JP3367531B2 - Epoxy resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polythiol-based epoxy resin composition which is rapidly cured at a relatively low heating temperature, has a strong adhesive strength, and has a long pot life so that it has good workability. It is a thing.

[0002]

2. Description of the Related Art Epoxy resin compositions using polythiols as curing agents and liquid tertiary amines as curing accelerators are known as low-temperature fast-curing type epoxy resin compositions which can be cured even at -20 ° C to 0 ° C. Adhesive, sealing agent,
Widely used for casting, etc.

However, such an epoxy resin composition has a drawback in that its pot life is usually very short, from several seconds to several minutes after mixing, and sufficient time cannot be taken for mixing, defoaming and coating operations. In addition, since the worker has to prepare the composition each time, the workability is poor, and the surplus composition cannot be stored and must be discarded, which saves resources and environmental problems. Was also unfavorable.

Therefore, it has been earnestly desired to develop a polythiol type epoxy resin composition having a sufficient pot life and improved workability. However, in general, a mixture of an epoxy resin and a commercially available thiol compound has poor storage stability, and it has been difficult to extend the pot life of an epoxy resin composition using a thiol curing agent.

As a method for solving such a problem,
A method of adding an acid anhydride or a mercapto organic acid as a curing retarder to extend the pot life has been investigated (Japanese Patent Laid-Open No. 61-159417), but it has not been fully satisfactory. .

On the other hand, an example in which a thiol compound obtained by an esterification reaction of a polyol and a mercapto organic acid is used as a curing agent for an epoxy resin is disclosed in JP-B-41-723.
No. 6, JP-B 42-26535, JP-B 47-323
19, JP-A-46-732, JP-B-60-2164.
As described in each publication of No. 8, the curing accelerator used in these epoxy resin compositions is a liquid amine or the like. And, the compositions using these liquid amines have a very short working life of several minutes to several tens of minutes, and have a serious drawback in working.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polythiol-based epoxy resin composition having a sufficient pot life, being rapidly cured at a relatively low heating temperature and having a strong adhesive strength. That is.

[0008]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have used a polythiol compound having two or more thiol groups in the molecule as a curing agent and a solid dispersion as a curing accelerator. By using a type amine adduct-based latent curing accelerator, it is possible to obtain a polythiol-based epoxy resin composition that has a sufficient pot life, is rapidly cured at a relatively low temperature, and has stronger adhesive strength. Found and completed the present invention.

That is, the present invention provides (1) an epoxy resin having two or more epoxy groups in the molecule, and (2) a polythiol compound having two or more thiol groups in the molecule ,
It is necessary to use a basic catalyst as a reaction catalyst in the manufacturing process.
As a polythiol compound or as a reaction catalyst in the manufacturing process
In the case of using a basic catalyst,
A polythiol compound having an on concentration of 50 ppm or less ,
And (3) an epoxy resin composition containing a solid dispersion type amine adduct-based latent curing accelerator.

The epoxy resin used in the present invention may be one having an average of two or more epoxy groups per molecule. For example, polyglycidyl ethers obtained by reacting polychlorophenol such as bisphenol A, bisphenol F, bisphenol AD, catechol and resorcinol, polyhydric alcohols such as glycerin and polyethylene glycol with epichlorohydrin: p-hydroxybenzoic acid, β-hydroxynaphthoate Glycidyl ether ester obtained by reacting hydroxycarboxylic acid such as acid with epichlorohydrin; polyglycidyl ester obtained by reacting polycarboxylic acid such as phthalic acid and terephthalic acid with epichlorohydrin; and epoxidized phenol novolac resin, Examples include epoxidized cresol novolac resin, epoxidized polyolefin, cycloaliphatic epoxy resin, and other urethane-modified epoxy resins, but are not limited to these. Not intended to be.

Examples of the polythiol compound used in the present invention include trimethylolpropane tris (thioglycolate), pentaerythritol tetrakis (thioglycolate), ethylene glycol dithioglycolate, trimethylolpropane tris (β-thiopropionate). ), Pentaerythritol tetrakis (β-thiopropionate), dipentaerythritol poly (β-thiopropionate) and other thiol compounds obtained by the esterification reaction of mercapto organic acid with polyols There are thiol compounds having two or more thiol groups in the molecule that do not require the use of substances.

Similarly, 1,4-butanedithiol, 1,
Alkyl polythiol compounds such as 6-hexanedithiol and 1,10-decanedithiol; terminal thiol group-containing polyethers; terminal thiol group-containing polythioethers;
A thiol compound obtained by a reaction between an epoxy compound and hydrogen sulfide; a basic substance is used as a reaction catalyst in the manufacturing process such as a thiol compound having a terminal thiol group obtained by a reaction between a polythiol compound and an epoxy compound In this case, a thiol compound having two or more thiol groups in the molecule which has been subjected to dealkalization treatment and has an alkali metal ion concentration of 50 ppm or less can be used.

As a method for dealkalizing a polythiol compound produced by using a basic substance as a reaction catalyst, for example, the polythiol compound to be treated is treated with acetone,
A method of dissolving in an organic solvent such as methanol, neutralizing by adding an acid such as dilute hydrochloric acid or dilute sulfuric acid, and then desalting after extraction and washing, a method of adsorbing using an ion exchange resin, a method of purifying by distillation However, the present invention is not limited to these.

The solid dispersion type amine adduct-based latent curing accelerator used in the present invention is an amine compound and an epoxy compound which are solids insoluble in an epoxy resin at room temperature and which are solubilized by heating and function as an accelerator. And the surface of these reaction products treated with an isocyanate compound or an acidic compound.

Examples of the epoxy compound used as a raw material for producing the latent curing accelerator used in the present invention include polyhydric phenols such as bisphenol A, bisphenol F, catechol and resorcinol, and polyhydric compounds such as glycerin and polyethylene glycol. Polyglycidyl ether obtained by reacting alcohol with epichlorohydrin, glycidyl ether ester obtained by reacting epicarboxylic acid with hydroxycarboxylic acid such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid, polyphthalic acid such as terephthalic acid Polyglycidyl ester obtained by reacting carboxylic acid with epichlorohydrin, 4,4'-diaminodiphenylmethane or m
-Glycidylamine compounds obtained by reacting aminophenol and the like with epichlorohydrin, and further polyfunctional epoxy compounds such as epoxidized phenol novolac resin, epoxidized cresol novolac resin, epoxidized polyolefin, butyl glycidyl ether, phenyl glycidyl ether Examples thereof include monofunctional epoxy compounds such as glycidyl methacrylate, but are not limited thereto.

The amine compound used as a raw material for producing the latent curing accelerator used in the present invention has at least one active hydrogen in the molecule capable of undergoing an addition reaction with an epoxy group, and has a primary amino group and a secondary amino group. Any amino group and tertiary amino group may be used as long as they have at least one substituent selected from the group. Examples of such amine compounds are shown below, but the amine compounds are not limited thereto. For example,
Diethylenetriamine, triethylenetetramine, n-
Propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4'-diamino-
Aliphatic amines such as dicyclohexylmethane, 4,
Aromatic amine compounds such as 4'-diaminodiphenylmethane, 2-methylaniline, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethyl-4-
Methyl imidazoline, 2,4-dimethyl imidazoline,
Examples thereof include nitrogen-containing heterocyclic compounds such as piperidine and piperazine.

Among these compounds, the compound having a tertiary amino group in the molecule is a raw material for providing a latent curing accelerator having an excellent curing accelerator, and examples of such a compound include , For example, amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, N-methylpiperazine, and 2-methylimidazole, Primary or secondary amines having a tertiary amino group in the molecule, such as imidazole compounds such as 2-ethylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole, and 2-dimethylaminoethanol. , 1-methyl-2-dimethylami Ethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1- (2-hydroxy-3-phenoxypropyl) -2-methylimidazole, 1- ( 2-hydroxy-3-phenoxypropyl) -2-ethyl-4-
Methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazole, 1- (2-
Hydroxy-3-butoxypropyl) -2-ethyl-4
-Methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-phenylimidazoline, 1-
(2-Hydroxy-3-butoxypropyl) -2-methylimidazoline, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, N-β-hydroxyethylformoline, 2-
Dimethylaminoethanethiol, 2-mercaptopyridine, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N, N
-Dimethylaminobenzoic acid, N, N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N, N
Alcohols, phenols, thiols, carboxylic acids, hydrazides having a tertiary amino group in the molecule, such as dimethylglycine hydrazide, N, N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide, isonicotinic acid hydrazide Etc.

In order to further improve the storage stability of the epoxy resin composition of the present invention, a third component is added when the latent curing accelerator used in the present invention is produced by subjecting the above epoxy compound and an amine compound to an addition reaction. It is also possible to add an active hydrogen compound having two or more active hydrogens in the molecule. Examples of such active hydrogen compounds are shown below, but the invention is not limited thereto. For example, polyphenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, and phenol novolac resin,
Polyhydric alcohols such as trimethylolpropane, adipic acid, polycarboxylic acids such as phthalic acid, 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, mercaptoacetic acid, Examples thereof include anthranilic acid and lactic acid.

Typical examples of the isocyanate compound used as a surface treating agent in the production of the latent curing accelerator used in the present invention are shown below, but the present invention is not limited thereto. For example, monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, benzyl isocyanate, etc., hexamethylene diisocyanate, toluylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate,
Isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-
Hexamethylene triisocyanate, polyfunctional isocyanate compounds such as bicycloheptane triisocyanate, further obtained by the reaction of these polyfunctional isocyanate compounds and active hydrogen compounds, it is also possible to use a terminal isocyanate group-containing compound, Examples of such a compound include an addition reaction product having a terminal isocyanate group obtained by the reaction of toluylene diisocyanate and trimethylolpropane, an addition reaction product having a terminal isocyanate group obtained by the reaction of toluylene diisocyanate and pentaerythritol, and the like. Is mentioned.

As the acidic substance used as the surface treatment agent in the production of the latent curing accelerator used in the present invention, there are gas, liquid inorganic acid or organic acid, and typical examples thereof are shown below. However, the present invention is not limited to these. For example, carbon dioxide, sulfurous acid gas, sulfuric acid, hydrochloric acid, oxalic acid,
Phosphoric acid, acetic acid, formic acid, propionic acid, adipic acid, caproic acid, lactic acid, succinic acid, tartaric acid, sebacic acid, p-toluenesulfonic acid, salicylic acid, boric acid, tannic acid,
Examples thereof include alginic acid, polyacrylic acid, polymethacrylic acid, phenol, pyrogallol, phenol resin and resorcin resin.

The latent curing accelerator used in the present invention is
The above (a) epoxy compound and (b) amine compound, or (a) epoxy compound and (b) amine compound and (c)
After mixing the respective components of the active hydrogen compound and reacting at room temperature to 200 ° C., solidification, pulverization or reaction in a solvent such as methyl ethyl ketone, dioxane, tetrahydrofuran, etc., and removing the solid content after desolvation It can be easily obtained by crushing. Further, the surface treatment of these latent curing accelerators is methyl ethyl ketone,
It can be carried out by contacting with the above-mentioned isocyanate compound or acidic compound in a solvent such as toluene or without solvent.

Typical examples of the above solid dispersion type amine adduct-based latent curing accelerator which are commercially available are shown below, but the present invention is not limited thereto. For example, "Amicure PN-23" (trade name of Ajinomoto Co., Inc.), "Amicure PN-H" (trade name of Ajinomoto Co., Ltd.), "Amicure MY-24" (trade name of Ajinomoto Co., Ltd.), "Hardener X" -3661S "(AC R Co., Ltd.)
(Product name), "Hardener X-3670S" (trade name of AC R Co., Ltd.), "Nova Cure HX-37"
42 "(trade name of Asahi Kasei Corporation)," Nova Cure HX-
3721 ”(trade name of Asahi Kasei Co., Ltd.) and the like.

The mixing ratio of the epoxy resin and the polythiol compound in the epoxy resin composition of the present invention is 0.5 to 1.2 in terms of SH equivalent number / epoxy equivalent number ratio, and solid dispersion type amine adduct type latent curing acceleration is promoted. The addition amount of the agent is 0.1 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin.

If desired, various additives such as a filler, a diluent, a solvent, a pigment, a flexibility-imparting agent, a coupling agent and an antioxidant can be added to the epoxy resin composition of the present invention. .

When an isocyanate group-containing compound is used as an additive, the adhesive strength can be improved without significantly impairing the curability. Such an isocyanate group-containing compound is not particularly limited, but typical examples are n-butyl isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, benzyl isocyanate, hexamethylene. Diisocyanate, 2-ethylphenyl isocyanate, 2,6
-Dimethylphenyl isocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, tolidine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate,
Examples include 1,3,6-hexamethylene triisocyanate and bicycloheptane triisocyanate.

The addition amount of the isocyanate group-containing compound in the epoxy resin composition of the present invention is the epoxy resin 10
It is in the range of 0.1 to 20 parts by weight with respect to 0 parts by weight.

[0027]

The present invention will be described in more detail with reference to the following examples. (Evaluation method) Pot life: The prepared epoxy resin composition was put in a 50 cc glass sample bottle, and the time until the fluidity disappeared at 25 ° C was visually measured. Viscosity: Measured according to JIS K-6833. Tensile shear adhesive strength: A test piece prepared according to JIS K-6850 is cured at a predetermined temperature for a predetermined time, and a Tensilon universal testing machine (Tensilon manufactured by Toyo Seiki Co., Ltd.)
UTM-5T). Measurement temperature: 25 ° C. Tension speed: 1 mm / min T-type peeling adhesive strength: A test piece prepared according to JIS K-6854 is cured at a predetermined temperature for a predetermined time, and a Tensilon universal testing machine (RTM manufactured by Orientec Co., Ltd.) -500)
It was measured at. Measurement temperature; 25 ° C. Pulling speed; 50 mm / min Alkali metal ion concentration: Flame spectrophotometer (Hitachi 180
-50 type) and quantified by an atomic absorption method.

(Production Example 1) 100 g of a thiol-based curing agent "Epomate QX-12" (trade name of Yuka Shell Co., Ltd.) was placed in a 1-liter Erlenmeyer flask, and 500 ml of acetone was added and dissolved. This solution showed strong alkalinity by pH test paper. While stirring this solution, concentrated hydrochloric acid was added dropwise to adjust the pH of the solution to be weakly acidic, and then the solvent was distilled off under reduced pressure. Add 500 ml of distilled water to the residue and add chloroform 5
Extraction was performed 3 times with 00 ml. Anhydrous magnesium sulfate was added to the organic layer and the mixture was allowed to stand overnight, magnesium sulfate was filtered off, and the filtrate was concentrated under reduced pressure to give purified QX-12. The alkali metal ion concentration of this product was K ⁺ ; 11.2 ppm and Na ⁺ ; 1420 ppm before dealkalization treatment, whereas K ^{+ was} 0.5 ppm after dealkalization treatment.
Below, Na ⁺ was 3.2 ppm.

(Production Example 2) "Epomate QX-12" 2
Add 0 g to a 300 ml Erlenmeyer flask and add methanol 2
00 ml was added and dissolved. Cation exchange resin "Diaion PK216H" (Mitsubishi Kasei)
20 g) was added and the mixture was stirred for 3 hours. After that, the ion exchange resin was filtered off, and the filtrate was concentrated under reduced pressure to obtain purified QX-12. The alkali metal ion concentration of this product is K ⁺ ;
It was 2.2 ppm, Na ⁺ ; 7.9 ppm.

(Example 1) 100 parts by weight of bisphenol A type epoxy resin "EP828" (trade name of Yuka Shell Co., Ltd.) was added with 1 part by weight of "Amicure PN-H" and mixed at room temperature. Purified QX-12 obtained in 2
90 parts by weight of was added and mixed at room temperature to obtain epoxy resin compositions (a) and (b). The pot life of the compositions (a) and (b) was 3 hours. Further, the gel time of the composition (b) at 60 ° C. was 925 seconds.

Comparative Example 1 As a polythiol compound,
"Epomate QX-1 which has not been dealkalized
An epoxy resin composition (c) was obtained in the same manner as in Example 1 except that "2" was used. The pot life of composition (c) was 3 minutes.

(Examples 2 to 5) As an epoxy resin, "E"
P828 "," TMTP "as polythiol compound
(Trimethylolpropane tris (β-thiopropionate), trade name of Yodo Chemical Co., Ltd. K ⁺ ; <0.5 ppm, N
a ⁺ ; 2.9 ppm), and epoxy resin compositions (d) to (g) were prepared using the solid dispersion-type amine adduct-based latent curing accelerators shown in Table 1. Composition (d)
Characteristics of (g) to (g) are shown in Table 1.

(Comparative Examples 2 to 7) Instead of the solid dispersion type amine adduct type latent curing accelerator, "Epomate B-02" (3,9-bis (3-aminopropyl)) which is a liquid curing accelerator is used. -2,4,8,10-Tetraoxaspiro- [5,5] -undecane and butyl glycidyl ether adduct (liquid) (Yukaka Shell Co., Ltd. product name), "2.
E4MZ "(2-ethyl-4-methylimidazole (Shikoku Chemicals trade name)) and" DMP-30 "(2,4,6-tris (dimethylaminomethyl) phenol) were used, and Examples 2 to 5 were used. Epoxy resin compositions (h) to (m) were prepared in the same manner as in. The characteristics of the compositions (h) to (m) are shown in Table 1. Compared with an example using a liquid or soluble amine compound as an accelerator, the present invention has a long pot life,
Moreover, there is a feature that the time required for curing is short.

[0034]

[Table 1]

(Example 6) To 100 parts by weight of "EP828", 2 parts by weight of "Amicure PN-H" was added and mixed at room temperature. Then, "TMTP" was added and defoamed to obtain an epoxy resin composition (n). )-(R) were prepared. Table 2 shows the properties of each composition and the physical properties of the cured product after curing each composition at 80 ° C. for 20 minutes.

[0036]

[Table 2]

(Example 7) To 100 parts by weight of "EP828", 3 parts by weight of "Amicure PN-H" was added and mixed at room temperature, then 74 parts by weight of "TMTP" was added and mixed by defoaming, and then "MR-200". "(Diphenylmethane-4,4'-
Diisocyanate: manufactured by Nippon Polyurethane Co., Ltd. was added to prepare epoxy resin compositions (s) to (v). Table 3 shows the gel time of each composition at 80 ° C. and the shear adhesive strength after curing at 80 ° C. for 20 minutes.

[0038]

[Table 3]

[0039]

The polythiol-based epoxy resin composition of the present invention is excellent in curability at a relatively low heating temperature and has strong adhesive strength, so that it can be used in adhesives, sealing agents, castings and the like. Suitable for use. By adding an isocyanate group-containing compound to the epoxy resin composition of the present invention, the adhesive strength can be further improved without significantly impairing the curability. Further, the epoxy resin composition of the present invention has a very long pot life, and thus is very useful in terms of improving workability. Furthermore, since the excess composition can be stored after use, it is not necessary to dispose of the composition, and the composition of the present invention is very useful in terms of resource saving and environmental protection.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kiyoki Hirai 1-1 Suzuki-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Ajinomoto Co., Inc. Central Research Laboratory (72) Inventor Koji Takeuchi 1 Suzuki-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa -1 Central Research Institute of Ajinomoto Co., Inc. (56) Reference JP 62-285913 (JP, A) JP 2-171720 (JP, A) JP 56-26965 (JP, A) JP Sho-60-21648 (JP, B1) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 59/40 C08G 59/50 C08G 59/66

Claims (3)

(57) [Claims] 1. A (1) epoxy resin having two or more epoxy groups in a molecule, and (2) a polythiol compound having two or more thiol groups in a molecule, which are reacted in a manufacturing process.
Polythiols that do not require the use of basic catalysts as catalysts
Base compound or a basic catalyst as a reaction catalyst in the manufacturing process
Depending on what is used, the alkali metal ion concentration should be 50
An epoxy resin composition containing a polythiol compound in ppm or less , and (3) a solid dispersion type amine adduct-based latent curing accelerator. 2. The epoxy resin composition according to claim 1,
An epoxy resin composition comprising 0.1 to 20 parts by weight of an isocyanate group-containing compound with respect to 100 parts by weight of an epoxy resin. 3. An epoxy resin cured product obtained by heating the epoxy resin composition according to claim 1.