JP5263521B2 - Curable resin composition - Google Patents

Description

The present invention relates to a curable composition, relates to a curable resin composition that is cured in a short time by heating and / or moisture, and is excellent in elasticity, heat resistance, and moisture resistance in a wide temperature range, It can be widely applied to adhesives, sealants, coating agents, casting agents and the like.

Conventionally, one-component resin compositions are known in which a polyamine compound powder that is solid at room temperature is dispersed or mixed as a curing agent in a compound having two or more isocyanate groups in one molecule. (Hereinafter, the polyamine compound powder is referred to as polyamine powder.) It is known that the polyamine compound dissolves and reacts quickly with an isocyanate group when heated to a temperature equal to or higher than the melting point of the polyamine compound, and thus is useful as a thermosetting composition. ing. However, when polyamine powder is added as it is to a compound having an isocyanate group, the storage stability is remarkably reduced due to thickening and gelation, so that it is difficult to make a practical one-component solution. In particular, it is known that a fine powdery polyamine powder of 100 μm or less has a high specific surface area, which further reduces storage stability.

In order to improve the storage stability, a method of dispersing or mixing the polyamine powder whose surface has been treated by various methods is known. In the example shown in paragraph 0040 in Patent Document 1, it is described that the preservability can be maintained when polyamine powder treated with liquid paraffin is added to an isocyanate group-terminated prepolymer. On the other hand, in the comparative example of paragraph 0043, it is shown that when the polyamine powder is not surface-treated with liquid paraffin and the polyamine powder is added to the isocyanate group-terminated prepolymer, the storage stability is significantly lowered. Thus, it can be seen that the surface treatment of the polyamine powder is indispensable for maintaining the storage stability.

Other known surface treatment methods include a method in which inorganic or organic fine powders of 2 μm or less as in Patent Document 2 are physically fixed and coated, or a specific ratio in advance as in Patent Document 3 There are known a method in which a solid polyamine surface is subjected to a reactive surface treatment with an isocyanate compound, and a method in which the solid polyamine surface is coated with a reaction product of paratoluenesulfonyl isocyanate and orthoformate methyl ester as in Patent Document 4. However, these methods are accompanied by a cost reduction due to a decrease in quality accompanying an increase in the number of processes and an increase in processing costs.

Polymers that are liquid at room temperature are known in which a polyol compound and an isocyanate compound are urethane-bonded and have an isocyanate group at the terminal. (Hereinafter, a polymer having an isocyanate group at the liquid end at normal temperature is called a prepolymer.) The polyol compound often has a polyester skeleton or a polyether skeleton. However, as shown in paragraph 0004 of Patent Document 5, these cured products tend to become hardened by reliability tests (100 ° C high temperature test, 85 ° C x 85% RH moisture resistance test, etc.). Have been known for some time, such as peeling from the adherend and cracks in the cured product.

JP-A-5-32948 Special republication WO 1995-26374 JP 7-173243 A JP 2002-302600 A JP 2003-155321 A

Conventionally, by preserving the preservability by treating the surface of the curing agent, a composition having excellent curability has been obtained. However, the manufacturing process of the surface treatment of polyamine powder is complicated, and there are problems in stabilizing the quality and increasing the processing fee. Furthermore, many of the prepolymers conventionally used have a polyester skeleton and a polyether skeleton, and no cured product having such a skeleton satisfies the flexibility, heat resistance and moisture resistance at the same time.

As a result of diligent investigations to achieve the above object, the present inventors have found that a prepolymer in which a powdery curing agent is dispersed or mixed as an isocyanate group at the terminal obtained by reacting a hydrogenated castor oil-based polyol with a polyisocyanate compound. By using a prepolymer containing, a one-part composition having sufficiently stable storage stability even with a powdery curing agent that has not been surface-treated is obtained, which is easily cured by heating and is flexible, heat resistant and moisture resistant. It has been found that a cured product having excellent properties can be obtained.

The gist of the present invention will be described next. The first embodiment of the present invention is a curable resin composition comprising a component (A) and a component (B).
(A) Component: Prepolymer having an isocyanate group at the terminal obtained by reacting (a-1) component with (a-2) component (a-1) Component: Hydrogenated castor oil-based polyol (a-2) Component: Compound (B) having two or more isocyanate groups in one molecule Component: Powder of a compound having two or more primary amine groups and / or secondary amine groups in one molecule

2nd embodiment of this invention is curable resin composition of Claim 1 containing the compound which has a 1 or more isocyanate group in 1 molecule as (C) component.

The third embodiment of the present invention is the curable resin composition according to claim 1 or 2, wherein the component (D) includes a compound having one or more epoxy groups and / or thiirane groups in one molecule.

The fourth embodiment of the present invention is the curable resin composition according to claims 1 to 3, wherein the component (B) is an aliphatic polyamine compound and / or a hydrazide compound.

The fifth embodiment of the present invention is a curing method for curing the curable resin composition according to claims 1 to 4 with heat and / or moisture and a cured product obtained by the curing method.

The present invention quickly cures by heating or moisture in the air to form a cured product having excellent elasticity, heat resistance and moisture resistance, and is used in a wide range of fields such as electric and electronic fields, transportation equipment fields, general bonding, Widely applicable as sealant, casting agent, etc.

Details of the present invention will be described below. In the present invention, the prepolymer having an isocyanate group at the terminal which can be used as the component (A) includes (a-1) component: hydrogenated castor oil-based polyol, and (a-2) component: in one molecule. It is not limited as long as it is a prepolymer obtained by reacting a compound having two or more isocyanate groups.

As a synthesis method, it can be produced by reacting the component (a-1) with an excess amount of the component (a-2) so that the equivalent ratio of isocyanate group / hydroxyl group is 1.2 to 3.5. . The reaction can be carried out by stirring at 20 ° C. to 90 ° C. for 1 to 24 hours under solvent-free and catalyst-free conditions. If necessary, a solvent such as ethyl acetate, toluene, xylene and the like , Organotin catalysts such as dibutyltin dilaurate, bismuth catalysts such as bismuth octylate, titanium catalysts such as titanium alkoxide, tertiary amine catalysts such as 1,4-diaza [2.2.2] bicyclooctane, etc. The polymerization catalyst may be used.

The castor oil-based polyol in the component (a-1) has a broad meaning made of castor oil or a castor oil derivative. Castor oil is refined oil obtained from castor seeds, and is a glycerin ester of fatty acid mainly composed of ricinoleic acid. Among castor oil-based polyols, castor oil is preferably used, and castor oil derivatives include transesterification products of castor oil and polyhydric alcohol, partially dehydrated castor oil, partially acylated castor oil (partially acetylated castor oil, etc. ), Castor oil alkylene oxide adduct, castor oil epoxidized product, castor oil halide, castor oil fatty acid mono- or diester of bisphenol alkylene oxide adduct, esterified product of dimer acid and castor oil-based polyol, polymerized castor A reaction product of a transesterification product of oil and caprolactone, a condensate of dimers or more of castor oil fatty acid, or an ester of the condensate with a polyhydric alcohol, etc. may be used. There is no problem. Two or more kinds may be used in combination.

The hydrogenation in the component (a-1) is obtained by saturation bonding of unsaturated double bonds present in the compound, and is not limited to the method. When using a hydrogenated castor oil-based polyol, long-term heat resistance is superior to using a castor oil polyol.

Hydrogenated castor oil is readily available commercially. For example, castor hardened oil A, castor hardened oil B manufactured by Ito Oil Co., Ltd., K-3-wax manufactured by Kawaken Fine Chemical Co., Ltd., K-3-wax-500, castor wax manufactured by Nippon Oil & Fats Co., Ltd., etc. Is mentioned. Hydrogenated castor oil derivatives can also be easily obtained commercially. Examples thereof include URICPH-5001, PH-5002, PH-6000, URIC1815U, URIC1886U manufactured by Ito Oil Co., Ltd., HS-3G-500B manufactured by Toyokuni Oil Co., Ltd., and the like.

The component (a-2) may be any compound containing two or more isocyanate groups in one molecule, and any of those belonging to aromatic, chain aliphatic or cycloaliphatic can be used. Specifically, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 3,3′-dimethyl-4,4′-biphenylene diisocyanate, 1,4-phenylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, Naphthylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, crude TDI, polymethylene polyphenylisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isomers thereof, isocyanurates, carbodiimides, burettes However, it is not limited to these. Moreover, you may use for the use of these 1 type, or 2 or more types of mixtures.

The component (B) that can be used in the present invention is a powder of a compound having two or more primary amine groups and / or secondary amine groups in the molecule. (Hereinafter, a powder of a compound having a primary amine group and / or a secondary amine group is referred to as a polyamine powder.) Specific examples include 4,4′-diaminodiphenylmethane, 2,4′-diaminodiphenylmethane, 3,3 ′. -Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminobiphenyl, 2,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,4-diaminophenol, 2,5-diaminophenol, o-phenylenediamine, m-phenylenediamine, 2,3-tolylenediamine, 2,4-tolylenediamine, 2,5-tolylenediamine, 2,6-tolylenediamine, 3,4-tolylenediamine, etc. Aromatic polyamine compounds, 1,12-dodecanediamine, 1,10-decanediamine, 1,9-nona Aliphatic polyamine compounds such as diamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, adipic acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, 1,3-bis- (hydrazinocarboethyl) -5-isopropyl Hydantoin eicosane diacid dihydrazide, hydroquinone diglycolic acid dihydrazide, resorcinol diglycolic acid dihydrazide, 4,4'-ethylidenebisphenol diglycolic acid dihydrazide, 7,11-octadecadienene-1,18-dicarbohydrazide, 3,3 Examples include, but are not limited to, hydrazide compounds such as'-(4-isopropyl-2,5-dioxo-1,3-diazolidine-1,3-diyl) dipropionohydrazide. These can be used alone or in combination of two or more. From the viewpoint of storage stability, it is preferable to use an aliphatic polyamine compound and a hydrazide compound. In addition, if the number of steps is not considered and the processing cost is increased, a polyamine compound whose particle surface is inactivated may be used as necessary. By using these inactivated amines, a composition having further improved storage stability is obtained.

(B) As an average particle diameter of a component, 100 micrometers or less, Preferably it is 40 micrometers or less, More preferably, it adjusts to 0.1-20 micrometers. When the center particle diameter exceeds 100 μm, the non-uniformity of the heat-cured product tends to be large and desired physical properties cannot be obtained. The method for adjusting the particles is not particularly limited, and any chemical method and mechanical grinding method can be used.

Known pulverization methods include a jet mill, a planetary ball mill, and a hammer mill. When the melting point of the compound is low, freeze pulverization is effective. On the other hand, as a method for confirming the average particle diameter, there are image analysis such as a particle size / shape distribution measuring instrument of a laser diffraction scattering method or a microsorting control method, an optical microscope, an electron microscope and the like.

(C) component which can be used for this invention can add the compound which has a 1 or more isocyanate group in 1 molecule. As specific examples, in addition to the ianate compound which is the component (a-2), phenyl isocyanate, p-toluenesulfonyl isocyanate, isocyanate ethyl methacrylate, 3-isopropenyl-α, α'-dimethylbenzyl isocyanate, 3-isocyanatepropyl Although triethoxysilane etc. can be used, it is not limited to this. These can be used alone or in combination of two or more. By adding the component (C), the viscosity can be adjusted and the adhesiveness is improved. (Hereinafter, a compound having one or more isocyanate groups in one molecule is referred to as an isocyanate compound.) (C) Component (C) is added in an amount of 0.1 to 100 parts by weight of component (A). Most preferably, it is added in the range of 20 parts by weight.

The blending ratio of the component (A), the component (B), and the component (C) is not particularly limited, and can be used in any ratio according to the purpose. Most preferably, the ratio of the isocyanate equivalent of the sum of components (A) and (C) and the amine equivalent of component (B) falls within the range of 1: 0.4 to 1: 3.0, It is excellent in fast curability of curing within 10 minutes at 100 ° C. and maintaining hardness in the cured product.

To the composition of the present invention, a compound having one or more epoxy groups and / or thiirane groups such as Chemical Formula 1 in one molecule may be added as component (D). (Hereinafter, compounds having one or more epoxy groups or thiirane groups in one molecule are referred to as epoxy compounds or thiirane compounds, respectively.) Preferably, they can be mixed with the prepolymer of the component (A) without separation and at room temperature. It is a liquid compound. They may be used alone or in combination of two or more.

Specific examples of the compound having an epoxy group include diglycidyl ether derived from bisphenol A and epichlorohydrin, and derivatives thereof, diglycidyl ether derived from bisphenol F and epichlorohydrin, and derivatives thereof, so-called epi-bis type. Liquid epoxy resin, glycidyl ether derived from aliphatic / aromatic alcohol and epichlorohydrin, glycidyl ester derived from polybasic acid and epichlorohydrin, and derivatives thereof, glycidyl ether derived from hydrogenated bisphenol A and epichlorohydrin, 3, 4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, vinylcyclohexene oxide, bis (3,4-epoxy-6-methylsilane) Aliphatic cyclic epoxy such as (rohexylmethyl) adipate, and derivatives thereof, 5,5′-dimethylhydantoin type epoxy resin, triglycidyl isocyanate, substituted epoxy derived from isobutylene, γ-glycidoxypropyltrimethoxysilane, etc. A compound containing an alkoxysilyl group in the molecule, 2,2-bis (4- (2,3-epithiopropoxy) phenyl) propane, bis (4- (2,3-epithiopropoxy) phenyl) methane, , 6-di (2,3-epithiopropoxy) naphthalene, 1,1,1-tris- (4- (2,3-epithiopropoxy) phenyl) ethane, 2,2-bis (4- (2, 3-epithiopropoxy) cyclohexyl) propane, bis (4- (2,3-epithiopropoxy) cyclohexyl) methane, 1 , 1,1-tris- (4- (2,3-epithiopropoxy) cyclohexyl) ethane, 1,5-pentanediol 2,3-epithiocyclohexyl) ether, 1,6-hexanediol di (3 , 4-epithiooctyl) ether and the like, but are not limited thereto. Examples of these commercially available products include JER828, 1001, 801, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000, Cardura E10P, YL7000, YL7007, Dainippon, manufactured by Japan Epoxy Resin Co., Ltd. Epiklon 830, 835LV, HP4032D, 703, 720, 726, HP820, manufactured by Ink Industries, Ltd., EP4100, EP4000, EP4080, EP4085, EP4088, EPU6, EPR4023, EPR1309, EP49-20, Nagase Chem, manufactured by Asahi Denka Kogyo Co., Ltd. Denacor EX411, EX314, EX201, EX212, EX252, EX111, EX146, EX721, manufactured by Tex Co., Ltd., Denalex FCA-061L FCA-061M, but manufactured by Shin-Etsu Chemical Co. KBM403, KBE402, etc. it is not limited thereto.

Specific examples of the compound having a thiirane group include 2,2-bis (4- (2,3-epithiopropoxy) phenyl) propane, bis (4- (2,3-epithiopropoxy) phenyl) methane, 1,6-di (2,3-epithiopropoxy) naphthalene, 1,1,1-tris- (4- (2,3-epithiopropoxy) phenyl) ethane, 2,2-bis (4- (2 , 3-epithiopropoxy) cyclohexyl) propane, bis (4- (2,3-epithiopropoxy) cyclohexyl) methane, 1,1,1-tris- (4- (2,3-epithiopropoxy) cyclohexyl) Ethane, 1,5-pentanediol 2,3-epithiocyclohexyl) ether, 1,6-hexanediol di (3,4-epithiooctyl) ether, and the like. The present invention is not limited to these.

By adding the component (D), properties such as viscosity reduction, adhesive strength and durability are improved. Although the compounding ratio of an epoxy compound is not specifically limited, It can add in arbitrary ratios according to the objective, However The said (D) component is 0.1-100 with respect to a total of 100 mass parts of (A) component and (C) component. When added in the range of parts by weight, the viscosity can be reduced, the adhesive force and the durability can be improved without impairing the flexibility that is a characteristic of the cured product.

In the composition of the present invention, an organic tin catalyst, a bismuth catalyst, a titanium catalyst, a moisture polymerization catalyst such as amines, dicyanamide, an amine-epoxy adduct, a urea type adduct, as long as the characteristics of the present invention are not impaired. Epoxy latent catalyst such as solid imidazole, preservability improver such as phosphate ester and borate ester, colorant such as pigment and dye, calcium carbonate, talc, silica, alumina, aluminum hydroxide, magnesium hydroxide, carbon, etc. Inorganic fillers and inorganic fillers whose surfaces are treated with organic acids and coupling agents, flame retardants, organic fillers such as acrylic rubber and silicon rubber, plasticizers, reactive functionalities such as acrylic groups in the molecule Reactive plasticizers containing groups, antioxidants, UV absorbers, antifoaming agents, coupling agents, dehydrating agents, leveling agents, rheology components An additive such as a roll material may be appropriate amount. By these additions, a composition excellent in flexibility, resin strength, adhesive strength, flame retardancy, thermal conductivity, workability, and the like and a cured product thereof can be obtained.

The order in which the constituent components of the present invention are mixed is not particularly limited, but it is preferable to mix other components after first mixing the component (A) and the component (B) in order to improve the storage stability of the composition.

The composition of the present invention can be cured rapidly by heating, but can be cured by moisture in the air without heating. This means that a portion that is insufficiently cured by heating due to uneven heating can be cured by moisture by leaving it indoors, and as a result, the reliability of the adhesive can be further improved.

EXAMPLES Next, although an Example is given and this invention is demonstrated further in detail, this invention is not limited only to these Examples.

[Prepolymer 1]
In a planetary stirrer having a capacity of 3 liters equipped with a heating temperature controller, 800.0 g of (a-1) component: hydrogenated castor oil-based polyol (URIC1815U made by Ito Oil Co., Ltd.) and (a-2) component: diphenylmethane Charge 161.0 g of -4,4'-diisocyanate (Cosmonate PH, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.). The mixture was reacted under stirring in a nitrogen atmosphere at 40 ° C. for 1 hour and at 60 ° C. for 5 hours to obtain a prepolymer 1 as component (A) having a viscosity of 142,000 mPa · s (25 ° C.).

[Prepolymer 2]
To a planetary stirrer having a capacity of 3 liters equipped with a heating temperature controller, 800.0 g of component (a-1): hydrogenated castor oil-based polyol (URIC1815U made by Ito Oil Co., Ltd.) and component (a-2): tri 115.0 g of range isocyanate (Cosmonate T100, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) is charged. The mixture was reacted under stirring in a nitrogen atmosphere at 40 ° C. for 1 hour and at 60 ° C. for 5 hours to obtain a prepolymer 2 as component (A) having a viscosity of 38000 mPa · s (25 ° C.).

[Prepolymer 3]
To a planetary stirrer with a capacity of 3 L equipped with a heating temperature control device, (0.0-1) component (a-1): hydrogenated castor oil-based polyol (URIC1815U made by Ito Oil Co., Ltd.) and (a-2) component: tolylene Add 100.0 g of isocyanate (Cosmonate T80, Mitsui Chemicals Polyurethane Co., Ltd.). The mixture was reacted under stirring in a nitrogen atmosphere at 40 ° C. for 1 hour and at 60 ° C. for 5 hours to obtain a prepolymer 3 as component (A) having a viscosity of 60000 mPa · s (25 ° C.).

[Prepolymer 4]
To a planetary stirrer with a capacity of 3 L equipped with a heating temperature controller, (0.0) component (a-1): hydrogenated castor oil-based polyol (URIC1815U made by Ito Oil Co., Ltd.) and (a-2) component: hexamethylene 81.0 g of diisocyanate (Takenate 700, manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.) and 0.4 g of tin-based catalyst (Neostan U-100, manufactured by Nitto Kasei Co., Ltd.) were added, and the nitrogen atmosphere was 40 ° C for 1 hour at 60 ° C. The prepolymer 4 which is (A) component with a viscosity of 35000 mPa * s (25 degreeC) was obtained by making it react by stirring for 5 hours.

[Prepolymer 5] (Comparative Example)
In a planetary stirrer with a capacity of 3 L equipped with a heating temperature controller, 800.0 g of polyether diol (P3000, manufactured by ADEKA) and (a-2) component: Tolylene diisocyanate (Cosmonate T100, manufactured by Mitsui Chemicals Polyurethanes, Inc.) 94.0 g was charged, and the mixture was reacted under stirring in a nitrogen atmosphere at 40 ° C. for 1 hour and at 60 ° C. for 5 hours to obtain a prepolymer 5 having a viscosity of 5600 mPa · s (25 ° C.).

[Prepolymer 6] (Comparative Example)
A planetary stirrer with a capacity of 3 L equipped with a heating temperature controller, caster oil-based polyol (URIC H-56, manufactured by Ito Oil Co., Ltd.) 600.0 g and (a-2) component: tolylene diisocyanate (Cosmonate T100 Mitsui) (Chemical Polyurethane Co., Ltd.) 148.0 g was added, and the mixture was reacted with stirring at 40 ° C. for 1 hour and at 60 ° C. for 5 hours in a nitrogen atmosphere to obtain a prepolymer 6 having a viscosity of 7300 mPa · s (25 ° C.).

[Polyamine powder 1]
1,10-decanediamine (melting point: 62 ° C.) in the crystal lump state is coarsely pulverized with a crushing and granulating granulator and then pulverized with a jet mill to form an amine fine powder having an average particle size of 5 μm and a maximum particle size of 17 μm Powder 1 was obtained. For the measurement of the particle size, a laser diffraction / scattering type particle size distribution measuring device (LMS-30 manufactured by Seishin Enterprise) was used.

[Polyamine powder 2]
Crystallized 1,12-dodecanediamine (melting point 71 ° C.) was pulverized with a crushing granulator and classified with a sieve to obtain polyamine powder 2 which is an amine fine powder having a maximum particle size of 70 μm.

[Examples 1 to 22]
The following ingredients were prepared to prepare the compositions of Examples 1-22.
Component (A): Prepolymer / Prepolymer 1
・ Prepolymer 2
・ Prepolymer 3
・ Prepolymer 4
(B) component: Polyamine powder / polyamine powder 1
・ Polyamine powder 2
1,3-bis (hydrazinocarbonoethyl) -5-isopropylhydantoin (Amicure VDH-J Ajinomoto Fine Chemical Co., Ltd.)
Component (C): Isocyanate compound / tolylene diisocyanate (T-80 Mitsui Chemicals Polyurethanes)
・ P-Toluenesulfonyl isocyanate (Tokyo Chemical Industry Co., Ltd.)
・ Γ-Isocyanatopropyltriethoxysilane (A-1310 Momentive Performance Material Japan GK)
・ Polyisocyanate (TLA-100 Asahi Kasei Chemicals Corporation)
Component (D): epoxy compound / bisphenol F type epoxy resin (JER807 Japan Epoxy Resin Co., Ltd.)
・ Hydrogenated bisphenol A epoxy resin (YX8000 Japan Epoxy Resin Co., Ltd.)
・ Long chain aliphatic epoxy resin (Denalex FCA-061L Nagase ChemteX Corporation)
Component (D): thiirane compound / episulfide resin (YL7007 Japan Epoxy Resin Co., Ltd.)
Others: Additive-3-glycidoxypropyltrimethoxysilane (KBM-403 Shin-Etsu Chemical Co., Ltd.)
・ Calcium carbonate powder (Softon 1800 Bihoku Powder Chemical Co., Ltd.)
・ Alumina powder (A-43M Showa Denko KK)
・ Plasticizer (GR-301 Ito Oil Co., Ltd.)

[Comparative Examples 1-2]
In order to prepare the compositions of Comparative Examples 1 and 2, the following components were prepared.
Component (A ′): Prepolymer prepolymer 5 not included in component (A)
・ Prepolymer 6
(B) component: Polyamine powder / polyamine powder 1
Component (C): Isocyanate compound / tolylene diisocyanate (T-80 Mitsui Chemicals Polyurethanes)
(D) Component 1: Epoxy compound / bisphenol F type epoxy resin (JER807 Japan Epoxy Resin Co., Ltd.)
Others: Additive-3-glycidoxypropyltrimethoxysilane (KBM-403 Shin-Etsu Chemical Co., Ltd.)
・ Calcium carbonate powder (Softon 1800 Bihoku Powder Chemical Co., Ltd.)

The manufacturing method of Examples 1-22 and Comparative Examples 1-2 is as follows. The component (A) or the component (A ′) and the component (B) are weighed and stirred with a stirrer for 30 minutes. (C) Component, (D) component, and other components are weighed and added to a stirrer, and then stirred for another 30 minutes. Detailed preparation amounts follow Table 1, and all numerical values are expressed in parts by mass. In stirring, it is preferable to stir while vacuum degassing.

The following test was implemented with respect to the curable resin composition of Examples 1-22 and Comparative Examples 1-2. Table 2 shows the results of reactivity, storage stability and hardness.

<Confirmation of reactivity>
Masking 10 mm × 10 mm on the cover glass to squeeze the composition, and removing the mask forms a composition with a coating thickness of 0.3 mm. The cover glass is placed on a hot plate set at 80 ° C. The time until the composition becomes hardened or rubbery and does not flow is observed every 10 seconds to be “gel time” (seconds). However, only Example 3 confirms at 150 degreeC.

<Confirmation of storage stability>
Each composition is placed in a glass bottle with a capacity of 20 ml, and the lid is closed, and then left in a room set at 25 ° C. The number of days until the composition gels and no longer flows is observed every 10 days to be “storage stability” (days). The longest 40-day storage stability is confirmed, and “40 days or more” is described for a composition that has secured the storage stability for 40 days or more.

<Measurement of hardness>
The composition was heated for 10 minutes at 80 ° C. in a state where the composition was sandwiched between PET films that had been release-treated so as to have a thickness of 2 mm, and a sheet-like cured product was created. The sheet-like cured product is punched into a disk having a diameter of 20 mm, and this disk is stacked for three sheets so that no air bubbles enter. “Hardness” (no unit) was measured by using an A hardness durometer with three pieces as one test piece. The details follow JISK6253.

Using Example 19, the “hardness” was measured when the following curing conditions were changed. All measurements are taken immediately at 25 ° C. for 10 minutes. From the following results, it can be seen that a favorable rubber-like cured product is formed under any conditions of heat curing alone, combined use of heat curing and moisture curing, and moisture curing alone.
10 minutes at 60 ° C .: 55
10 minutes at 80 ° C .: 60 (the above hardness measurement)
10 days at 60 ° C. + 25 ° C. × 55% RH for 3 days: 60
30 minutes at 80 ° C .: 60
30 days at 80 ° C. + 3 days at 25 ° C. × 55% RH: 60
7 days at 25 ° C. × 55% RH: 60

<Measurement of tensile shear bond strength>
A test piece of 25 mm × 100 mm × 1.6 mm iron (SPCC) is used. The composition is applied to one test piece and uniformly spread, and then the other test piece is bonded together by superimposing 25 mm in the width direction and 10 mm in the length direction. A test piece was prepared by heating at 80 ° C. for 10 minutes with the jig fixed. After returning to room temperature, the bonded test piece is measured with a tensile tester at a pulling speed of 50 mm / min to obtain “tensile shear bond strength” (MPa). For details, follow JISK6850.

Using Example 20, the tensile shear bond strength was measured using a test piece made of a material other than iron. The measurement results are shown in Table 3 together with details of the materials. As can be seen from these results, it can be seen that even a difficult-to-adhere material has cohesive failure, and therefore has a useful adhesive force as an adhesive.

<Reliability test>
A heat resistance test or a moisture resistance test was performed on the cured products of the compositions of Example 1, Examples 12 to 19, Example 22, and Comparative Examples 1 and 2. The test items were two kinds of tests, the above-mentioned hardness and tensile shear bond strength. The heat resistance test uses a constant temperature furnace set at 130 ° C., and the humidity resistance test uses a constant temperature and humidity furnace set at 85 ° C. × 85% RH, and the test is carried out 14 days after the cured product is charged. When performing the test, the test is performed after the cured product or test piece has returned to room temperature. The results of the heat resistance test are summarized in Table 4, and the results of the moisture resistance test are summarized in Table 5. “NG” in the table represents a state where the measurement cannot be performed because the cured product becomes brittle and collapses.

When the gel times of Examples 1 to 22 and Comparative Examples 1 and 2 in Table 2 are compared, the reactivity is the same because they are cured in the same time, and the storage stability of the table is compared with that of hydrogenated castor oil. In Examples 1 to 22 having a skeleton, the storage stability is improved even if the amine powder is not surface-treated. In the heat resistance test and the moisture resistance test of the reliability test, Comparative Examples 1 and 2 have deteriorated to a state where they cannot be measured due to deterioration of the cured product after the test, but in Examples 1 to 22, the measurement is possible and the initial value The value is not so different. Therefore, the curable resin composition of the present invention is effective in the reliability test.

The present invention relates to a one-component composition that cures in a short time by heating and / or moisture and gives a curable resin composition having excellent elasticity, heat resistance, and moisture resistance in a wide temperature range. It can be widely applied to adhesives, sealants, coating agents, casting agents, etc. in a wide range of fields such as transportation equipment and general adhesion.

Claims (5)

A curable resin composition containing the component (A) and the component (B).
(A) Component: Prepolymer having an isocyanate group at the terminal obtained by reacting (a-1) component with (a-2) component (a-1) Component: Hydrogenated castor oil-based polyol (a-2) Component: Compound (B) having two or more isocyanate groups in one molecule Component: Nothing fixed to the powder surface, Compound having two or more primary amine groups and / or secondary amine groups in one molecule Powder of (C) The curable resin composition of Claim 1 containing the compound which has a 1 or more isocyanate group in 1 molecule as a component. (D) The curable resin composition in any one of Claim 1 or 2 containing the compound which has a 1 or more epoxy group and / or thiirane group in 1 molecule as a component. The curable resin composition according to claim 1 , wherein the component (B) is an aliphatic polyamine compound and / or a hydrazide compound. A curing method for curing the curable resin composition according to claim 1 with heat and / or moisture, and a cured product obtained by the curing method.