reaction for 24 hours. Thereafter, the solvent was removed with an evaporator and dried under reduced pressure to obtain 1.3 g of a light yellow liquid curing agent C.

Example 4 [Production of one-pack type epoxy resin composition A]
Adeka Resin EP-4100L (bisphenol A diglycidyl ether type epoxy resin manufactured by ADEKA Co., Ltd .: Epoxy equivalent 170 g / eq, total chlorine amount 600 ppm) 340 g, and 14.1 g of curing agent A were added and mixed uniformly. The intended one-pack type epoxy resin composition A was obtained by sufficiently defoaming.

Example 5 [Production of one-pack type epoxy resin composition B]
A target one-pack type epoxy resin composition B was obtained in the same manner as in Example 4 except that 16.9 g of curing agent B was used.

Example 6 [Production of one-pack type epoxy resin composition C]
A target one-pack type epoxy resin composition C was obtained in the same manner as in Example 4 except that 15.7 g of the curing agent C was used.

Comparative Example 1 [Production of One-Part Epoxy Resin Composition D]
A target one-pack type epoxy resin composition D was obtained in the same manner as in Example 4 except that 8.2 g of 1-methylimidazole was used.

Comparative Example 2 [Production of one-pack type epoxy resin composition E]
A target one-pack type epoxy resin composition E was obtained in the same manner as in Example 4 except that 11 g of 2-ethyl-4-methylimidazole was used.

Comparative Example 3 [Production of One-Part Epoxy Resin Composition F]
A target one-pack type epoxy resin composition F was obtained in the same manner as in Example 4 except that 9.8 g of 1-metyl-1,4,5,6-tetrahydropyrimidine was used.

  The physical property evaluation test of the one-pack type epoxy resin composition manufactured by the Example and the comparative example was done with the method described below.

<Evaluation method>
(1) One-component stability test After the composition was manufactured, it was stored at 40 ° C. in a sealed state, and the one-component stability was evaluated by measuring the time required until the fluidity of the sample disappeared.

(2) Evaluation of curability The curability was evaluated by measuring the gel time of a one-pack type epoxy resin composition on a hot plate at 150 ° C and 180 ° C.

<Evaluation results>

  As is clear from the evaluation results in Table 1, by using a nitrogen-containing salt compound having a thiocyanate in an anionic structure as a thermosetting latent curing agent for epoxy resin, not only one-component stability but also curability is achieved. In addition, an excellent one-pack type epoxy resin composition can be produced.

Claims (4)

The compound represented by the following general formula (I-1) or (I-2).

(Wherein, R2 'represents an alkyl group or an aryl group, R3 represents a hydrogen atom, R4-R8 each independently represents a hydrogen atom, an alkyl group or an aryl group.)   A curing agent comprising the compound according to claim 1. An epoxy resin composition comprising (A) an epoxy resin and (B) at least one or two or more compounds represented by formula (I-1) or (I-2).

(Wherein, R2 'represents an alkyl group or an aryl group, R3 represents a hydrogen atom, R4-R8 each independently represents a hydrogen atom, an alkyl group or an aryl group.)   4. The epoxy resin composition according to claim 3, wherein the epoxy resin composition is one-component thermosetting.

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